Membrane electrode assembly

Abstract

The present application relates to membrane electrodes, in particular electrolytic cell devices, including novel materials and membrane electrode design and fabrication methods.

Description

[0001] By incorporating relevant applications This application claims priority to and is based on 35 USC §119(e), U.S. Provisional Application No. 63 / 520,820, filed August 21, 2023, the entire contents of which are incorporated herein by reference in their entirety.

[0002] Invention Field This application relates to membrane electrodes, particularly electrolytic cell apparatus, including novel materials and membrane electrode design and manufacturing methods.

[0003] background Water electrolysis, also known as "water splitting," breaks down liquid water (H2O) into oxygen (O2) and hydrogen (H2). Gases escape when an electric current flows through the device at a voltage of at least 1.23V applied between the anode and cathode. Hydrogen and oxygen escape at the cathode and anode, respectively. Hydrogen has been described as a fuel for a cleaner future, and it can be used for transportation and industrial applications, such as in the Haber-Bosch process to produce ammonia. Oxygen is used as an oxidant or as a component of the breathable air used by astronauts and cosmonauts residing on the International Space Station (ISS) to maintain their life-sustaining oxygen supply.

[0004] Currently, the two main commercially available water electrolysis methods include alkaline electrolysis and proton exchange membrane (PEM) electrolysis. Alkaline electrolyzers are less efficient than PEM electrolyzers and rely on a typically corrosive liquid electrolyte. The initial capital expenditure and ancillary equipment (support components and auxiliary systems) for these systems are expensive, requiring larger plants to produce the same material output. PEM electrolyzers achieve higher current densities than alkaline electrolyzers, but they have their own drawbacks. Although they can operate with pure water without adding an electrolyte, they operate in an acidic environment, requiring expensive anode and cathode catalyst materials (e.g., platinum group metal electrodes) and expensive bipolar plates, such as titanium. Therefore, the initial capital expenditure increases significantly.

[0005] Anion exchange membrane electrolyzers (AEMELs) can be operated using relatively inexpensive polymer membrane materials and low-cost non-precious metal catalysts, offering the potential to significantly reduce the capital expenditure of electrolyzer units. Despite this great potential, the development of scalable electrodes for efficient electrochemical reactions is necessary. While conventional anion exchange membrane materials exhibit good ionic conductivity, their incorporation into devices unfortunately presents challenges leading to lower efficiency and poor durability. AEMELs must also overcome the high H2 cross-permeability at the higher pressure differentials used in production facilities. Furthermore, in addition to material-level challenges, innovation is required in the fabrication methods for the membrane electrode assemblies.

[0006] Overview Recognizing the need for improved materials and manufacturing processes for AEMELs, the inventors of this application have invented novel polymer materials, methods for preparing such materials, and methods for incorporating such materials into electrolyzers (including water electrolyzers). The inventors of this application have incorporated anion-exchange polymers that exhibit excellent durability and high current density in electrochemical applications such as electrolysis (water, carbon dioxide, etc.), fuel cells, and electrodialysis. As discussed in more detail herein, the anion-exchange polymers of this application directly address the need for improved electrode functionality in AEMELs.

[0007] Specifically, embodiments of this application enable the use of anion-exchange polymers, which may or may not be crosslinked with organic or metal-organic portions, and are functionalized to form quaternary ammonium groups, which can be used as membranes or ionomers. Embodiments of this application also enable the achievement of 1.5+ A / cm 2 The high current density, durability of 1000+ hours, and operation at very low concentrations (<100 mM) of electrolytes (e.g., KOH, K2CO3, KHCO3), or even enabling operation with pure deionized water, are all advantages of this invention. Embodiments of this application also substantially prevent any H2 or O2 leakage to the opposite side of the electrolyzer, maintaining the amount of unwanted gas on the opposite side below 4%, even at high pressure differentials. Embodiments of this application can also be used in membrane electrode assembly processes by sequentially roll-coating multiple layers of such polymers as catalyst ink layers or polymer layers using a multi-slit die or multiple slit dies in a coating production line.

[0008] Therefore, in one aspect, this application provides a method for incorporating anion exchange polymers into electrodes and electrochemical devices. In some embodiments discussed herein, the anion exchange polymer of this application (discussed in more detail below) can be used as a membrane material. When used as a membrane material, the anion exchange polymer may be referred to as an anion exchange membrane or AEM. In some embodiments discussed herein, the anion exchange polymer of this application can be used as an ionomer material. When used as an ionomer material, the anion exchange polymer may be referred to as an anion exchange ionomer or AEI. In the context of this application, such uses are not mutually exclusive, i.e., the anion exchange polymer material of this application can be used as both AEM and AEI.

[0009] When with attachment Figure 1 When considered, further objects, features and advantages of this application will become apparent from the detailed description of the preferred embodiments set forth below. Brief description of the attached diagram Figure 1 An implementation scheme of an electrolytic cell incorporating the materials discussed herein is described.

[0011] Figure 2 An embodiment of a combustion / oxidation catalyst with fine dispersion throughout the membrane implementation is described.

[0012] Figure 3 An embodiment of a combustion / oxidation catalyst layer embedded in a membrane embodiment is described.

[0013] Figure 4 An implementation scheme for a combustion / oxidation catalyst layer between the membrane and the anode catalyst layer is described.

[0014] Figure 5 An implementation scheme for a combustion / oxidation catalyst layer dispersed in an anode catalyst layer is described.

[0015] Figure 6 An embodiment of a combustion / oxidation catalyst layer between an anode catalyst layer and an anode substrate layer is described.

[0016] Figure 7 An embodiment of a combustion / oxidation catalyst layer between anode substrate layers is described.

[0017] Figure 8 An embodiment of a combustion / oxidation catalyst layer disposed at the edge of an anode substrate layer is described.

[0018] Figure 9 An embodiment of a combustion / oxidation catalyst layer dispersed in an anode substrate layer is described.

[0019] Figure 10An implementation scheme is described, outlining an overview of polymer modification for enhancing activity or mechanical properties.

[0020] Figure 11 A schematic diagram of a slit-type die coating operation is depicted.

[0021] Figure 12 An implementation scheme for a multi-layer coatable slit mold head is described.

[0022] Figure 13 An implementation scheme in which multiple slit-type die heads are used to coat the film is described.

[0023] Figure 14 The following embodiment is described: wherein catalyst-coated electrodes using the materials described in this invention are assembled in stacks of two replicates to evaluate performance from 1.5+ to 0 A / cm. 2 Voltage-current polarization curves obtained from current density scanning.

[0024] Figure 15 An implementation scheme depicting the durability of a stack with two coated electrodes operating for approximately 1000 hours was described.

[0025] Detailed Explanation The inventors of this application have invented novel polymer membrane materials, methods for preparing such materials, and methods for incorporating such materials into electrolyzers (including water electrolyzers). The inventors of this application have developed anion-exchange polymers that exhibit excellent durability and high current density in electrochemical applications such as electrolysis (water, carbon dioxide, etc.), fuel cells, and electrodialysis. As discussed in more detail herein, the anion-exchange polymers of this application directly address the need for improved electrode functionality in AEMELs.

