阅读说明：本技术 用于锂硫电池的碳气凝胶基阴极 (Carbon aerogel-based cathode for lithium sulfur battery ) 是由 尼古拉斯·扎菲罗普洛斯 乔治·古尔德 于 2020-03-22 设计创作，主要内容包括：本发明涉及纳米多孔碳基支架或结构,并且具体地涉及碳气凝胶及它们的制造和其用途。实施方式包括在锂-硫电池内的硫掺杂的阴极材料,其中阴极无集流体并且由不含粘合剂的整体聚酰亚胺衍生的碳气凝胶形成。碳气凝胶包括围绕元素硫并在转化为硫化锂期间适应硫的膨胀的孔。阴极和下面的碳气凝胶为在锂-硫电池内使用提供了最佳性能。(The present invention relates to nanoporous carbon-based scaffolds or structures, and in particular to carbon aerogels and their manufacture and use. Embodiments include a sulfur-doped cathode material within a lithium-sulfur battery, wherein the cathode is devoid of a current collector and is formed from a binder-free monolithic polyimide-derived carbon aerogel. Carbon aerogels include pores that surround elemental sulfur and accommodate expansion of the sulfur during conversion to lithium sulfide. The cathode and the underlying carbon aerogel provide the best performance for use in a lithium-sulfur battery.)

1. A sulfur-doped nanoporous carbon material comprising a pore structure comprising a fibrous morphology and surrounding an array of pores of elemental sulfur.

2. A sulfur-doped nanoporous carbon material comprising:

a pore structure comprising a fibrous morphology;

a Young's modulus of at least about 0.2 GPa; and

a density between about 0.10g/cc and about 1.5 g/cc.

3. A sulfur-doped nanoporous carbon material comprising:

a pore structure comprising a fibrous morphology;

a conductivity of at least about 1S/cm; and

a density between about 0.10g/cc and about 1.5 g/cc.

4. The nanoporous carbon material of claim 1 and/or claim 2, wherein the carbon material has an electrical conductivity of at least about 1S/cm.

5. The nanoporous carbon material of claim 1 and/or claim 3, wherein the carbon material has a Young's modulus of at least about 0.2 GPa.

6. The nanoporous carbon material according to any one or more of claims 1 to 5, wherein the nanoporous carbon material comprises a carbon aerogel.

7. The nanoporous carbon material according to claim 6, wherein the carbon material comprises a polyimide-derived carbon aerogel.

8. The nanoporous carbon material of claim 6 and/or claim 7, wherein the carbon aerogel is in monolithic or powder form.

9. The nanoporous carbon material of claim 8, wherein the monolithic carbon aerogel is substantially or completely free of binder.

10. The nanoporous carbon material of claim 6 and/or claim 7, wherein the monolithic carbon aerogel has a thickness between about 10 μ ι η and about 1000 μ ι η.

11. The nanoporous carbon material according to any one or more of claims 1 to 10, wherein the pore structure is characterized by pores surrounding sulfur.

12. A nanoporous carbon material according to claim 11, wherein the pores form an interconnected structure around the sulphur, characterized in that there are a plurality of connection points between the sulphur and the pore walls of each pore in which the sulphur is enclosed.

13. The nanoporous carbon material according to any one or more of claims 1 to 12, wherein the carbon material is doped with between about 5% and 90% sulphur by weight of the carbon material.

14. The nanoporous carbon material of any one or more of claims 1 to 13, wherein the carbon material has a pore volume of at least 0.3 cc/g.

15. The nanoporous carbon material according to any one or more of claims 1 to 14, wherein the carbon material has a porosity between about 10% and about 90%.

16. The nanoporous carbon material according to any one or more of claims 1 to 15, wherein the carbon material has a capacity of between about 800mAh/g and about 1700 mAh/g.

17. The nanoporous carbon material according to any one or more of claims 1 to 16, wherein the pore structure comprises a full width at half maximum of about 50nm or less.

18. The nanoporous carbon material according to any one or more of claims 1 to 17, wherein the pore structure comprises a pore size at a maximum peak of the distribution of about 100nm or less.

19. The nanoporous carbon material according to any one or more of claims 1 to 18, wherein the fibrous morphology of the nanoporous carbon material comprises an average strut width of about 2 to 10 nm.

20. A sulfur-containing, monolithic polyimide-derived carbon aerogel composite formed from a nanoporous carbon material, wherein the composite is free of binder and wherein elemental sulfur is entrapped within pores of the monolithic polyimide-derived carbon aerogel composite.

21. A current collector-free, binder-free, interconnected cathode material for a lithium sulfur battery comprising an open-celled, monolithic, polyimide-derived nanoporous carbon aerogel having a fibrous network and an array of pores; and elemental sulfur surrounded by the array of pores.

22. An electrode comprising a nanoporous carbon material according to any one or more of the preceding claims 1 to 20.

23. The electrode of claim 22, wherein the electrode is a cathode.

24. The electrode of claim 23, wherein the cathode is free of significant current collectors.

25. An electrochemical cell comprising a nanoporous carbon material according to any one or more of the preceding claims 1 to 20.

26. An electrochemical cell comprising an electrode according to any one or more of claims 22 to 24.

27. An energy storage device comprising a nanoporous carbon material according to any one or more of the preceding claims 1 to 20.

28. An energy storage device comprising an electrochemical cell according to claim 25 and/or claim 26.

29. The energy storage device of any one of claims 27 and 28, wherein the energy storage device is a battery.

30. The energy storage device of claim 29, wherein the battery is a lithium sulfur battery.

31. A method of forming a continuous porous carbon-sulfur composite, the method comprising:

providing a polyimide precursor;

chemically or thermally imidizing the polyimide precursor;

drying the imidized mixture to produce a continuous porous polyimide;

pyrolyzing the porous polyimide to produce a continuous porous carbon; and

sulfur is incorporated onto or within the continuous porous carbon to produce a continuous porous sulfur composite having greater than 0% and less than about 95% sulfur by weight and having a porosity of between about 10% and about 90%.

32. The method of claim 31, wherein the porous carbon sulfur composite is monolithic.

33. The method of claim 31, wherein the porous carbon sulfur composite is free-standing.

34. The method of claim 31, wherein the porous carbon sulfur composite is prepared on a substrate.

35. The method of any one or more of claims 31 to 34, wherein the porous carbon-sulfur composite is reinforced with a non-woven material.

36. The method of any one or more of claims 31 to 34, wherein the porous carbon-sulfur composite is reinforced with a braided material.

37. The method of any one or more of claims 31 or 34-36, wherein the porous carbon-sulfur composite is micronized to form a powder.

38. The method of any one or more of claims 31 to 37, wherein a polyimide wet gel composite is dried using subcritical carbon dioxide and/or supercritical carbon dioxide to form the porous polyimide.

39. The method of any one or more of claims 31 to 38, wherein the composite comprises an aerogel.

40. The method of any one or more of claims 31 to 39, wherein the maximum pyrolysis temperature is between about 750 ℃ and 1600 ℃.

41. The method of claim 40, wherein the porous carbon sulfur composite is graphitized at up to about 3000 ℃.

42. The method of any one or more of claims 31 to 39, wherein the porous polyimide is compressed, preferably uniaxially compressed, to increase density.

43. The method of claim 42, wherein the porous polyimide is compressed to a strain of up to about 95%.

44. The method of claim 42, wherein the porous carbon sulfur composite has an adjustable density of up to about 1.5g/cc based on the amount compressed.

45. The method of any one or more of claims 31 to 44, wherein the sulfur is incorporated onto or into the continuous porous carbon by melt injection.

46. The method according to any one or more of claims 31 to 45, wherein sulfur is incorporated onto or into the continuous porous carbon by surface treating the continuous porous carbon with chemical functional groups having affinity for sulfur and polysulfides.

47. The method of any one or more of claims 31 to 46, wherein the polyimide precursor comprises a diamine and a dianhydride in a suitable solvent.

48. The method of claim 47, wherein at least one of the diamine and the dianhydride comprises an aromatic group.

49. The method of claim 47 and/or claim 48, wherein the suitable solvent comprises a polar aprotic solvent.

Technical Field

The present invention generally relates to nanoporous carbon-based materials. More particularly, it relates to carbon aerogels suitable for use in environments involving electrochemical reactions, for example as electrode materials in lithium sulfur batteries.

Background

Aerogels are solid materials comprising a highly porous network of micropores and mesopores. Depending on the precursor material used and the processing performed, the pores of the aerogel will typically comprise more than 90% by volume when the aerogel has a density of about 0.05 g/cc. Aerogels are typically prepared by removing the solvent from the gel (the solid network containing its solvent) in such a way that the capillary forces of the gel at its surface can minimize or eliminate shrinkage of the gel. Methods of solvent removal include, but are not limited to, supercritical drying (or drying using supercritical fluids such that the low surface tension of the supercritical fluid exchanges with the transient solvent within the gel), solvent exchange with supercritical fluids, solvent exchange with fluids that subsequently transition to a supercritical state, subcritical or near-critical drying, and sublimation of the frozen solvent during freeze-drying, see, for example, PCT patent application publication No. WO2016127084a 1. It is noted that upon drying at ambient conditions, gel shrinkage may occur as the solvent evaporates and a xerogel may be formed. Thus, the preparation of aerogels by a sol-gel process or other polymerization processes is generally carried out in a series of steps: dissolution of a solute in a solvent, formation of a sol/solution/mixture, formation of a gel (which may involve additional cross-linking), and removal of the solvent by supercritical drying techniques or any other method that removes the solvent from the gel without causing pore collapse.

Aerogels can be formed from inorganic and/or organic materials. When formed from organic materials, such as phenols, Resorcinol Formaldehyde (RF), Phloroglucinol Furfural (PF), Polyacrylonitrile (PAN), Polyimides (PI), Polyurethanes (PU), polybutadiene, polydicyclopentadiene, and precursors or polymeric derivatives thereof, for example-the aerogel can be carbonized (e.g., by pyrolysis) to form carbon aerogels, which can have different or overlapping properties (e.g., pore volume, pore size distribution, morphology, etc.) with respect to each other, depending on the precursor materials and methods used. In all cases, however, there are certain drawbacks based on materials and applications, such as low pore volume, broad pore size distribution, low mechanical strength, etc. Recently, efforts have been made to develop and characterize carbon aerogels as electrode materials with improved performance for energy storage devices, such as Lithium Sulfur Batteries (LSBs).

