阅读说明：本技术 生产氢气的方法 (Method for producing hydrogen ) 是由 马修·达姆森 尼古拉斯·法兰多斯 金·达姆森 于 2020-01-10 设计创作，主要内容包括：一种生产氢气的方法包括：提供一种装置,将包含燃料的第一流引入装置,将包含水的第二流引入装置,将第二流中的水还原为氢气,以及从装置中提取氢气。第一流和第二流在装置中彼此不接触。(A method of producing hydrogen comprising: an apparatus is provided for introducing a first stream comprising a fuel into the apparatus, introducing a second stream comprising water into the apparatus, reducing the water in the second stream to hydrogen, and extracting the hydrogen from the apparatus. The first and second streams do not contact each other in the apparatus.)

1. A method of producing hydrogen, the method comprising: providing an apparatus, introducing a first stream comprising a fuel into the apparatus, introducing a second stream comprising water into the apparatus, reducing the water in the second stream to hydrogen, and extracting the hydrogen from the apparatus, wherein the first stream and the second stream do not contact each other in the apparatus.

2. The method of claim 1, wherein the first stream is not in contact with the hydrogen.

3. The method of claim 1, wherein the first and second flows are separated in the device by an electrolyte.

4. The method of claim 3, wherein the electrolyte is oxygen ion conductive and is in a solid state.

5. The method of claim 3, wherein the electrolyte comprises doped ceria, or wherein the electrolyte comprises lanthanum chromite or a conductive metal, or a combination thereof, and a material selected from the group consisting of: doped ceria, YSZ, LSGM, SSZ, and combinations thereof.

6. The method of claim 5, wherein the lanthanum chromite comprises an undoped lanthanum chromite, a strontium-doped lanthanum chromite, an iron-doped lanthanum chromite, a lanthanum calcium chromite, or a combination thereof; and wherein the conductive metal comprises Ni, Cu, Ag, Au, or a combination thereof.

7. The method of claim 4, wherein the electrolyte also conducts electrons, and wherein the device does not include an interconnect.

8. The method of claim 1, wherein the device is tubular.

9. The method of claim 1, wherein the fuel comprises a hydrocarbon or hydrogen or carbon monoxide or a combination thereof.

10. The method of claim 1, wherein the second stream comprises hydrogen.

11. The method of claim 1, wherein the first stream further comprises water or carbon dioxide.

12. The method of claim 1, wherein the first stream comprises the fuel with little to no water.

13. The method of claim 1, wherein the device is planar.

14. The method of claim 13, wherein the device comprises a plurality of repeating units separated by interconnects, wherein each repeating unit comprises two electrodes with an electrolyte between the electrodes.

15. The method of claim 14, wherein the electrode comprises a fluid channel or a fluid dispersion assembly and the interconnect does not comprise a fluid dispersion element.

16. The method of claim 1, comprising introducing the first stream into a reformer before the first stream enters the apparatus.

17. The method of claim 16, wherein the reformer is a steam reformer or an autothermal reformer.

18. The method of claim 1, wherein the device is operated at a temperature of not less than 500 ℃.

19. The method of claim 1, wherein the device comprises a first electrode and a second electrode separated by an electrolyte, wherein the first electrode or the second electrode comprises Ni or NiO and a material selected from the group consisting of: YSZ, CGO, SDC, SSZ, LSGM, and combinations thereof.

20. The method of claim 1, wherein the device comprises a first electrode and a second electrode separated by an electrolyte, wherein the first electrode comprises doped or undoped ceria and a material selected from the group consisting of: cu, CuO, Cu₂O、Ag、Ag₂O、Au、Au₂O、Au₂O₃Pt, Pd, Ru, Rh, stainless steel and combinations thereof.

21. The method of claim 20, wherein the first electrode comprises a catalyst.

Technical Field

The present invention generally relates to electrochemical reactors. More particularly, the present invention relates to electrochemical reactors for producing synthesis gas and hydrogen.

Background

Syngas (i.e., synthesis gas) is a mixture consisting primarily of hydrogen, carbon monoxide, and usually carbon dioxide. It is used as an intermediate in the production of a variety of products such as synthetic natural gas, ammonia, methanol, hydrogen, synthetic fuels, synthetic lubricants. Syngas can be produced from almost any hydrocarbon feedstock, such as natural gas, coal, biomass, by steam reforming, dry reforming, partial oxidation or gasification. Syngas is combustible and is often used in internal combustion engines or for electricity production, although its energy density is less than half that of natural gas.

Large amounts of hydrogen are required in the petroleum and chemical industries. For example, large amounts of hydrogen are used for fossil fuel upgrading and the production of ammonia or methanol or hydrochloric acid. Petrochemical plants require hydrogen for hydrocracking, hydrodesulfurization, hydrodealkylation. Hydrogenation processes that increase the saturation level of unsaturated fats and oils also require hydrogen. Hydrogen is also a reducing agent for metal ores. Hydrogen can be produced from electrolysis of water, steam reforming, laboratory-scale metal-acid processes, thermochemical processes or anoxic corrosion. Many countries aim for the economy of hydrogen.

Clearly, there is still a need and interest in developing methods and systems for producing these important gases.

Disclosure of Invention

Other aspects and embodiments are provided in the following figures, detailed description, and claims. Unless specifically stated otherwise, features as described herein are combinable and all such combinations are within the scope of the present disclosure.

One aspect of the invention is a method of producing hydrogen gas comprising providing a device, introducing a first stream comprising fuel into the device, introducing a second stream comprising water into the device, reducing the water in the second stream to hydrogen gas, and withdrawing hydrogen gas from the device. The first and second streams do not contact each other in the apparatus.

In another method aspect, the first stream is not contacted with hydrogen.

In another method aspect, the first and second streams are separated in the apparatus by an electrolyte.

In other method aspects, the electrolyte is oxygen ion conducting (oxide ion conducting, oxygen ion conducting) and is in a solid state.

In still further method aspects, the electrolyte comprises doped ceria or wherein the electrolyte comprises lanthanum chromite or a conductive metal or a combination thereof and a material selected from the group consisting of doped ceria, YSZ, LSGM, SSZ, and combinations thereof. Lanthanum chromite includes undoped lanthanum chromite, strontium-doped lanthanum chromite, iron-doped lanthanum chromite, lanthanum calcium chromite (lanthanum calcium chromite), or combinations thereof. The conductive metal includes Ni, Cu, Ag, Au, or a combination thereof.

In a still further method aspect, the electrolyte also conducts electrons and wherein the device does not include interconnects.

In another method aspect, the device is tubular.

In yet another method aspect, the fuel comprises a hydrocarbon or hydrogen or carbon monoxide or a combination thereof.

In still other method aspects, the second stream comprises hydrogen.

In still other method aspects, the first stream further comprises water or carbon dioxide.

In yet another method aspect of the invention, the first stream comprises a fuel having little to no (little to no) water.

In another method aspect, the device is planar.

In yet another method aspect, a device includes a plurality of repeat units separated by interconnects. Each repeating unit includes two electrodes with an electrolyte therebetween.

In still other method aspects, the electrode comprises a fluid channel or fluid dispersing component and the interconnect does not comprise a fluid dispersing element.

In still other method aspects, a method of producing hydrogen includes introducing a first stream into a reformer prior to the first stream entering a device.

In yet another process aspect of the invention, the reformer is a steam reformer or an autothermal reformer.

In still other process aspects, a process for producing hydrogen comprises operating a plant at a temperature of not less than 500 ℃.

In another method aspect, an apparatus includes a first electrode and a second electrode separated by an electrolyte. The first electrode or the second electrode comprises Ni or NiO and a material selected from the group consisting of YSZ, CGO, SDC, SSZ, LSGM, and combinations thereof.

In yet another method aspect, an apparatus includes a first electrode and a second electrode separated by an electrolyte. The first electrode comprises doped or undoped cerium dioxide and is selected from the group consisting of Cu, CuO, Cu₂O、Ag、Ag₂O、Au、Au₂O、Au₂O₃Pt, Pd, Ru, Rh, stainless steel and combinations thereof.

In still other method aspects, the first electrode comprises a catalyst.

Drawings

The following figures are provided to illustrate certain embodiments described herein. The drawings are illustrative only and are not intended to limit the scope of the claimed invention and are not intended to show every possible feature or embodiment of the claimed invention. The figures are not necessarily to scale; in some instances, certain elements of the drawings may be exaggerated relative to other elements of the drawings for illustrative purposes.

Fig. 1A shows an Electrochemical (EC) gas generator according to an embodiment of the present disclosure.

Fig. 1B shows an EC gas generator according to an embodiment of the present disclosure.

Fig. 2A shows a tubular EC gas generator according to an embodiment of the present disclosure.

Fig. 2B shows a cross-section of a tubular EC gas generator according to an embodiment of the present disclosure.

Fig. 3A shows a cross-section of a multi-tubular EC gas generator according to an embodiment of the present disclosure;

fig. 3B shows a cross-section of a multi-tubular EC gas generator according to an embodiment of the present disclosure;

fig. 3C shows a cross-section of a multi-tubular EC gas generator according to an embodiment of the present disclosure;

fig. 3D shows a cross-section of an EC gas generator according to an embodiment of the present disclosure;

fig. 4A shows a portion of a method of producing an EC gas generator using a single point EMR source, according to an embodiment of the present disclosure.

FIG. 4B shows a portion of a method of producing an EC gas generator using an annular lamp EMR source, according to an embodiment of the present disclosure.

Fig. 4C shows a portion of a method of producing an EC gas generator using a single point EMR source, according to an embodiment of the present disclosure.

FIG. 4D shows a portion of a method of producing an EC gas generator using a tubular EMR source, in accordance with an embodiment of the present disclosure;

FIG. 5A shows a first step in a tape casting method for forming a tubular or multi-tubular EC gas generator, according to an embodiment of the present disclosure;

FIG. 5B shows steps 2-4 in a tape casting process for forming a tubular or multi-tubular EC gas generator, according to embodiments of the present disclosure;

fig. 6A shows an example of a hydrogen production system 600 without an external heat source, according to an embodiment of the present disclosure;

FIG. 6B shows an alternative hydrogen production system without an external heat source, according to embodiments of the present disclosure;

FIG. 7 shows a fuel cell assembly according to an embodiment of the present disclosure;

FIG. 8 schematically shows two fuel cells in a fuel cell stack according to an embodiment of the present disclosure;

fig. 9A shows a perspective view of a Fuel Cell Cartridge (FCC), according to an embodiment of the present disclosure;

fig. 9B shows a perspective view of a cross-section of a Fuel Cell Cartridge (FCC), according to an embodiment of the present disclosure;

fig. 9C shows a cross-sectional view of a Fuel Cell Cartridge (FCC), according to an embodiment of the present disclosure;

Fig. 9D shows top and bottom views of a Fuel Cell Cartridge (FCC), according to an embodiment of the present disclosure;

fig. 10A shows a cross-sectional view of a TFC according to an embodiment of the present disclosure;

fig. 10B shows a cross-sectional view of a TFC according to an embodiment of the present disclosure;

fig. 10C shows a cross-sectional view of a TFC according to an embodiment of the present disclosure;

FIG. 11A shows a cross-sectional view of a TFC containing support (support), according to an embodiment of the present disclosure;

fig. 11B shows a cross-sectional view of a TFC with a support, according to an embodiment of the disclosure;

fig. 11C shows a cross-sectional view of a TFC with a support, according to an embodiment of the disclosure;

fig. 12A shows an impermeable interconnect 1202 with a fluid dispersion assembly 1204, according to an embodiment of the disclosure;

fig. 12B shows an impermeable interconnect 1202 with two fluid dispersion assemblies 1204, in accordance with an embodiment of the present disclosure;

fig. 12C shows a segmented fluid dispersing component 1204 having a similar shape but different size on impermeable interconnect 1202, in accordance with embodiments of the present disclosure;

fig. 12D shows a segmented fluid dispersion assembly 1204 having a similar shape and similar dimensions on an impermeable interconnect 1202, in accordance with embodiments of the present disclosure;

FIG. 12E shows a similarly shaped and similarly sized but close-packed (close-packed) segmented fluid dispersion assembly 1204 on an impermeable interconnect 1202, in accordance with embodiments of the present disclosure;

fig. 12F shows segmented fluid dispersion assemblies 1204 having different shapes and different sizes on impermeable interconnects 1202, in accordance with embodiments of the present disclosure;

fig. 12G shows an impermeable interconnect 1202 and a fluid dispersing component segment 1204, in accordance with embodiments of the present disclosure;

FIG. 12H shows an impermeable interconnect and a fluid dispersion assembly segment, according to an embodiment of the disclosure;

FIG. 12I shows an impermeable interconnect and a fluid dispersion assembly segment, according to an embodiment of the disclosure;

fig. 12J shows an impermeable interconnect 1202 and a fluid dispersion assembly segment 1204, in accordance with embodiments of the present disclosure;

fig. 12K shows the fluid dispersion assembly 1204, according to an embodiment of the disclosure;

fig. 13A shows a template 1300 for fabricating a channeled electrode, in accordance with embodiments of the present disclosure;

fig. 13B is a cross-sectional view of a half cell positioned between a first interconnect and an electrolyte, according to an embodiment of the present disclosure;

Fig. 13C is a cross-sectional view of a half cell positioned between a second interconnect and an electrolyte, according to an embodiment of the present disclosure;

fig. 13D is a cross-sectional view of a half cell positioned between a first interconnect and an electrolyte, according to an embodiment of the present disclosure;

fig. 13E is a cross-sectional view of a half cell positioned between a second interconnect and an electrolyte, according to an embodiment of the present disclosure;

FIG. 14A schematically illustrates a number of segments (segments) of a fluid dispersion member in a first layer, in accordance with an embodiment of the present disclosure;

FIG. 14B schematically illustrates a fluid dispersion assembly in a first layer and a second layer, according to an embodiment of the disclosure;

FIG. 14C schematically illustrates a fluid dispersion assembly in the first layer and the second and third layers, according to an embodiment of the disclosure;

FIG. 14D schematically illustrates a fluid dispersion assembly in a first layer and a second layer, according to an embodiment of the disclosure;

FIG. 15 is an illustrative example of an electrode having dual porosity (dual porosity) in accordance with an embodiment of the present disclosure;

FIG. 16 shows a system for integrated deposition (integrated deposition) and heating using electromagnetic radiation (EMR), according to an embodiment of the present disclosure;

FIG. 17 is a scanning electron microscope image; and

figure 18 schematically shows an example of a half cell in an EC reactor.

Detailed Description

SUMMARY

Embodiments of the methods, materials, and processes described herein are directed to electrochemical reactors. The electrochemical reactor comprises a solid oxide fuel cell, a solid oxide fuel cell stack, an electrochemical gas generator, an electrochemical compressor, a solid state battery, or a solid oxide flow battery.

Electrochemical gas generators may be used to produce syngas, hydrogen, or other gases for use as fuel or feedstock for fuel cells, for ammonia production, fertilizer production, hydrogenation reactions, Bosch reactions, or other applications. The disclosure herein describes a method of producing hydrogen using a device. The device may be an electrochemical gas generator and may be planar or tubular in shape.

Definition of

The following description sets forth various aspects and embodiments of the invention disclosed herein. The particular embodiments are not intended to limit the scope of the invention. However, the embodiments provide non-limiting examples of various compositions and methods that are encompassed within the scope of the claimed invention. This description will be read from the perspective of one of ordinary skill in the art. Thus, it is not necessary to include information that is well known to those of ordinary skill.

Unless otherwise provided herein, the following terms and phrases have the meanings indicated below. The disclosure may use other terms and phrases not expressly defined herein. These other terms and phrases should have the meaning that they would have in the context of this disclosure to those of ordinary skill in the art. In some instances, terms or phrases may be defined in the singular or plural. In these cases, it is to be understood that any term in the singular may include its plural counterpart and vice versa, unless explicitly stated to the contrary.

As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. For example, reference to "an alternative" encompasses a single alternative as well as two or more alternatives, and the like. As used herein, "for example," "such as," or "including" means to introduce examples that further clarify more general subject matter. These examples are provided merely as an aid to understanding the embodiments described in this disclosure and are not intended to be limiting in any way unless explicitly stated otherwise. Nor do these phrases indicate any sort of preference for the disclosed embodiments.

As used herein, unless otherwise specified, compositions and materials are used interchangeably. Each composition/material may have multiple elements, phases and components. As used herein, heating refers to the active addition of energy to a composition or material.

The term "in situ" in this disclosure refers to a treatment (e.g., heating) process performed at the same location or in the same apparatus as the formation process of the composition or material. For example, the deposition process and the heating process are carried out in the same apparatus and at the same location, in other words, without changing the apparatus and without changing the location within the apparatus. For example, the deposition process and the heating process are performed at different locations in the same apparatus, which is also considered to be in-situ.

In the present disclosure, a major face of an object is a face of the object having a surface area greater than the average surface area of the object, where the average surface area of the object is the total surface area of the object divided by the number of object faces. In some cases, a major face refers to a face of an object or object having a surface area greater than a minor face. In the case of a planar fuel cell or a non-SIS type fuel cell, the major surface is a lateral surface or surface.

As used herein, lateral refers to a direction perpendicular to the stacking direction of layers in a non-SIS type fuel cell. Thus, the lateral direction refers to a direction perpendicular to the stacking direction of layers in the fuel cell or the stacking direction of sheets (slices) that form an object during deposition. Lateral also refers to the direction of diffusion of the deposition process.

In the present disclosure, a liquid precursor of a substance refers to a dissolved form containing the substance, such as a salt in an aqueous solution. For example, copper salts dissolved in aqueous solutions are considered to be liquid precursors of copper. Copper particles suspended/dispersed (not dissolved) in a liquid are not considered to be liquid precursors of copper.

As used herein, CGO refers to gadolinium doped ceria, alternatively also referred to as gadolinium oxide doped ceria, gadolinium doped ceria (IV), GDC or GCO (formula Gd: CeO)₂). Unless otherwise specified, CGO and GDC are used interchangeably.

In the present disclosure, syngas (i.e., synthesis gas) refers to a mixture consisting primarily of hydrogen, carbon monoxide, and carbon dioxide.

In this disclosure, absorbance is a measure of the ability of a substance to absorb electromagnetic radiation (EMR) at a certain wavelength. Radiation absorption refers to the energy absorbed by a substance when exposed to radiation.

As used herein, ceria refers to cerium oxide (cerium oxide), also known as ceria (ceric oxide), ceria (ceric dioxide), or ceria (cerium dioxide), which is an oxide of the rare earth metal cerium. Doped ceria refers to ceria doped with other elements, such as samarium oxide doped ceria (SDC) or gadolinium doped ceria (GDC or CGO).

As used herein, chromite (chromite) refers to chromium oxide, which includes all oxidation states of chromium oxide.

As used herein, "having little to no water" means having a water content of no greater than 1 g/m³Or not more than 200 mg/m³Or not more than 50 mg/m³。

Interconnects in electrochemical devices (e.g., fuel cells) are typically metallic or ceramic, which are disposed between individual cells or repeating units. The purpose is to connect each cell or repeating unit so that electricity can be distributed or combined. Interconnects are also referred to as bipolar plates in electrochemical devices. An interconnect as an impermeable layer as used herein means that it is a layer that is impermeable to fluid flow. For example, the permeability of the impermeable layer is less than 1 microdarcy, or less than 1 nadarcy.

In the present disclosure, an interconnect without a fluid dispersion element refers to an interconnect without an element (e.g., channel) that disperses a fluid. The fluid may comprise a gas or a liquid or a mixture of a gas and a liquid. These fluids may include one or more of hydrogen, methane, ethane, propane, butane, oxygen, ambient air, or light hydrocarbons (i.e., pentane, hexane, octane). Such interconnects may have an inlet and an outlet (i.e., openings) for the passage of materials or fluids.

In the present disclosure, the term "microchannel" is used interchangeably with microfluidic channel or microfluidic flow channel.

In the present disclosure, sintering refers to a method of forming a solid block of material by heat or pressure or a combination thereof without melting the material to a degree of liquefaction. For example, the material particles are agglomerated into a solid or porous mass by heating, wherein atoms in the material particles diffuse through the particle boundaries, causing the particles to fuse together and form a solid mass. In the present disclosure and appended claims, T_SinteringRefers to the temperature at which this phenomenon begins to occur.

As used herein, the term "pore former" is intended to have a relatively broad meaning. "pore former" may refer to any particulate material contained in the composition during formation that may be partially or completely vacated by a process such as heating, burning, or evaporation. As used herein, the term "electrically conductive components" is intended to mean electrically conductive components in a fuel cell, such as electrodes and interconnects.

For illustrative purposes, the production of Solid Oxide Fuel Cells (SOFC) will be used herein as an example system to describe various embodiments. As recognized by one of skill in the art, the methods and production methods described herein are applicable to any electrochemical device, reactor, vessel, catalyst, or the like. Examples of electrochemical devices or reactors include Electrochemical (EC) gas generators, Electrochemical (EC) compressors, solid oxide fuel cells, solid oxide fuel cell stacks, solid state batteries, or solid oxide flow batteries. In one embodiment, the electrochemical reactor comprises a solid oxide fuel cell, a solid oxide fuel cell stack, an electrochemical gas generator, an electrochemical compressor, a solid state battery, or a solid oxide flow battery. The catalyst comprises a Fischer-Tropsch (FT) catalyst or a reformer catalyst. The reactor/vessel includes an FT reactor or heat exchanger.

Electrochemical (EC) gas generator

Fig. 1A shows an Electrochemical (EC) gas generator 100 according to an embodiment of the present disclosure. EC gas generatorThe device 100 comprises a first electrode 101, an electrolyte 103 and a second electrode 102. The first electrode 101 is configured to receive fuel and not oxygen 104. The second electrode 102 is configured to receive water or nothing, as indicated by arrow 105. The apparatus 100 is configured to simultaneously produce hydrogen 107 from the second electrode 102 and syngas 106 from the first electrode 101. In one embodiment, 104 represents methane and water or methane and carbon dioxide entering the apparatus 100. In other embodiments, 103 represents an oxygen ion conducting membrane (oxide ion conducting membrane). In one embodiment, the first electrode 101 and the second electrode 102 may comprise Ni-YSZ or NiO-YSZ. Arrows 104 represent hydrocarbon and water or hydrocarbon and carbon dioxide inflow. Arrows 105 represent the inflow of water or water and hydrogen. In some embodiments, the electrode 101 comprises Cu-CGO, which further optionally comprises CuO or Cu₂O or a combination thereof. The electrode 102 comprises Ni-YSZ or NiO-YSZ. Arrows 104 represent inflow of hydrocarbons with little to no water, no carbon dioxide and no oxygen, and 105 represents inflow of water or water and hydrogen. Water is considered to be an oxidant in this case, since it provides the oxygen ions (which are transported through the electrolyte) needed to oxidize the hydrocarbon/fuel at the opposite electrode.

Fig. 1B shows an EC gas generator 110 according to an embodiment of the present disclosure. The EC gas generator device 110 comprises a first electrode 111, a second electrode 112 and an electrolyte 113 located between the electrodes. The first electrode 111 is configured to receive fuel and not oxygen 104, wherein the second electrode 112 is configured to receive water or nothing. In some embodiments, 113 represents a proton conducting membrane (proton conducting membrane), 111 and 112 represent Ni-barium zirconate electrodes. Hydrogen 107 is produced from the second electrode 112 and syngas 106 is produced from the first electrode 111.

In the present disclosure, oxygen-free means that there is no oxygen or at least insufficient oxygen present at the first electrode 101, 111 to interfere with the reaction. In addition, in the present disclosure, water merely means that the predetermined raw material is water and does not exclude trace elements or inherent components in water. For example, water containing salts or ions is considered to be in the range of water alone. Water alone also does not require 100% pure water, but includes such embodiments. In an embodiment, the hydrogen gas produced from the second electrode 102, 112 is pure hydrogen, meaning that hydrogen is the predominant component in the gas phase produced from the second electrode. In some cases, the hydrogen content is not less than 99.5%. In some cases, the hydrogen content is not less than 99.9%. In some cases, the hydrogen gas produced from the second electrode is of the same purity as that produced from the electrolysis of water.

In one embodiment, the first electrodes 101, 111 are configured to receive methane and water or methane and carbon dioxide. In one embodiment, the fuel comprises hydrocarbons having a carbon number in the range of 1-12, 1-10, or 1-8. Most preferably, the fuel is methane or natural gas, which is primarily methane. In one embodiment, the device does not generate electricity. In one embodiment, the apparatus includes a mixer configured to receive at least a portion of the first electrode product and at least a portion of the second electrode product. The mixer may be configured to produce a gas stream wherein the ratio of hydrogen to carbon oxide is not less than 2, or not less than 3, or between 2 and 3.

In one embodiment, the first electrode 101, 111 or the second electrode 102, 112, or both the first electrode 101, 111 and the second electrode 102, 112, comprise a catalyst and a substrate, wherein the mass ratio between the catalyst and the substrate is not less than 1/100, or not less than 1/10, or not less than 1/5, or not less than 1/3, or not less than 1/1. In one embodiment, the catalyst comprises nickel oxide, silver, cobalt, cesium, nickel, iron, manganese, nitrogen, tetranitrogen (tetra-nitro), molybdenum, copper, chromium, rhodium, ruthenium, palladium, osmium, iridium, or platinum, or a combination thereof. In one embodiment, the substrate comprises gadolinium, CeO ₂、ZrO₂、SiO₂、TiO₂Steel, cordierite (2 MgO-2 Al)₂O₃-5SiO₂) Aluminum titanate (Al)₂TiO₅) Silicon carbide (SiC), all phases of alumina, yttria-or scandia-stabilized zirconia (YSZ), gadolinia or samaria-doped ceria, or combinations thereof. In some embodimentsWherein the first electrode 101, 111 or the second electrode 102, 112, or both the first electrode 101, 111 and the second electrode 102, 112 comprise a promoter, wherein the promoter is selected from the group consisting of Mo, W, Ba, K, Mg, Fe, and combinations thereof. In one embodiment, the anode (e.g., the first electrode or the second electrode) comprises a catalyst, wherein the catalyst is selected from the group consisting of nickel, iron, palladium, platinum, ruthenium, rhodium, cobalt, and combinations thereof.

In some embodiments, the electrode and the electrolyte form a repeating unit. The device may comprise two or more repeating units separated by an interconnect. In a preferred embodiment, the interconnect does not contain a fluid dispersion element. In one embodiment, either the first electrode 101, 111 or the second electrode 102, 112, or both the first electrode 101, 111 and the second electrode 102, 112, comprise a fluidic channel. Alternatively, the first electrode 101, 111 or the second electrode 102, 112, or both the first electrode 101, 111 and the second electrode 102, 112 comprise a fluid dispersion member.

Also discussed herein are methods of assembly that include forming first electrodes 101, 111, forming second electrodes 102, 112, and forming electrolytes 103, 113 positioned between the electrodes, wherein the electrodes and electrolytes are assembled as they are formed. Forming may include material jetting, binder jetting, ink jet printing, aerosol jetting or aerosol jet printing, vat photopolymerization, powder layer fusion, material extrusion, directed energy deposition, sheet lamination, ultrasonic ink jet printing, or combinations thereof. The electrodes and electrolyte may form a repeating unit. The method can also include forming two or more repeating units and forming an interconnect between the two or more repeating units. The assembly method may further comprise forming a fluid channel or fluid dispersion member in the first electrode 101, 111 or the second electrode 102, 112, or both the first electrode 101, 111 and the second electrode 102, 112. The forming method may include in situ heating. In a preferred embodiment, the heating comprises EMR. The EMR may include one or more of UV light, near ultraviolet light, near infrared light, visible light, laser light, or electron beams.

The first electrode 101, 111 is configured to receive fuel and not oxygen, wherein the second electrode 102, 112 is configured to receive only water or nothing, wherein the apparatus is configured to simultaneously produce hydrogen from the second electrode 102, 112 and syngas from the first electrode 101, 111.

Further discussed herein are methods that include providing an apparatus comprising a first electrode 101, 111, a second electrode 102, 112, and an electrolyte 103, 113 positioned between the electrodes, introducing an oxygen-free fuel into the first electrode 101, 111, introducing water only or nothing into the second electrode 102, 112 to produce hydrogen, extracting hydrogen from the second electrode 102, 112, and extracting a syngas from the first electrode 101, 111. In a preferred embodiment, the fuel comprises methane and water or methane and carbon dioxide. In preferred embodiments, the fuel comprises hydrocarbons having a carbon number in the range of from 1 to 12, or from 1 to 10, or from 1 to 8.

In one embodiment, the process comprises feeding at least a portion of the extracted syngas to a fischer-tropsch reactor. In one embodiment, the process comprises feeding at least a portion of the extracted hydrogen to a fischer-tropsch reactor. In one embodiment, at least a portion of the extracted syngas and at least a portion of the extracted hydrogen are adjusted such that the ratio of hydrogen to carbon oxides is not less than 2, or not less than 3, or between 2 and 3.