[0026] definition Unless otherwise stated, the following definitions as used herein shall apply.

[0027] In the context of this application, the term "ionomer" refers to a functional polymer that may or may not be cross-linked and contains functional groups that enable the conduction of anions through itself or to facilitate catalytic reactions.

[0028] In the context of this application, the term "catalyst" means an element or metal oxide or organometallic complex that enables electrocatalytic reactions such as hydrogen release, oxygen release, or combustion to occur.

[0029] As used herein, the term "unsaturated" refers to a portion having one or more unsaturated units, while a "saturated" portion has no unsaturated units.

[0030] The term "organometallic" refers to a molecule that has a metal ion that is bound to an organic ligand group.

[0031] The term "ligand" refers to an organic molecule that is typically composed of elements used in polymers or crosslinking agents and can bind to metal groups to act as a catalyst.

[0032] The term "functional additive" refers to molecules composed of organic molecules that can act as cross-linking agents or anion carriers, or molecules that promote catalytic reactions.

[0033] In the context of this application, using substantially pure water in the context of an electrolytic cell means water with a liquid electrolyte concentration of less than 250 mM. The AEMEL of this application is preferably operated using substantially pure water. The AEMEL of this application can also be operated using liquid electrolytes with concentrations of less than 200 mM, 150 mM, 100 mM, 50 mM, 10 mM, or 1 mM.

[0034] Anion exchange polymers In one aspect, this application provides a novel anion exchange polymer for use in electrolytic cells, preferably water electrolyzers. In particular, this novel anion exchange polymer is especially suitable for use as a membrane, a coating material for electrodes in electrochemical devices, or as a filter medium, etc.

[0035] Anion exchange polymers are random and / or block copolymers having one or more types of optionally crosslinked monomer units. Typically, some regions of anion exchange polymers are hydrophobic, while others are hydrophilic, due to the characteristics of the monomers constituting each region. Crosslinking is accomplished by a crosslinking agent, i.e., molecules that chemically bond two or more (hydrophilic and / or hydrophobic) monomer units. Anion exchange polymers may also contain charged or uncharged functional groups attached to one or more monomer units. The polymer is optionally a random or block copolymer containing, but not limited to, hydrocarbons. The general structure of anion exchange polymers is shown in the following formula I: I in: Each — represents an optional chemical bond, which can be a single or double bond, an ionic bond (or an electrovalent bond), a hydrogen bond, or a polar covalent bond; Each M n (where n≥2) represents a single unit, where each M n Choose from different types or categories (hydrophilic, hydrophobic); and Each C n (where n≥1) represents the crosslinking agent, where each C n Choose any of the different types or categories.

[0036] In some embodiments of Formula I, M n It can be directly combined with the adjacent M. n This ensures that there is no crosslinking between the two monomer units. In some embodiments, the monomer unit can be directly connected to the adjacent monomer unit and connected to another monomer unit via a crosslinking agent.

[0037] For the anion exchange polymer of formula I shown above, each monomer unit M n It may contain C, H, N, F, Cl, Br, and / or I atoms. In some cases, the monomer unit is selected from: , , , , , , , Rn, Rn1, Rn2, Rn3, Rn4, Rn5 and Rn6 are defined as follows in equations II to VII.

[0038] For anion-exchange polymers of formula I, monomer unit M n Each can optionally be linked to another monomer unit via a crosslinking chemical or crosslinking agent. In some cases, the crosslinking agent is selected from: W, Z, R2, Rn, Rn1, Rn2, Rn3, Rn4, Rn5 and Rn6 are defined as shown in equations II to VII below.

[0039] For anion-exchange polymers of formula I, monomer unit M n Each can be attached to a functional group capable of conducting anions. In some cases, the functional groups are selected from: W, Z, R2, Rn1, Rn2, Rn3, and Rn4 are defined as shown in equations II to VII below.

[0040] In the context of this application, the block or random copolymers discussed herein are macromolecules that can be engineered to achieve certain desired properties, such as ion conduction without sacrificing mechanical properties. Each monomer unit or block can be designed according to hydrophobicity and hydrophilicity to enable phase separation, which, in the case of a water electrolyzer, improves anion conduction in the ion channels of the hydrophilic block while maintaining overall mechanical properties due to the hydrophobic block.

[0041] In some embodiments, the multiblock copolymer of this application may include multiple blocks (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more), wherein each block is either hydrophilic or hydrophobic. In some embodiments, the blocks include hydrophilic and / or hydrophobic regions. In some embodiments, the blocks are monomers based on norbornene, olefins, or fluorocarbons. In some embodiments, the multiblock copolymer may include one or more hydrophobic norbornene-based blocks and one or more hydrophilic norbornene-based blocks. In some embodiments, the multiblock copolymer may also include one or more hydrophilic norbornene-based blocks and one or more hydrophobic olefin-based blocks. In some embodiments, the multiblock copolymer may include 2 to 8 blocks. In some embodiments, the hydrophobic and hydrophilic blocks are in (AB) n or A-(BA) n Or B-(AB) n The components are arranged alternately. In some embodiments, the multiblock copolymer comprises a fully hydrocarbon backbone. In some embodiments, the multiblock copolymer may also comprise a fluorocarbon-based backbone.

[0042] In embodiments of this application, the amount of hydrophilic groups in the copolymer can vary. In some embodiments, the copolymer contains 30 to 40 mol% hydrophilic groups, with the remaining groups being hydrophobic. In some embodiments, the copolymer contains 40 to 50 mol% (hydrophilic groups), with the remaining groups being hydrophobic. In some embodiments, the copolymer contains 50 to 60 mol% (hydrophilic groups), with the remaining groups being hydrophobic. In some embodiments, the copolymer contains 60 to 70 mol% (hydrophilic groups), with the remaining groups being hydrophobic. In some embodiments, the copolymer contains 70 to 80 mol% (hydrophilic groups), with the remaining groups being hydrophobic. In some embodiments, the copolymer contains 90 to 99 mol% (hydrophilic groups), with the remaining groups being hydrophobic.

[0043] In some embodiments, the anion exchange polymer of this application has Formula II: II in: i, j, k, l, a, b, c, and d are each independently between 1 and 1000, wherein the regions defined by the repeating units i, j, k, l, a, b, c, and d are each blocks in anion-exchange polymers; R1 and R2 are each independently substituted or unsubstituted, branched or unbranched C1-C. 20 Aliphatic or heteroaliphatic; Y is independently a quaternary aliphatic amine or a quaternary heterocyclic amine; and Z is an independent crosslinking group, wherein the crosslinking group Z is optionally present in each block.

[0044] In some embodiments, R1 is a C1-C bond containing halogenated groups such as Cl, Br, I, and F. 20 Aliphatic or heteroaliphatic.

[0045] In some implementations, Y is N + R, where R is a saturated aliphatic or heterocyclic group (e.g., N). + (C5H 10 ) or quaternary ammonium spirocyclic groups (e.g., N) + (C4H 10 )-N + (C5H 10 )).