LSBs have become an increasingly attractive alternative to electrochemical energy storage forms and Lithium Ion Batteries (LIBs) because of their potential to achieve high reversible energy storage and high cycling at low cost. LSB is a type of rechargeable battery in which lithium ions move from the anode to the cathode during discharge and from the cathode to the anode during charge. Typically, for the LSB system, the anode is formed of lithium metal and the cathode is formed of a carbon-sulfur composite, with elemental sulfur and polysulfides located in the porous structure of the carbon, and a polymeric binder is used to maintain the composite integrity. Sulfur is an abundant element on earth and when used as a cathode in the LSB it is known to have a very high theoretical specific capacity (about 1672mAh/g, an order of magnitude greater than the metal oxide cathode materials commonly used in LIB).

Despite the opportunity to achieve ultra-high energy densities with LSBs, conventional LSBs have not gained as widespread commercial adoption as their LIB counterparts, which are characterized by higher cycle life but lower energy density. The conventional LSB faces two significant challenges. The first challenge is the high resistivity of sulfur and the formation of Li-S species during discharge. This formation of lithium sulfide (Li)₂S) with up to 80% volume expansion. Another major challenge is the solubility or dissolution of the intermediate lithium polysulfides into the electrolyte over multiple charge-discharge cycles, ultimately resulting in a reduction in the available sulfur for the necessary conversion reactions during discharge.

Accordingly, there is a need for improved nanoporous carbon materials that include a functional morphology and an optimal pore structure in which optimal sulfur loading can be achieved and in which sulfur is trapped in a uniform-sized environment (e.g., narrow pore size distribution). However, it will not be obvious to one of ordinary skill in the art of the present invention how to overcome the disadvantages of the prior art in view of the technology considered as a whole when making the present invention.

While certain aspects of conventional technology have been discussed to facilitate disclosure of the present invention, applicants in no way deny these technical aspects, and contemplate that the claimed invention may include one or more of the conventional technical aspects discussed herein, particularly in combination with the innovative aspects described herein.

The present invention may address one or more of the problems and deficiencies in the art discussed above. However, it is contemplated that the present invention may prove useful in addressing other problems and deficiencies in a number of technical areas. Accordingly, the claimed invention should not necessarily be construed as limited to addressing any of the specific problems or deficiencies discussed herein.

In this specification, when a document, act, or item of knowledge is referred to or discussed, this reference or discussion is not an admission that the document, act, or item of knowledge or any combination thereof was at the priority date, publicly available, publicly known, part of the common general knowledge, or otherwise forms part of the prior art under the applicable legal provisions; or known to be associated with an attempt to solve any problem with which this specification is concerned.

Disclosure of Invention

The long but heretofore unmet need for improved nanoporous carbon materials is now met by a new, useful and unobvious invention.

A first general aspect relates to sulfur-doped nanoporous carbon materials. The sulfur-doped nanoporous carbon material comprises a pore structure comprising a fibrous morphology and an array of pores surrounding elemental sulfur.

A second general aspect relates to a sulfur-doped nanoporous carbon material comprising a pore structure having a fibrous morphology, a young's modulus of at least about 0.2 GPa; and a density between about 0.10g/cc and about 1.5 g/cc. In an exemplary embodiment, the nanoporous carbon material has an electrical conductivity of at least about 1S/cm.

A third general aspect relates to a sulfur-doped nanoporous carbon material comprising a pore structure having a fibrous morphology, an electrical conductivity of at least about 1S/cm, and a density between about 0.10g/cc and about 1.5 g/cc. In an exemplary embodiment, the nanoporous carbon material has a young's modulus of at least about 0.2 GPa.

In an exemplary embodiment, the nanoporous carbon material comprises a carbon aerogel. For example, the carbon material includes polyimide-derived carbon aerogel. In certain embodiments, the carbon aerogel may be monolithic (monolith form) or in powder form (powder form). In monolithic embodiments, the carbon aerogel is substantially or completely free of binder. For example, the monolithic carbon may have a thickness between about 10 μm and about 1000 μm.

In exemplary embodiments, the pore structure of the nanoporous carbon material is characterized by pores surrounding the sulfur. For example, the pores may form an interconnected structure around sulfur, characterized by a plurality of points of attachment between the sulfur and the walls of the pores of each pore in which the sulfur is surrounded. The carbon material may be doped with about 5% to about 90% sulfur by weight of the carbon material.

In any embodiment, the carbon material may have a pore volume of at least 0.3 cc/g. In any embodiment, the carbon material may have a porosity between about 10% and about 90%. In any embodiment, the carbon material may have a capacity of between about 800mAh/g and about 1700 mAh/g. In any embodiment, the pore structure of the carbon material comprises a full width at half maximum (full width at half max) of about 50nm or less. In any embodiment, the pore structure comprises a pore size at max peak from distribution at a maximum peak of the distribution of about 100nm or less. In any embodiment, the fibrous morphology of the nanoporous carbon material may comprise an average strut width of about 2 to 10 nm.

A further general aspect relates to a sulfur-containing, monolithic polyimide-derived carbon aerogel composite formed from a nanoporous carbon material, wherein the composite is free of binder and wherein elemental sulfur is encased within pores of the monolithic polyimide-derived carbon aerogel composite.

Another general aspect relates to a current collector-free, binder-free, interconnected cathode material for a lithium sulfur battery comprising an open-celled, monolithic, polyimide-derived nanoporous carbon aerogel having a fibrous network and an array of pores; and elemental sulfur surrounded by an array of pores.

Exemplary embodiments include electrodes comprising the nanoporous carbon materials of any of the other embodiments. For example, the electrode may be a cathode. The cathode may not have a distinct current collector. Further exemplary embodiments include electrochemical cells or energy storage devices comprising the nanoporous carbon material or electrode of any of the other embodiments. For example, the energy storage device may be a battery, such as a lithium sulfur battery.

A further general aspect relates to a method of forming a continuous porous carbon-sulfur composite. In an exemplary embodiment, the method includes providing a polyimide precursor, imidizing the polyimide precursor chemically or thermally, drying the imidized mixture to produce a continuous porous polyimide, pyrolyzing the porous polyimide to produce continuous porous carbon, and incorporating sulfur onto or into the continuous porous carbon to produce a continuous porous sulfur composite greater than 0% and less than about 95% sulfur by weight and having a porosity of about 10% to about 90%.

In an exemplary embodiment, the polyimide precursor includes a diamine and a dianhydride in a suitable solvent. For example, suitable solvents may include polar aprotic solvents. In some embodiments, at least one of the diamine and the dianhydride may include an aromatic group.

In an exemplary embodiment, the porous carbon sulfur composite may be monolithic. For example, the porous carbon sulfur composite may be a free standing structure. The porous carbon-sulfur composite material can be prepared on a substrate. In some embodiments, the porous carbon sulfur composite is reinforced with a non-woven material, such as a woven material. In some embodiments, the porous carbon sulfur composite may be micronized to form a powder.

In exemplary embodiments, the polyimide wet gel composite may be dried using subcritical carbon dioxide and/or supercritical carbon dioxide to form a porous polyimide. In some embodiments, the composite material may comprise an aerogel.

In exemplary embodiments, the maximum pyrolysis temperature is between about 750 ℃ and about 1600 ℃.

In some embodiments, the porous carbon sulfur composite is graphitized at up to about 3000 ℃. In some embodiments, the porous polyimide is compressed, preferably unidirectionally, to increase the density. For example, the porous polyimide may be compressed to a strain of up to about 95%. The porous carbon sulfur composite may have a density that can be adjusted up to about 1.5g/cc based on the amount of compression.

In exemplary embodiments, sulfur may be incorporated onto or into the continuous porous carbon by melt injection. In some embodiments, sulfur is incorporated onto or into the continuous porous carbon by surface treating the continuous porous carbon with chemical functional groups having affinity for sulfur and polysulfides.

Drawings

For a more complete understanding of the present invention, reference should be made to the following detailed description, taken in conjunction with the accompanying drawings, in which:

fig. 1 is a flow diagram illustrating the formation of sulfur-doped carbon aerogels for use in energy storage applications, such as lithium sulfur batteries.

Fig. 2A is a schematic illustration of a carbon aerogel optionally disposed on a substrate.

Fig. 2B is a schematic illustration of a carbon aerogel, optionally disposed on a substrate, wherein the electrochemically active species (e.g., elemental sulfur) has formed a conformal coating on the carbon surface.

Fig. 2C is a schematic illustration of a carbon aerogel, optionally disposed on a substrate, wherein electrochemically active species (e.g., elemental sulfur) form nanoparticles within and are connected to the aerogel network.

Fig. 3A is an SEM image of a sulfur-doped carbon material according to embodiments disclosed herein.

Fig. 3B is an SEM image of a sulfur-doped carbon material according to embodiments disclosed herein.

Fig. 4A shows half-cell capacity at 0.1C for the first cycle using an electrode made from a sulfur-doped carbon material prepared from a polyimide gel prepared at a target density of 0.05 g/cc.

Fig. 4B shows half-cell capacity for the first cycle at 1C using an electrode made from sulfur-doped carbon material prepared from polyimide gel prepared at a target density of 0.05 g/cc.

Fig. 5A shows half-cell capacity at 0.1C for the first cycle using an electrode made from sulfur-doped carbon material prepared from polyimide gel prepared at a target density of 0.125 g/cc.

Fig. 5B shows half-cell capacity for the first cycle at 1C using an electrode made from sulfur-doped carbon material prepared from polyimide gel prepared at a target density of 0.125 g/cc.

Fig. 6 shows half-cell cycle performance of an electrode made using a sulfur-doped carbon material prepared from a polyimide gel prepared at a target density of 0.05 g/cc.

