Polymer electrolyte membrane, method for manufacturing same, and membrane-electrode assembly, water electrolysis cell, and fuel cell each comprising same

Abstract

The present invention relates to a polymer electrolyte membrane, a method for manufacturing same, and a membrane-electrode assembly, a water electrolysis cell, and a fuel cell each comprising same. The polymer electrolyte membrane comprises, as an electrolyte, a reaction product of a cation conductor and an amine compound, wherein the cation conductor includes at least one sulfonic acid group as a side chain, and the amine compound includes at least one sulfonic acid group as a side chain and at least one amino group as a side chain, a terminal, or a combination thereof.

Description

Polymer electrolyte membrane, method for manufacturing the same, membrane-electrode assembly including the same, water electrolysis cell and fuel cell

[0001] The invention relates to a polymer electrolyte membrane, a method for manufacturing the same, a membrane-electrode assembly including the same, a water electrolysis cell, and a fuel cell.

[0002] The present disclosure relates to the results of a project (Project No.: 00418612) carried out with the support of the Ministry of Trade, Industry and Energy (MOTIE) and the Korea Energy Technology Evaluation Institute (KETEP).

[0003]

[0004] Recent energy demands and environmental conditions require sustainable supply, eco-friendliness, and high efficiency, and among these, hydrogen is attracting attention as a raw material for renewable energy.

[0005] In a system of a Polymer Electrolyte Membrane Water Electrolysis Cell (PEMWE), the Membrane Electrode Assembly (MEA) that actually generates hydrogen has a structure in which an oxygen evolution electrode, where the oxygen evolution reaction takes place, and a hydrogen evolution electrode, where the hydrogen evolution reaction takes place, are positioned with respect to a polymer electrolyte membrane containing a hydrogen ion-conducting polymer.

[0006] Polymer electrolyte fuel cells (PEMFCs) are known to be the most promising for transportation systems as well as small-scale stationary power generation equipment, as they operate at low temperatures compared to other fuel cells and enable miniaturization due to their high power density.

[0007] A technology is known for applying a cation conductor having a sulfonic acid side chain to such polymer electrolyte membranes for water electrolysis or fuel cells.

[0008] However, the cation conductivity of cation conductors with sulfonic acid side chains is sensitive to moisture content and is vulnerable under low humidity conditions; increasing the ion exchange capacity (IEC) to improve cation conductivity may instead lead to excessive membrane expansion and reduced dimensional stability.

[0009]

[0010] One embodiment provides a polymer electrolyte membrane that can enhance cation conductivity, stability in humidified environments, and durability while using a cation conductor having sulfonic acid side chains.

[0011]

[0012] One embodiment provides a polymer electrolyte membrane comprising a reaction product of a cation conductor and an amine compound as an electrolyte, wherein the cation conductor comprises at least one sulfonic acid group as a side chain and the amine compound comprises at least one sulfonic acid group as a side chain; and at least one amino group as a side chain, a terminal, or a combination thereof.

[0013]

[0014] A polymer electrolyte membrane according to one embodiment includes a cation conductor having a sulfonic acid side chain, and has improved cation conductivity and limited swelling in a humidified environment, thereby improving stability and durability.

[0015] Accordingly, a water electrolysis cell or fuel cell manufactured by assembling the above-mentioned polymer electrolyte membrane as a membrane-electrode assembly may have excellent electrochemical properties, mechanical properties, etc.

[0016]

[0017] FIGS. 1 to 3 schematically illustrate a reaction scheme in which a complex of a cation conductor and an amine compound is formed in one embodiment.

[0018] Figure 4 schematically illustrates a polymer electrolyte membrane with a reinforced membrane structure according to one embodiment.

[0019]

[0020] Hereinafter, embodiments of the present disclosure are described in detail so that those skilled in the art to which the present disclosure pertains can easily implement them. However, the present disclosure may be embodied in various different forms and is not limited to the embodiments described herein.

[0021] In this specification, “combination thereof” means a mixture of components, laminates, composites, copolymers, alloys, blends, reaction products, etc.

[0022] In this specification, terms such as “comprising,” “having,” or “having” are intended to specify the existence of the implemented features, numbers, steps, components, or combinations thereof, and should be understood as not excluding in advance the existence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0023] In this specification, terms are used solely for the purpose of distinguishing one component from another. The singular expression includes the plural expression unless the context clearly indicates otherwise.

[0024]

[0025] polymer electrolyte membrane

[0026] One embodiment provides a polymer electrolyte membrane comprising a reaction product of a cation conductor and an amine compound as an electrolyte, wherein the cation conductor comprises at least one sulfonic acid group as a side chain and the amine compound comprises at least one sulfonic acid group as a side chain; and at least one amino group as a side chain, a terminal, or a combination thereof.

[0027]

[0028] The reaction product of the above cation conductor and the amine compound, in contrast to the above cation conductor itself, H3O +By effectively forming a hydrogen bond network with it, cation conduction can be promoted, while limiting excessive self-aggregation, thereby improving the stability and durability of the polymer electrolyte.

[0029] A polymer electrolyte membrane of one embodiment is described in detail below.

[0030]

[0031] electrolytes

[0032] One embodiment includes a reaction product of a cation conductor and an amine compound as an electrolyte. In this case, the electrolyte may be in a solid state, but the phase is not limited. Examples include a mixture state contained in a solvent, etc., but are not limited to the above examples.

[0033]

[0034] The above cation conductor includes at least one sulfonic acid group as a side chain, and the side chain (sulfonic acid group, -SO2OH) of the cation conductor may be bonded to the amino group (-NH2) of the amine compound to form a sulfonamide (Sulfonamide, -SO2-NH-).

[0035] Here, the amine compound may also include at least one sulfonic acid group as a side chain, and accordingly, the cation conductivity can be improved while forming a sulfonamide without quantitative loss of the sulfonic acid group.

[0036] For every 1 mole of sulfonic acid groups in the above-mentioned cation conductor, the sulfonamide groups may be included in an amount of 0.01 to 1 mole, 0.05 to 1 mole, or 0.1 to 1 mole. By increasing the acidity of the composite formed within this range to increase conductivity while limiting excessive self-aggregation, a polymer electrolyte membrane with improved stability and durability can be expected. Additionally, within this range, a certain level of free water for the formation of cation conduction channels can be included to prevent performance degradation.

[0037]

[0038] cation conductor

[0039] The above cation conductor includes a hydrocarbon-based ion conductor, a fluorine-based ion conductor, or a combination thereof, and may include at least one sulfonic acid group as a side chain.

[0040] The above-mentioned fluorine-based ion conductor may be (i) a fluorine-based polymer comprising fluorine in a main chain and at least one sulfonic acid group as a side chain; (ii) a polymer comprising repeating units of a polystyrene-based polymer and having a main chain of a partially fluorinated polymer and comprising at least one sulfonic acid group as a side chain; or a combination thereof. In this case, the polymer comprising repeating units of a polystyrene-based polymer and partially fluorinated in (ii) may be a graft polymer, but is not limited thereto.