[0046] In some embodiments, the anion exchange polymer of this application has Formula III: III in: i, j, k, l, a, b, c, and d are each independently between 1 and 1000, wherein the regions defined by the repeating units i, j, k, l, a, b, c, and d are each blocks in anion-exchange polymers; R1 and R2 are each independently substituted or unsubstituted, branched or unbranched C1-C. 20 Aliphatic or heteroaliphatic; Y is independently a quaternary aliphatic amine or a quaternary heterocyclic amine; and Z is an independent crosslinking group, wherein the crosslinking group Z is optionally present in each block.

[0047] In some embodiments, R1 is a C1-C bond containing halogenated groups such as Cl, Br, I, and F. 20 Aliphatic or heteroaliphatic.

[0048] In some implementations, Y is N + R, where R is a saturated aliphatic or heterocyclic group (e.g., N). + (C5H 10 ) or quaternary ammonium spirocyclic groups (e.g., N) + (C4H 10 )-N + (C5H 10 )).

[0049] In some embodiments, the anion exchange polymer of this application has Formula IV: IV in: i, j, a, and b are each independently between 1 and 1000, wherein the regions defined by the repeating units i, j, a, and b are each blocks in anion-exchange polymers; R1 and R2 are each independently substituted or unsubstituted, branched or unbranched C1-C. 20 Aliphatic or heteroaliphatic; Y is independently a quaternary aliphatic amine or a quaternary heterocyclic amine; and Z is an independent crosslinking group, wherein the crosslinking group Z is optionally present in each block.

[0050] In some embodiments, R1 is a C1-C bond containing halogenated groups such as Cl, Br, I, and F. 20 Aliphatic or heteroaliphatic.

[0051] In some implementations, Y is N + R, where R is a saturated aliphatic or heterocyclic group (e.g., N). + (C5H 10 ) or quaternary ammonium spirocyclic groups (e.g., N) + (C4H 10 )-N + (C5H 10 )).

[0052] In some embodiments, the anion exchange polymer of this application has formula V: V in: i, j, k, l, a, b, c, and d are each independently between 1 and 1000, wherein the regions defined by the repeating units i, j, k, l, a, b, c, and d are each blocks in anion-exchange polymers; R (n) (where n = 1 to 12) are each independently substituted or unsubstituted, branched or unbranched C1-C 20 Aliphatic or heteroaliphatic; Y is independently a quaternary aliphatic amine or a quaternary heterocyclic amine; and Z is an independent crosslinking group, wherein the crosslinking group Z is optionally present in each block.

[0053] In some embodiments, R1 is a C1-C bond containing halogenated groups such as Cl, Br, I, and F. 20 Aliphatic or heteroaliphatic.

[0054] In some implementations, Y is N + R, where R is a saturated aliphatic or heterocyclic group (e.g., N). + (C5H 10) or quaternary ammonium spirocyclic groups (e.g., N) + (C4H 10 )-N + (C5H 10 )).

[0055] In some embodiments, the anion exchange polymer of this application has formula VI: VI in: i, j, k, l, a, b, c, and d are each independently between 1 and 1000, wherein the regions defined by the repeating units i, j, k, l, a, b, c, and d are each blocks in anion-exchange polymers; R (n) (where n = 1 to 12) are each independently substituted or unsubstituted, branched or unbranched C1-C 20 Aliphatic or heteroaliphatic; Y is independently a quaternary aliphatic amine or a quaternary heterocyclic amine; and Z is an independent crosslinking group, wherein the crosslinking group Z is optionally present in each block.

[0056] In some embodiments, R1 is a C1-C bond containing halogenated groups such as Cl, Br, I, and F. 20 Aliphatic or heteroaliphatic.

[0057] In some implementations, Y is N + R, where R is a saturated aliphatic or heterocyclic group (e.g., N). + (C5H 10 ) or quaternary ammonium spirocyclic groups (e.g., N) + (C4H 10 )-N + (C5H 10 )).

[0058] In some embodiments, the anion exchange polymer of this application has formula VII: VII in: i, j, k, l, a, b, c, d, x, and y are each independently between 1 and 1000, wherein the regions defined by the repeating units i, j, k, l, a, b, c, d, x, and y are each blocks in anion-exchange polymers; R1 is independently a substituted or unsubstituted, branched or unbranched C1-C. 20 Aliphatic or heteroaliphatic; Y is independently a quaternary aliphatic amine or a quaternary heterocyclic amine; and Z is an independent crosslinking group, wherein the crosslinking group Z is optionally present in each block.

[0059] In some embodiments, R1 is a C1-C bond containing halogenated groups such as Cl, Br, I, and F. 20 Aliphatic or heteroaliphatic.

[0060] In some implementations, Y is N + R, where R is a saturated aliphatic or heterocyclic group (e.g., N). + (C5H 10 ) or quaternary ammonium spirocyclic groups (e.g., N) + (C4H 10 )-N + (C5H 10 )).

[0061] For equations II to VII, in some implementations, Y is selected from... in: R2 and R n For substituted or unsubstituted, branched or unbranched C1-C 20 Aliphatic or heteroaliphatic groups, Z is defined as above for equations II to VII. W is either C1-C 20 Aliphatic or heteroaliphatic, such that Y contains a single heterocyclic group, or 1-20 independent groups associated with N. + Connecting C 4-10 Allocyclic or heterocyclic groups; and Each R n(i) It is H or a carbon-containing part, where i ≥ 1 (e.g., R). n1 R n2 wait).

[0062] In some implementations, Y acts as a crosslinking bridge between one block of the polymer and another block of the polymer.

[0063] In some implementations, Z represents substituted or unsubstituted, branched or unbranched C1-C. 20 Aliphatic or heteroaliphatic. In some embodiments, Z is [(R3)]. x N + (R4) y ] q R3 and R4 are alkyl spacer chains, wherein each spacer chain is substituted or unsubstituted, branched or unbranched, C1-C. 20 Alkyl group, wherein q ranges from 1 to 10. In some embodiments, Z is [(R3)N + (R4)(R5)]r R3 and R4 are alkyl spacer chains, each of which is substituted or unsubstituted, branched or unbranched C1-C. 20 Alkyl group, R5 is a heterocyclic or spirocyclic entity attached to a quaternary ammonium molecule, wherein r ranges from 1 to 10.

[0064] It will also be understood that each crosslinking group Z can crosslink to an independent polymer chain.

[0065] In some embodiments, Y is a metal-organic complex, wherein Rn, R ni (Where i = 1 to 99) can be H or other carbon-containing atoms. In some embodiments, the metal complex comprises a metal atom / molecule -M coordinated to another organic molecule, which may contain, but is not limited to, C, H, N, O, F, and S atoms. In some embodiments, M may also contain one or more metal groups, such as Co, Fe, Ni, Pt, Ru, Ir, Mo, Ce, Mn, Cu, and Si. In some embodiments, L ni (I=1 to 99) are ligand molecules that form coordinate bonds with metal complexes and are attached to the polymer backbone. Ligand molecules contain, but are not limited to, C, H, N, O, F, and S atoms. An example of such metal-organic complexes is, but is not limited to, the following molecules: in Each R n(i) It is H or a carbon-containing part, where i ≥ 1 (e.g., R). n1 R n2 wait); Y is a metallic group, such as Ni, Fe, Pt, Ru, Ir, Mo, or Co.