Fig. 7 shows half-cell cycle performance of an electrode made using a sulfur-doped carbon material prepared from a polyimide gel prepared at a target density of 0.125 g/cc.

Detailed Description

In the following detailed description of the present invention, reference is made to the accompanying drawings that form a part hereof, and in which is shown by way of illustration specific embodiments in which the invention may be practiced. It is to be understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the present invention.

As used in this specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. As used in this specification and the appended claims, the term "or" is generally employed in its sense including "and/or" unless the context clearly dictates otherwise.

As used herein, "about" means about or nearly, and in the context of the stated value or range, means ± 15% of the value. In one embodiment, the term "about" may include conventional rounding according to the significant figures of the numerical values. In addition, the phrase "about 'x' to 'y'" includes "about 'x' to about 'y'".

In the context of the present disclosure, the term "aerogel" or "aerogel material" refers to a gel comprising a framework of interconnected structures, having a corresponding network of interconnected pores integrated within the framework, and containing a gas, such as air, as the dispersed interstitial medium; and characterized in that the aerogel has the following physical and structural characteristics (tested according to nitrogen porosimetry): (a) an average pore size in the range of about 2nm to about 100 nm; (b) a porosity of at least 80% or more, and (c) a surface area of about 20m²(ii) a ratio of/g or more. It is understood that inclusion of additives, such as reinforcing materials or electrochemically active species, can reduce the porosity of the resulting aerogel composite. Densification may also reduce the porosity of the resulting aerogel composite. This will become clearer as the present description continues.

Accordingly, aerogel materials of the present disclosure include any aerogel or other open-celled compound that satisfies the defined elements set forth in the preceding paragraphs, including compounds that may be otherwise classified as xerogels, crystal gels, ambigels, microporous materials, and the like.

In the context of the present disclosure, the term "framework" or "framework structure" refers to a network of interconnected oligomers, polymers or colloidal particles that form a solid structure of a gel or aerogel. The polymers or particles that make up the framework structure typically have a diameter of about 100 angstroms. However, the framework structures of the present disclosure may also include a network of interconnected oligomer, polymer or colloidal particles of all diameter sizes that form a solid structure in a gel or aerogel.

In the context of the present disclosure, the term "aerogel composition" refers to any composite material that includes aerogel material as a component of the composite material. Examples of aerogel compositions include, but are not limited to, fiber reinforced aerogel composites; aerogel composites comprising additive elements such as opacifiers and electrochemically active species; an aerogel foam composite; an aerogel polymer composite; and composites, such as adhesives, resins, cements, foams, polymers, or similar solid materials, that incorporate aerogel particles, granules, beads, or powders into the solid or semi-solid material.

In the context of the present disclosure, the term "reinforced aerogel composition" refers to an aerogel composition that includes a reinforcing phase within the aerogel material that is not part of the aerogel framework or that can be modified in a manner that is covalently bonded to the aerogel framework. The reinforcing phase can be any material that provides added flexibility, elasticity, conformability, or structural stability to the aerogel material. Examples of well-known reinforcing materials include, but are not limited to, open cell foam reinforcements, closed cell foam reinforcements, open cell films, honeycomb reinforcements, polymer reinforcements, and fiber reinforcements, such as discrete fibers, woven materials, non-woven materials, batts, nets, mats, and felts. Furthermore, the reinforcing agent may be combined with one or more other reinforcing materials and may be continuously oriented throughout or in a limited preferred portion of the composition. In other embodiments, if the aerogel material and/or aerogel frame itself is structurally stable (i.e., self-sustaining), then no reinforcing phase may be used at all. This self-sustaining nature of certain carbon aerogels will become clearer as the present description continues.

In the context of the present disclosure, the term "wet gel" refers to a gel in which the mobile interstitial phase within the network of interconnected pores consists essentially of a liquid phase, such as a conventional solvent, a liquefied gas, such as liquid carbon dioxide, or a combination thereof. Aerogels generally require first the production of a wet gel, followed by processing and extraction to replace the mobile interstitial liquid phase in the gel with air or other gas. Examples of wet gels include, but are not limited to, alcogels, hydrogels, ketone gels, carbon gels, and any other wet gel known to one skilled in the art.

In the context of the present disclosure, the term "additive" or "additive element" refers to a material that can be added to a composition before, during, or after production of the composition. For example, additives can be added to alter or improve desired properties in the aerogel composition, or to counteract or mitigate undesired properties in the aerogel composition. Additives are typically added to the aerogel composition prior to or during gelation. Additives can also be added to the aerogel composition by atomic layer deposition or Chemical Vapor Deposition (CVD). One particular example of an additive is an electrochemically active species, such as elemental sulfur.

In the context of the present disclosure, the term "self-supporting" refers to the ability of an aerogel material or composition to have flexibility and/or elasticity based primarily on the physical properties of the aerogel. The self-supporting aerogel materials or compositions of the present disclosure can be distinguished from other aerogel materials (e.g., coatings) by relying on an underlying substrate or reinforcement material to provide flexibility and/or elasticity to the material.

In the context of the present disclosure, the term "density" refers to a measure of the mass per unit volume of the aerogel material or composition. The term "density" generally refers to the true density of the aerogel material, as well as the bulk density of the aerogel composition. The density is usually reported as kg/m³Or g/cc. The density of the aerogel material or composition can be determined by methods known in the art, including but not limited to: standard test methods for dimensions and density of precast block and panel thermal insulation (ASTM C303, ASTM International, West Conshohocken, Pa.); standard test methods for thickness and density of blanket or batting thermal insulation (ASTM C167, ASTM International, West Conshohocken, Pa.); or the measurement of the apparent density of prefabricated pipe insulation (ISO 18098, International Organization for Standardization, Switzerland). In the context of the present disclosure, unless otherwise indicated, density measurements are taken according to the ASTM C167 standard. Preferably, the aerogel materials or compositions of the present disclosure have a density of about 1.50g/cc or less, 1.40g/cc or less, 1.30g/cc or less, 1.20g/cc or less, 1.10g/cc or less, 1.00g/cc or less, 0.90g/cc or less, 0.80g/cc or less, 0.70g/cc or less, 0.60g/cc or less, 0.50g/cc or less, 0.40g/cc or less, 0.30g/cc or less, 0.20g/cc or less, 0.10g/cc or less, or ranges between any two of these values.

According to certain embodiments, the production of aerogels generally comprises the steps of: i) forming a solution containing a gel precursor; ii) forming a gel from the solution; and iii) extracting the solvent from the gel material to obtain a dried aerogel material. This process is discussed in more detail below, particularly in the context of forming organic aerogels, such as polyimide aerogels. However, the specific examples and illustrations provided herein are not intended to limit the present disclosure to any particular type of aerogel and/or method of preparation. The present disclosure can include any aerogel formed by any relevant method of preparation known to those skilled in the art.

An exemplary solution for producing silica aerogel is formed by combining at least one gelling precursor with a solvent. Suitable solvents for forming the solution include lower alcohols having from 1 to 6 carbon atoms, preferably from 2 to 4 carbon atoms, although other solvents known to those skilled in the art may also be used. Examples of useful solvents include, but are not limited to: methanol, ethanol, isopropanol, ethyl acetate, ethyl acetoacetate, acetone, dichloromethane, tetrahydrofuran, and the like. Multiple solvents may also be combined to achieve a desired level of dispersion or to optimize the properties of the gel material. Thus, the choice of the best solvent for the polymerization and gel-forming steps depends on the particular precursors, fillers and additives incorporated into the solution; as well as the target processing conditions for gelation and liquid phase extraction, and the desired characteristics of the final aerogel material.

An exemplary solution for producing polyimide aerogels is formed by combining at least one diamine and at least one dianhydride in one or more common polar aprotic solvents. Additional details regarding polyimide gel/aerogel formation can be found in U.S. patent nos. 7,074,880 and 7,071,287 to Rhine et al; U.S. patent No. 6,399,669 to Suzuki et al; U.S. patent No. 9,745,198 to Leventis et al; leventis et al, Polymer Aerogels by Ring-Opening methods Polymerization (ROMP), chem.Mater.2011,23,8, 2250-2261; leventis et al, Isokyanite-Derived Organic Aerogels, Polyureas, Polyimids, Polyamides, MRS Proceedings,1306(2011), Chidamarescharattatar et al, doi: 10.1557/opl.2011.90; chidambarwararattatar et al, One-step pole-temperature synthesis of fiber polymide aerogels from anhydrides and isocyanates and conversion to isocomphic carbon boxes, J.Mater.chem.,2010,20, 9666-; guo et al, Polyimide Aerogels Cross-Linked through Amine Functionalized Polyoligomerics silsesquioxane, ACS appl.Mater. interfaces 2011,3, 546-; nguyen et al, Development of High Temperature, Flexible Polymer Aerogels, American Chemical Society, proceedings published 2011; meador et al, mechanical strength, Flexible polymer Aerogels Cross-Linked with Aromatic Triamine, ACS appl.mater.interfaces,2012,4(2), pp 536-; meador et al, Polyimide Aerogels with Amide Cross-Links, ALow code Alternative for mechanical Strong Polymer Aerogels, ACS appl.Mater.Interfaces 2015,7, 1240-; pei et al, Preparation and Characterization of high sea polymers Based on polymer containment, Langmuir 2014,30,13375-13383, the entire contents of each of which are incorporated herein by reference. Triamines, tetraamines, pentamines, hexamines, and the like can also be used in place of or in addition to diamines or combinations thereof to optimize the performance of the gel material. It is also possible to use a tri-, tetra-, penta-, hexa-anhydride instead of or in addition to a dianhydride or a combination thereof to optimize the properties of the gel material. A dehydrating agent and a catalyst may be incorporated into the solution to initiate and drive imidization.

