阅读说明：本技术 独立式层压件、其制造方法和制作铅碳电池的方法 (Free standing laminate, method of manufacturing the same and method of making a lead carbon battery ) 是由 王巍 布雷特·基尔赫尼 马克·圣·让 于 2021-04-21 设计创作，主要内容包括：提供了独立式层压件、其制造方法和制作铅碳电池的方法。独立式层压件包括隔板和阳极层。阳极层包括导电碳质活性材料,该导电碳质活性材料包括特定量的以下组分：活性炭；粘合剂；和导电填料。阳极层与隔板的第一侧直接物理接触。该独立式层压件对于在各种能量存储装置中使用是特别有用的。(Free standing laminates, methods of making the same, and methods of making lead carbon batteries are provided. The free standing laminate comprises a separator and an anode layer. The anode layer includes an electrically conductive carbonaceous active material including the following components in specific amounts: activated carbon; a binder; and a conductive filler. The anode layer is in direct physical contact with the first side of the separator. The free standing laminate is particularly useful for use in various energy storage devices.)

1. A free standing laminate comprising:

a partition plate; and

an anode layer comprising an electrically conductive carbonaceous active material, the electrically conductive carbonaceous active material comprising:

greater than or equal to 60% by weight of activated carbon;

1 to 40% by weight of a binder; and

0 to 10% by weight of a conductive filler;

wherein the weight percent of each component is based on the total weight of the anode layer; and wherein the anode layer is in direct physical contact with the first side of the separator.

2. The free standing laminate of claim 1, wherein the separator comprises an acid resistant perforated sheet having a thickness of 3 millimeters or less and a porosity of greater than 30%.

3. The free standing laminate of claim 1 or 2, wherein the separator comprises a water absorbent glass mat, polyvinyl chloride, polyolefin, non-woven fiber glass mat, activated carbon cloth, carbon nanofiber cloth, or carbon nanotube cloth.

4. The free standing laminate of any of claims 1 to 3, wherein the electrically conductive filler is present and comprises at least one of: carbon black, graphite, carbon nanotubes, carbon fibers or graphene.

5. The free standing laminate of any one of claims 1 to 4, wherein the binder comprises poly (vinylidene fluoride), preferably fibrillated poly (vinylidene fluoride), more preferably wherein poly (vinylidene fluoride) comprises a poly (vinylidene fluoride) copolymer or a poly (vinylidene fluoride) copolymer with chlorotrifluoroethylene.

6. The free standing laminate of any of claims 1 to 5, wherein the anode layer comprises: 85 to 99 weight percent of the activated carbon, based on the total weight of the active layer; and 1 to 15 weight percent of the binder based on the total weight of the active layer.

7. The free standing laminate of any of claims 1 to 6, wherein the anode layer has a thickness of 0.5 to 10 millimeters, or 2 to 10 millimeters, or 1.5 to 2.5 millimeters.

8. The free standing laminate of any of claims 1 to 7, wherein the anode layer has a density of 0.5 to 1.0 grams per cubic centimeter.

9. The standalone laminate of any of claims 1 to 8, wherein the anode layer has a porosity of 30 to 75% by volume.

10. The free standing laminate of any of claims 1 to 9, wherein the anode layer further comprises a reinforcing filler.

11. The free standing laminate of claim 10, wherein the reinforcing fillers comprise glass fibers, carbon fibers, polymer fibers, or combinations thereof, preferably glass fibers.

12. A method of making a free standing laminate comprising:

a partition plate; and

an anode layer comprising an electrically conductive carbonaceous active material, the electrically conductive carbonaceous active material comprising:

greater than or equal to 60% by weight of activated carbon;

1 to 40% by weight of a binder; and

0 to 10% by weight of a conductive filler;

wherein the weight percent of each component is based on the total weight of the anode layer; and wherein the anode layer is in direct physical contact with the first side of the separator;

the method comprises the following steps:

applying the anode layer to the first side of the separator.

13. The method of claim 12, wherein the applying comprises:

forming a powder comprising the electrically conductive carbonaceous active material;

applying the powder to the separator; and

calendering is performed to provide the free standing laminate.

