A dual-effect membrane electrode for water electrolysis and fuel cells and a method of preparation

Abstract

The present application belongs to the field of fuel cell and water electrolysis membrane material and membrane electrode material, and relates to a double-effect membrane electrode for water electrolysis and fuel cell and a preparation method. The double-effect membrane electrode comprises a double-effect polymer exchange membrane and double-effect catalytic layers on two sides. The special structure in the double-effect polymer membrane can adsorb OH- or protons, respectively obtaining the ability to conduct OH- or protons, thereby preparing a proton exchange membrane or an anion exchange membrane. The main chain of the double-effect exchange membrane is a quaternized arylpyridine polymer, which has excellent acid and alkali stability and a simple synthesis method and process. Secondly, double-effect membrane electrode catalytic layers are coated on the two sides of the double-effect polymer membrane. In the catalyst slurry of the catalytic layers, the same stereoscopic resin material as the double-effect polymer membrane is used, which can effectively reduce the interface resistance and assist the catalyst in conducting ions, thereby obtaining higher water electrolysis or fuel cell performance. The double-effect membrane electrode prepared by the present application can be applied to water electrolysis and fuel cells.

Description

Technical Field

[0001] This invention relates to a dual-effect membrane electrode for water electrolysis and fuel cells and its preparation method, belonging to the field of fuel cell and water electrolysis membrane materials and membrane electrode materials. Background Technology

[0002] The membrane electrode assembly (MEA) is one of the core components of fuel cells and water electrolyzers, determining the overall performance, lifespan, and price of the cell / electrolyzer. As a core component, the MEA mainly consists of a proton exchange membrane in the middle and catalyst layers on both sides. Therefore, the performance of the proton exchange membrane and catalyst layers directly affects the performance of the MEA. For proton exchange membranes, arylpyridine polymers are commonly used as the polymeric framework in current research. This type of polymer, which lacks ether bonds, effectively addresses degradation issues and offers advantages such as good film-forming properties, chemical stability, and thermal stability. However, due to limitations in the functional groups of arylpyridine polymers and severe swelling after impregnation with phosphoric acid, the amount of impregnation is typically limited to ensure mechanical strength. Furthermore, the inherent limited adsorption sites within the molecular structure also restrict the amount of impregnation, thus affecting conductivity and the mechanical strength of the membrane, consequently impacting the conductivity and mechanical strength of the membrane electrode assembly. Regarding the catalyst layer, perfluorosulfonic acid resin is often used as a binder in the catalyst slurry to ensure the proton transport rate and adhesion between the catalyst and the proton exchange membrane. However, this approach fails to consider the transport rate under low humidity and high temperature conditions and the interfacial resistance between the two components, thus affecting transport performance.

[0003] As can be seen from the above analysis, to prepare high-performance membrane electrodes, the properties of the material itself must be combined with the process conditions for preparing the membrane electrode to meet the requirements of the final performance of the membrane electrode. Summary of the Invention

[0004] The purpose of this invention is to provide a dual-effect membrane electrode and its preparation method for water electrolysis and fuel cells. First, an arylpyridine polymer without unstable end groups such as ether bonds is used, and the polymer is modified with imidazole-functionalized graphene oxide to obtain the ability to conduct OH- or protons, respectively. Proton exchange membranes or anion exchange membranes are then prepared in one step to obtain a dual-effect exchange membrane, which effectively improves the acid-base chemical stability of the membrane while maintaining good acid-base retention capacity. Second, a dual-effect membrane electrode catalyst layer is coated on both sides of the dual-effect polymer membrane. The catalyst slurry of the catalyst layer uses the same stereochemical resin material as the dual-effect polymer membrane, which can effectively reduce interfacial resistance and assist the catalyst in conducting ions, thereby obtaining higher water electrolysis or fuel cell performance.

[0005] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0006] This invention provides a dual-effect membrane electrode for water electrolysis and fuel cells, wherein the membrane electrode is formed by coating an anode anti-reverse electrode catalyst slurry and a cathode catalyst slurry on both sides of a dual-effect exchange membrane, respectively.