The solution may include additional cogelled precursors, as well as filler materials and other additives. The filler material and other additives may be dispensed into the solution at any point prior to or during gel formation. Filler materials and other additives may also be incorporated into the gel material after gelation by various techniques known to those skilled in the art. Preferably, the solution comprising the gelling precursor, solvent, catalyst, water, filler and other additives is a homogeneous solution, which is capable of effectively forming a gel under suitable conditions.

Once the solution is formed and optimized, the gel-forming components in the solution can be converted into a gel material. The process of converting the gel-forming components into a gel material includes an initial gel-forming step in which the gel is cured to the gel point of the gel material. The gel point of a gel material may be considered as the point where the gelling solution exhibits a flow resistance and/or forms a substantially continuous polymeric framework throughout its volume. A range of gel forming techniques are known to those skilled in the art. Examples include, but are not limited to: maintaining the mixture in a quiescent state for a sufficient period of time; adjusting the concentration of the catalyst; adjusting the temperature of the solution; directing some form of energy onto the mixture (ultraviolet, visible, infrared, microwave, ultrasonic, particle radiation, electromagnetic); or a combination thereof.

The process of converting the gel-forming components into a gel material may also include an aging step (also known as curing) prior to liquid phase extraction. Aging of the gel material after reaching its gel point may further strengthen the gel framework by increasing the number of crosslinks within the network. The duration of gel aging can be adjusted to control various properties within the resulting aerogel material. This aging process can be used to prevent potential volume loss and shrinkage during liquid phase extraction. Aging may involve keeping the gel (before extraction) in a quiescent state for a long time; maintaining the gel at an elevated temperature; adding a crosslinking promoting compound; or any combination thereof. The preferred temperature for aging is generally between about 10 ℃ and about 200 ℃. Aging of the gel material generally continues until liquid phase extraction of the wet gel material.

The time period for the transition of the gel-forming material to the gel material includes the duration of the initial gel formation (from the onset of gelation to the gel point), as well as the duration of any subsequent curing and aging of the gel material prior to liquid phase extraction (from the gel point to the onset of liquid phase extraction). The total time to convert the gel-forming material to a gel material is generally between about 1 minute and several days, preferably about 30 hours or less, about 24 hours or less, about 15 hours or less, about 10 hours or less, about 6 hours or less, about 4 hours or less, about 2 hours or less, about 1 hour or less, about 30 minutes or less, or about 15 minutes or less.

The resulting gel material may be washed in a suitable secondary solvent to replace the primary reaction solvent present in the wet gel. Such secondary solvents may be straight chain monohydric alcohols having one or more aliphatic carbon atoms, glycols having two or more carbon atoms, branched alcohols, cyclic alcohols, alicyclic alcohols, aromatic alcohols, polyhydric alcohols, ethers, ketones, cyclic ethers, or derivatives thereof.

Once the gel material is formed and processed, the liquid phase of the gel can then be at least partially extracted from the wet gel using extraction methods, including processing and extraction techniques, to form an aerogel material. Liquid phase extraction plays an important role in designing aerogel properties (such as porosity and density) and related properties (such as thermal conductivity), among other factors. Typically, aerogels are obtained when the liquid phase is extracted from the gel in a manner that results in low shrinkage of the porous network and framework of the wet gel.

Aerogels are typically formed by removing a liquid mobile phase from a gel material at temperatures and pressures near or above the critical point of the liquid mobile phase. Once the (near-critical) or (supercritical) critical point is reached (i.e., the pressure and temperature of the system are at or above the critical pressure and critical temperature, respectively), a new supercritical phase occurs in the fluid, which is distinct from the liquid or gas phase. The solvent can then be removed without introducing a liquid-vapor interface, capillary pressure, or any associated mass transfer limitations typically associated with liquid-vapor boundaries. Furthermore, the supercritical phase is generally more miscible with organic solvents and therefore has better extractability. Co-solvents and solvent exchange are also commonly used to optimize the supercritical fluid drying process.

If evaporation or extraction occurs below the supercritical point, the capillary forces generated by the evaporation of the liquid can cause shrinkage and pore collapse within the gel material. Maintaining the mobile phase near or above the critical pressure and temperature during solvent extraction reduces this negative impact of capillary forces. In certain embodiments of the present disclosure, the use of near-critical conditions just below the critical point of the solvent system may allow for the production of aerogel materials or compositions with sufficiently low shrinkage to produce a commercially viable end product.

Several additional aerogel extraction techniques are known in the art, including a series of different methods of drying the aerogel using supercritical fluids, as well as ambient drying techniques. For example, Kistler (j. phys. chem. (1932)36:52-64) describes a simple supercritical extraction process in which the gel solvent is maintained above its critical pressure and temperature, thereby reducing evaporative capillary forces and maintaining the structural integrity of the gel network. Us patent No. 4,610,863 describes an extraction process in which a gel solvent is exchanged with liquid carbon dioxide, followed by extraction under conditions in which the carbon dioxide is in a supercritical state. US patent No. US 6,670,402 teaches extraction of a liquid phase from a gel via rapid solvent exchange by injecting supercritical (rather than liquid) carbon dioxide into an extractor that has been preheated and pre-pressurized to substantially supercritical conditions or above, thereby producing an aerogel. Us patent No. 5,962,539 describes a method for obtaining aerogels from polymeric materials in the form of sol-gels in organic solvents by exchanging the organic solvent for a fluid having a critical temperature below the decomposition temperature of the polymer and extracting the fluid/sol-gel supercritical. U.S. patent No. 6,315,971 discloses a method of producing a gel composition comprising: the wet gel comprising gel solids and desiccant is dried to remove the desiccant under drying conditions sufficient to reduce gel shrinkage during drying. U.S. patent No. 5,420,168 describes a method whereby resorcinol/formaldehyde aerogels can be made using a simple air drying procedure. U.S. Pat. No. 5,565,142 describes a drying technique in which the gel surface is modified to be stronger and more hydrophobic so that the gel framework and pores can resist collapse during ambient drying or subcritical extraction. Other examples of extraction of liquid phases from aerogel materials are known from U.S. Pat. nos. 5,275,796 and 5,395,805.

One preferred embodiment for extracting the liquid phase from the wet gel uses supercritical conditions of carbon dioxide, including, for example: fully exchanging main solvent existing in a gel pore network by liquid carbon dioxide; the wet gel (typically in an autoclave) is then heated above the critical temperature of carbon dioxide (about 31.06 ℃) and the system pressure is increased to a pressure greater than the critical pressure of carbon dioxide (about 1070 psig). The pressure around the gel material may fluctuate slightly to facilitate removal of the supercritical carbon dioxide fluid from the gel. Carbon dioxide may be recycled through the extraction system to facilitate continuous removal of the primary solvent from the wet gel. Finally, the temperature and pressure are slowly returned to ambient conditions to produce a dry aerogel material. The carbon dioxide may also be pre-conditioned to a supercritical state prior to injection into the extraction chamber. In other embodiments, the extraction may be performed using any suitable mechanism, such as varying the pressure, time, and solvent described above.

In certain embodiments of the present disclosure, the dried polyimide aerogel composition can be subjected to one or more heat treatments for a duration of 3 hours or more, between 10 seconds and 3 hours, between 10 seconds and 2 hours, between 10 seconds and 1 hour, between 10 seconds and 45 minutes, between 10 seconds and 30 minutes, between 10 seconds and 15 minutes, between 10 seconds and 5 minutes, between 10 seconds and 1 minute, between 1 minute and 3 hours, between 1 minute and 1 hour, between 1 minute and 45 minutes, between 1 minute and 30 minutes, between 1 minute and 15 minutes, between 1 minute and 5 minutes, between 10 minutes and 3 hours, between 10 minutes and 1 hour, between 10 minutes and 45 minutes, between 10 minutes and 30 minutes, between 30 minutes and 15 hours, between 30 minutes and 1 hour, between 30 minutes and 45 minutes, between 10 minutes and 15 minutes, between 30 minutes and 3 hours, between 30 minutes and 1 hour, between 30 minutes and 45 minutes, or more, Between 45 minutes and 3 hours, between 45 minutes and 90 minutes, between 45 minutes and 60 minutes, between 1 hour and 3 hours, between 1 hour and 2 hours, between 1 hour and 90 minutes, or within a range between any two of these values.

In certain embodiments, the present invention relates to the formation and use of nanoporous carbon-based scaffolds or structures (e.g., carbon aerogels) as electrode materials within energy storage devices, e.g., as the primary cathode material in LSBs. The pores of the nanoporous scaffold are designed, organized and structured to accommodate sulfur, iron phosphate or other suitable species. Alternatively, the pores of the nanoporous scaffold can be filled with a sulfide, hydride, any suitable polymer, or other additive, wherein it is advantageous to contact the additive with the conductive material (i.e., scaffold/aerogel) to provide a more efficient electrode.

To further expand the exemplary application within the LSB, when a carbon aerogel material is used as the primary cathode material as in certain embodiments of the present invention, the aerogel nanoporous structure has a narrow pore size distribution and provides high electrical conductivity, high mechanical strength, and morphology and sufficient pore volume (at final density) to accommodate a high weight percentage of elemental sulfur and its expansion. Structurally, certain embodiments of the present invention have a fibrous morphology with strut sizes that result in the aforementioned narrow pore size distribution and high pore volume, as well as enhanced connectivity, among other properties.

As will be discussed further below, the surface of the carbon aerogel can be modified by chemical, physical, or mechanical methods to enhance the properties of the sulfur and polysulfides contained within the pores of the carbon aerogel.

In additional or alternative embodiments, the carbon aerogel itself acts as a current collector due to its electrical conductivity and mechanical strength, thus, in preferred embodiments, eliminating the need for a different current collector on the cathode side (when the cathode is formed of carbon aerogel). It is noted that in the conventional LSB, an aluminum foil is connected to the cathode as its current collector. However, depending on the application of the carbon aerogel, removing one or both of these components provides additional space for more electrode material, resulting in an even greater capacity for the battery/individual electrode, and an overall greater energy density of the packaged battery system. However, in certain embodiments, existing current collectors may be integrated with the cathode materials of various other embodiments to increase the current collector capacity or capacity of the aluminum foil.

