CN117822042A - High-peel-strength electrolytic water film electrode and preparation method thereof - Google Patents
High-peel-strength electrolytic water film electrode and preparation method thereof Download PDFInfo
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- CN117822042A CN117822042A CN202311644531.XA CN202311644531A CN117822042A CN 117822042 A CN117822042 A CN 117822042A CN 202311644531 A CN202311644531 A CN 202311644531A CN 117822042 A CN117822042 A CN 117822042A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 72
- 239000012528 membrane Substances 0.000 claims abstract description 72
- 229920000642 polymer Polymers 0.000 claims abstract description 59
- 239000003446 ligand Substances 0.000 claims abstract description 52
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 42
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 42
- 239000000654 additive Substances 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 21
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 18
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 17
- 150000003254 radicals Chemical class 0.000 claims abstract description 13
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 7
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 37
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000010023 transfer printing Methods 0.000 claims description 13
- 238000005342 ion exchange Methods 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000007731 hot pressing Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical class FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229920005597 polymer membrane Polymers 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910000667 (NH4)2Ce(NO3)6 Inorganic materials 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 229920000554 ionomer Polymers 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- -1 hydrogen ions Chemical class 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- XLXCHZCQTCBUOX-UHFFFAOYSA-N 1-prop-2-enylimidazole Chemical compound C=CCN1C=CN=C1 XLXCHZCQTCBUOX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the technical field of membrane electrode materials, and particularly relates to an electrolytic water membrane electrode with high peel strength and a preparation method thereof. The cathode catalyst and the anode catalyst of the membrane electrode both contain free perfluorinated sulfonic acid ion exchange resin A and an additive with free radical resistance function; the additive is a metal complex formed by a polymer ligand B and a metal M; the polymer ligand B is branched polyethyleneimine polymer containing imidazole structure. The membrane electrode not only has higher free radical oxidation tolerance, but also can improve the adhesive force between the catalytic layer and the ion membrane and prolong the service life of the membrane electrode.
Description
Technical Field
The invention belongs to the technical field of membrane electrode materials, and particularly relates to an electrolytic water membrane electrode with high peel strength and a preparation method thereof.
Background
Along with the consumption of fossil energy and the continuous deterioration of ecological environment, the development and utilization of renewable clean energy to solve the current energy crisis becomes urgent. However, renewable energy sources have low utilization and occupation due to their own non-uniformity and intermittent nature. Because hydrogen has the advantages of cleanness, zero carbon emission, high energy density and the like, the renewable energy source is converted and stored into hydrogen energy to become a solution, the water electrolysis hydrogen production technology is mature, and particularly, the water electrolysis hydrogen production system based on the Proton Exchange Membrane (PEM) has the characteristics of high response speed and adaptation to dynamic operation, is suitable for the renewable energy source to absorb hydrogen, and is applied to industrial production as an energy carrier.
The Membrane Electrode (MEA) is a core composition in a water electrolysis cell hydrogen production system based on a Proton Exchange Membrane (PEM), and consists of three parts, namely the Proton Exchange Membrane (PEM), a Catalytic Layer (CL) and a Gas Diffusion Layer (GDL), from inside to outside.
The catalytic layer formed by the catalyst is the actual place where the reaction takes place in the membrane electrode of the PEM water electrolyzer, precisely where the electrochemical reaction takes place on the catalyst surface. PEM water baths operate with three components, namely water, electrons and protons, which participate in the electrochemical reaction, so that the reaction can only occur at locations on the catalyst surface where all three components can reach. The catalyst layer is prepared by mixing catalyst and ionomer by a certain method and transferring to PEM. Wherein the ionomer serves to transfer hydrogen ions H + The pores between the catalyst and ionomer provide channels for diffusion of gases and drainage of product water.
However, the membrane electrode currently has the following problems: (1) Reactive radicals generated by the electrochemical process can react with the functional groups of the ionomer in the catalytic layer, resulting in the ionomer degrading or failing; (2) The adhesion between the catalytic layer and the substrate in the existing membrane electrode is poor, the catalytic layer can be peeled off in the long-term use process, and the current method for improving the adhesion of the catalytic layer is to improve the content of a binder (taking PVDF as an example) in the electrode, but the method is at the cost of sacrificing the conductivity of the electrode, and as a result, the multiplying power performance of the battery is damaged, and the polarization internal resistance of the battery is increased.
CN109440124a provides a method for preparing membrane electrode for water electrolysis, which comprises coating adhesive on both sides of proton exchange membrane, setting adhesive to make the adhesion between catalyst and proton exchange membrane more stable, reducing possibility of stripping catalyst in actual use, thereby improving service performance and service life of membrane electrode. However, the preparation process of the method is complicated, and the polarization internal resistance of the battery is increased in an intangible way due to the two layers of adhesive.