14. The method of claim 12, wherein the applying comprises:

applying a flocculating material comprising the electrically conductive carbonaceous active material to the separator; and

calendering is performed to provide the free standing laminate.

15. The method of claim 12, wherein the applying comprises:

forming a powder comprising the electrically conductive carbonaceous active material;

applying the powder to the separator; and

compression molding the powder to the separator to provide the free-standing laminate.

16. The method of any one of claims 12 to 15, further comprising cutting the free standing laminate into a preselected shape.

17. An energy storage device comprising the free standing laminate of any of claims 1 to 11.

18. A method of making a lead-carbon battery, the method comprising:

attaching a lead oxide cathode to the separator of the free standing laminate of any one of claims 1 to 11;

encapsulating the lead oxide cathode adhered to the free-standing laminate in a casing; and

introducing an acid into the housing such that the cathode and the anode are at least partially immersed in the acid.

Technical Field

The present disclosure relates to battery laminates, methods of making laminates, and batteries containing laminates.

Background

Batteries are a common energy source. Generally, a battery includes a negative electrode and a positive electrode. Conventional commercial lead-acid batteries rely on a negative electrode (anode) composed of lead metal and a positive electrode (cathode) composed of lead dioxide, while lead-carbon batteries include an anode containing a carbonaceous material. The electrodes of lead acid batteries or lead carbon batteries are placed in an acidic electrolytic medium. During discharge of the battery, a chemical reaction occurs in which the active positive electrode material is reduced and the active negative electrode material is oxidized. During the reaction, electrons flow from the negative electrode to the positive electrode through the load, and ions in the electrolytic medium flow between the electrodes. In order to prevent direct reaction of the active positive electrode material and the active negative electrode material, the electrodes are usually mechanically and electrically isolated from each other by separators (separators).

It would be advantageous to provide a separator-anode laminate as a single structure that can be easily processed, cut into a desired shape, and adhered to a cathode material for direct use in energy storage device applications, particularly bipolar battery applications.

Disclosure of Invention

A free standing laminate comprising: a partition plate; and an anode layer, and the anode layer includes an electrically conductive carbon active material (electrically conductive carbonaceous active material) including: greater than or equal to 60% by weight of activated carbon; 1 to 40% by weight of a binder; and 0 to 10 weight percent of a conductive filler; wherein the weight percent of each component is based on the total weight of the anode layer; and wherein the anode layer is in direct physical contact with the first side of the separator.

A method of making a free-standing laminate includes applying an anode layer to a first side of a separator.

An energy storage device includes the free-standing laminate.

A method of making a lead-carbon battery comprising: attaching a lead oxide cathode to a separator of a free standing laminate; encapsulating the lead oxide cathode adhered to the free-standing laminate in a casing; and introducing an acid into the housing such that the cathode and the anode are at least partially immersed in the acid.

The above described and other features are exemplified by the following figures and detailed description.

Drawings

The following figures are exemplary aspects in which like elements are numbered alike. The drawings are illustrative embodiments and are not intended to limit devices made in accordance with the present disclosure to the materials, conditions, or process parameters set forth herein.

Fig. 1 is a schematic illustration of a free standing laminate according to one aspect.

Fig. 2 is a schematic illustration of a lead-carbon battery according to one aspect.

Detailed Description

The present inventors have advantageously found that it is possible to prepare free standing laminates comprising a separator and an anode layer. The free standing laminate may be used in various energy storage devices, such as lead carbon batteries. The use of free-standing laminates to produce lead-carbon batteries greatly simplifies the manufacturing process and also advantageously allows the use of existing lead-acid bipolar battery production equipment. The free standing laminate can be easily handled and cut into a desired shape for direct use in an energy storage device.

Accordingly, one aspect of the present disclosure is a free standing laminate. The free standing laminate comprises a separator and an anode layer. As used herein, the term "free standing laminate" refers to a laminate that is not adhered or supported by any other layer (e.g., an underlying substrate). In one aspect, the free standing laminate is a self-supporting laminate that can be mechanically manipulated or moved without the need for a substrate (or other support layer) to be adhered or attached to the laminate. Thus, in one aspect, a free standing laminate of the present disclosure refers to a free standing laminate without any other support layer. In some aspects, the free standing laminate may be comprised of a separator and an anode layer. The anode layer is in direct physical contact with the first side of the separator.