In one embodiment, the fuel is introduced directly into the first electrode 101, 111, or the water is introduced directly into the second electrode 102, 112, or both the first electrode 101, 111 and the second electrode 102, 112. In one embodiment, the first electrode 101, 111 or the second electrode 102, 112, or both the first electrode 101, 111 and the second electrode 102, 112, comprise a catalyst and a substrate, wherein the mass ratio between the catalyst and the substrate is not less than 1/100, or not less than 1/10, or not less than 1/5, or not less than 1/3, or not less than 1/1. In a preferred embodiment, the catalyst comprises nickel oxide, silver, cobalt, cesium, nickel, iron, manganese, nitrogen, tetranitrogen, molybdenum, copper, chromium, rhodium, ruthenium, palladium, osmium, iridium, platinum, or combinations thereof. In a preferred embodiment, the substrate comprises gadolinium, CeO ₂、ZrO₂、SiO₂、TiO₂Steel, cordierite (2 MgO-2 Al)₂O₃-5SiO₂) Aluminum titanate (Al)₂TiO₅) Silicon carbide (SiC), all phases of alumina, yttria-or scandia-stabilized zirconia (YSZ), gadolinia or samaria-doped ceria, or combinations thereof.

In one embodiment, the method comprises applying a potential difference between the first electrode 101, 111 and the second electrode 102, 112. In one embodiment, the method comprises using the extracted hydrogen in one or a combination of the following reactions: fischer-tropsch (FT) reactions, dry reforming reactions, Sabatier (Sabatier) reactions catalysed by nickel, Bosch (Bosch) reactions, reverse water gas shift reactions, electrochemical reactions producing electricity, production of ammonia and/or fertilizers, electrochemical compressors for hydrogen storage or hydrogen vehicle fueling, or hydrogenation reactions.

In various embodiments, the gas generator is not a fuel cell and does not generate electricity. In some cases, electricity may be applied to the gas generator at the anode and cathode. In other cases, no electricity is required.

Disclosed herein are devices comprising a first electrode, a second electrode, and an electrolyte disposed between the electrodes, wherein the first electrode and the second electrode comprise a metal phase that is free of platinum group metals when the device is in use, and wherein the electrolyte is oxygen ion conductive. In one embodiment, wherein the first electrode comprises Ni or NiO and a material selected from the group consisting of YSZ, CGO, samarium oxide doped ceria (SDC), Scandia Stabilized Zirconia (SSZ), LSGM, and combinations thereof. In one embodiment, the first electrode is configured to receive fuel and water or fuel and carbon dioxide. In one embodiment, the fuel comprises a hydrocarbon or hydrogen or carbon monoxide or a combination thereof.

In one embodiment, the first electrode comprises doped or undoped ceria and is selected from the group consisting of Cu, CuO, Cu2O, Ag₂O、Au、Au₂O、Au₂O₃Stainless steel, and combinations thereof. At one isIn an embodiment, the first electrode is configured to receive fuel having little to no water. In one embodiment, the fuel comprises a hydrocarbon or hydrogen or carbon monoxide or a combination thereof. In one embodiment, the second electrode comprises Ni or NiO and a material selected from the group consisting of Yttria Stabilized Zirconia (YSZ), Cerium Gadolinium Oxide (CGO), samarium oxide doped ceria (SDC), Scandia Stabilized Zirconia (SSZ), strontium magnesium doped lanthanum gallate (LSGM), and combinations thereof. In one embodiment, the second electrode is configured to receive water and hydrogen gas and is configured to reduce the water to hydrogen gas. In one embodiment, the electrolyte comprises doped ceria or wherein the electrolyte comprises lanthanum chromite or a conductive metal or a combination thereof and a material selected from the group consisting of doped ceria, YSZ, LSGM, SSZ, and combinations thereof. In one embodiment, the lanthanum chromite comprises an undoped lanthanum chromite, a strontium-doped lanthanum chromite, an iron-doped lanthanum chromite, a lanthanum calcium chromite, or a combination thereof. In one embodiment, the conductive metal comprises Ni, Cu, Ag, Au, or a combination thereof.

In one embodiment, the first electrode 101, 111 or the second electrode 102, 112 or both the first electrode 101, 111 and the second electrode 102, 112 comprise a fluidic channel. Alternatively, the first electrode 101, 111 or the second electrode 102, 112 or both the first electrode 101, 111 and the second electrode 102, 112 comprise a fluid dispersion member. In one embodiment, the electrodes and electrolytes 103, 113 form a repeating unit and wherein the device comprises a plurality of repeating units separated by interconnects. In one embodiment, the interconnect does not contain a fluid dispersion element. In one embodiment, the electrodes 101, 102, 111, 112 and electrolytes 103, 113 may be planar. The fluid dispersion members or fluid channels in the electrodes function to distribute fluids, e.g., reactive gases (e.g., methane, hydrogen, carbon monoxide, air, oxygen, steam, etc.) in the electrochemical reactor. As such, conventional interconnects with channels are no longer required. The design and production of these conventional interconnects with channels is complex and expensive. According to the present disclosure, the interconnect is simply an impermeable layer that conducts or collects electrons, without a fluid dispersion element.

In one embodiment, the device does not include an interconnect. In one embodiment, the electrolytes 103, 113 conduct oxygen ions and electrons. In one embodiment, the electrodes 101, 102, 111, 112 and electrolytes 103, 113 are tubular. In some embodiments, the electrochemical reactions at the anode and cathode are spontaneous without applying a potential/current to the reactor. In these cases, no interconnects are required, which significantly simplifies the device. In these cases, the electrolyte in the device conducts both oxygen ions and electrons.

In one embodiment, the apparatus comprises a reformer upstream of the first electrode 101, 111, wherein the first electrode 101, 111 comprises Ni or NiO, or a combination thereof. In one embodiment, the reformer is a steam reformer or an autothermal reformer. In one embodiment, the device is configured to operate at a temperature of not less than 500 ℃, or not less than 600 ℃ or not less than 700 ℃.

In one embodiment, the electrodes and the electrolyte are tubular, wherein the first electrode is the outermost layer and the second electrode is the innermost layer, wherein the first electrode comprises doped or undoped ceria and is selected from the group consisting of Cu, CuO, Cu ₂O、Ag、Ag₂O、Au、Au₂O、Au₂O₃Stainless steel, and combinations thereof. In one embodiment, the electrodes and electrolyte are tubular, wherein the first electrode is the outermost layer and the second electrode is the innermost layer, wherein the second electrode is configured to receive water and hydrogen.

Also disclosed herein are devices comprising a first electrode, a second electrode, and an electrolyte positioned between the electrodes, wherein the first electrode comprises a doped lanthanum chromium oxide (lanthanum chromium oxide) and a doped or undoped ceria, wherein the second electrode comprises Ni or NiO and a material selected from the group consisting of YSZ, CGO, samarium oxide doped ceria (SDC), Scandia Stabilized Zirconia (SSZ), LSGM, ceria, and combinations thereof, and wherein the electrolyte is oxygen ion conductive. In one embodiment, the electrolyte comprises YSZ, CGO, LSGM, SSZ, SDC, ceria, or a combination thereof. In one embodiment, the device is planar. In one embodiment, the device is tubular.

Further discussed herein are methods of making a device comprising forming a first electrode, forming a second electrode, and forming an electrolyte between the electrodes, wherein the first electrode comprises a doped lanthanum chromium oxide and doped or undoped ceria, wherein the second electrode comprises Ni or NiO and a material selected from the group consisting of YSZ, CGO, samarium oxide doped ceria (SDC), Scandia Stabilized Zirconia (SSZ), LSGM, ceria, and combinations thereof, and wherein the electrolyte is oxygen ion conductive. In one embodiment, the electrolyte comprises YSZ, CGO, LSGM, SSZ, SDC, ceria, or a combination thereof. In one embodiment, the forming comprises material jetting, binder jetting, ink jet printing, aerosol jetting or aerosol jet printing, slot photo polymerization, powder layer fusion, material extrusion, directed energy deposition, sheet lamination, or ultrasonic ink jet printing, or a combination thereof. In one embodiment, forming includes extruding, dip coating, spray coating, spin coating, brush coating, pasting, or a combination thereof. In one embodiment, forming includes heating using a source of electromagnetic radiation or an oven.

Discussed herein are methods of making a device comprising forming a first electrode, forming a second electrode, and forming an electrolyte positioned between the electrodes, wherein the first electrode and the second electrode comprise a metal phase that is free of platinum group metals when the device is in use, and wherein the electrolyte is oxygen ion conductive. In one embodiment, the electrodes and electrolyte are assembled as they are formed. In one embodiment, the electrodes and electrolyte form repeating units and the method includes forming the plurality of repeating units and forming interconnects between the repeating units. In one embodiment, the interconnect does not contain a fluid dispersion element. In one embodiment, the method comprises forming a fluid channel or a fluid dispersion member in the first electrode or the second electrode or both the first electrode and the second electrode.

In one embodiment of the method of the present invention,the first electrode comprises Ni or NiO and a material selected from the group consisting of YSZ, CGO, samarium oxide doped ceria (SDC), Scandia Stabilized Zirconia (SSZ), LSGM, and combinations thereof. In one embodiment, the first electrode comprises doped or undoped ceria and is selected from the group consisting of Cu, CuO, Cu ₂O、Ag、Ag₂O、Au、Au₂O、Au₂O₃Stainless steel, and combinations thereof. In one embodiment, the second electrode comprises Ni or NiO and a material selected from the group consisting of YSZ, CGO, samarium oxide doped ceria (SDC), Scandia Stabilized Zirconia (SSZ), LSGM, ceria, and combinations thereof. In one embodiment, the electrolyte comprises YSZ, CGO, LSGM, SSZ, SDC, ceria, or a combination thereof.

In one embodiment, forming includes material jetting, binder jetting, ink jet printing, aerosol jetting, aerosol jet printing, slot photo polymerization, powder layer fusion, material extrusion, directed energy deposition, sheet lamination, ultrasonic ink jet printing, or a combination thereof. In one embodiment, the method comprises in situ heating. In one embodiment, the heating comprises electromagnetic radiation (EMR). In one embodiment, the EMR includes UV light, near ultraviolet light, near infrared light, visible light, laser, electron beam, or combinations thereof. In one embodiment, the EMR is provided by a xenon lamp. In one embodiment, the electrodes and electrolyte are planar. In one embodiment, the device does not include an interconnect. In one embodiment, the electrolyte conducts oxygen ions and electrons.

In one embodiment, forming comprises a) depositing the composition on a substrate to form a sheet (slice); b) drying the sheet using a non-contact dryer; c) the heating sheet is heated using electromagnetic radiation (EMR) or conduction or both. In one embodiment, the method comprises repeating steps a) -c) to generate the device piece by piece (slice by slice). In one embodiment, the method includes d) measuring the temperature T of the sheet without contacting the sheet for a time T after the last EMR exposure, where T is no greater than 5 seconds, or no greater than 4 seconds, or no greater than 3 secondsSeconds, not greater than 2 seconds, or not greater than 1 second. In one embodiment, the method comprises e) combining T with T_SinteringIn contrast, wherein if the composition is non-metallic, then T_SinteringNot less than 45% of the melting point of the composition; or wherein if the composition is metallic, then T_SinteringNot less than 60% of the melting point of the composition. In one embodiment, the method comprises e) combining T with T_SinteringIn comparison, wherein T was previously determined by correlating the measured temperature with a microstructure image of the sheet, a scratch test of the sheet, an electrochemical performance test of the sheet, a dilatometry measurement of the sheet, a conductivity measurement of the sheet, or combinations thereof _Sintering. In one embodiment, the method includes if T is less than T_Sintering90% of the total volume of the wafer, the heating blade is heated in a second stage using EMR or conduction or both.

In one embodiment, the drying is carried out for a period of time within the following ranges: no greater than 5 minutes, alternatively no greater than 3 minutes, alternatively no greater than 1 minute, alternatively from 1 s to 30 s, alternatively from 3 s to 10 s. In one embodiment, the non-contact dryer comprises an infrared heater, a hot air blower, an ultraviolet light source, or a combination thereof.

For example, all layers of the EC gas generator are formed and assembled by printing. The materials used to make the anode, cathode, electrolyte and interconnect are made into an ink form (ink form) containing solvent and particles (e.g., nanoparticles), respectively. The ink optionally comprises a dispersant, binder, plasticizer, surfactant, co-solvent, or a combination thereof. For the anode and cathode of the gas generator, the NiO and YSZ particles were mixed with a solvent, where the solvent was water (e.g., deionized water) or an alcohol (e.g., butanol) or a mixture of alcohols. Organic solvents other than alcohols may also be used. For the electrolyte, the YSZ particles are mixed with a solvent, where the solvent is water (e.g., deionized water) or an alcohol (e.g., butanol) or a mixture of alcohols. Organic solvents other than alcohols may also be used. For interconnects, metal particles (e.g., silver nanoparticles) are dispersed or suspended in a solvent, where the solvent may include water (e.g., deionized water), organic solvents (e.g., mono-, di-, or tri-or higher ethylene glycols, propylene glycol, 1, 4-butanediol or ethers of these glycols, thiodiglycol, glycerol and its ethers and esters, polyglycerol, mono-, di-, and tri-ethanolamine, propanolamine, N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, 1, 3-dimethylimidazolidinone, methanol, ethanol, isopropanol, N-propanol, diacetone alcohol, acetone, methyl ethyl ketone, propylene carbonate), and combinations thereof. For the barrier layer, the CGO particles may be dissolved, dispersed or suspended in a solvent, wherein the solvent is water (e.g., deionized water) or an alcohol (e.g., butanol) or a mixture of alcohols. Organic solvents other than alcohols may also be used. CGO was used as a barrier layer for LSCF. YSZ may also be used as a barrier layer for LSM.

Tubular and multi-tubular EC gas generators

Fig. 2A shows (not to scale) a tubular EC gas generator 200 according to an embodiment of the disclosure. The tubular EC gas generator 200 includes an inner tubular structure 202, an outer tubular structure 204, and an electrolyte 206 disposed between the inner and outer tubular structures 202, 204, respectively. In some embodiments, the electrolyte 206 may instead comprise a membrane. The tubular gas generator 200 also includes a void space 208 for the passage of fluid.

Fig. 2B shows (not to scale) a cross-section of a tubular EC gas generator 200 according to an embodiment of the disclosure. The tubular EC gas generator 200 includes a first inner tubular structure 202, a second outer tubular structure 204, and an electrolyte 206 located between the inner and outer tubular structures 202, 204. In some embodiments, the electrolyte 206 may be referred to as a membrane. The tubular gas generator 200 also includes a void space 208 for the passage of fluid.

In one embodiment, the inner tubular structure 202 contains electrodes. The inner tubular structure 202 may be an anode or a cathode. In one embodiment, the inner tubular structure 202 may be porous. The inner tubular structure 202 may comprise Ni or NiO and a material selected from the group consisting of YSZ, CGO, samarium oxide doped ceria (SDC), Scandia Stabilized Zirconia (SSZ), LSGM, and combinations thereof . The inner tubular structure 202 may comprise doped or undoped ceria and be selected from the group consisting of Cu, CuO, Cu₂O、Ag、Ag₂O、Au、Au₂O、Au₂O₃Stainless steel, and combinations thereof. In one embodiment, the outer tubular structure 204 comprises an electrode. The outer tubular structure 204 may be an anode or a cathode. The outer tubular structure 204 may comprise Ni or NiO and a material selected from the group consisting of YSZ, CGO, samarium oxide doped ceria (SDC), Scandia Stabilized Zirconia (SSZ), LSGM, and combinations thereof. The outer tubular structure 204 may comprise doped or undoped ceria and be selected from the group consisting of Cu, CuO, Cu₂O、Ag、Ag₂O、Au、Au₂O、Au₂O₃Stainless steel, and combinations thereof. It should be noted that the above list of materials is not limiting.

In an embodiment, the electrolyte 206 comprises doped ceria or wherein the electrolyte comprises lanthanum chromite or a conductive metal or a combination thereof and a material selected from the group consisting of doped ceria, YSZ, LSGM, SSZ, and combinations thereof. In one embodiment, the lanthanum chromite comprises an undoped lanthanum chromite, a strontium-doped lanthanum chromite, an iron-doped lanthanum chromite, a lanthanum calcium chromite, or a combination thereof. In one embodiment, the conductive metal comprises Ni, Cu, Ag, Au, or a combination thereof. The electrolyte 206 is oxygen ion conductive. In some cases, the electrolyte 206 is oxygen ion conductive and is electron conductive (electronically reducing). In some embodiments, generator 200 also includes one or more interconnects.

Fig. 3A shows a cross-section of a multi-tubular EC gas generator 300 according to an embodiment of the present disclosure. EC gas generator 300 comprises an inner electrode 302, an outer electrode 304, and an electrolyte 306 positioned between electrodes 302, 304. In some embodiments, the electrolyte 306 is referred to as a membrane. The inner electrode 302 includes a plurality of radially connected tube-like void spaces 308. Void space 308 allows fluid to pass through. The void space 308 may also be referred to as a flow passage. The multi-tubular structure 300 contains a plurality of flow channels 308 in the axial direction of the tubular structure 300. The cross-section of void space 308 may be circular-like, oval-like, or other similar shapes. The cross-section of the space 308 may be irregular in shape as shown in fig. 3A. The generator 300 has a cross-section having a length and a width, wherein the length is at least 2 times the width and the cross-section is perpendicular (orthogonal) to the axial direction of the tube. The multi-tubular structure 300 is comprised of a plurality of individual tubular structures 309 (represented by dashed lines).

The inner electrode 302 in the generator 300 may have a unitary construction and may not have brazed or welded components. In one embodiment, the generator 300 has a unitary structure and does not have brazed or welded components. In one embodiment, electrolyte 306 is oxygen ion conductive and is a solid state. In one embodiment, the electrolyte comprises the materials listed previously herein for the electrolyte 206 in the tubular reactor 200. In embodiments, the electrodes 302, 304 may comprise one or more of the materials previously listed herein for the tubular structures 202, 204 in the tubular reactor 200. In some embodiments, the generator 300 further comprises one or more interconnects.

Fig. 3B shows a cross-section of a multi-tubular EC gas generator 320 according to an embodiment of the present disclosure. The gas generator has a rectangular-like cross section. EC gas generator 320 comprises an inner electrode 302, an outer electrode 304, and an electrolyte 306 positioned between electrodes 302, 304. In some embodiments, a membrane may be used in place of the electrolyte 306. The inner electrode 302 includes a plurality of void spaces 308 connected radially of the tube-like void spaces 308. Void space 308 allows fluid to pass through. The multi-tubular structure 320 contains a plurality of flow channels 308 in the axial direction of the tubular structure 320. The cross-section of void spaces 308 may be circular-like, oval-like, square-like, hexagonal-like, triangular-like, or other similar shapes in a random or regular manner. The generator 320 has a cross-section having a length and a width, wherein the length is at least 2 times the width and the cross-section is perpendicular to the axial direction of the tube.

The inner electrode 302 in the generator 320 may have a unitary structure and have no brazed or welded components. The generator 320 may be of unitary construction and have no brazed or welded components. In one embodiment, the electrolyte 306 is oxygen ion conductive. In embodiments, the electrolyte may comprise one or more of the materials previously listed herein for the electrolyte 206 in the tubular reactor 200. In embodiments, the electrodes 302, 304 may comprise one or more of the materials previously listed herein for the tubular structures 202, 204 in the tubular reactor 200. In some embodiments, generator 320 also includes one or more interconnects.

Fig. 3C shows a cross-section of a multi-tube EC gas generator 340 according to an embodiment of the present disclosure. The gas generator 340 has a rectangular-like cross section. EC gas generator 340 comprises inner electrode 302, outer electrode 304, and electrolyte 306 located between electrodes 302, 304. In some embodiments, the electrolyte 306 is referred to as a membrane. The inner electrode 302 contains a plurality of void spaces 308 connected in the axial direction of the tube. Void space 308 allows fluid to pass through. The multi-tubular structure 340 includes a plurality of flow channels 308 in the axial direction of the tubular structure 340. The cross-section of the void spaces 308 may be square-like or rectangular-like as shown in fig. 3C or other similar shapes in a regular manner, wherein the cross-sectional area of each void space is substantially the same. The generator 340 has a cross-section having a length and a width, wherein the length is at least 2 times the width and the cross-section is perpendicular to the axial direction of the tube.

The inner electrode 302 in the generator 340 may have a unitary structure and have no brazed or welded components. The generator 340 may have a unitary construction and no brazed or welded components. In one embodiment, the electrolyte 306 is oxygen ion conductive. In embodiments, the electrolyte may comprise one or more of the materials previously listed herein for the electrolyte 206 in the tubular reactor 200. In embodiments, the electrodes 302, 304 may comprise one or more of the materials previously listed herein for the tubular structures 202, 204 in the tubular reactor 200. In some embodiments, generator 340 also includes one or more interconnects.

Fig. 3D shows a cross-section of an EC gas generator 360 in accordance with an embodiment of the present disclosure. The gas generator 360 has a rectangular-like cross section. The EC gas generator 360 is similar to the gas generator 340 of fig. 3C, except that the flow path 380 is single, as shown in fig. 3D.

Production of tubular and multi-tubular EC gas generators

Methods of making tubular EC gas generators as shown by devices 200, 300, 320, 340, and 360 are discussed further herein, which are merely examples of some tubular designs. At least three methods are discussed herein regarding how to prepare the first tube: extrusion, substrate, and the methods shown in fig. 5A-5B.

In one embodiment, a method of making a tubular EC gas generator includes forming a first tubular structure by extrusion. In some embodiments, the first tubular structure is the inner electrode 202. The method further includes depositing a layer on an outer cylindrical surface of the first tubular structure 202, wherein the layer includes an electrolyte 206, and depositing the second tubular structure 204 on the electrolyte 206, wherein the electrolyte 206 is oxygen ion conductive. In one embodiment, the first tubular structure 202 and the second tubular structure 204 comprise a metal phase free of platinum group metals when the apparatus is in use. In one embodiment, the device does not contain interconnects and wherein the electrolyte is electronically conductive.

In another production method embodiment, the method includes extruding the inner tubular structure 202; sintering the inner tubular structure 202 in a furnace or by EMR to form a first electrode; coating the outer surface of the inner tubular structure 202 with an electrolyte material; sintering the electrolyte material in an oven or EMR to form an electrolyte 206; coating the electrolyte 206 with an electrode material; the electrode material is sintered in a furnace or using electromagnetic radiation (EMR) to form the outer tubular structure 204, where the outer tubular structure 204 is a second electrode. In one embodiment, the outer tubular structure 204 comprises doped or undoped ceria and is selected from the group consisting of Cu, CuO, Cu₂O、Ag、Ag₂O、Au、Au₂O、Au₂O₃Stainless steel and materials of the group consisting of the sameFeeding; and sintering the outer tubular structure 204 using EMR. In one embodiment, the method further comprises reducing the outer tubular structure 204 or reducing the inner tubular structure 202 or both tubular structures 202, 204. These methods describe an "inside-out" method, wherein the first extruded layer is an internal electrode layer.

The following method describes an "out-in" method, wherein the first layer formed is the outer tubular structure 204 or the outer electrode layer. The method includes extruding an outer tubular structure 204; sintering the outer tubular structure 204 in a furnace or by EMR to form a first electrode; coating the inner surface of the outer tubular structure 204 with an electrolyte material; sintering the electrolyte material in an oven or EMR to form an electrolyte 206; coating the inner surface of the electrolyte 206 with an electrode material; the electrode material is sintered in a furnace or using electromagnetic radiation (EMR) to form the inner tubular structure 202, where the inner tubular structure 202 is the second electrode. In one embodiment, the inner tubular structure 202 comprises doped or undoped ceria and is selected from the group consisting of Cu, CuO, Cu ₂O、Ag、Ag₂O、Au、Au₂O、Au₂O₃Stainless steel, and combinations thereof; and sintering the inner tubular structure 202 using EMR. In one embodiment, the method further comprises reducing the outer tubular structure 204 or reducing the inner tubular structure 202 or both tubular structures 202, 204.

In one embodiment, the coating steps for use in the "inside-out" and "outside-in" processes include dip coating, spray coating, ultrasonic spray coating, spin coating, brush coating, pasting, or combinations thereof. Electromagnetic radiation includes UV light, near ultraviolet light, near infrared light, visible light, lasers, electron beams, microwaves, or combinations thereof. In one embodiment, the electromagnetic radiation is provided by a xenon lamp. In some embodiments, a device may include one or more interconnects. In one embodiment, the inner tubular structure 202 and the outer tubular structure 204 contain one or more fluid channels or one or more fluid dispersion members or both fluid channels and fluid dispersion members.

In anotherIn embodiments, the inner tubular structure 202 or the outer tubular structure 204 may be formed from particles and not from a liquid precursor, particularly when the inner tubular structure 202 or the outer tubular structure 204 comprises doped or undoped ceria and is selected from the group consisting of Cu, CuO, Cu ₂O、Ag、Ag₂O、Au、Au₂O、Au₂O₃Stainless steel, and combinations thereof. The particles are suspended in a liquid prior to deposition or coating, such as dip coating, spray coating, spin coating, brush coating, coating with a paste, or a combination thereof. In these cases, either the inner tubular structure 202 or the outer tubular structure 204 is sintered using electromagnetic radiation (EMR).

In other embodiments, a first tube-like substrate is provided. The tubular substrate is substantially in the desired shape of the EC gas generator. In a first embodiment, a first electrode material is deposited outside the tubular substrate. The first electrode material is sintered to form the inner electrode 202. Then, an electrolyte material is deposited on the surface of the internal electrode layer 202. The electrolyte material is sintered to form the electrolyte 206. A second electrode material is then deposited on the electrolyte 206. Then, the second electrode material is sintered to form the external electrode 204. The method may be described as an "inside-out substrate method" in which the first layer formed on the substrate is the inner electrode layer 202, then the electrolyte 206 layer, then the outer electrode layer 204. The first and second electrodes may be anodes or cathodes. Sintering may include heating or EMR sintering.

In another similar method, a tube-like substrate is provided. A first electrode material is deposited inside the tubular substrate. The first electrode material is sintered to form the outer electrode 204. Then, an electrolyte material is deposited on the surface of the external electrode layer 204. The electrolyte material is sintered to form the electrolyte 206. A second electrode material is then deposited on the electrolyte 206. Then, the second electrode material is sintered to form the internal electrode 202. The method may be described as an "outside-in substrate method" in which the first layer formed on the substrate is the inner electrode layer 202, then the electrolyte 206 layer, then the outer electrode layer 204. The first and second electrodes may be anodes or cathodes. Sintering may include heating or EMR sintering.

In some embodiments, once the final electrode is formed, the substrate may then be removed. The substrate may be removed by physical means. The substrate may be dissolved and removed by a solvent. In some methods, the substrate may be composed of a low melting point material, such as a polymer, where the substrate may be melted or vaporized and removed during any thermal sintering step. For example, the substrate may comprise a combustible material, such that during one thermal sintering step, the substrate is burned off.

In one embodiment, the first tube (inner or outer) and the electrolyte are sintered separately in an oven. In one embodiment, the first tube (inner or outer) and the electrolyte are co-sintered in an oven, meaning that the first tube is coated with the electrolyte material prior to sintering. Depositing a second tube (external or internal) on the electrolyte, and then sintering using EMR, wherein the second tube comprises doped or undoped ceria and is selected from the group consisting of Cu, CuO, Cu₂O、Ag、Ag₂O、Au、Au₂O、Au₂O₃Stainless steel, and combinations thereof. Fig. 4A-4D show various arrangements for sintering tubes using EMR sources. The EMR source and the tube can be moved relative to each other, for example, in an axial direction or in a helical trajectory, to ensure that the entire surface of the tube (internal or external) is sintered by sufficiently exposing it to the EMR source. In one embodiment, the EMR source is a xenon lamp, such as a circular xenon lamp, a long tubular xenon lamp, a spot tubular xenon lamp.

Fig. 4A-4D illustrate a sintering method and system for producing tubular EC gas generators using EMR. Fig. 4A shows a portion of a method 400 of producing an EC gas generator using a single point EMR source, according to an embodiment of the present disclosure. The EMR source (e.g., xenon lamp) 402 and the tubular structure 404 can be moved relative to each other. As shown in fig. 4A, the single point EMR 402 may be rotated (e.g., in a spiral trace) around the tubular structure 404 in either direction as indicated by arrow 406. Alternatively, the tubular structure 404 may be rotated about the single point EMR 402. In another embodiment, the tubular structure 404 may rotate about its own axis 408 or move along its own long axis in an upward or downward direction 410, or a combination thereof. The single point EMR source 402 may also be moved in an upward or downward direction 412.

FIG. 4B shows a portion of a method 420 of producing an EC gas generator using an annular lamp EMR source, according to an embodiment of the present disclosure. As shown in fig. 4B, a circular ring lamp (e.g., xenon lamp) 422 is shown as the EMR source, with a hollow circle in the center. The tubular structure 404 is placed in the center of the circular ring shaped lamp 422. In some embodiments, the tubular structure 404 may be moved up or down 410, or rotated 408 about its own axis, while holding the annular light 422 in a fixed manner. In other embodiments, the tubular structure 404 may be held in a fixed manner while the annular shaped lamp 422 may be moved along the length of the tubular structure 404. The annular lamp 422 may be moved in an upward or downward 424 fashion, or in a rotational (426) fashion about its own axis to ensure complete and thorough sintering. In other embodiments, both the tubular structure 402 and the annular lamp 422 may be able to move relative to each other to ensure that the entire tubular structure 404 is completely and fully sintered. Fig. 4A-4B show embodiments in which the outer surface of the tubular structure 404 is sintered by EMR. These methods may be used to sinter anodes, cathodes, electrolytes, and other components of tubular EC gas generators.