[0041] For example, the above-mentioned fluorine-based ion conductor may be (i) a fluorine-based polymer having fluorine in a main chain and having at least one sulfonic acid group as a side chain; (ii) having a main chain of a partially fluorinated polymer such as a polystyrene-graft-ethylene-tetrafluoroethylene copolymer, a polystyrene-graft-polytetrafluoroethylene copolymer, etc., and having at least one sulfonic acid group as a side chain; or a combination thereof.

[0042] For example, the above-mentioned fluorine-based ion conductor comprises (i) poly(perfluorosulfonic acid), (ii) poly(perfluorocarboxylic acid), (iii) a copolymer of tetrafluoroethylene and fluorovinyl ether containing a sulfonic acid group, and (iv) defluorinated sulfated polyetherketone, but is not limited to these.

[0043] The above hydrocarbon-based ion conductor may include, for example, a structure selected from imidazole, benzimidazole, polybenzoxazole, polybenzthiazole, polyamide, polyamideimide, polyimide, polyimidesulfone, polyacetal, polyethylene, polypropylene, acrylic resin, polyester, polysulfone, polyether, polyetherimide, polyarylene ether-based polymer, polyarylene ketone, polyarylenephosphine oxide, polyester, polyethersulfone, polycarbonate, polystyrene, polyphenylene-based polymer, polyphenylene oxide, polyphenylene sulfide, polyphenylene sulfidesulfone, polyparaphenylene, polyetheretherketone, polyetherketone, polyetherphosphine oxide, polyarylethersulfone, polyphosphazene, and polyphenylquinoxaline in its main chain, wherein the above polysulfone, polyethersulfone, polyetherketone, etc., have sulfone bonds in the molecular chain. A general term for structures having ether bonds and / or ketone bonds, wherein the hydrocarbon ion conductor may have these structures and / or a combination of these structures as a main chain and include at least one sulfonic acid group as a side chain.

[0044] For example, the hydrocarbon-based ion conductor is sulfonated polyimide (S-PI), sulfonated polyarylethersulfone (S-PAES), sulfonated polyetheretherketone (SPEEK), sulfonated polybenzimidazole (SPBI), sulfonated polysulfone (S-PSU), sulfonated polystyrene (S-PS), sulfonated polyphosphazene, sulfonated polyquinoxaline, sulfonated polyketone, sulfonated polyphenylene oxide, sulfonated polyether sulfone, sulfonated polyether ketone, sulfonated sulfonated polyphenylene sulfone, sulfonated polyphenylene sulfide, sulfonated polyphenylene sulfide sulfone, sulfonated polyphenylene sulfide sulfone nitrile, sulfonated polyarylene ether, sulfonated polyarylene ether nitrile,and sulfonated polyarylene ether sulfone ketones, but are not limited to these.

[0045]

[0046] The above cation conductor may have a weight-average molecular weight of 10,000 to 10,000,000 g / mol, 30,000 to 6,000,000 g / mol, or 50,000 to 300,000 g / mol as measured by the GPC method. Within this range, a cation conductor can be selected that is desirable in terms of process aspects such as solution preparation and coating, in terms of the mechanical properties of the polymer electrolyte membrane.

[0047]

[0048] amine compounds

[0049] The above amine compound is a substance containing one or more sulfonic acid groups as a side chain, and since the side chain of the cation conductor is modified to form a sulfonamide without quantitative loss of sulfonic acid groups, an improvement in cation conductivity can be expected.

[0050]

[0051] FIGS. 1 to 3 schematically illustrate a reaction scheme in which a complex of a cation conductor and an amine compound is formed in one embodiment.

[0052] As shown in Figure 1, when the amine compound has one amino group, conductivity is improved through hydrogen bonding interactions, and the side chain is extended to limit excessive self-aggregation.

[0053] For example, the above amine compound may include sulfamic acid, taurine, sulfanilic acid, 4-amino-1,3-benzenedisulfonic acid, or a combination thereof.

[0054] Meanwhile, as shown in FIG. 2, when the amine compound has two or more amino groups, it forms a crosslink by bonding with a sulfonic acid group, thereby limiting the distance between ion channels that swell upon moisture absorption and improving stability, and as the number of crosslinked functional groups increases, this swelling limiting effect may be increased.

[0055] For example, the amine compound may include 4,4'-diaminostilbene-2,2'-disulfonic acid, 2,2'-benzidinedisulfonic acid, 4,6-diaminobenzene-1,3-disulfonic acid, 9,9-bis(4-aminophenyl)fluorene-2,7-disulfonic acid, or a combination thereof.

[0056] However, the above is merely an example, and the above amine compound is not limited to those comprising at least one amino group as a side chain, terminal, or a combination thereof.

[0057]

[0058] As shown in Fig. 3, if a process of reacting the cation conductor with N,N-carbonyldiimidazole is added prior to the process of introducing the amine compound, an activated cation conductor containing sulfonimidazole groups within the molecule can be formed.

[0059] For every 1 mole of sulfonic acid group included in the above cation conductor, the sulfonimidazole group may be included in an amount of 0.01 to 1 mole, 0.01 to 0.8 mole, or 0.01 to 0.5 mole.

[0060] When the cation conductor activated as described above is reacted with the amine compound, the bonding between the amino group of the amine compound and the sulfonic acid group of the cation conductor is promoted, thereby allowing for the expectation of improved effects of the invention.

[0061]

[0062] Structure of polymer electrolyte membranes

[0063] The polymer electrolyte membrane of one embodiment may have a structure of a single membrane or a reinforced membrane.

[0064]

[0065] The above single membrane may consist solely of a complex of the above cation conductor and amine compound.

[0066]

[0067] As shown in FIG. 4, the reinforcing film (50) may include a first coating layer (54) and a second coating layer (56). Specifically, the first coating layer (54) may be disposed on a first surface (52a) of the porous support (52), and the second coating layer (56) may be disposed on a second surface (52b) opposite to the first surface (52a). Accordingly, the coating layer (55) may be formed on the surface of the porous support (52) and may include the aforementioned ion conductor.

[0068] The porosity of the porous support (52) may be 30 to 90%, and preferably 60 to 85%. If the porosity of the porous support (52) is less than the above numerical range, a problem of reduced impregnation of the mixed polymer solution may occur, and if it exceeds the above numerical range, shape stability may be reduced, which may prevent the subsequent process from proceeding smoothly.

[0069] The above porosity can be calculated by the ratio of the volume of air within the porous support to the total volume of the porous support according to the following Equation 1. At this time, the total volume is calculated by manufacturing a rectangular sample and measuring its width, length, and thickness, and the volume of air is obtained by measuring the mass of the sample and subtracting the volume of the polymer, which is inversely calculated from the density, from the total volume.

[0070] [Equation 1]

[0071] Porosity (%) = (Volume of air in porous support / Total volume of porous support) X 100

[0072]

[0073] The porous support (52) may be a fluorine-based support or a nanoweb support.