A free standing laminate according to the present disclosure is depicted in fig. 1. The free standing laminate 10 comprises a separator 11 (which may sometimes also be referred to as a separator layer), the separator 11 having an anode layer 12 disposed on the separator, wherein the separator is in direct physical contact with the anode layer.

The separator of the free standing laminate may generally comprise any acid resistant perforated sheet having a thickness of 3 millimeters or less and a porosity of greater than 30%. As used herein, an "acid resistant" sheet is a sheet that is capable of functioning in the presence of a sulfuric acid electrolyte (e.g., an "acid resistant" sheet is a sheet that is capable of being stable in dilute aqueous sulfuric acid solutions having a specific gravity of 1 to 1.4 (as is commonly used in lead acid batteries) at temperatures of-40 ℃ to 80 ℃). For example, the separator may include a water-absorbent glass mat, polyvinyl chloride, polyolefin, non-woven fiber glass mat, activated carbon cloth, carbon nanofiber cloth, carbon nanotube cloth, and the like. In one aspect, the separator may be a non-fibrous separator. Particularly preferred may be materials that can be used in a roll-to-roll process. Exemplary polyolefins may include polyethylene, polypropylene, polytetrafluoroethylene, ethylene-propylene copolymers, and the like. An exemplary separator comprises polyvinyl chloride (PVC) having a volume porosity of 30% to 95%, preferably 70% to 80%, more preferably 75%. Methods for determining the porosity of the separator material are generally known and can be readily determined by one skilled in the art.

In one aspect, the separator can have a thickness of 3 millimeters or less, such as a thickness of 0.005 to 3 millimeters, or 0.005 to 1.5 millimeters, or 0.025 to 0.3 millimeters.

The free standing laminate further comprises an anode layer. The anode layer includes an electrically conductive carbonaceous active material. The conductive carbonaceous active material includes activated carbon, a binder, and optionally a conductive filler.

Activated carbon is electrochemically stable in sulfuric acid. The activated carbon can have a carbon content of greater than or equal to 50 square meters per gram (m)²/g) or greater than or equal to 500m²(ii)/g, or greater than or equal to 1000m²/g、1500m²Per g, or 500m²G to 3000m²Surface area in g. The activated carbon may have a D of 0.1 to 100 microns, or 1 to 50 microns, or 5 to 10 microns, or 15 to 50 microns, or 0.1 to 10 microns by weight₅₀The size of the particles. In one aspect, the activated carbon can be a D having a particle size of 0.01 to 10 microns by weight₅₀Particle size and/or at least 50m²G and preferably greater than 1000m²Particles of BET surface area per g. By weight D₅₀The particle size can be determined by generally known methods, for example, by laser light scattering. The activated carbon may have a multimodal particle size, e.g., at least seven times larger in the first mode than in the second mode. For example, the first mode may have a peak value greater than or equal to 7 microns, or greater than or equal to 35 microns, and the second mode may have a peak value less than or equal to 1 micron, or less than or equal to 5 microns. Exemplary activated carbons may include ELITE-C available from Cargon Carbon (Calgon Carbon) LLC or POWDERED-S available from General Carbon Corporation.

The activated carbon may be present in the anode layer in an amount greater than or equal to 60 weight percent based on the total weight of the anode layer. Within this range, the activated carbon may be present in a weight percent of 85% to 99%, or 90 wt% to 98 wt%, or 90 wt% to 96 wt%.