[0066] In some embodiments, each block defined by i, j, k, l, a, b, c, and d in formulas II to VII above has a crosslinking degree between 0% and 100%, where the crosslinking degree represents the number of monomers in blocks i, j, k, l, a, b, c, and d that are crosslinked with a monomer in another block. In some embodiments, the crosslinking degree is between 1% and 50%. When a monomer is not crosslinked with another monomer, the crosslinking group Z may be absent, or may be present partially or entirely without forming a chemical bond with the other monomer.

[0067] Crosslinking agent As discussed above, in some embodiments, the multiblock copolymers of this application are crosslinked with a crosslinking agent. As those skilled in the art will understand, crosslinking bonds are bonds (typically one or more covalent bonds) between individual polymer chains that link such chains together, and in this way, macromolecules with multiple blocks can be produced. In some embodiments of this application, the degree of crosslinking and hydrophobic groups within the polymer can be varied to tune water absorption and mechanical properties. Generally, a higher degree of crosslinking increases chain compactness and limits swelling when the multiblock copolymer is exposed to water (e.g., in an electrolyzer).

[0068] In some embodiments, the crosslinking agent may contain functional groups capable of conducting anions, particularly 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more cations. In some embodiments, the crosslinking agent may not contain any cationic functional groups. In some embodiments, the crosslinking agent may consist of two or more chemical bonds forming reactive sites. In some embodiments, suitable reactive sites on the crosslinking agent may include (but are not limited to) nucleophilic groups, such as amines. In some embodiments, the crosslinking agent is an organometallic compound composed of organic covalent bonds and inorganic metal atoms or molecules. In some embodiments, the crosslinking agent also has catalytic activity for, for example, oxygen escape reaction (OER) or hydrogen escape reaction (HER).

[0069] In some implementations, the crosslinking agent is via C 2-20 The crosslinking agent is one or more heterocyclic or spirocyclic polyamines linked by alkyl spacer chains, or heterocyclic or spirocyclic member rings linked via heteroatoms such as N. In some embodiments, the number of atoms in the heterocycle can be 4 to 20, comprising both carbon and nitrogen atoms (or other heteroatoms). In some embodiments, the member ring can be composed of atoms other than C, H, and N. In some embodiments, the crosslinking agent can be a heterocyclic or spirocyclic quaternary ammonium linked via a heteroatom such as (but not limited to) an N atom at either end of the ring (as shown in some embodiments above). Exemplary examples of crosslinking agents include, but are not limited to, 1,1'-(1,6-hexamethylenedimethyl)piperidine.

[0070] In some embodiments, the crosslinking agent is a molecule having one or more amine groups. In some embodiments, the amine groups are optionally located at the terminal positions. In some embodiments, the crosslinking agent is a molecule containing (but not limited to) C, H, N, O, F, and S atoms.

[0071] Therefore, in some embodiments, the crosslinking agent has one of the following chemical structures: in: Each R n(i)It is H or a carbon-containing part, where i ≥ 1 (e.g., R). n1 R n2 wait); R n For substituted or unsubstituted, branched or unbranched C1-C 20 Aliphatic or heteroaliphatic groups, W is a saturated or unsaturated, branched or unbranched, substituted or unsubstituted C1-C. 99 A hydrocarbon chain, optionally containing one or more heteroatoms (e.g., N, S, or O).

[0072] In some embodiments, the crosslinking agent comprises an organometallic (metal-organic) complex. In a preferred embodiment, the molecule thus possesses electrocatalytic activity. In some embodiments, the crosslinking agent has the following structure: in: Each R n(i) It is H or a carbon-containing part, where i ≥ 1 (e.g., R). n1 R n2 wait); M is an organometallic complex containing a metal atom or metal molecule coordinated to an organic molecule or atom, wherein the organic molecule optionally contains C, H, N, O, F and / or S atoms and / or the organic atom is C, H, N, O, F and / or S, wherein the metal of M is optionally Co, Fe, Ni, Pt, Ru, Ir, Mo, Ce, Mn, Cu or Si; Each L n(i) It is a ligand molecule that forms coordination bonds with metal complexes and is attached to the polymer backbone; where i ≥ 1 (e.g., L n1 L n2 (etc.), wherein the ligand molecule contains, but is not limited to, C, H, N, O, F, and S atoms, wherein the ligand molecule may be linked to one or more monomer units, said monomer units may be hydrophilic or hydrophobic, Where R n(i) It can be omitted arbitrarily, and L n(i) One or more of them are directly combined with M.

[0073] In some embodiments, the polymer contains suitable functional groups to promote crosslinking with a crosslinking agent. In some embodiments, the functional groups may include (but are not limited to) electrophilic carbon atoms that are bonded to electronegative atoms, such as halogens (e.g., Cl, Br, F, I), sulfonates (e.g., methanesulfonate, trifluoromethanesulfonate, p-toluenesulfonate), oxygen, or nitrogen. The electrophilic groups on the copolymer undergo a nucleophilic substitution reaction with a crosslinking agent containing a nucleophilic functional group such as an amine (-NR2, where R is H, alkyl, heterocyclic, or spirocyclic molecule) to crosslink the copolymer. The amount of crosslinking can be controlled by selecting the desired amount of crosslinking agent. The degree of crosslinking can be determined by the stoichiometry of the crosslinking agent. Based on the total number of moles available for the reaction, the molar percentage of the crosslinking agent can be 1% or more. The amount of crosslinking can be from about 1% to 50%.

[0074] Functional additives In some embodiments, the polymer includes a functional additive, which is a tertiary amine, such as N(CH3)3, or a heterocyclic amine, such as N-methylpiperidine. In some embodiments, the tertiary amine is one of the following: in: Each R n(i) It is H or a carbon-containing part, where i ≥ 1 (e.g., R). n1 R n2 wait); R2 is defined above; Z is a crosslinking group, wherein the crosslinking group Z is optionally present in each block; W is either C1-C 20 Aliphatic or heteroaliphatic, resulting in functional additives containing a single heterocyclic group, or 1-20 independent N-type groups. + Connecting C 4-10 Allocyclic or heterocyclic groups.

[0075] In one embodiment, this application provides a method for manufacturing a crosslinked block copolymer comprising one or more hydrophilic blocks and one or more hydrophobic blocks. In some embodiments, the method provides a method for manufacturing such copolymers using a desired molar percentage of a crosslinking agent. In some embodiments, the crosslinking agent is a C1-C... 20 Polyhexacyclic amines or spirocyclic amines linked by alkyl or cyclic groups. One or more hydrophilic monomer units in the copolymer contain saturated C1-C2 bonds. 20 Halogenated alkyl chains. The alkyl chains may contain at least one or more electrophilic carbon atoms. In some embodiments, the crosslinked copolymer comprises a crosslinking agent having one or more branched / unbranched saturated C2-C atoms. 20An alkyl chain, heterocyclic chain, or spirocyclic chain is bonded to one or more cationic head groups of one or more hydrophilic monomers based on norbornene. For example, in some embodiments, the crosslinked copolymer comprises a crosslinking agent group having a C3 to C9 alkyl chain. In some embodiments, multiple cationic head groups are present on the crosslinking agent, which are spaced by heterocyclic or spirocyclic chains with C3-C9 saturated alkyl chains or quaternary ammonium groups. In some embodiments, the cationic head groups of one or more hydrophilic monomers based on norbornene are crosslinked to each other via an alkyl spacer chain crosslinking agent or via heterocyclic or spirocyclic chains. The concentration of the crosslinking agent in the copolymer can vary. This concentration can vary between 1 and about 50 mol%.