[0007] The dual-effect exchange membrane is an exchange membrane that can adsorb OH- or protons, comprising quaternized arylpyridine polymer and imidazole-functionalized graphene oxide;

[0008] The anode anti-reverse electrode catalyst slurry includes compound I, catalyst I, quaternized arylpyridine polymer, imidazole functionalized graphene oxide, and alcohol diluent.

[0009] The compound I is one or more of Ru, Ir, Co, Ni, Ta, Re, Sn, Sb or their oxides; the catalyst I is 40-70 wt% Pt / C or one or two of Pt black;

[0010] The cathode catalyst slurry comprises compound II, catalyst II, quaternized arylpyridine polymer, imidazole-functionalized graphene oxide, and alcohol-based diluent.

[0011] The compound II is one or more combinations of MnO, MnO2, CeO2 and ZrO2; the catalyst II is one or more combinations of 40-70 wt% Pt / C, Pt Black, Iridium Black and Iridium Oxide;

[0012] The quaternized arylpyridine polymer is obtained by an affinity substitution reaction between an arylpyridine polymer and a haloalkane.

[0013] The imidazole-functionalized graphene oxide is obtained by attaching imidazole groups to epoxy groups on graphene oxide.

[0014] In the above technical solution, further, in the anode anti-reverse electrode catalyst slurry: the mass ratio of compound I: catalyst I: quaternized arylpyridine polymer: imidazole functionalized graphene oxide: alcohol diluent is (0.1-2):(3-10):(2.1-7):(0.1-2):(40-70);

[0015] In the cathode catalyst slurry, the mass ratio of compound II: catalyst II: quaternized arylpyridine polymer: imidazole functionalized graphene oxide: alcohol diluent is (0.3-2): (3-10): (2.1-7): (0.1-2): (40-70).

[0016] The catalyst loading in both the anode anti-reverse electrode catalyst slurry and the cathode catalyst slurry is 0.01-2.5 mg / cm³. 2 ;

[0017] The alcohol diluents are all mixtures of deionized water and ethanol, or deionized water and isopropanol, and the mass ratio of deionized water and ethanol, or deionized water and isopropanol, is 1:0.1-5.

[0018] Furthermore, in the above technical solution, the preparation method of the aforementioned dual-effect membrane electrode for water electrolysis and fuel cells includes the following steps:

[0019] Synthetic dual-effect exchange membrane:

[0020] Step 1) The aryl hydrocarbon is copolymerized with 4-acetylpyridine to obtain an arylpyridine polymer. Then, the arylpyridine polymer is mixed with a haloalkanes to undergo a nucleophilic substitution reaction to obtain a quaternized arylpyridine polymer.

[0021] Step 2) Imidazole groups are attached to the epoxy groups on the graphene oxide to obtain imidazole-functionalized graphene oxide.

[0022] Step 3) The quaternized arylpyridine polymer from step 1) is dissolved in a high-boiling-point solvent to form solution one. The imidazole-functionalized graphene oxide from step 2) is dispersed in a high-boiling-point solvent to form solution two. Solution one and solution two are mixed to form a film-forming slurry. The film-forming slurry is cast into a film and dried to obtain a dual-effect exchange membrane.

[0023] Fabrication of dual-effect film electrodes:

[0024] Step 4) Preparation of anode anti-reverse electrode catalyst slurry: Compound I, catalyst I, quaternized arylpyridine polymer, imidazole functionalized graphene oxide and alcohol diluent are thoroughly mixed and set aside for later use;

[0025] Step 5) Preparation of cathode catalyst slurry: Compound II, catalyst II, quaternized arylpyridine polymer, imidazole functionalized graphene oxide and alcohol diluent are thoroughly mixed and set aside for later use;

[0026] Step 6) Coat both sides of the double-effect exchange membrane in step 3) with cathode catalyst slurry and anode anti-reverse electrode slurry respectively, and dry them to obtain a ready-to-use double-effect membrane electrode.

[0027] Step 7) Immerse the spare dual-effect membrane electrode prepared in step 6) in an alkaline solution and dry it to obtain an anion exchange membrane electrode; Immerse the spare dual-effect membrane electrode prepared in step 6) in an acidic solution and dry it to obtain a proton exchange membrane electrode.