Disclosure of Invention
The invention aims to provide an electrolytic water film electrode with high peeling strength, which not only has higher free radical oxidation tolerance, but also can improve the adhesive force between a catalytic layer and an ion film and prolong the service life of the film electrode.
In order to achieve the above purpose, the following technical scheme is adopted:
the electrolytic water film electrode with high peeling strength has cathode catalyst and anode catalyst containing free perfluorinated sulfonic acid ion exchange resin A and additive with free radical resisting function.
The additive is a metal complex formed by a polymer ligand B and a metal M.
The polymer ligand B is branched polyethyleneimine polymer containing imidazole structure.
The structural formulas of the perfluorosulfonic acid ion exchange resin A and the polymer ligand B are shown as the formula (I):
in the structure of the formula (I) A, x is 1-20, y is 1-20, z is 500-10000, m is an integer of 0-5, and n is an integer of 1-6.
In the structure of the formula (I) B, xx is 30-1000;
R 1 is-H, -NH 2 、-CH 2 NH 2 -Ph (Ph represents a benzene ring), -PhNH 2 、-PhCOOH、-Cl、-O-CH 3 or-CH 3 Any one of them;
R 2 is-H, -NH 2 、-PhNH 2 -Cl, -PhCOOH or-CH 3 Any one of them;
R 3 is-H, -NH 2 、-PhNH 2 -PhCOOH, -Br, -Ph or-CH 3 Any one of them.
The metal M in the additive is selected from CeO 2 、CePO 4 、Ce(NO 3 ) 3 ·6H 2 O、Ce(SO 4 ) 2 、Ce(OH) 4 、(NH 4 ) 2 Ce(NO 3 ) 6 、Ce 2 (CO 3 ) 3 ·xH 2 O or Ce (CH) 3 COO) 3 ·xH 2 One or more of O; wherein x is 1 to 20.
In the present invention, in the structure of the formula (I) a, m is an integer of 0 to 3, and n is an integer of 1 to 3.
In the structure of the formula (I) B, R in an imidazole structural unit 1 is-CH 3 、-NH 2 、-PhNH 2 or-H;
R 2 is-NH 2 -H or-PhNH 2 Any one of them;
R 3 is-H, -NH 2 、-PhNH 2 or-CH 3 Any one of them.
In the invention, the molar ratio of imidazole structural units in the polymer ligand B structure of the high-peel strength electrolytic water film electrode is 5-35%.
Preferably, the molar ratio of imidazole structural units in the polymer ligand B structure is 10-20%.
The molar ratio of the metal M to the amount of the polymer ligand B is 1:1-5.
In the invention, the ion exchange capacity of the perfluorinated sulfonic acid ion exchange resin A of the high-peel strength electrolytic water film electrode is 0.5-2.5 mmol/g, and the number average molecular weight is 10-90 ten thousand.
Preferably, the ion exchange capacity of the perfluorinated sulfonic acid ion exchange resin A is 1.0-1.5 mmol/g, and the number average molecular weight is 30-75 ten thousand.
More preferably, the ion exchange capacity of the perfluorosulfonic acid ion exchange resin A is 1.05 to 1.25mmol/g and the number average molecular weight is 35 to 55 ten thousand.
The preparation method of the high-peel strength electrolytic water film electrode comprises the following steps:
(1) Preparation of perfluorosulfonic acid ion exchange resin a: soaking perfluorinated sulfonyl fluoride resin in alkali liquor and acid liquor to complete ion exchange, and carrying out-SO (sulfur-oxygen) treatment 2 All F groups are converted to-SO 3 And H, washing and drying the product to obtain the perfluorosulfonic acid ion exchange resin A.
(2) Preparation of Polymer ligand B: grafting an imidazole group on polyethyleneimine and an M-Ar reagent with the imidazole group in a solvent through a grafting reaction, and washing and drying a product to obtain a polymer ligand B; wherein the M-Ar reagent isWherein R is 1 、R 2 、R 3 Independently selected from-H, -NH 2 、-PhNH 2 -Cl, -PhCOOH or-CH 3 Any one of them.
The reaction formula of the grafting reaction is as follows:
(3) Preparing a perfluorosulfonic acid proton exchange membrane: and (3) dissolving the perfluorosulfonic acid ion exchange resin A in an organic solvent to prepare perfluorosulfonic acid ion polymer membrane preparation liquid, and directly preparing the perfluorosulfonic acid proton exchange membrane by adopting a solution casting method.