[0074] The above-mentioned fluorine-based support may correspond, for example, to expanded polytetrafluoroethylene (e-PTFE) having a microstructure of polymer fibrils or a microstructure in which nodes are connected to each other by fibrils. Additionally, a film having a microstructure of polymer fibrils in which nodes are not present may also be used as the above-mentioned porous support (52).

[0075] The above fluorine-based support may include a perfluorinated polymer. The porous support (52) may correspond to a more porous and stronger porous support by extruding dispersed polymerized PTFE onto a tape in the presence of a lubricant and stretching the material obtained thereby.

[0076] In addition, the amorphous content of the PTFE may be increased by heat-treating the e-PTFE at a temperature exceeding the melting point (approx. 342°C) of the PTFE. The e-PTFE film produced by the above method may have micropores of various diameters and porosity. The e-PTFE film produced by the above method may have at least 35% porosity, and the diameter of the micropores may be approximately 0.01 to 1 μm (micrometer).

[0077] The nanoweb support may be a non-woven fibrous web composed of a plurality of randomly oriented fibers. The non-woven fibrous web refers to a sheet having the structure of individual fibers or filaments that are interlaid but not in the same manner as a woven fabric. The non-woven fibrous web may be manufactured by any one method selected from the group consisting of carding, garneting, air-laying, wet-laying, melt blowing, spun bonding, and stitch bonding.

[0078] The above fiber may comprise one or more polymer materials, and any material generally used as a fiber-forming polymer material may be used; specifically, hydrocarbon-based fiber-forming polymer materials may be used. For example, the fiber-forming polymer material may comprise any one selected from the group consisting of polyolefins, e.g., polybutylene, polypropylene, and polyethylene; polyesters, e.g., polyethylene terephthalate and polybutylene terephthalate; polyamides (Nylon-6 and Nylon-6,6); polyurethanes, polybutene; polylactic acid; polyvinyl alcohol; polyphenylene sulfide; polysulfone; fluid crystalline polymers; polyethylene-co-vinyl acetate; polyacrylonitrile; cyclic polyolefins; polyoxymethylene; polyolefin-based thermoplastic elastomers; and combinations thereof. However, the technical concept of the present invention is not limited thereto.

[0079] The above nanoweb support may be a support in which nanofibers are integrated in the form of a nonwoven fabric containing a number of pores.

[0080] The above nanofibers may preferably be hydrocarbon-based polymers that exhibit excellent chemical resistance and hydrophobicity, so there is no concern about shape deformation due to moisture in high-humidity environments. Specifically, the above hydrocarbon-based polymer may be selected from the group consisting of nylon, polyimide, polyaramid, polyetherimide, polyacrylonitrile, polyaniline, polyethylene oxide, polyethylene naphthalate, polybutylene terephthalate, styrene butadiene rubber, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyvinylidene fluoride, polyvinyl butylene, polyurethane, polybenzoxazole, polybenzimidazole, polyamideimide, polyethylene terephthalate, polyphenylene sulfide, polyethylene, polypropylene, copolymers thereof, and mixtures thereof.

[0081] The above nanoweb support is an aggregate of nanofibers in which nanofibers manufactured by electrospinning are randomly arranged. In this case, considering the porosity and thickness of the nanoweb, it is preferable that the nanofibers have an average diameter of 40 to 5,000 nm (nanometers) when 50 fiber diameters are measured using a scanning electron microscope (JSM6700F, JEOL) and calculated from the average.

[0082] If the average diameter of the nanofiber is less than the above numerical range, the mechanical strength of the porous support may be reduced, and if the average diameter of the nanofiber exceeds the above numerical range, the porosity may be significantly reduced and the thickness may be increased.

[0083] The thickness of the nonwoven fiber web may be 3 to 60 μm (micrometers), specifically 8 to 50 μm (micrometers). If the thickness of the nonwoven fiber web is less than the above numerical range, the mechanical strength may decrease, and if it exceeds the above numerical range, the resistance loss increases, and the lightweighting and integration may decrease.

[0084] The above nonwoven fibrous web has a basic weight of 5 to 30 mg / cm² 2 It may be. If the basis weight of the above nonwoven fibrous web is less than the above numerical range, visible pores may be formed, making it difficult to function as a porous support, and if it exceeds the above numerical range, it may be manufactured in the form of paper or fabric in which pores are hardly formed.

[0085]

[0086] Thickness of the polymer electrolyte membrane

[0087] The thickness of the polymer electrolyte membrane may be, for example, 5 to 200 μm. However, it is not limited thereto, and various thickness ranges may be applied.

[0088]

[0089] Method for manufacturing a polymer electrolyte membrane

[0090] One embodiment provides a method for manufacturing a polymer electrolyte membrane, comprising the steps of: introducing an amine compound into a cation conductor solution and reacting it to prepare a polymer electrolyte membrane forming solution; and forming a film from the polymer electrolyte membrane forming solution, wherein the cation conductor comprises at least one sulfonic acid group as a side chain, and the amine compound comprises at least one sulfonic acid group as a side chain; and at least one amino group as a side chain, a terminal, or a combination thereof.

[0091]

[0092] Through this, the polymer electrolyte membrane of the aforementioned embodiment can be manufactured.

[0093]

[0094] Hereinafter, descriptions that overlap with the above content will be omitted, and a manufacturing method of one embodiment will be described in detail.

[0095]

[0096] Preparation steps of the cation conductor solution

[0097] The above cation conductor can be dissolved using a polar amphoteric solvent such as DMSO, DMAc, DMF, or NMP.

[0098]

[0099] Activation stage of cation conductor

[0100] After preparing the above-mentioned cation conductor solution, the method may further include the step of adding N,N-carbonyldiimidazole to the above-mentioned cation conductor solution. This is for the activation of the above-mentioned cation conductor.

[0101]

[0102] Reaction step of cation conductor and amine compound

[0103] Immediately after the step of preparing the above-mentioned cation conductor solution or after the step of activation by N,N-carbonyldiimidazole, a reaction step with the above-mentioned amine compound may be carried out. Accordingly, a polymer electrolyte membrane forming solution comprising a complex of a cation conductor and an amine compound may be prepared.

[0104]

[0105] Step of obtaining a polymer electrolyte membrane

[0106] The step of forming the polymer electrolyte film forming solution described above may involve forming an electrolyte film by applying the polymer electrolyte film forming solution prepared as described above onto a substrate (e.g., a glass substrate) and then drying and / or heat treating. The drying temperature may be 20 to 120 ℃, and the heat treatment temperature may be 120 to 300 ℃.

[0107] Through this, the aforementioned single-membrane structure polymer electrolyte membrane can be obtained.

[0108]

[0109] Alternatively, the step of forming the polymer electrolyte membrane forming solution may include the step of applying the polymer electrolyte membrane forming solution to one or both sides of a porous support.

[0110] After the step of applying the polymer electrolyte membrane forming solution to one or both sides of the porous support, the method may further include a step of drying the applied product. The drying temperature may be 20 to 120 ℃.

[0111]

[0112] Membrane-electrode assemblies, water electrolysis cells, and fuel cells

[0113] The above polymer electrolyte membrane can be used as an electrolyte membrane for water electrolysis cells requiring cation conductivity, an electrolyte membrane for fuel cells, etc.