Fig. 4C-4D show embodiments in which the inner surface of the tubular structure 404 is sintered by EMR. Fig. 4C shows a portion of a method 440 of producing an EC gas generator using a single point EMR source, according to an embodiment of the present disclosure. FIG. 4C shows a single point EMR source (e.g., a xenon lamp) 402 disposed inside a tubular structure 404. In a first embodiment, the tubular structure 404 may be held in a stationary manner while the single point EMR source may be moved in an upward or downward 412 manner. In a preferred embodiment, the single point EMR source 402 may irradiate all directions substantially equally. In another embodiment, the single point EMR source may be held in a stationary manner while the tubular structure 404 may be moved in an upward or downward direction 410, or rotated 408 about its own axis. In another embodiment, both the tubular structure 404 and the single-point EMR source 402 are moved relative to each other so that the entire inner surface of the tubular structure 404 is thoroughly and substantially sintered.

Fig. 4D shows a portion of a method 460 of producing an EC gas generator using a tubular EMR source, according to an embodiment of the present disclosure. Fig. 3E4D shows a cylindrical lamp (e.g., a tubular xenon lamp) 462 as an EMR source disposed inside the tubular structure 404 to be sintered. In this case, the length of the lamp is such that the entire inner surface of the tubular structure 404 can be sintered without the need for the tubular lamp 462 and the tubular structure 404 to move relative to each other. In one embodiment, the tubular light 462 may be held in a fixed manner while the tubular structure 404 may be moved over the light 462. The tubular structure 404 may be moved in an upward or downward manner 464. For example, the unsintered tubular structure 404 may be moved over the tubular lamp 462 to the indicated position, held in that position until sufficient irradiation has occurred and the tubular structure 404 is substantially sintered, and then moved away from the tubular lamp 462 in an upward or downward direction as indicated by arrow 464 for the next production step. In another embodiment, the unsintered tubular structure 404 may be held in a fixed position while the tubular lamp EMR source 462 is moved into the tubular structure 404. The tubular light 462 may be moved in an upward or downward manner, as indicated by arrow 464. The tubular structure 404 may be formed using any suitable method, such as those discussed herein. For the embodiment of fig. 4C-4D, the coating and sintering occurs on the inner surface of the tubular structure 404.

Many variations are possible for sintering as shown in fig. 4A-4D. For example, the outer tubular structure 204 may be formed and thermally sintered in a furnace to form an anode or a cathode. The electrolyte material can then be coated onto the inner surface of the outer tubular structure 204 and then sintered in a furnace or using a single point of EMR 402 or tubular lamp EMR 462 inside the tubular structure to form the electrolyte 206. Another electrode material may then be applied to the inner surface of the electrolyte 206 and then sintered in a furnace or using an EMR source 402, 462 to form the inner tubular structure 202, such as an anode or cathode. For example, for anodes containing copper, gold, or silver, the internal electrodes are sintered using an EMR source. For example, for anodes containing Ni or NiO, the internal electrodes are sintered in a furnace or by an EMR source.

In some embodiments, a combination of an EMR source internal to the tubular electrodes 202, 204 or the electrolyte 206 and an EMR source external to the tubular electrodes 202, 204 or the electrolyte 206 may be used simultaneously for sintering. For example, the tubular EMR source 462 and the annular-like EMR source 422 can be used to sinter sequentially or simultaneously in the same sintering apparatus.

Fig. 5A-5B illustrate another method of forming the first tube or tubes in an EC gas generator. Fig. 5A shows a first step in a tape casting process 500 for forming a tubular or multi-tubular EC gas generator, according to an embodiment of the present disclosure. In a first step, the support 504 is placed on the substrate 502, wherein the height of the support 504 is preconfigured to ensure the desired thickness of the tubular electrode 506 on the bottom side. The substrate 502 and support 504 may be made of metal, glass, plastic, wood, or any suitable material known in the art. Electrode material 506 in the form of a dispersion or slurry is deposited on substrate 502 between supports 504. The term slurry will be used in the description, but the dispersions may also be used interchangeably. One or more spacers 508 are then placed on top of the slurry 506 and on the support 504. View 501 is a top or plan view that further illustrates and shows an example of how substrate 502, support 504, electrode material 506, and spacers 508 may be arranged.

Fig. 5B shows steps 2-4 in a casting process 500 for forming a first tube or a first multi-tube in an EC gas generator, according to an embodiment of the present disclosure. In step 2, additional slurry 510 is deposited to cover the spacer 508 and the previously deposited slurry 506. A blade, such as a doctor blade, may be used to draw across the top of the additional slurry 510 to ensure the proper thickness of the tubular electrode on the top side. In a preferred embodiment, the slurry contains mainly organic solvents.

Step 3 shown in fig. 5B includes immersing the substrate 502, support 504, spacer 508, first slurry 506, and second slurry 510 in deionized water to allow phase inversion of the slurries to occur. Phase inversion is a form of precipitation when a slurry containing a low polarity organic solvent is placed in high polarity deionized water. Thus, the slurry components precipitate out due to the incompatibility of the components with water.

Then, after phase inversion, the substrate 502 and support 504 are removed as a whole from the slurry 506, 510. The slurry 506, 510 is dried (e.g., in ambient air) to remove excess deionized water. The shim 508 is then removed, for example, by pulling it out from either end. The electrode materials 506, 510 are sintered to form a first tubular electrode 512 having a flow channel 514. The spacers 508 may have any regular or irregular shape, such as circular, oval-like, square-like, diamond-like, trapezoidal, rectangular, triangular, pentagonal, hexagonal, octagonal, or other various cross-sectional shapes or combinations thereof, as desired. If the spacer 508 has a rectangular cross-section, the plurality of connected tubular flow channels 514 will have the same rectangular cross-section as the flow channels 514 in the inner electrode 512 shown in FIG. 3C. 3C-3D, the inner electrode 302 has a cross-section having a length and a width, wherein the length is at least 2 times the width and the cross-section is perpendicular to the axial direction of the tube. Similarly, the reactor has a cross-section having a length and a width, wherein the length is at least 2 times the width and the cross-section is perpendicular to the axial direction of the tube.

In one embodiment, the method shown in step 4 in fig. 5B further comprises coating the outer surface of the first tubular electrode 512 with an electrolyte material. The electrolyte material may then be sintered in a furnace or by using electromagnetic radiation to form the electrolyte 516. Step 4 also includes coating the electrolyte 516 with a second electrode material. The second electrode material may be sintered in a furnace or using electromagnetic radiation to form the second outer tubular electrode 518. In one embodiment, the second electrode material comprises doped or undoped ceria and is selected from the group consisting of Cu, CuO, Cu₂O、Ag、Ag₂O、Au、Au₂O、Au₂O₃Stainless steel, and combinations thereof; and sintered using EMR to form the second outer tubular electrode 518. In one embodiment, the method includes reducing the second outer tubular electrode 518 or reducing the first inner tubular electrode 512 or both.

In one embodiment, the coating step comprises dip coating, spray coating, ultrasonic spray coating, spin coating, brush coating, pasting, or a combination thereof. In one embodiment, the electromagnetic radiation comprises UV light, near ultraviolet light, near infrared light, visible light, laser, electron beam, microwave, or combinations thereof. In one embodiment, the electromagnetic radiation is provided by a xenon lamp. In one embodiment, the first tubular electrode 512 has a cross-section with a length and a width, wherein the length is at least 2 times the width and the cross-section is perpendicular to the axial direction of the tubular flow channel 514. In one embodiment, the EC gas generator does not include an interconnect.

Operation of EC gas generator

Disclosed herein are methods comprising providing a device comprising a first electrode, a second electrode, and an electrolyte disposed between the electrodes, introducing a first stream to the first electrode, introducing a second stream to the second electrode, and extracting hydrogen gas from the second electrode, wherein the first electrode and the second electrode comprise a metal phase free of platinum group metals when the device is in use. In one embodiment, the electrolyte is oxygen ion conductive. In one embodiment, the device is operated at a temperature of not less than 500 ℃, or not less than 600 ℃ or not less than 700 ℃. In one embodiment, the first stream comprises fuel and water or fuel and carbon dioxide. In one embodiment, the fuel comprises a hydrocarbon or hydrogen or carbon monoxide or a combination thereof. In one embodiment, the first stream is introduced directly into the first electrode, or the second stream is introduced directly into the second electrode, or both.

In one embodiment, the first stream comprises a fuel having little to no water. In one embodiment, the fuel comprises a hydrocarbon or hydrogen or carbon monoxide or a combination thereof. In one embodiment, the second stream consists of water and hydrogen.

In one embodiment, the method comprises providing a reformer upstream of a first electrode, wherein a first stream is passed through the reformer prior to introduction of the first electrode, wherein the first electrode comprises Ni or NiO. In one embodiment, the reformer is a steam reformer or an autothermal reformer.

In one embodiment, the method comprises in one of the following reactions: the extracted hydrogen is used in a fischer-tropsch (FT) reaction, a dry reforming reaction, a Sabatier (Sabatier) reaction catalyzed by nickel, a Bosch (Bosch) reaction, a reverse water gas shift reaction, an electrochemical reaction to generate electricity, the production of ammonia, the production of fertilizer, an electrochemical compressor or hydrogenation reaction for hydrogen storage, hydrogen vehicle fueling, or a combination thereof.

Disclosed herein is a method of producing hydrogen gas comprising providing an EC gas generator device, introducing a first stream comprising a fuel into the device, introducing a second stream comprising water into the device, reducing the water in the second stream to hydrogen gas, and extracting the hydrogen gas from the device, wherein the first and second streams do not contact each other in the device. In one embodiment, the first stream does not contact hydrogen. In one embodiment, the first and second streams are separated by a membrane in the device. In one embodiment, the fuel comprises a hydrocarbon or hydrogen or carbon monoxide or a combination thereof. In one embodiment, the second stream comprises hydrogen. In one embodiment, the first stream comprises fuel and water or fuel and carbon dioxide. In one embodiment, the first stream comprises a fuel having little to no water.

Hydrogen production system

Further discussed herein are hydrogen production systems that include a fuel source; a water source; a hydrogen generator; wherein the fuel source and the water source are in fluid communication with the generator, and wherein the fuel and the water do not contact each other in the generator. The system may not include an external heat source. In one embodiment, the fuel and water do not contact each other in the system. In one embodiment, the generator comprises a first electrode, a second electrode, and an electrolyte disposed between the first and second electrodes; wherein the fuel source is in fluid communication with the first electrode and the water source is in fluid communication with the second electrode. In one embodiment, the fuel source provides heat to the hydrogen generator, and the hydrogen generator has no other heat source.

In one embodiment, the electrolyte comprises YSZ, CGO, LSGM, SSZ, SDC, ceria, lanthanum chromite, or a combination thereof or wherein the electrolyte comprises doped or undoped ceria and optionally a material selected from the group consisting of YSZ, LSGM, SSZ, and a combination thereof. In one embodiment, the lanthanum chromite comprises an undoped lanthanum chromite, a strontium-doped lanthanum chromite, an iron-doped lanthanum chromite, a lanthanum calcium chromite, or a combination thereof. The electrolyte may also include any of the materials listed for the electrolyte 206 in the "tubular and multi-tubular EC gas generator" sections herein. In one embodiment, the electrolyte comprises doped ceria or wherein the electrolyte comprises lanthanum chromite or a conductive metal or a combination thereof and a material selected from the group consisting of doped ceria, YSZ, LSGM, SSZ, and combinations thereof. In one embodiment, the lanthanum chromite comprises an undoped lanthanum chromite, a strontium-doped lanthanum chromite, an iron-doped lanthanum chromite, a lanthanum calcium chromite, or a combination thereof. In one embodiment, the conductive metal comprises Ni, Cu, Ag, Au, or a combination thereof.

In one embodiment, the first and second electrodes comprise Ni or NiO and a material selected from the group consisting of YSZ, CGO, samarium oxide doped ceria (SDC), Scandia Stabilized Zirconia (SSZ), LSGM, and combinations thereof. In one embodiment, the first electrode comprises doped or undoped ceria and is selected from the group consisting of Cu, CuO, Cu₂O、Ag、Ag₂O、Au、Au₂O、Au₂O₃Stainless steel and combinations thereof; wherein the second electrode comprises Ni or NiO and a material selected from the group consisting of YSZ, CGO, samarium oxide doped ceria (SDC), Scandia Stabilized Zirconia (SSZ), LSGM, and combinations thereof. The first and second electrodes may comprise any of the materials listed for the inner tubular structure 202 or the outer tubular structure 204 in the "tubular and multi-tubular EC gas generator" section herein.

In one embodiment, the system comprises an oxidant source and a boiler (boiler, evaporator, boiler), wherein the boiler is in fluid communication with the oxidant source, the water source, and the generator. In one embodiment, the boiler is in thermal communication with the generator, a fuel input of the generator, an oxidant, water, or a combination thereof. In one embodiment, the boiler is configured to receive exhaust gas from a first electrode of the generator and feed steam into a second electrode of the generator. In one embodiment, the fuel is partially oxidized in the generator and further oxidized in the boiler. In one embodiment, the system includes a steam turbine located between and in fluid communication with the boiler and the generator.

In one embodiment, the water is reduced in a generator to produce hydrogen. In one embodiment, the system includes a condenser configured to receive the exhaust gas from the second electrode of the generator and circulate water back to the boiler and output hydrogen. In one embodiment, the condenser is in thermal communication with the fuel. In one embodiment, the system comprises a desulfurization unit positioned between and in fluid communication with the fuel source and the generator. In one embodiment, the generator is configured to have a fuel inlet temperature of no greater than 1000 ℃, or no greater than 900 ℃, or 800 ℃ to 850 ℃. In one embodiment, the generator is configured to have a fuel outlet temperature of no less than 600 ℃.

Fig. 6A shows an example of a hydrogen production system 600 without an external heat source, according to an embodiment of the present disclosure. The system 600 includes a water source 602, an air/oxidant source 604, a fuel (e.g., methane) source 606, a hydrogen generator 608, and a boiler 610. The system 600 produces hydrogen 612 and an exhaust gas. The hydrogen generator 608 includes an anode and a cathode separated by an electrolyte. The anode and cathode receive fuel and water, respectively, and the fuel and water do not contact each other in the generator 608. In many cases, the fuel and water do not contact each other throughout the system 600. The system itself fully satisfies the thermal load without any external heat source. For example, boiler 610 heats a fuel input stream into generator 608, oxidant 604, and water 602. The generator 608 in operation has a fuel inlet temperature of no greater than 1000 ℃, alternatively no greater than 900 ℃, alternatively 800 ℃ to 850 ℃, and has a fuel outlet temperature of no less than 600 ℃.

The fuel exits fuel source 606 as stream 600-1, passes through desulfurization unit 614 and becomes stream 600-2. Stream 600-2 enters condenser 616 and functions as a coolant for condenser 616 and exits as stream 600-3, which is the preheated fuel. Stream 600-3 enters heat exchanger (HX 2) 618 and is further heated to an appropriate temperature by exhaust gas stream 600-6 from boiler 610 and enters generator 608 as stream 600-4. Stream 600-4 is received by an anode in generator 608 and partially oxidized before exiting generator 608 as stream 600-5. Stream 600-5 is introduced into boiler 610 and is further oxidized by the oxidant in boiler 610, thereby generating heat. The flue gas exits from boiler 610 as stream 600-6, passes through heat exchanger HX 2618 to heat the fuel input into generator 608 and becomes stream 600-7. Stream 600-7 heats generator 608 to ensure proper operating temperature of generator 608 and becomes stream 600-19. Streams 600-19 pass through heat exchanger HX 1620 to heat the oxidant and exit as streams 600-20. Streams 600-20 pass through heat exchanger HX 3622 to heat water and exit as streams 600-21.

The water leaves the water source as stream 600-8, passes through the pump and becomes stream 600-9. Streams 600-9 are heated by streams 600-20 in heat exchanger HX 3622 and become streams 600-10. Stream 600-10 enters boiler 610 and is turned into steam (stream 600-11) by the heat generated from the oxidation reaction in boiler 610. The stream 600-11 passes through the turbine 624 and becomes stream 600-12. The turbine 624 is used to drive the pump. Streams 600-12 enter hydrogen generator 608 and are received by the cathode of generator 608. The water/steam is reduced to hydrogen at the cathode. The mixture of steam and hydrogen exits the generator 608 as streams 600-13. Stream 600-13 enters condenser 616 and is cooled by the unheated fuel (stream 600-2). Water is stripped from the mixture and recycled from the condenser as streams 600-18. Streams 600-18 are combined with streams 600-9 and re-enter boiler 610 after passing through heat exchanger HX 3622. Hydrogen leaves the condenser 616 as stream 600-14.

Air exits the oxidant source as streams 600-15 and passes through air purifier 626 where particles and/or oxides are removed and become streams 600-16. Streams 600-16 are heated in heat exchanger HX 1620 by streams 600-19 and become streams 600-17. Stream 600-17 enters boiler 610 and reacts with stream 600-5 to further oxidize the fuel and generate heat. The reaction products exit boiler 610 as stream 600-6.

Fig. 6B shows an alternative hydrogen production system 650 without an external heat source, according to an embodiment of the present disclosure. Steam Generator (SG) 652 functions similarly to boiler 610 in system 600 in fig. 6A. Air enters the condenser as stream 650-1 and is used as a coolant in condenser 616. The air stream 650-2 is then heated in heat exchanger HX 1620 and mixed with the anode output stream before entering the hydrogen generator 608 as stream 650-3. The fuel enters as stream 650-4 and is heated in heat exchanger HX 2618 by the exhaust gas before entering hydrogen generator 608 as stream 650-5. The fuel is oxidized in the anode of the hydrogen generator 608 to an anode output stream and is further oxidized by air to an exhaust 650-6. The exhaust gas provides heat energy to the heat exchangers (HX 1620 and HX 2618) and SG 652 to generate steam from the water. The steam enters the hydrogen generator 608 and is reduced to hydrogen at the cathode. The cathode output stream 650-7 is directed to a condenser 616. Water from condenser 616 is recycled as stream 650-8 and hydrogen is extracted from condenser 616.

Fuel cell

A fuel cell is an electrochemical device that converts chemical energy from a fuel into electricity through an electrochemical reaction. As mentioned above, there are various types of fuel cells, for example, proton-exchange membrane fuel cells (PEMFCs), Solid Oxide Fuel Cells (SOFCs). A fuel cell typically includes an anode, a cathode, an electrolyte, an interconnect, an optional barrier layer, and/or an optional catalyst. Both the anode and the cathode are electrodes. In some cases, the list of materials for electrodes, electrolytes, and interconnects in the fuel cell are applicable to EC gas generators and EC compressors. These lists are merely examples and are not limiting. In addition, the nomenclature of the anode material and cathode material is also not limiting, as the function of the material during operation (e.g., whether it is oxidizing or reducing) determines whether the material functions as an anode or a cathode.

Fig. 7-8 illustrate various embodiments of components in a fuel cell or fuel cell stack. In these embodiments, the anode, cathode, electrolyte and interconnect are cuboids or rectangular prisms.

Fig. 7 shows an assembly of a fuel cell according to an embodiment of the present disclosure. Layer 701 schematically shows the anode, layer 702 represents the cathode, layer 703 represents the electrolyte, layer 704 represents the barrier layer, layer 705 represents the catalyst and layer 706 represents the interconnect.

Figure 8 schematically shows two fuel cells in a fuel cell stack according to an embodiment of the present disclosure. The two fuel cells are denoted as "fuel cell 1" and "fuel cell 2". Each fuel cell in fig. 8 includes an anode layer 801, a cathode layer 802, an electrolyte layer 803, a barrier layer 804, a catalyst layer 805, and an interconnect layer 806. As shown, two fuel cell repeat units or two fuel cells form a stack. As shown, on one side, the interconnect 806 is in contact with the largest surface of the cathode 802 of the fuel cell 2 (or fuel cell repeat unit), and on the opposite side, the interconnect 806 is in contact with the largest surface of the catalyst 805 (optional) or anode 801 of the bottom fuel cell 2 (or fuel cell repeat unit). These repeat units or fuel cells are connected in parallel by stacking on top of each other and sharing the interconnects between them by direct contact with the interconnects rather than by wires. This configuration shown in fig. 8 is in contrast to a segmented series (SIS) type fuel cell.

Cathode electrode

In some embodiments, the cathode comprises a perovskite, such as LSC, LSCF, or LSM. In some embodiments, the cathode includes one or more of lanthanum, cobalt, strontium, or manganite. In one embodiment, the cathode is porous. In some embodiments, the cathode comprises one or more of YSZ, nitrogen boron doped graphene, la0.6sr0.4co0.2fe0.8o3, srco0.5sc0.5o3, bafe0.75ta0.25o3, bafe0.875re0.125o3, ba0.5la0.125zn0.375nio3, ba0.75sr0.25fe0.875ga0.125o3, bafe0.125co0.125, zr0.75o3. In some embodiments, the cathode comprises LSCo, LCo, LSF, LSCoF, or a combination thereof. In some embodiments, the cathode comprises perovskite LaCoO3, laceo 3, LaMnO3, (La, Sr) MnO3, LSM-GDC, LSCF-GDC, LSC-GDC. Cathodes containing LSCF are suitable for moderate temperature fuel cell operation.

In some embodiments, the cathode comprises a material selected from the group consisting of: lanthanum strontium manganite, lanthanum strontium ferrite, and lanthanum strontium cobalt ferrite. In a preferred embodiment, the cathode comprises lanthanum strontium manganite.

Anode

In some embodiments, the anode comprises copper, nickel oxide-YSZ, NiO-GDC, NiO-SDC, aluminum doped zinc oxide, molybdenum oxide, lanthanum, strontium, chromite, ceria, perovskite (e.g., LSCF [ La {1-x } Sr { x } Co {1-y } Fe { y } O)₃]Or LSM [ La {1-x } Sr { x } MnO₃]Where x is typically in the range of 0.15-0.2 and y is in the range of 0.7 to 0.8). In some embodiments, the anode includes a SDC or bzcyb coating or barrier layer to reduce coking and sulfur poisoning. In one embodiment, the anode is porous. In some embodiments, the anode comprises a combination of an electrolyte material and an electrochemically active material or a combination of an electrolyte material and a conductive material.

In a preferred embodiment, the anode comprises nickel and yttria stabilized zirconia. In a preferred embodiment, the anode is formed by reduction of a material comprising nickel oxide and yttria stabilised zirconia. In a preferred embodiment, the anode comprises nickel and gadolinium stabilized ceria. In a preferred embodiment, the anode is formed by reduction of a material comprising nickel oxide and gadolinium stabilised ceria.

Electrolyte

In one embodiment, the electrolyte in the fuel cell comprises a stabilized zirconia (e.g., YSZ-8, Y)_0.16Zr_0.84O₂). In one embodiment, the electrolyte comprises doped LaGaO3 (e.g., LSGM, La)_0.9Sr_0.1Ga_0.8Mg0.2O₃). In one embodiment, the electrolyte comprises doped ceria (e.g., GDC, Gd)_0.2Ce_0.8O₂). In one embodiment, the electrolyte comprises a stable bismuth oxide (e.g., BVCO, Bi 2V)_0.9Cu_0.1O_5.35）。

In some embodiments, the electrolyte comprises zirconium oxide, oxygenYttria stabilized zirconium oxide (also known as YSZ, YSZ8 (8 mol% YSZ)), ceria, gadolinia, scandia, magnesia, or calcia, or combinations thereof. In one embodiment, the electrolyte is sufficiently impermeable to prevent significant gas transport and to prevent significant electrical conduction (electrical conduction); and allows ionic conductivity. In some embodiments, the electrolyte comprises a doped oxide, such as cerium oxide, yttrium oxide, bismuth oxide, lead oxide, lanthanum oxide. In some embodiments, the electrolyte comprises a perovskite, such as laccofeo₃Or LaCoO₃Or Ce_0.9Gd_0.1O₂(GDC) or Ce_0.9Sm_0.1O₂(SDC, samarium oxide doped ceria) or scandia stabilized zirconia or combinations thereof.

In some embodiments, the electrolyte comprises a material selected from the group consisting of: zirconia, ceria and gallium oxide (gallia). In some embodiments, the material is stabilized with a stabilizing material selected from the group consisting of: scandium, samarium, gadolinium and yttrium. In one embodiment, the material comprises yttria stabilized zirconia.

Interconnect member

In some embodiments, the interconnect comprises silver, gold, platinum, AISI441, ferritic stainless steel, lanthanum, chromium oxide, chromite, cobalt, cesium, Cr₂O₃Or a combination thereof. In some embodiments, the anode comprises Cr located therein₂O₃Or NiCo₂O₄Or MnCo₂O₄LaCrO on coating₃And (4) coating. In some embodiments, the interconnect surface is coated with cobalt and/or cesium. In some embodiments, the interconnect comprises a ceramic. In some embodiments, the interconnect comprises lanthanum chromite or doped lanthanum chromite. In one embodiment, the interconnect comprises a material further comprising a metal, stainless steel, ferritic steel, crofer, lanthanum chromite, silver, metal alloy, nickel oxide, ceramic, or lanthanum calcium chromite, or combinations thereof.

Catalyst and process for preparing same

In various embodiments, the fuel cell includes a catalyst, such as platinum, palladium, scandium, chromium, cobalt, cesium, CeO₂Nickel, nickel oxide, zinc, copper, titanium dioxide, ruthenium, rhodium, MoS₂Molybdenum, rhenium, vanadium, manganese, magnesium or iron or combinations thereof. In various embodiments, the catalyst promotes the methane reforming reaction to produce hydrogen and carbon monoxide, which can be oxidized in the fuel cell. Typically, the catalyst is part of an anode, particularly a nickel anode, which has inherent methane reforming properties. In one embodiment, the catalyst is between 1% -5% or 0.1% to 10% by mass. In one embodiment, a catalyst is used on the surface of or in the anode. In various embodiments, these anode catalysts reduce detrimental coking reactions and carbon deposition. In various embodiments, a simple oxide form or perovskite of the catalyst may be used as the catalyst. For example, about 2% by mass of CeO₂The catalyst is used in a methane-driven fuel cell. In various embodiments, the catalyst may be immersed or coated on the anode. In various embodiments, the catalyst is prepared by an Additive Manufacturing Machine (AMM) and introduced into the fuel cell using the AMM.

The unique production methods discussed herein have described the assembly of ultra-thin fuel cells and fuel cell stacks. Typically, to achieve structural integrity, fuel cells have at least one thick layer per repeat unit. This may be the anode (e.g., an anode-supported fuel cell) or an interconnect (e.g., an interconnect-supported fuel cell). As discussed above, a pressing or compression step is typically necessary in conventional production methods to assemble the fuel cell assembly to achieve hermeticity and/or proper electrical contact. As such, thick layers are necessary not only because traditional methods (such as tape casting) cannot produce ultra-thin layers, but also because the layers must be thick to withstand the extrusion or compression steps. The preferred production method of the present disclosure eliminates the need for extrusion or compression. The preferred production method of the present disclosure also enables the preparation of ultra-thin layers. When they are prepared according to the present disclosure, the various layers in the fuel cell or fuel cell stack provide sufficient structural integrity for proper operation.

Disclosed herein are fuel cells comprising an anode no greater than 1 mm, or 500 microns, or 300 microns, or 100 microns, or 50 microns, or no greater than 25 microns thick. The cathode thickness is no greater than 1 mm, or 500 microns, or 300 microns, or 100 microns, or 50 microns, or no greater than 25 microns. The electrolyte has a thickness of no greater than 1 mm, or 500 microns, or 300 microns, or 100 microns, or 50 microns, or 30 microns. In one embodiment, the fuel cell comprises an interconnect having a thickness of no less than 50 microns. In some cases, the fuel cell comprises an anode no greater than 25 microns thick, a cathode no greater than 25 microns thick, and an electrolyte no greater than 10 microns or 5 microns thick. In one embodiment, the fuel cell comprises an interconnect having a thickness of no less than 50 microns. In one embodiment, the thickness of the interconnect is in the range of 50 micrometers to 5 cm.

In a preferred embodiment, the fuel cell comprises an anode no greater than 100 microns thick, a cathode no greater than 100 microns thick, an electrolyte no greater than 20 microns thick and an interconnect no greater than 30 microns thick. In a more preferred embodiment, the fuel cell comprises an anode no greater than 50 microns thick, a cathode no greater than 50 microns thick, an electrolyte no greater than 10 microns thick and an interconnect no greater than 25 microns thick. In one embodiment, the thickness of the interconnect is in a range of 1 micron to 20 microns.

In a preferred embodiment, the fuel cell comprises a barrier layer between the anode and the electrolyte, or a barrier layer between the cathode and the electrolyte, or both. In some cases, the barrier layer is an interconnect. In these cases, the reactants are injected directly into the anode and cathode.

In one embodiment, the cathode has a thickness of no greater than 15 microns, alternatively no greater than 10 microns, alternatively no greater than 5 microns. In one embodiment, the thickness of the anode is no greater than 15 microns, alternatively no greater than 10 microns, alternatively no greater than 5 microns. In one embodiment, the electrolyte has a thickness of no greater than 5 microns, alternatively no greater than 2 microns, alternatively no greater than 1 micron, alternatively no greater than 0.5 microns. In one embodiment, the interconnect is composed of a material comprising a metal, stainless steel, silver, metal alloy, nickel oxide, ceramic, lanthanum chromite, doped lanthanum chromite, or lanthanum calcium chromite. In one embodiment, the total thickness of the fuel cell is not less than 1 micron.