(4) Preparing a mixed solution of perfluorosulfonic acid ion exchange resin A and polymer ligand B: the perfluorinated sulfonic acid ion exchange resin A and the polymer ligand B are dissolved in a water/alcohol mixed solvent to prepare a mixed solution with the concentration of 2-10wt%.
(5) Preparing a cathode catalyst: adding Pt/C catalyst and metal M into the obtained mixed solution, uniformly mixing to obtain cathode catalyst slurry, ultrasonically dispersing, spraying onto a vacuum adsorption transfer template, and drying at 60-140 ℃ under vacuum condition to obtain the cathode catalyst.
(6) Preparing an anode catalyst: in the resulting mixtureIrO is added to the solution 2 Uniformly mixing the catalyst and the metal M to obtain anode catalyst slurry, performing ultrasonic dispersion, spraying the anode catalyst slurry onto a vacuum adsorption transfer printing template, and drying the anode catalyst under the vacuum condition of 60-140 ℃ to obtain the anode catalyst.
(7) Preparing a membrane electrode: and (3) respectively fixing transfer printing templates of two supported anode catalysts and cathode catalysts with proper sizes on two sides of the perfluorinated sulfonic acid proton exchange membrane prepared in the step (3), removing the transfer printing templates through hot pressing treatment, then placing the transfer printing templates in a vacuum drying oven at 60-135 ℃ for at least 2 hours, and taking out the transfer printing templates to prepare the membrane electrode.
In the invention, the mole fraction of the perfluorinated sulfonic acid ion exchange resin A in the mixed solution in the step (4) of the preparation method of the high-peel strength electrolytic water film electrode is 25-80%, and the mole fraction of the polymer ligand B is 20-75%.
Preferably, the mole fraction of the perfluorinated sulfonic acid ion exchange resin A is 70-80%, and the mole fraction of the polymer ligand B is 20-30%.
In the step (1) of the preparation method of the high-peel-strength electrolytic water film electrode, the alkali liquor is a KOH solution with the weight percent of 20, and the acid liquor is a sulfuric acid solution with the weight percent of 20; the soaking temperature is 80 ℃ and the soaking time is 30 hours.
The washing in the step (1) and the washing in the step (2) are both carried out by adopting deionized water; the drying temperature is 55-65 ℃ and the drying time is 12-24 hours.
In the invention, the polyethyleneimine in the step (2) of the preparation method of the high-peel-strength electrolytic water film electrode comprises the following steps: 1:5-15 of M-Ar reagent.
Preferably, the polyethyleneimine: 1:5-10 of M-Ar reagent.
The solvent is at least one of water, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, ethanol, isopropanol, dichloromethane, acetone, dimethyl sulfoxide or ethyl acetate.
The reaction temperature of the grafting reaction is 30-150 ℃ and the reaction time is 1-48 hours.
Preferably, the reaction temperature of the grafting reaction is 80-120 ℃ and the reaction time is 8-12 hours.
In the invention, the preparation of the perfluorosulfonic acid proton exchange membrane by the solution casting method in the step (3) of the preparation method of the high-peel strength electrolytic water membrane electrode comprises the following specific operations: and (3) forming a film on glass by using the film forming solution, pre-drying the film at 60-90 ℃, drying the film at 120-140 ℃ for 60-120 min, taking out and demolding to obtain the homogeneous perfluorosulfonic acid proton exchange membrane.
The concentration of the film forming liquid is 5-25 wt%.
The organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetone, butanone, 1-5 carbon chain alcohol aqueous solution, formic acid or acetic acid.
The thickness of the perfluorinated sulfonic acid proton exchange membrane prepared in the step (3) is 5-200 mu m.
Preferably, the thickness of the obtained perfluorosulfonic acid proton exchange membrane is 10-150 μm.
More preferably, the thickness of the obtained perfluorosulfonic acid proton exchange membrane is 15-30 μm.
In the step (4) of the preparation method of the high-peel-strength electrolytic water film electrode, the alcohol in the water/alcohol mixed solvent is ethanol or isopropanol, and the water is as follows: the volume ratio of the alcohol is 1-3:7-9.
In the step (5) and the step (6), the ultrasonic dispersion time is 30-150 min.
In the step (5) and the step (6), the mass ratio of Pt/C in the cathode catalyst slurry is 1-30wt%.
Preferably, the mass ratio of Pt/C is 5-10wt%.
IrO in the anode catalyst slurry 2 The mass ratio of (2) is 1-30wt%.
Preferably, irO 2 The mass ratio of (2) is 5-10wt%.
The pressure of the hot pressing treatment in the step (7) is 0.1-5 MPa, the hot pressing temperature is 60-150 ℃, and the hot pressing treatment time is 30-180 s.
