Free radical protective film

Abstract

This disclosure relates to a polymer electrolyte membrane comprising a polymer electrolyte and a metal complex, wherein the metal complex comprises a metal cation and a ligand, and the ligand comprises three or more functional groups, each functional group independently selected from phosphonic acids, sulfonic acids, and carboxylic acids or their anions. This disclosure further relates to a method for fabricating a polymer electrolyte membrane, as well as a membrane electrode assembly and a fuel cell comprising the polymer electrolyte membrane.

Description

[Technical Field]

[0001] Related applications This application claims priority to U.S. Provisional Application No. 63 / 460,413, filed on 19 April 2023. All teachings of the said application are incorporated herein by reference. [Background technology]

[0002] Background of the Invention Proton exchange membrane fuel cells (PEMFCs) are environmentally friendly energy conversion devices that operate at low temperatures and are more efficient than existing internal combustion engines. With these advantages, PEMFCs are emerging as a common alternative to fossil fuels in the transportation industry and have potential for use in a wide range of applications, including portable devices and static power supply systems.

[0003] The proton exchange membrane (PEM), which conducts protons and works to separate the cathode and anode, is the most important component of a PEMFC. The PEM significantly impacts the overall performance of the fuel cell; therefore, improving fuel cell efficiency requires a PEM that has high ionic conductivity, low fuel crossover, and high physicochemical and mechanical stability. Because PEMFCs use a thin membrane as the electrolyte, these devices are more portable and compact than other types of fuel cells. However, the thin membrane can also allow for fuel gas (hydrogen) crossover, negatively impacting battery efficiency. Furthermore, especially in the presence of hydrogen crossover, the PEM material can lead to the formation of HO on the electrodes. · and HOO · It is susceptible to degradation due to the presence of free radicals such as ions. Therefore, PEMs with high ionic conductivity, reduced hydrogen crossover, and stability against radical oxidants are required. [Overview of the project]

[0004] Summary of the Invention In a first embodiment, the disclosure relates to a polymer electrolyte membrane comprising a polymer electrolyte and a metal complex, wherein the metal complex comprises a metal cation and a ligand, and the ligand comprises three or more functional groups, each functional group independently selected from phosphonic acids, sulfonic acids, and carboxylic acids, or their anions.

[0005] In a second embodiment, the Disclosure relates to a method for producing a polymer electrolyte membrane as described herein in relation to a first embodiment and various aspects thereof, the method comprising: (a) providing a casting surface and a suspension comprising a metal complex, a polymer electrolyte, and (i) a crosslinking reagent and / or (ii) a crosslinking initiator; (b) placing the suspension on the casting surface to provide a layer of membrane; and (c) exposing the layer of membrane to conditions sufficient to allow (i) the polymer electrolyte and the crosslinking reagent to undergo a crosslinking reaction, or (ii) the crosslinking initiator to initiate crosslinking of the polymer electrolyte, thereby providing a polymer electrolyte membrane.

[0006] In a third embodiment, the present disclosure relates to a method for producing a polymer electrolyte membrane as described herein in relation to a first embodiment and various aspects thereof, the method comprising: (a) providing a suspension comprising a porous matrix and a metal complex and a polymer electrolyte; (b) contacting the porous matrix with the suspension to provide an immersed porous matrix; and (c) drying the immersed porous matrix to provide a polymer electrolyte membrane.

[0007] In a fourth aspect, the disclosure relates to a membrane electrode assembly (MEA), the MEA comprising a polymer electrolyte membrane; a cathode; and an anode as described herein in relation to a first aspect and various aspects thereof, wherein the polymer electrolyte membrane is positioned between the anode and the cathode.

[0008] In a fifth embodiment, the disclosure relates to a fuel cell, which includes one or more MEAs and one or more gas flow bipolar plates as described herein in relation to a fourth embodiment and various aspects thereof. [Brief explanation of the drawing]

[0009] Brief explanation of the drawing [Figure 1] Figure 1 shows a schematic diagram of the free radical scavenging (FSR) mechanism in hydrocarbon films, such as sulfonated polyphenylsulfone (sPPS or sPPSU). [Figure 2] Figure 2 shows the chemical structures of aminotris(methylphosphonic acid) (ATMP) and complexes containing a Ce cation, ATMP as a ligand, and NO3- as a complex anion. [Figure 3] Figure 3 is a bar graph showing Ce retention in a perfluorosulfonic acid (PFSA) film after 250 hours of accelerated stress testing, characterized by X-ray fluorescence spectroscopy. [Figure 4] Figure 4 is a bar graph showing the enhanced chemical durability of sPPS membranes with Ce(ATMP) complex additives compared to sPPS membranes without additives or membranes containing Ce nitrate, as measured by the Fenton reagent test. [Figure 5] Figure 5 is a bar graph showing the relative remaining weight of crosslinked sPPS membranes with Ce(ATMP) complex additive (1 wt.% Ce loading) after a Fenton reagent test at 80°C for 48 hours, and depends on the Ce to ATMP ratio. [Figure 6] Figure 6 is a bar graph showing the relative remaining weight of crosslinked sPPS films with Ce(ATMP) complex additive (1 wt.% Ce loading) after a Fenton reagent test at 80°C for 48 hours, and is dependent on the Ce oxidation state. [Figure 7] Figure 7 is a bar graph showing the relative residual weight of crosslinked sPPS films with Ce(ATMP) complex additive (1 wt.% Ce load) after a Fenton reagent test at 80°C for 48 hours, and depends on the acid used in the synthesis of the Ce(ATMP) complex. [Figure 8] Figure 8 shows the single-cell polarization and power curves of films prepared using Nafion™212 (N212) and crosslinked sPPS. [Figure 9]Figure 9 is a plot showing the hydrogen crossover of N212, Nafion™ 117 (N117), and cross-linked sPPS. [Figure 10] Figure 10 shows the polarization curves of an 8 μm thick PFSA D2020 (D2020) film containing 1.4 mol% Ce complex along with various ligands. [Figure 11] Figure 11 is a plot showing hydrogen crossover of an 8 μm thick D2020 film containing 1.4 mol% of a complex along with various ligands. [Figure 12] Figure 12 shows the polarization curve of an 8 μm thick D2020 film containing 1.4 mol% of a Co, Cu, Ni, or Fe complex along with ATMP ligand. [Figure 13] Figure 13 is a plot showing the hydrogen crossover of an 8 μm thick D2020 film containing 1.4 mol% of a Co, Cu, Ni, or Fe complex along with ATMP ligand. [Modes for carrying out the invention]

[0010] The foregoing is evident from the following more specific description of exemplary embodiments of the invention, as illustrated in the attached drawings, where similar reference numerals refer to the same parts through different drawings. The drawings are not necessarily made in a fixed proportion, but rather are intended to illustrate embodiments of the invention.

[0011] Detailed description of the invention The following describes exemplary embodiments of the present invention.

[0012] Current (incumbent) PEM technology is dominated by perfluorosulfonic acid (PFSA) polymer electrolytes that combine a polytetrafluoroethylene (PTFE) backbone with sulfonic acid side groups. PFSA materials have various drawbacks, including insufficient membrane durability for robust fuel cells, high ionomer costs, and the threat of regulatory restrictions that can exacerbate cost concerns or outright illegal use. Sulfonated hydrocarbon membranes are a promising future alternative to PFSA, particularly those based on polymers with existing supply chains. Sulfonated hydrocarbon membranes offer reduced membrane costs and a more secure path towards a hydrogen economy.

[0013] Hydrocarbon membranes have historically had substantial swelling, insufficient conductivity, water solubility, or insufficient durability. The most prominent of these concerns is the low chemical durability as a result of damage caused by free radicals formed in side reactions after gas crossover. Previous work has shown that hydrocarbon membranes are substantially more susceptible to radical attack than PFSA membranes due to easier radical attack reactions (about 10 9 -10 10 M -1 s -1 for hydrocarbon membranes compared to about 10 6 M -1 s -1 for PFSA). These processes are accelerated under aggressive and harsh load cycles, where higher power demands result in higher device temperatures. After membrane and ionomer decomposition, acidic by-products cause further decomposition of bipolar plates and catalyst layers, while also causing further acceleration of membrane decomposition. In short, fuel cell durability is closely related to membrane durability, which is indicated by gas permeability and resistance to radical attack.

[0014] Two main approaches have been investigated to improve the durability of hydrocarbon membranes, namely i) the use of hydrocarbon polymers with highly branched aromatic rings, and ii) the addition of free radical scavengers (FRS) to the membrane.

[0015] The first approach pursues chemical durability using highly branched aromatic polymers, such as sulfophenylated polyphenylenes. These systems can successfully replicate PFSA performance in terms of swelling, conductivity, and polarization, but also exhibit a hydrogen crossover approximately 20–30% lower than PFSA. While sulfophenylated polyphenylenes recently achieved the DOE severe durability target in accelerated stress testing (AST), these polymers remain susceptible to oxidation and radical attack. Sulfophenylated polyphenylenes lose approximately 80% of their weight when immersed in 1% H2O2 at 80°C for just 24 hours, and decompose further when subjected to Fenton reagent testing. These concerns motivate research into further increasing hydrocarbon film durability.

[0016] The second approach involves incorporating redox-active species as FRS in either the film or catalyst layer. Additives can range from molecular species such as Ce and Mn compounds or related metal oxides such as CeO2 and MnO2, introduced by cation exchange reactions, sol-gel synthesis, or simple addition. It is hypothesized that the metal redox pair directly scavenges the formed aromatic radical rather than the hydroxyl radical. This prevents ring-breaking secondary reactions, which are significantly slower (10 2 ~10 5 M -1 s -1), and free radical scavengers are used as an effective strategy to protect hydrocarbons from radical-induced decomposition (Figure 1). Incorporation of cerium-based FRS additives, such as cerium chloride in sulfophenylated polyphenylene (sPPB) with biphenyl linkers, into hydrocarbon membranes shows a significant improvement in membrane durability, including up to a 3x increase in sPPB weight retention after 24 hours of immersion at 80°C in 1% H2O2. However, these effects are temporary due to metal oxide dissolution or cation transfer from the membrane.

[0017] Hydrogen crossover is the unwanted diffusion of hydrogen from the anode to the cathode through the membrane in a fuel cell. Hydrogen crossover can have at least three effects: reduced fuel efficiency, a decrease in cathode potential, and the formation of aggressive peroxide radicals. Crossover hydrogen can react directly with oxygen at the cathode surface, resulting in a lower cathode potential than in a lower fuel cell. More significantly, this direct reaction of H2 and O2 at the cathode can produce peroxide radicals, which attack not only the catalyst layer but also the membrane, leading to significant decomposition of the catalyst layer and membrane. Furthermore, it has been confirmed that the formation of hot spots or hydrogen peroxides due to the highly exothermic chemical reaction of H2 and O2 can create pinholes in the membrane, destroy the MEA, and lead to safety issues. Accelerated sintering of the catalyst can also be caused by this hydrogen crossover. The presence of adventitious Cu and Fe further catalyzes the decomposition of H2O2 into reactive oxygen radicals. To address this underlying cause, the membrane can be made more durable by introducing FRS into the membrane. In some embodiments, this disclosure shows that insoluble complexes of reducing metals can act as FRS in PEM.

[0018] In some embodiments, the disclosure shows that water-insoluble metal complexes exhibit sustained free radical scavenging in PEMs. The FRSs of the disclosure protect both hydrocarbon and PFSA membranes from radical attack, remain insoluble under PEM fuel cell conditions, and are redox-active additives. The insoluble FRSs are incorporated into hydrocarbon membranes to provide radical attack protection to the underlying hydrocarbons.

[0019] Cerium species, such as cerium nitrates or cerium oxides, are frequently used as FRS additives in PEM films to improve film durability. However, they are susceptible to etching and leaching, limiting their efficacy. Complexation of metals, such as cerium, with ligands containing multiple functional groups, such as tridentate, quaternate, pentate, or hexadentate ligands, yields water-insoluble complexes that persist in acidic environments. The insolubility of such complexes prevents cerium migration after 250 hours under accelerated stress test (AST) conditions in PFSA films, addressing a major drawback of conventional cerium additives (Figure 3).

[0020] In several embodiments, membranes containing Ce and aminotris(methylphosphonic acid) (ATMP) (Figure 2) exhibited durability three times greater than the baseline value for Nafion® XL (containing conventional Ce salt FRS). In several embodiments, the membranes of this disclosure showed increased material retention after 48 hours of exposure to Fenton reagent at 80°C (Figure 4). A control sample, a crosslinked sulfonated polyphenylsulfone (sPPS) membrane without FRS additives, was almost completely digested, while sPPS or Ce(ATMP) complexes with 1 wt.% Ce as cerium nitrate retained 20% and 30% of the initial membrane, respectively. Ce(ATMP) complex + sPPS retained 10 times more material than the control and 33% more material than cerium nitrate + sPPS, indicating that Ce(ATMP) complex is an effective FRS additive for protecting hydrocarbons from radical attack.

[0021] In some embodiments, this disclosure describes highly tunable synthesis of Ce(ATMP) complexes using simple free radical scavenging capabilities (Figures 5-7). Ce(ATMP) complexes are tunable by the Ce-to-ATMP ratio (Figure 5), the Ce oxidation state (Figure 6), and the Ce secondary counterion, also known as the complex anion (Figure 7). Membranes containing sPPS+Ce(ATMP) complexes (1 wt.% Ce) exposed to the Fenton test showed significantly different material retention depending on the introduced Ce(ATMP) species, and in most cases showed higher material retention than when using cerium nitride. These tests unexpectedly demonstrate that the chemical durability of Ce(ATMP)-containing membranes depends on parameters such as the Ce-to-ligand ratio, the Ce oxidation state, and the properties of the complex anion.

[0022] In some embodiments, the disclosure further intends to prepare composite films containing sPPS+Ce(ATMP) complexes for evaluation of conductivity and Fenton reagent test stability. In some embodiments, the Ce(ATMP) complex additives are synthesized with various Ce formal charges, Ce:ATMP ratios, and Ce anions prior to incorporation into sPPS inks with Ce(ATMP) complex loadings of 0.5, 1, 3, 5, and 7 wt.% Ce. Ce species homogeneity and oxidation state are evaluated by energy-dispersive X-ray analysis and X-ray spectroscopy, respectively, to ensure a uniform distribution of redox-active species.

[0023] In some embodiments, Ce(ATMP) complexes may form particles that are too large to be uniformly distributed throughout the film. Mortars and pestles, sonication, and expanded ink stirring may be used to improve film uniformity. Alternatively, adjusting the synthesis concentration is valued to achieve smaller particles.

[0024] In some embodiments, blade coatings are used to scale up supported hydrocarbon film casting. A solution containing the sPPS+Ce(ATMP) complex is used to cast the film onto a porous PTFE support, and the effects of blade thickness, casting rate, and solution concentration on film uniformity and support filling are determined. Support filling is evaluated by sPPS optical annihilation in Fourier transform infrared spectroscopy.