The conductive carbonaceous active material includes a binder in addition to the activated carbon. The binder may be a fluoropolymer. As used herein, "fluoropolymer" includes homopolymerization of repeat units comprising repeating units derived from a fluorinated alpha-olefin monomer (i.e., an alpha-olefin monomer including at least one fluorine atom substituent) and a non-fluorinated ethylenically unsaturated monomer optionally reacted with the fluorinated alpha-olefin monomerAnd copolymers. Exemplary fluorinated alpha-olefin monomers include CF₂＝CF₂、CHF＝CF₂、CH₂＝CF₂、CHCl＝CHF、CClF＝CF₂、CCl₂＝CF₂、CClF＝CClF、CHF＝CCl₂、CH₂＝CClF、CC1₂＝CClF、CF₃CF＝CF₂、CF₃CF＝CHF、CF₃CH＝CF₂、CF₃CH＝CH₂、CHF₂CHF, and CF₃CH＝CH₂And perfluoro (C)_2-8Alkyl) vinyl ethers such as perfluoromethyl vinyl ether, perfluoropropyl vinyl ether and perfluorooctyl vinyl ether. The fluorinated alpha-olefin monomer may include at least one of: tetrafluoroethylene (CF)₂＝CF₂) Chlorotrifluoroethylene (CClF ═ CF)₂) (perfluorobutyl) ethylene, vinylidene fluoride (CH)₂＝CF₂) Or hexafluoropropylene (CF)₂＝CFCF₃). Exemplary non-fluorinated monoethylenically unsaturated monomers include ethylene, propylene, butylene, or ethylenically unsaturated aromatic monomers such as styrene or alpha-methyl-styrene. Exemplary fluoropolymers include poly (chlorotrifluoroethylene) (PCTFE), poly (chlorotrifluoroethylene-propylene), poly (ethylene-tetrafluoroethylene) (ETFE), poly (ethylene-chlorotrifluoroethylene) (ECTFE), poly (hexafluoropropylene), poly (tetrafluoroethylene) (PTFE), poly (tetrafluoroethylene-ethylene-propylene), poly (tetrafluoroethylene-hexafluoropropylene) (also known as fluorinated ethylene-propylene copolymer (FEP)), poly (tetrafluoroethylene-propylene) (also known as Fluoroelastomer (FEPM)), poly (tetrafluoroethylene-perfluoropropylene vinyl ether), copolymers having a tetrafluoroethylene backbone and fully fluorinated alkoxy side chains (also known as perfluoroalkoxy Polymers (PFA)), such as poly (tetrafluoroethylene-perfluoropropylene vinyl ether), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), and mixtures thereof, Poly (vinylidene fluoride-chlorotrifluoroethylene), perfluoropolyether, perfluorosulfonic acid, or perfluoropolyoxetane, preferably perfluoroalkoxyalkane polymers, fluorinated ethylene-propylene, or more preferably perfluoroalkoxyalkane polymers.

In one aspect, the fluoropolymer may comprise poly (vinylidene fluoride). The poly (vinylidene fluoride) may includeAt least one of: a poly (vinylidene fluoride) homopolymer or a poly (vinylidene fluoride) copolymer. In one aspect, the binder may comprise fibrillated poly (vinylidene fluoride), preferably wherein the poly (vinylidene fluoride) comprises a poly (vinylidene fluoride) copolymer. The poly (vinylidene fluoride) copolymer may include repeat units derived from at least one of: chlorotrifluoroethylene, tetrafluoroethylene (CF)₂＝CF₂) Chlorotrifluoroethylene (CClF ═ CF)₂) (perfluorobutyl) ethylene, hexafluoropropylene (CF)₂＝CFCF₃) Ethylene, propylene, butylene or ethylenically unsaturated aromatic monomers such as styrene or alpha-methyl-styrene. In one aspect, the poly (vinylidene fluoride) copolymer comprises repeat units derived from chlorotrifluoroethylene. An example of poly (vinylidene fluoride) is KYNAR 761 available from Arkema.

The binder may be present in an amount of 1 to 40 weight percent based on the total weight of the anode layer. Within this range, the binder may be present in an amount of 1 to 20 weight percent, or 1 to 15 weight percent, or 1 to 10 weight percent, or 5 to 10 weight percent.