[0028] In the above technical solution, further, the synthesis step of the quaternized arylpyridine polymer in step 1) specifically includes:

[0029] a. Add 4-acetylpyridine and aryl hydrocarbons to dichloromethane solvent, add catalyst and protonating agent at low temperature, then return to room temperature, react for one time and then purify to obtain arylpyridine polymer;

[0030] b. Dissolve the arylpyridine polymer from step a in a high-boiling-point solvent, add a haloalkane and heat, react for two hours and then purify to obtain a quaternized arylpyridine polymer; the high-boiling-point solvent is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.

[0031] The molar ratio of 4-acetylpyridine to aryl hydrocarbon is (1:1.5)-(3:1), preferably (1:1)-(1.6:1);

[0032] The molar ratio of the arylpyridine polymer to the haloalkane is (1:1.2)-(1:10), preferably (1:1)-(1:5).

[0033] The aryl hydrocarbon is present in dichloromethane at a concentration of 0.1-5 mol / L;

[0034] The molar ratio of 4-acetylpyridine to the catalyst is (1:3)-(1:10);

[0035] The molar ratio of 4-acetylpyridine to the protonating agent is (1:3)-(1:20);

[0036] The catalyst is selected from trifluoroacetic acid and trichloroacetic acid, and the protonating agent is selected from trifluoromethanesulfonic acid and trinitrobenzenesulfonic acid;

[0037] The low temperature is -20 to 5°C;

[0038] The reaction time is 2-72 hours.

[0039] The halogenated hydrocarbon is selected from one or more of iodomethane, bromoethane, bromobutane, and bromohexane; the heating temperature is 50-200℃;

[0040] The second reaction time is 2-100 hours;

[0041] The arylpyridine polymer is present at a concentration of 0.01-2 mol / L in a high-boiling-point solvent.

[0042] In the above technical solution, further, the synthesis step of imidazole-functionalized graphene oxide in step 2) specifically includes:

[0043] Graphene oxide was dispersed in alkaline solution II for 30 min to 5 h to open the epoxy group. Then, an imidazole salt with an amino side chain was added and heated and stirred. After purification, the imidazole functionalized graphene oxide was obtained, which is to attach an imidazole group to the epoxy group of graphene oxide.

[0044] The alkaline solution is selected from either NaOH or KOH.

[0045] The mass ratio of the graphene oxide to the volume ratio of the alkaline solution II is (1:50)-(1:200) g / mol;

[0046] The molar ratio of the graphene oxide to the imidazole salt with amino groups on the side chain is (1:1)-(1:3); the heating temperature for the heating and stirring is 30-80℃; and the stirring time is 5-40h.

[0047] The imidazole salt with an amino group on its side chain is selected from one or more of 1-methyl-3-(3-aminopropyl)-3-chloroimidazolium, aminopropyl-3-methylimidazolium tetrafluoroborate, 1,2-dimethyl-1H-imidazolium-1-propylamine hydrogen bromide, 1-methyl-3-imidazolium-propylamine hydrogen bromide, and 1-methyl-2-isopropyl-3-aminopropylimidazolium hydrogen bromide.

[0048] In the above technical solution, further, the high-boiling point solvents mentioned in step (3) are all selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone;

[0049] The mass-to-volume ratio of the quaternized arylpyridine polymer to the high-boiling solvent is (1:5)-(1:100) g / ml;

[0050] The mass-to-volume ratio of the imidazole-functionalized graphene oxide to the high-boiling-point solvent is (1:20)-(1:200) g / ml;

[0051] The mass ratio of imidazole-functionalized graphene oxide to quaternized arylpyridine polymer is 1:1000-1:10;

[0052] The wet thickness of the dual-effect exchange membrane is 40-350 μm;

[0053] The drying process employs vacuum drying, with a vacuum drying temperature of 50-200℃.

[0054] In the above technical solution, further, the drying temperature in step (6) is 40-195℃;

[0055] The alkaline solution in step (7) is selected from one or more of NaOH, Na2CO3, NaHCO3, KOH, K2CO3, and KHCO3 solutions; the acid in the acidic solution is selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, and silicotungstic acid.

[0056] The concentration of the alkaline solution is 0.1-10 mol / L;

[0057] The concentration of the acidic solution is 0.01-5 mol / L;

[0058] The soaking time is 12-100 hours;

[0059] The drying temperature is 25-80℃.