[0025] In some embodiments, the ionic conductivity of the prepared membrane is evaluated using AC impedance spectroscopy as a function of temperature and humidity in a Scribner fuel cell test stand having a membrane conductive attachment. The temperature can vary from 30°C to 120°C, and the relative humidity can vary from 95% to anhydrous conditions.

[0026] In some embodiments, the mechanical properties of the prepared films are evaluated under dry and water-immersion conditions at ambient temperature. Briefly, the samples are measured in an Instron microtension tester to obtain stress-strain curves, as well as elongation at fracture per ASTM 1708 sample preparation and ASTM D882 measurement standards. Thickness is measured using a standard caliper capable of measuring thicknesses down to the micrometer range.

[0027] In some embodiments, the H2 crossover is monitored using the limited current density method in accordance with DOE guidelines. H2 flows at the anode and N2 flows at the cathode, and the cathode potential is swept from the resting potential to 900mV with respect to the anode while measuring the anode current.

[0028] In some embodiments, the membrane is dried at 80°C for 12 hours before initial size, thickness, and weight measurements are collected. The membrane is then immersed in 30°C water for 24 hours, and remeasured for size, thickness, and weight, and swelling in water is measured. After the swelling test, the membrane is submerged in 100°C water for 200 hours, then dried at 80°C for 12 hours, and gravimetrically measured to identify any weight changes.

[0029] In some embodiments, hydrocarbon + Ce(ATMP) complex membranes are tested for fuel cell operation. In some embodiments, sPPS + Ce(ATMP) complex membranes have a density of 0.2 mg Pt / cm². 2 A gas diffusion electrode with a nominal load is used to load the fuel cell at the test stand. The membrane electrode assembly (MEA) is then tested for fuel cell operation by measuring the cell voltage versus current density as a function of temperature and degree of humidification. The catalyst coating film (CCM) is then subjected to accelerated decomposition testing by holding the CCM at an open-circuit voltage in accordance with DOE guidelines.

[0030] In some embodiments, AST is used to evaluate membrane durability. This stress test includes RH cycling under wet and dry conditions, along with monitoring of fuel cell open-circuit potential and hydrogen crossover, and is used to quantify membrane durability. Membrane degradation is evaluated using hydrogen crossover, shortening resistance, hydrogen-air polarization curve measurement, and fluoride release rate. Post-analysis of membranes and MEAs is performed to identify microstructural changes, such as cerium migration, membrane thinning, and pinhole formation.

[0031] In some embodiments, a CCM comprising a core sPPS+Ce(ATMP) complex film and a catalyst coating (sPPS+Ce(ATMP) complex, Pt, carbon black) is achieved by directly coating the catalyst layer onto the film, resulting in a 0.5 mg Pt / cm² 2 It is manufactured with a nominal load. Briefly, the catalyst material is placed by spray coating using a Sonotek ExactaCoat system with an ultrasonic nozzle, prior to the annealing process that crosslinks the hydrocarbon polymer. The morphology is characterized by top-down and cross-sectional electron microscopy to determine the microstructure, with particular attention to the interface with the underlying film. General uniformity is monitored by optical microscopy. Viscosity, layer thickness, and uniformity are adjusted by placement temperature and solution concentration.

[0032] In some embodiments, this disclosure describes the preparation of Ce complexes having the following polydentate coordinating ligands: diethylenetriaminepentakis(methylenephosphonic acid) (DTPMP), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), and mellitic acid. The complexes were prepared in a Ce:ligand ratio of 3:1. The synthesized complexes were combined with PFSA in a suspension, and the suspension was applied to a porous ePTFE layer to form a composite polymer electrolyte membrane. The resulting supported polymer electrolyte membrane containing the PFSA ionomer (D2020) and 1.4 mol% Ce complex in the ePTFE matrix functions as an effective PEM fuel cell membrane, as indicated by the generation of polarization curves under H2 and air conditions (Figure 10). Furthermore, the membrane is an effective PEM fuel cell membrane, exhibiting measurably low hydrogen crossover, as shown in H2 crossover experiments (Figure 11). These data demonstrate that the incorporation of Ce complexes with various polydentate coordinating ligands into polymer electrolyte membranes does not result in increased hydrogen permeability.

[0033] In some embodiments, this disclosure describes the preparation of complexes having ATMP as a ligand with various metals (Co, Cu, Fe, Ni). The complexes were prepared in a metal:ligand ratio of 3:1. The synthesized complexes were combined with PFSA in a suspension, and the suspension was applied to a porous ePTFE layer to form a composite polymer electrolyte membrane. The resulting supported polymer electrolyte membrane containing the PFSA ionomer (D2020) and 1.4 mol% of the metal complex in the ePTFE matrix functions as an effective PEM fuel cell membrane, as indicated by the generation of polarization curves under H2 and air conditions (Figure 12). Furthermore, the membrane is an effective PEM fuel cell membrane, exhibiting a measurably low hydrogen crossover, as shown in H2 crossover experiments (Figure 13). These data demonstrate that the incorporation of complexes containing ATMP as a ligand with various metals into polymer electrolyte membranes does not increase hydrogen permeability.

[0034] definition A numerical range includes the number that defines the range. For example, "x is an integer between 5 and 14" means that x can be 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14. Measurable and measurable values ​​are understood to be approximations, taking into account significant figures and errors associated with measurement. As used in this application, the terms "about" and "approximately" have their meanings as understood in the art; the use of one for the other does not necessarily imply a different range. Unless otherwise indicated, numerical values ​​as used in this application should be understood to include normal deviations and / or variations as understood by a person skilled in the art in the relevant field, with or without modifiers such as "about" or "approximately." In some embodiments, the terms “approximately” or “about” mean a range of values ​​that, unless otherwise stated or it is evident from the context (except where such number exceeds 100% of a possible value), are 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, or less in either direction (greater than or less than) of the given reference value.

[0035] As used herein, the term “polymer electrolyte” means a polymer that, under certain conditions, has a net positive or negative charge due to the presence of charged repeating units. In some embodiments, the polymer electrolyte is or contains a polycation; in some embodiments, the polymer electrolyte is or contains a polyanion. In some embodiments, the polymer electrolyte has a neutral charge under certain conditions, for example, at a certain range of pH values, but can be a polycation or a polyanion under different conditions. A polycation has a net positive charge, and a polyanion has a net negative charge. The net charge of a given polymer electrolyte may depend on the surrounding chemical conditions, for example, pH.

[0036] As used herein, the term “degree of sulfonation” means the number of repeating units having at least one sulfonic acid / sulfonate group. For example, a 20% degree of sulfonation indicates a polymer in which 20 percent of its repeating units are sulfonated, and a 100% degree of sulfonation indicates that all repeating units in the polymer contain one sulfonic acid / sulfonate group. This may include polymers containing multiple sulfonic acid / sulfonate groups per repeating unit (e.g., disulfonation, trisulfonation, tetrasulfonation, etc.). In some embodiments, a sulfonated polymer may contain an average of 2 sulfonic acid groups per repeating unit, which corresponds to a 200% degree of sulfonation. In some embodiments, a sulfonated polymer may contain an average of 2, 3, 4, or 5 sulfonic acid groups per repeating unit, which corresponds to a 200%, 300%, 400%, or 500% degree of sulfonation, respectively. In some embodiments, the sulfonated polymer may contain an average of 1.5 to 2.5 sulfonic acid groups per repeating unit, which corresponds to a degree of sulfonation of 150% to 250%.

[0037] The sulfonated polymers of this disclosure may also be characterized by the average number of sulfonic acid groups per repeating unit. For example, sulfonated polyphenylsulfone (sPPS) may contain 1, 2, 3, 4, 5, 6, 7, or 8 sulfonic acid groups per repeating unit. For example, a repeating unit of sPPS may have 2 sulfonic acid groups: [ka] It may include. Alternatively, the repeating unit of sPPS may consist of 4 or 6 sulfonic acid groups: [ka] It may include.

[0038] In a given polymer, some repeating units may have, for example, one sulfonic acid group, some repeating units may have two sulfonic acid groups, and some repeating units may have three or more sulfonic acid groups. Therefore, analysis, for example,1 The number of sulfonic acid groups per repeating unit in a bulk polymer, as measured by 1H NMR spectroscopy or ion exchange capacity, corresponds to the average number of sulfonates across all repeating units of the polymer.

[0039] As used herein, the term "polyphenylsulfone" refers to the following repeating units: [ka] This refers to polymers that contain [a specific compound / substance].

[0040] As used herein, the term "polyetheretherketone" refers to the following repeating units: [ka] This refers to polymers that contain [a specific compound / substance].

[0041] As used herein, the term "polybenzimidazole" refers to the following repeating units: [ka] This refers to polymers that contain [a specific compound / substance].

[0042] As used herein, the term "polyethersulfone" refers to the following repeating units: [ka] This refers to polymers that contain [a specific compound / substance].

[0043] As used herein, the term "polyphenylene oxide" refers to the following repeating units: [ka] This refers to polymers that contain [a specific compound / substance].

[0044] As used herein, the term "polyarylene ether ketone" refers to the following repeating units: [ka] This refers to a polymer containing one or more of the following:

[0045] As used herein, the term "poly(sulfone)" refers to the following repeating units: [ka] This refers to polymers that contain [a specific compound / substance].

[0046] As used herein, the term "poly(sulfidesulfone)" refers to the following repeating units: [ka] This refers to polymers that contain [a specific compound / substance].

[0047] As used herein, the term "polyimide" refers to the following repeating units: [ka] This refers to polymers that contain [a specific compound / substance].

[0048] As used herein, the term "poly(etherimide)" refers to the following repeating units: [ka] This refers to polymers that contain [a specific compound / substance].

[0049] As used herein, the term "polyetherpyridine" refers to the following repeating units: [ka] This refers to polymers that contain [a specific compound / substance].

[0050] As used herein, the term "polyphosphazene" refers to the following repeating units: [ka] This refers to polymers that contain [a specific compound / substance].

[0051] As used herein, the term "sulfophenylated polyphenylene" refers to the following repeating units: [ka] This refers to polymers that contain [a specific compound / substance].

[0052] As used herein, the term "mellitic acid" refers to the following compounds: [ka] It refers to.

[0053] As used herein, the term "nitrilotriacetic acid" refers to the following compounds: [ka] It refers to.

[0054] Any of the above polymer repeating units may be -CN, -NO2, -N3, -OH, F, Cl, Br, I, oxo, -SO2H, -SO3H, -OR aa , -NH(R aa ), -N(R aa )2, -N(R aa )3 + X - -SH, -SR aa -C(=O)R aa -CO2H, -CHO, -CO2R aa -OC(=O)R aa , -OCO2R aa -C(=O)N(R aa )2, -OC(=O)N(R aa )2, -NR aa C(=O)R aa , -NR aa CO2R aa , -NR aa C(=O)N(R aa )2, -C(=NR aa )R aa -C(=O)NR aa SO2R aa , -NRaa SO2R aa , -SO2N(R aa )2, -SO2R aa , -SO2OR aa , -OSO2R aa -S(=O)R aa -OS(=O)R aa , -Si(R aa )3, -OSi(R aa )3, C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 Haloalkyl, C 3-12 Cycloalkyl, 3-16 member heterocyclyl, 5-12 member heteroaryl and C 6-12 It may have one or more hydrogen atoms substituted with aryl, X - R is a counterion, aa Each of these examples is independently H, -OH, and C. 1-10 Alkyl, C 1-10 Haloalkyl, C 3-12 Cycloalkyl, 3-16 member heterocyclyl, 5-12 member heteroaryl, and C 6-12 Selected from the aryl group, or two R's aa The groups combine to form 3- to 16-membered heterocyclines.

[0055] As used herein, “complex anion” is a negatively charged group associated with a positively charged group in order to maintain electronic neutrality. A complex anion may be monovalent (i.e., containing one formal negative charge). A complex anion may also be polyvalent (i.e., containing more than one formal negative charge), for example, divalent or trivalent. An exemplary complex anion is a halide ion (e.g., F - Cl - , Br - , I - ), NO3 - ClO4 - H2PO4 - , HCO3 - HSO4 -, sulfonate ions (e.g., methanesulfonate, trifluoromethanesulfonate, p - toluenesulfonate, benzenesulfonate, 10 - camphorsulfonate, naphthalene - 2 - sulfonate, naphthalene - 1 - sulfonic acid - 5 - sulfonate, ethane - 1 - sulfonic acid - 2 - sulfonate, etc.), carboxylate ions (e.g., formate, acetate, propanoate, benzoate, glycerate, lactate, tartrate, glycolate, gluconate, etc.), BF4 - , PF4 - , PF6 - , AsF6 - , SbF6 - , B[3,5-(CF3)2C6H3]4 - , B(C6F5)4 - , BPh4 - , Al(OC(CF3)3)4 - and carborane anions (e.g., CB 11 H 12 - or (HCB 11 Me5Br6) - ) may be mentioned. Exemplary anionic counterions that can be polyvalent include CO3 2- , HPO4 2- , PO4 3- , B4O7 2- , SO4 2- , S2O3 2- , carboxylate anions (e.g., tartrate, citrate, fumarate, maleate, malate, malonate, gluconate, succinate, glutarate, adipate, pimelate, suberate, azelate, sebacate, salicylate, phthalate, aspartate, glutamate, etc.), and carborane may be mentioned.

[0056] As used herein, the term “polyalcohol” means an alcohol containing one or more hydroxyl groups. Examples of polyalcohols include, but are not limited to, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, glycerol, erythriol, xylitol, hydroquinone, catechol, resorcinol, and phloroglucinol.

[0057] As used herein, the term “perfluorosulfonic acid” or “PFSA” refers to the following structural formula: [ka] This refers to a polymer represented by the formula, where R f x represents a perfluoroalkylene or perfluorooxyalkylene group, where x and y represent the relative proportions of the perfluoro monomer and the sulfonated monomer, respectively. As used herein, the terms “perfluoroalkylene” or “perfluorooxyalkylene” mean an alkylene or oxyalkylene group, where all hydrogen atoms are substituted with fluorine. One class of PFSA is shown in structural formula (I): [ka] These are represented by [the following symbols]. Such PFSAs are usually classified according to their side chain length. For example, Aquivion® (formerly Dow SSC) PFSAs are generally classified as short-side-chain (SSC) PFSAs, while Nafion® is considered a long-side-chain (LSC) PFSA. Examples of commercially available PFSAs include: [Table 1] These are some examples.

[0058] As used herein, the term “crosslinking” refers to the formation of a covalent or ionic bond between another repeating unit which is part of the same or a different main chain as a polymer repeating unit, or between a polymer repeating unit and a crosslinking reagent.

[0059] As used herein, the term "crosslinked polymer" refers to a polymer in which two or more non-adjacent repeating units of the same or different main chains are linked via a crosslinking moiety. The term "crosslinked polymer" also refers to two or more different main chains linked via a plurality of crosslinking moieties.