The electrically conductive carbonaceous active material may optionally include an electrically conductive filler in addition to the activated carbon and the binder. In one aspect, a conductive filler is present. When present, the conductive filler may advantageously provide a beneficial reduction in voltage drop in the anode layer when incorporated into a lead carbon battery structure. This may enable the battery cell to operate at high power with less energy converted to heat, and may also increase battery capacity over a given operating voltage range. The conductive filler may include at least one of: graphite, carbon nanotubes, carbon fibers, graphene, or carbon black. Examples of carbon blacks are SUPER-P from Yiruite (Imersys), VULCAN XC-72 from Cabot Corporation, and SHAWINIGAN BLACK from Chevron Corporation. Examples of carbon nanotubes are those commercially available from Showa Denko k.k. and Bayer (Bayer) AG.

The electrically conductive filler may be present in an amount of 0 to 10 weight percent based on the total weight of the anode layer. Within this range, the conductive filler may be present in an amount of greater than 0 to 10 weight percent, or 1 to 5 weight percent.

The anode layer may optionally include reinforcing fillers. The reinforcing filler may generally comprise any reinforcing filler, preferably a filler having a high aspect ratio (e.g., a filler having an aspect ratio greater than 1:1, or greater than 5:1, or greater than 10:1, or greater than 20:1, or greater than 40: 1). For example, the reinforcing filler may comprise nanofibers or nanoplates. Without wishing to be bound by theory, it is believed that such reinforcing fillers may improve the cohesion or mechanical properties of the composite.

Possible reinforcing fillers may include, for example, mica, clay, feldspar, quartz, quartzite, perlite, diatomaceous earth, aluminium silicates (mullite), synthetic calcium silicates, fused silica, fumed silica, sand, boron nitride powder, boron silicate powder, calcium sulfate, calcium carbonate (e.g. chalk, limestone, marble and synthetic precipitated calcium carbonate) talc (including fibrous talc, modular talc, acicular talc and lamellar talc), wollastonite, hollow or solid glass spheres, silicate spheres, hollow microspheres, aluminosilicates or (atmospheric), kaolin, alumina, boron carbide, iron, nickel or copper, whiskers of silicon carbide, continuous and chopped carbon or glass fibers, molybdenum sulfide, zinc sulfide, barium titanate, barium ferrite, barium sulfate, barite, TiO, perlite, boron carbide, iron, nickel or copper₂Aluminum oxide, magnesium oxide, particulate or fibrous aluminum, bronze, zinc, copper or nickel, glass flake, flaked silicon carbide, flaked aluminum diboride, flaked aluminum, steel flake, natural fillers (such as wood flour, fibrous cellulose, cotton, sisal, jute, starch, lignin, ground nut shells or rice hulls), reinforcing organic fibrous fillers (such as poly (ether ketone), polyimide, polybenzoxazole, poly (phenylene sulfide), polyesters, polyethylene, aromatic polyamides, aromatic polyimides, polyetherimides, polytetrafluoroethylene and poly (vinyl alcohol) and combinations thereof.

In one aspect, the reinforcing filler may preferably be a fibrous reinforcing filler, such as glass fibers, carbon fibers, polymeric fibers, so long as the polymeric fibers are selected such that they are acid resistant high modulus fibers, inorganic fibers such as those derived from blends comprising at least one of aluminum silicates, aluminum oxides, magnesium oxides, calcium sulfate hemihydrate or the like, silica micro or nanotubes, carbon micro or nanotubes, or the like, or a combination of any of the foregoing fibrous fillers. For example, suitable polymer fibers may include poly (ether ketone), polyimide, polybenzoxazole, poly (phenylene sulfide), polyesters, polyethylene, aromatic polyamides, aromatic polyimides, polyetherimides, polytetrafluoroethylene, and poly (vinyl alcohol), and combinations thereof. Preferably, the polymer fibers may comprise aramid fibers (e.g., NOMEX fibers). The reinforcing filler may be coated with a layer of metallic material to facilitate conduction, or may be surface treated with silane to improve adhesion and dispersion with the anode layer. The glass fibers may include E, A, C, ECR, R, S, D, or NE glasses, and the like. The reinforcing filler may be provided in the form of monofilament or multifilament fibres and may be used alone or in combination with other types of fibres, for example by co-weaving or core/sheath, side-by-side, orange type or construction of matrix and fibrils, or by other methods known to those skilled in the art of fibre manufacture. The co-woven structure includes glass fiber-carbon fiber, carbon fiber-aromatic polyimide (aramid) fiber, aromatic polyimide glass fiber, and the like. The fibrous filler may be provided, for example, in the form of: rovings, woven fiber reinforcements, such as 0 to 90 degree fabrics, and the like; non-woven fibrous reinforcements, such as continuous mats (continuous strand mats), chopped strand mats (chopped strand mats), tissue paper, paper and felt, and the like. In one aspect, when present, the reinforcing filler may comprise glass fibers, carbon fibers, polymer fibers, or a combination thereof, preferably glass fibers.