[0076] Anion exchange membranes and ionomers In some embodiments of this application, the polymer materials discussed herein are used in anion exchange membranes (AEMs) and ionomer materials (AEIs). Therefore, one aspect of this application includes anion exchange membranes composed of copolymers of this application. In some embodiments, the AEM of this application comprises one or more non-crosslinked multiblock copolymers as described herein. In some embodiments, the AEM of this application comprises hydrophobic and hydrophilic regions within the polymer and / or AEM, formed due to phase separation within the block polymer. Phase separation results in the formation of anion conduction pathways. In some embodiments, the AEM has an ion exchange capacity in the range of 0.1 to above 8.0.

[0077] In some embodiments, the AEM of this application comprises one or more crosslinked multiblock copolymers as described herein. In some embodiments, the AEM of this application comprises hydrophobic and hydrophilic regions within the polymer and / or the AEM, formed due to phase separation within the block polymer. Phase separation results in the formation of anion conduction pathways. In some embodiments, the AEM has an ion exchange capacity in the range of 0.1 to above 8.0.

[0078] Integrating catalysts to mitigate H2 or O2 leakage through either compartment In an electrolytic cell, because hydrogen is the smallest known molecule in the universe, hydrogen gas can actually leak through the membrane from the cathode compartment to the anode compartment. This leakage is undesirable and potentially dangerous for reasons that will become apparent. Similarly, oxygen generated in the anode compartment can also leak through the membrane to the cathode compartment, which can again pose a danger. These hydrogen and / or oxygen leaks can result in a situation where the gas leaving the electrolytic unit is a mixture of hydrogen and oxygen. Depending on the proportion of hydrogen in the mixture, this mixture can be hazardous, increasing concerns about the safety of the device. Hydrogen is 4% to 94% flammable in air and 4% to 94% flammable in oxygen, meaning that if there is too much leakage, both the hydrogen or oxygen product streams can be flammable. The inventors of this application propose a novel modification to the prior art that mitigates the leakage of these two gases through the membrane.

[0079] In some embodiments, the proposed modification involves a membrane electrode assembly including a catalyst capable of undergoing a combustion reaction between H2 and O2 on its surface to remove any leaked gases from the final product stream or reduce the concentration of leaked gases to a level insufficient to allow combustion. The catalytic combustion reaction can also be referred to as a hydrogenation reaction. This reaction is as follows: (1) Here, when one or two reactants are in a gaseous and / or dissolved aqueous state, the combustion catalyst can promote the reaction.

[0080] In addition, catalysts can also promote the following oxidation reactions: (2) In some embodiments, the catalyst used to enable reactions (1) and (2) is based on a single atom. In some embodiments, the catalyst is a noble metal or a non-noble metal, such as Pt, Pd, Ni, Fe, Ag, Bi, Cr, Ce, Ge, Mo, Mg, Mn, Co, Ti, Al, Cu, Ir, In, Nb, Rh, Re, Si, Sn, Sb, Sm, Se, Te, Tb, Tm, Ta, V, W, Y, Yb, Zn, Zr, Ru, etc. In some embodiments, the catalyst is in the form of a metal oxide, such as PtO, PdO, NiO, MgO, CoO, Co2O3, Co3O4, Cr2O3, CuO, Cu2O, Cu(OH)2, Dy2O3, Er2O3, Eu2O3, FeOOH, Fe2O3, Fe3O4, Fe(OH)3, GdO3, HfO2, In2O3, In(OH)3, La2O3, Mg(OH)2, MoO2, MoO3, MnO2, Mn2O3, Mn3O4, Nd2O3, Ni(OH)2, Ni2O3, Ni3O4, Sb2O3, SiO2, Sm2O3, SnO2, Tb4O7, Co3O4, TiO2, Al2O3, Al(OH)3, Bi2O3, CeO2, WO3, W 20 O 58 WO4H2, V2O5, Y2O3, ZnO, ZnCO3, ZrO2, Zr(OH)4, CuO, IrO2, etc. In some embodiments, the catalyst is a multi-element oxide, such as BaFe. 12 O 19 , BaTiO3, CoFe2O4, MnFe2O4, MgAl2O4, NiFe2O4, Ni 0.5 Zn 0.5 Fe2O4, Ni 0.5 Co 0.5 Fe2O4, SrFe 12 O 19 SrTiO3, Y3Al5O 12 ZnFe2O4, Zn 0.5 Co 0.5 Fe2O4, Zn 0.5 Mn 0.5 Fe2O4, Zr 0.2 BaTi 0.8 O3, Al2O5Ti, AlCeO3, BaTiO3, SrTiO3, CoAl2O4, Ce 0.5 Zr 0.5 O2, CoNiO2, C 32 H 16CuN8, ZrO2, Y2O3, etc. In some embodiments, the catalyst is supported on a carrier such as carbon, or an oxide carrier such as graphene oxide, TiO2, or any other metal carrier. In some embodiments, the catalyst is an inorganic metal compound comprising phosphides, nitrates, sulfides, hydroxides, carbonates, bicarbonates, nitrides, cyanides, isocyanates, silicides, carbides, borides, sulfates, fluorides, fluorates, silicates, etc., or combinations thereof, of any of the aforementioned metals. In some embodiments, the catalyst is in ionic form, which can subsequently be reduced in situ within the battery assembly. In some embodiments, the catalyst is a metal-organic compound described in the preceding section. As described in the preceding section, the metal-organic compound can be integrated as a crosslinking agent. In some embodiments, the catalyst is a multi-metal alloy having any combination of the aforementioned catalysts, such as PtNi, etc.

[0081] According to this application, the catalyst may be located in any or all of the following components: a membrane (polymer phase), an anode catalyst layer, an anode substrate layer, a cathode catalyst layer, a hydrogen manifold, a water / oxygen manifold, water plenums, and a cathode substrate layer. An illustrative, non-limiting example of a MEA structure having a catalyst is as follows: Example: Catalysts dispersed throughout the membrane This application also provides a method for manufacturing a membrane with a finely dispersed catalyst, and the resulting structure ( Figure 2 In some embodiments, the catalyst may be incorporated into the pre-cast polymer solution, which will be in liquid solution form. The catalyst and polymer solution can also be mixed using high-shear or ultrasonic techniques.

[0082] Example: Catalyst layer embedded in membrane This application also provides a method for manufacturing a membrane having an embedded catalyst layer, and the resulting structure ( Figure 3 In some embodiments, the catalyst layer thickness can be any thickness between 0 and X μm, where X represents the total thickness of the film. The catalyst layer can be located anywhere across the film, such as closer to the cathode, at the center, or closer to the anode. In some embodiments, the layer is approximately equidistant from both the cathode and anode. In some embodiments, the layer is closer to the cathode than the anode. In some embodiments, the layer is closer to the anode than the cathode.