IrO in the obtained membrane electrode 2 The dry weight content of (C) is 0.5-3.0 mg/cm 2 。
The dry weight content of Pt/C in the obtained membrane electrode is 0.1-0.5 mg/cm 2 。
The beneficial effects of the invention are as follows: compared with the prior art, the invention has at least the following advantages:
the electrolytic water film electrode provided by the invention introduces the additive metal with the free radical resistance function and imidazole groups together to effectively capture or quench the free radicals, so that the attenuation of the performance of the film electrode is weakened or slowed down, the chemical stability of the film electrode is improved, and the service life of the film electrode is prolonged. After 1000 hours the voltage increase is less than 40. Mu.V/h.
The electrolytic water film electrode disclosed by the invention simultaneously contains the perfluorinated sulfonic acid ion exchange resin A and the branched polyethylenimine polymer containing an imidazole structure in the cathode catalyst and the anode catalyst, so that the catalyst has higher adhesive force on the surface of the substrate ionic film, the peeling strength between the catalytic layer and the substrate is improved, the 90-degree peeling strength is more than 20N/mm, and the service life of the catalytic layer is prolonged.
Drawings
FIG. 1 is an infrared spectrum of a branched polyethyleneimine polymer containing imidazole structures described in the present invention.
Detailed Description
The present invention will be described in detail by way of examples. The reaction apparatus, polymer, reagent, organic solvent, etc. according to the examples are commercially available.
Example 1
The cathode catalyst and the anode catalyst of the high-peel-strength electrolytic water film electrode both contain free perfluorinated sulfonic acid ion exchange resin A and an additive with free radical resistance function.
The additive is a metal complex formed by a polymer ligand B and a metal M.
The polymer ligand B is branched polyethyleneimine polymer containing imidazole structure.
The structural formulas of the perfluorosulfonic acid ion exchange resin A and the polymer ligand B are shown as the following formulas:
wherein x of structure A is 4, y is 2, z is 6000, m is 1, n is 1;
wherein xx of structure B is 100;
R 1 is-H; r is R 2 is-H; r is R 3 is-H.
The metal M in the additive is Ce 2 (CO 3 ) 3 ·3H 2 O。
The molar ratio of imidazole structural units in the polymer ligand B is 5%.
The preparation method of the high-peel strength electrolytic water film electrode comprises the following specific steps:
(1) Preparation of perfluorosulfonic acid ion exchange resin a: the perfluorosulfonyl fluoride resin (number average molecular weight: 40 ten thousand, molar equivalent E w =880 g/mol) were soaked in 20wt% KOH, 20wt% sulfuric acid solution at 80 ℃ for 24h to complete ion exchange, and-SO was added 2 All F groups are converted to-SO 3 And H, repeatedly cleaning the product by deionized water for three times, and drying at 60 ℃ to obtain the perfluorosulfonic acid ion exchange resin A.
(2) Preparation of Polymer ligand B: 50g of polyethyleneimine were reacted with 0.18g of 1-allylimidazole (M-Ar reagent, R 1 ＝R 2 ＝R 3 =h) dissolved in a solvent, polyethylenimine: the molar ratio of the 1-allyl imidazole is 1:8; and (3) carrying out grafting reaction for 12 hours at 80 ℃, grafting imidazole groups, washing and drying the product to obtain the polymer ligand B.
The reaction formula of the grafting reaction is as follows:
FIG. 1A is an infrared spectrum of polyethyleneimine, 3300cm -1 And 2974cm -1 The vicinity is attributed to polyethyleneimine-NH 2 and-CH 2 Characteristic peaks.
FIG. 1B is an infrared spectrum of a branched polyethyleneimine polymer containing imidazole structures showing characteristic peaks of-C=C-and-C=N in imidazole ring structural units, the characteristic peaks appearing at 1560cm -1 A vicinity; at the same time at 2820cm -1 Characteristic peaks of-CH-groups appear nearby, and infrared results prove that the target product ligand B is successfully synthesized.
(3) Preparing a perfluorosulfonic acid proton exchange membrane: and (3) dissolving the perfluorosulfonic acid ion exchange resin A in an organic solvent to prepare 5wt% of perfluorosulfonic acid ion polymer membrane preparation liquid, directly casting the membrane preparation liquid on a glass plate by adopting a solution casting method, pre-drying at 60 ℃, drying in a 135 ℃ oven for 100 minutes, taking out and demolding to prepare the 22 mu m perfluorosulfonic acid proton exchange membrane with IEC of 1.16mmol/g.
(4) Preparing a mixed solution of perfluorosulfonic acid ion exchange resin A and polymer ligand B: a mixed solution with a concentration of 4.0wt% was prepared by dissolving 75.0 mol% of perfluorosulfonic acid ion exchange resin A and 25.0 mol% of polymer ligand B in a water/alcohol mixed solvent.