When present, the reinforcing filler may be included in the anode layer in an amount of up to 20 weight percent, for example in an amount of greater than 0 to 20 weight percent, 0.1 to 20 weight percent, based on the total weight of the anode layer.

The anode layer may have a thickness of 0.01 mm to 10 mm, or 0.1 mm to 8 mm. The anode layer may have an increased thickness of greater than or equal to 0.5 mm, or 0.5 mm to 10 mm, or 2 mm to 10 mm, or 1 mm to 5 mm, or 1.5 mm to 2.5 mm, or 2.5 mm to 5 mm. The anode layer can have 0.5 grams per cubic centimeter to 1.0 grams per cubic centimeter (g/cm)³) The density of (c). The anode layer may have a porosity of 30 to 75 volume percent, or 40 to 75 volume percent, or 50 to 75 volume percent, or 40 to 70 volume percent, based on the total volume of the active layer.

The free standing laminate may comprise: a partition plate; and an anode layer including an electrically conductive carbonaceous active material, the electrically conductive carbonaceous active material including: greater than or equal to 60% by weight of activated carbon; 1 to 40% by weight of a binder; and 0 to 10 weight percent of a conductive filler; wherein the weight percent of each component is based on the total weight of the anode layer; and wherein the anode layer is in direct physical contact with the first side of the separator. The separator may comprise an acid-resistant perforated sheet having a thickness of 3 mm or less and a porosity of greater than 30%. The separator may include a water-absorbent glass mat, polyvinyl chloride, polyolefin, non-woven fiber glass mat, activated carbon cloth, carbon nanofiber cloth, carbon nanotube cloth. The electrically conductive filler may be present in the electrically conductive carbonaceous active material, and may include at least one of: carbon black, graphite, carbon nanotubes, carbon fibers or graphene. The binder may comprise poly (vinylidene fluoride), preferably fibrillated poly (vinylidene fluoride), more preferably wherein the poly (vinylidene fluoride) comprises a poly (vinylidene fluoride) copolymer or a poly (vinylidene fluoride) copolymer with chlorotrifluoroethylene. The anode layer may include 85 to 99 wt% of activated carbon based on the total weight of the active layer and 1 to 15 wt% of a binder based on the total weight of the active layer. The anode layer may have a thickness of 0.5 mm to 10 mm, or 2 mm to 10 mm, or 1.5 mm to 2.5 mm. The anode layer may have a density of 0.5 grams per cubic centimeter to 1.0 grams per cubic centimeter. The anode layer may have a porosity of 30 to 75 volume percent. The anode layer may also include reinforcing fillers. The reinforcing filler may comprise glass fibers, carbon fibers, polymer fibers or a combination thereof, preferably glass fibers.

The free standing laminate may be made by a process comprising applying an anode layer to a first side of a separator. Application of the anode layer to the separator can be accomplished by various methods including calendering (calendaring), papermaking processes, and compression molding (compression molding). For example, in one aspect, the method comprises: the method includes forming a powder composition including an electrically conductive carbonaceous active material, applying the powder composition to a first side of a separator, and calendering the combination of the powder composition and the separator to form a free-standing laminate including an anode layer and a separator in direct physical contact. In one aspect, the method comprises: the method includes applying a flocculated material including an electrically conductive carbonaceous active material to a separator (e.g., by discharging the flocculated material onto the separator and then drying), and calendering the dried combination of flocculated material and separator to form a free standing laminate including an anode layer and separator in direct physical contact. Calendering may be performed, for example, using a pressure of 0.1MPa to 1.5MPa and a temperature of 20 ℃ to 200 ℃ to provide a laminate. In one aspect, the method comprises: the method includes forming a powder composition including an electrically conductive carbonaceous active material, applying the powder composition to a first side of a separator, and compression molding the powder to the separator to provide a free-standing laminate. Compression molding may be heated, for example, at a temperature of 25 ℃ to 80 ℃.