[0083] In some embodiments, the catalyst layer can be introduced into the membrane by forming an ink (catalyst and binder) and coating it using techniques such as, but not limited to, slit-die coating, spraying, blade coating, dip coating, screen printing, gravure roller coating, bar coating, etc. The coated surface can then be dried, with or without methods such as heating, convection, or vacuum. An additional layer of anion exchange polymer is then deposited on top of the coated catalyst layer and dried to form a membrane in which the catalyst layer is embedded within itself.

[0084] Example: Catalyst layer between membrane and anode / cathode catalyst layer This application also provides a method for providing a catalyst layer between a membrane and an anode / cathode catalyst layer, and the resulting structure ( Figure 4 In some embodiments, an ink (catalyst + binder) can be formed to coat the film using techniques such as, but not limited to, slit coating, spraying, blade coating, dip coating, screen printing, gravure roller coating, bar coating, etc., thereby introducing a layer between the film and the anode / cathode catalyst layer. The coated surface can then be dried, with or without methods such as heating, convection, or vacuum. Alternatively, the catalyst layer can be coated on top of the anode / cathode substrate instead of the film.

[0085] Example: Catalyst layer dispersed throughout the anode catalyst layer This application also includes a method for providing a catalyst layer dispersed throughout the anode catalyst layer, and the resulting structure ( Figure 5 In some embodiments, the catalyst can be dispersed within the anode catalyst layer by forming an ink (catalyst + anode catalyst + binder and / or AEI) and coating it onto the film using techniques including, but not limited to, slit-die coating, spraying, blade coating, dip coating, screen printing, gravure roller coating, bar coating, etc. The coated surface can then be dried, with or without methods such as heating, convection, or vacuum. Alternatively, the ink can be applied on top of the anode substrate layer instead of the film.

[0086] Example: Catalyst layer between the anode catalyst layer and the anode substrate layer This application also includes a method for providing a catalyst layer between an anode catalyst layer and an anode substrate layer, and the resulting structure ( Figure 6In some embodiments, the catalyst can be introduced between the anode catalyst layer and the anode substrate layer by forming an ink (catalyst + binder) and coating it onto the anode substrate layer using techniques including, but not limited to, slit-die coating, spraying, blade coating, dip coating, etc. The coated surface can then be dried, with or without methods such as heating, convection, or vacuum. Afterward, the dried surface can be coated with a standard anode catalyst layer using the techniques described above. Alternatively, other techniques such as chemical vapor deposition, atomic layer deposition, electrochemical deposition, etc., can be used to deposit the catalyst layer.

[0087] Example: Catalyst layer between anode substrate layers This application also includes a method for providing a catalyst layer between anode substrate layers, and the resulting structure ( Figure 7 In some embodiments, the catalyst can be introduced between the anode substrate layers by forming an ink (catalyst + binder) and applying it to the anode substrate layer using techniques including, but not limited to, slit-die coating, spraying, blade coating, dip coating, etc. The coated surface can then be dried, with or without methods such as heating, convection, or vacuum. Alternatively, other techniques such as chemical vapor deposition, atomic layer deposition, electrochemical deposition, thermochemical deposition, etc., can be used to deposit the catalyst layer. If the anode substrate layer consists of a total of X layers, the catalyst layer can be between any layers, on top of layers, at the bottom of layers, within layers, or on all layers. Here, X corresponds to any value between 0 and 100.

[0088] Example: Catalyst layer at the edge of the anode substrate layer This application also includes a method for providing a catalyst layer at the edge of an anode substrate layer, and the resulting structure ( Figure 8 In some embodiments, the layer can be introduced to the edge of the anode substrate layer by forming an ink (catalyst + binder) and applying it using techniques such as, but not limited to, slit-die coating, spraying, blade coating, dip coating, etc. The coated surface can then be dried, with or without methods such as heating, convection, or vacuum. Other techniques such as chemical vapor deposition, atomic layer deposition, electrochemical deposition, etc., can also be used to deposit the catalyst layer. The catalyst layer can also be deposited on a surface in direct contact with the substrate layer.

[0089] Example: Catalyst layer dispersed throughout the anode substrate layer This application also includes a method for providing a catalyst layer dispersed throughout the anode substrate layer. Figure 9In some embodiments, the layer can be incorporated into the anode substrate layer by forming an ink (catalyst + binder) and applying it using techniques such as, but not limited to, slit coating, spraying, blade coating, dip coating, etc. The coated surface can then be dried, with or without methods such as heating, convection, or vacuum. Other techniques, such as chemical vapor deposition, atomic layer deposition, electrochemical deposition, thermochemical deposition, etc., can also be used to deposit the catalyst layer.

[0090] The introduction of a combustion / oxidation catalyst can be in any one or all of the above situations.

[0091] Electrolytic cell and electrolytic cell On the other hand, this application also relates to electrolytic cells and battery stacks comprising multiple electrolytic cells. Thus, in one aspect, this application provides a water electrolyzer. In a preferred embodiment of this application, the water electrolyzer is an anion exchange membrane water electrolyzer (or AEMEL), which uses a solid polymer anion exchange membrane and substantially pure water, thus requiring a very low concentration of liquid electrolyte (e.g., <250 mM alkaline electrolyte, such as KOH or NaHCO3). A preferred structure of such an AEMEL includes end plates between which “n” electrochemical cells are arranged, each electrochemical cell having its own gas diffusion layer, membrane, and porous transport layer, while being separated from each other by bipolar plates (sometimes called intermediate plates). The number of cells “n” can be 1 (referred to as a single cell) or multiple (referred to as a stack).

[0092] In embodiments of this application, the anion exchange polymer is used as an AEM (anion exchange membrane) or AEI (anion exchange ionomer) to facilitate ion conduction in the electrolytic cell. Figure 1 As shown, anion exchange polymers can be used as AEIs in both the anode and cathode catalyst layers. AEIs can also be used as binders for any of the other ink formulations and coatings described above. For example, AEIs can be used as binders to coat a combustion / oxidation catalyst onto a substrate. Another material discussed is a crosslinking agent having functions such as ion conduction and promoting catalytic reactions. These materials can be linked to the anion exchange polymers discussed herein via crosslinking. This applies to anion exchange polymers used as membranes and AEIs. Another material discussed is a catalyst that promotes the combustion reaction of H2 with O2 to minimize H2 leakage in the O2 compartment, or vice versa. This catalyst has a different purpose compared to conventional hydrogen and oxygen evacuation catalysts used in the anode and cathode catalyst layers. The combustion / oxidation catalyst can be present in one or more of the following layers: membrane, anode catalyst layer, anode substrate layer. The catalyst can also be present in... Figure 1 Between any of the layers shown.