In certain embodiments, a nanoporous carbon-based scaffold or structure, particularly a carbon aerogel, may be used as a conductive network or current collector for the cathode side of the energy storage device. The fully interconnected carbon aerogel network is filled with electrochemically active species, wherein the electrochemically active species are in direct contact with or physically connected to the carbon network. The loading of the electrochemically active species is adjusted according to pore volume and porosity to obtain high and stable capacity and to improve the safety of the energy storage device. When used on the cathode side, the electrochemically active species may include, for example, sulfur, iron phosphate, or other functionally suitable species. In yet another embodiment, the cathode may comprise a nanoporous carbon-based scaffold or structure, and in particular a carbon aerogel.

In the context of the present disclosure, the term "current collector-less" refers to the absence of a unique current collector that is directly connected to the electrode. As described above, in the conventional LSB, an aluminum foil is generally attached to the cathode as a current collector thereof. According to embodiments of the present invention, an electrode formed from a nanoporous carbon-based scaffold or structure (e.g., a carbon aerogel) may be a free standing structure or otherwise have the ability to be collector-free, as the scaffold or structure itself acts as a current collector due to its high electrical conductivity. In an electrochemical cell, by embedding a solid, reticulated, braided sheet during the solution step of preparing the continuous porous carbon; or the non-collector electrodes may be joined to form an electrical circuit by soldering, welding or metal deposition of a lead to a portion of the porous carbon surface. Other mechanisms of contacting carbon with the rest of the system are also contemplated herein. In alternative embodiments, nanoporous carbon-based supports or structures, particularly carbon aerogels, may be disposed on or otherwise in communication with a dedicated current collecting substrate (e.g., copper foil, aluminum foil, etc.). In this case, the carbon aerogel may be attached to the solid current collector using a conductive adhesive and applying varying amounts of pressure.

Further, it is contemplated herein that the nanoporous carbon-based scaffold or structure, particularly the carbon aerogel, may take the form of a monolithic structure or a powder form. When monolithic in nature, the carbon aerogel eliminates the need for any binder; in other words, the cathode may be binderless. As used herein, the term "monolithic" refers to aerogel materials wherein the majority (by weight) of the aerogel contained in the aerogel material or composition is in the form of single, continuous, interconnected aerogel nanostructures. Monolithic aerogel materials include aerogel materials that are initially formed with a single interconnected gel or aerogel nanostructure, but which can subsequently be cracked, fractured, or otherwise segmented into non-single aerogel nanostructures. Monolithic aerogels can take the form of free-standing structures or reinforced (fibrous or foam) materials. In contrast, using the LSB example, sulfur incorporated into the monolithic aerogel can be more efficiently utilized relative to theoretical capacity than if the same amount of sulfur were incorporated into the slurry using conventional processes.

Monolithic aerogel materials are distinct from particulate aerogel materials. The term "particulate aerogel material" refers to aerogel materials in which a majority (by weight) of the aerogel contained in the aerogel material is in the form of particles, granules, beads, or powder, which can be combined together (i.e., by a binder, such as a polymeric binder) or compressed together but which lack interconnected aerogel nanostructures between individual particles. Collectively, aerogel materials in this form will be referred to as having a powder or particulate form (as opposed to a monolithic form). It should be noted that although the individual particles of the powder have a single structure, the individual particles are not considered to be monolithic herein. Integration of aerogel powders into electrochemical cells typically involves preparing a paste or slurry from the powder, casting on a substrate, and drying, and may optionally include calendaring.

In the context of the present disclosure, the term "binder-free" or "binder-free" (or derivatives thereof) refers to a material that is substantially free of an adhesive or cohesive agent to hold the material together. For example, the monolithic nanoporous carbon material is free of binder because its framework is formed as a single, continuous, interconnected structure. The advantages of adhesive-free include avoiding any negative effects of the adhesive, such as effects on conductivity and pore volume. Aerogel powders or particles, on the other hand, require a binder to bind them together to form a larger functional material; such larger materials are not considered herein to be monolithic. Furthermore, this term "adhesive-free" does not exclude all uses of the adhesive. For example, a monolithic aerogel according to the present invention can be secured to another monolithic aerogel or non-aerogel material by disposing a binder or adhesive on a major surface of the aerogel material. In this manner, the adhesive is used to make a laminate composite, but the adhesive does not function to maintain the stability of the monolithic aerogel frame itself.

In addition, monolithic polymeric aerogel materials or compositions of the present disclosure can be compressed to up to 95% strain without significantly damaging or rupturing the aerogel framework, while densifying the aerogel and minimizing porosity. In certain embodiments, the compressed polymeric aerogel material or composition is subsequently carbonized using various methods described herein to form a nanoporous carbon material. It will be appreciated that the amount of compression affects the thickness of the resulting carbon material, where thickness has an effect on capacity, as will become clearer as the present description continues. The embodiments described below will illustrate the different thicknesses formed and contemplated by the present invention, wherein the thickness can be adjusted based on compression. Thus, the thickness of the composite (typically compressed) may be about 10 to 1000 μm, or any narrower range therein, based on the desired benefits of the final composite. The present invention also contemplates powder or particle forms of carbon aerogels where a binder is required and particle size is optimized. The particle size may range from about 5 to 50 μm.

According to the present invention, nanoporous carbon, e.g., carbon aerogel, can be formed from any suitable organic precursor material. Examples of such materials include, but are not limited to, RF, PF, PI, polyamide, polyacrylate, polymethylmethacrylate, acrylate oligomers, polyoxyalkylene, polyurethane, polyphenol, polybutylenealkane, trialkoxysilyl-terminated polydimethylsiloxane, polystyrene, polyacrylonitrile, polyfurfural, melamine formaldehyde, cresol formaldehyde, phenol-furfural, polyether, polyol, polyisocyanate, polyhydroxybenzene, polyvinyl alcohol dialdehyde, polycyanurate, polyacrylamide, various epoxy resins, agar, agarose, chitosan, and combinations and derivatives thereof. Any precursor of these materials can be used to produce and use the resulting materials. In an exemplary embodiment, the carbon aerogel is formed from a pyrolyzed/carbonized polyimide-based aerogel, i.e., polymerization of polyimide. Even more specifically, polyimide-based aerogels can be prepared using one or more of the methods described in U.S. patent nos. 7,071,287 and 7,074,880 to Rhine et al, for example, by imidizing a polyamic acid and drying the resulting gel using a supercritical fluid. Other suitable methods of producing polyimide aerogels (and carbon aerogels derived therefrom) are also contemplated herein, for example, as described in U.S. patent nos. 6,399,669 to Suzuki et al; U.S. patent No. 9,745,198 to Leventis et al; leventis et al, Polymer Aerogels by Ring-Opening methods Polymerization (ROMP), chem.Mater.2011,23,8, 2250-2261; leventis et al, Isokyanite-Derived Organic Aerogels, Polyureas, Polyimids, Polyamides, MRS Proceedings,1306(2011), Chidamarescharattatar et al, doi: 10.1557/opl.2011.90; chidambarwararattatar et al, One-step pole-temperature synthesis of fiber polymide aerogels from anhydrides and isocyanates and conversion to isocomphic carbon boxes, J.Mater.chem.,2010,20, 9666-; guo et al, Polyimide Aerogels Cross-Linked through Amine Functionalized Polyoligomerics silsesquioxane, ACS appl.Mater. interfaces 2011,3, 546-; nguyen et al, Development of High Temperature, Flexible Polymer Aerogels, American Chemical Society, proceedings published 2011; meador et al, mechanical strength, Flexible polymer Aerogels Cross-Linked with Aromatic Triamine, ACS appl.mater.interfaces,2012,4(2), pp 536-; meador et al, Polyimide Aerogels with Amide Cross-Links A Low Cost Alternative for mechanical Strong Polymer Aerogels, ACS appl.Mater.Interfaces 2015,7, 1240-1249; pei et al, Preparation and Characterization of high sea polymers Based on polymer containment, Langmuir 2014,30, 13375-13383. The resulting polyimide aerogel is then pyrolyzed to form a polyimide-derivatized carbon aerogel.

Carbon aerogels, e.g., polyimide-derived carbon aerogels, according to exemplary embodiments of the present disclosure can have a residual nitrogen content of at least about 4 wt%. For example, carbon aerogels according to embodiments disclosed herein can have a residual nitrogen content of at least about 0.1 wt%, at least about 0.5 wt%, at least about 1 wt%, at least about 2 wt%, at least about 3 wt%, at least about 4 wt%, at least about 5 wt%, at least about 6 wt%, at least about 7 wt%, at least about 8 wt%, at least about 9 wt%, at least about 10 wt%, or a range between any two of these values.

In certain embodiments of the present disclosure, the dried polymeric aerogel composition can be subjected to a treatment temperature of 200 ℃ or more, 400 ℃ or more, 600 ℃ or more, 800 ℃ or more, 1000 ℃ or more, 1200 ℃ or more, 1400 ℃ or more, 1600 ℃ or more, 1800 ℃ or more, 2000 ℃ or more, 2200 ℃ or more, 2400 ℃ or more, 2600 ℃ or more, 2800 ℃ or more, or within a range between any two of these values, for carbonization of organic (e.g., polyimide) aerogels. In exemplary embodiments, the dried polymeric aerogel composition can be subjected to a processing temperature in the range of about 1000 ℃ to about 1100 ℃, for example at about 1050 ℃. Without being bound by theory, it is contemplated herein that the electrical conductivity of the aerogel composition increases with carbonization temperature.

In the context of the present disclosure, the term "conductivity" refers to a measure of the ability of a material to conduct an electrical current or otherwise allow electrons to flow therethrough or therein. Conductivity is specifically measured as the conductivity/susceptance/admittance of the material per unit size of the material. It is usually reported as S/m (Siemens/meter) or S/cm (Siemens/centimeter). The conductivity or resistivity of a material can be determined by methods known in the art, including, but not limited to: on-line four-point resistivity (using ASTM F84-99, Dual configuration test method). In the context of the present disclosure, unless otherwise indicated, a measurement of electrical conductivity is obtained according to ASTM F84 — a resistivity (R) measurement obtained by measuring voltage (V) divided by current (I). In certain embodiments, aerogel materials or compositions of the present disclosure have an electrical conductivity of about 1S/cm or more, about 5S/cm or more, about 10S/cm or more, 20S/cm or more, 30S/cm or more, 40S/cm or more, 50S/cm or more, 60S/cm or more, 70S/cm or more, 80S/cm or more, or within a range between any two of these values.