(5) Preparing a cathode catalyst and an anode catalyst: two 1.5mL mixed solutions were taken, and 0.3wt% Ce was added first 2 (CO 3 ) 3 ·3H 2 O (ligand B and Ce) 3+ Is 3:1) in terms of molar ratio; then 25.0mg of IrO is added 2 And 12.5mgPt/C catalyst, and carrying out ultrasonic treatment for 100min to obtain anode catalyst slurry and cathode catalyst slurry; irO for anode in water electrolysis apparatus 2 As a catalyst, pt/C for cathode; and spraying the catalyst slurry on a weighed polytetrafluoroethylene transfer template (thickness 5mm; length x width 5 x 5 cm), and drying to obtain the transfer template carrying the anode catalyst and the cathode catalyst. IrO in catalyst 2 And Pt/C loading equivalent of 1.0mg/cm, respectively 2 And 0.5mg/cm 2 。
(6) Preparing a membrane electrode: and (3) respectively fixing transfer printing templates of two supported anode catalysts and cathode catalysts with proper sizes on two sides of the perfluorinated sulfonic acid proton exchange membrane prepared in the step (3), carrying out hot pressing treatment by a press, wherein the pressure of the press is 1.0MPa, the hot pressing temperature is 140 ℃, the duration time is 60 seconds, opening the press, removing the transfer printing templates, and finally, placing a sample in a vacuum drying oven at 100 ℃ for 2 hours, and taking out to prepare the membrane electrode.
Example 2
The preparation method of the high-peel-strength electrolytic water film electrode is different from the embodiment 1 in that the grafting reaction time of polyethylenimine and 1-allylimidazole in the preparation of the polymer ligand B in the step (2) is prolonged to 24 hours, and the molar ratio of imidazole structural units in the ligand B structure is 30%.
The molar content of the perfluorosulfonic acid ion exchange resin A in the mixed solution of the step (4) is 65.0 percent, and the molar content of the polymer ligand B is 35.0 percent.
Example 3
The preparation method of the high-peel strength electrolytic water film electrode is different from the embodiment 1 in that CeO is selected 2 As metal M, ligand B and Ce 4+ The molar ratio of (2) is 3:1.
Increasing the catalyst content in the anode catalyst slurry and the cathode catalyst slurry in the step (5), and IrO in the transfer template of the obtained supported anode catalyst and cathode catalyst 2 And Pt/C loading equivalent of 2.5mg/cm, respectively 2 And 0.35mg/cm 2 。
Example 4
The cathode catalyst and the anode catalyst of the high-peel-strength electrolytic water film electrode both contain free perfluorinated sulfonic acid ion exchange resin A and an additive with free radical resistance function.
The additive is a metal complex formed by a polymer ligand B and a metal M.
The polymer ligand B is branched polyethyleneimine polymer containing imidazole structure.
The structural formulas of the perfluorosulfonic acid ion exchange resin A and the polymer ligand B are shown as the following formulas:
wherein x of the A structure is 4, y is 2, z is 5000, m is 1, and n is 1.
Wherein xx of structure B is 150;
R 1 is-CH 3 ；R 2 is-H; r is R 3 is-H.
The metal M in the additive is Ce 2 (CO 3 ) 3 ·3H 2 O。
The preparation method of the high-peel strength electrolytic water film electrode is different from the embodiment 1 in that the step (2) is 1-allylmethylimidazole (R 1 ＝CH 3， R 2 ＝R 3 =h) ligand B was prepared as M-Ar reagent.
Example 5
The cathode catalyst and the anode catalyst of the high-peel-strength electrolytic water film electrode both contain free perfluorinated sulfonic acid ion exchange resin A and an additive with free radical resistance function.
The additive is a metal complex formed by a polymer ligand B and a metal M.
The polymer ligand B is branched polyethyleneimine polymer containing imidazole structure.
The structural formulas of the perfluorosulfonic acid ion exchange resin A and the polymer ligand B are shown as the following formulas:
wherein x of the A structure is 5, y is 1, z is 5500, m is 1, and n is 1.
Wherein xx of structure B is 160.
R 1 is-CH 3 ；R 2 is-H; r is R 3 is-H.
The metal M in the additive is Ce 2 (CO 3 ) 3 ·3H 2 O。
The method for preparing the high-peel strength electrolytic water film electrode is different from example 1 in that the perfluorosulfonyl fluoride resin selected in the step (1) has a number average molecular weight of 45 ten thousand and a molar equivalent E w ＝950g/mol。
Example 6
The cathode catalyst and the anode catalyst of the high-peel-strength electrolytic water film electrode both contain free perfluorinated sulfonic acid ion exchange resin A and an additive with free radical resistance function.