[0093] Preparation of polymer materials, AEM and AEI Another aspect of this application relates to methods for preparing and / or manufacturing the polymer materials, AEMs, AEIs, electrolyzer assemblies, catalysts, and electrolyzers discussed herein. It should be understood that the materials discussed above are incorporated into these methods, even if not explicitly stated below. For example, when the term "crosslinking agent" is used in discussions of the preparation of materials according to this application, it should be understood that a crosslinking agent can be the crosslinking agent discussed above, even if not repeated below (which is avoided to minimize repetition).

[0094] Therefore, in another embodiment, this application provides approaches and methods for manufacturing random (copolymer) or multiblock copolymers from monomer units, manufacturing multiblock copolymers from blocks, and crosslinking multiblock copolymers. Another aspect of this application relates to methods for manufacturing AEMs using one or more monomers.

[0095] In some embodiments, methods for producing the polymers of this application include (but are not limited to) vinyl addition or ring-opening metathesis polymerization (ROMP) reactions. For example, in the presence of a metal catalyst such as Pd and a solvent, polymerization of substituted norbornene molecules results in the formation of polymerized hydrophobic and / or hydrophilic polymer blocks based on norbornene and / or olefin molecules, wherein the polymer has a fully hydrocarbon backbone. In some embodiments, the monomer-to-catalyst ratio can range from about 1500:1 to about 1:1. Sequential and alternating addition of hydrophilic and / or hydrophobic monomers to the grown polymer produces a multiblock copolymer. The solvent can be nonpolar, such as toluene, xylene, chloroform, etc. The reaction mixture can be left at ambient temperature or elevated temperatures.

[0096] Another aspect of this application relates to the production of multiblock copolymers via a ring-opening metathesis (ROMP) reaction. In some embodiments, the copolymers formed using this method comprise hydrophobic and / or hydrophilic blocks. The hydrophobic blocks may have substituted C2 to C3 configurations. 20 Branched or unbranched alkyl spacer chains. Hydrophilic blocks may have substituted alkyl spacer chains with electrophilic carboxylic groups. Two or more hydrophilic blocks may be linked via a crosslinking agent, including but not limited to those with C2 to C3 linkages. 20 Alkyl spacer chains, or polyheterocyclic or spirocyclic amines linked by heterocyclic spacer chains (linked by heteroatoms such as N). The hydrophilic groups may also be functionalized to generate heterocyclic or spirocyclic amine functional groups. In one embodiment of this application, the copolymer can be used as an ion-bonding layer between any layers to prevent delamination. In some embodiments, this bonding layer may be referred to as or understood as an "intermediate layer".

[0097] In some embodiments, the AEM of this application is stabilized and / or reinforced with stabilizers. Examples of stabilizers include, but are not limited to, perfluoroethylene, ethylene tetrafluoroethylene, polybenzimidazole, styrene-butadiene, or styrene-ethylene-butene-styrene or polyolefins. Stabilizers may be in the form of woven or nonwoven fabrics, or monofilaments, or as a microporous inert substrate that can form an interpenetrating polymer network. The size of the strands can range from molecular size to large strands with a size of 0.01 to 1 mm or larger. The amount of stabilizer can vary between 1% by weight and 80% by weight.

[0098] Some embodiments of this application provide in-situ functionalization of the polymer materials discussed herein. In some embodiments, the polymer may be dissolved in a solvent or a mixture of solvents, such as H₂O, isopropanol, n-propanol, ethanol, methanol, acetone, tetrahydrofuran, toluene, chloroform, etc. The polymer may also be dissolved in a functionalized organic amine, which may be a liquid, such as trimethylamine, N-methylpiperidine, etc. In some embodiments, the functionalized organic amine, such as N-methylpiperidine or trimethylamine, is a crosslinking agent. In some embodiments, the functional additive is added to the dried resin with or without the solvent. The functional additive can alter the chemical structure of the polymer. In various aspects, the functional additive may be a crosslinking agent or a molecule that functionalizes polymer groups.

[0099] In some embodiments, polymer modification (e.g., to enhance activity or mechanical properties) is achieved by adding dried ionomer powder to a solvent to produce an ionomer solution. A functionalizing additive is then optionally added to the ionomer solution to obtain a modified polymer solution. Functionalization and / or crosslinking can be initiated via polymerization between two monomer units, via halide-containing end groups, or similar reactions. If the polymer is used as an ink, an optional catalyst can be added to prepare a catalyst-containing ink, or a catalyst-free ink can be prepared without using a catalyst.

[0100] An overview of polymer modification for enhancing activity or mechanical properties, such as... Figure 10 As described in the text. Specifically, the dried ionomer powder can be dissolved in a solvent to produce an ionomer solution. Functional additives can be added to the ionomer solution to produce a modified polymer solution. Optionally, a catalyst can be added to prepare a catalyst-containing ink. If no catalyst is added, a catalyst-free ink can be prepared.

[0101] In some embodiments, the prepared ink may optionally be homogenized using ultrasonic and shear mixing and then coated onto a substrate, which in some embodiments is a felt, foam, mesh, sintered plate, or sheet. In some embodiments, the felt is made of stainless steel or nickel, or an alloy thereof, or of carbon fibers in the form of graphite, carbon black, coke, or other allotropes thereof. In some embodiments, the foam is made of stainless steel or nickel, or an alloy thereof. In some embodiments, the sheet is made of stainless steel or nickel, or an alloy thereof, or may optionally be composed of a polymer film, which may or may not be a separate component relative to the AEM discussed herein. In some embodiments, the sheet is mechanically perforated or expanded to alter physical properties, such as, but not limited to, porosity, specific gravity, and permeability to gases and liquids. In some embodiments, the mesh is made of stainless steel or nickel, or an alloy thereof. In some embodiments, the sintered plate is made of stainless steel or nickel, or an alloy thereof, and is formed by sintering together the powders, fibers, threads, and / or net substrates discussed herein.

[0102] In some implementations, the prepared ink is coated onto the substrate by spraying, slit-die coating, scraping, dip coating, screen printing, gravure roller coating, bar coating, or chemical vapor deposition.

[0103] Roll-to-roll manufacturing components: Another aspect of this application includes a method for simultaneously manufacturing multiple layers of the components of this application at high speeds (e.g., between 1-25 m / min). As mentioned above, the electrolytic cell has multiple components in the form of several layers. Therefore, this application describes how to simultaneously produce these layers in two or more combinations.

[0104] Figure 11 The diagram illustrates a slit-die coating operation. In this embodiment, the substrate passes around a roller and under a slit die, which distributes coating fluid across the desired coating width before coating the substrate. As the coating is applied to the substrate, the substrate moves relative to the slit die. In some embodiments, the substrate is heated before, during, or after passing under the slit die to regulate the drying of the coating.

[0105] Example: Multi-layer slit mold head In one embodiment of this application, a slit-type die machine can be used to coat multiple layers in the form of a viscous liquid. As depicted in Figure 11, conventionally, only a single layer is coated onto a substrate. This application provides a method and apparatus for simultaneously coating multiple layers in liquid form.

[0106] Figure 12An embodiment of a multilayer coatable slit die is described. Here, N layers of liquid can be simultaneously coated on the coating side of the substrate. In a preferred embodiment, N is between 2 and 15.