Also discussed herein is a fuel cell stack comprising a plurality of fuel cells, wherein each fuel cell comprises an anode that is no greater than 25 microns thick, a cathode that is no greater than 25 microns thick, an electrolyte that is no greater than 10 microns thick, and an interconnect having a thickness in a range of 100 nm to 100 microns. In one embodiment, each fuel cell comprises a barrier layer between the anode and the electrolyte, or a barrier layer between the cathode and the electrolyte, or both. In one embodiment, the barrier layer is an interconnect. For example, the interconnects are made of silver. For example, the thickness of the interconnect is in the range of 500 nm to 1000 nm. In one embodiment, the interconnect is composed of a material comprising a metal, stainless steel, silver, metal alloy, nickel oxide, ceramic, or lanthanum calcium chromite.

In one embodiment, the cathode has a thickness of no greater than 15 microns, alternatively no greater than 10 microns, alternatively no greater than 5 microns. In one embodiment, the thickness of the anode is no greater than 15 microns, alternatively no greater than 10 microns, alternatively no greater than 5 microns. In one embodiment, the electrolyte has a thickness of no greater than 5 microns, alternatively no greater than 2 microns, alternatively no greater than 1 micron, alternatively no greater than 0.5 microns. In one embodiment, the total thickness of each fuel cell is not less than 1 micron.

Further discussed herein are methods of making a fuel cell comprising (a) forming an anode that is no greater than 25 microns thick, (b) forming a cathode that is no greater than 25 microns thick, and (c) forming an electrolyte that is no greater than 10 microns thick. In one embodiment, steps (a) - (c) are performed using additive manufacturing. In various embodiments, the additive manufacturing uses one or more of extrusion, photopolymerization, powder layer fusion, material jetting, binder jetting, directed energy deposition, or lamination.

In one embodiment, the method includes assembling an anode, a cathode, and an electrolyte using additive manufacturing. In one embodiment, the method includes forming an interconnect and assembling the interconnect with an anode, a cathode, and an electrolyte.

In a preferred embodiment, the method comprises preparing at least one barrier layer. In a preferred embodiment, at least one barrier layer is used between the electrolyte and the cathode or between the electrolyte and the anode or both. In one embodiment, the at least one barrier layer also functions as an interconnect.

In a preferred embodiment, the method includes heating the fuel cell so that the shrinkage rates of the anode, cathode and electrolyte are matched. In some embodiments, this heating is performed for no more than 30 minutes, preferably no more than 30 seconds, and most preferably no more than 30 milliseconds. When the fuel cell comprises a first composition and a second composition, wherein the first composition has a first shrinkage and the second composition has a second shrinkage, the heating described in the present disclosure is preferably performed such that the difference between the first shrinkage and the second shrinkage is no greater than 75% of the first shrinkage.

In a preferred embodiment, the heating uses electromagnetic radiation (EMR). In various embodiments, the EMR includes UV light, near ultraviolet light, near infrared light, visible light, laser, electron beam. Preferably, the heating is performed in situ.

Also disclosed herein is a method of making a fuel cell stack comprising a plurality of fuel cells, the method comprising: (a) forming an anode no greater than 25 microns thick in each fuel cell, (b) forming a cathode no greater than 25 microns thick in each fuel cell, (c) forming an electrolyte no greater than 10 microns thick in each fuel cell and (d) producing an interconnect 100 nm to 100 microns thick in each fuel cell.

In one embodiment, steps (a) - (d) are performed using AM. In various embodiments, the AM utilizes one or more of extrusion, photopolymerization, powder layer fusion, material jetting, binder jetting, directed energy deposition, or lamination processes.

In one embodiment, a method of making a fuel cell stack includes assembling an anode, a cathode, an electrolyte, and an interconnect using AM. In one embodiment, the method includes preparing at least one barrier layer in each fuel cell. In one embodiment, at least one barrier layer is used between the electrolyte and the cathode or between the electrolyte and the anode or both. In one embodiment, the at least one barrier layer also functions as an interconnect.

In one embodiment, a method of making a fuel cell stack includes heating each fuel cell such that the shrinkage rates of the anode, cathode, and electrolyte match. In one embodiment, this heating is performed for no more than 30 minutes, alternatively no more than 30 seconds, alternatively no more than 30 milliseconds. In a preferred embodiment, the heating comprises one or more electromagnetic radiations (EMRs). In various embodiments, the EMR includes UV light, near ultraviolet light, near infrared light, visible light, laser, electron beam. In one embodiment, the heating is performed in situ.

In one embodiment, the method includes heating the entire fuel cell stack such that the shrinkage rates of the anode, cathode, and electrolyte are matched. In some embodiments, such heating is performed for no more than 30 minutes, alternatively no more than 30 seconds, alternatively no more than 30 milliseconds.

Discussed herein are methods of making an electrolyte comprising (a) formulating a colloidal suspension, wherein the colloidal suspension comprises an additive, particles having a range of diameters and particle size distributions, and a solvent; (b) forming an electrolyte comprising a colloidal suspension; and (c) heating at least a portion of the electrolyte; wherein the formulation of the colloidal suspension is preferably optimized by controlling the pH of the colloidal suspension, or the concentration of the binder in the colloidal suspension, or the composition of the binder in the colloidal suspension, or the range of diameters of the particles, or the maximum diameter of the particles, or the median diameter of the particles, or the particle size distribution of the particles, or the boiling point of the solvent, or the surface tension of the solvent, or the composition of the solvent, or the thickness of the smallest dimension of the electrolyte, or the composition of the particles, or a combination thereof.

A method of making a fuel cell is discussed herein, comprising (a) obtaining a cathode and an anode; (b) modifying the surface of the cathode and the surface of the anode; (c) preparing a colloidal suspension, wherein the colloidal suspension comprises an additive, particles having a range of diameters and particle size distributions, and a solvent; (d) forming an electrolyte comprising a colloidal suspension between the modified anode surface and the modified cathode surface; and (e) heating at least a portion of the electrolyte; wherein formulating the colloidal suspension comprises controlling the pH of the colloidal suspension, or the concentration of the binder in the colloidal suspension, or the composition of the binder in the colloidal suspension, or the range of diameters of the particles, or the maximum diameter of the particles, or the median diameter of the particles, or the particle size distribution of the particles, or the boiling point of the solvent, or the surface tension of the solvent, or the composition of the solvent, or the thickness of the smallest dimension of the electrolyte, or the composition of the particles, or a combination thereof. In various embodiments, the anode and cathode are obtained by any suitable method. In one embodiment, the modified anode surface and the modified cathode surface have a maximum height profile roughness (maximum height profile roughness) that is less than the average diameter of the particles in the colloidal suspension. The maximum height profile roughness 900 refers to the maximum distance between any groove (trough) 902 and an adjacent peak 904 of the anode surface or cathode surface, as shown in fig. 9. In various embodiments, the anode surface and the cathode surface are modified by any suitable method.

Further disclosed herein is a method of making a fuel cell comprising (a) obtaining a cathode and an anode; (b) preparing a colloidal suspension, wherein the colloidal suspension comprises an additive, particles having a range of diameters and particle size distributions, and a solvent; (c) forming an electrolyte comprising a colloidal suspension between an anode and a cathode; and (d) heating at least a portion of the electrolyte; wherein formulating the colloidal suspension comprises controlling the pH of the colloidal suspension, or the concentration of the binder in the colloidal suspension, or the composition of the binder in the colloidal suspension, or the range of diameters of the particles, or the maximum diameter of the particles, or the median diameter of the particles, or the particle size distribution of the particles, or the boiling point of the solvent, or the surface tension of the solvent, or the composition of the solvent, or the thickness of the smallest dimension of the electrolyte, or the composition of the particles, or a combination thereof. In various embodiments, the anode and cathode are obtained by any suitable method. In one embodiment, the surface of the anode in contact with the electrolyte and the surface of the cathode in contact with the electrolyte have a maximum height profile roughness that is less than the average diameter of the particles in the colloidal suspension.

In a preferred embodiment, the solvent comprises water. In a preferred embodiment, the solvent comprises an organic component. The solvent may include ethanol, butanol, an alcohol, terpineol, diethyl ether, 1, 2-dimethoxyethane (DME (ethylene glycol dimethyl ether), 1-propanol (n-propanol ), or butanol, or a combination thereof.

In some embodiments, the electrolyte is formed adjacent to the first substrate or between the first substrate and the second substrate. In some embodiments, the first substrate has a maximum height profile roughness that is less than the average diameter of the particles. In some embodiments, the particles have a bulk density of greater than 40%, alternatively greater than 50%, alternatively greater than 60%. In one embodiment, the particles have a packing density close to a Random Close Packing (RCP) density.

Random compact packing density (RCP) is an empirical parameter used to characterize the maximum volume fraction of solid objects obtained upon random packing. The container is randomly filled with the object and then shaken or tapped until the object is no longer compacted further, at which point the stacking state is RCP. The packing fraction is the volume occupied by a certain number of particles in a given volume of space. The number of stacked fractions determines the bulk density. For example, when a solid container is filled with particles, shaking the container will reduce the volume occupied by the object, thus allowing more particles to be added to the container. Sloshing increases the density of the bulk object. A limit is reached when the sloshing no longer increases the packing density, and if this limit is reached without significant packing in the tetragonal crystal lattice, this is an empirical random close packing density.

In some embodiments, the median particle size is between 50 nm and 1000 nm, alternatively between 100 nm and 500 nm, alternatively about 200 nm. In some embodiments, the first substrate comprises particles having a median particle diameter, wherein the median particle diameter of the electrolyte may be no greater than 10 times the median particle diameter of the first substrate and no less than 1/10 thereof. In some embodiments, the first substrate comprises a bimodal particle size distribution having a first mode (first mode) and a second mode, wherein each peak has a median particle size. In some embodiments, the first mode of the first substrate has a median particle size that is greater than 2 times, or greater than 5 times, or greater than 10 times that of the second mode. The particle size distribution of the first substrate may be adjusted to alter the behavior of the first substrate during heating. In some embodiments, the first substrate has a shrinkage that varies with heating temperature. In some embodiments, the particles in the colloidal suspension can have a maximum particle size and a minimum particle size, wherein the maximum particle size is less than 2 times, or less than 3 times, or less than 5 times, or less than 10 times the minimum particle size. In some embodiments, the minimum dimension of the electrolyte is less than 10 microns, or less than 2 microns, or less than 1 micron, or less than 500 nm.

In some embodiments, the gas permeability of the electrolyte is no greater than 1 millidarcy, preferably no greater than 100 microdarcy, and most preferably no greater than 1 microdarcy. Preferably, the electrolyte has no cracks of minimum size that penetrate through the electrolyte. In some embodiments, the boiling point of the solvent is not less than 200 ℃, or not less than 100 ℃, or not less than 75 ℃. In some embodiments, the solvent has a boiling point of no greater than 125 ℃, alternatively no greater than 100 ℃, alternatively no greater than 85 ℃, and no greater than 70 ℃. In some embodiments, the pH of the colloidal suspension is not less than 7, or not less than 9, or not less than 10.

In some embodiments, the additive comprises polyethylene glycol (PEG), ethyl cellulose, polyvinylpyrrolidone (PVP), polyvinyl butyral (PVB), Butyl Benzyl Phthalate (BBP), polyalkylene glycol (PAG), or a combination thereof. In one embodiment, the additive concentration is no greater than 100 mg/cm3, alternatively no greater than 50 mg/cm3, alternatively no greater than 30 mg/cm3, alternatively no greater than 25 mg/cm 3.

In one embodiment, the colloidal suspension is milled. In one embodiment, the colloidal suspension is milled using a rotary mill, wherein the rotary mill is operated at not less than 20 rpm, or not less than 50 rpm, or not less than 100 rpm, or not less than 150 rpm. In one embodiment, the colloidal suspension is milled using zirconia milling balls or tungsten carbide milling balls, wherein the colloidal suspension is milled for no less than 2 hours, or no less than 4 hours, or no less than 1 day, or no less than 10 days.

In some embodiments, the concentration of particles in the colloidal suspension is no greater than 30 wt%, alternatively no greater than 20 wt%, alternatively no greater than 10 wt%. In other embodiments, the concentration of particles in the colloidal suspension is not less than 2 wt%. In some embodiments, the concentration of particles in the colloidal suspension is no greater than 10 vol%, alternatively no greater than 5 vol%, alternatively no greater than 3 vol%, alternatively no greater than 1 vol%. In one embodiment, the concentration of particles in the colloidal suspension is not less than 0.1 vol%.

In a preferred embodiment, the electrolyte is formed using an Additive Manufacturing Machine (AMM). In a preferred embodiment, the first substrate is formed using AMM. In a preferred embodiment, the heating comprises the use of electromagnetic radiation (EMR), wherein EMR comprises one or more of UV light, near ultraviolet light, near infrared light, visible light, or laser light. In a preferred embodiment, the first substrate and the electrolyte are heated to cause co-sintering. In a preferred embodiment, the first substrate, the second substrate and the electrolyte are heated to cause co-sintering. In one embodiment, the EMR is controlled to preferentially sinter the first substrate relative to the electrolyte.

In one embodiment, the electrolyte is compressed after heating. In one embodiment, the first substrate and the second substrate exert pressure on the electrolyte after heating. In one embodiment, the first and second substrates to which pressure is applied are the anode and cathode of a fuel cell. In some embodiments, the minimum dimension of the electrolyte is between 500 nm and 5 microns or between 1 micron and 2 microns.

The detailed discussion described herein uses the production of Solid Oxide Fuel Cells (SOFCs) as an illustrative example. As will be appreciated by those skilled in the art, the methods and production methods described herein are applicable to all fuel cell types. As such, the production of all fuel cell types is within the scope of the present disclosure.

Reactor box (reactor cartridge)

In various embodiments, the Electrochemical (EC) reactor is formed in the form of a cartridge. The discussion herein uses a fuel cell or fuel cell stack as an example. The cartridge design is suitable for other electrochemical reactors such as EC gas generators, EC compressors, flow batteries. In various embodiments, the fuel cell stack is configured in the form of a cartridge, such as an easily removable flange Fuel Cell Cartridge (FCC) design. Fig. 9A shows a perspective view of a Fuel Cell Cartridge (FCC) 900, according to embodiments of the present disclosure. The FCC 900 includes a rectangular shape as shown in fig. 9A. Other form factors are possible, such as square-like, cylindrical-like, hexagonal-like, or combinations thereof. The form factor may depend on the application in which the FCC is used, such as in industrial, home, automotive or other applications. The FCC 900 also includes holes 902 for bolts that secure the FCC in the system or in series with other FCC's or both. The housing of the FCC cartridge 900 may be composed of aluminum, steel, plastic, ceramic, or a combination thereof. The FCC 900 includes a top interconnect 904.

Fig. 9B shows a perspective view of a cross-section of a Fuel Cell Cartridge (FCC) 900, according to an embodiment of the present disclosure. The FCC 900 includes bolted holes 902, a cathode layer 906, a barrier layer 908, an anode layer 910, gas channels 912 in the electrodes (anode and cathode), an electrolyte layer 914, an air heat exchanger 916, a fuel heat exchanger 918, and a top interconnect 904. The combined air heat exchanger 916 and fuel heat exchanger 918 form an integrated multifluid heat exchanger. In some embodiments, there is no barrier layer between cathode 906 and electrolyte 914. The FCC 900 includes a second interconnect 920, such as between the anode layer 910 and the fuel heat exchanger 918. The FCC 900 also includes openings 922, 924 for fuel passages.

Fig. 9C shows a cross-sectional view of a Fuel Cell Cartridge (FCC), according to an embodiment of the present disclosure. The FCC 900 in fig. 9C includes electrical bolt insulation 926, an anode 910, a seal 928 that isolates the anode 910 from air flow, a cathode 906, and a seal 930 that isolates the cathode 906 from fuel flow. The bolts may also be electrically insulated by the seal. In various embodiments, the seal may be a Dual Function Seal (DFS) comprising YSZ (yttria stabilized zirconia) or 3YSZ (ZrO) including ₂Middle 3 mol% of Y₂O₃) And 8YSZ (ZrO)₂Middle 8 mol% of Y₂O₃) A mixture of (a). In some embodiments, the DFS is impermeable to non-ionic species and electrically insulating. In some embodiments, the mass ratio of 3YSZ/8YSZ is in the range of 10/90 to 90/10. In some embodiments, the mass ratio of 3YSZ/8YSZ is about 50/50. In some embodiments, the mass ratio of 3YSZ/8YSZ is 100/0 or 0/100.

Fig. 9D shows top and bottom views of a Fuel Cell Cartridge (FCC), according to embodiments of the present disclosure. The FCC 900 includes bolt holes 902, air inlets 932, air outlets 934, fuel inlets 922, fuel outlets 924, a bottom 936 of the FCC 900, and a top interconnect 904. FIG. 9D also shows top and bottom views of an embodiment of FCC 900, wherein the length of the oxidant side of the FCC 900 is shown as L_oThe length of the fuel side of the FCC 900 is shown as L_fThe width of the oxidant (air inlet 932) inlet is shown as W_oAnd the width of fuel inlet 922 is shown as W_f. In fig. 9D, two fluid outlets (air outlet 934 and fuel outlet 924) are shown. In some embodiments, the anode exhaust gas and the cathode exhaust gas may be mixed and extracted through one fluid outlet. In some cases, the base 936 is an interconnect and 932, 934, 922, 924 are openings of flow channels, e.g., in a direction perpendicular to the lateral direction.

Disclosed herein is a Fuel Cell Cartridge (FCC) 900 comprising an anode 910, a cathode 906, an electrolyte 914, at least one interconnect, a fuel inlet on the fuel side of the FCC 900, an FCCAt least one fluid outlet, wherein the fuel inlet has W_fWidth of FCC fuel side has L_fLength of oxidant inlet having W_oWidth of FCC oxidant side has L_oLength of (1), wherein W_f/L_fWithin the following ranges: 0.1 to 1.0, or 0.1 to 0.9, or 0.2 to 0.9, or 0.5 to 1.0, and W_o/L_oWithin the following ranges: 0.1 to 1.0, alternatively 0.1 to 0.9, alternatively 0.2 to 0.9, alternatively 0.5 to 1.0.

In some embodiments, the air and fuel inlets and outlets are on a surface of the FCC 900, wherein the FCC 900 does not include protruding flow channels (protruding flow channels ) on the surface. In some embodiments, the surface is smooth with a maximum rise variation of no greater than 1 mm, alternatively no greater than 100 microns, alternatively no greater than 10 microns.

In some embodiments, the FCC 900 includes a barrier layer located between the electrolyte and the cathode or between the electrolyte and the anode or both. In one embodiment, the FCC includes a Dual Function Seal (DFS) that is impermeable to non-ionic substances and electrically insulating. In some embodiments, the DFS comprises YSZ (yttria-stabilized zirconia) or 3YSZ (ZrO) ₂Middle 3 mol% of Y₂O₃) And 8YSZ (ZrO)₂Middle 8 mol% of Y₂O₃) A mixture of (a).

In some embodiments, the interconnect does not comprise a fluid dispersing element, and the anode and cathode comprise a fluid dispersing assembly. In some embodiments, the interconnect does not comprise a fluid dispersing element, while the anode and cathode comprise fluid channels.

In some embodiments, a Fuel Cell Cartridge (FCC) 900 includes an anode, a cathode, an electrolyte, an interconnect, a fuel inlet, an oxidant inlet, at least one fluid outlet, wherein the inlet and outlet are located on one surface of the FCC, and the FCC does not include an extended flow path located on the surface. In some embodiments, the surface may be smooth with a maximum rise variation of no greater than 1 mm, alternatively no greater than 100 microns, alternatively no greater than 10 microns.

In some embodiments, the FCC 900 includes DFS that is impermeable to non-ionic substances and electrically insulating. In one embodiment, the interconnect does not comprise a fluid dispersing element, and the anode and cathode comprise a fluid dispersing assembly. In one embodiment, the interconnect does not comprise a fluid dispersing element, and the anode and cathode comprise fluid channels.

In one embodiment, the FCC 900 is removably secured to a mating surface (mating surface) and is not welded or soldered to the mating surface. In one embodiment, the FCC is bolted or extruded to the mating surface. The mating surfaces include a mating fuel inlet, a mating oxidant inlet, and at least one mating fluid outlet.

Also disclosed herein is an assembly comprising a Fuel Cell Cartridge (FCC) and mating surfaces, wherein the FCC comprises an anode, a cathode, an electrolyte, an interconnect, a fuel inlet on a fuel side of the FCC, an oxidant inlet on an oxidant side of the FCC, at least one fluid outlet, wherein the fuel inlet has a W_fWidth of FCC fuel side has L_fLength of oxidant inlet having W_oWidth of FCC oxidant side has L_oLength of (1), wherein W_f/L_fWithin the following ranges: 0.1 to 1.0, or 0.1 to 0.9, or 0.2 to 0.9, or 0.5 to 1.0, and W_o/L_oWithin the following ranges: 0.1 to 1.0, or 0.1 to 0.9, or 0.2 to 0.9, or 0.5 to 1.0, wherein the FCC is removably secured to the mating surface.

In some embodiments, the inlet and outlet are on a surface of the FCC, and wherein the FCC does not include an extended flowpath on the surface. The surface may be smooth with a maximum rise variation of no greater than 1 mm, alternatively no greater than 100 microns, alternatively no greater than 10 microns.

In one embodiment, the interconnect does not include a fluid dispersing element, and the anode and cathode include a fluid dispersing assembly. In one embodiment, the interconnect does not include a fluid dispersing element, and the anode and cathode include a fluid channel.

Methods are discussed herein that include pressing or bolting together a Fuel Cell Cartridge (FCC) and mating surfaces. The method does not include welding or soldering together the FCC and the mating surface, wherein the FCC includes an anode, a cathode, an electrolyte, an interconnect, a fuel inlet on a fuel side of the FCC, an oxidant inlet on an oxidant side of the FCC, at least one fluid outlet, wherein the fuel inlet has a width W_fThe FCC fuel side has a length L_fThe oxidant inlet having a width W_oThe oxidant side of the FCC has a length L_oWherein W is_f/L_fIn the range of 0.1 to 1.0, or 0.1 to 0.9, or 0.2 to 0.9, or 0.5 to 1.0, and W_o/L_oIn the range of 0.1 to 1.0, or 0.1 to 0.9, or 0.2 to 0.9, or 0.5 to 1.0, wherein the FCC and mating surfaces are removable.

In one embodiment, the inlet and outlet are on a surface of the FCC, wherein the FCC does not include an extended flow path on the surface. The surface is smooth with a maximum rise variation of no greater than 1 mm, alternatively no greater than 100 microns, alternatively no greater than 10 microns. In one embodiment, the interconnect does not include a fluid dispersing element, and the anode and cathode include a fluid dispersing assembly. In one embodiment, the interconnect does not include a fluid dispersing element, and the anode and cathode include a fluid channel.

Disclosed herein is a Fuel Cell Cartridge (FCC) comprising a fuel cell and a fuel cell housing, wherein the fuel cell comprises an anode, a cathode, and an electrolyte, wherein at least a portion of the fuel cell housing is made of the same material as the electrolyte. In one embodiment, the electrolyte is in contact with a portion of the fuel cell housing made of the same material. In one embodiment, the electrolyte and a portion of the fuel cell housing are made of DFS, wherein the DFS comprises 3YSZ (ZrO)₂Middle 3 mol% of Y₂O₃) And 8YSZ (ZrO)₂Middle 8 mol% of Y₂O₃) Wherein the mass ratio of 3YSZ/8YSZ is in the following range: 100/0 to 0/100 or 10/90 to 90/10, and wherein the DFS is impermeable to non-ionic species and electrically insulating. In one embodiment, the mass ratio of 3YSZ/8YSZ is about 50/50, or 40/60, or 60/40, or 30/70, or 70/30, or 20/80, or 80/20.

In one embodiment, the fuel cell housing comprises a fuel inlet and fuel channel for the anode, an oxidant inlet and oxidant channel for the cathode, and at least one fluid outlet. In one embodiment, the inlet and the at least one outlet are located on a surface of the FCC, wherein the FCC does not include an extended flowpath located on the surface. In one embodiment, the fuel cell housing is in contact with at least a portion of the anode.

In one embodiment, the FCC includes a barrier layer between the electrolyte and the cathode and between the fuel cell housing and the cathode. In one embodiment, the FCC includes an interconnect, wherein the interconnect does not include a fluid dispersing element, and the anode and cathode include a fluid dispersing assembly. In one embodiment, the FCC includes an interconnect, wherein the interconnect does not include a fluid dispersing element, and the anode and cathode include a fluid channel.

In one embodiment, the FCC is removably secured to the mating surface and is not welded or soldered to the mating surface. In one embodiment, the mating surfaces include a mating fuel inlet, a mating oxidant inlet, and at least one mating fluid outlet.

Also discussed herein are compositions comprising 3YSZ (ZrO)₂Middle 3 mol% of Y₂O₃) And 8YSZ (ZrO)₂Middle 8 mol% of Y₂O₃) Wherein the mass ratio of 3YSZ/8YSZ is in the range of 10/90 to 90/10, and wherein the DFS is impermeable to non-ionic species and electrically insulating. In one embodiment, the mass ratio of 3YSZ/8YSZ is about 50/50, or 40/60, or 60/40, or 30/70, or 70/30, or 20/80, or 80/20. In one embodiment, the DFS is used as an electrolyte in a fuel cell or as a portion of a fuel cell housing or both.

Also disclosed herein are methods comprising providing a DFS in a fuel cell system, wherein the DFS comprises 3YSZ (ZrO)₂Middle 3 mol% of Y₂O₃) And 8YSZ (ZrO)₂Middle 8 mol% of Y₂O₃) Wherein the mass ratio of 3YSZ/8YSZ is in the following range: 100/0 to 0/100 or 10/90 to 90/10, and wherein the DFS is impermeable to non-ionic species and electrically insulating. In one embodiment, the mass ratio of 3YSZ/8YSZ is about 50/50, or 40/60, or 60/40, or 30/70, or 70/30, or 20/80, or 80/20.

In one embodiment, the DFS is used as an electrolyte or as part of the fuel cell housing or both in a fuel cell system. A portion of the fuel cell housing may be the entire fuel cell housing. A portion of the fuel cell housing is a coating on the fuel cell housing. An electrolyte is in contact with a portion of the fuel cell housing.

Disclosed herein is a fuel cell system including an anode having 6 surfaces, a cathode having 6 surfaces, an electrolyte, and an anode surround (anode surround) in contact with at least 3 surfaces of the anode, wherein the electrolyte is part of the anode surround, and the anode surround is made of the same material as the electrolyte. In one embodiment, the same material is a material comprising 3YSZ (ZrO) ₂Middle 3 mol% of Y₂O₃) And 8YSZ (ZrO)₂Middle 8 mol% of Y₂O₃) Wherein the mass ratio of 3YSZ/8YSZ is in the following range: 100/0 to 0/100 or 10/90 to 90/10, and wherein the DFS is impermeable to non-ionic species and electrically insulating. In one embodiment, the mass ratio of 3YSZ/8YSZ is about 50/50, or 40/60, or 60/40, or 30/70, or 70/30, or 20/80, or 80/20. In one embodiment, the anode enclosure is in contact with 5 surfaces of the anode.

In one embodiment, the fuel cell system comprises a barrier layer located between the cathode and a cathode surround (cathode surround), wherein the barrier layer is in contact with at least 3 surfaces of the cathode, wherein the electrolyte is part of the cathode surround, and the cathode surround is made of the same material as the electrolyte.

In one embodiment, a fuel cell system includes fuel and oxidant passages in an anode enclosure and a cathode enclosure. In one embodiment, the fuel cell system includes an interconnect, wherein the interconnect does not include a fluid dispersing element, and the anode and cathode include a fluid dispersing assembly. In one embodiment, the fuel cell system includes an interconnect, wherein the interconnect does not include a fluid dispersing element, and the anode and cathode include a fluid channel.

Tubular design

In many cases, the electrochemical reactor as discussed in this disclosure is tubular. The discussion in this section takes a Tubular Fuel Cell (TFC) as an example of a tubular electrochemical reactor. The tubular design is suitable for other types of electrochemical reactors, such as EC gas generators, EC compressors, or flow batteries. Disclosed herein is a Tubular Fuel Cell (TFC) comprising an inner cathode, an outer anode, an electrolyte disposed between the anode and the cathode, and an interconnect. In some embodiments of the TFC, the electrolyte is considered a membrane. The cathode has a cross-section that is a rounded non-circular shape (rounded non-circular shape) without sharp corners, wherein the cross-section is perpendicular to the longitudinal axis of the TFC, wherein the interconnect is in contact with the cathode but not in contact with the anode, and the interconnect has a contact surface configured to contact the anode of an adjacent TFC, wherein the anode has a contact surface and a non-contact surface configured to contact the interconnect of another adjacent TFC.

In one embodiment, the TFC comprises a blocking layer that is positioned between the cathode and the electrolyte or between the anode and the electrolyte or both. In one embodiment, the rounded non-circular shape comprises a rounded rectangle, a rounded square, a rounded hexagon, a rounded trapezoid, a rounded parallelogram, a rounded pentagon, a rounded triangle, a rounded octagon, an ellipse, an ellipsoid, or a rounded irregular shape, or a combination thereof.