[0114]

[0115] One embodiment provides a membrane-electrode assembly for a water electrolysis cell comprising: a hydrogen generating electrode; an oxygen generating electrode; and a polymer electrolyte membrane according to the above-described embodiment located between the hydrogen generating electrode and the hydrogen generating electrode.

[0116] One embodiment provides a water electrolysis cell comprising a membrane-electrode assembly for the water electrolysis cell.

[0117]

[0118] One embodiment provides a membrane-electrode assembly for a fuel cell comprising: an anode electrode; a cathode electrode; and a polymer electrolyte membrane of the above-described embodiment located between the anode electrode and the cathode electrode.

[0119] One embodiment provides a fuel cell comprising a membrane-electrode assembly for the fuel cell.

[0120]

[0121] The above membrane-electrode assembly for a water electrolysis cell and the water electrolysis cell including the same are described below.

[0122] The catalyst layer included in the oxygen generation electrode comprises a catalyst for an oxygen generation reaction and an ion conductor, and the catalyst for the oxygen generation reaction comprises active particles comprising a precious metal oxide.

[0123] The above precious metal oxide is not limited in type as long as it can be applied as a catalyst for the oxygen evolution reaction of a water electrolysis cell.

[0124] For example, the above precious metal oxide is IrO x (The above x is an integer from 1 to 3), RuO x (The above x is an integer from 1 to 3), IrMO x (M comprises Ru, Pt, Sn, Se, Sb, Ta, Te, Nb, W, Zn, Au or a combination thereof, and x is an integer from 1 to 3), or may comprise a combination thereof.

[0125] The above catalyst for the oxygen generation reaction may use only the active particle alone, or may further include a carrier that supports the active particle.

[0126] The above-mentioned carrier is not limited in type as long as it can be applied to a catalyst for the oxygen generation reaction of a water electrolysis cell.

[0127] For example, the carrier may be a metal oxide, and the carrier may be titanium dioxide (TiO2).

[0128] The above ion conductor is included to improve the adhesion of the catalyst layer and to transport hydrogen ions.

[0129] The ion conductor included in the oxygen generating electrode and the ion conductor included in the reinforced polymer electrolyte membrane for the water electrolysis cell may be the same.

[0130] The above hydrogen generation electrode may include a catalyst for a hydrogen generation reaction. The above catalyst for a hydrogen generation reaction may include active particles and a support material that supports the active particles.

[0131] The above active particles may include precious metals.

[0132] For example, the above precious metal may be a platinum-based precious metal.

[0133] Platinum (Pt) and / or a Pt-M alloy may be used as the platinum-based precious metal. M may be palladium (Pd), ruthenium (Ru), iridium (Ir), osmium (Os), gallium (Ga), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), silver (Ag), gold (Au), zinc (Zn), tin (Sn), molybdenum (Mo), tungsten (W), lanthanum (La), or rhodium (Rh).

[0134] Specifically, as the above Pt-M alloy, Pt-Pd, Pt-Sn, Pt-Mo, Pt-Cr, Pt-W, Pt-Ru, Pt-Ni, Pt-Co, Pt-Y, Pt-Ru-W, Pt-Ru-Ni, Pt-Ru-Mo, Pt-Ru-Rh-Ni, Pt-Ru-Sn-W, Pt-Ru-Ir-Ni, Pt-Co-Mn, Pt-Co-Ni, Pt-Co-Fe, Pt-Co-Ir, Pt-Co-S, Pt-Co-P, Pt-Fe, Pt-Fe-Ir, Pt-Fe-S, Pt-Fe-P, Pt-Au-Co, Pt-Au-Fe, Pt-Au-Ni, Pt-Ni, Pt-Ni-Ir, Pt-Cr, Pt-Cr-Ir, or a mixture thereof may be used. there is.

[0135] The above carrier may be a carbon-based carrier.

[0136] The carbon-based carrier may be graphite, super P, carbon fiber, carbon sheet, carbon black, Ketjen black, Denka black, acetylene black, carbon nanotube (CNT), carbon sphere, carbon ribbon, fullerene, activated carbon, carbon nanofiber, carbon nanowire, carbon nanoball, carbon nanohorn, carbon nanocage, carbon nanoring, ordered nano- / meso-porous carbon, carbon aerogel, mesoporous carbon, graphene, stabilized carbon, activated carbon, or a combination thereof.

[0137] The oxygen generation electrode and the hydrogen generation electrode may each include only a catalyst layer comprising a catalyst for an oxygen generation reaction and a catalyst for a hydrogen generation reaction, respectively, but may also include an electrode substrate together with the catalyst layer.

[0138] At this time, the electrode substrate can perform the role of supporting the electrode while diffusing fuel and oxidant into the catalyst layer.

[0139] The above electrode substrate may be any known electrode substrate without specific limitations, but specifically, carbon paper, carbon cloth, carbon felt, or metal cloth that can be used as a conductive substrate (referring to a porous film composed of a metal cloth in a fibrous state or a metal film formed on the surface of a cloth formed of polymer fibers).

[0140] The above electrode substrate may be treated with a fluorine-based resin for water repellency, in which case the reduction in reactant diffusion efficiency caused by water generated after operating the water electrolysis cell can be prevented.

[0141] As the above fluorine-based resin, polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, polyperfluoroalkyl vinyl ether, polyperfluorosulfonyl fluoride, alkoxyvinyl ether, fluorinated ethylene propylene, polychlorotrifluoroethylene, or copolymers thereof may be used.

[0142]

[0143] A water electrolysis cell according to one embodiment may include the membrane-electrode assembly.

[0144] Since the above-mentioned water electrolysis cell is identical to the known one except for including the above-mentioned membrane-electrode assembly, a detailed description is omitted.

[0145]

[0146] The above-described membrane-electrode assembly for a fuel cell and the fuel cell including the same are described below.

[0147] A membrane-electrode assembly according to one embodiment is a membrane-electrode assembly comprising the polymer electrolyte membrane, wherein the anode electrode and a cathode electrode are positioned opposite each other, and the polymer electrolyte membrane is positioned between the anode electrode and the cathode electrode.

[0148] The above anode and cathode electrodes include an electrode substrate and a catalyst layer formed on the surface of the electrode substrate, and may further include a microporous layer containing conductive fine particles such as carbon powder or carbon black between the electrode substrate and the catalyst layer to facilitate material diffusion from the electrode substrate.

[0149] The catalyst layers of the anode and cathode electrodes described above contain a catalyst. Any catalyst that participates in the reaction of the cell and is typically usable as a catalyst for a fuel cell may be used. Preferably, a platinum-based metal may be used.

[0150] The platinum-based metal may include one selected from the group consisting of platinum (Pt), palladium (Pd), ruthenium (Ru), iridium (Ir), osmium (Os), platinum-M alloys, non-platinum alloys, and combinations thereof, and more preferably, a combination of two or more metals selected from the group of platinum-based catalyst metals may be used, but is not limited thereto, and any platinum-based catalyst metal available in the field of the present technology may be used without limitation.

[0151] The above M may correspond to one or more selected from the group consisting of palladium (Pd), ruthenium (Ru), iridium (Ir), osmium (Os), gallium (Ga), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), silver (Ag), gold (Au), zinc (Zn), tin (Sn), molybdenum (Mo), tungsten (W), lanthanum (La), and rhodium (Rh). Specifically, the platinum alloy mentioned above may be used alone or in a mixture of two or more selected from the group consisting of Pt-Pd, Pt-Sn, Pt-Mo, Pt-Cr, Pt-W, Pt-Ru, Pt-Ru-W, Pt-Ru-Mo, Pt-Ru-Rh-Ni, Pt-Ru-Sn-W, Pt-Co, Pt-Co-Ni, Pt-Co-Fe, Pt-Co-Ir, Pt-Co-S, Pt-Co-P, Pt-Fe, Pt-Fe-Ir, Pt-Fe-S, Pt-Fe-P, Pt-Au-Co, Pt-Au-Fe, Pt-Au-Ni, Pt-Ni, Pt-Ni-Ir, Pt-Cr, Pt-Cr-Ir, and combinations thereof.

[0152] In addition, the above-mentioned non-platinum alloy may be used alone or in a mixture of two or more selected from the group consisting of Ir-Fe, Ir-Ru, Ir-Os, Co-Fe, Co-Ru, Co-Os, Rh-Fe, Rh-Ru, Rh-Os, Ir-Ru-Fe, Ir-Ru-Os, Rh-Ru-Fe, Rh-Ru-Os, and combinations thereof.

[0153] The above catalyst may be used as the catalyst itself (black) or supported on a carrier.

[0154]

[0155] A fuel cell according to one embodiment may include the membrane-electrode assembly.

[0156] Since the above fuel cell is identical to the known one except for including the above membrane-electrode assembly, a detailed description is omitted.

[0157]

[0158] Hereinafter, embodiments are described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0159]

[0160] (Single membrane)

[0161]

[0162] Example 1

[0163] (1) Preparation of polymer electrolyte membrane

[0164] As a cation conductor containing at least one sulfonic acid group as a side chain, SPAES (Sulfonated Poly(arylene ether sulfone) was prepared, having a degree of sulfonation of 50% and a weight-average molecular weight of 12,500 g / mol as measured by GPC.

[0165] The above cation conductor is added to DMSO at a concentration of 15 wt% and stirred at 80°C for 6 hours to prepare a cation conductor solution.

[0166] Meanwhile, sulfamic acid was prepared as an amine compound containing at least one sulfonic acid group as a side chain.

[0167] The sulfamic acid was added to the above cation conductor solution. At this time, 30 molar parts of the sulfamic acid were added based on 100 molar parts of sulfonic acid groups contained in the solid portion of the cation conductor. Subsequently, the mixture was stirred for an additional 6 hours to obtain a polymer electrolyte membrane forming solution containing a complex of the cation conductor and the amine compound.

[0168] The above complex may be formed by the side chain (sulfonic acid group, -SO2OH) of the cation conductor being bonded to the amino group (-NH2) of the amine compound to form sulfonamide (Sulfonamide, -SO2-NH-).

[0169] After applying the above polymer electrolyte membrane forming solution onto a glass substrate, it was dried in an 80°C convection oven for 24 hours. Here, a single membrane for a fuel cell with a thickness of 15 μm and a single membrane for water electrolysis with a thickness of 70 μm were each prepared.

[0170] (2) Manufacture of membrane-electrode assembly for water electrolysis

[0171] IrO as a catalyst for oxygen evolution reaction x A composition for forming a first electrode was prepared by dispersing a composition of 5g of / TiO2 (Alfa Aesar, 43396), 12.5g of Nafion D2021 (Dupont) as an ion conductor, and water and n-propanol as solvents in a weight ratio of 4:6 (=water:n-propanol) using a homogeneous mixer.

[0172] A second electrode composition was prepared by dispersing a composition in a homogeneous mixer that included 5g of Pt / C (Tanaka, TEC10E50E) as a catalyst for hydrogen generation reaction, 10g of Nafion D2021 (Dupont) as an ion conductor, and water and n-propanol as solvents in a weight ratio of 4:6 (=water:n-propanol).

[0173] 1.0 mg / cm² of the above-mentioned first electrode-forming composition on the first surface of a polyimide film of PI Advanced Materials Co., Ltd. having a thickness of 150 μm as a release film 2 , the above second electrode forming composition is applied to the second surface facing the first surface at a concentration of 0.2 mg / cm 2 After applying with a doctor blade to achieve the desired result, the first electrode (oxygen generating electrode) was prepared on the first surface and the second electrode (hydrogen generating electrode) was prepared on the second surface by drying at 60°C for 8 hours.

[0174] A polymer electrolyte membrane prepared in (1) is interposed between the first electrode and the second electrode prepared above, and at 160°C and 20 kgf / cm² 2 A membrane-electrode assembly in which the first electrode and the second electrode are bonded to a polymer electrolyte membrane was manufactured by applying heat and pressure for 3 minutes under certain conditions and then peeling off the polyimide film.

[0175] (3) Manufacture of membrane-electrode assembly for fuel cell

[0176] A composition for forming an electrode was prepared by mixing 5g of Pt / C (Tanaka, TEC10E50E) as a catalyst, 10g of Nafion D2021 (Dupont) as an ion conductor, and 25g of a mixture of dipropylene glycol and distilled water in a weight ratio of 1:1 (=dipropylene glycol:distilled water) as a solvent, and uniformly dispersing the composition using a 3-roll mill (EXAKT 50).

[0177] 0.1 mg / cm² of the above electrode-forming composition on the first surface of a Teflon release film 2 , 0.4 mg / cm on the second surface facing the first surface above 2 After applying with a doctor blade to achieve the desired result, the first electrode was prepared on the first surface and the second electrode on the second surface by drying at 60°C for 8 hours.

[0178] A polymer electrolyte membrane prepared in (1) is interposed between the first electrode and the second electrode, and at 160°C and 20 kgf / cm² 2 A membrane-electrode assembly for a fuel cell, in which the first electrode and the second electrode are bonded to a hydrocarbon-based polymer electrolyte membrane, was manufactured by applying heat and pressure for 3 minutes under certain conditions and then peeling off the Teflon release film.

[0179]

[0180] Example 2

[0181] (1) Preparation of polymer electrolyte membrane

[0182] As a cation conductor containing at least one sulfonic acid group as a side chain, SPAES (Sulfonated Poly(arylene ether sulfone) was prepared, having a degree of sulfonation of 50% and a weight-average molecular weight of 12,500 g / mol as measured by GPC.

[0183] N,N-carbonyldiimidazole was prepared as a substance to activate the above-mentioned cation conductor.

[0184] The above cation conductor was added to DMSO at a concentration of 15 wt% and stirred at 80°C for 6 hours to prepare a cation conductor solution. The above N,N-carbonyldiimidazole was added to the cation conductor solution. At this time, 50 molar parts of the above N,N-carbonyldiimidazole were added based on 100 molar parts of sulfonic acid groups contained in the solid portion of the cation conductor. Subsequently, the mixture was stirred for an additional 3 hours to prepare an activated cation conductor solution containing intramolecular sulfonimidazole groups.

[0185] Meanwhile, sulfamic acid was prepared as an amine compound containing at least one sulfonic acid group as a side chain.

[0186] The sulfamic acid was added to the above-mentioned activated cation conductor solution. At this time, 30 molar parts of the sulfamic acid were added based on 100 molar parts of sulfonic acid groups contained in the solid portion of the activated cation conductor. Subsequently, the mixture was stirred for an additional 3 hours to obtain a polymer electrolyte membrane forming solution containing a complex of the activated cation conductor and an amine compound.

[0187] The above complex may be formed by the side chain (sulfonic acid group, -SO2OH) of the cation conductor being bonded to the amino group (-NH2) of the amine compound to form sulfonamide (Sulfonamide, -SO2-NH-).

[0188] After applying the above polymer electrolyte membrane forming solution onto a glass substrate, it was dried in an 80°C convection oven for 24 hours. Here, a single membrane for a fuel cell with a thickness of 15 μm and a single membrane for water electrolysis with a thickness of 70 μm were prepared, respectively.

[0189] (2) Manufacture of membrane-electrode assembly for water electrolysis

[0190] A membrane-electrode assembly for water electrolysis was manufactured in substantially the same way as Example 1, except that the polymer electrolyte membrane manufactured in (1) above was used.

[0191] (3) Manufacture of membrane-electrode assembly for fuel cell

[0192] A membrane-electrode assembly for a fuel cell was manufactured in substantially the same way as Example 1, except that the polymer electrolyte membrane manufactured in (1) above was used.

[0193]

[0194] Example 3

[0195] A polymer electrolyte membrane, a membrane-electrode assembly for water electrolysis, and a membrane-electrode assembly for a fuel cell were manufactured substantially identically, except that sulfamic acid was changed to 2,2'-benzidine disulfonic acid in Example 1 above.

[0196]

[0197] Example 4

[0198] A polymer electrolyte membrane, a membrane-electrode assembly for water electrolysis, and a membrane-electrode assembly for a fuel cell were manufactured substantially identically, except that sulfamic acid was changed to 2,2'-benzidine disulfonic acid in Example 2 above.

[0199]

[0200] Example 5

[0201] A polymer electrolyte membrane, a membrane-electrode assembly for water electrolysis, and a membrane-electrode assembly for a fuel cell were manufactured substantially identically, except that the SPAES ion conductor was replaced with Nafion powder, a fluorine-based ion conductor, in Example 3 above.

[0202]

[0203] Example 6

[0204] A polymer electrolyte membrane, a membrane-electrode assembly for water electrolysis, and a membrane-electrode assembly for a fuel cell were manufactured substantially identically, except that the SPAES ion conductor was replaced with Nafion powder, a fluorine-based ion conductor, in Example 4 above.

[0205]

[0206] Comparative Example 1

[0207] A polymer electrolyte membrane, a membrane-electrode assembly for water electrolysis, and a membrane-electrode assembly for a fuel cell were prepared in substantially the same manner as in Example 1, except that no amine compound was used.

[0208]

[0209] Comparative Example 2

[0210] A polymer electrolyte membrane, a membrane-electrode assembly for water electrolysis, and a membrane-electrode assembly for a fuel cell were manufactured substantially identically, except that the SPAES ion conductor was replaced with Nafion powder, a fluorine-based ion conductor, in Comparative Example 1 above.

[0211]

[0212] (Reinforcement)

[0213]

[0214] Example 7

[0215] A polymer electrolyte membrane with a reinforced membrane structure was prepared by impregnating a PPS (polyphenylene sulfide) support having an average pore size of 0.2 μm and a porosity of 70% with a composite solution according to Example 3, and then drying the impregnated product at 80°C for 24 hours.

[0216] A membrane-electrode assembly for water electrolysis and a membrane-electrode assembly for fuel cells were manufactured substantially in the same manner as in Example 3, except that a polymer electrolyte membrane with the above-mentioned reinforced membrane structure was used.

[0217]

[0218] Example 8

[0219] A polymer electrolyte membrane with a reinforced membrane structure was prepared by impregnating a PPS (polyphenylene sulfide) support having an average pore size of 0.2 μm and a porosity of 70% with a composite solution according to Example 4, and then drying the impregnated product at 80°C for 24 hours.

[0220] A membrane-electrode assembly for water electrolysis and a membrane-electrode assembly for fuel cells were manufactured substantially in the same manner as in Example 4, except that a polymer electrolyte membrane with the above-mentioned reinforced membrane structure was used.

[0221]

[0222] Example 9

[0223] A polymer electrolyte membrane was prepared by impregnating an e-PTFE (expanded-polytetrafluoroethylene) support having an average pore size of 0.2 μm and a porosity of 75% with a composite solution according to Example 5, and then drying the impregnated PTFE (polytetrafluoroethylene) support at 80°C for 12 hours.

[0224] A membrane-electrode assembly for water electrolysis and a membrane-electrode assembly for fuel cells were manufactured in substantially the same manner as in Example 5, except that a polymer electrolyte membrane with the above-mentioned reinforced membrane structure was used.

[0225]

[0226] Example 10

[0227] A polymer electrolyte membrane was prepared by impregnating an e-PTFE (expanded-polytetrafluoroethylene) support having an average pore size of 0.2 μm and a porosity of 75% with a composite solution according to Example 6, and then drying the impregnated PTFE (polytetrafluoroethylene) support at 80°C for 12 hours.

[0228] A membrane-electrode assembly for water electrolysis and a membrane-electrode assembly for fuel cells were manufactured in substantially the same manner as in Example 6, except that a polymer electrolyte membrane with the above-mentioned reinforced membrane structure was used.

[0229]

[0230] Comparative Example 3

[0231] A polymer electrolyte membrane, a membrane-electrode assembly for water electrolysis, and a membrane-electrode assembly for a fuel cell were prepared in substantially the same manner as in Example 7, except that no amine compound was used.

[0232]

[0233] Comparative Example 4

[0234] A polymer electrolyte membrane, a membrane-electrode assembly for water electrolysis, and a membrane-electrode assembly for a fuel cell were prepared in substantially the same manner as in Example 9, except that no amine compound was used.

[0235]

[0236] Evaluation Example 1: Evaluation of Polymer Electrolyte Membrane

[0237] (1) Water uptake rate (%)

[0238] The polymer electrolyte membranes according to Examples 1 to 10 and Comparative Examples 1 to 4 were dried in a vacuum oven at 80°C for 12 hours, and then their weight was measured (W dry ). Subsequently, the same membrane was immersed in distilled water at room temperature for 24 hours, then removed, the water present on the surface was removed, and the weight was measured again (W wet The water absorption rate was calculated using the following Equation 2.

[0239] [Equation 2]

[0240] Water uptake rate (%) = 100*(W wet - W dry ) / W dry

[0241] (2) Rate of change in area and rate of change in volume (%)

[0242] The method for measuring the dimensional change rate of the polymer electrolyte membrane according to Examples 1 to 10 and Comparative Examples 1 to 4 was performed in the same manner as the method for measuring water absorption rate, but instead of measuring weight, the area and volume changes of the polymer electrolyte membrane were measured, and then each area change rate and volume change rate were calculated using Equations 3 and 4 below.

[0243] [Equation 3]

[0244] Area change rate (%) = 100 * [(Film area (wet)) - (Film area (dry))] / (Film area (dry))

[0245] [Equation 4]

[0246] Volume change rate (%) = 100 * [(Film area * Film thickness (wet)) - (Film area * Film thickness (dry))] / (Film area * Film thickness (dry))

[0247] (3) Cation conductivity measurement

[0248] Cation conductivity (Proton conductivity: σ) of the polymer electrolyte membranes according to Examples 1 to 10 and Comparative Examples 1 to 4 above membrane) was measured by the constant current four-terminal method. Specifically, the resistance (R) was determined by applying a constant alternating current to both sides of a polymer electrolyte membrane while controlling the relative humidity from 50% to 100% at a temperature of 80°C. The alternating potential difference generated within the membrane was measured. membrane ) was obtained, and the conductivity of the polymer electrolyte membrane (σ) was calculated using Equation 5 below. membrane ) was obtained. A Scribner Associates MTS 740 was used as the conductivity measuring device, and in-plane conductivity was measured.

[0249] [Equation 5]

[0250] Ionic conductivity (σ membrane )(mS / cm) = (distance between electrodes (L)) / [(film resistance (R) membrane ))*(film area(A))]

[0251]

[0252] Information on the polymer electrolyte membranes for fuel cells prepared in Examples 1 to 10 and Comparative Examples 1 to 4 is listed in Table 1 below, and the experimental results are shown in Table 2.

[0253]

[0254] Type of ion conductor Type of amine compound Presence of N,N-carbonyl-diimidazole Membrane structure Example 1 SPAES Sulfamic acid X Single membrane Example 2 SPAES Sulfamic acid O Single membrane Example 3 SPAES 2,2'-Benzidine disulfonic acid X Single membrane Example 4 SPAES 2,2'-Benzidine disulfonic acid O Single membrane Example 5 Nafion 2,2'-Benzidine disulfonic acid X Single membrane Example 6 Nafion 2,2'-Benzidine disulfonic acid O Single membrane Example 7 SPAES 2,2'-Benzidine disulfonic acid X Reinforced membrane Example 8 SPAES 2,2'-Benzidine disulfonic acid O Reinforced membrane Example 9 Nafion 2,2'-Benzidine disulfonic acid X Reinforced membrane 10 Nafion 2,2'-Benzidine disulfonic acid O Reinforced Membrane Comparison Example 1 SPAESXX Single Membrane Comparison Example 2 Nafion XX Single Membrane Comparison Example 3 SPAESXX Reinforced Membrane Comparison Example 4 Nafion XX Reinforced Membrane

[0255] Water absorption rate (%) Area change rate (%) Volume change rate (%) Cation conductivity (mS / cm, @80℃) RH 50% RH 100% Example 1 60.3 5.4 69.7 11.7 117.3 Example 2 62.8 5.7 73.6 12.5 121.3 Example 3 56.4 4.8 52.1 14.6 109.2 Example 4 53.2 4.1 50.7 16.3 108.9 Example 5 15.5 6.5 24.3 16.3 106.8 Example 6 14.1 5.3 23.1 18.1 106.7 Example 7 36.6 0.5 17.5 10.2 72.4 Example 8 33.3 0.3 15.4 12.3 72.5 Example 99.10.211.713.673.9 Example 108.50.110.116.273.6 Comparative Example 151.85.265.17.483.4 Comparative Example 212.57.128.712.684.1 Comparative Example 331.11.220.33.545.7 Comparative Example 47.30.412.06.646.2

[0256] Referring to Tables 1 and 2 above, it can be seen that when amine compounds are introduced, weakly acidic sulfonamide groups are formed, increasing acidity and acting as cation conduction channels, thereby improving cation conductivity in both the single membrane and the reinforced membrane. Additionally, it can be confirmed that further improved results are observed when N,N-carbonyldiimidazole is introduced. When 2,2'-benzidine disulfonic acid, which has two amino groups and two sulfonic acid groups each, is introduced as an amine compound, crosslinking is formed. Under low humidity conditions, the polymer spacing between chains expands, allowing for improved cation conductivity. Under high humidity conditions, the polymer spacing is limited, and although the water absorption rate increases slightly, the rate of dimensional change, including the rate of change in area and volume, decreases. Furthermore, when N,N-carbonyldiimidazole is introduced, the number of crosslinking functional groups increases, further reducing the rate of dimensional change while maintaining cation conductivity. As described above, an improvement in cation conductivity can be expected when amine compounds and N,N-carbonyldiimidazole are introduced, and it can be seen that it is particularly effective in improving mechanical stability when amine compounds having two or more amino groups and sulfonic acid groups are introduced.

[0257]

[0258] Evaluation Example 2: Evaluation of Performance and Durability of Membrane-Electrode Assembly

[0259] (Electrolytic cell)

[0260] The membrane-electrode assembly for the water electrolysis cell was evaluated for cell performance and chemical durability as follows.

[0261] Membrane-electrode assemblies for water electrolysis cells prepared in Examples 2, 4, and 6 and Comparative Examples 1 and 2 were applied inside unit cells designed and fabricated for water electrolysis cells, and measurements were taken by applying a protocol to measure voltage and resistance at specific currents from 1 mA to 20 A under conditions of cell temperature 80°C, water temperature 80°C, and flow rate 5 ml / min. The current density was measured at a voltage of 1.8 V, and the higher the result value, the better the output performance.

[0262] Chemical durability was evaluated after the initial performance evaluation of the above membrane-electrode assembly at a cell temperature of 80°C and a current density of 1 A / cm². 2 The voltage growth rate was measured after driving a constant current for 500 hours. The voltage growth rate was measured using a BioLogic instrument and calculated according to Equation 6 below, and the results are shown in Table 3 below. During the evaluation process, the evaluation was terminated if the voltage growth rate was 20% or higher after reaching 100 hours.

[0263] [Equation 6]

[0264] Voltage Increase Rate (%) = 100 * (Voltage after driving - Initial voltage) / (Initial voltage)

[0265] Battery performance evaluation (A / cm) 2 Voltage Increase Rate (%) Example 22.38 81.1 (100 hours) Example 4 2.06 18.1 Example 6 2.02 5.9 Comparative Example 11.76 74.6 (100 hours) Comparative Example 21.75 16.2

[0266] Referring to Table 3 above, the membrane-electrode assemblies of Examples 2, 4, and 6 showed improved performance compared to the membrane-electrode assemblies of Comparative Examples 1 and 2, and it was confirmed that both performance and durability were improved in the case of Examples 4 and 6. This demonstrates that the introduction of the amine compound and N,N-carbonyldiimidazole, previously identified in the polymer electrolyte membrane stage, is effective in improving performance and durability even in the cell stage.