The additive is a metal complex formed by a polymer ligand B and a metal M.
The polymer ligand B is branched polyethyleneimine polymer containing imidazole structure.
The structural formulas of the perfluorosulfonic acid ion exchange resin A and the polymer ligand B are shown as the following formulas:
wherein x of the A structure is 6, y is 2, z is 5600, m is 2, and n is 1.
Wherein xx of structure B is 200;
R 1 is-CH 3 ；R 2 is-H; r is R 3 is-H.
The metal M in the additive is Ce 2 (CO 3 ) 3 ·3H 2 O。
The method for preparing the high-peel strength electrolytic water film electrode is different from example 1 in that the perfluorosulfonyl fluoride resin selected in the step (1) has a number average molecular weight of 46 ten thousand and a molar equivalent E w ＝735g/mol。
The molar content of the perfluorosulfonic acid ion exchange resin A in the mixed solution of the step (4) is 60.0 percent, and the molar content of the polymer ligand B is 40.0 percent.
Comparative example 1
A method for preparing an electrolytic water membrane electrode, which is different from example 1 in that: only the perfluorosulfonic acid ion exchange resin A is selected to prepare the catalyst slurry, and no additive with free radical resistance function is added.
Comparative example 2
A method for preparing an electrolytic water membrane electrode, which is different from example 1 in that: only select and usePerfluorosulfonic acid polymer and metal Ce 2 (CO 3 ) 3 ·3H 2 O to prepare a catalyst slurry, no branched polyethylenimine polymer containing imidazole structure was added to ligand B.
The membrane electrodes obtained in each example and each comparative example were subjected to performance test.
1. The electrolytic water film electrodes prepared in each example and each comparative example are assembled into a water electrolytic cell: the anode current collecting plate, the anode gas diffusion layer, the membrane electrode, the cathode gas diffusion layer and the cathode current collecting plate are assembled into the water electrolytic cell in sequence, wherein the cathode porous diffusion layer is made of Dongli carbon paper, and the anode diffusion layer is made of porous titanium with a platinum coating. The flow rate of pure water is 300ml/min, the water temperature is controlled at 80 ℃, a constant current test method is adopted for stability test, and the purity of hydrogen at the cathode side and oxygen at the anode side are respectively detected by a gas chromatograph.
2. The stability of each prepared electrolytic water film electrode is characterized by adopting a fluoride ion release rate, and the testing method comprises the following steps: 80ppm of Fe was added to 100mL of 30wt% hydrogen peroxide solution 2+ The ions were carefully weighed and a mass of 0.1g of membrane electrode was placed in the solution, and after 100 hours of holding at 80℃the sample was taken out of the solution. Washed with deionized water, dried at 80 ℃ for 2h, and weighed. Calculation of weight loss and determination of F in solution ﹣ Is contained in the composition.
3. 90 ° peel strength: the adhesion of the catalytic layer to the substrate (ionic membrane) was investigated using peel strength, the method of detection of peel strength being referred to standard GB/T2792.
4. Membrane electrode durability test: at 0.1A/cm 2 And (3) the flow rate of pure water is 300ml/min, the water temperature is controlled at 25 ℃, the stability of the membrane electrode sample is evaluated, and the voltage increase rate after the electrolytic cell is operated for 1000 hours is monitored.
5. Titration of Ion Exchange Capacity (IEC): accurately weighing a certain weight of dry target product, performing ion exchange with NaCl water solution with concentration of about 1M for more than 12h, collecting ion exchanged solution, titrating with 0.1M NaOH standard solution with phenolphthalein as indicator until the solution turns pink, and determining Ion Exchange Capacity (IEC) value of target productCan be calculated according to the following formula: iec= (V NaOH ×C NaOH )/m。
Wherein: v (V) NaOH -volume of NaOH standard solution consumed, mL; c (C) NaOH -molar concentration of NaOH standard solution, mmol/mL; m-mass of dry target product, g.
Table 1 results of performance test of electrolytic water membrane electrode of each example and each comparative example
Note that: current density @1.75V (or 2.0V) refers to a current density at 1.75V (or 2.0V).
As can be seen from the comparison of examples 1-6 and comparative examples 1-2, the electrolytic water membrane electrode of the present invention can effectively reduce the chemical degradation of the ionomer in the membrane by introducing the additive, reduce the release rate of fluorine ions, and improve the thermal stability and chemical stability of the membrane electrode.
In addition, the electrolytic water film electrode provided by the invention can effectively improve the adhesive force between the catalytic layer and the substrate, and ensures that the catalytic layer has higher peeling strength.