[0060] As used herein, the term "crosslinking moiety" refers to a polyvalent, e.g., divalent or trivalent moiety, which forms a covalent bond with one or more non-adjacent repeating units of the same polymer main chain or one or more repeating units of different main chains. The crosslinking moiety may include a charged group, e.g., an ammonium group, a metal ion, a carboxylate group, or a sulfate group. In some embodiments, the crosslinking moiety has the following structural formula:

Chemical formula

[0061] As used herein, the term “crosslinking reaction” refers to a chemical reaction between functional groups bonded to repeating units of a polymer, or between functional groups bonded to repeating units of a polymer and a crosslinking reagent, resulting in the formation of covalent or electrostatic / ionic bonds between polymer chains, or between polymer chains and the crosslinking reagent. The polymers of the films disclosed herein may contain one or more functional groups, which are not limited to NH2, -CN, -NCO, -N3, -OH, F, Cl, Br, I, oxo, -SO2H, -SO3H, -OCO2H, -OCO2Cl, -SH, -CO2H, -CHO, -CO2Cl, C 2-12 Alkenyl and C 2-12 Alkinyl is one example.

[0062] As used herein, the term “conditions sufficient for the polymer and crosslinking reagent to experience a crosslinking reaction” means the external stimuli (e.g., heat, UV light, microwave irradiation, presence of a chemical initiator, e.g., a radical initiator) and time required for the formation of a crosslinked polymer.

[0063] As used herein, the term “degree of crosslinking” in a polymer is defined as the percentage of repeating units of the polymer that can experience crosslinking and form crosslinked portions. In some embodiments, the degree of crosslinking is about 5% to about 95%, about 10% to about 80%, about 20% to about 80%, about 30% to about 70%, about 40% to about 60%, about 30% to about 50%, about 20% to about 50%, about 40% to about 70%, about 20% to about 50%, or about 10% to about 50%. In some embodiments, the degree of crosslinking is about 5%, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, or about 90%.

[0064] As used herein, the term “repeating unit” (also known as “monomer unit”) refers to a chemical moiety that repeats periodically itself, and which, when linked together in a continuous manner, produce a complete polymer chain (excluding terminal groups). A polymer may contain one or more different repeating units.

[0065] As used herein, the “backbone” or “backbone” of a polymer is a series of bonded atoms that come together to form a continuous chain of molecules. As used herein, the “side chains” of a polymer are a series of bonded atoms that hang from the backbone of the polymer.

[0066] As used herein, the term "alkyl" means a radical of a linear or branched saturated hydrocarbon group having 1 to 10 carbon atoms ("C"). 1-10 Alkyl). In some embodiments, the alkyl group has 1 to 9 carbon atoms ("C"). 1-9 Alkyl). In some embodiments, the alkyl group has 1 to 8 carbon atoms ("C"). 1-8 Alkyl). In some embodiments, the alkyl group has 1 to 7 carbon atoms ("C"). 1-7 Alkyl). In some embodiments, the alkyl group has 1 to 6 carbon atoms ("C"). 1-6 Alkyl). In some embodiments, the alkyl group has 1 to 5 carbon atoms ("C"). 1-5 Alkyl). In some embodiments, the alkyl group has 1 to 4 carbon atoms ("C"). 1-4 Alkyl). In some embodiments, the alkyl group has 1 to 3 carbon atoms ("C"). 1-3 Alkyl). In some embodiments, the alkyl group has 1-2 carbon atoms ("C"). 1-2 Alkyl). In some embodiments, the alkyl group has one carbon atom ("C1 alkyl"). In some embodiments, the alkyl group has 2 to 6 carbon atoms ("C1 alkyl"). 2-6 Alkyl). C 1-6Examples of alkyl groups include methyl (C1), ethyl (C2), propyl (C3) (e.g., n-propyl, isopropyl), butyl (C4) (e.g., n-butyl, tert-butyl, sec-butyl, iso-butyl), pentyl (C5) (e.g., n-pentyl, 3-pentanyl, amyl, neopentyl, 3-methyl-2-butanyl, tertiary amyl), and hexyl (C6) (e.g., n-hexyl). Further examples of alkyl groups include n-heptyl (C7), n-octyl (C8), etc. Unless otherwise specified, each example of alkyl group is independently either unsubstituted ("unsubstituted alkyl") or substituted with one or more substituents (e.g., halogens such as F) ("substituted alkyl"). In some embodiments, the alkyl group is unsubstituted C 1-10 Alkyl (unsubstituted C) 1-6 Alkyl groups include, for example, -CH3(Me), unsubstituted ethyl (Et), unsubstituted propyl (Pr, for example, unsubstituted n-propyl (n-Pr), unsubstituted isopropyl (i-Pr)), and unsubstituted butyl (Bu, for example, unsubstituted n-butyl (n-Bu), unsubstituted tert-butyl (tert-Bu or t-Bu), unsubstituted sec-butyl (sec-Bu), unsubstituted isobutyl (i-Bu), etc.). In one embodiment, the alkyl group is substituted C 1-10 Alkyl (substituted C) 1-6 These are alkyl groups (e.g., -CF3, Bn, etc.).

[0067] The term "aryl" refers to a radical of a monocyclic or polycyclic (e.g., bicyclic or tricyclic) 4n+2 aromatic ring system (e.g., having 6, 10, or 14 π electrons shared in a cyclic array) having 6 to 14 ring carbon atoms and 0 heteroatoms within the aromatic ring system. 6-14 In some embodiments, the aryl group has six ring carbon atoms ("C6 aryl"; e.g., phenyl). In some embodiments, the aryl group has ten ring carbon atoms ("C6 aryl"). 10 "Aryl"; for example, naphthyl (such as 1-naphthyl and 2-naphthyl). In some embodiments, the aryl group has 14 ring carbon atoms ("C"). 14"Aryl" (e.g., anthracyl). "Aryl" also includes ring systems, where an aryl ring, as defined above, is condensed with one or more carbocyrillic or heterocyclyl groups, and the radical or bonding point is on the aryl ring, and in such examples the number of carbon atoms continues to specify the number of carbon atoms in the aryl ring system. Unless otherwise specified, each example of an aryl group is independently either unsubstituted ("unsubstituted aryl") or substituted with one or more substituents ("substituted aryl"). In some embodiments, the aryl group is unsubstituted C 6-14 It is aryl. In one embodiment, the aryl group is a substituted C 6-14 It is Ariel.

[0068] The term "haloalkyl" refers to a substituted alkyl group, where one or more hydrogen atoms are independently substituted with a halogen, such as fluoro, bromo, chloro, or iodine. In some embodiments, the haloalkyl moiety has 1 to 12 carbon atoms ("C"). 1-12 ("Haloalkyl"). In some embodiments, the haloalkyl portion has 1 to 6 carbon atoms ("C"). 1-6 ("Haloalkyl"). In some embodiments, the haloalkyl portion has 1 to 4 carbon atoms ("C"). 1-4 ("Haloalkyl"). In some embodiments, the haloalkyl portion has 1 to 3 carbon atoms ("C"). 1-3 ("Haloalkyl"). In some embodiments, the haloalkyl portion has 1 to 2 carbon atoms ("C"). 1-2 Haloalkyl groups are a subset of haloalkyl groups. Examples include -CHF2, -CH2F, -CF3, -CH2CF3, -CF2CF3, -CF2CF2CF3, -CCl3, -CFCl2, and -CF2Cl.

[0069] The term “heterocyclyl” or “heterocyclic” refers to a radical of a 3- to 16-membered non-aromatic ring system having a ring carbon atom and 1-4 ring heteroatoms, where each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“3-16 membered heterocyclyl”). In a heterocyclyl group containing one or more nitrogen atoms, the bond site can be a carbon or nitrogen atom, if the valence allows. A heterocyclyl group can be monocyclic (“monocyclic heterocyclyl”) or polycyclic (e.g., condensed, bridging, or spirocyclic systems, e.g., bicyclic systems (“bicyclic heterocyclyl”) or tricyclic systems (“tricyclic heterocyclyl”)), and may be saturated or contain one or more carbon-carbon double or triple bonds. A heterocyclyl polycyclic ring system may contain one or more heteroatoms in one or both rings. "Heterocyclyl" also refers to a ring system in which the heterocyclyl ring defined above is fused with one or more carbocyclyl groups, with the bonding point located on either the carbocyclyl or heterocyclyl ring, or a ring system in which the heterocyclyl ring defined above is fused with one or more aryl or heteroaryl groups, with the bonding point located on the heterocyclyl ring, in which case the number of ring members continues to specify the number of ring members in the heterocyclyl ring system. Unless otherwise specified, each example of a heterocyclyl is independently unsubstituted ("unsubstituted heterocyclyl") or substituted with one or more substituents ("substituted heterocyclyl"). In certain embodiments, the heterocyclyl group is an unsubstituted 3- to 14-membered heterocyclyl. In certain embodiments, the heterocyclyl group is a substituted 3- to 14-membered heterocyclyl.

[0070] In some embodiments, the heterocyclyl group is a 4-10 membered non-aromatic ring system having a ring carbon atom and 1-4 ring heteroatoms, where each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("4-10 membered heterocyclyl"). In some embodiments, the heterocyclyl group is a 4-8 membered non-aromatic ring system having a ring carbon atom and 1-4 ring heteroatoms, where each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("5-8 membered heterocyclyl"). In some embodiments, the heterocyclyl group is a 5-6 membered non-aromatic ring system having a ring carbon atom and 1-4 ring heteroatoms, where each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("5-6 membered heterocyclyl"). In some embodiments, the 5-6 membered heterocyclyl has 1-3 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, the 5-6 membered heterocyclyl has 1-2 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, a 5-6 membered heterocycline has one ring heteroatom selected from nitrogen, oxygen, and sulfur.

[0071] The term "heteroaryl" refers to a 5- to 14-membered monocyclic or polycyclic (e.g., bicyclic, tricyclic) 4n+2 aromatic ring system (e.g., having 6, 10, or 14 π electrons shared in the ring array) radical having a ring carbon atom and 1-4 ring heteroatoms, where each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("5- to 14-membered heteroaryl"). In a heteroaryl group containing one or more nitrogen atoms, the bonding site can be a carbon or nitrogen atom, if the valence allows. A heteroaryl polycyclic ring system may contain one or more heteroatoms in one or both rings. Examples of "heteroaryl" include ring systems in which the heteroaryl ring defined above is fused with one or more carbocyrill or heterocyclyl groups, and the bonding site lies on the heteroaryl ring, in which case the number of ring members continues to specify the number of ring members in the heteroaryl ring system. A "heteroaryl" also refers to a ring system in which a heteroaryl ring, as defined above, is fused with one or more aryl groups, and the bonding point lies on either an aryl or heteroaryl ring, in which case the number of ring members specifies the number of ring members in the fused polycyclic (aryl / heteroaryl) ring system. A polycyclic heteroaryl group, where one ring does not contain a heteroatom (e.g., indolyl, quinolinyl, carbazolyl, etc.), and the bonding point may lie on either a ring, i.e., a ring that holds a heteroatom (e.g., 2-indolyl) or a ring that does not contain a heteroatom (e.g., 5-indolyl).

[0072] In some embodiments, the heteroaryl group is a 5-12 membered aromatic ring system having a ring carbon atom and 1-4 ring heteroatoms, where each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("5-12 membered heteroaryl"). In some embodiments, the heteroaryl group is a 5-10 membered aromatic ring system having a ring carbon atom and 1-4 ring heteroatoms, where each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("5-10 membered heteroaryl"). In some embodiments, the heteroaryl group is a 5-8 membered aromatic ring system having a ring carbon atom and 1-4 ring heteroatoms, where each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("5-8 membered heteroaryl"). In some embodiments, the heteroaryl group is a 5-6 membered aromatic ring system having a ring carbon atom and 1-4 ring heteroatoms provided to the aromatic ring system, where each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("5-6 membered heteroaryl"). In some embodiments, the 5-6 membered heteroaryl has 1-3 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, the 5-6 membered heteroaryl has 1-2 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, the 5-6 membered heteroaryl has 1 ring heteroatom selected from nitrogen, oxygen, and sulfur. Unless otherwise specified, each example of a heteroaryl group is independently unsubstituted ("unsubstituted heteroaryl") or substituted with one or more substituents ("substituted heteroaryl"). In certain embodiments, the heteroaryl group is an unsubstituted 5-14 membered heteroaryl. In certain embodiments, the heteroaryl group is a substituted 5-14 membered heteroaryl.

[0073] The term "carbocyclyl" or "carbocyclic formula" refers to a non-aromatic ring system with 3 to 14 ring carbon atoms ("C"). 3-14 "Carbocyclyl" refers to a radical of a non-aromatic ring hydrocarbon group having 0 heteroatoms. In some embodiments, "cycloalkyl" is a monocyclic saturated carbocyclyl group having 3 to 12 ring carbon atoms ("C").3-12 ("Cycloalkyl"). In some embodiments, the cycloalkyl group has 3 to 10 ring carbon atoms ("C"). 3-10 ("Cycloalkyl"). In some embodiments, the cycloalkyl group has 3 to 8 ring carbon atoms ("C"). 3-8 ("Cycloalkyl"). In some embodiments, the cycloalkyl group has 3 to 6 ring carbon atoms ("C"). 3-6 ("Cycloalkyl"). In some embodiments, the cycloalkyl group has 4 to 6 ring carbon atoms ("C"). 4-6 ("Cycloalkyl"). In some embodiments, the cycloalkyl group has 5-6 ring carbon atoms ("C"). 5-6 ("Cycloalkyl"). In some embodiments, the cycloalkyl group has 5 to 10 ring carbon atoms ("C"). 5-10 Cycloalkyl). C 5-6 Examples of cycloalkyl groups include cyclopentyl (C5) and cyclohexyl (C6). 3-6 Examples of cycloalkyl groups include the aforementioned C 5-6 Examples include cycloalkyl groups, as well as cyclopropyl (C3) and cyclobutyl (C4). 3-8 Examples of cycloalkyl groups include the aforementioned C 3-6 Examples include cycloalkyl groups, as well as cycloheptyl (C7) and cyclooctyl (C8). Unless otherwise specified, each example of a cycloalkyl group is independently either unsubstituted ("unsubstituted cycloalkyl") or substituted with one or more substituents ("substituted cycloalkyl"). In certain embodiments, the cycloalkyl group is unsubstituted C 3-14 It is a cycloalkyl group. In certain embodiments, the cycloalkyl group is a substituted C 3-14 It is a cycloalkyl group.