[0107] Example: Multiple slit-type dies along the coated roll material Figure 13 An embodiment using multiple slit dies is described. Therefore, this application provides a method and apparatus for applying multiple layers along a coating production line using at least two coating slit dies. In a preferred embodiment, N slit dies can be used to coat the substrate. In a preferred embodiment, N is from 1 to 25.

[0108] In some embodiments, each slit die head may be coated with two or more layers. In some embodiments, the slit dies are placed one after another, i.e., combined. Figure 12 and 13 The methods described herein (and discussed above) are described in some embodiments. In some embodiments, the slit die is placed together with other processing units (e.g., dryers or more rollers) that separate them. In some embodiments, the roll material consists of a combination of various types of coating tools such as plasma treatment, dryers, gravure rollers, sprayers, heated rollers, etc.

[0109] In some embodiments, the coated substrate (coated with ionomer) may be further treated with functional additives according to this application, such as tertiary amines or heterocyclic amines discussed herein. In some embodiments, the coated ionomer containing the functional additive does not contain an added catalyst. In some embodiments, the coated substrate may be treated with an aqueous salt solution, such as a solution containing KOH, NaOH, NaCl, KCl, KBr, NaBr, etc.

[0110] Conventionally, battery assembly is accomplished by sandwiching the membrane between prepared electrodes. However, in one embodiment, an anion-exchange polymer layer can be coated onto a substrate (anode or cathode) to allow the membrane to be cast directly onto the substrate rather than as a separate component. Once the polymer cures, it behaves like a membrane, separating one electrode from another. This minimizes boundary resistance, increases polymer adhesion, reduces battery degradation due to erosion, and so on.

[0111] Example: Preparation and testing of cathode catalyst ink A dry polymer powder was prepared using a poly(norbornene) backbone. Random copolymers were synthesized using two types of monomers—those with hydrophobic alkyl-terminated side chains and those with hydrophilic alkyl halide-terminated side chains. After synthesis, 6.9 g of the dry polymer powder was used to prepare catalyst ink. The powder was placed in a Pyrex glass wide-mouth flask. The solvent in the catalyst ink then had the following composition: ethanol (99.5%): 194 ml, methanol: 56.4 ml, deionized water: 14.1 ml, and trimethylamine (46% aqueous solution). 39.24 g of Pt / C (47% Pt by weight) was added to the solution. The ink was then ultrasonically and high-shear mixed to achieve homogeneity. Following this, the ink was coated onto a gas diffusion substrate (GDS) made of carbon paper. The ink was coated onto a GDS roller at a speed of approximately 1 cm / s. A total of approximately 15 m of roller was coated with catalyst ink. After coating, the roller was passed through a drying section, which subsequently removed all residual solvent from the coated layer. After drying, the coated rollers are wound up for compact storage.

[0112] Small rectangular slices were cut from the coated GDS for evaluation in a small electrolyzer test stack. The test stack consisted of samples with 0.5 mg Pt / cm³. 2 The cathode was coated. The membrane used was a similar polymer with a poly(norbornene) backbone functionalized with N-methylpiperidine quaternary ammonium. The anode used was NiFe. 10 mM K2CO3 was used as the supporting electrolyte and flowed into the anode side. The supporting electrolyte was heated to 60-70°C using external heating before entering. After the temperature reached equilibrium, the stack power was turned on. The current density was increased from 0 to a constant value. The stack was maintained at this current overnight and varied from 1.5 to 0 A / cm at a step rate of 0.1 A / 15 s. 2 A slow voltage-current polarization profile was obtained. The battery polarization profile is shown in... Figure 14 As shown in Figure 14, the two identical coated electrode replicas are perfectly matched, demonstrating the repeatability and quality of the ink formulation and coating.

[0113] Following the polarization profile, the reactor was maintained at a constant current density for approximately 1000 h. Durability data are shown below. Figure 15 In the middle. For example Figure 15 As shown, we have demonstrated that the membrane-electrode assembly manufactured using the polymer materials described in this invention exhibits very good durability for use in higher performance, repeatable, and more durable electrolyzer devices.

[0114] The above description of preferred embodiments has been presented for illustrative and descriptive purposes only. It is not intended to be exhaustive or to limit the application to the precise forms disclosed, and modifications and variations are possible and / or will be obvious or readily apparent from practice in light of the above teachings. The embodiments were chosen and described to explain the principles of the application and its practical application, enabling those skilled in the art to utilize the application with various embodiments and modifications suitable for the particular intended use. The scope of this application is intended to be defined by the appended claims, and the claims cover all embodiments of the application, including the disclosed embodiments and their equivalents.

Claims

1. An anion exchange polymer comprising a compound of formula (I). (I) in: Each — represents an optional chemical bond, which can be a single or double bond, an ionic bond (or an electrovalent bond), a hydrogen bond, or a polar covalent bond; Each M n (where n≥2) represents a single unit, where each M n Choose from different types or categories (hydrophilic, hydrophobic); and Each C n (where n≥1) represents the crosslinking agent, where each C n Choose any of the different types or categories.

2. The anion exchange polymer according to claim 1, The anion exchange polymer is dissolved in a solvent and functionalized with a tertiary amine.

3. The anion exchange polymer according to claim 1, It further comprises a metal-organic compound bound to the anion exchange polymer via crosslinking, the metal-organic compound having the following formula: in: Each R n(i) It is H or a carbon-containing part, where i ≥ 1 (e.g., R). n1 R n2 wait); M is an organometallic complex comprising a metal atom or metal molecule coordinated to an organic molecule or atom, wherein the organic molecule optionally contains C, H, N, O, F and / or S atoms and / or the organic atom is C, H, N, O, F and / or S, wherein the metal of M is optionally Co, Fe, Ni, Pt, Ru, Ir, Mo, Ce, Mn, Cu or Si; Each L n(i) The ligand molecule forms a coordination bond with the metal complex and is attached to the polymer backbone; where i ≥ 1 (e.g., L n1 L n2 (etc.), wherein the ligand molecule comprises, but is not limited to, C, H, N, O, F, and S atoms, wherein the ligand molecule may be linked to one or more monomer units, wherein the monomer units may be hydrophilic or hydrophobic. Where R n(i) It can be omitted, and L n(i) One or more of them are directly combined with M.

4. An electrolytic cell, comprising: Cathode substrate layer; Cathode catalyst layer; membrane; Anode catalyst layer; as well as Anode substrate layer.

5. A method for incorporating a catalyst into a layer of an electrolytic cell, said electrolytic cell layer being selected from a cathode substrate layer, a cathode catalyst layer, a membrane, an anode catalyst layer, and an anode substrate layer, the method comprising: Formulating inks with or without anion exchange ionomers (AEI), and The layer is coated using a technique selected from slot die, gravure, spraying, atomic layer deposition, and chemical vapor deposition.

6. The method of claim 5, The coating step is performed using multi-layer simultaneous roll production, which is carried out using a multi-layer coatable slit die.

7. The method of claim 5, The coating step involves multi-layer simultaneous roll production, which is performed using multiple slit dies positioned along the coated roll.

8. A method for promoting oxidation, reduction, or combustion, the method comprising: Provided anion exchange polymer according to claim 1.

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