The method of making a free-standing laminate may further comprise cutting the laminate into a preselected shape, such as by die-cutting the laminate. For example, the free standing laminate may be die cut into a preselected shape, which may be, but is not limited to, rectangular, square, circular, oval, disc-shaped, and the like. In one aspect, the free standing laminate can be rectangular and can be complementary to the shape of a positive electrode used in a battery, which can also be generally rectangular in shape.

Powder compositions comprising electrically conductive carbonaceous active materials for making the anode layer can be made, for example, by the methods described in U.S. patent application nos. 16/404,858 and 16/675,408, each of which is incorporated herein by reference in its entirety.

In a particularly advantageous feature, the use of free-standing laminates may provide an improved method of making lead-carbon batteries. Accordingly, one aspect of the present disclosure is a method of making a lead-carbon battery. The method includes attaching a lead oxide cathode to a second side of the separator (i.e., the side opposite the anode layer) of the free standing laminate. Advantageously, because the anode layer is provided in the form of a laminate with a separator, no additional attachment step (i.e. a step of attaching the anode layer to the separator) is required when the laminate is used. Furthermore, the use of the laminate of the present disclosure enables the use of existing methods as these are associated with lead acid batteries. Thus, the free standing laminate provides significant commercial advantages to a process for making a lead carbon battery.

The method also includes encapsulating the combination of lead oxide cathodes adhered to the free-standing laminate in a housing. An acid is introduced into the housing such that the cathode and anode are at least partially immersed in the acidic medium. The acidic medium may comprise, for example, sulfuric acid, preferably liquid sulfuric acid. The medium may include a gel electrolyte including a thickener and an aqueous sulfuric acid solution in an amount sufficient to cause the electrolyte to become a gel. The gel electrolyte may comprise an alkaline earth metal (e.g., a silicate, sulfate, or phosphate of calcium or strontium). The anode, cathode and separator may be in direct physical contact with the medium. The assemblies described herein may be fabricated by methods such as lamination, printing, and/or roll-to-roll processes, preferably roll-to-roll processes.

Accordingly, the present disclosure advantageously provides an improved method of manufacturing a lead carbon battery by using a free standing laminate comprising an anode layer and a separator. The free standing laminate can be easily handled and cut to a desired shape as needed, and also simplifies the process of manufacturing the battery. Thus, the present disclosure provides significant improvements.

The present disclosure also encompasses the following aspects.

Aspect 1: a free standing laminate comprising: a partition plate; and an anode layer comprising an electrically conductive carbonaceous active material, the electrically conductive carbonaceous active material comprising: greater than or equal to 60% by weight of activated carbon; 1 to 40% by weight of a binder; and 0 to 10 weight percent of a conductive filler; wherein the weight percent of each component is based on the total weight of the anode layer; and wherein the anode layer is in direct physical contact with the first side of the separator.

Aspect 2: the free standing laminate of aspect 1, wherein the separator comprises an acid resistant perforated sheet having a thickness of 3 millimeters or less and a porosity of greater than 30%.

Aspect 3: the free-standing laminate of aspect 1 or aspect 2, wherein the separator comprises a water-absorbent glass mat, polyvinyl chloride, polyolefin, non-woven fiber glass mat, activated carbon cloth, carbon nanofiber cloth, or carbon nanotube cloth.

Aspect 4: the free standing laminate of any of aspects 1 to 3, wherein the electrically conductive filler is present and comprises at least one of: carbon black, graphite, carbon nanotubes, carbon fibers or graphene.

Aspect 5: the free standing laminate of any of aspects 1 to 4, wherein the binder comprises poly (vinylidene fluoride), preferably fibrillated poly (vinylidene fluoride), more preferably wherein poly (vinylidene fluoride) comprises a poly (vinylidene fluoride) copolymer or a poly (vinylidene fluoride) copolymer with chlorotrifluoroethylene.