[0074] The term "alkoxy" refers to an alkyl group as defined herein, which is partially added to the parent molecule via an oxygen atom. In some embodiments, the alkoxy moiety has 1 to 12 carbon atoms ("C"). 1-12 (alkoxy). In some embodiments, the alkoxy moiety has 1 to 6 carbon atoms ("C").1-6 (alkoxy). In some embodiments, the alkoxy moiety has 1 to 4 carbon atoms ("C"). 1-4 (alkoxy). In some embodiments, the alkoxy moiety has 1 to 3 carbon atoms ("C"). 1-3 (alkoxy). In some embodiments, the alkoxy moiety has 1-2 carbon atoms ("C"). 1-2 Alkoxy). Typical examples of alkoxys include, but are not limited to, methoxy, ethoxy, propoxy, 2-propoxy, butoxy, and tert-butoxy.

[0075] The term "sulfonic acid group" refers to the following group: -S(O)2OH.

[0076] The term "sulfonate" refers to a salt or ester of a sulfonic acid, -S(O)2OR, where R represents a cation, such as a metal or ammonium cation, or an aliphatic or aromatic substituent. Examples of sulfonates include salts of lithium sulfonate, sodium sulfonate, potassium sulfonate, or ammonium sulfonate. In some embodiments, the term "sulfonate" refers to an ester of a sulfonic acid, such as an optionally substituted C 1-12 Alkyl sulfonate or optionally substituted C 6-12 This refers to aryl sulfonates. In some embodiments, R is a polyvalent (e.g., divalent or trivalent) radical that forms covalent or ionic bonds with one or more sulfonic acid groups attached to the same or different sulfonated polymer chains, and thus together with two or more -S(O)2O- groups to which it is attached, it forms a crosslinked moiety.

[0077] The term "sulfonamide" refers to the sulfonic acid amide, -S(O)2NRR', where R and R' are hydrogen or optionally substituted aliphatic or aromatic substituents, such as optionally substituted C. 1-12 Alkyl or optionally substituted C 6-12It is aryl. In some embodiments, R and / or R' are each polyvalent (e.g., divalent or trivalent) radicals that form covalent or ionic bonds with one or more sulfonic acid groups attached to the same or different sulfonated polymer chains, and thus together with two or more -S(O)2O- groups to which it is attached, form a crosslinked moiety.

[0078] Adding the suffix "-en" to a base indicates that the base is a divalent part. For example, alkylene is the divalent part of alkyl, alkenylene is the divalent part of alkenyl, alkynylene is the divalent part of alkynyl, and arylene is the divalent part of aryl.

[0079] The term “substituted” refers to a portion of a skeleton having substituents that substitute for hydrogens on one or more carbon atoms. “Substituted” or “substituted with” can be understood to include an implicit condition that such substitutions are subject to the acceptable valencies of the substituted atom and substituent, and that the substitutions result in stable compounds that are not transformed, for example, by spontaneous rearrangement, cyclization, exclusion, etc. As used herein, the term “substituted” is intended to include all acceptable substituents of an organic compound. In a broad context, acceptable substituents include those of acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic organic compounds. There may be one or more acceptable substituents, and they may be the same or different for a given organic compound. For the purposes of the present invention, heteroatoms such as nitrogen may have any acceptable substituents of the organic compounds described herein that satisfy the hydrogen substituent and / or the valency of the heteroatom. Substituents may include any substituents described herein, such as halogens, hydroxyls, carbonyls (e.g., carboxyls, alkoxycarbonyls, formyls, or acyls), thiocarbonyls (e.g., thioesters, thioacetates, or thioformates), alkoxyls, phosphoryls, phosphates, phosphonates, phosphinates, aminos, amides, amidines, imines, cyanos, nitros, azides, sulfhydryls, alkylthios, sulfates, sulfonates, sulfamoyls, sulfonamides, sulfonyls, heterocyclyls, aralkyls, or aromatic or heteroaromatic moieties. It will be understood by those skilled in the art that substituents may be substituted themselves where appropriate. Unless specifically stated as “unsubstituted,” references to chemical moieties herein are understood to include substituted variants. For example, references to “aryl” groups or moieties implicitly include both substituted and unsubstituted variants.

[0080] Examples of carbon atom substituents include, but are not limited to, halogens, -CN, -NO2, -N3, -OH, F, Cl, Br, I, oxo, -SO2H, -SO3H, -OR aa , -NH(R aa )2, -N(R aa)2, -N(R aa )3 + X - -SH, -SR aa -C(=O)R aa -CO2H, -CHO, -CO2R aa -OC(=O)R aa , -OCO2R aa -C(=O)N(R aa )2, -OC(=O)N(R aa )2, -NR aa C(=O)R aa , -NR aa CO2R aa , -NR aa C(=O)N(R aa )2, -C(=NR aa )R aa -C(=O)NR aa SO2R aa , -NR aa SO2R aa , -SO2N(R aa )2, -SO2R aa , -SO2OR aa , -OSO2R aa -S(=O)R aa -OS(=O)R aa , -Si(R aa )3, -OSi(R aa )3, C 1-12 Alkyl, C 1-12 Haloalkyl, 3-16 membered heterocyclyl and C 6-12 Aaryl is mentioned, and in the formula, X - R is a counterion, aa Each of these examples is independent of H, -OH, and C. 1-10 Alkyl, C 1-10 Haloalkyl, C 3-12 Cycloalkyl, 5-16 member heterocyclyl and C 6-12 Selected from the aryl or two R aa The groups are linked together to form a 3-16 member heterocycline.

[0081] In a first embodiment, the disclosure relates to a polymer electrolyte membrane comprising a polymer electrolyte and a metal complex, wherein the metal complex comprises a metal cation and a ligand, and the ligand comprises three or more functional groups, each functional group independently selected from phosphonic acids, sulfonic acids, and carboxylic acids, or their anions.

[0082] In the first aspect of the first embodiment, the metal cation is selected from the cations of Ce, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Sm, Gd, and Th. For example, the metal cation is selected from the cations of Ce, Mn, and Zr. In some embodiments, the metal cation is selected from the cations of Ce, Cu, Fe, Co, and Ni. For example, the metal cation is a Ce cation. In some embodiments, the Ce cation is a Ce 4+ Alternatively, Ce cations are Ce 3+ That is the case.

[0083] In the second aspect of the first embodiment, the ligand comprises 3, 4, 5, or 6 functional groups. For example, the ligand comprises 3 functional groups. For example, the ligand comprises 4 functional groups. For example, the ligand comprises 5 functional groups. For example, the ligand comprises 6 functional groups. The remaining features and exemplary features of the second aspect are as described above with respect to the first aspect of the first embodiment.

[0084] In the third aspect of the first embodiment, the ligand is aminotris(methylenephosphonic acid) (ATMP), diethylenetriaminepentakis(methylenephosphonic acid) (DTPMP), ethylenediaminetetra(methylenephosphonic acid) (EDTMP), hexamethylenediaminetetra(methylenephosphonic acid) (HDTMP), bis(hexamethylenetriaminepenta(methylenephosphonic acid) (BHMTMP), benzenetrisulfonic acid, naphthalenetrisulfonic acid, pyrenetetrasulfonic acid Phosphate, triphenylphosphine-3,3',3"-trisulfonic acid, nitrilotriacetic acid (NTA), citric acid, ethylenediaminetetraacetic acid (EDTA), benzenetricarboxylic acid, benzenetetracarboxylic acid, benzenepentacarboxylic acid, benzene-1,3,5-triacetic acid, mellitic acid, N,N-bis(phosphonomethyl)glycine, 2,2'-((phosphonomethyl)azandiyl)diacetic acid, ethylene glycol-bis(2-aminoethyl ether)-N,N,N',N'-tetraacetic acid Acids, 1,2-bis(2-aminophenoxy)ethane-N,N,N',N'-tetraacetic acid, ethylenediamine N,N'-disuccinate N-(2-hydroxyethyl)ethylenediamine N,N',N'-triacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, 1,2,3,4-butanetetracarboxylic acid, 1,3-diamino2-hydroxypropane-N,N,N',N'-tetraacetic acid, 1,6-diaminohexane-N,N,',N'-tetraacetic acid, 1,2-diaminosyl The ligand is selected from chlorohexane-N,N,N',N'-tetraacetic acid and 3,3'-dimethoxybenzidine-N,N,N',N'-tetraacetic acid or its anion. In some embodiments, the ligand is selected from ATMP, DTPMP, NTA, EDTA, and mellitic acid or its anion. For example, the ligand is ATMP or its anion. The remaining features and exemplary features of the third aspect are as described above with respect to the first and second aspects of the first embodiment.

[0085] In the fourth aspect of the first embodiment, the metal complex comprises a metal cation and a ligand in a molar ratio of about 20:1 to about 1:10. For example, the metal complex comprises a metal cation and a ligand in a ratio of about 20:1 to about 1:5; about 15:1 to about 1:1; about 15:1 to about 2:1; about 12:1 to about 3:1; about 12:1 to about 2:1; about 12:1 to about 1:1; about 12:1 to about; about 9:1 to about 3:1; about 9:1 to about 2:1; about 9:1 to about 1:1; about 6:1 to about 3:1; about 6:1 to about 2:1; or a molar ratio of about 6:1 to about 1:1. For example, the metal complex contains a metal cation and a ligand in molar ratios of approximately 20:1; approximately 15:1; approximately 12:1; approximately 10:1; approximately 9:1; approximately 8:1; approximately 7:1; approximately 6:1; approximately 5:1; approximately 4:1; approximately 3:1; approximately 2:1; or approximately 1:1. In some embodiments, the metal complex contains a metal cation and a ligand in a molar ratio of approximately 6:1. In some embodiments, the metal complex contains a metal cation and a ligand in a molar ratio of approximately 3:1. The remaining features of the fourth aspect and exemplary features are as described above with respect to the first to third aspects of the first embodiment.

[0086] In the fifth aspect of the first embodiment, the metal complex further comprises a complex anion. For example, the complex anion is NO3 - Cl - F - BF4 - SO4 2- HSO4 - [(NH4)2(NO3)6] 2- CO3 2- , HCO3 - CH3CO2 - and HCO2 - Selected from. In some embodiments, the complex anion is NO3 - or Cl - For example, the complex anion is NO3 - Alternatively, the complex anion is Cl - The remaining features and exemplary features of the fifth phase are as described above with respect to the first to fourth phases of the first embodiment.

[0087] In the sixth aspect of the first embodiment, the polymer electrolyte and the metal complex form a mixture. For example, the polymer electrolyte and the metal complex form a homogeneous mixture. The remaining features and exemplary features of the sixth aspect are as described above with respect to the first to fifth aspects of the first embodiment.

[0088] In the eighth aspect of the first embodiment, the polymer electrolyte membrane contains about 0.1 wt.% to about 10 wt.% of metal cations. For example, the polymer electrolyte membrane contains about 0.5 wt.% to about 5 wt.%, for example, about 0.7 wt.% to about 2 wt.%, or about 0.8 wt.% to about 1.2 wt.% of metal cations. For example, the polymer electrolyte membrane contains about 0.1 wt.%, about 0.2 wt.%, about 0.3 wt.%, about 0.4 wt.%, about 0.6 wt.%, about 0.7 wt.%, about 0.8 wt.%, about 0.9 wt.%, about 1.0 wt.%, about 2 wt.%, about 3 wt.%, about 4 wt.%, about 5 wt.%, about 6 wt.%, about 7 wt.%, about 8 wt.%, about 9 wt.%, or about 10 wt.% of metal cations. For example, the polymer electrolyte membrane contains about 1 wt.% of metal cations. The remaining features and exemplary features of the eighth aspect are as described above with respect to the first to sixth aspects of the first embodiment.

[0089] In the ninth aspect of the first embodiment, the polymer electrolyte comprises a plurality of sulfonic acid moieties, and the polymer electrolyte membrane contains about 0.001 to about 0.1 metal cations per sulfonic acid group. For example, the polymer electrolyte membrane contains about 0.005 to about 0.05, about 0.007 to about 0.02, or about 0.008 to about 0.018 metal cations per sulfonic acid group. For example, the polymer electrolyte membrane contains about 0.001, about 0.002, about 0.003, about 0.004, about 0.005, about 0.006, about 0.007, about 0.008, about 0.009, about 0.01, about 0.02, about 0.03, about 0.04, about 0.05, about 0.06, about 0.07, about 0.08, about 0.09, or about 0.1 metal cations per sulfonic acid group. In some embodiments, the polymer electrolyte membrane contains about 0.014 metal cations per sulfonic acid group. The remaining features of the ninth aspect and exemplary features are as described above with respect to the first to eighth aspects of the first embodiment.

[0090] In the tenth aspect of the first embodiment, the polyelectrolyte is sulfonated. In some embodiments, the sulfonated polyelectrolyte comprises a plurality of sulfonic acid groups and / or a plurality of sulfonates. For example, the sulfonated polyelectrolyte comprises a plurality of sulfonic acid groups. The remaining features and exemplary features of the tenth aspect are as described above with respect to the first to ninth aspects of the first embodiment.

[0091] In the eleventh aspect of the first embodiment, the polymer electrolyte is selected from or a combination thereof from sulfonated polyphenylsulfone (sPPS), sulfonated polyetheretherketone (sPEEK), sulfonated polyphosphazene (sPOP), sulfonated polybenzimidazole (sPBI), sulfonated polyethersulfone (sPES), sulfonated polyphenylene oxide (sPPO), sulfonated polyarylene etherketone (sPAEK), sulfonated polyphenylsulfone, sulfonated poly(sulfone), sulfonated poly(sulfidesulfone), sulfonated polyimide (sPI), sulfonated poly(etherimide) (sPEI), sulfonated poly(amine), sulfophenylated polyphenylene, and sulfonated polyetherpyridine. For example, the polymer electrolyte is sPPS. The remaining features and exemplary features of the eleventh phase are as described above with respect to the first to tenth phases of the first embodiment.

[0092] In the twelfth aspect of the first embodiment, the polyelectrolyte is perfluorosulfonic acid (PFSA). In some embodiments, PFSA has the structural formula (I): [ka] A polymer containing repeating units represented by the formula, where x is an integer from 1 to 15, m is an integer from 0 to 2, and n is an integer from 1 to 5, and the symbol [ka] The ∫ indicates a point of bonding to an adjacent repeating unit. For example, PFSA is a polymer containing repeating units represented by structural formula (I), where x is an integer from 5 to 14, m is 1 or 2, and n is 2 or 3. The remaining features of the twelfth aspect and exemplary features are as described above with respect to the first to eleventh aspects of the first embodiment.