In the context of the present disclosure, the term "electrochemically active species" refers to an additive capable of accepting and releasing ions within an energy storage device. Using the LSB as an example, the electrochemically active species within the cathode accept lithium ions during discharge (and thus undergo conversion to lithium sulfide species) and release lithium ions during charge. By having a direct/physical connection to the nanoporous carbon, the electrochemically active species can be stabilized within the cathode. In certain embodiments, the nanoporous carbon network forms an interconnected structure around the electrochemically active species. The electrochemically active species are attached to the nanoporous carbon at a plurality of points. One example of an electrochemically active species is sulfur, which expands when converted to lithium sulfide. However, due to the multiple points of attachment of sulfur to the nanoporous carbon (aerogel), sulfur can remain within the pores and remain active. The amount of sulfur incorporated into the nanoporous carbon material may be increased relative to a conventional cathode in LSBs. In certain embodiments, the aerogel materials or compositions of the present disclosure have a sulfur content between about 5 weight percent of the cathode and about 90 weight percent of the cathode, or any range between these two values.

In the context of the present disclosure, the terms "compressive strength", "flexural strength" and "tensile strength" refer to the resistance of a material to fracture or rupture under compressive, flexural or bending forces and tensile or tensile forces, respectively. These strengths are measured specifically as the amount of load/force per unit area that resists the load/force. It is typically reported in pounds per square inch (psi), megapascals (MPa), or gigapascals (GPa). The compressive, flexural and tensile strength of the material collectively affect the structural integrity of the material, which is beneficial in the LSB, among other factors. With particular reference to young's modulus, which is an indicator of mechanical strength, modulus can be determined by methods known in the art, including, but not limited to: standard test practice for instrumental indentation testing (ASTM E2546, ASTM International, West Conshocken, PA); or standardized nanoindentation (ISO 14577, International Organization for Standardization, Switzerland). In the context of the present disclosure, the measurement of young's modulus is obtained according to ASTM E2546 and ISO 14577, unless otherwise indicated. In certain embodiments, the aerogel materials or compositions of the present disclosure have a young's modulus of about 0.2GPa or greater, 0.4GPa or greater, 0.6GPa or greater, 1GPa or greater, 2GPa or greater, 4GPa or greater, 6GPa or greater, 8GPa or greater, or a range between any two of these values.

In the context of the present disclosure, the term "pore size distribution" refers to the statistical distribution or relative amount of each pore size within a sample volume of a porous material. A narrower pore size distribution means that there is a relatively large proportion of pores in a narrower pore size range, thereby optimizing the amount of pores that can surround the electrochemically active species and maximizing the utilization of pore volume. Conversely, a broader pore size distribution refers to a relatively smaller proportion of pores within a narrower range of pore sizes. Thus, the pore size distribution is typically measured as a function of pore volume and is reported as the unit size of the full width at half maximum of the main peak in the pore size distribution plot. The pore size distribution of the porous material can be determined by methods known in the art, for example including but not limited to surface area and porosity analyzer by nitrogen adsorption and desorption, from which the pore size distribution can be calculated. In the context of the present disclosure, unless otherwise indicated, measurements of pore size distribution are obtained according to the method. In certain embodiments, the aerogel materials or compositions of the present disclosure have a relatively narrow pore size distribution (full width at half maximum) of about 50nm or less, 45nm or less, 40nm or less, 35nm or less, 30nm or less, 25nm or less, 20nm or less, 15nm or less, 10nm or less, 5nm or less, or in a range between any two of these values.

In the context of the present disclosure, the term "pore volume" refers to the total volume of pores within a sample of porous material. Pore volume is specifically measured as the volume of void space within the porous material, where the void space may be measurable and/or accessible by another material, for example, an electrochemically active species such as sulfur. It is usually reported as cubic centimeters per gram (cm)³In/g or cc/g). The pore volume of the porous material can be determined by methods known in the art, for example including but not limited to surface area by nitrogen adsorption and desorption and a porosity analyzer, from which the pore volume can be calculated. In the context of the present disclosure, unless otherwise indicated, a measurement of pore volume is obtained according to the method. In certain embodiments, aerogel materials or compositions of the present disclosure (that do not incorporate electrochemically active species, e.g., sulfur) have a relatively large pore volume of about 1cc/g or more, 1.5cc/g or more, 2cc/g or more, 2.5cc/g or more, 3cc/g or more, 3.5cc/g or more, 4cc/g or more, or a range between any two of these values. In other embodiments, aerogel materials or compositions of the present disclosure (incorporating)An electrochemically active species, such as sulfur) has a pore volume of about 0.10cc/g or more, 0.3cc/g or more, 0.6cc/g or more, 0.9cc/g or more, 1.2cc/g or more, 1.5cc/g or more, 1.8cc/g or more, 2.1cc/g or more, 2.4cc/g or more, 2.7cc/g or more, 3.0cc/g or more, 3.3cc/g or more, 3.6cc/g or more, or ranges between any two of these values.

In the context of the present disclosure, the term "porosity" refers to the volume ratio of pores that do not contain another material (e.g., an electrochemically active species, such as sulfur) bound to the pore walls. For purposes of clarity and illustration, it should be noted that in the particular implementation of sulfur-doped carbon aerogel as the primary cathode material in LSB, porosity refers to the void space after elemental sulfur is included. Porosity can be determined by methods known in the art, including, for example, but not limited to, the ratio of the pore volume of the aerogel material to its bulk density. In the context of the present disclosure, unless otherwise indicated, a measure of porosity is obtained according to the method. In certain embodiments, the aerogel materials or compositions of the present disclosure have a porosity of about 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, or within a range between any two of these values.

It is noted that pore volume and porosity are different measures of the same property of the pore structure, i.e. "white space" within the pore structure. For example, when sulfur is used as the electrochemically active species enclosed within the pores of the nanoporous carbon material, the pore volume and porosity refer to "empty" spaces, i.e., spaces not utilized by the carbon or electrochemically active species. It will be appreciated that densification of the pre-carbonized nanoporous material, for example by compression, may also have an effect on pore volume and porosity, as well as other properties.

In the context of the present disclosure, the term "pore size at the maximum peak from the distribution" refers to the value at the discernible peak on a graph illustrating the pore size distribution. The pore size at the maximum peak of the distribution is specifically measured as the pore size at which the maximum percentage of pores is formed. It is usually reported as any unit length of the pore size, e.g. μm or nm. The pore size at the maximum peak of the distribution can be determined by methods known in the art, for example including but not limited to surface area and porosity analyzer by nitrogen adsorption and desorption, from which the pore size distribution can be calculated and the pore size at the maximum peak can be determined. In the context of the present disclosure, unless otherwise indicated, pore size measurements at the maximum peak of the distribution are obtained according to the method. In certain embodiments, the pore size of the aerogel material or composition of the present disclosure at the maximum peak of the distribution is about 150nm or less, 140nm or less, 130nm or less, 120nm or less, 110nm or less, 100nm or less, 90nm or less, 80nm or less, 70nm or less, 60nm or less, 50nm or less, 40nm or less, 30nm or less, 20nm or less, 10nm or less, 5nm or less, 2nm or less, or within a range between any two of these values.

In the context of the present disclosure, the term "strut width" refers to the average diameter of the nano-struts, nanorods, nanofibers, or nanowires that form the aerogel having a fibrous morphology. It is usually recorded as any unit length, e.g. μm or nm. Strut width can be determined by methods known in the art, including, but not limited to, scanning electron microscope image analysis, for example. In the context of the present disclosure, unless otherwise indicated, measurements of strut width are obtained according to the method. In certain embodiments, the aerogel materials or compositions of the present disclosure have a strut width of about 10nm or less, 9nm or less, 8nm or less, 7nm or less, 6nm or less, 5nm or less, 4nm or less, 3nm or less, 2nm or less, or within a range between any two of these values. Smaller pillar widths, such as those in the range of about 2 to 5nm, allow a greater number of pillars to be present in the network and thus contact the electrochemically active species, thereby allowing more electrochemically active species to be present in the network. This increases the electrical conductivity and mechanical strength.

In the context of the present disclosure, the term "fibrous morphology" refers to the structural morphology of nanoporous carbon (e.g., aerogel), including struts, rods, fibers, or filaments. For example, in one embodiment, the choice of solvent, such as Dimethylacetamide (DMAC), can affect the generation of this form. Further, in certain embodiments, when the carbon aerogel is derived from a polyimide, the crystalline polyimide results from the polyimide forming a linear polymer. As will become clearer in the following embodiments, it was surprisingly observed that certain embodiments comprise a fibrous morphology as an interconnected polymer structure, wherein long linear structures are expected based on the known behavior of polyimide precursors. In contrast, the product form of the nanoporous carbon may alternatively be particulate in nature or a powder, wherein the fibrous morphology of the carbon aerogel still exists. As will become clearer as the present description continues, the fibrous morphology may provide certain advantages over the particulate morphology, such as mechanical stability/strength and electrical conductivity, particularly when the nanoporous carbon is implemented in a particular application, such as a cathode material in an LSB. It should be noted that such fibrous morphologies can be found in nanoporous carbon in bulk and powder form; in other words, the monolithic carbon may have a fibrous morphology and the aerogel powder/particles may have a fibrous morphology. Furthermore, in certain embodiments, when the nanoporous carbon material comprises an additive, such as sulfur or other additives, the fibrous nanostructure inherent to the carbon material is retained and serves as a bridge between the additive particles.