In one embodiment, the ratio of the area of the contact surface of the interconnect to the area of the non-contact surface of the anode is no greater than 1, alternatively no greater than 0.75, alternatively no greater than 0.5. In one embodiment, the ratio of the area of the contact surface of the interconnect to the area of the non-contact surface of the anode is no greater than 0.3, alternatively no greater than 0.1, alternatively no greater than 0.05.

In one embodiment, the thickness of the cathode is in the following range: about 10 microns to about 1,000 microns; or from about 50 to about 150 microns; or about 90 to about 110 microns; or about 100 microns. In one embodiment, the thickness of the anode is in the following range: about 1 micron to about 50 microns; or from about 5 microns to about 25 microns; or from about 8 microns to about 12 microns; or about 10 microns. In one embodiment, the thickness of the electrolyte is in the following range: about 100 nm to about 10 microns; or from about 500 nm to about 5 microns; or from about 800 nm to about 2 microns; or about 1 micron. In one embodiment, the thickness of the barrier layer is in the following range: about 100 nm to about 10 microns; or from about 500 nm to about 5 microns; or from about 800 nm to about 2 microns; or about 1 micron. In one embodiment, the thickness of the interconnect is in the range of: about 10 microns to about 1000 microns; or from about 50 microns to about 500 microns; or from about 80 microns to about 200 microns; or about 100 microns.

In one embodiment, the TFC has a length L and the cross-section has a characteristic length W, wherein the ratio of L/W is not less than 1. In one embodiment, the ratio of L/W is not less than 2, or not less than 10, or not less than 100.

In one embodiment, the TFC comprises a support located in the cathode. In one embodiment, the support is in contact with the cathode. In one embodiment, the support is an integral part of the cathode. In one embodiment, the support and the cathode are made of the same material. In one embodiment, the support and the cathode are made of different materials. In one embodiment, the electrolyte is impermeable to the fluid. In one embodiment, the cathode and anode are porous.

Also discussed herein is a fuel cell stack comprising a plurality of Tubular Fuel Cells (TFCs), wherein each of the TFCs comprises an inner cathode, an outer anode, an electrolyte disposed between the anode and the cathode, and an interconnect, wherein a cross-section of the cathode is a rounded non-circular shape without sharp corners, wherein the cross-section is perpendicular to a longitudinal axis of the TFC, wherein the interconnect is in contact with the cathode but not in contact with the anode, and the interconnect has a contact surface configured to contact the anode of an adjacent TFC, wherein the anode has a contact surface and a non-contact surface configured to contact the interconnect of another adjacent TFC.

In one embodiment, each of the TFCs includes a blocking layer positioned between the cathode and the electrolyte or between the anode and the electrolyte or both. In one embodiment, the rounded non-circular shape comprises a rounded rectangle, a rounded square, a rounded hexagon, a rounded trapezoid, a rounded parallelogram, a rounded pentagon, a rounded triangle, a rounded octagon, an ellipse, an ellipsoid, or a rounded irregular shape.

In one embodiment, the ratio of the area of the contact surface of the interconnect to the area of the non-contact surface of the anode is no greater than 1, alternatively no greater than 0.75, alternatively no greater than 0.5. In one embodiment, the ratio of the area of the contact surface of the interconnect to the area of the non-contact surface of the anode is no greater than 0.3, alternatively no greater than 0.1, alternatively no greater than 0.05.

In one embodiment, each of the TFCs has a length L and a cross-section has a characteristic length W, wherein the ratio of L/W is not less than 1, or not less than 2, or not less than 10, or not less than 100.

In one embodiment, each of the TFCs includes a support located in the cathode. In one embodiment, the support is in contact with the cathode. In one embodiment, the support is an integral part of the cathode. In one embodiment, the support and the cathode are made of the same material.

Disclosed herein is a Tubular Fuel Cell (TFC) comprising an inner anode, an outer cathode, an electrolyte disposed between the anode and the cathode, and an interconnect, wherein a cross-section of the anode is a rounded non-circular shape without sharp corners, wherein the cross-section is perpendicular to a longitudinal axis of the TFC, wherein the interconnect is in contact with the anode but not in contact with the cathode, and the interconnect has a contact surface configured to contact the cathode of an adjacent TFC, wherein the cathode has a contact surface and a non-contact surface configured to contact the interconnect of another adjacent TFC.

In one embodiment, the rounded non-circular shape comprises a rounded rectangle, a rounded square, a rounded hexagon, a rounded trapezoid, a rounded parallelogram, a rounded pentagon, a rounded triangle, a rounded octagon, an ellipse, an ellipsoid, a rounded irregular shape, or a combination thereof. In one embodiment, the ratio of the area of the contact surface of the interconnect to the area of the non-contact surface of the cathode is no greater than 1, or no greater than 0.75, or no greater than 0.5, no greater than 0.3, or no greater than 0.1, or no greater than 0.05. In one embodiment, the TFC comprises a blocking layer that is positioned between the cathode and the electrolyte or between the anode and the electrolyte or both.

Fig. 10A-10C show different aspect ratios (aspect ratios) of fuel cells and how they may be connected in a multi-Tubular Fuel Cell (TFC) unit containing two or more TFCs. The TFC includes a rounded corner edge. Fig. 10A shows a cross-sectional view of a TFC 1000 in accordance with an embodiment of the disclosure. The TFC 1000 includes an inner cathode layer 1002, a barrier layer 1004, an electrolyte layer 1006, an outer anode layer 1008, an interconnect 1010, and a flow channel 1012. In some cases, barrier layer 1004 is disposed between anode 1008 and electrolyte 1006. In some cases, two barrier layers are disposed (1) between the cathode 1002 and the electrolyte 1006 and (2) between the anode 1008 and the electrolyte 1006. The interconnect 1010 is in contact with the cathode 1002, but not the anode 1008. The top surface of interconnect 1010 is configured to contact anode 1008 of an adjacent TFC. The anode 1008 has a contact surface on the bottom that is configured to contact an interconnect 1010 of another adjacent TFC. The anode 1008 has non-contact surfaces on both sides in the configuration shown in fig. 10A-10C. In this example in fig. 10A, the TFC 1000 has a rounded rectangular shape connected by interconnects 1010 located on the short ends of the rectangular shape.

Fig. 10B shows a cross-sectional view of TFC 1020, according to an embodiment of the present disclosure. TFC 1020 is similar in construction to TFC 1000, but is connected by interconnects 1010 located on the long sides of the rectangular shape.

Fig. 10C shows a cross-sectional view of TFC 1040, according to an embodiment of the disclosure. TFC 1040 in fig. 10C is similar in structure to the TFCs in fig. 10A-10B, but includes rounded square-like shapes in which the length of each side is substantially the same. TFC 1040 is further connected by interconnect 1010.

In alternative embodiments, the anode 1008 may be configured internally and the cathode 1002 may be external. In some cases, a barrier layer may be disposed between the cathode and the electrolyte. In some cases, two barrier layers are placed (1) between the cathode and the electrolyte and (2) between the anode and the electrolyte. All other configurations and features as discussed above are also applicable in the present embodiment.

In some embodiments, the TFC can further comprise one or more supports positioned in the cathode layer, as shown in fig. 11A-11C. Fig. 11A shows a cross-sectional view of a TFC 1100 including a support, according to an embodiment of the disclosure. The TFC 1100 includes a cathode 1002, a barrier layer 1004, an electrolyte 1006, an anode layer 1008, an interconnect 1010, and at least one flow channel 1012. How the TFC 1100 is arranged is similar in shape and design to the TFC in fig. 10A. The TFC 1100 also includes one or more supports. The support may be in any suitable shape, number, size and material. In some cases, the support 1102 is made of the same material as the internal electrode layers, such as the cathode layer 1002. In some cases, the support 1104 is made of a material different from the material of the inner electrode layer, such as the cathode 1002. For example, inert materials with respect to the fuel cell. In some cases, the support body may be made of more than one material. In one embodiment, one or more supports 1102, 1104 are in contact with the cathode 1002. In one embodiment, one or more of the supports 1102, 1104 are an integral part of the cathode. In one embodiment, one or more of the supports 1102, 1104 are formed as an integral part of the cathode.

Fig. 11B shows a cross-sectional view of a TFC 1120 including a support, according to an embodiment of the disclosure. How the TFC 1120 is arranged is similar in shape and design to the TFC in fig. 10B. The TFC 1120 also contains one or more supports. The support 1102 may be a support having a linear shape of the same material as the internal electrode, such as the cathode 1002. The support 1104 may be a linear shaped support 1104 that is not composed of the same material. The support 1106 may be an oval or round-like shaped support constructed of the same material as the internal electrode, such as the cathode 1002. The support 1108 may be an oval or round-like shaped support that is not composed of the same material as the inner electrode, such as the cathode 1002. As shown in fig. 11B, the TFC can include linear-shaped supports 1102, 1104 and circular-shaped supports 1106, 1108.

Fig. 11C shows a cross-sectional view of a TFC 1140 that includes a support, according to an embodiment of the disclosure. How the TFC 1140 is arranged is similar in shape and design to the TFC in fig. 10C. The TFC 1140 also contains one or more supports. In this embodiment, all of the supports 1106, 1108 may be circular-like or oval-like in shape, although linear shaped supports 1102, 1104 may also be used.

In some embodiments, the internal electrode may be the anode layer 1008 in TFC 1100, 1120, 1140. The supports 1102, 1104, 1106, 1108 may be comprised of the same material as the inner anode layer or not comprised of the anode layer 1008 or a combination thereof.

Methods are discussed herein that include placing a fluid mixture between two Tubular Fuel Cells (TFCs), wherein the two TFCs have a gap with a minimum distance of no greater than 1 mm; heating the fluid mixture to thereby connect the two TFCs; wherein the fluid mixture has a viscosity of no greater than 1000 centipoise. In one embodiment, the viscosity of the fluid mixture is no greater than 500 centipoise, alternatively no greater than 300 centipoise, alternatively no greater than 200 centipoise, alternatively no greater than 100 centipoise, alternatively no greater than 50 centipoise. In one embodiment, the minimum distance of the gap is no greater than 500 microns, alternatively no greater than 300 microns, alternatively no greater than 200 microns, alternatively no greater than 100 microns, alternatively no greater than 50 microns.

In one embodiment, disposing the fluid mixture includes aerosol jetting, material jetting, inkjet printing, or a combination thereof. In one embodiment, the fluid mixture comprises a fluid and a solid, and wherein heating the fluid mixture causes the fluid to escape and the solid to remain. In one embodiment, heating the fluid mixture causes it to cure. In one embodiment, the heating includes the use of electromagnetic radiation (EMR). In one embodiment, the EMR includes UV light, near ultraviolet light, near infrared light, visible light, laser, electron beam, microwave, or combinations thereof. In one embodiment, the heating comprises oven heating, furnace heating, kiln heating, plasma heating, hot surface heating, or a combination thereof. In one embodiment, the heating is accomplished by conduction, convection, radiation, or a combination thereof. In one embodiment, the heating results in sintering, co-sintering, annealing, densification, curing, evaporation, drying, or a combination thereof.

In one embodiment, the fluid mixture comprises gold, silver, platinum, nickel, iron, steel, stainless steel, chromium, cobalt, carbon, or inconel (inconel). In one embodiment, the fluid mixture comprises a material for an electrode in a fuel cell or a material for an interconnect in a fuel cell, or both.

In one embodiment, each TFC comprises an inner cathode, an outer anode, an electrolyte disposed between the anode and the cathode, and an interconnect, wherein a cross-section of the cathode is a rounded non-circular shape without sharp corners, wherein the cross-section is perpendicular to a longitudinal axis of the TFC, wherein the interconnect is in contact with the cathode but not in contact with the anode, and the interconnect has a contact surface configured to contact the anode of an adjacent TFC, wherein the anode has a contact surface and a non-contact surface configured to contact the interconnect of another adjacent TFC.

In one embodiment, each TFC comprises an inner anode, an outer cathode, an electrolyte disposed between the anode and the cathode, and an interconnect, wherein a cross-section of the anode is a rounded non-circular shape without sharp corners, wherein the cross-section is perpendicular to a longitudinal axis of the TFC, wherein the interconnect is in contact with the anode but not in contact with the cathode, and the interconnect has a contact surface configured to contact the cathode of an adjacent TFC, wherein the cathode has a contact surface and a non-contact surface configured to contact the interconnect of another adjacent TFC.

Also discussed herein are methods comprising applying a contact paste (contact paste) to a first Tubular Fuel Cell (TFC) and contacting a second TFC with the contact paste on an opposite side of the first TFC, wherein each of the first TFC and the second TFC comprises an inner cathode, an outer anode, an electrolyte disposed between the anode and the cathode, and an interconnect, wherein a cross-section of the cathode is a rounded non-circular shape without sharp corners, wherein the cross-section is perpendicular to a longitudinal axis of the TFC, wherein the interconnect is in contact with the cathode but not in contact with the anode, and the interconnect has a contact surface configured to contact the anode of an adjacent TFC, wherein the anode has a contact surface and a non-contact surface configured to contact the interconnect of another adjacent TFC.

In one embodiment, the contact paste is applied by immersion, coating, painting, spraying, spray pyrolysis or brushing or a combination thereof. In one embodiment, the contact paste comprises gold, silver, platinum, nickel, iron, steel, stainless steel, chromium, cobalt, carbon, or inconel or combinations thereof. In one embodiment, the contact paste comprises a material for an electrode in a fuel cell or a material for an interconnect in a fuel cell, or both. In one embodiment, the TFC comprises a blocking layer that is positioned between the cathode and the electrolyte or between the anode and the electrolyte or both.

In one embodiment, the rounded non-circular shape comprises a rounded rectangle, a rounded square, a rounded hexagon, a rounded trapezoid, a rounded parallelogram, a rounded pentagon, a rounded triangle, a rounded octagon, an ellipse, an ellipsoid, or a rounded irregular shape. In one embodiment, the ratio of the area of the contact surface of the interconnect to the area of the non-contact surface of the anode is no greater than 1, alternatively no greater than 0.75, alternatively no greater than 0.5. In one embodiment, the ratio of the area of the contact surface of the interconnect to the area of the non-contact surface of the anode is no greater than 0.3, alternatively no greater than 0.1, alternatively no greater than 0.05. In one embodiment, the TFC has a length L and wherein the cross-section has a characteristic length W, wherein the ratio of L/W is not less than 1, or not less than 2, or not less than 10, or not less than 100.

In one embodiment, the TFC comprises a support located in the cathode. In one embodiment, the support is in contact with the cathode. In one embodiment, the support is an integral part of the cathode. In one embodiment, the support and the cathode are made of the same material.

In one embodiment, the method includes heating the contact paste. In one embodiment, the heating includes the use of electromagnetic radiation (EMR). In one embodiment, the EMR includes UV light, near ultraviolet light, near infrared light, visible light, laser, electron beam, or combinations thereof. In one embodiment, the heating comprises oven heating, furnace heating, kiln heating, plasma heating, hot surface heating, or a combination thereof. In one embodiment, the heating is accomplished by conduction, convection, radiation, or a combination thereof. In one embodiment, the heating results in sintering, co-sintering, annealing, densification, curing, evaporation, drying, or a combination thereof.

Further discussed herein are methods comprising applying a contact paste to a first Tubular Fuel Cell (TFC) and contacting a second TFC with the contact paste on an opposite side of the first TFC, wherein each of the first TFC and the second TFC comprises an inner anode, an outer cathode, an electrolyte disposed between the anode and the cathode, and an interconnect, wherein a cross-section of the anode is a rounded non-circular shape without sharp corners, wherein the cross-section is perpendicular to a longitudinal axis of the TFC, wherein the interconnect is in contact with the anode but not in contact with the cathode, and the interconnect has a contact surface configured to contact the cathode of an adjacent TFC, wherein the cathode has a contact surface and a non-contact surface configured to contact the interconnect of another adjacent TFC.

In one embodiment, the contact paste is applied by immersion, coating, painting, spraying, brushing, or a combination thereof. In one embodiment, the contact paste comprises gold, silver, platinum, nickel, iron, steel, stainless steel, chromium, cobalt, carbon, or inconel or combinations thereof. In one embodiment, the contact paste comprises a material for an electrode in a fuel cell or a material for an interconnect in a fuel cell, or both. In one embodiment, the TFC comprises a blocking layer that is positioned between the cathode and the electrolyte or between the anode and the electrolyte or both. In one embodiment, the ratio of the area of the contact surface of the interconnect to the area of the non-contact surface of the anode is no greater than 1, or no greater than 0.75, or no greater than 0.5, or no greater than 0.3, or no greater than 0.1, or no greater than 0.05. In one embodiment, the TFC has a length L and wherein the cross-section has a characteristic length W, wherein the ratio of L/W is not less than 1, or not less than 2, or not less than 10, or not less than 100.

In one embodiment, the TFC comprises a support located in the anode. In one embodiment, the support is in contact with the anode. In one embodiment, the support is an integral part of the anode. In one embodiment, the support and the anode are made of the same material.

In one embodiment, the method includes heating the contact paste. In one embodiment, the heating includes the use of electromagnetic radiation (EMR). In one embodiment, the EMR includes UV light, near ultraviolet light, near infrared light, visible light, laser, electron beam, microwave. In one embodiment, the heating comprises oven heating, furnace heating, kiln heating, plasma heating, hot surface heating, or a combination thereof. In one embodiment, the heating is accomplished by conduction, convection, radiation, or a combination thereof. In one embodiment, the heating results in sintering, co-sintering, annealing, densification, curing, evaporation, drying, or a combination thereof.

Integrated heat exchanger

Disclosed herein is an Electrochemical (EC) reactor, such as an EC gas generator or a Solid Oxide Reactor (SOR), comprising a first electrode, a second electrode, an electrolyte positioned between the first and second electrodes, and a first heat exchanger, wherein the first heat exchanger is in fluid communication with the first electrode. The minimum distance between the first electrode and the first heat exchanger is no greater than 10 cm. In some embodiments, the minimum distance is no greater than 5 cm. In other embodiments, the minimum distance is no greater than 1 cm. In other embodiments, the minimum distance is no greater than 5 mm. In other embodiments, the minimum distance is no greater than 1 mm. In one embodiment, the EC reactor comprises a second heat exchanger, wherein the second heat exchanger is in fluid communication with the second electrode. The minimum distance between the second electrode and the second heat exchanger is no greater than 10 cm. In some embodiments, the minimum distance is no greater than 5 cm. In other embodiments, the minimum distance is no greater than 1 cm. In other embodiments, the minimum distance is no greater than 5 mm. In other embodiments, the minimum distance is no greater than 1 mm.

In one embodiment, the first heat exchanger is adjacent to the first electrode, or alternatively, wherein the second heat exchanger is side-by-side or adjacent to the second electrode. One or more heat exchangers may be placed side-by-side with components in the EC reactor, or above or below components (i.e., electrodes) of the EC reactor. Fig. 9B is an illustrative example where the integrated multi-fluid heat exchanger containing 916 and 918 is located at the bottom of a repeating unit/stack in a fuel cell separated from the anode 910 only by the interconnect layer 920. In this case, the minimum distance between the heat exchanger and the repeating unit/stack is simply the thickness of the interconnect, which is 1 mm or less, 0.5 mm or less, 200 microns or less, or in the range of about 100 nm to about 100 microns. In some embodiments, the first heat exchanger and the second heat exchanger are the same heat exchanger, wherein the heat exchangers form a multifluid heat exchanger. The EC reactor may comprise a solid oxide fuel cell, a solid oxide flow battery, an electrochemical gas generator, or an electrochemical compressor. The EC reactor may comprise a reformer upstream of the first electrode or in contact with the first electrode or in the first heat exchanger. The EC reactor may include two or more repeating units separated by an interconnect, where each repeating unit comprises a first electrode, a second electrode, and an electrolyte. Each repeating unit may include at least one heat exchanger adjacent to the repeating unit.

Also disclosed herein are EC reactors, such as Solid Oxide Reactors (SOR), comprising a stack of cells and a heat exchanger. The stack has a stack height and comprises a plurality of repeating units separated by interconnects, wherein each repeating unit comprises a first electrode, a second electrode, and an electrolyte between the first and second electrodes. The heat exchanger is in fluid communication with the stack, and wherein the minimum distance between the stack and the heat exchanger is no greater than 2 times the height of the stack, or no greater than half the height of the stack. The heat exchanger may be adjacent to the cell stack. The heat exchanger comprises at least 3 fluid inlets and at least 3 fluid channels, wherein each of the at least 3 fluid channels has a smallest dimension of no greater than 30 mm. The stack or heat exchanger may also contain a reformer. The reformer may be constructed as a cell stack or a heat exchanger. In one embodiment, the interconnect does not contain a fluid dispersion element, and the electrode contains a fluid dispersion member or a fluid channel.

In one embodiment, the EC reactor is in the form of a cassette (as shown in fig. 9A-9D). The cartridge may comprise a fuel inlet on a fuel side of the cartridge, an oxidant inlet on an oxidant side of the cartridge, at least one fluid outlet, wherein the fuel inlet has a width W _fThe fuel side of the cartridge having a length L_fThe oxidant inlet having a width W_oThe oxidant side of the cartridge having a length L_oWherein W is_f/L_fIn the range of 0.1 to 1.0, 0.1 to 0.9, 0.2 to 0.9, 0.5 to 0.9 or 0.5 to 1.0, and W_o/L_oIn the range of 0.1 to 1.0, 0.1 to 0.9, 0.2 to 0.9, 0.5 to 0.9 or 0.5 to 1.0. In some embodiments, the inlet and outlet are located on one surface of the cartridge, wherein the cartridge does not contain a protruding flow channel located on the surface. The cartridge may be removably secured to the mating surface and not welded or soldered to the mating surface. The cassette may be bolted or pressed to the mating surface. The mating surfaces may include a mating fuel inlet, a mating oxidant inlet, and at least one mating fluid outlet.

Also disclosed herein are EC reactor cartridges, such as Solid Oxide Reactor Cartridges (SORCs), comprising a first electrode, a second electrode, an electrolyte positioned between the first and second electrodes, and a heat exchanger, wherein the heat exchanger is in fluid communication with the first electrode or the second electrode or both. The minimum distance between the heat exchanger and the first or second electrode is no greater than 10 cm, alternatively no greater than 5 cm, alternatively no greater than 1 cm, alternatively no greater than 5 mm, alternatively no greater than 1 mm.

In one embodiment, the EC reactor cartridge comprises a reformer upstream of the first electrode or in contact with the first electrode or in a heat exchanger. The EC reactor cartridge may comprise a fuel inlet on a fuel side of the cartridge, an oxidant inlet on an oxidant side of the cartridge, at least one fluid outlet, wherein the fuel inlet has a width W_fThe fuel side of the cartridge having a length L_fThe oxidant inlet having a width W_oThe oxidant side of the cartridge having a length L_o。W_f/L_fThe ratio of (A) is in the following range: 0.1 to 1.0, 0.1 to 0.9, 0.2 to 0.9, 0.5 to 0.9 or 0.5 to 1.0, and W_o/L_oThe ratio of (A) is in the following range: 0.1 to 1.0, 0.1 to 0.9, 0.2 to 0.9, 0.5 to 0.9 or 0.5 to 1.0. The inlet and outlet may be located on one surface of the cartridge, and wherein the cartridge does not contain a protruding flow channel located on the surface. The EC reactor cartridge may be removably secured to the mating surface and not welded or soldered to the mating surface.

Methods of forming an EC reactor, such as a Solid Oxide Reactor (SOR), are discussed herein that include forming a first electrode in a device, forming an electrolyte in the same device, forming a second electrode in the same device, and forming a heat exchanger in the same device, wherein the electrolyte is between and in contact with the first electrode and the second electrode. The heat exchanger may be in fluid communication with the first electrode or the second electrode or both. The forming method may include one or more of material jetting, binder jetting, ink jet printing, aerosol jetting, aerosol printing, slot photo polymerization, powder layer fusing, material extrusion, directed energy deposition, sheet lamination, ultrasonic ink jet printing, direct (dry) powder deposition, or combinations thereof. Preferably, the forming is effected by ink jet printing.

In one embodiment, the method of forming an EC reactor further comprises heating the EC reactor. The heating may be performed in situ. Heating may be performed using electromagnetic radiation (EMR). The method of forming an EC reactor can further include forming a plurality of repeating units and an interconnect between the repeating units, wherein the repeating units comprise a first electrode, an electrolyte, and a second electrode. In one embodiment, the formation of the repeating units and the interconnects occurs in the same device. In a preferred embodiment, the method comprises heating the repeating cells and interconnects in situ using EMR. In a preferred embodiment, the method further comprises forming a reformer. The reformer may be formed in the same apparatus.

In one embodiment, the interconnect in the EC reactor does not include a fluid dispersing element. In one embodiment, a method of forming an EC reactor includes forming a first template while forming a first electrode, wherein the first template is in contact with the first electrode; at least a portion of the first template is removed to form a channel in the first electrode. The method further includes forming a second template while forming a second electrode, wherein the second template is in contact with the second electrode; at least a portion of the second template is removed to form a channel in the second electrode. In one embodiment, the first electrode comprises a fluid dispersion assembly (FDC) or fluid channel; wherein the second electrode comprises a fluid dispersion assembly (FDC) or a fluid channel.

In one embodiment, an EC reactor, such as an SOR, is formed into a cassette. The cartridge comprises a fuel inlet on a fuel side of the cartridge, an oxidant inlet on an oxidant side of the cartridge, at least one fluid outlet, wherein the fuel inlet has a width W_fThe fuel side of the cartridge having a length L_fThe oxidant inlet having a width W_oAnd the oxidant side of the cartridge has a length L_o。W_f/L_fThe ratio of (d) may be in the following range: 0.1 to 1.0, 0.1 to 0.9, 0.2 to 0.9, 0.5 to 0.9 or 0.5 to 1.0, and W_o/L_oThe ratio of (A) is in the following range: 0.1 to 1.0, 0.1 to 0.9, 0.2 to 0.9, 0.5 to 0.9 or 0.5 to 1.0. In one embodiment, the inlet and outlet are located on one surface of the cartridge, and the cartridge does not contain a protruding flow channel located on the surface. In one embodiment, the cassette is removably secured to the mating surface and is not welded or solderedTo the mating surface. The cassette may be bolted or pressed to the mating surface. In one embodiment, the method comprises forming a reformer upstream of the first electrode, or a reformer in contact with the first electrode, or a reformer in a heat exchanger. The reformer may be formed in the same apparatus.

Also disclosed herein are methods comprising forming an EC reactor stack and a heat exchanger, wherein the reactor stack having a reactor stack height comprises a plurality of repeating units separated by interconnects, wherein each repeating unit comprises a first electrode, a second electrode, and an electrolyte located between the first and second electrodes. The heat exchanger may be in fluid communication with the stack, and wherein the minimum distance between the stack and the heat exchanger is no greater than 2 times the stack height, or no greater than half the stack height.

In one embodiment, the EC reactor stack is formed in the same apparatus, such as an SOR and a heat exchanger. The method may include forming the stack and the heat exchanger into a cassette. The cartridge may be removably secured to the mating surface and not welded or soldered to the mating surface.

Further discussed herein are methods that include forming an EC reactor, such as an SOR, that includes a first electrode, a second electrode, an electrolyte positioned between the first and second electrodes, and a heat exchanger. The heat exchanger may be in fluid communication with the first electrode or the second electrode or both. The minimum distance between the heat exchanger and the first electrode or the second electrode is no greater than 10 cm, no greater than 5 cm, no greater than 1 cm, no greater than 5 mm, or no greater than 1 mm. In some cases, the electrodes, electrolyte, and heat exchanger are formed in the same device. In some cases, the method further comprises forming the EC reactor into a cartridge. The cartridge may be removably secured to the mating surface and not welded or soldered to the mating surface.

Disclosed herein are methods including forming an EC reactor cartridge comprising forming a first electrode, forming a second electrode, forming an electrolyte between the first and second electrodes, and forming a heat exchanger. In one embodiment, the heat exchanger is in fluid communication with the first electrode or the second electrode or both. In one embodiment, the electrodes, electrolyte and heat exchanger are formed in the same device. In one embodiment, the method comprises forming a reformer upstream of the first electrode, or a reformer in contact with the first electrode, or a reformer in a heat exchanger. In one embodiment, the reformer is formed in the same apparatus.

Fischer-tropsch

The methods and systems of the present disclosure are suitable for preparing a catalyst or catalyst composite, such as a fischer-tropsch (FT) catalyst or catalyst composite. Disclosed herein are fischer-tropsch (FT) catalyst composites comprising a catalyst and a substrate, wherein the mass ratio between the catalyst and the substrate is not less than 1/100, or not less than 1/10, or not less than 1/5, or not less than 1/3, or not less than 1/1. In one embodiment, the catalyst comprises Fe, Co, Ni, or Ru. The substrate comprises Al₂O₃、ZrO₂、SiO₂、TiO₂、CeO₂Modified Al₂O₃Modified ZrO₂Modified SiO₂Modified TiO₂Modified CeO₂Gadolinium, steel, cordierite (2 MgO-2 Al)₂O₃-5SiO₂) Aluminum titanate (Al)₂TiO₅) Silicon carbide (SiC), all phases of alumina, yttria-or scandia-stabilized zirconia (YSZ), gadolinia or samaria-doped ceria, or combinations thereof. In one embodiment, the catalyst composite comprises a promoter, wherein the promoter comprises a noble metal, a metal cation, or a combination thereof. The promoter may comprise B, La, Zr, K, Cu, or combinations thereof. In one embodiment, the catalyst composite comprises a fluid channel or, alternatively, a fluid dispersion member.

The FT reactor/system of the present disclosure is much smaller (e.g., 3-100 times smaller or 100+ times smaller for the same FT product production rate) than conventional FT reactors/systems. High catalyst to substrate ratios are not achievable by conventional methods of preparing FT catalysts. As such, in some embodiments, the FT reactor/system is miniaturized compared to conventional FT reactors/systems.

Also discussed herein are methods comprising depositing FT catalyst to a substrate to form a FT catalyst composite, wherein the depositing comprises material jetting, binder jetting, ink jet printing, aerosol jetting or aerosol jet printing, slot photo polymerization, powder layer fusing, material extrusion, directed energy deposition, sheet lamination, ultrasonic ink jet printing, or combinations thereof. In one embodiment, the mass ratio between the catalyst and the substrate is not less than 1/100, or not less than 1/10, or not less than 1/5, or not less than 1/3, or not less than 1/1. In a preferred embodiment, the deposition process comprises forming fluid channels in the catalyst composite or, alternatively, fluid dispersion members.

Also discussed herein are systems comprising a fischer-tropsch (FT) reactor containing a FT catalyst composite comprising a catalyst and a substrate, wherein the mass ratio between the catalyst and the substrate is not less than 1/100, or not less than 1/10, or not less than 1/5, or not less than 1/3, or not less than 1/1. In one embodiment, the catalyst comprises Fe, Co, Ni, or Ru. In one embodiment, the substrate comprises Al ₂O₃、ZrO₂、SiO₂、TiO₂、CeO₂Modified Al₂O₃Modified ZrO₂Modified SiO₂Modified TiO₂Modified CeO₂Gadolinium, steel, cordierite (2 MgO-2 Al)₂O₃-5SiO₂) Aluminum titanate (Al)₂TiO₅) Silicon carbide (SiC), all phases of alumina, yttria-or scandia-stabilized zirconia (YSZ), gadolinia or samaria-doped ceria, or combinations thereof. In one embodiment, the catalyst composite comprises a promoter.

For example, the FT catalyst composite is formed by printing. The catalyst and substrate/support are prepared in the form of an ink comprising a solvent and particles (e.g., nanoparticles). The ink optionally comprises a dispersant, binder, plasticizer, surfactant, co-solvent, or a combination thereof. The ink may be any kind of suspension. The ink may be treated with mixing methods such as sonication or high shear mixing. In some cases, the iron ink is in an aqueous environment. In some cases, the iron ink is in an organic environment. The iron ink may also include an accelerator. The substrate/support may be a suspension or ink of alumina in an aqueous environment or an organic environment. The base ink may be treated with a mixing process, such as ultrasonic or high shear mixing. In some cases, the base ink includes an accelerator. In some cases, the accelerator is added as its own ink in an aqueous environment or an organic environment. In some cases, multiple inks are printed separately and sequentially. In some cases, for example, multiple inks are printed separately and simultaneously by different print heads. In some cases, multiple inks are printed in combination as a mixture.

For example, the exhaust gas from a fuel cell comprises hydrogen, carbon dioxide, water and optionally carbon monoxide. The exhaust gas is passed through an FT catalyst (e.g., an iron catalyst) to produce a synthetic fuel or lubricant. The FT iron catalyst has the property of promoting the water gas shift reaction or the reverse water gas shift reaction. The FT reaction occurs at a temperature in the range of 150-350 ℃ and a pressure in the range of one to several tens of atmospheres (e.g., 15 atm, or 10 atm, or 5 atm, or 1 atm). Additional hydrogen may be added to the waste stream to achieve a hydrogen to carbon oxide (carbon dioxide and carbon monoxide) ratio of no less than 2, or no less than 3, or between 2 and 3.

Fluid dispersion assembly

Fig. 12A shows an impermeable interconnect 1202 with a fluid dispersion assembly 1204, according to an embodiment of the disclosure. Fig. 12B shows an impermeable interconnect 1202 with two fluid dispersion assemblies 1204, according to an embodiment of the disclosure. The fluid dispersion assembly 1204 is in contact with both sides (major faces) of the interconnect 1202. As such, the interconnect is shared between two repeating units in an electrochemical reactor, such as an EC gas generator. The fluid distribution assembly 1204 is used to distribute a fluid, such as a reactive gas (e.g., methane, hydrogen, carbon monoxide, air, oxygen, etc.) within the electrochemical reactor. As such, conventional interconnects with channels are no longer required. The design and production of these conventional interconnects with channels is complex and expensive. According to the present disclosure, the interconnect is simply an impermeable layer that conducts or collects electrons, without a fluid dispersion element.

Fig. 12C-F schematically illustrate a segmented fluid dispersion assembly 1204 on top of an impermeable interconnect 1202, according to embodiments of the present disclosure. The segments may have different compositions, shapes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof. The segments may be discontinuous. Fig. 13C shows segmented fluid dispersion assemblies 1204 of similar shape but different sizes on impermeable interconnects 1202. Fig. 13D shows a segmented fluid dispersion assembly 1204 of similar shape and similar size on an impermeable interconnect 1202, according to embodiments of the present disclosure. Fig. 12E shows a segmented fluid dispersion assembly 1204 of similar shape and similar size but closely packed on an impermeable interconnect 1202, according to embodiments of the present disclosure. Fig. 12F shows segmented fluid dispersion assemblies 1204 having different shapes and different sizes on impermeable interconnects 1202, according to embodiments of the present disclosure. It is also contemplated that the segments have different compositions, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof.

Fig. 12G-I schematically illustrate an impermeable interconnect 1202 having a fluid dispersion assembly 1204, in accordance with embodiments of the present disclosure. Different fluid inlet and outlet designs are also shown. The fluid dispersion member may have different densities, porosities, pore sizes, pore shapes, compositions, or permeabilities, or combinations thereof, in different portions (e.g., in the transverse direction or a direction perpendicular to the transverse direction). These degrees of differentiation provide control and adjustability of fluid flow in the fluid dispersion assembly. Fig. 12G shows an impermeable interconnect 1202 and a fluid dispersion assembly 1204, according to embodiments of the disclosure. Fig. 12H shows an impermeable interconnect 1202 and a fluid dispersion assembly 1204, according to embodiments of the disclosure. Fig. 12I shows an impermeable interconnect 1202 and a fluid dispersion assembly 1204, according to embodiments of the present disclosure. 1206 and 1208 in FIGS. 12G-I represent different inlet and outlet designs according to embodiments of the present disclosure. For each configuration, the interconnect 1202 has matching inlets and outlets. In fig. 12I, 1206 represents a fluid inlet and 1208 represents a fluid outlet. Fluid flow is indicated by arrows 1210. Fig. 12J shows an impermeable interconnect 1202 and a fluid dispersion assembly 1204, according to embodiments of the present disclosure. An alternative fluid flow design is further shown in fig. 12J, as indicated by the arrows. For example, fluid may flow through the fluid dispersion assembly from left to right; or the fluid may flow through the fluid dispersion assembly from front to back.

Fig. 12K shows a fluid dispersion assembly 1204, according to an embodiment of the disclosure. The fluid dispersion assembly 1204 design includes 4 corners labeled A, B, C and D. Position a includes a fluid flow inlet 1212. Position B includes a fluid flow outlet 1214.

An electrochemical reactor (e.g., a fuel cell) is discussed herein that includes an impermeable interconnect without a fluid dispersion element, an electrolyte, and a fluid dispersion assembly (FDC) between the interconnect and the electrolyte. In one embodiment, the fuel cell comprises two FDCs. Two FDCs may be placed symmetrically to contact interconnects on opposite sides or major faces thereof. As such, the interconnect shares two repeating units in the electrochemical reactor, each repeating unit comprising one of the two FDCs. FDCs may be foams, open foams, or contain lattice structures.

In preferred embodiments, the FDC is segmented, wherein the segments have different compositions, materials, shapes, sizes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof. The shape of the segments may include a cylinder, a hollow cylinder, a cube, a rectangular cuboid, a trigonal rhombohedral, a quadrangular frustum, a parallelepiped, a double triangular pyramid, a quadrangular inverse wedge (tetragonal anti-wedge), a pyramid, a pentagonal pyramid, a prism, or a combination thereof.

In some embodiments, the FDCs have different densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof, wherein the density, porosity, pore size, pore shape, or permeability, or combinations thereof, are controlled. In some embodiments, the density, porosity, pore size, pore shape, or permeability, or a combination thereof, is controlled to regulate fluid flow through the FDC. In other embodiments, the density, porosity, pore size, pore shape, or permeability, or a combination thereof, is controlled to result in uniform fluid flow from a first point in the FDC to a second point in the FDC. The fluid flow pattern can be adjusted as desired. For example, it need not be uniform. The fluid flow may be increased or decreased depending on the reactivity of the FDC or the rate of reaction of the fluid in various portions of the FDC. Alternatively and/or in combination, the fluid flow may be increased or decreased depending on the fluid flow rate of the anode or cathode in the various sections of the FDC. Alternatively and/or in combination, the fluid flow may be increased or decreased depending on the reaction rate in the anode or cathode associated with or in contact with the various portions of the FDC.

In one embodiment, the density of FDC centers is higher. In one embodiment, the density of FDC centers is lower. In one embodiment, the porosity or permeability or pore throat size (pore throat size) is smaller towards the center of the FDC. In one embodiment, the porosity or permeability or pore throat size is larger towards the center of the FDC.

In one embodiment, at least a portion of the FDC is part of the anode or part of the cathode. In a preferred embodiment, the FDC is an anode or a cathode. In one embodiment, the impermeable interconnect has a thickness of no greater than 10 microns, or no greater than 1 micron, or no greater than 500 nm. In a preferred embodiment, the impermeable interconnect comprises an inlet and an outlet for fluid. In a preferred embodiment, the fluid comprises a reactant of the fuel cell.

Also disclosed herein are methods of making a fuel cell comprising (a) forming an impermeable interconnect without a fluid dispersion element; (b) forming an electrolyte; (c) forming a fluid dispersion assembly (FDC); and (d) placing FDC between the interconnect and the electrolyte.

In one embodiment, the FDC is formed by creating a plurality of segments and assembling the segments. The segments have different compositions, materials, shapes, sizes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof, wherein the shapes include columns, hollow cylinders, cubes, rectangular cuboids, trigonal rhombohedrons, quadrilateral frustums, parallelepipeds, double triangular pyramids, quadrilateral inverse wedges (quadrangular cones), pyramids, pentagonal pyramids, prisms, or combinations thereof. FDC may be foam, open cell foam; or comprise a lattice structure.

In preferred embodiments, the method of forming the FDC comprises varying the density, porosity, pore size, pore shape, permeability, or combinations thereof. In one embodiment, the method comprises controlling the density, porosity, pore size, pore shape, permeability, or a combination thereof, of the FDC. The method may include controlling the density, porosity, pore size, pore shape, or permeability of the FDC, or a combination thereof, to regulate the flow of fluid through the FDC. The method may include controlling a density, porosity, pore size, pore shape, permeability, or a combination thereof of the FDC to cause uniform fluid flow from a first point in the FDC to a second point in the FDC. The method may include controlling a density, porosity, pore size, pore shape, permeability, or a combination thereof of the FDC to cause a patterned fluid flow from a first point in the FDC to a second point in the FDC.

The fluid flow pattern can be adjusted as desired. For example, it need not be uniform. The fluid flow may be increased or decreased depending on the reactivity of the FDC or the rate of reaction of the fluid in various portions of the FDC. Alternatively and/or in combination, the fluid flow may be increased or decreased depending on the fluid flow rate of the anode or cathode in the various sections of the FDC. Alternatively and/or in combination, the fluid flow may be increased or decreased depending on the reaction rate in the anode or cathode associated with or in contact with the various portions of the FDC.

In one embodiment, step (c) comprises altering the composition of the material used to form the FDC. In one embodiment, step (c) comprises varying the particle size used to form the FDC. In one embodiment, step (c) comprises heating different portions of the FDC to different temperatures. In one embodiment, the heating comprises electromagnetic radiation (EMR). In one embodiment, the EMR includes one or more of UV light, near ultraviolet light, near infrared light, visible light, laser light, or electron beams.

In one embodiment, steps (a) - (d) or steps (b) - (d) are performed using Additive Manufacturing (AM). In various embodiments, AM comprises extrusion, photopolymerization, powder layer fusion, material jetting, binder jetting, directed energy deposition, or lamination, or combinations thereof.

In one embodiment, a method of forming the FDC includes heating the fuel cell such that the shrinkage of the FDC and the electrolyte, or the shrinkage of the interconnect, the FDC, and the electrolyte, match. In a preferred embodiment, the heating comprises EMR. In one embodiment, the EMR includes UV light, near ultraviolet light, near infrared light, visible light, laser, or electron beam, or a combination thereof. In a preferred embodiment, the heating is performed in situ. In preferred embodiments, the heating is performed for no more than 30 minutes, alternatively no more than 30 seconds, alternatively no more than 30 milliseconds.

In a preferred embodiment, at least a portion of the FDC is part of the anode or part of the cathode. In a preferred embodiment, the FDC is an anode or a cathode. In a preferred embodiment, the impermeable interconnect has a thickness of no greater than 10 microns, or no greater than 1 micron, or no greater than 500 nm. Preferably, the impermeable interconnect comprises an inlet and an outlet for fluid. More preferably, the fluid comprises a reactant of the fuel cell.

Channelized electrode (channeled electrode)

Disclosed herein are methods comprising providing a template, wherein the template is in contact with an electrode material; and removing at least a portion of the template to form channels in the electrode material, such as in an EC gas generator. Fig. 13A shows a template 1300 for making a channeled electrode, according to an embodiment of the present disclosure. These templates may be removed by oxidation, melting, evaporation, reduction or any suitable method after the electrochemical reactor is prepared or at the beginning of the utilization of the reactor.

In one embodiment, the channeled electrode material comprises NiO, YSZ, GDC, LSM, LSCF, or combinations thereof. The channeled electrode material can include any of the materials previously used herein for the cathode or anode. In one embodiment, providing the template includes printing the template or a precursor assembled to form the template. Providing the template includes polymerizing one or more monomers or photoinitiators or both. In one embodiment, the method comprises curing the monomers and/or oligomers by internal or external techniques. In various embodiments, the internal techniques include polymerization initiated by free radical molecules and/or initiated by in situ reduction/oxidation. In various embodiments, the external techniques include photolysis, exposure to ionizing radiation, (ultra) sonication, and thermal decomposition to form the initiator species. In a preferred embodiment, the curing comprises UV curing. In one embodiment, the method includes adding a polymerization agent, wherein the polymerization agent includes a photoinitiator. In one embodiment, the polymerization agent is printed on top of the monomer or within each monomer sheet.

In one embodiment, providing the stencil includes dispersing the metal oxide particles in a monomer ink prior to printing the stencil. In one embodiment, the metal oxide comprises NiO, CuO, LSM (strontium lanthanum manganite), LSCF (strontium lanthanum cobalt ferrite), GDC (gadolinium doped ceria), SDC (samarium oxide doped ceria), or combinations thereof. In one embodiment, the monomer includes alcohol, aldehyde, carboxylic acid, ester, and/or ether functional groups. In one embodiment, the template comprises NiO, Cu (I) O, Cu (II) O, an organic compound, a photopolymer, or a combination thereof.

In one embodiment, removing at least a portion of the template comprises heating, combustion, solvent treatment, oxidation, reduction, or a combination thereof. In one embodiment, the combustion leaves no deposits and is not explosive. In one embodiment, the reduction is carried out in a metal oxide and a porous template is created. In one embodiment, the method of providing a template comprises in situ heating.

In one embodiment, the stencil and electrode material are printed piece by piece and a second sheet is printed on top of the first sheet before heating the first sheet, wherein the heating removes at least a portion of the stencil. In one embodiment, the heating comprises EMR. In one embodiment, the EMR includes one or more of UV light, near ultraviolet light, near infrared light, visible light, laser light, electron beams.

In one embodiment, the channels and the electrode material form an electrode layer. In one embodiment, the channels have regular traces within the electrode layer. For example, the channels are parallel to each other. The channels may lead from one end, edge or corner of the electrode layer to the opposite end, edge or corner. The channel may be turned 90 degrees from one end, side or corner of the electrode to the other. The channels have random traces within the electrode layers. For example, the channels may have irregular meandering traces. A channel may have more than one entry point and more than one exit point. More than one entry point and more than one exit point are distributed across the electrode layer. The entry and exit points of the channels in the electrode layer may be located on either side of the electrode layer, including the upper surface or side and the lower surface or side.

In some embodiments, the volume fraction of template in the electrode layer is in the following range: 5% -95%, or 10% -90%, or 20% -80%, or 30% -70%, or 40% -60%. The volume fraction of channels in the electrode layer is in the following range: 10% -90%, or 20% -80%, or 30% -70%, or 40% -60%. The total effective porosity of the electrode layer with channels is preferably in the range of 20% -80%, alternatively 30% -70%, alternatively 40% -60%. This total effective porosity of the electrode layer with channels is not less than the porosity of the electrode material. The electrode layer with the channels has a degree of twist that is no greater than the natural degree of twist of the electrode material.

In a preferred embodiment, the gas channels span the height of the electrode layer. The gas channels may occupy a height that is less than the height of the electrode layer. For example, the electrode layer is about 50 microns thick. In one embodiment, the gas channel width is not less than 10 microns. In one embodiment, the gas channel width is not less than 100 microns.

Also discussed herein are methods comprising (a) printing a first template and a first electrode material to form a first electrode layer, wherein the first template is in contact with the first electrode material; (b) printing the electrolyte layer; (c) printing a second template and a second electrode material to form a second electrode layer, wherein the second template is in contact with the second electrode material; and (d) printing the interconnect. In a preferred embodiment, the steps are performed in any order. In a preferred embodiment, the method comprises repeating steps (a) - (d) in any order to form a stack or repeating units of a stack.

In one embodiment, the method includes (e) removing at least a portion of the first template and the second template to form channels in the first and second electrode layers. In one embodiment, the removing comprises heating, combustion, solvent treatment, oxidation, reduction, or a combination thereof. In one embodiment, the removal is performed in situ. The removal may occur after printing the stack or repeating units of the stack. Removal may occur when the stack is caused to operate. In one embodiment, the printing is done on a sheet-by-sheet basis and a second sheet is printed on top of the first sheet before heating the first sheet, wherein the heating removes at least a portion of the stencil. The printing step comprises material jetting, binder jetting, ink jet printing, aerosol jetting, or aerosol jet printing, or a combination thereof.

Further discussed herein are methods comprising (a) printing a first electrode layer; (b) printing the electrolyte layer; (c) printing a second electrode layer; and (d) printing the interconnect. In one embodiment, the printing comprises material jetting, adhesive jetting, ink jet printing, aerosol jetting, or aerosol jet printing. In a preferred embodiment, the steps are performed in any order. In a preferred embodiment, the method comprises repeating steps (a) - (d) in any order to form a stack or repeating units of a stack. Also disclosed herein are methods comprising aerosol jetting or aerosol jet printing an electrode layer, or an electrolyte layer, or an interconnect, or a combination thereof.

Fig. 13B is a cross-sectional view of a half cell positioned between a first interconnect and an electrolyte, according to an embodiment of the disclosure. The stack in fig. 13B includes a bottom/first interconnect 1301, an optional layer 1302 containing a bottom interconnect material and a first electrode material, a first electrode segment 1303, a first fill material 1304 that forms a first template, and an electrolyte 1305.

Fig. 13C is a cross-sectional view of a half cell positioned between a second interconnect and an electrolyte, according to an embodiment of the present disclosure. The half cell includes an electrolyte 1305, a second electrode segment 1306, a filler material 1307 forming a second template, and a top/second interconnect 1308. The views shown in fig. 13B and 13C are perpendicular to each other.

Fig. 13D is a cross-sectional view of a half cell positioned between a first interconnect and an electrolyte, according to an embodiment of the disclosure. The half cell comprises a bottom interconnect 1301, an optional layer 1302 containing a bottom interconnect material and a first electrode material, a first electrode segment 1303, a first filler material 1304 forming a first template, an electrolyte 1305 and an optional protective layer (shield) 1409 of the first filler material when the first electrode is heated and/or sintered.

Fig. 13E is a cross-sectional view of a half cell positioned between a second interconnect and an electrolyte, according to an embodiment of the disclosure. The half cell includes an electrolyte 1305, a second electrode segment 1306, a filler material 1307 that forms a second template, a top interconnect 1308, and an optional protective layer of the second filler material when the top interconnect is heated and/or sintered. The views shown in fig. 13D and 13E are perpendicular to each other.

In some embodiments, there is a layer (not shown) between 1307 and 1308 that contains the top interconnect material and the second electrode material. In some embodiments, 1305 represents an electrolyte with a barrier layer to the first electrode or the second electrode. 1309 represents an optional protective layer for the first filler when the first electrode is heated/sintered. 1310 represents an optional protective layer of a second filler when the top interconnect is heated/sintered. In some cases, the electrolyte 1305 or electrolyte-barrier layer is in continuous contact with the first and second electrodes along its opposing major faces. The shapes of the electrode segments and the filler in these cross-sectional views are merely representative and not exact. They may have any regular or irregular shape. When an electrochemical reactor (e.g., a fuel cell stack or a gas generator) is prepared, for example, by heating in a furnace, the packing and/or template is removed. Or alternatively removed when the electrochemical reactor operation is initiated using the effects of oxidation, melting, evaporation, gasification, reduction, or a combination thereof, via hot gases/fluids passing therethrough. These removed fillers and/or templates become channels in the electrode. In various embodiments, there are multiple rows of channels in the electrode. For the illustrative example, the electrode is 25 microns thick with multiple channels of 20 microns in height. For another illustrative example, the electrode is 50 microns thick with 2 rows of multiple channels, each row having a height of 20 microns. In various embodiments, the filler comprises carbon, graphite, graphene, cellulose, metal oxide, polymethylmethacrylate, nanodiamond, or a combination thereof.

In one embodiment, a cell in an electrochemical reactor comprising an interconnect, a first electrode, an electrolyte, and a second electrode is fabricated by the method: providing an interconnect, depositing segments of a first electrode material on the interconnect, sintering the first electrode material, depositing a first filler material between the segments of the first electrode material, depositing additional first electrode material to cover the filler material, sintering the additional first electrode material and form a first electrode, depositing an electrolyte material on the first electrode, sintering the electrolyte material to form an electrolyte, depositing a second electrode material on the electrolyte to form a plurality of valleys (valley) in the second electrode material, sintering the second electrode material to form a second electrode, depositing a second filler material in the valleys of the second electrode, depositing a second interconnect material to cover the second electrode and the second filler material, and sintering the second interconnect material. In various embodiments, the deposition is performed using ink jet printing or ultrasonic ink jet printing. In various embodiments, the sintering is performed using electromagnetic radiation (EMR). In some cases, the first and second filler materials absorb little EMR; the absorption is too small so that the filler material does not have a measurable change. In some cases, the protective layer is deposited to cover the first filler material or the second filler material or both so that the heating and/or sintering process of the top layer does not cause a measurable change in the first filler material or the second filler material or both. In some cases, protection The layer comprises YSZ, SDC, SSZ, CGO, NiO-YSZ, Cu, CuO, Cu₂O, LSM, LSCF, lanthanum chromite, stainless steel, LSGM, or combinations thereof.

Dual porosity electrode (dual porosity electrode)

Fig. 14A-D show various embodiments of electrodes with dual porosity with 1, 2, or 3 layers shown in detail that can be used in electrochemical reactors, such as EC gas generators. FIG. 14A schematically illustrates a segment of a fluid dispersion member in a first layer, according to an embodiment of the disclosure; first layer 1400 includes fluid dispersion assembly segments 1402. The segments 1402 may have different compositions, shapes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof. The channel volume fraction (VFc) relative to the channel-containing layer 1400 is also shown. Electrodes in an EC reactor comprising materials and channels that form a first layer in the electrode having a first layer porosity are discussed herein. The material has a material porosity. The channel has a volume fraction VFc that is the ratio of the channel volume to the first layer volume. The first layer porosity refers to the average porosity of the first layer as a whole. The first layer has a porosity at least 5% greater than the porosity of the material. VFc was in the following range: 0-99%, or 1-30%, or 10-90%, or 5-50%, or 3-30%, or 1-50%. VFc is not less than 5%, or 10%, or 20%, or 30%, or 40%, or 50%.

Fig. 14B schematically shows a fluid dispersion member in a first layer and a second layer in an electrode, according to an embodiment of the disclosure. The electrode embodiment in fig. 14B shows a first layer 1404 and a second layer 1406 of the fluid dispersion member segment 1405. As shown in fig. 14B, the segments may have different compositions, shapes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof. The electrode includes a second layer, wherein the second layer has a second layer porosity. The second layer porosity refers to the average porosity of the second layer as a whole. In one embodiment, the second layer porosity is not greater than the first layer porosity, or the second layer porosity is not less than the first layer porosity. The second layer 1406 may comprise the same material as in the first layer. The second layer 1406 can also include a change in composition, shape, density, porosity, pore size, pore shape, permeability, or a combination thereof, in the transverse or perpendicular direction.

Fig. 14D schematically illustrates a fluid dispersion assembly in the first layer 1408 and the second layer 1412, according to an embodiment of the disclosure. The electrode embodiment in fig. 14D is similar to the embodiment in fig. 14B. The electrode in fig. 14D includes a first layer 1408 that also includes a fluid dispersion member segment 1410, where the segment 1410 may have different compositions, shapes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof. The second layer 1412 may comprise the same material as in the first layer. The second layer 1412 can also include a change in composition, shape, density, porosity, pore size, pore shape, permeability, or a combination thereof in the transverse or perpendicular direction.

Fig. 14C schematically illustrates a fluid dispersion assembly in the first layer and the second and third layers, according to an embodiment of the disclosure. The electrode embodiment in fig. 14C includes a first layer 1414, a second layer 1416, and a third layer 1418. In one embodiment, the second layer and the third layer are located on both sides of the first layer. In one embodiment, the second layer and the third layer are in continuous contact with both sides of the first layer. The first layer 1414 may include segments 1420 having different compositions, shapes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof. The second layer or the third layer may comprise the same material as the first layer. The second or third layer may also include a change in composition, shape, density, porosity, pore size, pore shape, permeability, or a combination thereof in the transverse or perpendicular direction.

In one embodiment, the material porosity of the first, second or third layer is in the range of 20-60%, in the range of 30-50%, in the range of 30-40% or in the range of 25-35%. In one embodiment, the material porosity is not less than 25%, alternatively 35%, alternatively 45%.

In one embodiment, the thickness of the electrode is no greater than 10 cm, or 5 cm, or 1 cm. In one embodiment, the thickness of the electrode is no greater than 8 mm, or 5 mm, or 1 mm. In one embodiment, the thickness of the electrode is no greater than 100 microns, or 80 microns, or 60 microns.

In one embodiment, the first layer from the channel contributes more to the permeability than the first layer from the material. In one embodiment, no less than 50%, or 70%, or 90% of the permeability of the first layer is due to the permeability of the channel. In one embodiment, the permeability of the material in the first layer is no greater than 50%, alternatively no greater than 10%, alternatively no greater than 1%, alternatively no greater than 0.001% of the permeability of the channels in the first layer.

Disclosed herein is a method of making an electrically conductive assembly (ECC) for an electrochemical reactor (e.g., a fuel cell), comprising: (a) depositing a first composition comprising a first pore-former on a substrate, the first pore-former having a first pore-former volume fraction VFp 1; (b) depositing a second composition comprising a second pore former having a second pore former volume fraction VFp2 on the substrate, wherein the first and second compositions form a first layer in the ECC; and (c) heating the first layer to make the first pore-forming agent and the second pore-forming agent empty spaces. In one embodiment, the VFp1 is in the following range: 0-100%, or 10-90%, or 30-70%, or 50-100%, or 90-100%. In one embodiment, VFp2 is within the following range: 0-100%, alternatively 0-70%, alternatively 25-75%, alternatively 30-60%. In one embodiment, the heating comprises a reduction reaction or an oxidation reaction, or both a reduction and an oxidation reaction.

Fig. 15 is an illustrative example of an electrode having dual porosity in accordance with an embodiment of the disclosure. Fig. 15 shows an EC assembly 1500 comprising a channeled electrode with dual porosity. The apparatus 1500 includes an anode gas inlet 1501, an anode gas outlet 1502, a cathode gas inlet 1503 and a cathode gas outlet 1504. Exploded view 1505 is a view of a portion of a cathode layer. View 1506 is a close-up view of the cathode, where view 1506 represents a slice through the cathode layer consisting of cathode 1507. The cathode 1507 is a porous cathode formed using a microporous pore former. Channels 1508 represent channels formed by the macroporous pore-forming agent.

In one embodiment (a) and (b) are achieved by printing, or by extrusion, or by Additive Manufacturing (AM), or by tape casting, or by spraying, or by deposition, or by sputtering, or by screen printing. In one embodiment, the additive manufacturing comprises extrusion, photo-polymerization, powder layer fusion, material jetting, binder jetting, directed energy deposition, lamination.

In one embodiment, the first pore former and the second pore former are the same. In one embodiment, the first pore former and the second pore former are different. In one embodiment, the first pore former or the second pore former has an average diameter in the range of from 10 nm to 1 mm, alternatively from 100 nm to 100 microns, alternatively from 500 nm to 50 microns. In one embodiment, the first pore former or the second pore former has a particle size distribution. In one embodiment, the first or second pore former comprises carbon, graphite, polymethyl methacrylate (PMMA), cellulose, metal oxides, or combinations thereof.

In one embodiment, the method comprises repeating (a) and (b) to form a second layer in the ECC; and heating the second layer. In one embodiment, heating the second layer is performed simultaneously with heating the first layer. In one embodiment, heating the second layer is performed at a different time than heating the first layer. In one embodiment, heating the second layer and heating the first layer have at least partially overlapping time periods. In one embodiment, the method comprises repeating (a) and (b) to form a third layer in the ECC; and heating the third layer. In one embodiment, the second layer and the third layer are located on both sides of the first layer. In one embodiment, the heating of the first, second and third layers is simultaneous. Alternatively, the first, second and third layers are heated at different times. In one embodiment, the heating of the first, second and third layers has overlapping time periods. In one embodiment, the first, second or third layer is heated more than once.

In one embodiment, at least a portion of the empty spaces created by the second pore former or the first pore former, or both, become channels in the first layer. In one embodiment, the channel has a volume fraction VFc that is the ratio of the channel volume to the first layer volume. In one embodiment, the VFc is within the following range: 0-99%, or 1-30%, or 10-90%, or 5-50%, or 3-30%, or 1-50%. In one embodiment, the VFc is not less than 5%, or 10%, or 20%, or 30%, or 40%, or 50%.

In one embodiment, VFp1 is different from VFp 2. In one embodiment, the first layer has dual porosity, material porosity and layer porosity. In one embodiment, the material porosity is in the following range: 20-60%, or 30-50%, or 30-40%, or 25-35%. In one embodiment, the material porosity is not less than 25%, alternatively 35%, alternatively 45%.

In one embodiment, the thickness of the ECC is no greater than 10 cm, or 5 cm, or 1 cm. In one embodiment, the thickness of the ECC is no greater than 8 mm, or 5 mm, or 1 mm. In one embodiment, the thickness of the ECC is no greater than 100 microns, or 80 microns, or 60 microns.

In one embodiment, after (c) the first layer comprises a channel and a material, wherein the first layer from the channel contributes more to the permeability than the first layer from the material. In one embodiment, no less than 50%, or 70%, or 90% of the permeability of the first layer is due to the permeability of the channel. In one embodiment, the permeability of the material in the first layer is no greater than 50%, alternatively no greater than 10%, alternatively no greater than 1%, alternatively no greater than 0.001% of the permeability of the channels in the first layer.

Methods are discussed herein, comprising: (a) providing a first material to an Additive Manufacturing Machine (AMM); (b) providing a second material to the AMM; (c) mixing a first material and a second material into a mixture; and (d) forming the mixture into a part. In one embodiment, the first material or the second material is a gas, or a liquid, or a solid, or a gel.

In one embodiment, the additive manufacturing comprises extrusion, photo-polymerization, powder layer fusion, material jetting, binder jetting, directed energy deposition, lamination. In one embodiment, the AM comprises Direct Metal Laser Sintering (DMLS), Selective Laser Sintering (SLS), Selective Laser Melting (SLM), Directed Energy Deposition (DED), Laser Metal Deposition (LMD), Electron Beam (EBAM), or metal binder jetting. In one embodiment, steps (c) and (d) occur sequentially.

In one embodiment, step (c) comprises varying the ratio of the first material to the second material in the mixture. In one embodiment, the ratio of the first material to the second material in the mixture is changed in situ. In one embodiment, the ratio of the first material to the second material in the mixture is varied in real time. In one embodiment, the ratio of the first material to the second material in the mixture is continuously varied. In one embodiment, the ratio of the first material to the second material in the mixture is varied according to the composition profile. In one embodiment, the ratio of the first material to the second material in the mixture is varied according to a manual algorithm, a computational algorithm, or a combination thereof. In one embodiment, the ratio of the first material to the second material in the mixture is varied by controlling the material flow rate or pumping speed.

In one embodiment, step (d) comprises placing the mixture in a pattern on a substrate. In one embodiment, step (d) comprises placing the mixture according to a predefined specification.

In one embodiment, the formed components have different properties. In one embodiment, the property comprises strength, weight, density, electrical performance, electrochemical performance, or a combination thereof. In various embodiments, the formed components have superior properties, such as strength, density, weight, electrical or electrochemical properties, or a combination thereof, when compared to similar components formed by different methods.

In one embodiment, step (d) comprises depositing the mixture on a substrate. In one embodiment, mixing is performed prior to deposition, during deposition, or after deposition. In one embodiment, the mixing is performed in the AMM either in air or on a substrate. In one embodiment, the mixing is performed by advection, dispersion, diffusion, melting, fusion, pumping, stirring, heating, or a combination thereof.

Disclosed herein is an Additive Manufacturing Machine (AMM), comprising: (a) a first material source; (b) a second material source; and (c) a mixer configured to mix the first material and the second material into a mixture; wherein the AMM is configured to form the mixture into a part. In one embodiment, the first material or the second material is a gas, or a liquid, or a solid, or a gel.

In one embodiment, the AMM is configured for extrusion, photopolymerization, powder layer fusion, material jetting, adhesive jetting, directed energy deposition, or lamination. In one embodiment, the AMM is configured to perform Direct Metal Laser Sintering (DMLS), Selective Laser Sintering (SLS), Selective Laser Melting (SLM), Directed Energy Deposition (DED), Laser Metal Deposition (LMD), Electron Beam (EBAM), or metal bond jetting.

In one embodiment, the mixer is configured to continuously mix the first material and the second material, and the AMM forms the mixture into a part. In one embodiment, the mixer is configured to vary the ratio of the first material to the second material in the mixture. In one embodiment, the mixer is configured to change the ratio of the first material to the second material in the mixture in situ. The mixer can be configured to change the ratio of the first material to the second material in the mixture in real time. In one embodiment, the mixer can be configured to continuously vary the ratio of the first material to the second material in the mixture. In one embodiment, the mixer is configured to vary the ratio of the first material and the second material in the mixture according to the composition profile. In one embodiment, the mixer is configured to vary the ratio of the first material and the second material in the mixture according to a manual algorithm, a computational algorithm, or a combination thereof. In one embodiment, the mixer is configured to vary the ratio of the first material to the second material in the mixture by controlling the material flow rate or pumping speed.

In one embodiment, the AMM is configured to place the mixture in a pattern on a substrate. In one embodiment, the AMM is configured to place the mixture according to a predefined specification.

In one embodiment, the formed components have different properties. In one embodiment, the property comprises strength, weight, density, electrical performance, electrochemical performance, or a combination thereof. In various embodiments, the formed components have superior properties, such as strength, density, weight, electrical or electrochemical properties, or a combination thereof, when compared to similar components formed using different devices.

In one embodiment, the AMM is configured to deposit the mixture on a substrate. In one embodiment, mixing is performed prior to deposition, during deposition, or after deposition. In one embodiment, the mixing is performed in the AMM either in air or on a substrate. In one embodiment, the mixing is performed by advection, dispersion, diffusion, melting, fusion, pumping, stirring, heating, or a combination thereof.

Integrated deposition and heating

Disclosed herein are methods comprising depositing a composition on a substrate sheet-by-sheet (which may also be referred to as line-by-line deposition) to form an object; heating an object in situ using electromagnetic radiation (EMR); wherein the composition comprises a first material and a second material, wherein the second material has a higher EMR absorption rate than the first material. In various embodiments, the heating may cause the following effects: drying, curing, sintering, annealing, sealing, alloying, evaporating, reconstituting, foaming, or combinations thereof. In some embodiments, the peak wavelength of EMR is in the range of 10 to 1500 nm, and the lowest energy density is 0.1 joules/cm ²Wherein the peak wavelength is based on radiation relative to wavelength. In some embodiments, the EMR includes one or more of UV light, near ultraviolet light, near infrared light, visible light, laser light, or electron beams.

FIG. 16 shows a system for integrated deposition and heating using electromagnetic radiation (EMR), according to an embodiment of the present disclosure. The system 1600 may be used to assemble an electrochemical reactor, such as a fuel cell or an EC gas generator. FIG. 16 also shows a system 1600 according to an embodiment of the present disclosure, which is an object 1603 on a receptor 1604 formed by a deposition nozzle 1601 and EMR 1602 for in-situ heating. The receiver 1604 may be a platform that moves and may further receive deposition, heating, radiation, or a combination thereof. The receptacle 1604 may also be referred to as a chamber, wherein the chamber may be completely enclosed, partially enclosed, or completely open to the atmosphere.

In some embodiments, the first material comprises Yttria Stabilized Zirconia (YSZ), 8YSZ (8 mol% YSZ powder), yttrium, zirconium, gadolinia doped ceria (GDC or CGO), Samaria Doped Ceria (SDC), Scandia Stabilized Zirconia (SSZ), strontium lanthanum manganite (LSM), strontium lanthanum cobalt ferrite (LSCF), Lanthanum Strontium Cobaltite (LSC), lanthanum strontium gallium magnesium oxide (LSGM), nickel, NiO-YSZ, Cu-CGO, Cu ₂O, CuO, cerium, copper, silver, crofer, steel, lanthanum chromite, doped lanthanum chromite, ferritic steel, stainless steel, or combinations thereof. In other embodiments, the first material comprises YSZ, SSZ, CGO, SDC, NiO-YSZ, LSM-YSZ, CGO-LSCF, doped lanthanum chromite, stainless steel, or combinations thereof. In some embodiments, the second material comprises carbon, nickel oxide, nickel, silver, copper, CGO, SDC, NiO-YSZ, NiO-SSZ, LSCF, LSM, doped lanthanum chromite, ferritic steel, or combinations thereof. The first material may comprise any of the electrode materials previously disclosed herein.

In some embodiments, object 1603 comprises a catalyst, a catalyst support, a catalyst composite, an anode, a cathode, an electrolyte, an electrode, an interconnect, a seal, a fuel cell, an electrochemical gas generator, an electrolyzer, an electrochemical compressor, a reactor, a heat exchanger, a vessel, or a combination thereof.

In some embodiments, the second material may be deposited in the same sheet as the first material. In other embodiments, the second material may be deposited in a sheet adjacent to another sheet containing the first material. In some embodiments, the heating can remove at least a portion of the second material. In a preferred embodiment, the heating leaves minimal residue of the second material such that there is no significant residue in the process or operation of building the device that would interfere with subsequent steps. More preferably, this leaves no measurable residual portion of the second material.

In some embodiments, the second material may add thermal energy to the first material during heating. In other embodiments, the second material has a radiation absorptivity that is at least 5 times that of the first material; the second material has a radiation absorptivity at least 10 times that of the first material; the second material has a radiation absorptivity at least 50 times that of the first material; or the second material has a radiation absorption of at least 100 times that of the first material.

In some embodiments, the second material may have a peak absorption wavelength of no less than 200 nm, or 250 nm, or 300 nm, or 400 nm, or 500 nm. In other embodiments, the first material has a peak absorption wavelength of no greater than 700 nm, or 600 nm, or 500 nm, or 400 nm, or 300 nm. In other embodiments, the peak wavelength of EMR is not less than 200 nm, or 250 nm, or 300 nm, or 400 nm, or 500 nm.

In some embodiments, the second material may include carbon, nickel oxide, nickel, silver, copper, CGO, NiO-YSZ, LSCF, LSM, ferritic steel, other metal oxides, or combinations thereof. In some cases, the ferritic steel is Crofer 22 APU. In some embodiments, the first material comprises YSZ, CGO, NiO-YSZ, LSM-YSZ, other metal oxides, or combinations thereof. In one embodiment, the second material comprises LSCF, LSM, carbon, nickel oxide, nickel, silver, copper or steel. In some embodiments, the carbon comprises graphite, graphene, carbon nanoparticles, nanodiamonds, or a combination thereof. The second material may comprise any of the electrode materials previously disclosed herein.

In some embodiments, the deposition method comprises material jetting, binder jetting, ink jet printing, aerosol jetting, aerosol jet printing, slot photo polymerization, powder layer fusion, material extrusion, directed energy deposition, sheet lamination, ultrasonic ink jet printing, or a combination thereof.

In some embodiments, the deposition method further comprises one or more of the following steps: controlling the distance of the EMR from the receiver, the energy density of the EMR, the spectrum of the EMR, the voltage of the EMR, the time of exposure of the EMR, the area of exposure of the EMR, the volume of exposure of the EMR, the pulse frequency of the EMR, the number of repetitions of exposure of the EMR. In one embodiment, the object does not change position between the deposition and heating steps. In one embodiment, the power output of the EMR is no less than 1W, or 10W, or 100W, or 1000W.

Also disclosed herein are systems that include at least one deposition nozzle, an electromagnetic radiation (EMR) source, and a deposition receiver, wherein the deposition receiver is configured to receive EMR exposure and deposition at the same location. In some cases, the receiver is configured such that it receives a first time period of deposition, moves to a different location in the system to receive a second time period of EMR exposure.

The following detailed description describes the production of a Solid Oxide Fuel Cell (SOFC) for illustrative purposes. As will be appreciated by those skilled in the art, the methods and production methods are applicable to all fuel cell types. As such, the production of all fuel cell types is within the scope of the present disclosure.

Additive manufacturing

Additive Manufacturing (AM) refers to a set of techniques that typically combine materials, either piece-wise or layer-wise, to prepare an object. AM is in contrast to subtractive manufacturing methods, which involve removing material portions by machining, cutting, grinding or etching away. AM may also be referred to as additive manufacturing, additive methods, additive techniques, additive layer production, or free-form fabrication. Some examples of AM are extrusion, photo-polymerization, powder layer fusion, material jetting, binder jetting, directed energy deposition, lamination, Direct Metal Laser Sintering (DMLS), Selective Laser Sintering (SLS), Selective Laser Melting (SLM), Directed Energy Deposition (DED), Laser Metal Deposition (LMD), Electron Beam (EBAM), and metal binder jetting. A 3D printer is a type of AM machine (AMM). Inkjet printers or ultrasonic inkjet printers are other examples of AMMs.

In a first aspect, the present invention is a method of making an electrochemical reactor, such as an EC gas generator or a fuel cell, comprising: (a) producing an anode using AMM; (b) generating an electrolyte using AMM; and (c) preparing a cathode using AMM. In a preferred embodiment, the anode, electrolyte and cathode are assembled into a fuel cell using AMM, except for other steps that are accomplished without AMM. In a preferred embodiment, only AMM is used to form the fuel cell. In other embodiments, steps (a), (b), and (c) do not include tape casting and screen printing. In one embodiment, the method of assembling a fuel cell using an AMM does not include compression during assembly. In other embodiments, the layers are deposited layers on top of one another in a step-wise fashion, such that assembly is completed at the same time as deposition. The methods described herein are useful in the preparation of planar fuel cells. The methods described herein are also useful in the preparation of fuel cells in which the current flow is perpendicular to the electrolyte in the transverse direction when the fuel cell is in use.

In one embodiment, the interconnect, anode, electrolyte and cathode are formed layer by layer, for example, printed layer by layer. It is important to note that the order in which these layers are formed may vary within the scope of the present invention. In other words, either the anode or the cathode may be formed before the other. Naturally, the electrolyte is formed so that it is between the anode and the cathode. The barrier layer, catalyst layer, and interconnects are formed so as to be in place within the fuel cell to perform their functions.

In some embodiments, each of the interconnect, anode, electrolyte, and cathode has 6 faces. In a preferred embodiment, the anode is printed onto and in contact with the interconnect; printing an electrolyte onto and in contact with the anode; the cathode is printed onto and in contact with the electrolyte. Each print may be sintered, for example, using EMR. As such, the assembly process and the formation process are simultaneous, which is not possible by conventional methods. Furthermore, by the preferred embodiment, the required electrical contact and gas tightness are also simultaneously achieved. In contrast, conventional fuel cell assembly processes accomplish this by compression or compression of the fuel cell components or layers. The compression and compression process can cause undesirable cracking in the fuel cell layers.

In some embodiments, the AM method includes preparing at least one barrier layer using AMM. In preferred embodiments, at least one barrier layer may be located between the electrolyte and the cathode or between the electrolyte and the anode or both. In other embodiments, at least one barrier layer may be assembled using AMM, using an anode, an electrolyte, and a cathode. In some embodiments, no barrier layer is required or used in the fuel cell.

In some embodiments, the AM method includes preparing the interconnect using the AMM. In other embodiments, the interconnect may be assembled using AMM, using an anode, an electrolyte, and a cathode. In some embodiments, the AMM forms a catalyst and introduces the catalyst into the fuel cell.

In some embodiments, the anode, electrolyte, cathode, and interconnect are prepared at a temperature greater than 100 ℃. In some embodiments, an AM method comprises heating a fuel cell, wherein the fuel cell comprises an anode, an electrolyte, a cathode, an interconnect, and optionally at least one barrier layer. In some embodiments, the fuel cell comprises a catalyst. In some embodiments, the method comprises heating the fuel cell to a temperature greater than 500 ℃. In some embodiments, the fuel cell is heated using one or both of EMR or oven curing.

In a preferred embodiment, the AMM utilizes a multi-nozzle additive manufacturing method. In a preferred embodiment, the multi-nozzle additive manufacturing method comprises nanoparticle jetting. In some embodiments, a first nozzle delivers a first material, a second nozzle delivers a second material, and a third nozzle delivers a third material. In some embodiments, the fourth material particles are placed in contact with and bonded to the partially fabricated fuel cell using a laser, a photoelectric effect, light, heat, polymerization, or bonding. In one embodiment, the anode, cathode or electrolyte comprises a first, second, third or fourth material. In a preferred embodiment, the AMM implements a plurality of AM technologies. In various embodiments, AM techniques include one or more of extrusion, photopolymerization, powder layer fusion, material jetting, binder jetting, directed energy deposition, or lamination. In various embodiments, AM is a deposition technique that includes material jetting, binder jetting, ink jet printing, aerosol jetting or aerosol jet printing, slot photo polymerization, powder layer fusion, material extrusion, directed energy deposition, sheet lamination, ultrasonic ink jet printing, or combinations thereof.

Further described herein is an AM method of making a fuel cell stack comprising: (a) producing an anode using an Additive Manufacturing Machine (AMM); (b) generating an electrolyte using AMM; (c) preparing a cathode using AMM; (d) fabricating interconnects using AMM; wherein the anode, the electrolyte, the cathode, and the interconnect form a first fuel cell; (e) repeating steps (a) - (d) to produce a second fuel cell; and (f) assembling the first fuel cell and the second fuel cell into a fuel cell stack.

In some embodiments, the first fuel cell and the second fuel cell are formed from an anode, an electrolyte, a cathode, and an interconnect using AMM. In one embodiment, only AMM is used to form the fuel cell stack. In other embodiments, steps (a) - (f) do not include one or both of casting and screen printing.

In some embodiments, the AM method includes preparing at least one barrier layer using AMM. In some embodiments, for the first fuel cell and the second fuel cell, at least one barrier layer is located between the electrolyte and the cathode or between the electrolyte and the anode or both.

In some embodiments, steps (a) - (d) are performed at a temperature greater than 100 ℃. In other embodiments, steps (a) - (d) are performed at a temperature in the range of 100 ℃ to 500 ℃. In some embodiments, the AMM prepares a catalyst and introduces the catalyst into the fuel cell stack.

In some embodiments, the AM method comprises heating the fuel cell stack. In one embodiment, the AM method includes heating the fuel cell stack to a temperature greater than 500 ℃. In some embodiments, the fuel cell stack is heated using EMR and/or oven curing. In some embodiments, the laser has a laser beam, wherein the laser beam is expanded to create a heating zone with a uniform power density. In some embodiments, the laser beam is expanded by using one or more mirrors. In some embodiments, each layer of the fuel cell can be cured individually by EMR. In some embodiments, a combination of one or more fuel cell layers may be cured together by EMR. In some embodiments, the first fuel cell EMR is cured, assembled with the second fuel cell EMR, and then the second fuel cell EMR is cured. In other embodiments, the first fuel cell is assembled with the second fuel cell, and then the first fuel cell and the second fuel cell are individually cured by EMR. In some embodiments, the first fuel cell and the second fuel cell can be cured separately by EMR and then assembled to form a fuel cell stack. In some embodiments, a first fuel cell is assembled with a second fuel cell to form a fuel cell stack, which can then be cured by EMR.

Also discussed herein is an AM method of making a plurality of fuel cells, comprising (a) simultaneously producing a plurality of anodes using an Additive Manufacturing Machine (AMM); (b) simultaneously producing a plurality of electrolytes using AMM; and (c) simultaneously preparing a plurality of cathodes using AMM. In a preferred embodiment, AMM is used to simultaneously assemble the anode, electrolyte and cathode into a fuel cell. In other preferred embodiments, only AMM is used to form the fuel cell.

In some embodiments, the method includes simultaneously fabricating at least one barrier layer using AMM for each of a plurality of fuel cells. The at least one barrier layer may be located between the electrolyte and the cathode or between the electrolyte and the anode or both. In a preferred embodiment, for each fuel cell, at least one barrier layer may be assembled using AMM, using an anode, an electrolyte and a cathode.

In some embodiments, the method includes simultaneously preparing an interconnect using the AMM for each of the plurality of fuel cells. For each fuel cell, an interconnect may be assembled using AMM, an anode, an electrolyte, and a cathode. In other embodiments, the AMM forms a catalyst simultaneously for each of the plurality of fuel cells and introduces the catalyst into each fuel cell. In other embodiments, the heating of each layer or the heating of a combination of layers of multiple fuel cells is performed simultaneously. The plurality of fuel cells may include two or more fuel cells.

In a preferred embodiment, the AMM uses two or more different nozzles to eject or print different materials simultaneously. For the first example, while in AMM, a first nozzle deposits the anode layer of the fuel cell 1, a second nozzle deposits the cathode layer of the fuel cell 2 and a third nozzle deposits the electrolyte of the fuel cell 3. For the second example, while in AMM, a first nozzle deposits the anode of fuel cell 1, a second nozzle deposits the cathode of fuel cell 2, a third nozzle deposits the electrolyte of fuel cell 3 and a fourth nozzle deposits the interconnect of fuel cell 4.

An Additive Manufacturing Machine (AMM) comprising a chamber in which fuel cell production is performed is disclosed herein. The chamber is capable of withstanding a temperature of at least 100 ℃. In one embodiment, the chamber is capable of producing a fuel cell. The chamber is capable of heating the fuel cell in situ while the fuel cell assembly is being deposited.

In some embodiments, the chamber can be heated by a laser, electromagnetic waves/radiation (EMR), thermal fluid, or a heating element associated with the chamber, or a combination thereof. The heating element may comprise a heating surface, a heating coil or a heating rod. In other embodiments, the chamber may be configured to apply pressure to the interior of the fuel cell. The pressure may be applied by a moving element associated with the chamber. The moving element may move the punch or the piston. In some embodiments, the chamber may be configured to withstand pressure. The chamber may be configured to be pressurized or depressurized by a fluid. The fluid in the chamber may be changed or replaced as necessary.

In some cases, the chamber may be closed. In some cases, the chamber may be sealed. In some cases, the chamber may be open to the ambient atmosphere or to a controlled atmosphere. In some cases, the chamber may be a platform without a top wall and sidewalls.

Referring to FIG. 16, a system 1600 includes a deposition or material ejection nozzle 1601, an EMR source 1602 (e.g., a xenon lamp), an object 1603 being formed, and a chamber or receiver 1604 that is part of an AMM. As shown in FIG. 16, a chamber or receiver 1604 is configured to receive the deposits from the nozzles and the radiation from the EMR source 1602. In various embodiments, the deposition nozzle 1601 may be movable. In various embodiments, the chamber or receptacle 1604 may be movable. In various embodiments, the EMR source 1602 is movable. In various embodiments, the object comprises a catalyst, a catalyst support, a catalyst composite, an anode, a cathode, an electrolyte, an electrode, an interconnect, a seal, a fuel cell, an electrochemical gas generator, an electrolyzer, an electrochemical compressor, a reactor, a heat exchanger, a container, or a combination thereof.

AM technologies suitable for the present disclosure include extrusion, photopolymerization, powder layer fusion, material jetting, binder jetting, directed energy deposition, and lamination. In some embodiments, extrusion may be used for AM. Extruding AM involves spatially controlled deposition of a material (e.g., a thermoplastic). In the present disclosure, extruded AM may also be referred to as fuse fabrication (FFF) or Fused Deposition Modeling (FDM).

In some embodiments, for the methods of the present disclosure, AM comprises photopolymerization (i.e., Stereolithography (SLA)). SLA includes spatially defined curing of photoactive liquids ("photosensitive resins") using a scanning laser or high resolution projected images and conversion of the photoactive liquid to a crosslinked solid. Photopolymerization can produce parts with details and dimensions in the micrometer to meter scale range.

In some embodiments, the AM comprises powder layer fusion (PBF). The PBF AM method builds objects by melting a powder feedstock, such as a polymer or metal. The PBF process is initiated by distributing a thin layer of powder within the build area. Then, one layer cross-section is melted at a time, most often using a laser, electron beam or intense infrared lamp. In some embodiments, the PBF of metal may use Selective Laser Melting (SLM) or Electron Beam Melting (EBM). In other embodiments, the polymeric PBF may use Selective Laser Sintering (SLS). In various embodiments, the SLS system may print thermoplastic polymer materials, polymer composites, or ceramics. In various embodiments, the SLM system can be adapted to a variety of pure metals and alloys, where the alloy is compatible with the rapid solidification that occurs in the SLM.

In some embodiments, AM may comprise material jetting. AM by material ejection can be accomplished by spatially controlled deposition of droplets (or drops) of the material. In various embodiments, 3-dimensional (3D), 2-dimensional (2D) material jetting, or both, is performed. In a preferred embodiment, the 3D jetting is done layer by layer. In a preferred embodiment, print preparation translates computer-aided design (CAD) and specification of material composition, color and other variables into print instructions for each layer. Binder jetting AM involves inkjet deposition of a liquid binder onto a powder layer. In some cases, binder jetting is combined with other AM processes, such as, for example, powder diffusion to prepare a powder layer (similar to SLS/SLM) and inkjet printing.

In some embodiments, the AM comprises Directed Energy Deposition (DED). Instead of the use of powder layers as discussed above, the DED method uses a directed powder flow or wire feed (wire feed), and an energy intensive source such as a laser, arc or electron beam. In a preferred embodiment, the DED is a direct write method, where the material deposition location is determined by moving the deposition head, which enables large metal structures to be built without the restriction of a powder layer.

In some embodiments, the AM comprises laminated AM or Layered Object Manufacturing (LOM). In a preferred embodiment, successive layers of sheet material are continuously bonded and cut to form a 3D structure.

Conventional methods of producing fuel cell stacks may include over 100 steps. These steps may include, but are not limited to, milling, grinding, filtering, analyzing, mixing, binding, evaporating, aging, drying, extruding, diffusing, casting, screen printing, stacking, heating, pressing, sintering, and compressing. The methods disclosed herein describe the production of a fuel cell or fuel cell stack using an AMM.

The AMM of the present disclosure preferably implements both extrusion and ink jetting to produce a fuel cell or fuel cell stack. Extrusion can be used to produce thicker layers of fuel cells such as anodes and/or cathodes. Ink jet can be used to produce thin layers for fuel cells. Inkjet can be used to produce electrolytes. The AMM may be operated within a temperature range sufficient to enable curing in the AMM itself. These temperature ranges are 100 ℃ or higher, 100-.

As a preferred example, all fuel cell layers are formed and assembled by printing. The materials used to make the anode, cathode, electrolyte, and interconnect can be made in the form of an ink containing a solvent and particles (e.g., nanoparticles), respectively. There are two types of ink formulations-aqueous and non-aqueous inks. In some cases, the aqueous ink includes an aqueous solvent (e.g., water, deionized water), particles, a dispersant, and a surfactant. In some cases, the aqueous ink comprises an aqueous solvent, particles, a dispersant, a surfactant, but no polymeric binder. The aqueous ink may optionally include a co-solvent, such as an organic miscible solvent (methanol, ethanol, isopropanol). These co-solvents preferably have a boiling point lower than that of water. The dispersant may be an electrostatic dispersant, a stereochemical dispersant, an ionic dispersant or a nonionic dispersant, or a combination thereof. The surfactant may preferably be non-ionic, such as an alcohol alkoxylate or alcohol ethoxylate. The non-aqueous ink may include an organic solvent (e.g., methanol, ethanol, isopropanol, butanol) and particles.

For example, CGO powder is mixed with water to form an aqueous ink that also contains added dispersant and surfactant, but no added polymeric binder. The CGO fraction on a mass basis (expressed herein as weight% (wt%)) is in the range of 10 wt% to 25 wt%. For example, the CGO powder is mixed with ethanol to form a non-aqueous ink further comprising polyvinyl butyral having a CGO fraction in the range of 3 wt% to 30 wt%. For example, LSCF is mixed with n-butanol or ethanol to form a non-aqueous ink that also comprises polyvinyl butyral having an LSCF fraction in the range of 10 wt% to 40 wt%. For example, YSZ particles are mixed with water to form an aqueous ink that also contains added dispersant and surfactant, but no added polymeric binder. The YSZ fraction ranges from 3 wt% to 40 wt%. For example, NiO particles are mixed with water to form an aqueous ink that also contains added dispersant and surfactant, but no added polymeric binder, with a NiO fraction in the range of 5 wt% to 25 wt%.

For example, for a cathode of a fuel cell, LSCF or LSM particles are dissolved in a solvent, where the solvent is water or an alcohol (e.g., butanol) or a mixture of alcohols. Organic solvents other than alcohols may also be used in other examples. For example, LSCF is deposited (e.g., printed) as a layer. By EMR, xenon lamps can be used to irradiate the LSCF layer to sinter the LSCF particles. The xenon flash lamp may be a 10 kW unit with a voltage of 400V and a frequency of 10 Hz for a total exposure time of 1000 ms.

For example, for an electrolyte, YSZ particles are mixed with a solvent, where the solvent is water (e.g., deionized water) or an alcohol (e.g., butanol) or a mixture of alcohols. Organic solvents other than alcohols may also be used in other examples. For interconnects, metal particles (e.g., silver nanoparticles) are dissolved in a solvent, where the solvent may include water (e.g., deionized water) and an organic solvent. The organic solvent may include mono-, di-, or tri-or higher ethylene glycols, propylene glycol, 1, 4-butanediol or ethers of these glycols, thiodiglycol, glycerol and its ethers and esters, polyglycerol, mono-, di-, and tri-ethanolamine, propanolamine, N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, 1, 3-dimethylimidazolidinone, methanol, ethanol, isopropanol, N-propanol, diacetone alcohol, acetone, methyl ethyl ketone, or propylene carbonate, or combinations thereof. For barrier layers in fuel cells, the CGO particles are dissolved in a solvent, where the solvent may be water (e.g., deionized water) or an alcohol. The alcohol may comprise methanol, ethanol, butanol, or a mixture of alcohols. Organic solvents other than alcohols may also be used. CGO may be used as a barrier layer for LSCF. YSZ may also be used as a barrier layer for LSM. In some cases, for aqueous inks in which water is the solvent, no polymeric binder may be added to the aqueous ink.

The production method of the conventional fuel cell sometimes includes more than 100 steps and uses several tens of machines. According to an embodiment of the present disclosure, a method of making a fuel cell includes producing a fuel cell using only one AMM, wherein the fuel cell includes an anode, an electrolyte, and a cathode. In a preferred embodiment, the fuel cell comprises at least one barrier layer located, for example, between the electrolyte and the cathode or both. Preferably, the at least one barrier layer is also prepared by the same AMM. In a preferred embodiment, the AMM may also produce interconnects and assemble the interconnects with the anode, the cathode, the at least one barrier layer and the electrolyte. These production methods and systems are not only suitable for the production of fuel cells, but also for the production of other types of electrochemical devices. The following discussion uses a fuel cell as an example, but any reactor or catalyst is within the scope of the present disclosure.

In various embodiments, a single AMM produces a first fuel cell, wherein the fuel cell comprises an anode, an electrolyte, a cathode, at least one barrier layer, and an interconnect. In various embodiments, a single AMM produces a second fuel cell. In various embodiments, a single AMM is used to assemble a first fuel cell with a second fuel cell to form a fuel cell stack. In various embodiments, the production of fuel cells using AMM is repeated as many times as necessary. Thus, a fuel cell stack containing two or more fuel cells is assembled using the AMM. In some embodiments, the layers of the fuel cell are produced by AMM above ambient temperature. For example, the temperature may be above 100 ℃, in the range of 100 ℃ to 500 ℃, or in the range of 100 ℃ to 300 ℃. In various embodiments, the fuel cell or fuel cell stack is heated after it is assembled. In some embodiments, the fuel cell or fuel cell stack is heated at a temperature greater than 500 ℃. In a preferred embodiment, the fuel cell or fuel cell stack is heated at a temperature in the range of 500 ℃ to 1500 ℃.

In various embodiments, the AMM comprises a chamber in which fuel cell production is performed. The chamber may be capable of withstanding high temperatures to enable the production of a fuel cell, wherein the high temperature is at least 300 ℃, at least 500 ℃, at least 1000 ℃, or at least 1500 ℃. In some cases, the chamber may also enable heating of the fuel cell to occur in the chamber. Various heating methods may be applied, such as laser heating/curing, electromagnetic wave heating, thermal fluid heating, or one or more heating elements associated with the chamber. The heating element may be a heating surface, heating coil or heating rod, and is integrated with the chamber to heat the contents of the chamber to a desired temperature range. In various embodiments, the chamber of the AMM may also be capable of applying pressure to the interior of the fuel cell. For example, the pressure may be applied by moving elements, such as a moving punch or piston. In various embodiments, the chamber of the AMM is capable of withstanding pressure. The chamber may be pressurized or depressurized by a fluid as desired. The fluid in the chamber may also be changed or replaced as desired.

In a preferred embodiment, EMR is used to heat the fuel cell or fuel cell stack. In other embodiments, the fuel cell or fuel cell stack may be heated using oven curing. In other embodiments, the laser beam may be expanded (e.g., by using one or more mirrors) to create a heating zone with a uniform power density. In a preferred embodiment, each layer of the fuel cell can be cured individually by EMR. In a preferred embodiment, a combination of fuel cell layers, e.g., a combination of an anode, an electrolyte, and a cathode layer, can be EMR cured individually. In some embodiments, the first fuel cell EMR is cured, assembled with the second fuel cell EMR, and then the second fuel cell EMR is cured. In one embodiment, a first fuel cell is assembled with a second fuel cell, and then the first fuel cell and the second fuel cell are EMR cured separately. In one embodiment, a first fuel cell is assembled with a second fuel cell to form a fuel cell stack, and the fuel cell stack is EMR cured. A fuel cell stack comprising two or more fuel cells can be EMR cured. The sequence of laser heating/curing and assembly is applicable to all other heating methods.

In a preferred embodiment, the AMM produces each layer of the plurality of fuel cells simultaneously. In a preferred embodiment, the AMM assembles each layer of the plurality of fuel cells simultaneously. In a preferred embodiment, the heating of each layer or the heating of a combination of layers of a plurality of fuel cells is performed simultaneously. All discussion herein and all features of a fuel cell or fuel cell stack apply to the production, assembly and heating of a plurality of fuel cells. In preferred embodiments, the plurality of fuel cells may be 2 or more, 20 or more, 50 or more, 80 or more, 100 or more, 500 or more, 800 or more, 1000 or more, 5000 or more, or 10,000 or more.

Processing method

Disclosed herein are treatment methods that include one or more of the following effects: heating, drying, curing, sintering, annealing, sealing, alloying, evaporating, reconstituting, foaming, or sintering. The preferred method of treatment is sintering. The treatment method includes exposing the substrate to an electromagnetic radiation (EMR) source. In some embodiments, EMR is exposed to a substrate having a first material. In various embodiments, the EMR has a peak wavelength in the range of 10 to 1500 nm. In various embodiments, the EMR has 0.1 Joule/cm ²The lowest energy density of. In one embodiment, the EMR has a value of 10^-4-a pulse frequency of 1000 Hz, or 1-1000 Hz, or 10-1000 Hz. In one embodiment, the exposure distance of EMR is no greater than 50 mm. In one embodiment, the exposure time of EMR is not less than 0.1 ms or 1 ms. In one embodiment, a capacitor voltage of no less than 100V is applied to the EMR. For example, a single pulse of EMR is applied at an exposure distance of about 10 mm and an exposure time of 5-20 ms. For example, multiple pulses of EMR are applied at a pulse frequency of 100 Hz with an exposure distance of about 10 mm and an exposure time of 5-20 ms. In some embodiments, the EMR consists of one exposure. In other embodiments, the EMR comprises no more than 10 exposures, alternatively no more than 100 exposures, alternatively no more than 1000 exposures, alternatively no more than 10,000 exposuresAnd (5) exposing.

In various embodiments, metals and ceramics are nearly instantaneously sintered (for pulsed light) using pulsed light<<10 microns, milliseconds). The sintering temperature may be controlled in the range of 100 ℃ to 2000 ℃. The sintering temperature may be adjusted as a function of depth. In one example, the surface temperature is 1000 ℃, and the shallow surface (sub-surface, subsurface) is maintained at 100 ℃, wherein the shallow surface is 100 microns below the surface. In some embodiments, materials suitable for this treatment process include Yttria Stabilized Zirconia (YSZ), 8YSZ (8 mol% YSZ powder), yttrium, zirconium, gadolinia doped ceria (GDC or CGO), samarium oxide doped ceria (SDC), Scandia Stabilized Zirconia (SSZ), strontium lanthanum manganite (LSM), strontium lanthanum cobalt ferrite (LSCF), Lanthanum Strontium Cobaltite (LSC), lanthanum strontium gallium magnesium oxide (LSGM), nickel, NiO-YSZ, Cu-CGO, Cu ₂O, CuO, cerium, copper, silver, crofer, steel, lanthanum chromite, doped lanthanum chromite, ferritic steel, stainless steel, or combinations thereof. The treatment method may be adapted to any of the electrode or electrolyte materials previously listed herein.

This treatment method is applicable to a production method of a fuel cell. In preferred embodiments, the layers (i.e., anode, cathode, electrolyte, seal, catalyst, etc.) in the fuel cell are treated using the methods described herein to heat, cure, sinter, seal, alloy, foam, evaporate, reconstitute, dry, or anneal, or combinations thereof. In preferred embodiments, portions of layers in a fuel cell are treated using the methods described herein to heat, cure, sinter, seal, alloy, foam, evaporate, reconstitute, dry, anneal, or a combination thereof. In preferred embodiments, the combination of layers of the fuel cell, which may be complete or partial layers, are processed using the methods described herein to heat, cure, sinter, seal, alloy, foam, evaporate, reconstitute, dry, anneal, or combinations thereof.

The treatment method of the present disclosure is preferably rapid with treatment durations varying from microseconds to milliseconds. The treatment duration can be accurately controlled. The treatment methods of the present disclosure may produce fuel cell layers with no or minimal cracking. The treatment method of the present disclosure controls the power density or energy density in the treatment volume of the material to be treated (the volume of the object to be treated). The treatment volume can be accurately controlled. In one embodiment, the treatment methods of the present disclosure provide the same energy density or different energy densities in the treatment volume. In one embodiment, the treatment methods of the present disclosure provide the same treatment duration or different treatment durations in the treatment volume. In one embodiment, the treatment method of the present disclosure provides for simultaneous treatment of one or more treatment volumes. In one embodiment, the treatment methods of the present disclosure provide for simultaneous treatment of one or more fuel cell layers or portions of layers or combinations of layers. In one embodiment, the treatment volume is changed by changing the treatment depth.

In one embodiment, a first portion of the treatment volume is treated by electromagnetic radiation having a first wavelength; a second portion of the treatment volume is treated by electromagnetic radiation having a second wavelength. In some cases, the first wavelength is the same as the second wavelength. In some cases, the first wavelength is different from the second wavelength. In one embodiment, the first portion of the processing volume has a different energy density than the second portion of the processing volume. In one embodiment, the first portion of the treatment volume has a different treatment duration than the second portion of the treatment volume.

In one embodiment, the EMR has a broad emission spectrum, thereby achieving the desired effect for a wide range of materials with different absorption characteristics. In this disclosure, absorption of electromagnetic radiation (EMR) refers to a process in which an electron of a substance, such as an atom, absorbs photon energy. Thus, the electromagnetic energy is converted into an internal energy of the absorber, e.g., thermal energy. For example, the EMR spectrum extends from the far Ultraviolet (UV) range to the near Infrared (IR) range with peak pulse power at 220 nm wavelength. The power of this EMR is about megawatts. Such EMR sources perform tasks such as breaking chemical bonds, sintering, ablating, or sterilizing.

In one embodiment, the EMR has an energy density of not less than 0.1, 1, or 10 joules/cm². In one embodiment, the power output of the EMR is no less than 1 watt (W), 10W, 100W, 1000W. EMR delivers no less than 1W, 10W, 100W, 1000W of power to the substrate. In one embodiment, this EMR exposure heats the material in the substrate. In one embodiment, the EMR has a range or spectrum of different wavelengths. In various embodiments, the treated substrate is at least a portion of an anode, a cathode, an electrolyte, a catalyst, a barrier layer, or an interconnect of a fuel cell.

In one embodiment, the peak wavelength of EMR is between 50 and 550 nm or between 100 and 300 nm. In one embodiment, at least a portion of the substrate has an absorption of at least one frequency of EMR between 10 and 1500 nm of not less than 30% or not less than 50%. In one embodiment, at least a portion of the substrate has an absorption of at least one frequency between 50 and 550 nm of not less than 30% or not less than 50%. In one embodiment, at least a portion of the substrate has an absorption of at least one frequency between 100 and 300 nm of not less than 30% or not less than 50%.

Sintering is a process of compacting and forming a solid mass of material by heat or pressure without melting it to a point of liquefaction. In the present disclosure, the substrate under EMR exposure is sintered but does not melt. In preferred embodiments, the EMR comprises one or more of UV light, near ultraviolet light, near infrared light, visible light, laser, electron beam, microwave. In one embodiment, the substrate is exposed to EMR for no less than 1 microsecond, no less than 1 millisecond. In one embodiment, the substrate is exposed to EMR for less than 1 second at a time or less than 10 seconds at a time. In one embodiment, the substrate is exposed to EMR for less than 1 second or less than 10 seconds. In one embodiment, the substrate is repeatedly exposed to EMR, for example, more than 1 time, more than 3 times, more than 10 times. In one embodiment, the substrate is less than 50 cm, less than 10 cm, less than 1 cm, or less than 1 mm from the EMR source.

In some embodiments, the second material is added to or placed on the first material after EMR exposure. In many cases, the second material is the same as the first material. The second material may be exposed to EMR. In some cases, a third material may be added. The third material is exposed to EMR.

In some embodiments, the first material comprises YSZ, 8YSZ, yttrium, zirconium, GDC, SDC, LSM, LSCF, LSC, nickel, NiO, or cerium, or a combination thereof. The second material may comprise graphite. In some embodiments, the electrolyte, anode, or cathode comprises a second material. In some cases, the volume fraction of the second material in the electrolyte, anode, or cathode is less than 20%, 10%, 3%, or 1%. The second material has an absorbance of greater than 30% or greater than 50% for at least one frequency (e.g., between 10 and 1500 nm, or between 100 and 300 nm, or between 50 and 550 nm).

In various embodiments, one or a combination of parameters can be controlled, wherein the parameters include the distance between the EMR source and the substrate, the energy density of the EMR, the spectrum of the EMR, the voltage of the EMR, the exposure time, the pulse frequency, and the number of EMR exposures. Preferably, these parameters are controlled to minimize the formation of cracks in the substrate.

In one embodiment, EMR energy is delivered to no less than 1 mm²Or not less than 1 cm²Or not less than 10 cm²Or not less than 100 cm²Surface area of (a). In some cases, at least a portion of an adjacent material is at least partially heated by thermal conduction from the first material during EMR exposure of the first material. In various embodiments, the fuel cell (e.g., anode, cathode, electrolyte) layer is thin. Preferably, they are no greater than 30 microns, no greater than 10 microns, or no greater than 1 micron.

In some embodiments, the first material of the substrate is in the form of a powder, a sol-gel, a colloidal suspension, a hybrid solution, or a sintered material. In various embodiments, the second material may be added by vapor deposition. In a preferred embodiment, the second material coats the first material. In a preferred embodiment, the second material reacts with light (e.g., focused light), such as light by a laser, and sinters or anneals with the first material.

Advantages of

The preferred processing methods of the present disclosure enable rapid production of fuel cells by eliminating conventional, expensive, time consuming, expensive sintering methods and, if desired, replacing them with rapid, in situ methods that allow the fuel cell layers to be produced continuously in a single machine. The method also shortens the sintering time from hours to days to seconds or milliseconds or even microseconds.

In various embodiments, this processing method is used in combination with production techniques such as screen printing, tape casting, spraying, sputtering, physical vapor deposition, and additive manufacturing.

This preferred treatment method enables the heating to be adjusted and controlled by adjusting the EMR characteristics (such as wavelength, fluence, pulse frequency, and exposure time) in combination with controlling the thickness of the substrate layer and the thermal conduction to adjacent layers such that each layer sinters, anneals, or cures at each desired target temperature. The method allows for more uniform energy application, reducing or eliminating cracking, which improves electrolyte performance. Substrates treated with this preferred method also have lower thermal stress due to more uniform heating.

Particle size control

Without wishing to be bound by any theory, we have surprisingly found that if the particle size distribution of the particles in the material is controlled to meet certain criteria, the sintering process may require less energy consumption and shorter time than conventionally required. In some cases, such a particle size distribution comprises D10 and D90, wherein 10% of the particles have a diameter no greater than D10 and 90% of the particles have a diameter no greater than D90, wherein D90/D10 is in the range of 1.5 to 100. In some cases, the particle size distribution is bimodal such that the average particle size in the first mode is at least 5 times the average particle size in the second mode. In some cases, such a particle size distribution includes D50, wherein 50% of the particles have a diameter no greater than D50, wherein D50 is no greater than 100 nm. The sintering process uses electromagnetic radiation (EMR), or plasma, or furnace, or hot fluid, or heating elements, or combinations thereof. Preferably, the sintering process uses electromagnetic radiation (EMR). For example, without the use of a method as disclosed herein, the EMR source is only sufficient to sinter a material having a power capacity P. Using the methods as disclosed herein, the material is sintered with an EMR source having a much lower power capacity, e.g., 50% P or less, 40% P or less, 30% P or less, 20% P or less, 10% P or less, 5% P or less.

Herein, a method of sintering a material is disclosed, comprising mixing particles with a liquid to form a dispersion, wherein the particles have a particle size distribution comprising D10 and D90, wherein 10% of the particles have a diameter no greater than D10 and 90% of the particles have a diameter no greater than D90, wherein D90/D10 is in the range of 1.5 to 100; depositing the dispersion on a substrate to form a layer; and treating the layer to cause sintering of at least a portion of the particles.

In some embodiments, the particle size distribution is a number average distribution determined by dynamic light scattering. Dynamic Light Scattering (DLS) is a technique that can be used to determine the particle size distribution of small particles in a dispersion or suspension. In the context of DLS, temporal fluctuations are typically analyzed by an intensity or photon autocorrelation function (also known as photon correlation spectroscopy or quasi-elastic light scattering). In time domain analysis, the autocorrelation function (ACF) typically decays from zero delay time, and the faster dynamics due to the smaller particles will result in faster decorrelation of the scatter intensity traces. The intensity ACF has been shown to be a fourier transform of the power spectrum and therefore DLS measurements can be made equally well in the spectral domain.

In one embodiment, the particle size distribution is determined by Transmission Electron Microscopy (TEM). TEM is a microscopy technique in which an electron beam is transmitted through a sample to form an image. In this case, the sample is most commonly a suspension on a grid (grid). As the beam is transmitted through the sample, an image is formed due to the interaction of the electrons with the sample. The image is then magnified and focused onto an imaging device, such as a phosphor screen or a sensor, such as a scintillator attached to a charge-coupled device.

Herein, a method of sintering a material is disclosed, comprising mixing particles with a liquid to form a dispersion, wherein the particles have a particle size distribution comprising D50, wherein 50% of the particles have a diameter of no greater than D50, wherein D50 is no greater than 100 nm; depositing the dispersion on a substrate to form a layer; and treating the layer to cause sintering of at least a portion of the particles. In various embodiments, D50 is no greater than 50 nm, alternatively no greater than 30 nm, alternatively no greater than 20 nm, alternatively no greater than 10 nm, alternatively no greater than 5 nm. In one embodiment, the thickness of the layer is no greater than 1 mm, alternatively no greater than 500 microns, alternatively no greater than 300 microns, alternatively no greater than 100 microns, alternatively no greater than 50 microns.

In some embodiments, the depositing comprises material jetting, binder jetting, ink jet printing, aerosol jetting or aerosol jet printing, slot photo polymerization, powder layer fusion, material extrusion, directed energy deposition, sheet lamination, ultrasonic ink jet printing, or combinations thereof. In some embodiments, the liquid comprises water and at least one organic solvent having a lower boiling point than water and which is miscible with water. In some embodiments, the liquid comprises water, a surfactant, a dispersant, and no polymeric binder. In some embodiments, the liquid comprises one or more organic solvents and does not comprise water. In some embodiments, the particles comprise Cu, CuO, Cu₂O、Ag、Ag₂O、Au、Au₂O、Au₂O₃Titanium, yttria-stabilized zirconia (YSZ), 8YSZ (8 mol% YSZ powder), yttrium, zirconium, gadolinia-doped ceria (GDC or CGO), samaria-doped ceria (SDC), scandia-stabilized zirconia (SSZ), Lanthanum Strontium Manganite (LSM), lanthanum cobalt ferrite (LSCF), Lanthanum Strontium Cobaltite (LSC), lanthanum strontium gallium magnesium oxide (LSGM), nickel (Ni), NiO-YSZ, Cu-CGO, cerium, crofer, steel, lanthanum chromite, doped lanthanum chromite, ferritic steel, stainless steel, or combinations thereof. The particles may comprise any of the materials listed herein previously for the electrodes or electrolytes.

In some embodiments, the particles have a bimodal particle size distribution such that the average particle size in the first mode is at least 5 times the average particle size in the second mode. In some embodiments, D10 is in the range of 5 nm to 50 nm, alternatively 5 nm to 100 nm, alternatively 5 nm to 200 nm. In some embodiments, D90 is in the range of 50 nm to 500 nm, or 50 nm to 1000 nm. In some embodiments, D90/D10 is in the range of 2 to 100, or 4 to 100, or 2 to 20, or 2 to 10, or 4 to 20, or 4 to 10.

In some embodiments, the method comprises drying the dispersion after deposition. In some embodiments, drying comprises heating the dispersion prior to deposition, heating the substrate in contact with the dispersion, or a combination thereof. Drying may occur over a period of time in the range of 1 ms to 1 min, or 1 s to 30 s, or 3 s to 10 s. In some embodiments, the dispersion may be deposited at a temperature in the range of 40 ℃ to 100 ℃, or 50 ℃ to 90 ℃, or 60 ℃ to 80 ℃, or a temperature of about 70 ℃.

In some embodiments, the treatment comprises the use of electromagnetic radiation (EMR), or an oven, or a plasma, or a thermal fluid, or a heating element, or a combination thereof. In some embodiments, the EMR comprises UV light, near ultraviolet light, near infrared light, visible light, laser, electron beam, or microwave, or a combination thereof. In one embodiment, the EMR consists of one exposure. In other embodiments, the frequency of EMR exposure is 10 ^-4-1000 Hz, or 1-1000 Hz, or 10-1000 Hz. In one embodiment, the exposure distance of EMR is no greater than 50 mm. In one embodiment, the exposure time of EMR is not less than 0.1 ms or 1 ms. In one embodiment, a capacitor voltage of no less than 100V is applied to the EMR.

Examples

The following examples are provided as part of the disclosure of various embodiments of the invention. As such, the information provided below is not to be taken as limiting the scope of the invention.

Example 1. preparation of an EC reactor stack.

Example 1 illustrates a preferred method of making an EC reactor stack, e.g., a fuel cell stack. The method uses AMM type 0012323 from ceradorop and EMR type 092309423 from Xenon corp. The interconnect substrate is lowered to begin printing.

As a first step, the anode layer is prepared by AMM. This layer was deposited by AMM as slurry a, which had the composition shown in the table below. Heat was applied by infrared lamp to dry the layer. The anode layer was sintered by irradiating it for 1 second with an electromagnetic pulse from a xenon pulse tube.

A slurry B having the composition shown in the table below was deposited by AMM, forming an electrolyte layer on top of the anode layer. Heat was applied by infrared lamp to dry the layer. The electrolyte layer was sintered by irradiating it with an electromagnetic pulse from a xenon pulse tube for 60 seconds.

Then, a cathode layer was formed on top of the electrolyte layer by depositing a slurry C by AMM, said slurry C having the composition shown in the table below. Heat was applied by infrared lamp to dry the layer. The cathode layer was sintered by irradiating it with an electromagnetic pulse from a xenon pulse tube for 1/2 seconds.

An interconnect layer was formed on top of the cathode layer by AMM deposition of a paste D having the composition shown in the table below. Heat was applied by infrared lamp to dry the layer. The interconnect layer was sintered by irradiating it with an electromagnetic pulse from a xenon pulse tube for 30 seconds.

These steps are then repeated 60 times, wherein an anode layer is formed on top of the interconnects. The result is a fuel cell stack with 61 fuel cells.

Example 2 LSCF in ethanol

200 ml of ethanol was mixed with 30 grams of LSCF powder in a beaker. The mixture was centrifuged and an upper dispersion and a lower dispersion were obtained. The upper dispersion was extracted and deposited on the substrate using a 3D printer and the LSCF layer was formed. The LSCF layer was irradiated using a xenon lamp (10 kW) at a voltage of 400V and a pulse frequency of 10 Hz for a total exposure time of 1,000 ms.

Example 3 CGO in ethanol

200 ml of ethanol was mixed with 30 g of CGO powder in a beaker. The mixture was centrifuged and an upper dispersion and a lower dispersion were obtained. The upper dispersion was extracted and deposited on the substrate using a 3D printer and a CGO layer was formed. The CGO layer was irradiated using a xenon lamp (10 kW) at a voltage of 400V and a pulse frequency of 10 Hz for a total exposure time of 8,000 ms.

Example 4 CGO in Water

200 ml of deionized water was mixed with 30 grams of CGO powder in a beaker. The mixture was centrifuged and an upper dispersion and a lower dispersion were obtained. The upper dispersion was extracted and deposited on the substrate using a 3D printer and a CGO layer was formed. The CGO layer was irradiated using a xenon lamp (10 kW) at a voltage of 400V and a pulse frequency of 10 Hz for a total exposure time of 8,000 ms.

EXAMPLE 5 NiO in Water

200 ml of deionized water was mixed with 30 grams of NiO powder in a beaker. The mixture was centrifuged and an upper dispersion and a lower dispersion were obtained. The upper layer dispersion was extracted and deposited on the substrate using a 3D printer and a NiO layer was formed. The NiO layer was irradiated using a xenon lamp (10 kW) at a voltage of 400V and a pulse frequency of 10 Hz for a total exposure time of 15,000 ms.

Example 6 sintering results

Fig. 17 is a scanning electron microscope image (side view). Fig. 17 shows an electrolyte (YSZ) 1701 printed and sintered on an electrode (NiO-YSZ) 1702. Scanning electron microscope images show a side view of the sintered construction, which confirms the hermetic contact between the electrolyte and the electrode, the complete densification of the electrolyte and the microstructure of the sintered and porous electrode.

EXAMPLE 7 Fuel cell Stack construction

A 48-volt fuel cell stack has 69 cells with a power output of about 1000 watts. The fuel cells in the stack have dimensions of about 4 cm x 4 cm (length x width) and about 7 cm high. A 48-volt fuel cell stack has 69 cells with a power output of about 5000 watts. The fuel cells in the stack have dimensions of about 8.5 cm x 8.5 cm (length x width) and about 7 cm high.

EXAMPLE 8 channeled electrode/fluid Dispersion Assembly

Figure 18 schematically shows an example of a half cell in an EC reactor. As shown in fig. 18, half cell 1700 includes interconnect 1801. The interconnect 1801 includes a doped lanthanum chromite. The half cell 1800 includes an anode segment 1802 printed onto the interconnect 1801. The anode segment consisted of NiO-YSZ. The anode segment 1802 was sintered using EMR (see example 1). The half cell 1800 includes a filler material deposited between the anode segments 1802. The filling material is polymethyl methacrylate (PMMA). Half cell 1800 includes a protective layer 1804 printed onto a filler material 1803 comprised of YSZ. Additional anode material 1806 is printed to cover anode segment 1802 and protective layer 1804, which is then sintered using EMR. Other anode materials consist of NiO-YSZ. The electrolyte 1805 is printed onto the other anode material 1806 and sintered using EMR. Electrolyte 1805 is YSZ. A barrier layer (not shown) consisting of CGO was further printed onto the electrolyte and sintered using EMR. A cathode layer (not shown) consisting of LSCF was printed onto the CGO barrier layer and sintered. A cathode segment (not shown) consisting of LSCF was printed onto this layer and sintered. The segments form valleys and the filler PMMA is deposited to fill the valleys (not shown). A protective layer consisting of YSZ was printed onto the filler (not shown). The doped lanthanum chromite is printed to cover the protective layer and the cathode segments and then sintered to form another interconnect (not shown). The filler is removed by furnace heating and a channeled electrode is created or a fluid dispersion assembly (not shown) is formed between the electrolyte and the interconnect.

It is to be understood that this disclosure describes exemplary embodiments for implementing different features, structures and functions of the invention. Example embodiments of components, arrangements and configurations are described to simplify the present disclosure; however, these exemplary embodiments are provided as examples only and are not intended to limit the scope of the present invention. Embodiments as provided herein may be combined, unless otherwise specified. Such combinations do not depart from the scope of the present disclosure.

In addition, certain terms are used throughout the description and claims to refer to particular components or steps. As one skilled in the art will appreciate, various entities may represent the same component or method step by different names, and as such, the nomenclature used for the elements described herein is not intended to limit the scope of the invention. Further, the terms and nomenclature used herein are not intended to distinguish between components, features, and/or steps that differ in name but not function.

While the disclosure is susceptible to various modifications and alternative forms, specific embodiments thereof have been shown by way of example in the drawings and the description. It should be understood, however, that the drawings and detailed description thereto are not intended to limit the disclosure to the particular form disclosed, but on the contrary, the intention is to cover all modifications, equivalents and alternatives falling within the spirit and scope of the present disclosure.