[0093] In the thirteenth aspect of the first embodiment, the degree of sulfonation of the polymer electrolyte is approximately 100% to approximately 400%. For example, the degree of sulfonation of the polymer electrolyte is approximately 10% to approximately 100%, approximately 20% to approximately 100%, approximately 30% to approximately 100%, approximately 40% to approximately 100%, approximately 50% to approximately 100%, approximately 60% to approximately 100%, approximately 70% to approximately 100%, approximately 80% to approximately 100%, approximately 50% to approximately 200%, approximately 80% to approximately 200%, approximately 100% to approximately 200%, and approximately 100% to approximately 250%. These are approximately 150% to 200%, 100% to 300%, 100% to 350%, 100% to 400%, 150% to 250%, 150% to 300%, 150% to 350%, 150% to 400%, 200% to 300%, 200% to 350%, 200% to 400%, or 250% to 350%. For example, the degree of sulfonation of polyelectrolytes is approximately 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 120%, 140%, 160%, 180%, 200%, 220%, 240%, 260%, 280%, 300%, 320%, 340%, 360%, 380%, or 400%. For example, the degree of sulfonation of polyelectrolytes is approximately 100% to 300%. For example, the degree of sulfonation of polyelectrolytes is approximately 200%. For example, polyelectrolytes contain an average of approximately 1 to 3 sulfonic acid, sulfonate, and sulfonamide groups per repeating unit. For example, the polyelectrolyte contains, on average, about two sulfonic acid, sulfonate, and sulfonamide groups per repeating unit. The remaining features of the thirteenth aspect and exemplary features are as described above with respect to the first to twelfth aspects of the first embodiment.

[0094] In the fourteenth aspect of the first embodiment, the polymer electrolyte is crosslinked. For example, the polymer electrolyte has the following structural formula: [ka] [ka] The formula includes a bridge portion represented by one of the following, k is 0, 1, or 2; R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 Each of these is independently H, C 1-12 Alkyl, C 1-12 Haloalkyl, C 6-14 Aryl, and C 6-14 Ariel (C 1-12 Selected from alkylene; Each of A, E, G, J, L, and M is independently combined, C 1-12 Alkylene and C 6-14 Selected from Arirene; R a and R a* Each of these is independently H or C 1-12 It is alkyl; M 2+ Mg 2+ Ca 2+ Ba 2+ and Al(X) 2+ Selected from, where X is a halide, acetate, or nitrate; symbol " [ka] The symbol '' indicates the point of bond to the repeating units of the polymer electrolyte in the crosslinked portion. In some embodiments, the crosslinked portion has the following structural formula: [ka] It is represented by one of the following structural formulas. For example, the bridged portion is represented by the following structural formula: [ka] It is represented by one of the following structural formulas. In some embodiments, the bridged portion is represented by the following structural formula: [ka] This is represented by [the following]. The remaining features and exemplary features of the 14th phase are as described above with respect to the 1st to 13th phases of the first embodiment.

[0095] In the 15th aspect of the first embodiment, the degree of crosslinking of the polymer electrolyte is approximately 10% to approximately 95%. For example, the degree of crosslinking of the polymer electrolyte is approximately 15% to approximately 90%, approximately 20% to approximately 80%, approximately 20% to approximately 70%, approximately 20% to approximately 60%, approximately 20% to approximately 50%, approximately 20% to approximately 45%, approximately 20% to approximately 40%, approximately 30% to approximately 50%, approximately 25% to approximately 30%, or approximately 30% to approximately 35%. In some embodiments, the degree of crosslinking of the polymer electrolyte is approximately 30% to approximately 50%. For example, the degree of crosslinking of the polymer electrolyte is about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or about 95%. For example, the degree of crosslinking of the polymer electrolyte is about 70%. For example, the degree of crosslinking of the polymer electrolyte is about 40%. The remaining features and exemplary features of the 15th aspect are as described above with respect to the first to 14th aspects of the first embodiment.

[0096] In the sixteenth aspect of the first embodiment, the metal cation is a Ce cation; the ligand is selected from ATMP, DTPMP, NTA, EDTA, and mellitic acid or its anion; and the polyelectrolyte is PFSA. For example, the metal cation is Ce 3+ The ligand is selected from ATMP, DTPMP, NTA, EDTA, and meritol or its anion; the polymer electrolyte is PFSA. For example, the metal cation is Ce 4+The ligand is selected from ATMP, DTPMP, NTA, EDTA, and mellitic acid or its anion; the polyelectrolyte is PFSA. The remaining features and exemplary features of the 16th aspect are as described above with respect to the first to 15th aspects of the first embodiment.

[0097] In the 17th aspect of the first embodiment, the metal cation is selected from the cations of Ce, Cu, Fe, Co, and Ni; the ligand is ATMP; and the polymer electrolyte is PFSA. For example, the metal cation is a Ce cation; the ligand is ATMP; and the polymer electrolyte is PFSA. The remaining features and exemplary features of the 17th aspect are as described above with respect to the first to 16th aspects of the first embodiment.

[0098] In the 18th aspect of the first embodiment, the metal cation is selected from the cations of Ce, Zr, and Mn; the ligand is ATMP; and the polyelectrolyte comprises sPPS. For example, the metal cation is Ce; the ligand is ATMP; and the polyelectrolyte comprises sPPS. For example, the metal cation is Ce; the ligand is ATMP; and the polyelectrolyte comprises crosslinked sPPS. The remaining features and exemplary features of the 18th aspect are as described above with respect to the first to 17th aspects of the first embodiment.

[0099] In the 18th aspect of the first embodiment, sPPS is cross-linked sPPS. For example, cross-linked sPPS has the following structural formula: [ka] This includes the bridging portion represented by [the specified symbol]. The remaining features and exemplary features of the 19th aspect are as described above with respect to the first to 18th aspects of the first embodiment.

[0100] In the 20th aspect of the first embodiment, the metal cation is a Ce cation; the ligand is ATMP; and the metal complex is further NO 3-It contains; Ce cations and ATMP are present in a molar ratio of approximately 3:1; and the polymer is sPPS. For example, the metal cation is a Ce cation; the ligand is ATMP; and the metal complex is further NO 3- It contains; Ce cations and ATMP are present in a molar ratio of approximately 3:1; and the polymer is crosslinked sPPS. For example, the metal cation is Ce 3+ The ligand is ATMP, and the metal complex is further NO 3- It contains; Ce cations and ATMP are present in a molar ratio of approximately 3:1; and the polymer is crosslinked sPPS. For example, the metal cation is Ce 4+ The ligand is ATMP, and the metal complex is further NO 3- It contains; Ce cations and ATMP are present in a molar ratio of approximately 3:1; and the polymer is crosslinked sPPS. The remaining features of the 20th aspect and exemplary features are as described above with respect to the first to 19th aspects of the first embodiment.

[0101] In the 21st aspect of the first embodiment, the membrane is a self-supporting membrane comprising a polymer electrolyte and a metal complex. In some embodiments, the membrane is a single-layer membrane comprising a polymer electrolyte and a metal complex. For example, the membrane is a self-supporting membrane consisting of a polymer electrolyte and a metal complex. For example, the membrane is a single-layer membrane consisting of a polymer electrolyte and a metal complex. The remaining features and exemplary features of the 21st aspect are as described above with respect to the first to 20th aspects of the first embodiment.

[0102] In the 22nd aspect of the first embodiment, the polymer electrolyte membrane is approximately 2 μm to approximately 100 μm thick. For example, the polymer electrolyte membrane is approximately 2 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, or approximately 100 μm thick. The remaining features and exemplary features of the 22nd aspect are as described above with respect to the first to 21st aspects of the first embodiment.

[0103] In the 23rd aspect of the first embodiment, the polymer electrolyte membrane further comprises a support polymer. The remaining features and exemplary features of the 23rd aspect are as described above with respect to the first to 22nd aspects of the first embodiment.

[0104] In the 24th aspect of the first embodiment, the polymer electrolyte membrane comprises a porous matrix, the porous matrix comprises a support polymer; and the metal complex and polymer electrolyte are dispersed in the porous matrix. For example, the metal complex and polymer electrolyte are homogeneously dispersed in the porous matrix. For example, the polymer electrolyte and support polymer form a mutually interpenetrating network structure. The remaining features and exemplary features of the 24th aspect are as described above with respect to the first to 23rd aspects of the first embodiment.

[0105] In the 25th aspect of the first embodiment, the support polymer is polytetrafluoroethylene (PTFE). For example, the PTFE is stretched PTFE. The remaining features and exemplary features of the 25th aspect are as described above with respect to the first to 24th aspects of the first embodiment.

[0106] In the 26th aspect of the first embodiment, the polymer electrolyte membrane is approximately 0.5 μm to approximately 100 μm thick. For example, the polymer electrolyte membrane is approximately 0.6 μm, 0.8 μm, 1.0 μm, 2.0 μm, 3.0 μm, 4.0 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, or 100 μm thick. For example, the polymer electrolyte membrane is approximately 8 μm thick. The remaining features and exemplary features of the 26th phase are as described above with respect to the 1st to 25th phases of the first embodiment.

[0107] In a second embodiment, the Disclosure relates to a method for producing a polymer electrolyte membrane as described herein in relation to a first embodiment and various aspects thereof, the method comprising: (a) providing a casting surface and a suspension comprising a metal complex, a polymer electrolyte, and (i) a crosslinking reagent and / or (ii) a crosslinking initiator; (b) placing the suspension on the casting surface to provide a layer of membrane; and (c) exposing the layer of membrane to conditions sufficient to allow (i) the polymer electrolyte and the crosslinking reagent to undergo a crosslinking reaction, or (ii) the crosslinking initiator to initiate crosslinking of the polymer electrolyte, thereby providing a polymer electrolyte membrane.

[0108] In the first aspect of the second embodiment, the suspension contains about 0.01 wt.% to about 10 wt.% of the metal complex. In some embodiments, the suspension contains about 0.1 wt.% to about 10 wt.% of the metal complex. For example, 0.05 wt.%, about 0.1 wt.%, about 0.15 wt.%, about 0.2 wt.%, about 0.25 wt.%, about 0.3 wt.%, about 0.35 wt.%, about 0.4 wt.%, about 0.45 wt.%, and about 0.5 wt.% of the metal complex.

[0109] In the second aspect of the second embodiment, the suspension contains about 2 wt.% to about 50 wt.% of the polyelectrolyte. For example, the suspension contains about 2 wt.%, about 3 wt.%, about 4 wt.%, about 5 wt.%, about 6 wt.%, about 7 wt.%, about 8 wt.%, about 9 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.%, or about 20 wt.% of the polyelectrolyte. In some embodiments, the suspension contains about 10 wt.% of the polyelectrolyte. The remaining features and exemplary features of the second aspect are as described above with respect to the first aspect of the second embodiment.

[0110] In the third aspect of the second embodiment, the polymer electrolyte includes a crosslinkable group. For example, the crosslinkable group is OH, NH2, NH, SH, C(O)OH, C(O)Cl, C(O)Br, NHNH2, N3, S(O)2OH, S(O)2Cl, -NCO, [ka] Selected from: For example, crosslinkable groups include OH, NH2, SH, C(O)OH, C(O)Cl, C(O)Br, NHNH2, N3, S(O)2OH, S(O)2Cl, -NCO, [ka] Selected from: For example, the crosslinkable group is [ka] For example, the crosslinkable group is NH. For example, the crosslinkable group is S(O)2OH. The remaining features and exemplary features of the third aspect are as described above with respect to the first and second aspects of the second embodiment.

[0111] In the fourth aspect of the second embodiment, the suspension comprises a crosslinking initiator. For example, the crosslinking initiator is selected from 2,2-dimethoxy-2-phenylacetophenone (DMPA), azobisisobutyronitrile (AIBN), and benzoyl peroxide (BPO). The remaining features and exemplary features of the fifth aspect are as described above with respect to the first to fourth aspects of the second embodiment.

[0112] In the sixth aspect of the second embodiment, conditions sufficient for a crosslinking initiator to initiate crosslinking of a polymer electrolyte include visible light irradiation, UV light irradiation, application of heat, microwave irradiation, application of ultrasound, or gamma ray irradiation. The remaining features and exemplary features of the sixth aspect are as described above with respect to the first to fifth aspects of the second embodiment.

[0113] In the seventh aspect of the second embodiment, the suspension contains about 0.5 wt.% to about 50 wt.% of the crosslinking initiator. For example, the suspension contains about 5 wt.% to about 15 wt.% of the crosslinking initiator. For example, the suspension contains about 0.2 wt.%, about 0.3 wt.%, about 0.4 wt.%, about 0.6 wt.%, about 0.7 wt.%, about 0.8 wt.%, about 0.9 wt.%, about 1.0 wt.%, about 2 wt.%, about 3 wt.%, about 4 wt.%, about 5 wt.%, about 6 wt.%, about 7 wt.%, about 8 wt.%, about 9 wt.%, about 10 wt.%, about 15 wt.%, or about 20 wt.% of the crosslinking initiator. The remaining characteristics and exemplary features of the seventh phase are as described above with respect to the first to sixth phases of the second embodiment.

[0114] In the eighth aspect of the second embodiment, the suspension comprises a crosslinking agent. For example, the crosslinking agent is selected from compounds comprising polyalcohols, aldehydes, amines, epoxides, thiols, or terminal alkenes or alkynes. For example, the crosslinking agent is selected from glycerol, ethylene glycol, hydroquinone, 2,5-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzene-1,4-disulfonic acid, biphenyl, tetraglycidylbis(p-aminophenyl)methane, phenylenediamine, 4,4'-thiobisbenzenethiol, and tetrafluorostyrene. For example, the crosslinking agent is selected from glycerol, ethylene glycol, tetraglycidylbis(p-aminophenyl)methane, phenylenediamine, 4,4'-thiobisbenzenethiol, glutaraldehyde, styrene, and tetrafluorostyrene. For example, the crosslinking agent is a polyalcohol, e.g., glycerol or ethylene glycol. For example, the crosslinking agent is hydroquinone or 2,5-dihydroxybenzenesulfonic acid. The remaining characteristics and exemplary features of the eighth phase are as described above with respect to the first to seventh phases of the second embodiment.

[0115] In the ninth aspect of the second embodiment, conditions sufficient for the polymer electrolyte and crosslinking reagent to undergo a crosslinking reaction with the polymer electrolyte include visible light irradiation, UV light irradiation, application of heat, microwave irradiation, application of ultrasound, or gamma ray irradiation. The remaining features and exemplary features of the ninth aspect are as described above with respect to the first to eighth aspects of the second embodiment.

[0116] In the tenth aspect of the second embodiment, the suspension further comprises a solvent. In some embodiments, the solvent is selected from dimethylformamide, tetrahydrofuran, N-methylformamide, formamide, acetonitrile, dimethylacetamide, propylene carbonate, ethylene carbonate, N-methylpyrrolidone, dimethyl sulfoxide, or a combination thereof. The remaining features and exemplary features of the tenth aspect are as described above with respect to the first to ninth aspects of the second embodiment.

[0117] In a third embodiment, the Disclosure relates to a method for producing a polymer electrolyte membrane as described herein in relation to a first embodiment and various aspects thereof, the method comprising: (a) providing a suspension comprising a porous matrix and a metal complex and a polymer electrolyte; (b) contacting the porous matrix with the suspension to provide an immersed porous matrix; and (c) drying the immersed porous matrix to provide a polymer electrolyte membrane. In some embodiments, the method comprises repeating steps (b) and (c) one to five times, for example, one, two, three, four, or five times.