Aspect 6: the free standing laminate of any of aspects 1 to 5, wherein the anode layer comprises 85 to 99 weight percent of the activated carbon based on the total weight of the active layer and 1 to 15 weight percent of the binder based on the total weight of the active layer.

Aspect 7: the free-standing laminate of any of aspects 1 to 6, wherein the anode layer has a thickness of 0.5 to 10 millimeters, or 2 to 10 millimeters, or 1.5 to 2.5 millimeters.

Aspect 8: the free standing laminate of any of aspects 1 to 7, wherein the anode layer has a density of 0.5 to 1.0 grams per cubic centimeter.

Aspect 9: the free standing laminate of any of aspects 1 to 8, wherein the anode layer has a porosity of 30 to 75 volume percent.

Aspect 10: the free standing laminate of any of aspects 1 to 9, wherein the anode layer further comprises a reinforcing filler.

Aspect 11: the free standing laminate of aspect 10, wherein the reinforcing filler comprises glass fibers, carbon fibers, polymer fibers, or a combination thereof, preferably glass fibers.

Aspect 12: a method of making a free-standing laminate, the free-standing laminate comprising a separator and an anode layer, the anode layer comprising an electrically conductive carbonaceous active material, the electrically conductive carbonaceous active material comprising: greater than or equal to 60% by weight of activated carbon; 1 to 40% by weight of a binder; and 0 to 10 weight percent of a conductive filler; wherein the weight percent of each component is based on the total weight of the anode layer; and wherein the anode layer is in direct physical contact with the first side of the separator; the method includes applying the anode layer to the first side of the separator.

Aspect 13: the method of aspect 12, wherein the applying comprises forming a powder comprising the electrically conductive carbonaceous active material; applying the powder to the separator; and calendering to provide the free standing laminate.

Aspect 14: the method of aspect 12, wherein the applying comprises applying a flocculating material comprising the electrically conductive carbonaceous active material to the separator; and calendering to provide the free standing laminate.

Aspect 15: the method of aspect 12, wherein the applying comprises forming a powder comprising the electrically conductive carbonaceous active material; applying the powder to the separator; and compression molding the powder to the separator to provide the free-standing laminate.

Aspect 16: the method of any of aspects 12-15, further comprising cutting the free standing laminate into a preselected shape.

Aspect 17: an energy storage device comprising the free standing laminate of any one of aspects 1 to 11.

Aspect 18: a method of making a lead-carbon battery, the method comprising: attaching a lead oxide cathode to the separator of the free standing laminate of any one of aspects 1 to 11; encapsulating a lead oxide cathode adhered to the free-standing laminate in a casing; and introducing an acid into the housing such that the cathode and the anode are at least partially immersed in the acid.

The compositions, methods, and articles of manufacture may alternatively comprise, consist of, or consist essentially of any suitable material, step, or component disclosed herein. The compositions, methods, and articles of manufacture may additionally or alternatively be formulated to be free or substantially free of any material(s), step(s), or component(s) that is not necessary to the function or purpose of the composition, method, and article.

All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. "composition" includes blends, mixtures, alloys, reaction products, and the like. The terms "first," "second," and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms "a", "an" and "the" do not denote a limitation of quantity, and should be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Unless expressly stated otherwise, "or" means "and/or. Throughout the specification, references to "some aspects," "an aspect," and the like, mean that a particular element described in connection with the aspect is included in at least one aspect described herein, and may or may not be present in other aspects. The term "a combination thereof, as used herein, includes one or more of the enumerated elements, and is open-ended, allowing for the presence of one or more similar elements not enumerated. Further, it should be understood that the described elements may be combined in any suitable manner in the various aspects.

When an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" or "directly in physical contact with" another element, there are no intervening elements present.

Unless otherwise indicated herein, all test standards are the most recent standards in effect by the date of filing of the present application or, if priority is required, by the date of filing of the earliest priority application in which the test standard occurs.

Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term in the present application takes precedence over the conflicting term in the incorporated reference.

While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications, variations, improvements, and substantial equivalents.