In the context of the present disclosure, the term "cycle life" refers to the number of complete charge/discharge cycles that a cathode or battery (e.g., LSB) can support before its capacity is below about 80% of its original rated capacity. Cycle life may be affected by a number of factors that are not significantly affected over time, such as the mechanical strength of the underlying substrate (e.g., carbon aerogel), the connectivity of sulfur within the aerogel, the dissolution of sulfur or polysulfides into the electrolyte within the aerogel network, and the maintenance of the interconnectivity of the aerogel. It should be noted that it is a surprising aspect of certain embodiments of the present invention that these factors actually remain relatively constant over time. Cycle life may be determined by methods known in the art, including, for example and without limitation, a cycling test in which the battery is subjected to repeated charge/discharge cycles at a predetermined current rate and operating voltage. In the context of the present disclosure, unless otherwise indicated, a measure of cycle life is obtained according to the method. In certain embodiments of the present disclosure, an energy storage device, such as a battery or an electrode thereof, has a cycle life of about 25 cycles or more, 50 cycles or more, 75 cycles or more, 100 cycles or more, 200 cycles or more, 300 cycles or more, 500 cycles or more, 1000 cycles or more, or in a range between any two of these values.

In the context of the present disclosure, the term "capacity" refers to the amount of a particular energy or charge that a battery is capable of storing. Capacity is measured specifically as the discharge current that a battery can deliver over time per unit mass. It is usually reported as ampere hours or milliampere hours, Ah/g or mAh/g per gram of total electrode mass. The capacity of the cell (particularly the cathode) can be determined by methods known in the art, including, but not limited to: applying a fixed constant current load to the fully charged battery until the voltage of the battery reaches a discharge end voltage value; multiplying the time of reaching the discharge end voltage by the constant current to obtain the discharge capacity; the specific capacity and volumetric capacity can be determined by dividing the discharge capacity by the weight or volume of the electrode material. In the context of the present disclosure, unless otherwise indicated, a measure of capacity is obtained according to the method. In certain embodiments, aerogel materials or compositions of the present disclosure have a capacity of about 200mAh/g or more, 300mAh/g or more, 400mAh/g or more, 500mAh/g or more, 600mAh/g or more, 700mAh/g or more, 800mAh/g or more, 900mAh/g or more, 1000mAh/g or more, 1100mAh/g or more, 1200mAh/g or more, 1300mAh/g or more, 1400mAh/g or more, 1500mAh/g or more, 1600mAh/g or more, 1700mAh/g or more, or a range between any two of these values.

In certain embodiments, the invention is a PI-derivatized nanoporous carbon material (e.g., a carbon aerogel) having a series of pores that surround, contain, or encapsulate elemental sulfur therein. Nanoporous carbon materials can serve as ideal hosts for sulfur due to their optimal pore structure, functional pore morphology, and high mechanical integrity. Nanoporous carbon materials (carbon aerogels) are characterized by a narrow pore size distribution, resulting in consistent behavior of sulfur and polysulfide species throughout the interconnected network. The carbon material itself is also characterized by high electrical conductivity, which serves to overcome the major drawback of conventional LSBs, namely the high resistivity of sulfur and polysulfide species. The above-described properties of current nanoporous carbon materials, alone and in combination, impart certain benefits to increase the cycle life and battery life of the resulting LSB system or cathode thereof.

In one embodiment, the invention is a cathode for LSBs comprising a sulfur-doped, polyimide-derivatized carbon aerogel in which elemental sulfur is encased within the pores of the carbon aerogel (see fig. 2A-2C). It can be seen that the structure of the carbon aerogel pores can be tailored to have different properties (e.g., pore volume, pore diameter, pore size distribution, and surface area) as desired (e.g., size or capacity of the electrode in the LSB). In another embodiment, the invention is an electrode in an LSB or electrochemical cell comprising such a cathode. In the LSB, sulfur cathodes-such as those described herein as sulfur-doped nanoporous carbon materials or sulfur-doped carbon aerogels-are most often paired with lithium metal anodes to achieve equilibrium capacity. These sulfur cathodes may also be paired with non-lithium metal anodes that enable high capacity, including, for example, silicon-based, silicon-doped, or silicon-based anode materials. In further embodiments, the present invention is an apparatus or system incorporating such an energy storage device.

In certain embodiments, the present invention is a method of forming or making a sulfur-doped, continuous, porous carbon composite, such as a carbon aerogel. The polyimide precursor, for example, can each include aromatic and/or aliphatic groups of diamines and dianhydrides, mixed in a suitable solvent (e.g., a polar aprotic solvent). An imidization gelation catalyst is then added to initiate gelation of the mixture. In an alternative embodiment, imidization may be accomplished by thermal imidization, wherein any suitable temperature and time range is contemplated (e.g., about 100 ℃ to 200 ℃ for about 20 minutes to about 8 hours, followed by heating at about 300 ℃ to 400 ℃ for about 20 minutes to about 1 hour). The gel mixture is then dried to produce a continuous porous polyimide composite, where drying can be performed using subcritical carbon dioxide and/or supercritical carbon dioxide. Optionally, the polyimide composite may be compressed to increase the density, which may be adjusted to at most about 1.5g/cc based on the amount of compression. In an exemplary embodiment, the polyimide composite may be compressed to a strain of greater than about 80% prior to pyrolyzing the composite. Regardless of whether compression occurs, the polyimide composite is pyrolyzed to produce continuous porous carbon, wherein the carbon includes about 5% to 99% porosity. In certain embodiments, pyrolysis may be conducted at a maximum temperature between about 750 ℃ and about 1600 ℃, e.g., about 1050 ℃, optionally graphitizing from about 1600 ℃ up to about 3000 ℃.

After carbonization, sulfur is incorporated into the network of porous carbon using any suitable method to form a sulfur-doped continuous porous carbon composite. An exemplary method of incorporating sulfur into the carbon network is by melt injection. The incorporation can be controlled to achieve optimal sulfur weight loading and retained porosity. For example, an aerogel material or composition of the present disclosure can have a sulfur content of about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, or a range between any two of these values. In exemplary embodiments, the sulfur-doped nanoporous carbon materials of the present disclosure may have a sulfur content in the range of about 60 wt% to 75 wt%, for example about 70 wt%. The aerogel material or composition of the present disclosure can have a concentration of 10mg/cm²Or above, 8mg/cm²Or above, 7mg/cm²Or more, 6mg/cm²Or above, 5mg/cm²Or above, 4mg/cm²Or above, 3mg/cm²Or more than, 2.5mg/cm²Or more than, 2mg/cm²Or more than, 1.5mg/cm²Or more than, 1mg/cm²Or above, or in a range between any two of these values. In exemplary embodiments, the sulfur-doped nanoporous carbon materials of the present disclosure may have a carbon content of about 1.5mg/cm²To about 2.5mg/cm²In the range, for example, about 2mg/cm²Area mass loading of sulfur.

The incorporation of sulfur into the network of porous carbon results in a sulfur-doped carbon composite having a porosity that is lower than the porosity of the undoped material. As a result, the pore size in the sulfur-doped composite material is smaller than the pore size in the undoped material. In another example or in combination with melt injection, the natural carbon network may be surface treated with chemical functional groups having affinity for sulfur and polysulfides to enhance inclusion within the network and help stabilize cycle life capacity. In yet another embodiment, additives may be included with the gel precursor (i.e., pre-gelation) that will aid in the chemical or physical adaptation of the sulfur added after carbonization.

In certain embodiments, the carbon-sulfur composite material may be a monolithic or free-standing structure, may be prepared on or off a substrate, or may be micronized into powder form. In addition, the composite material may or may not be reinforced with a non-woven material or a woven material (e.g., fibers, foam, etc.). Optionally, the carbon sulfur composite may be selectively doped with nitrogen, alone or in combination with other suitable additives, to inhibit the diffusion of polysulfides, thereby maintaining a high cycle life.

In certain embodiments, the pore size of the sulfur-doped nanoporous carbon materials or compositions of the present disclosure at the maximum peak of the distribution is about 150nm or less, 140nm or less, 130nm or less, 120nm or less, 110nm or less, 100nm or less, 90nm or less, 80nm or less, 70nm or less, 60nm or less, 50nm or less, 40nm or less, 30nm or less, 20nm or less, 10nm or less, 5nm or less, 2nm or less, or within a range between any two of these values. Further, it is contemplated herein that the pore size can be adjusted as desired. For example, when a sulfur-doped carbon material is incorporated into a cell, the pore size can be adjusted to accommodate an amount of electrolyte sufficient for efficient cell operation. Five main methods of adjusting pore size are taught herein. First, the amount of solid content, particularly the amount of polyimide precursor monomers (e.g., aromatic or aliphatic diamines and aromatic or aliphatic dianhydrides), can be adjusted for pore size. The smaller pore size is due to the more solids per unit volume of fluid, because less space is available, so that the interconnections occur more tightly. It should be noted that the strut width does not change measurably regardless of the amount of solids used. The amount of solids is more related to the density of the network.

Another method of adjusting the pore size is to use radiation (e.g., radio waves, microwaves, infrared, visible light, ultraviolet, X-rays, gamma rays) on a composite material in a polyimide state or a carbon state. The radiation has an oxidizing effect, resulting in an increased surface area, an increased pore size and a broadened pore size distribution. Third, the pore size is affected by macro-compression of the polyimide composite. As shown in the following embodiments, the pore size decreases with compression.

Another method to adjust the pore size is ion bombardment of the composite material in the polyimide state or the carbon state. The effect of the ion bombardment depends on the specified method. For example, there is additional ion bombardment (e.g., CVD) where something is added, resulting in a reduction in the aperture. There is also destructive ion bombardment, in which the pore size is increased. Finally, the pore size can be adjusted (increased or decreased) by performing the heat treatment in different gas environments (e.g., the presence of carbon dioxide or carbon monoxide, a chemically active environment, a hydrogen reducing environment, etc.). For example, a carbon dioxide environment is known to produce activated carbon, in which case the mass is removed, the pore size increases, and the surface area increases.

Examples

The following examples are described for illustrative purposes only and are not intended to limit the scope of various embodiments of the present invention in any way.