[0118] In the first aspect of the third embodiment, the suspension contains about 0.01 wt.% to about 10 wt.% of the metal complex. In some embodiments, the suspension contains about 0.1 wt.% to about 10 wt.% of the metal complex. For example, 0.05 wt.%, about 0.1 wt.%, about 0.15 wt.%, about 0.2 wt.%, about 0.25 wt.%, about 0.3 wt.%, about 0.35 wt.%, about 0.4 wt.%, about 0.45 wt.%, and about 0.5 wt.% of the metal complex.

[0119] In the second aspect of the second embodiment, the suspension contains about 2 wt.% to about 50 wt.% of the polyelectrolyte. For example, the suspension contains about 2 wt.%, about 3 wt.%, about 4 wt.%, about 5 wt.%, about 6 wt.%, about 7 wt.%, about 8 wt.%, about 9 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.%, or about 20 wt.% of the polyelectrolyte. In some embodiments, the suspension contains about 10 wt.% of the polyelectrolyte. The remaining features and exemplary features of the second aspect are as described above with respect to the first aspect of the third embodiment.

[0120] In the third aspect of the third embodiment, the polymer electrolyte includes a crosslinkable group. For example, the crosslinkable group is OH, NH2, NH, SH, C(O)OH, C(O)Cl, C(O)Br, NHNH2, N3, S(O)2OH, S(O)2Cl, -NCO, [ka] Selected from: For example, crosslinkable groups include OH, NH2, SH, C(O)OH, C(O)Cl, C(O)Br, NHNH2, N3, S(O)2OH, S(O)2Cl, -NCO, [ka] Selected from: For example, the crosslinkable group is [ka] For example, the crosslinkable group is NH. For example, the crosslinkable group is S(O)2OH. The remaining features and exemplary features of the third aspect are as described above with respect to the first and second aspects of the third embodiment.

[0121] In the fourth aspect of the third embodiment, the suspension further comprises a crosslinking initiator. In some embodiments, the crosslinking initiator is selected from 2,2-dimethoxy-2-phenylacetophenone (DMPA), azobisisobutyronitrile (AIBN), and benzoyl peroxide (BPO). The remaining features of the fifth aspect and exemplary features are as described above with respect to the first to fourth aspects of the second embodiment.

[0122] In a sixth aspect of the third embodiment, the method further includes crosslinking a polyelectrolyte under conditions sufficient to cause the crosslinking initiator to initiate crosslinking of the first polymer. For example, conditions sufficient to cause the crosslinking initiator to initiate crosslinking of the polyelectrolyte include visible light irradiation, UV light irradiation, application of heat, microwave irradiation, application of ultrasound, or gamma ray irradiation. The remaining features and exemplary features of the sixth aspect are as described above with respect to the first to fifth aspects of the third embodiment.

[0123] In the seventh aspect of the third embodiment, the suspension contains about 0.5 wt.% to about 50 wt.% of the crosslinking initiator. For example, the suspension contains about 5 wt.% to about 15 wt.% of the crosslinking initiator. For example, the suspension contains about 0.2 wt.%, about 0.3 wt.%, about 0.4 wt.%, about 0.6 wt.%, about 0.7 wt.%, about 0.8 wt.%, about 0.9 wt.%, about 1.0 wt.%, about 2 wt.%, about 3 wt.%, about 4 wt.%, about 5 wt.%, about 6 wt.%, about 7 wt.%, about 8 wt.%, about 9 wt.%, about 10 wt.%, about 15 wt.%, or about 20 wt.% of the crosslinking initiator. The remaining characteristics and exemplary features of the seventh phase are as described above with respect to the first to sixth phases of the third embodiment.

[0124] In the eighth aspect of the third embodiment, the suspension further comprises a crosslinking agent. In some embodiments, the crosslinking agent is selected from compounds comprising polyalcohols, aldehydes, amines, epoxides, thiols, or terminal alkenes or alkynes. For example, the crosslinking agent is selected from glycerol, ethylene glycol, hydroquinone, 2,5-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzene-1,4-disulfonic acid, biphenyl, tetraglycidylbis(p-aminophenyl)methane, phenylenediamine, 4,4'-thiobisbenzenethiol, and tetrafluorostyrene. For example, the crosslinking agent is selected from glycerol, ethylene glycol, tetraglycidylbis(p-aminophenyl)methane, phenylenediamine, 4,4'-thiobisbenzenethiol, glutaraldehyde, styrene, and tetrafluorostyrene. For example, the crosslinking agent is a polyalcohol, e.g., glycerol or ethylene glycol. For example, the crosslinking agent is hydroquinone or 2,5-dihydroxybenzenesulfonic acid. The remaining characteristics and exemplary features of the eighth phase are as described above with respect to the first to seventh phases of the third embodiment.

[0125] In the ninth aspect of the third embodiment, the method further includes a step of crosslinking the polymer electrolyte under conditions sufficient to allow the polymer electrolyte and crosslinking reagent to undergo a crosslinking reaction. For example, conditions sufficient to allow the polymer electrolyte and crosslinking reagent to undergo a crosslinking reaction with the polymer electrolyte include visible light irradiation, UV light irradiation, application of heat, microwave irradiation, application of ultrasound, or gamma ray irradiation. The remaining features and exemplary features of the ninth aspect are as described above with respect to the first to eighth aspects of the third embodiment.

[0126] In the tenth aspect of the third embodiment, the suspension further comprises a solvent. In some embodiments, the solvent is selected from water, alcohol, dimethylformamide, tetrahydrofuran, N-methylformamide, formamide, acetonitrile, dimethylacetamide, propylene carbonate, ethylene carbonate, N-methylpyrrolidone, dimethyl sulfoxide, or a combination thereof. For example, the solvent is a mixture of water and alcohol. For example, the solvent is a mixture of water and methanol, ethanol, or isopropanol. The remaining features and exemplary features of the tenth aspect are as described above with respect to the first to ninth aspects of the third embodiment.

[0127] In the eleventh aspect of the third embodiment, the step of contacting the porous matrix with the suspension includes spray coating, spin coating, drop casting, zone casting, dip coating, blade coating, printing, vacuum filtration, slot die coating, curtain coating, or a combination thereof. For example, the step of contacting the porous matrix with the suspension includes dip coating and / or blade coating. The remaining features and exemplary features of the eleventh aspect are as described above with respect to the first to tenth aspects of the third embodiment.

[0128] In the twelfth aspect of the third embodiment, the step of drying the immersed porous matrix includes heating the immersed porous matrix at a temperature of about 150°C to about 200°C for a period of about 1 minute to about 1 hour. For example, the step of drying the immersed porous matrix includes heating the immersed porous matrix at a temperature of about 150°C, about 160°C, about 170°C, about 180°C, about 190°C, or about 200°C. For example, the step of drying the immersed porous matrix includes heating the immersed porous matrix at a temperature of about 2 minutes, about 3 minutes, about 4 minutes, about 5 minutes, about 6 minutes, about 7 minutes, about 8 minutes, about 9 minutes, about 10 minutes, about 20 minutes, about 30 minutes, about 40 minutes, about 50 minutes, or about 60 minutes. The remaining features and illustrative features of the twelfth phase are as described above with respect to the first to eleventh phases of the third embodiment.

[0129] In a fourth aspect, the disclosure relates to a membrane electrode assembly (MEA), the MEA comprising a polymer electrolyte membrane; a cathode; and an anode as described herein in relation to a first aspect and various aspects thereof, wherein the polymer electrolyte membrane is positioned between the anode and the cathode.

[0130] In a fifth embodiment, the disclosure relates to a fuel cell, which includes one or more MEAs described herein in relation to a fourth embodiment and various aspects thereof, and one or more gas flow bipolar plates. [Examples]

[0131] Examples material PFSA-dispersed D2020 (20 wt.%) was purchased from Fuel Cell Store (CAS#31175-20-9). Ethanol was purchased from Sigma-Aldrich (CAS#64-17-5). Isopropanol was purchased from Sigma-Aldrich (CAS#67-63-0). Hydrogen peroxide was purchased from Sigma-Aldrich (30%, CAS#7722-84-1). Hydrochloric acid (HCl) was purchased from Sigma-Aldrich (37%, CAS#7647-01-0). 8 μm thick ePTFE (stretched polytetrafluoroethylene) was purchased from UNM. Cerium(III) nitrate hexahydrate was purchased from Sigma-Aldrich (99.99%, CAS#16774-21-3). I purchased cerium(IV) ammonium nitrate from Sigma-Aldrich (99.999%, CAS#10294-41-4). I purchased iron(III) nitrate nonahydrate from Sigma-Aldrich (99.95%, CAS#7782-61-8). I purchased iron(II) sulfate heptahydrate from Sigma-Aldrich (99%, CAS#7782-63-0). I purchased nickel(II) chloride hexahydrate from Sigma-Aldrich (99.9%, CAS#7791-20-0). I purchased copper(II) chloride dihydrate from Sigma-Aldrich (reagent, CAS#10125-13-0). I purchased anhydrous cobalt(II) chloride from Sigma-Aldrich (synthetic grade, CAS#7646-79-9). ATMP (aminotrismethylenephosphonic acid) was purchased from Sigma-Aldrich (50%, CAS#6419-19-8). NTA (nitrilotriacetic acid) was purchased from Sigma-Aldrich (99%, CAS#139-13-9). DTPMP (diethylenetriaminepentakis(methylphosphonic acid)) was purchased from Sigma-Aldrich (50%, CAS#15827-60-8). EDTA (ethylenediaminetetraacetic acid) was purchased from Sigma-Aldrich (99%, CAS#60-00-4). Mellitic acid was purchased from Sigma-Aldrich (99%, CAS#517-60-2). PPS (Solvay Radel R-5000, MW=5000) was purchased from Solvay.Sulfuric acid (H2SO4) was purchased from Sigma-Aldrich (95 - 98%, CAS#7664-93-9). Hydroquinone was purchased from Sigma-Aldrich (≥99%, CAS#123-31-9).

[0132] Example 1. Sulfonation of PPS PPS was sulfonated by reacting the polymer with H2SO4. The PPS resin was ground into powder using an industrial grinder. PPS was dissolved in concentrated H2SO4 at a concentration of 25 mg / mL and stirred at 60 °C for 10 hr. The sulfonated polymer was precipitated by dropping the reaction mixture into H2O at 0 °C. The resulting precipitated polymer was isolated by centrifugation. Sulfonated PPS (sPPS) was redispersed in H2O at room temperature and washed using dialysis until a neutral pH was recorded. The washed sPPS was dried on a hot plate to obtain the final product. The yield of the reaction was determined to be 91% by mass. The obtained product had an ion exchange capacity (IEC) of 3.605 meq / g determined by titration (2.0 sulfonic acids per repeating unit). The degree of sulfonation of sPPS can be adjusted by adjusting the reaction time (1 - 8 hr).

[0133] Example 2. Determination of membrane durability using Fenton reagent test The membrane was dried in an oven at 80 °C for 24 h under a nitrogen atmosphere. Next, the mass of the dried membrane was recorded before placing the membrane in a 20 mL vial. DI water (89.267 mL) was added to the vial together with the membrane. In a separate 20 mL vial, 10 mg of iron(II) sulfate heptahydrate was dissolved in 10 mL of DI water. Hydrogen peroxide (10 mL, 30%) was added to the vial together with the membrane. Finally, 0.733 mL of the iron(II) sulfate heptahydrate solution was added to the vial together with the membrane. The vial with the membrane was capped and placed in an aluminum bead bath at 80 °C for 48 h. After the test, the membrane was rinsed three times with DI water and then dried in an oven at 80 °C for 24 h under a nitrogen atmosphere. The mass of the final dried membrane was recorded.

[0134] Example 3. Determination of Ce content in the membrane The cerium content after AST was determined using X-ray fluorescence (XRF) spectroscopy. After AST, coupons were pressed from the test area and the periphery from each membrane electrode assembly. The peripheral coupons were used to indicate the pre-cerium content and the test area indicated the post-case. The Ce peak from 4.658 keV to 5.821 keV was integrated. The sulfur peak from 2.154 keV to 2.6 keV was integrated and used as an internal standard.

[0135] Example 4. Preparation of Membrane Electrode Assembly The polymer electrolyte membrane was used in a membrane electrode assembly (MEA) and tested in a single fuel cell having an active area of 5 cm 2 For MEA preparation, a 3-inch x 3-inch membrane was placed between two gas diffusion electrodes (GDEs) having 0.2 mg Pt / cm 2 (20% Pt on Vulcan carbon) on Sigracet 22 BB, each having an area of 5 cm 2 The GDEs had a catalyst layer pre-deposited on the side of the microporous layer and were performed using the catalyst layer between the membranes. A 3-inch x 3-inch PTFE gasket having a window of 5 cm 2 was placed on each side of the membrane to enclose the gas diffusion electrodes and prevent leakage of the reactant gas. The gasket thickness was adjusted to allow 80% compression of the GDE when the MEA was clamped between two fuel cell end plates.

[0136] Example 5. Testing of Polymer Electrolyte Membrane in Fuel Cell The membrane performance was evaluated in a fuel cell via H2 crossover measurements, fuel cell polarization curves, and accelerated stress tests.

[0137] H2 crossover was measured by performing cyclic voltammetry where the cathode side electrode was scanned between 0.1 V and 0.8 V at a voltage scan rate of 2 mV / s at 80 °C and 100% RH with 0.4 lpm H2 flow on the anode side and 0.4 lpm Ar flow on the cathode side and no back pressure.

[0138] The fuel cell polarization curve was measured by taking steady-state voltage measurements at 80°C with various RH values, in increments of 0.5V between the open-circuit potential, 0.3V back from the open-circuit potential, and 0.7V, and in increments of 1V between 0.7V and 0.3V. The back pressure was 50kPag with a 0.2lpm H2 flow on the anode side and a 0.2lpm air or O2 flow on the cathode side.

[0139] An accelerated stress test was performed by applying a relative humidity (RH) cycle, where the gas was switched between 0 and 100% RH at 2-minute intervals, and the cell was maintained in an open circuit. The cell was kept at 90°C, with no back pressure, and a 0.1 lpm H2 flow on the anode and a 0.1 lpm air flow on the cathode. H2 crossover, polarization curve, and electrochemical impedance were measured, and exhaust water was collected periodically throughout the accelerated stress test.

[0140] Example 6. Casting of a self-supporting membrane Casting of self-supporting sPPS membranes containing Ce(ATMP) or Ce(NO3)3 A solution of 10 wt.% sPPS, 0.2 wt.% Ce(ATMP) or Ce(NO3)3, and 2.5 wt.% hydroquinone in water was added to a Kapton trough. The resulting mixture was dried overnight. The dried sPPS film was crosslinked by a condensation reaction with hydroquinone by heating at 210°C for 2 hours under a nitrogen flow, achieving a water-stable film.

[0141] Casting of self-supporting PFSA film containing Ce(ATMP) A PFSA film was cast using the MSK-AFA-III-HB tape casting coater system. The coating solution consisted of PFSA dispersion D2020 (20 wt.%) and 0.29 wt.% Ce(ATMP) complex (3:1 Ce:ATMP) in a water:isopropanol mixed solvent, resulting in 0.014 Ce atoms per sulfonic acid moiety in the PFSA. The solution was sonicated for 30 minutes before use. The resulting PFSA ink was blade-coated directly onto glass. The PFSA ink cast was placed in a 180°C oven for 5 minutes and allowed to cool to room temperature. Blade coating was performed at room temperature at 20 cm / min.

[0142] Example 7. Synthesis of metal complexes Ce(EDTA) complex (3:1 Ce:EDTA) In a 20 mL vial, 1.74 g of cerium(III) nitrate hexahydrate was dissolved in 1.228 mL of 1 M HCl in DI water under stirring. In a separate vial, 0.390 g of EDTA was dissolved in 1.229 mL of DI water. The Ce salt solution was added dropwise to the EDTA solution. The reaction mixture was stirred overnight at room temperature. After the reaction was complete, the reaction mixture was added to a centrifuge tube and centrifuged at 9000 RPM for 5 minutes. The solution phase was discarded, and 5 mL of water was added to the tube. Centrifugation and washing were repeated three times. The resulting solid was dried overnight at 80°C.

[0143] Ce(DTPMP) complex (3:1 Ce:DTPMP) In a 20 mL vial, 1.74 g of cerium(III) nitrate hexahydrate was dissolved in 1.228 mL of 1 M HCl in DI water with stirring. 1.229 mL of DTPMP solution (50 wt.%) in water was added to a separate vial. Ce salt solution was added dropwise to the DTPMP solution. The reaction mixture was stirred overnight at room temperature. After the reaction was complete, the reaction mixture was added to a centrifuge tube and centrifuged at 9000 RPM for 5 minutes. The solution phase was discarded, and 5 mL of water was added to the tube. Centrifugation and washing were repeated three times. The resulting solid was dried overnight at 80°C.

[0144] Ce(mellitic acid) complex (3:1 Ce:mellitic acid) In a 20 mL vial, 1.74 g of cerium(III) nitrate hexahydrate was dissolved in 1.228 mL of 1 M HCl in DI water with stirring. In a separate vial, 0.456 g of mellitic acid was dissolved in 1.229 mL of DI water. The Ce salt solution was added dropwise to the mellitic acid solution. The reaction mixture was stirred overnight at room temperature. After the reaction was complete, the reaction mixture was added to a centrifuge tube and centrifuged at 9000 RPM for 5 minutes. The solution phase was discarded, and 5 mL of water was added to the tube. Centrifugation and washing were repeated three times. The resulting solid was dried overnight at 80°C.

[0145] Ce(NTA) complex (3:1 Ce:NTA) In a 20 mL vial, 1.74 g of cerium(III) nitrate hexahydrate was dissolved in 1.228 mL of 1 M HCl in DI water under stirring. In a separate vial, 0.255 g of NTA was dissolved in 1.229 mL of DI water. The Ce salt solution was added dropwise to the NTA solution. The reaction mixture was stirred overnight at room temperature. After the reaction was complete, the reaction mixture was added to a centrifuge tube and centrifuged at 9000 RPM for 5 minutes. The solution phase was discarded, and 5 mL of water was added to the tube. Centrifugation and washing were repeated three times. The resulting solid was dried overnight at 80°C.

[0146] Fe(ATMP) complex (3:1 Fe:ATMP) In a 20 mL vial, 1.114 g of iron(III) nitrate notahydrate was dissolved in 1.228 mL of 1 M HCl in DI water under stirring. ATMP solution (50% in water, 1.229 mL) was added to a separate vial. The Fe salt solution was added dropwise to the ATMP solution. The reaction mixture was stirred overnight at room temperature. After the reaction was complete, the reaction mixture was added to a centrifuge tube and centrifuged at 9000 RPM for 5 minutes. The solution phase was discarded, and 5 mL of water was added to the tube. Centrifugation and washing were repeated three times. The resulting solid was dried overnight at 80°C.

[0147] Ni(ATMP) complex (3:1 Ni:ATMP) In a 20 mL vial, 0.475 g of nickel(II) chloride hexahydrate was dissolved in 18 mL of methanol under stirring. ATMP solution (50% in water, 0.614 mL) was added dropwise to the methanol solution. The reaction mixture was stirred overnight at room temperature. After the reaction was complete, the reaction mixture was added to a centrifuge tube and centrifuged at 9000 RPM for 5 minutes. The solution phase was discarded, and 5 mL of water was added to the tube. Centrifugation and washing were repeated three times. The resulting solid was dried overnight at 80°C.

[0148] Cu(ATMP) complex (3:1 Cu:ATMP) In a 20 mL vial, 0.341 g of copper(II) chloride dihydrate was dissolved in 18 mL of methanol with stirring. ATMP solution (50% in water, 0.614 mL) was added dropwise to the methanol solution. The reaction mixture was stirred overnight at room temperature. After the reaction was complete, the reaction mixture was added to a centrifuge tube and centrifuged at 9000 RPM for 5 minutes. The solution phase was discarded, and 5 mL of water was added to the tube. Centrifugation and washing were repeated three times. The resulting solid was dried overnight at 80°C.

[0149] Co(ATMP) complex (3:1 Co:ATMP) In a 20 mL vial, 0.260 g of anhydrous cobalt(II) chloride was dissolved in 18 mL of methanol under stirring. ATMP solution (50% in water, 0.614 mL) was added dropwise to the methanol solution. The reaction mixture was stirred overnight at room temperature. After the reaction was complete, the reaction mixture was added to a centrifuge tube and centrifuged at 9000 RPM for 5 minutes. The solution phase was discarded, and 5 mL of water was added to the tube. Centrifugation and washing were repeated three times. The resulting solid was dried overnight at 80°C.

[0150] Example 7. Synthesis of Ce(ATMP) complex 2:1 Ce:ATMP (Ce 3+ ) In a 20 mL vial, 1.74 g of cerium(III) nitrate hexahydrate was dissolved in 0.922 mL of 1 M HCl in DI water with stirring. The ATMP solution (50% in water, 0.922 mL) was added to a separate vial. The Ce salt solution was added dropwise to the ATMP solution. The reaction mixture was stirred at room temperature overnight. After completion of the reaction, the reaction mixture was added to a centrifuge tube and centrifuged at 9000 RPM for 5 minutes. The solution phase was discarded and 5 mL of water was added to the tube. Centrifugation and washing were repeated three times. The obtained solid was dried at 80 °C overnight.

[0151] 2:1 Ce:ATMP (Ce 4+ ) In a 20 mL vial, 2.19 g of cerium(IV) ammonium nitrate was dissolved in 0.922 mL of 1 M HCl in DI water with stirring. The ATMP solution (50% in water, 0.922 mL) was added to a separate vial. The Ce salt solution was added dropwise to the ATMP solution. The reaction mixture was stirred at room temperature overnight. After completion of the reaction, the reaction mixture was added to a centrifuge tube and centrifuged at 9000 RPM for 5 minutes. The solution phase was discarded and 5 mL of water was added to the tube. Centrifugation and washing were repeated three times. The obtained solid was dried at 80 °C overnight.

[0152] 3:1 Ce:ATMP In a 20 mL vial, 1.74 g of cerium(III) nitrate hexahydrate was dissolved in 0.922 mL of 1 M HCl in DI water with stirring. The ATMP solution (50% in water, 0.614 mL) was added to a separate vial. The Ce salt solution was added dropwise to the ATMP solution. The reaction mixture was stirred at room temperature overnight. After completion of the reaction, the reaction mixture was added to a centrifuge tube and centrifuged at 9000 RPM for 5 minutes. The solution phase was discarded and 5 mL of water was added to the tube. Centrifugation and washing were repeated three times. The obtained solid was dried at 80 °C overnight.

[0153] 3:1 Ce:ATMP (as HNO3 as the synthetic acid) In a 20 mL vial, 1.74 g of cerium(III) nitrate hexahydrate was dissolved in 0.614 mL of 1 M HNO3 in DI water with stirring. ATMP solution (50% in water, 0.614 mL) was added to a separate vial. Ce salt solution was added dropwise to the ATMP solution. The reaction mixture was stirred overnight at room temperature. After the reaction was complete, the reaction mixture was added to a centrifuge tube and centrifuged at 9000 RPM for 5 minutes. The solution phase was discarded, and 5 mL of water was added to the tube. Centrifugation and washing were repeated three times. The resulting solid was dried overnight at 80°C.

[0154] 4:1 Ce:ATMP In a 20 mL vial, 1.74 g of cerium(III) nitrate hexahydrate was dissolved in 0.922 mL of 1 M HCl in DI water with stirring. ATMP solution (50% in water, 0.461 mL) was added to a separate vial. Ce salt solution was added dropwise to the ATMP solution. The reaction mixture was stirred overnight at room temperature. After the reaction was complete, the reaction mixture was added to a centrifuge tube and centrifuged at 9000 RPM for 5 minutes. The solution phase was discarded, and 5 mL of water was added to the tube. Centrifugation and washing were repeated three times. The resulting solid was dried overnight at 80°C.

[0155] 5:1 Ce:ATMP In a 20 mL vial, 1.74 g of cerium(III) nitrate hexahydrate was dissolved in 0.922 mL of 1 M HCl in DI water with stirring. ATMP solution (50% in water, 0.369 mL) was added to a separate vial. Ce salt solution was added dropwise to the ATMP solution. The reaction mixture was stirred overnight at room temperature. After the reaction was complete, the reaction mixture was added to a centrifuge tube and centrifuged at 9000 RPM for 5 minutes. The solution phase was discarded, and 5 mL of water was added to the tube. Centrifugation and washing were repeated three times. The resulting solid was dried overnight at 80°C.

[0156] 6:1 Ce:ATMP In a 20 mL vial, 1.74 g of cerium(III) nitrate hexahydrate was dissolved in 0.922 mL of 1 M HCl in DI water with stirring. ATMP solution (50% in water, 0.307 mL) was added to a separate vial. Ce salt solution was added dropwise to the ATMP solution. The reaction mixture was stirred overnight at room temperature. After the reaction was complete, the reaction mixture was added to a centrifuge tube and centrifuged at 9000 RPM for 5 minutes. The solution phase was discarded, and 5 mL of water was added to the tube. Centrifugation and washing were repeated three times. The resulting solid was dried overnight at 80°C.

[0157] Example 8. Casting-supported membrane General procedure PFSA films were cast using the MSK-AFA-III-HB tape casting coater system. The coating solution consisted of a 10 wt.% PFSA dispersion (D2020 solution diluted 1:1 with isopropanol) and 0.1 wt.% to 0.5 wt.% of a metal complex in a water:isopropanol mixed solvent, with the solution containing 0.014 metal atoms per sulfonic acid portion. The solution was homogenized at 9000 RPM for 2 minutes and sonicated for 30 minutes before use. PFSA ink was cast directly onto glass using blade coating, and then ePTFE was placed on top of the wet ink. The resulting ePTFE immersed in PFSA ink was placed in a 180°C oven for 3 minutes and cooled to room temperature. A second deposition of ink was cast onto the ePTFE using blade coating. The ePTFE immersed in PFSA ink was again placed in a 180°C oven for 3 minutes and cooled to room temperature. Blade coating was performed at room temperature and a rate of 20 cm / min.

[0158] PFSA containing a Ce(mellitic acid) complex The general procedure described above was used with a coating solution containing 0.41 wt.% Ce(mellitic acid) complex (3:1 Ce:mellitic acid).

[0159] PFSA containing Ce(EDTA) complex membrane The general procedure described above was used with a coating solution containing 0.45 wt.% Ce(EDTA) complex (3:1 Ce:EDTA).

[0160] PFSA containing Ce(NTA) complex membrane The general procedure described above was used with a coating solution containing 0.43 wt.% of a Ce(NTA) complex (3:1 Ce:NTA).

[0161] Film containing Ce(DTPMP) complex in PFSA The general procedure described above was used with a coating solution containing 0.43 wt.% Ce(DTPMP) complex (3:1 Ce:DTPMP).

[0162] Membrane containing Cu(ATMP) complex in PFSA The general procedure described above was used with a coating solution containing 0.21 wt.% Cu(ATMP) complex.

[0163] Membrane containing Fe(ATMP) complex in PFSA The general procedure described above was used with a coating solution containing 0.29 wt.% Fe(ATMP) complex.

[0164] Membrane containing Co(ATMP) complex in PFSA The general procedure described above was used with a coating solution containing 0.11 wt.% of the Co(ATMP) complex.

[0165] Film containing Ni(ATMP) complex in PFSA The general procedure described above was used with a coating solution containing 0.11 wt.% Ni(ATMP) complex.

[0166] All patents, published applications, and references cited herein are incorporated by reference in their entirety.

[0167] While the present invention is particularly illustrated and described in terms of its exemplary embodiments, it will be understood by those skilled in the art that various modifications in form and detail can be made in the present invention without departing from the scope of the invention as encompassed in the appended claims.

Claims

1. A polymer electrolyte membrane containing a polymer electrolyte and a metal complex, comprising: A metal complex contains a metal cation and a ligand; A polymer electrolyte membrane in which the ligand comprises three or more functional groups, each of which is independently selected from phosphonic acids, sulfonic acids, and carboxylic acids, or their anions.

2. The polymer electrolyte membrane according to claim 1, wherein the metal cation is selected from the cations of Ce, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Sm, Gd, and Th.

3. The polymer electrolyte membrane according to claim 2, wherein the metal cation is selected from Ce, Mn, and Zr cations.

4. The polymer electrolyte membrane according to claim 2, wherein the metal cation is selected from cations of Ce, Cu, Fe, Co, and Ni.

5. The polymer electrolyte membrane according to claim 2, wherein the metal cation is a Ce cation.

6. Ce cation is Ce 4+ The polymer electrolyte membrane according to claim 5.

7. Ce cation is Ce 3+ The polymer electrolyte membrane according to claim 5.

8. The ligands are aminotris(methylenephosphonic acid) (ATMP), diethylenetriaminepentakis(methylenephosphonic acid) (DTPMP), ethylenediaminetetra(methylenephosphonic acid) (EDTMP), hexamethylenediaminetetra(methylenephosphonic acid) (HDTMP), bis(hexamethylenetriaminepenta(methylenephosphonic acid) (BHMTMP), benzenetrisulfonic acid, naphthalenetrisulfonic acid, pyrenetetrasulfonic acid, triphenylphosphine-3,3',3"-trisulfonic acid, nitriloto NTA, citric acid, ethylenediaminetetraacetic acid (EDTA), benzenetricarboxylic acid, benzenetetracarboxylic acid, benzenepentacarboxylic acid, benzene-1,3,5-triacetic acid, mellitic acid, N,N-bis(phosphonomethyl)glycine, 2,2'-((phosphonomethyl)azandiyl)diacetic acid, ethylene glycol bis(2-aminoethyl ether)-N,N,N',N'-tetraacetic acid, 1,2-bis(2-aminophenoxy)ethane-N,N,N',N'-tetraacetic acid, ethylenediamine N,N'-disuccinic acid A polymer electrolyte membrane according to any one of claims 1 to 7, wherein the anion is selected from or is an anion thereof from N-(2-hydroxyethyl)ethylenediamine N,N',N'-triacetic acid, 1,2-diaminopropane-N,N,N',N'-tetraacetic acid, 1,2,3,4-butanetetracarboxylic acid, 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid, 1,6-diaminohexane-N,N,N',N'-tetraacetic acid, 1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid, and 3,3'-dimethoxybenzidine-N,N,N',N'-tetraacetic acid.

9. The polymer electrolyte membrane according to claim 8, wherein the ligand is selected from ATMP, DTPMP, NTA, EDTA, and mellitic acid or an anion thereof.

10. The polymer electrolyte membrane according to claim 8, wherein the ligand is ATMP or its anion.

11. A polymer electrolyte membrane according to any one of claims 1 to 10, wherein the metal complex contains a metal cation and a ligand in a molar ratio of about 12:1 to about 1:

1.

12. The polymer electrolyte membrane according to claim 11, wherein the metal complex contains a metal cation and a ligand in a molar ratio of about 3:

1.

13. A polymer electrolyte membrane according to any one of claims 1 to 12, wherein the metal cation is a Ce cation and the ligand is ATMP or its anion.

14. The polymer electrolyte membrane according to claim 13, wherein the metal complex contains Ce cations and ATMP or its anions in a molar ratio of about 6:

1.

15. The polymer electrolyte membrane according to any one of claims 1 to 14, wherein the metal complex further comprises a complex anion.

16. The complex anion is NO 3 - , Cl - , F - , BF 4 - , SO 4 2- , HSO 4 - , [(NH 4 ) 2 (NO 3 ) 6 2- , CO 3 2- , HCO 3 - , CH 3 CO 2 - and HCO 2 - The polymer electrolyte membrane according to claim 15, selected from​

17. The complex anion is NO 3 - or Cl - The polymer electrolyte membrane according to claim 16.

18. The complex anion is NO 3 - The polymer electrolyte membrane according to claim 16.

19. A polymer electrolyte membrane according to any one of claims 1 to 18, wherein a polymer electrolyte and a metal complex form a mixture.

20. A polymer electrolyte membrane according to any one of claims 1 to 19, wherein the polymer electrolyte membrane contains about 0.1 wt.% to about 10 wt.% of metal cations.

21. The polymer electrolyte membrane according to claim 20, wherein the polymer electrolyte membrane contains about 1 wt.% of metal cations.

22. A polymer electrolyte membrane according to any one of claims 1 to 21, wherein the polymer electrolyte is sulfonated.

23. The polymer electrolyte membrane according to claim 22, wherein the polymer electrolyte is perfluorosulfonic acid (PFSA).

24. The polymer electrolyte membrane according to claim 22, wherein the polymer electrolyte is selected from or a combination of sulfonated polyphenylsulfone (sPPS), sulfonated polyetheretherketone (sPEEK), sulfonated polyphosphazene (sPOP), sulfonated polybenzimidazole (sPBI), sulfonated polyethersulfone (sPES), sulfonated polyphenylene oxide (sPPO), sulfonated polyaryleneetherketone (sPAEK), sulfonated polyphenylsulfone, sulfonated poly(sulfone), sulfonated poly(sulfidesulfone), sulfonated polyimide (sPI), sulfonated poly(etherimide) (sPEI), sulfonated poly(amine), sulfophenylated polyphenylene, and sulfonated polyetherpyridine.

25. The polymer electrolyte membrane according to claim 24, wherein the polymer electrolyte is sPPS.

26. A polymer electrolyte membrane according to any one of claims 22 to 25, wherein the degree of sulfonation of the polymer electrolyte is about 100% to about 300%.

27. The polymer electrolyte membrane according to claim 26, wherein the degree of sulfonation of the polymer electrolyte is about 200%.

28. The polymer electrolyte contains multiple sulfonic acid moieties, A polymer electrolyte membrane according to any one of claims 1 to 27, wherein the polymer electrolyte membrane contains about 0.0001 to about 0.1 metal cations per sulfonic acid portion.

29. The polymer electrolyte membrane according to claim 28, comprising approximately 0.014 metal cations per sulfonic acid portion.

30. A polymer electrolyte membrane according to any one of claims 1 to 29, wherein the polymer electrolyte is crosslinked.

31. The polymer electrolyte has the following structural formula: 【Chemistry 1-1】 【Chemistry 1-2】 It includes a bridge section represented by one of the following, where: k is 0, 1, or 2; R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 Each of these is independently H, C 1-12 Alkyl, C 1-12 Haloalkyl, C 6-14 Aryl and C 6-14 Ariel (C 1-12 Selected from alkylene; Each of A, E, G, J, L, and M is independently combined, C 1-12 Alkylene and C 6-14 Selected from Ariren; R a and R a* Each of these is independently H or C 1-12 It is alkyl; M 2+ Mg 2+ Ca 2+ Ba 2+ and Al(X) 2+ Selected from the following, where X is a halide, acetate, or nitrate; symbol" 【Chemistry 2】 " indicates the point of attachment of the crosslinking portion to the repeating unit of the polymer electrolyte. The polymer electrolyte membrane according to claim 30.

32. The cross-linked section has the following structural formula: 【Transformation 3】 A polymer electrolyte membrane according to claim 31, represented by one of the following.

33. The cross-linked section has the following structural formula: 【Chemistry 4】 A polymer electrolyte membrane according to claim 31, represented by one of the following.

34. The cross-linked section has the following structural formula: 【Transformation 5】 A polymer electrolyte membrane according to claim 31, as represented by [the specified method].

35. A polymer electrolyte membrane according to any one of claims 30 to 34, wherein the degree of crosslinking of the polymer electrolyte is approximately 10% to approximately 95%.

36. The polymer electrolyte membrane according to claim 35, wherein the degree of crosslinking of the polymer electrolyte is approximately 30% to approximately 50%.

37. The metal cation is a Ce cation; The ligand is selected from ATMP, DTPMP, NTA, EDTA, and melito acids or their anions; The polymer electrolyte membrane according to claim 1, wherein the polymer electrolyte is PFSA.

38. The metal cation is selected from the cations of Ce, Cu, Fe, Co, and Ni; The ligand is ATMP; The polymer electrolyte membrane according to claim 1, wherein the polymer electrolyte is PFSA.

39. The metal cation is selected from the cations of Ce, Zr, and Mn; The ligand is ATMP; The polymer electrolyte membrane according to claim 1, wherein the polymer electrolyte contains sPPS.

40. The polymer electrolyte membrane according to claim 38 or 39, wherein the metal cation is a Ce cation.

41. The polymer electrolyte membrane according to claim 39, wherein the sPPS is crosslinked sPPS.

42. The cross-linked sPPS has the following structural formula: 【Transformation 6】 A polymer electrolyte membrane according to claim 41, comprising a crosslinked portion represented by [the specified method].

43. The metal cation is a Ce cation; The ligand is ATMP; Metal complexes further NO 3- Including; Ce cations and ATMP are present in a molar ratio of approximately 3:1; The polymer electrolyte membrane according to claim 1, wherein the polymer electrolyte is sPPS.

44. A polymer electrolyte membrane according to any one of claims 1 to 43, which is a self-supporting membrane comprising a polymer electrolyte and a metal complex.

45. A polymer electrolyte membrane according to any one of claims 1 to 44, having a thickness of approximately 2 μm to approximately 100 μm.

46. A polymer electrolyte membrane according to any one of claims 1 to 43, further comprising a support polymer.

47. A polymer electrolyte membrane containing a porous matrix: The porous matrix contains a support polymer; The polymer electrolyte membrane according to claim 46, wherein a metal complex and a polymer electrolyte are dispersed in a porous matrix.

48. The composite film according to claim 46 or 47, wherein the support polymer is polytetrafluoroethylene (PTFE).

49. The composite film according to claim 48, wherein the PTFE is stretched PTFE.

50. A polymer electrolyte membrane according to any one of claims 46 to 59, having a thickness of approximately 0.5 μm to approximately 100 μm.

51. The composite film according to claim 50, wherein the polymer electrolyte membrane is approximately 8 μm thick.

52. (a) A step of providing a casting surface and a suspension comprising a metal complex, a polymer electrolyte and (i) a crosslinking reagent and / or (ii) a crosslinking initiator; (b) the step of placing a suspension on a casting surface, thereby providing a layer of film; and (c) A process of providing a polymer electrolyte membrane by (i) exposing a layer of the membrane to conditions sufficient for the polymer electrolyte and crosslinking reagent to undergo a crosslinking reaction, or (ii) for the crosslinking initiator to initiate crosslinking of the polymer electrolyte. A method for producing a polymer electrolyte membrane according to any one of claims 1 to 45, including the above.

53. The method according to claim 52, wherein the suspension contains about 0.01 wt.% to about 10 wt.% of the metal complex.

54. The method according to claim 53, wherein the suspension contains about 0.1 wt.% to about 1 wt.% of the metal complex.

55. The method according to any one of claims 52 to 54, wherein the suspension contains approximately 2 wt.% to approximately 50 wt.% of a polyelectrolyte.

56. The method according to claim 55, wherein the suspension contains about 10 wt.% of a polyelectrolyte.

57. The method according to any one of claims 52 to 56, wherein the polymer electrolyte contains a crosslinkable group.

58. Bridging groups: α, OH, NH 2 , NH, SH, C(O)OH, C(O)Cl, C(O)Br, NHNH 2 N 3 S(O) 2 OH, S(O) 2 Cl, -NCO, 【Transformation 7】 The method according to claim 57, selected from the following.

59. The method according to any one of claims 52 to 58, wherein the suspension contains a crosslinking initiator.

60. The method according to claim 59, wherein the crosslinking initiator is selected from 2,2-dimethoxy-2-phenylacetophenone (DMPA), azobisisobutyronitrile (AIBN), and benzoyl peroxide (BPO).

61. The method according to claim 59 or 60, wherein the conditions sufficient for the crosslinking initiator to initiate crosslinking of the polymer electrolyte include visible light irradiation, UV light irradiation, application of heat, microwave irradiation, application of ultrasound, or gamma ray irradiation.

62. The method according to any one of claims 52 to 61, wherein the suspension contains a crosslinking reagent.

63. The method according to claim 62, wherein the conditions sufficient for the polymer electrolyte and crosslinking reagent to undergo a crosslinking reaction include visible light irradiation, UV light irradiation, application of heat, microwave irradiation or ultrasound.

64. The method according to any one of claims 52 to 63, wherein the crosslinking reagent is selected from compounds comprising polyalcohols, aldehydes, amines, epoxides, thiols, or terminal alkenes or alkynes.

65. The method according to any one of claims 52 to 63, wherein the crosslinking reagent is selected from glycerol, ethylene glycol, hydroquinone, 2,5-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzene-1,4-disulfonic acid, biphenyl, tetraglycidylbis(p-aminophenyl)methane, phenylenediamine, 4,4'-thiobisbenzenethiol, and tetrafluorostyrene.

66. (a) A step of providing a suspension comprising a porous matrix, a metal complex, and a polymer electrolyte; (b) A step of bringing a porous matrix into contact with a suspension, thereby providing an immersed porous matrix; and (c) A step of drying the immersed porous matrix to provide a polymer electrolyte membrane. A method for producing a polymer electrolyte membrane according to any one of claims 47 to 51, including the above.

67. The method according to claim 66, wherein the suspension further comprises a solvent containing water and alcohol.

68. The method according to claim 66 or 67, wherein the suspension contains about 0.01 wt.% to about 10 wt.% of the metal complex.

69. The method according to claim 68, wherein the suspension contains about 0.1 wt.% to about 1 wt.% of the metal complex.

70. The method according to any one of claims 66 to 69, wherein the suspension contains approximately 2 wt.% to approximately 50 wt.% of a polyelectrolyte.

71. The method according to claim 70, wherein the suspension contains about 10 wt.% of a polyelectrolyte.

72. The method according to any one of claims 66 to 71, wherein the polymer electrolyte contains a crosslinkable group.

73. Bridging groups: α, OH, NH 2 , NH, SH, C(O)OH, C(O)Cl, C(O)Br, NHNH 2 N 3 S(O) 2 OH, S(O) 2 Cl, -NCO, 【Transformation 8】 The method according to claim 72, selected from the above.

74. The method according to any one of claims 66 to 73, wherein the suspension further comprises a crosslinking initiator.

75. The method according to claim 74, further comprising the step of crosslinking a polymer electrolyte under conditions sufficient to initiate crosslinking of a first polymer with a crosslinking initiator.

76. The method according to claim 75, wherein the conditions sufficient for the crosslinking initiator to initiate crosslinking of the polymer electrolyte include visible light irradiation, UV light irradiation, application of heat, microwave irradiation, application of ultrasound, or gamma ray irradiation.

77. The method according to any one of claims 74 to 76, wherein the crosslinking initiator is selected from 2,2-dimethoxy-2-phenylacetophenone (DMPA), azobisisobutyronitrile (AIBN), and benzoyl peroxide (BPO).

78. The method according to any one of claims 66 to 77, wherein the suspension further comprises a crosslinking agent.

79. The method according to any one of claims 66 to 78, further comprising the step of reacting a polymer electrolyte and a crosslinking reagent under conditions sufficient to allow the polymer electrolyte and the crosslinking reagent to undergo a crosslinking reaction.

80. The method according to claim 79, wherein the conditions sufficient for the polymer electrolyte and crosslinking reagent to undergo a crosslinking reaction include visible light irradiation, UV light irradiation, application of heat, microwave irradiation or ultrasound.

81. The method according to any one of claims 78 to 80, wherein the crosslinking reagent is selected from compounds comprising polyalcohols, aldehydes, amines, epoxides, thiols, or terminal alkenes or alkynes.

82. The method according to any one of claims 78 to 81, wherein the crosslinking reagent is selected from glycerol, ethylene glycol, hydroquinone, 2,5-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzene-1,4-disulfonic acid, biphenyl, tetraglycidylbis(p-aminophenyl)methane, phenylenediamine, 4,4'-thiobisbenzenethiol, and tetrafluorostyrene.

83. A polymer electrolyte membrane according to any one of claims 1 to 51; Cathode; and anode A membrane electrode assembly (MEA) including, A membrane electrode assembly (MEA) in which a polymer electrolyte membrane or a polymer electrolyte membrane is placed between the anode and the cathode.

84. A fuel cell comprising one or more MEAs according to claim 83 and one or more gas flow bipolar plates.

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