In addition, the voltage increase during the operation of the membrane electrode 1000h is small, and the characteristics of low energy consumption and long service life are shown.
Claims (10)
1. The electrolytic water film electrode with high peeling strength is characterized in that a cathode catalyst and an anode catalyst of the film electrode both contain free perfluorinated sulfonic acid ion exchange resin A and an additive with free radical resistance function;
the additive is a metal complex formed by a polymer ligand B and a metal M;
the polymer ligand B is branched polyethyleneimine polymer containing imidazole structure;
the structural formulas of the perfluorosulfonic acid ion exchange resin A and the polymer ligand B are shown as the formula (I):
in the structure of the formula (I) A, x is 1-20, y is 1-20, z is 500-10000, m is an integer of 0-5, and n is an integer of 1-6;
in the structure of the formula (I) B, xx is 30-1000;
R 1 is-H, -NH 2 、-CH 2 NH 2 、-Ph、-PhNH 2 、-PhCOOH、-Cl、-O-CH 3 or-CH 3 Any one of them;
R 2 is-H, -NH 2 、-PhNH 2 -Cl, -PhCOOH or-CH 3 Any one of them;
R 3 is-H, -NH 2 、-PhNH 2 -PhCOOH, -Br, -Ph or-CH 3 Any one of them;
the metal M in the additive is selected from CeO 2 、CePO 4 、Ce(NO 3 ) 3 ·6H 2 O、Ce(SO 4 ) 2 、Ce(OH) 4 、(NH 4 ) 2 Ce(NO 3 ) 6 、Ce 2 (CO 3 ) 3 ·xH 2 O or Ce (CH) 3 COO) 3 ·xH 2 One or more of O; wherein x is 1 to 20.
2. The high peel strength electrolytic water membrane electrode according to claim 1, wherein in the structure of formula (I) a, m is an integer of 0 to 3, and n is an integer of 1 to 3;
in the structure of the formula (I) B, R in an imidazole structural unit 1 is-CH 3 、-NH 2 、-PhNH 2 or-H;
R 2 is-NH 2 -H or-PhNH 2 Any one of them;
R 3 is-H, -NH 2 、-PhNH 2 or-CH 3 Any one of them.
3. The high peel strength electrolytic water membrane electrode according to claim 1, wherein the molar ratio of imidazole structural units in the polymer ligand B structure is 5 to 35%;
preferably, the molar ratio of imidazole structural units in the structure of the polymer ligand B is 10-30%;
the molar ratio of the metal M to the amount of the polymer ligand B is 1:1-5.
4. The high peel strength electrolytic water membrane electrode according to claim 1, wherein the ion exchange capacity of the perfluorosulfonic acid ion exchange resin a is 0.5 to 2.5mmol/g and the number average molecular weight is 10 to 90 tens of thousands;
preferably, the ion exchange capacity of the perfluorinated sulfonic acid ion exchange resin A is 1.0-1.5 mmol/g, and the number average molecular weight is 30-75 ten thousand;
more preferably, the ion exchange capacity of the perfluorosulfonic acid ion exchange resin A is 1.05 to 1.25mmol/g and the number average molecular weight is 35 to 55 ten thousand.
5. A method of preparing the high peel strength electrolytic water membrane electrode of any one of claims 1 to 4, comprising the steps of:
(1) Preparation of perfluorosulfonic acid ion exchange resin a: soaking perfluorinated sulfonyl fluoride resin in alkali liquor and acid liquor to complete ion exchange, and carrying out-SO (sulfur-oxygen) treatment 2 All F groups are converted to-SO 3 H, washing and drying the product to obtain perfluorinated sulfonic acid ion exchange resin A;
(2) Preparation of Polymer ligand B: grafting an imidazole group on polyethyleneimine and an M-Ar reagent with the imidazole group in a solvent through a grafting reaction, and washing and drying a product to obtain a polymer ligand B;
(3) Preparing a perfluorosulfonic acid proton exchange membrane: dissolving perfluorosulfonic acid ion exchange resin A in an organic solvent to prepare perfluorosulfonic acid ion polymer membrane preparation liquid, and directly preparing a perfluorosulfonic acid proton exchange membrane by adopting a solution casting method;
(4) Preparing a mixed solution of perfluorosulfonic acid ion exchange resin A and polymer ligand B: dissolving the perfluorinated sulfonic acid ion exchange resin A and the polymer ligand B in a water/alcohol mixed solvent to prepare a mixed solution with the concentration of 2-10wt%;
(5) Preparing a cathode catalyst: adding Pt/C catalyst and metal M into the obtained mixed solution, uniformly mixing to obtain cathode catalyst slurry, performing ultrasonic dispersion, spraying onto a vacuum adsorption transfer printing template, and drying under the vacuum condition at 60-140 ℃ to obtain a cathode catalyst;
(6) Preparing an anode catalyst: adding IrO into the obtained mixed solution 2 Uniformly mixing the catalyst and the metal M to obtain anode catalyst slurry, performing ultrasonic dispersion, spraying the anode catalyst slurry onto a vacuum adsorption transfer printing template, and drying the anode catalyst slurry under the vacuum condition of 60-140 ℃ to obtain an anode catalyst;
(7) Preparing a membrane electrode: and (3) respectively fixing transfer printing templates of two supported anode catalysts and cathode catalysts with proper sizes on two sides of the perfluorinated sulfonic acid proton exchange membrane prepared in the step (3), removing the transfer printing templates through hot pressing treatment, then placing the transfer printing templates in a vacuum drying oven at 60-135 ℃ for at least 2 hours, and taking out the transfer printing templates to prepare the membrane electrode.