Example 1: PI composite material

PI gels were prepared from pyromellitic dianhydride (PMDA) and 1, 4-Phenylenediamine (PDA) in DMAC solvent at target densities of 0.05g/cc (low density) and 0.125g/cc (high density) at a 1:1 molar ratio. The precursor was mixed at room temperature for 3 hours, then Acetic Anhydride (AA) was added to the PMDA at a 4.3 molar ratio and mixed with the solution for 2 hours. Imidization was catalyzed with pyridine (Py).

To prepare the PI composite, the solution was cast in a teflon container at a thickness of about 6 mm. The gel was allowed to cure overnight at room temperature and then under supercritical CO₂Ethanol exchange was performed at 68 ℃ before extraction. The PI aerogel composite was pyrolyzed under an inert atmosphere for 1 hour to be carbonized to form a monolithic PI composite. The lower target density PI (0.05g/cc target density) was pyrolyzed at 850 deg.C. The surface area of the obtained carbon aerogel material is 629.9m²Pore volume 4.0cc/g, and pore diameter 20.8 nm. The higher target density PI (0.125g/cc) was pyrolyzed at 1050 deg.C. The surface area of the obtained carbon aerogel material is 553.8m²Pore volume 1.7cc/g, and pore diameter 10.9 nm. Parameters of the porous Structure the nitrogen adsorption isotherm (S) at-196 ℃ was measured using a Quadrasorb gas adsorption analyzer (Quantachrome Instruments, Boynton Beach, USA)_BET-a surface area; v_tTotal pore volume). The pore width (in nm) was estimated using the Barrett-Joyner-Halenda model. Prior to analysis, the samples were degassed at 100mTorr and 60 ℃ for 12 hours.

Example 2: sulfur doping of PI composites

Each monolithic PI composite was ground to powder form. Mixing the obtained powdery PI material with sulfur powder at a ratio of 30:72 (wt%) and the mixture is milled for about 10 minutes. The sulfur and powdered PI mixture was then placed in a vial and in an Ar atmosphere at 155℃And annealing for 12 hours. The resulting sulfur-doped carbon material contained about 70 wt% sulfur. FIGS. 3A and 3B show SEM images of sulfur-doped carbon materials are shown.The sulfur-doped carbon aerogel material prepared from the lower target density PI (0.05g/cc target density) had a density of 109m²Surface area per gram, pore volume of 0.82cc/g and pore diameter of 17.6 nm. The sulfur-doped carbon aerogel material, prepared from a higher target density PI (0.125g/cc), had a 29m²Surface area per g, pore volume of 0.12cc/g and pore diameter of 12.4 nm. The parameters of the porous structure were calculated using the same method as in example 1.

Example 3: electrodes made using sulfur-doped carbon materials

The sulfur-doped carbon material of example 2 was dry-milled for 30 minutes, and then mixed with PVDF (polyvinylidene fluoride) and Super C45 (conductive carbon) at 80 wt% sulfur-doped carbon material, 10 wt% PVDF and 10 wt% Super C45 (ratio 8:1:1) in N-methylpyrrolidone (NMP) to make a slurry. The slurry was wet milled for 30 minutes. The resulting slurry was coated on aluminum foil with a doctor blade and vacuum dried for 12 hours. After drying, an areal mass loading of about 2mg/cm of S was obtained²The electrode of (1).

Example 4: half-cell unit made of sulfur-doped carbon electrode

Half cell unit (2032 coin cell) was constructed from the electrodes prepared according to example 3 with lithium foil as the counter electrode and CELGARD 2500 as the microporous separator between the electrodes. The electrolyte was 1.0M LiTFSI in dimethyl ether (DME)/1, 3-Dioxolane (DOL) (1:1 weight ratio). Fig. 4A shows half-cell capacity for the first cycle at 0.1C for an electrode made from low density sulfur-doped carbon prepared according to the above example. Fig. 4B shows half-cell capacity for the first cycle at 1C for an electrode made from low density sulfur-doped carbon prepared according to the above example. Fig. 5A shows half-cell capacity for the first cycle at 0.1C for an electrode made from high density sulfur-doped carbon prepared according to the above example. Fig. 5B shows half-cell capacity for the first cycle at 1C for an electrode made from high density sulfur-doped carbon prepared according to the above example. Fig. 6 shows half-cell cycle performance of electrodes made from low density sulfur-doped carbon prepared according to the above examples. Fig. 7 shows half-cell cycle performance of electrodes made from high density sulfur-doped carbon prepared according to the above examples.

Alternative method for producing PI aerogels

The previous examples discussed herein teach certain methods of forming PI aerogels. In certain embodiments, the present invention also contemplates alternative methods of forming PI aerogels. A non-exhaustive and non-limiting set of examples of such alternative methods will now be discussed.

For example, U.S. patent No. 6,399,669 to Suzuki et al teaches a four (4) related method of making PI xerogels (aerogels). In the first method, a PI precursor is synthesized, and then an imide is formed from the PI precursor, thereby producing a polyimide. A PI solution or swollen mass is prepared and the solution/swollen mass is gelled to produce a PI wet gel. This wet gel was dried to give a PI xerogel (aerogel). In the second method, a PI precursor is synthesized, and then a PI precursor solution or a swollen mass is prepared. The solution/swollen mass was gelled to produce a wet gel of PI precursor. An imide is then formed from the PI precursor to form a PI wet gel. This wet gel was dried to give a PI xerogel (aerogel). In a third method, a PI precursor is synthesized, and then a PI precursor solution or a swollen mass is prepared. An imide is then formed from the PI precursor while it is gelled to produce a PI wet gel. In a third method, a PI precursor is synthesized, and then a PI precursor solution or a swollen mass is prepared. The solution/swollen mass was gelled to produce a wet gel of PI precursor. The wet gel is then dried to produce a PI precursor xerogel. The imide is then formed from the PI precursor dry gel to form a PI xerogel (aerogel).

As a further example, Leventis et al, [ Polymer Aerogels by Ring-Opening methods Polymerization (ROMP), chem. Mater.2011,23,8, 2250-. A low molecular weight imidized oligomer end-capped with a polymerizable group is provided and mixed with a polymerization (e.g., ROMP) catalyst. Thus initiating polymerization to produce a crosslinked polyimide. The polyimide was gelled and dried to form a PI aerogel. Leventis et al [ U.S. patent No. 9,745,198; chidambarwarapattar et al, One-step-temperature synthesis of fiber polyimide aerogels from anhydrides and isocyanates and conversion to isocomphic carbon boxes, J.Mater.chem.,2010,20,9666-9678 also teaches the formation of PI aerogels by mixing a dianhydride (e.g., PMDA) with an isocyanate (e.g., 4,4' -diisocyanatodiphenylmethane or methylene bis-p-phenyl diisocyanate) to form a sol-gel material. The sol-gel material is then dried to produce a PI aerogel. Leventis et al, [ Isocynate-divided Organic Aerogels: polyurethanes, Polyimides, Polyamides, MRS Proceedings,1306(2011),. Mrsf10-1306-bb03-01.doi:10.1557/opl.2011.90] also indicate that DESMODUR N3300A, DESMODUR RE and DUMONR CD (all available from BAYER CORP.) can be used as isocyanates.

In an alternative approach, Guo et al, [ Polyimide Aerogels Cross-Linked through Amine Functionalized Polyoligomerics silsesquioxane, ACS appl.Mater. Interfaces 2011,3,546-552] discusses the formation of PI Aerogels by reacting an amino silsesquioxane with a polyamic acid oligomer end-capped with an anhydride group. The product was imidized (although thermal imidization is also contemplated) and gelled using pyridine, and then dried to obtain a PI aerogel. Nguyen et al, [ Development of High Temperature, Flexible Polymer Aerogels, American Chemical Society, 2011 published monographs ] discusses the production of branched polyimides by mixing diamines and dianhydrides and imidizing, followed by reaction with a polyamino compound (e.g., 1,3, 5-tris (4-aminophenoxybenzene)). The product was then reacted with 4,4' -methylene diisocyanate and dried to form PI-urea aerogel.

In other embodiments, Meador et al, [ mechanical Strong, Flexible Polymer Aerogels Cross-Linked with Aromatic Triamine, ACS appl.Mater.Interfaces,2012,4(2), pp 536-. The resulting wet was dried to form PI aerogel. In addition, Meador et al, [ Polyimide elastomers with Amide Cross-Links: A Low Cost Alternative for mechanical structural polymers, ACS appl. Mater. interfaces 2015,7, 1240-. The resulting gel was dried to form a PI aerogel.

In yet another embodiment, Pei et al, [ Preparation and Characterization of high chlorine Cross-Linked Polymer Aerogels Based on Polymer conjugation ] Trimethoxysilane Side Groups, Langmuir 2014,30,13375-13383] produce PI Aerogels from polyimides Containing pendant Trimethoxysilane Groups, which are condensation products of polyimides Containing pendant acid chloride Groups and 3-aminopropyltrimethoxysilane. The resulting gel was dried to form a PI aerogel.

In any of these methods, a suspension of Graphene may be added (see Zhang et al, Graphene/carbon aerogels derived from Graphene cross linked polymers as electrode materials for supercapacitors, RSC adv.,2015,5,1301).

Each of these methods can produce polyimide aerogels, and any suitable method for producing such polyimide aerogels is contemplated by the present invention. Regardless of the method used to produce the PI aerogel, the resulting PI aerogel can be pyrolyzed to form PI-derived carbon aerogels, according to certain embodiments of the present invention. Additives, such as sulfur, may also be incorporated according to certain embodiments discussed herein.

All cited publications are incorporated herein by reference in their entirety. Further, where a definition or use of a term in a reference, which is incorporated by reference herein is inconsistent or contrary to the definition of that term provided herein, then the definition of that term provided herein applies and the definition of that term in the reference should be omitted.

The advantages mentioned above, as well as those apparent from the preceding description, are effectively attained. As certain changes could be made in the above constructions without departing from the scope of the invention, it is intended that all matter contained in the above description and shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween.