Polymer and electrolyte membrane using the same

Abstract

To provide a polymer excellent in film-forming property and alkali durability, and an electrolyte membrane using the same.SOLUTION: A polymer comprising recurring units having the formula (1): (In Formula (1), Ar represents an aromatic group, R1 and R2 each independently represent a linear, branched, or cyclic alkyl group of C1 to C12 substituted with an ion exchange group or a halogeno group, R3 and R4 each independently represent a linear, branched, or cyclic alkyl group of C1 to C6, and X represents a counter anion.). ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymer having excellent membrane-forming properties and alkaline durability, and an electrolyte membrane using the same. More specifically, the present invention provides a polymer and an electrolyte membrane that are particularly excellent for anion-exchange membrane water electrolysis. [Background technology]

[0002] Electrolyte membranes are used in various fuel cells, such as polymer electrolyte fuel cells and solid alkaline fuel cells, as well as in various electrolysis technologies, such as water electrolysis. These electrolyte membranes are required to have excellent ionic conductivity and durability sufficient for long-term use.

[0003] Among water electrolysis methods, anion exchange membrane water electrolysis (AEMWE) has been proposed as an alternative technology to cation exchange membrane water electrolysis and alkaline water electrolysis, and has attracted attention in recent years. This method uses an anion exchange membrane (AEM) to separate the anode and cathode chambers, and pure water or an alkaline aqueous solution is supplied to the anode chamber as the anolyte. Pure water or an alkaline aqueous solution may be supplied to the cathode chamber as the anolyte, but it is also possible to use a dry cathode electrolytic cell in which no anolyte is supplied to the cathode chamber. In this dry cathode electrolytic cell, water permeates from the anode chamber to the cathode chamber through the anion exchange membrane, supplying water to the cathode chamber. Hydrogen gas and hydroxide ions are generated from the water in the cathode chamber through a cathode reaction.

[0004] Patent Document 1 discloses a proton-conducting material for electrolyte membranes for AEMWE that has high swelling resistance and high proton conductivity due to the high density of ion-exchange groups. The proton-conducting material has a specific hydrophilic portion and a specific hydrophobic portion, and at least one of the hydrophilic portion and the hydrophobic portion has a repeating unit containing a specific cyclic compound. The proton-conducting material has a structure in which the hydrophilic portion and the hydrophobic portion are bonded via an ether bond.

[0005] Patent Document 2 discloses a polymer having a structure in which divalent aromatic groups having ionic functional groups and spirobifluorene skeletons are alternately repeated as an anion-conducting polymer for electrolyte membranes that has excellent chemical durability and solubility in solvents.

[0006] Patent Document 3 reports an anion-conducting polymer for electrolyte membranes that has excellent chemical durability and ionic conductivity, and an electrolyte membrane using the same. However, there is a demand for polymers that have even greater chemical durability and membrane strength, as well as excellent membrane-forming properties. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-442424 [Patent Document 2] Japanese Patent Application Publication No. 2018-135487 [Patent Document 3] Patent Publication No. 2021-42351 Summary of the Invention [Problem to be solved by the invention]

[0008] In view of the above circumstances, the present invention proposes an electrolyte membrane, particularly a polymer useful for anion exchange membrane water electrolysis, and an electrolyte membrane using the polymer. Specifically, the present invention aims to provide a polymer for an electrolyte membrane that has excellent alkali durability, membrane strength, and membrane formability. [Means for solving the problem]

[0009] As a result of extensive research, the present inventors have found that a polymer having a specific structure can solve the above problems. That is, the present invention relates to the following 1) to 11). 1) A polymer having a repeating unit represented by the following formula (1): [C1] TIFF2026011586000001.tif51170 (In formula (1), Ar is an aromatic group, and R 1 and R 2 each independently represents a C1-C12 linear, branched, or cyclic alkyl group substituted with an ion exchange group or a halogeno group; R 3 and R 4 each independently represents a C1-C6 linear, branched, or cyclic alkyl group, and X represents a counter anion. 2) The polymer according to the above 1), wherein in the formula (1), Ar is one or more selected from the following formulae (a-1) to (a-5): [chemical a] TIFF2026011586000002.tif431703) In the formula (1), R 1 , and R 2 The polymer according to 1) or 2) above, wherein is a C1-C12 alkyl group substituted with a quaternary ammonium group or a bromo group. 4) The polymer according to any one of the above 1) to 3), further having a structure represented by the following formula (2) in the molecule: [C2] TIFF2026011586000003.tif40170 (In formula (2), * indicates the bonding position with other components.) 5) The polymer according to any one of 1) to 4) above, which has a weight average molecular weight of 100,000 or more. 6) An electrolyte membrane comprising the polymer according to any one of 1) to 5) above. 7) A catalyst-coated electrolyte membrane obtained by coating the electrolyte membrane according to 6) above with a catalyst. 8) An electrolyte membrane for water electrolysis using the electrolyte membrane described in 6) above. 9) An anion-exchange electrolyte membrane for water electrolysis, which uses the electrolyte membrane described in 6) above. 10) A water electrolysis device using the electrolyte membrane described in 6) above. 11) A method for producing hydrogen using the electrolyte membrane described in 6) above. [Effects of the Invention]

[0010] According to the present invention, it is possible to realize an electrolyte membrane that has excellent solubility, that is, good membrane-forming properties, and also has excellent alkali durability and membrane strength. DETAILED DESCRIPTION OF THE INVENTION

[0011] The polymer used in the electrolyte membrane of the present invention is characterized by satisfying the above formula (1). In formula (1), Ar is an aromatic group, and R 1 and R 2 each independently represents a C1-C12 linear, branched, or cyclic alkyl group substituted with an ion exchange group or a halogeno group; R 3 and R 4 each independently represents a C1-C6 linear, branched or cyclic alkyl group, and X represents a counter anion.

[0012] [About Ar] In formula (1), the aromatic group represented by Ar is not particularly limited as long as it has a structure having an aromatic ring, but is preferably any one of the structures (a-1) to (a-5) above. Regarding (a-1) to (a-5), R 1 , R 2 Examples of the substituent include a halogeno group, a C1-C12 alkyl group, a C1-C12 alkoxy group, a hydroxy group, and a carboxy group, and preferably a fluoro group, a bromo group, or a C1-C6 alkyl group.

[0013] [R 1 , R 2 About R 1 , and R 2 each independently represents a C1-C12 alkyl group substituted with an ion exchange group or a halogeno group. The ion-exchange group is a functional group that is dissociable and capable of ion exchange, contributes to the ion conduction of the present polymer, and can be appropriately selected depending on the application. When the polymer is to be imparted with proton conductivity, the ion exchange group is preferably an acidic group, more preferably a sulfonic acid group (-SO3H group), a phosphoric acid group (-H2PO4 group), or a carboxylic acid group (-COOH group), with a sulfonic acid group being even more preferred. When the polymer is to be imparted with anion conductivity, the ion exchange group is preferably a quaternary ammonium group or an imidazolium group, with a quaternary ammonium group being more preferred. From the viewpoint of alkaline durability, the quaternary ammonium group is preferably a quaternary alkylammonium group. The alkyl group bonded to the nitrogen atom of the quaternary alkylammonium group is a C1-C6 linear, branched, or cyclic alkyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or a cyclohexyl group. Of these, a methyl group, an ethyl group, or a propyl group is preferred. Incidentally, alkyl groups bonded to the nitrogen atom may also be bonded to each other to form a ring structure, such as an azaadamantyl group or a quinuclidinium group. The counter anion is not limited to a monovalent one, but may be a divalent or higher one. The counter anion is preferably an inorganic anion, specifically, a chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ), bicarbonate ion (HCO3 - ), carbonate ions (CO3 2- ), hydroxide ion (OH - ) etc. The halogeno group refers to a fluoro group (-F), a chloro group (-Cl), a bromo group (-Br), or an iodo group (-I), of which a chloro group or a bromo group is preferred, and a bromo group is particularly preferred. R 1 or R 2The C1-C12 alkyl group as the alkyl group may be a straight-chain, branched-chain, or cyclic alkyl group. Among these, straight-chain or branched-chain groups are preferred, with straight-chain being more preferred. The number of carbon atoms is C1-C12, preferably C2-C10, and more preferably C3-C9. Specific examples include straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl; branched-chain alkyl groups such as isopropyl, isobutyl, sec-butyl, t-butyl, isopentyl, isohexyl, and isooctyl; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Of these, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl are preferred, with n-hexyl, n-octyl, and n-decyl being particularly preferred.

[0014] [R 3 , R 4 , Regarding X] The polymer of the present invention has a piperidinium skeleton. The nitrogen of the piperidinium skeleton is R 3 , R 4 where R 3 , R 4 are each independently a C1-C6 linear, branched or cyclic alkyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or a cyclohexyl group. Of these, a methyl group, an ethyl group, or a propyl group is preferred. Incidentally, alkyl groups bonded to nitrogen atoms may also be bonded to each other to form a ring structure, such as an azaadamantyl group or a quinuclidinium group. Furthermore, the counter anion X is not limited to a monovalent anion, but may be a divalent or higher anion. The counter anion X is preferably an inorganic anion, specifically a chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ), bicarbonate ion (HCO3 - ), carbonate ions (CO32- ), hydroxide ion (OH - ) etc.

[0015] [Regarding the structure of formula (2)] In a more preferred embodiment, the polymer of the present invention has the structure of the above formula (2) (tetrafluorophenylene group) in the skeleton. The amount of the tetrafluorophenylene group may be about equimolar to 1 / 5 mol with respect to the content of the structure of formula (1).

[0016] Preferred examples of the polymer of the present invention are shown in the following Tables 1 to 4. However, the present invention is not limited to these.

[0017] [Table 1] [Table 2] [Table 3] [Table 4]

[0018] The polymer of the present invention preferably has a weight average molecular weight of 100,000 or more. The weight average molecular weight can be measured by GPC (gel permeation chromatography) under the following conditions. Equipment: EcoSEC-Elite (manufactured by Tosoh Corporation) Column: 3 TSKgel SuperMultiporeHZ-M (Tosoh Corporation) Measurement temperature: 40℃ Sample solution: 0.12 wt% THF solution Mobile phase: THF Solution injection volume: 10μL Flow rate: 0.4mL / min Detector: Refractive index detector Reference material: Standard polystyrene (TSKgel standard polystyrene) (8 types manufactured by Tosoh Corporation (weight average molecular weight: 1,110,000, 397,000, 189,000, 37,200, 15,700, 5,430, 3,120, 589))

[0019] The lower limit of the weight average molecular weight of the polymer of the present invention is 100,000, more preferably 180,000, 190,000, 200,000, 220,000, and particularly preferably 240,000. The upper limit of the weight average molecular weight of the polymer is 400,000, more preferably 380,000, 360,000, 350,000, 340,000, 320,000, 300,000, and particularly preferably 280,000. Therefore, the most preferred weight average molecular weight of the polymer is 240,000 or more and 280,000.

[0020] [Pore-filling membrane] The electrolyte membrane of the present invention preferably has a pore-filling membrane structure in which a porous substrate is used as the substrate film and the polymer is filled in. Such a structure can impart mechanical strength to the polyarylene polymer, which has excellent chemical durability. The porous substrate is a substrate having pores capable of holding a polymer, and it is preferable that at least some of the pores of the porous substrate form through-holes in order to improve ion conductivity. The substrate is preferably in the form of a nonwoven fabric or a porous film, more preferably in the form of a porous film, in order to provide mechanical strength. The porosity of the porous substrate (=void volume / bulk volume×100(%)) is preferably 30 to 95%, more preferably 40 to 80%, and even more preferably 45 to 70%, in order to achieve both mechanical strength and ion conductivity. The film thickness of the porous substrate is preferably 5 to 200 μm, more preferably 7 to 100 μm, and even more preferably 10 to 50 μm, in order to achieve both mechanical strength and ion conductivity. The pore size of the porous substrate is preferably 10 to 10,000 nm, more preferably 10 to 1,000 nm, in terms of filling and holding the polyarylene polymer and mechanical strength. The material of the porous substrate is preferably a polyolefin-based porous substrate in terms of chemical durability, particularly stability in alkali. The use of a polyolefin-based porous substrate also has the advantage of being easily filled with polyarylene polymers, particularly high-molecular-weight polyarylene polymers with a weight-average molecular weight of 100,000 or more. Among the polyolefin-based porous substrates, polyethylene porous substrates, polypropylene porous substrates, and polytetrafluoroethylene porous substrates are preferred in terms of mechanical strength and chemical resistance. Among the polyethylene porous substrates, ultra-high molecular weight polyethylene (e.g., with a weight-average molecular weight of 1,000,000 or more) porous substrates are particularly preferred.

[0021] An example of a method for producing a pore-filling film is a method in which a polyarylene polymer is applied to a porous substrate and then dried. Examples of methods for applying a polyarylene polymer to a porous substrate include preparing a solution of the polyarylene polymer and then using a dipping method, a spray method, a spin coating method, a barcode method, and the like. A pore-filling film can be obtained by permeating the polyarylene polymer solution into the porous substrate and then drying it. It should be noted that the filling of the porous substrate with the polyarylene polymer can be confirmed, for example, by Raman analysis.

[0022] [Method for producing the polymer of the present invention] The polymer of the present invention can be produced, for example, by carrying out the following processes [1] to [5] in sequence. [1] Alkylation reaction A compound represented by the following formula (11) is obtained by reacting an aromatic compound with an alkyl dihalide (Br is exemplified in the following formula) in the presence of a base. R bonded to Ar is the same as R in the above formula (1). 1 or R 2 After bonding to Ar, the terminal becomes halogen. [C3] TIFF2026011586000008.tif27170[2] Amination reaction Compound 11 is reacted with dialkylamine to convert the terminal halogen in compound 11 into a dialkylamino group (hereinafter, this compound is referred to as compound 12). [3] Condensation reaction Compound 12 is reacted with 1-alkylpiperidin-4-one under acidic conditions to obtain compound 13. Note that R bonded to N on piperidine is the same as R in the above formula (1). 3 or R 4 Represents. [C4] TIFF2026011586000009.tif62170[4] Quaternary amination reaction Compound 13 is treated with an alkyl halide to obtain compound 14. Note that R bonded to N on piperidine is the same as R in the above formula (1). 3 or R 4 Represents. [5] TIFF2026011586000010.tif62170

[0023] [Applications of electrolyte membranes] <Catalyst coated electrolyte membrane> The electrolyte membrane of the present invention can be used as a catalyst-coated electrolyte membrane in which one or both sides are coated with a catalyst. For example, an electrolyte membrane used for water electrolysis has an anode catalyst disposed on one side as an anode and a cathode catalyst disposed on the other side as a cathode. The anode catalyst is preferably a metal or a metal alloy, which can be appropriately selected from known metals and metal alloys, such as platinum, cobalt, nickel, palladium, iron, silver, gold, copper, iridium, molybdenum, rhodium, chromium, tungsten, manganese, ruthenium, compounds of these metals, metal oxides, and alloys containing two or more of these metals. The cathode catalyst is preferably a metal or a metal alloy, which can be appropriately selected from known metals and metal alloys, such as platinum, cobalt, nickel, palladium, iron, silver, gold, copper, iridium, molybdenum, rhodium, chromium, tungsten, manganese, ruthenium, metal compounds thereof, metal oxides, and alloys containing two or more of these metals. Examples of methods for forming the catalyst layer include pulse spray coating, ultrasonic spray coating, die coater coating, bar coater coating, electrode transfer coating, etc. Depending on the coating method, a drying step may be included.

[0024] <Water electrolyte membrane, anion exchange type water electrolysis electrolyte membrane and water electrolysis device> The catalyst-coated electrolyte membrane of the present invention has water electrolysis performance, particularly anion-exchange water electrolysis performance. Anion-exchange membrane water electrolysis performance refers to the ability to electrolyze water without a significant voltage increase when an alkaline solution is passed through an electrochemical cell that includes a catalyst layer formed on the cathode side of an electrolyte membrane with anion exchange groups, in which a metal powder with hydrogen generating ability is dispersed in an ionomer, and a catalyst layer formed on the other anode side, in which a metal powder with oxygen generating ability is dispersed in an ionomer. When an alkaline solution is passed through the electrochemical cell, the electrolyte membrane is ion-exchanged to OH ions by the alkaline solution, and a current is passed from a power source through the electrochemical cell that includes the ionomer. Specifically, platinum-supported carbon or platinum-ruthenium alloy-supported carbon is typically used as the hydrogen generating catalyst, while iridium oxide is typically used as the oxygen generating catalyst. When 1 mol / L potassium hydroxide is used as the alkaline solution and the electrochemical cell is at 80°C, the electrolysis performance is 1 A / cm. 2 At this time, it is sufficient if the voltage is 2.0V or less, preferably 1.7V to 1.8V, and particularly preferably 1.78V or less. The ion exchange capacity represents the amount of ions that can be adsorbed by an ion exchange resin. A higher value indicates higher ionic conductivity, but the water content also increases, causing the electrolyte membrane to swell and reducing the gas barrier properties. Therefore, the ion exchange capacity is preferably 1.0 mmol / g to 2.0 mmol / g, particularly preferably 1.2 mmol / g to 1.9 mmol / g, and most preferably 1.3 to 1.7 mmol / g. A water electrolysis device equipped with the above-described anion exchange type electrolyte membrane for water electrolysis has particularly high alkali resistance and can therefore be used as an excellent hydrogen generation device. [Example]

[0025] The present invention will be described in more detail below with reference to examples. Note that the present invention is not limited to these examples and may be modified as appropriate without departing from the spirit of the invention.

[0026] [Example 1] <Synthesis of compound (101) (9,9-bis(6-bromohexyl)-9H-fluorene)> [C101] TIFF2026011586000011.tif31170 compound 101 A 500 mL four-neck flask was charged with 50% aqueous sodium hydroxide solution (150.0 mL), 9H-fluorene (40.0 g), 1,6-dibromohexane (235.0 g), and tetrabutylammonium bromide (7.8 g) and reacted for 90 minutes. The resulting reaction solution was cooled to room temperature, and the organic layer was extracted with toluene. The resulting organic layer was washed with 1 M hydrochloric acid, and the toluene was removed using an evaporator. Dibromohexane was then removed by vacuum distillation. The resulting residue was subjected to silica gel column chromatography to obtain 14.8 g of compound 101.

[0027] <Synthesis of compound (102) (6,6'-(9H-fluorene-9,9-diyl)bis(N,N-dimethylhexane-1-amine)> [C102] TIFF2026011586000012.tif35170 compound 2 9,9-bis(6-bromohexyl)-9H-fluorene (12.7 g) was placed in a 300 mL recovery flask and dissolved in THF (100.0 mL). Dimethylamine (54.3 g) was added and the mixture was stirred at room temperature for 24 hours. The THF in the reaction mixture was removed using an evaporator, and the mixture was then separated into toluene and 0.1 M NaOH aqueous solution. The resulting organic layer was removed using an evaporator, yielding 12.1 g of compound 102.

[0028] <Synthesis of compound (103) (6,6'-(2-(1,4-dimethylpiperidin-4-yl)-7-methyl-9H-fluorene-9,9-diyl)bis(N,N-dimethylhexan-1-amine))> [C103] TIFF2026011586000013.tif35170 compound 3 In a 100 mL separable flask, 6,6'-(9H-fluorene-9,9-diyl)bis(N,N-dimethylhexane-1-amine) (4.2 g) and 1-methylpiperidin-4-one (1.1 g) were dissolved in dichloromethane (10.0 mL). A mixture of trifluoromethanesulfonic acid (39.0 g) and trifluoroacetic acid (3.0 g) was slowly added dropwise at 0 °C. The mixture was then stirred at 0 °C for 24 hours. Dimethyl sulfoxide (30.0 mL) was then added at 0 °C, followed by the slow addition of 1 M aqueous sodium hydroxide solution. The resulting solid was washed with distilled water to obtain 0.82 g of compound 103.

[0029] <Synthesis of compound (104) (1,1,4-trimethyl-4-(7-methyl-9,9-bis(6-(trimethylammonio)hexyl)-9H-fluoren-2-yl)piperidin-1-iumiodide)> [C104] TIFF2026011586000014.tif351706,6'-(2-(1,4-dimethylpiperidin-4-yl)-7-methyl-9H-fluorene-9,9-diyl)bis(N,N-dimethylhexan-1-amine) (0.55 g), potassium carbonate (0.035 g), methyl iodide (0.46 g), and dimethyl sulfoxide (10.0 mL) were added to a 100 mL recovery flask and stirred at room temperature for 24 hours. The resulting solution was reprecipitated with isopropanol to obtain 0.63 g of compound 104.

[0030] <Evaluation: Measurement of ion exchange capacity> 4, 50 mg of electrolyte was weighed into a 100 mL beaker, 80 mL of Millipore water was added, and the mixture was stirred for a while. Potentiometric titration was then performed with a 0.02 mol / L silver nitrate solution. The ion exchange capacity was calculated from the titration volume up to the inflection point and the weight of the electrolyte membrane. The titration was performed using a Hiranuma COM-A19. The calculation method is shown in Calculation Method 1, and the results are shown in Table 5.

[0031] (Calculation method 1) Exchange capacity (mmol / g) = (EP1-BL1)×TF×C1×K1 / S EP1: Titration volume required to reach the first endpoint (mL) BL1: Titration volume required for blank test (mL) TF: titrant factor (1.0003) C1: Concentration conversion factor (0.0001 mol / mL) K1: Unit conversion factor (1000) S...Amount of sample collected (g) [Table 5]

[0032] [Comparative Example 1] The ion exchange capacity of PiperION-A20-HCO3 (manufactured by Versogen) was calculated by the following method. <Ion exchange capacity test> Using 400 mg of electrolyte membrane, 450 mg was immersed in a 1 mol / L aqueous solution of sodium nitrate and left at 25°C for 24 hours. After sufficient ion exchange of chloride ions and nitrate ions in the electrolyte membrane had occurred, potentiometric titration was performed with a 0.02 mol / L aqueous solution of silver nitrate. The ion exchange capacity was calculated from the titration volume up to the inflection point and the weight of the electrolyte membrane. For the purpose of anion exchange, the sample was immersed in a sodium chloride solution for 48 hours, and then subjected to potentiometric titration using the method described above. The titration was performed using a Hiranuma COM-A19. The calculation method is as shown in the above calculation method 1. The results are shown in Table 6. [Table 6] [Industrial Applicability]

[0033] The polymer of the present invention has excellent solubility, that is, good membrane-forming properties, and can realize an electrolyte membrane having excellent alkali durability. This electrolyte membrane is useful for water electrolysis, particularly anion exchange membrane water electrolysis, and is capable of efficiently generating hydrogen.

Claims

1. A polymer having a repeating unit represented by the following formula (1): [Chemical formula 1] (In formula (1), Ar is an aromatic group, and R １ and R ２ each independently represents a C1-C12 linear, branched or cyclic alkyl group substituted with an ion exchange group or a halogeno group; R ３ and R ４ each independently represents a C1-C6 linear, branched, or cyclic alkyl group, and X represents a counter anion.

2. 2. The polymer according to claim 1, wherein, in the formula (1), Ar is one or more selected from the following formulae (a-1) to (a-5): [chemical a]

3. In the formula (1), R １ , and R ２ 2. The polymer of claim 1, wherein is a C1-C12 alkyl group substituted with a quaternary ammonium group or a bromo group.

4. The polymer according to claim 1 , further comprising a structure represented by the following formula (2) in the molecule: [Case 2] (In formula (2), * indicates the bonding position with other components.)

5. The polymer according to claim 1 , which has a weight-average molecular weight of 100,000 or more.

6. An electrolyte membrane comprising the polymer of claim 1 .

7. A catalyst-coated electrolyte membrane obtained by coating the electrolyte membrane according to claim 6 with a catalyst.

8. An electrolyte membrane for water electrolysis, comprising the electrolyte membrane according to claim 6.

9. An anion exchange electrolyte membrane for water electrolysis, comprising the electrolyte membrane according to claim 6.

10. A water electrolysis device using the electrolyte membrane according to claim 6.

11. A method for producing hydrogen using the electrolyte membrane according to claim 6.

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