[0267] (Fuel cell)

[0268] The membrane-electrode assembly for fuel cells was evaluated for cell performance and chemical durability as follows.

[0269] Active area of ​​25 cm² prepared in Examples 2, 4, 6, 8, and 10; and Comparative Examples 1 and 2 2 of The output performance of the membrane-electrode assembly for the fuel cell was evaluated through IV measurement. Specifically, to verify the output performance under actual fuel cell operating conditions, the membrane-electrode assembly was tested using a fuel cell unit cell evaluation device (Scribner 850 fuel cell test system).

[0270] Under conditions of 65℃, hydrogen (100%RH) and air (100%RH) were supplied to the first electrode and the second electrode, respectively, in amounts corresponding to Stoichiometry 1.5 / 2.0. The current density was measured at a voltage of 0.6V, and the higher the result value, the better the output performance.

[0271] Chemical durability was evaluated by performing the OCV hold method for 500 hours under conditions of 90°C, RH 30%, and 50kPa after the initial performance evaluation of the membrane-electrode assembly for the fuel cell, and then measuring the voltage loss for each. The measured values ​​are shown in Table 4 below. During the evaluation process, if the OCV loss was 20% or more, the evaluation was terminated.

[0272] Battery performance evaluation (A / cm) 2 )OCV Voltage Loss (%) Example 21.5 120 (325 hours) Example 4 1.3 320 (480 hours) Example 6 1.3 5 17.5 Example 8 1.3 10.3 Example 10 1.3 36.2 Comparative Example 11.1 220 (110 hours) Comparative Example 21.1 820 (240 hours)

[0273] Referring to Table 4 above, the membrane-electrode assemblies of Examples 2, 4, 6, 8, and 10 showed improved performance compared to the membrane-electrode assemblies of Comparative Examples 1 and 2. It was confirmed that in the case of Examples 4, 6, 8, and 10, where 2,2'-benzidine disulfonic acid was applied instead of sulfamic acid as the amine compound, both performance and durability were improved. This indicates that the introduction of amine compounds and N,N-carbonyldiimidazole, which were confirmed in the previous polymer electrolyte membrane and water electrolysis cell evaluation steps, is effective in improving performance and durability even when applied to fuel cells. Additionally, improved durability can be expected when a reinforced composite membrane including a porous support is introduced.

[0274] Although preferred embodiments have been described in detail above, the scope of the rights is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concepts defined in the following claims are also included within the scope of the rights.

Claims

1. Includes the reaction product of a cation conductor and an amine compound as an electrolyte, and The above cation conductor comprises at least one sulfonic acid group as a side chain, and The above amine compound comprises at least one sulfonic acid group as a side chain; and at least one amino group as a side chain, a terminal, or a combination thereof. Polymer electrolyte membrane.

2. In Paragraph 1, The above cation conductor Includes hydrocarbon-based ion conductors, fluorine-based ion conductors, or combinations thereof, comprising at least one sulfonic acid group as a side chain, Polymer electrolyte membrane.

3. In Paragraph 2, The above fluorine-based ion conductor (i) a fluorine-based polymer comprising fluorine in the main chain and at least one sulfonic acid group as a side chain; (ii) comprising repeating units of a polystyrene-based polymer, having a main chain of a partially fluorinated polymer, and comprising at least one sulfonic acid group as a side chain; or The combination of these, Polymer electrolyte membrane.

4. In Paragraph 2, The above hydrocarbon-based ion conductor It comprises a hydrocarbon main chain that is imidazole, benzimidazole, polyamide, polyamideimide, polyimide, polyacetal, polyethylene, polypropylene, acrylic resin, polyester, polysulfone, polyether, polyester, polyethersulfone, polyetherimide, polycarbonate, polystyrene, polyphenylene sulfide, polyetheretherketone, polyetherketone, polyarylethersulfone, polyphosphazene, polyphenylquinoxaline, or a combination thereof, The having at least one sulfonic acid group as a side chain, Polymer electrolyte membrane.

5. In Paragraph 1, The above amine compound comprises one amino group, and sulfamic acid, taurine, sulfanilic acid, 4-amino-1,3-benzenedisulfonic acid, or a combination thereof; The above amine compound comprises two or more amino groups, and 4,4'-diaminostilbene-2,2'-disulfonic acid, 2,2'-benzidinedisulfonic acid, 4,6-diaminobenzene-1,3-disulfonic acid, 9,9-bis(4-aminophenyl)fluorene-2,7-disulfonic acid, or a combination thereof, comprising Polymer electrolyte membrane.

6. In Paragraph 1, The above polymer electrolyte membrane is a single membrane, and The above single membrane is Comprising the reaction product of the above-mentioned cation conductor and amine compound, Polymer electrolyte membrane.

7. In Paragraph 1, The above polymer electrolyte membrane is a reinforced membrane, and The above reinforcing film is porous support and It includes a coating layer located on one or both sides of the above-mentioned porous support, and The above coating layer Comprising the reaction product of the above-mentioned cation conductor and amine compound, Polymer electrolyte membrane.

8. In Paragraph 7, The above porous support is a fluorine-based support or a nanoweb support, Polymer electrolyte membrane.

9. A step of preparing a polymer electrolyte membrane forming solution by adding an amine compound to a cation conductor solution and reacting it; and The method includes the step of forming a polymer electrolyte membrane-forming solution, and The above cation conductor comprises at least one sulfonic acid group as a side chain, and The above amine compound comprises at least one sulfonic acid group as a side chain; and at least one amino group as a side chain, a terminal, or a combination thereof. Method for manufacturing a polymer electrolyte membrane.

10. In Paragraph 9, Before adding the above amine compound to the above cation conductor solution, A method further comprising the step of adding N,N-carbonyldiimidazole to the above-mentioned cation conductor solution, Method for manufacturing a polymer electrolyte membrane.

11. In Paragraph 10, The step of forming the above polymer electrolyte membrane-forming solution is as follows: A step of applying the above polymer electrolyte membrane forming solution onto a substrate or a porous support; and A step comprising drying the above-mentioned applied polymer electrolyte membrane forming solution, Method for manufacturing a polymer electrolyte membrane.

12. Hydrogen generating electrode; Oxygen generating electrode; and A polymer electrolyte membrane according to claim 1, positioned between the hydrogen generation electrode and the hydrogen generation electrode. Membrane-electrode assembly for water electrolysis cell.

13. A water electrolysis cell comprising a membrane-electrode assembly for a water electrolysis cell according to paragraph 12.

14. Anode electrode; cathode electrode; and A polymer electrolyte membrane according to claim 1, positioned between the anode electrode and the cathode electrode. Membrane-electrode assembly for a fuel cell.

15. A fuel cell comprising a membrane-electrode assembly for a fuel cell according to paragraph 14.

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