6. The method for preparing a high peel strength electrolytic water membrane electrode according to claim 5, wherein the molar fraction of the perfluorosulfonic acid ion exchange resin a in the mixed solution of step (4) is 25 to 80% and the molar fraction of the polymer ligand B is 20 to 75%;
preferably, the mole fraction of the perfluorinated sulfonic acid ion exchange resin A is 70-80%, and the mole fraction of the polymer ligand B is 20-30%.
7. The method for preparing a high peel strength electrolytic water membrane electrode according to claim 5, wherein the alkaline solution in the step (1) is a 20wt% KOH solution, and the acid solution is a 20wt% sulfuric acid solution; the soaking temperature is 80 ℃ and the soaking time is 30 hours;
the washing in the step (1) and the washing in the step (2) are both carried out by adopting deionized water; the drying temperature is 55-65 ℃ and the drying time is 12-24 hours.
8. The method for preparing a high peel strength electrolytic water membrane electrode according to claim 5, wherein the polyethyleneimine in step (2): 1:5-15 of M-Ar reagent;
preferably, the polyethyleneimine: 1:5-10 of M-Ar reagent;
the M-Ar reagent isWherein R is 1 、R 2 、R 3 Independently selected from-H, -NH 2 、-PhNH 2 -Cl, -PhCOOH or-CH 3 Any one of them;
the solvent is at least one of water, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, ethanol, isopropanol, dichloromethane, acetone, dimethyl sulfoxide or ethyl acetate;
the reaction temperature of the grafting reaction is 30-150 ℃ and the reaction time is 1-48 hours;
preferably, the reaction temperature of the grafting reaction is 80-120 ℃ and the reaction time is 8-12 hours.
9. The method for preparing a high peel strength electrolyte membrane electrode according to claim 5, wherein the specific operation of preparing the perfluorosulfonic acid proton exchange membrane by solution casting in the step (3) is as follows: film forming liquid is formed on glass, after pre-drying is carried out at 60-90 ℃, the film forming liquid is dried at 120-140 ℃ for 60-120 min, and then demoulding is carried out, thus obtaining the homogeneous phase perfluorinated sulfonic acid proton exchange membrane;
the concentration of the film-forming liquid is 5-25 wt%;
the organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetone, butanone, 1-5 carbon chain alcohol aqueous solution, formic acid or acetic acid;
the thickness of the perfluorinated sulfonic acid proton exchange membrane prepared in the step (3) is 5-200 mu m;
preferably, the thickness of the obtained perfluorinated sulfonic acid proton exchange membrane is 10-150 μm;
more preferably, the thickness of the obtained perfluorosulfonic acid proton exchange membrane is 15-30 μm.
10. The method for preparing a high peel strength electrolytic water membrane electrode according to claim 5, wherein the alcohol in the water/alcohol mixed solvent in step (4) is ethanol or isopropanol, water: the volume ratio of the alcohol is 1-3:7-9;
in the step (5) and the step (6), the ultrasonic dispersion time is 30-150 min;
in the step (5) and the step (6), the mass ratio of Pt/C in the cathode catalyst slurry is 1-30wt%;
preferably, the mass ratio of Pt/C is 5-10wt%;
IrO in the anode catalyst slurry 2 The mass ratio of (2) is 1-30wt%;
preferably, irO 2 The mass ratio of (2) is 5-10wt%;
the pressure of the hot pressing treatment in the step (7) is 0.1-5 MPa, the hot pressing temperature is 60-150 ℃, and the hot pressing treatment time is 30-180 s;
IrO in the obtained membrane electrode 2 The dry weight content of (C) is 0.5-3.0 mg/cm 2 ；
The dry weight content of Pt/C in the obtained membrane electrode is 0.1-0.5 mg/cm 2 。
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