[0060] In the above technical solution, the aryl hydrocarbon is further selected from any one or more of the following structures:

[0061]

[0062] In the above technical solution, the quaternized arylpyridine polymer has the structural formula shown in formula (I); the imidazole functionalized graphene oxide is graphene oxide with an imidazole group attached to the epoxy group, and its structural formula is shown in formula (II).

[0063]

[0064] Wherein, Ar is selected from aryl groups; R1 is selected from H, methyl, ethyl, butyl, or hexyl;

[0065]

[0066] In equation (II), R3 is one of the following S1-S5 structures:

[0067]

[0068] The present invention also provides the application of the aforementioned dual-effect membrane electrode, which is used as a membrane electrode in water electrolysis and fuel cells, or applied in anhydrous systems and high-temperature proton exchange membrane fuel cells with an operating temperature of 120-200°C.

[0069] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0070] 1. The dual-effect membrane electrode catalytic layer proposed in this invention contains catalytic layers with different functions on both sides. The material of the catalytic layer not only serves as a good binder, but the anode catalytic layer also uses anti-reverse electrode materials, as well as the same stereochemical resin and graphene as the polymer membrane. Firstly, the anti-reverse electrode material is used because during stack operation, insufficient hydrogen supply to the anode can cause the voltage of a single cell to drop below zero volts. This phenomenon leads to severe corrosion of the anode catalyst, resulting in a decrease in the output performance of the hydrogen fuel cell. The membrane electrode developed in this invention incorporates an anti-reverse electrode material in one layer. This material can generate a certain current for a short time in the presence of low gas levels, compensating for the damage caused by insufficient gas supply to the normal catalyst. The transient current loss can effectively address insufficient hydrogen supply at the anode and resist corrosion of the catalyst layer. Furthermore, it maintains good catalytic performance under such conditions. The use of the same stereochemical resin in the catalyst layer provides superior charge transfer efficiency and capability compared to traditional resins. Therefore, with the combined effects of the anti-reverse electrode material and the use of the same stereochemical resin, the membrane electrode prepared by this invention exhibits better resilience to complex inlet environments, ensuring its performance in fuel cells. Consequently, compared to perfluorosulfonic acid binders, this invention offers higher conductivity and smoother ion conduction channels.

[0071] 2. Using the same stereochemical resin as the polymer and imidazole-modified graphene, the polymer film contains imidazole-functionalized graphene and functional groups inherent in the polymer backbone. Both work together to increase proton / OH- adsorption sites, ensuring high conductivity while maintaining strong mechanical strength and low swelling. Next, catalytic layers with different functions are constructed on the polymer film. These catalytic layers use the same stereochemical resin with the same molecular structure, and imidazole-functionalized graphene oxide and anti-reverse polarization materials are added. This effectively avoids interfacial resistance in the catalytic layers, increases acid and base adsorption sites, thereby improving conductivity and anti-reverse polarization capability.

[0072] 3. The cathode catalyst layer uses a catalyst with free radical quenching function and the same components are used as the stereochemical resin. The free radical quencher can effectively resist the free radicals generated in the battery and increase the chemical stability of the membrane and stereochemical resin. Since the membrane and stereochemical resin do not depend on liquid water when conducting protons / OH-, they can also have good transport capacity in a low-humidity gaseous environment. Therefore, the dual-effect membrane electrode prepared by this invention can achieve good battery / electrolyte performance in a low-humidity environment.

[0073] 4. In this invention, the steric resin of both the polymer film and the catalyst layer in the dual-effect membrane electrode is an arylpyridine polymer modified with imidazole-functionalized graphene oxide without unstable end groups such as ether bonds. The polymer also possesses highly chemically stable nitrogen heterocyclic functional groups, which further enhance chemical stability through steric hindrance. This effectively prevents degradation of the polymer backbone and functional groups within the membrane, resulting in excellent chemical stability. Furthermore, the imidazole groups, rich in electrons, neutralize the electron transfer from graphene oxide to the pyridine polymer, effectively preventing a reduction in the number of electrons transferred from graphene, which could lead to graphene shedding and decreased stability. Therefore, the dual-effect membrane electrode of this invention exhibits good film-forming properties and conductivity. Moreover, the dual-effect membrane electrode with high phosphoric acid adsorption capacity proposed in this invention (after adsorbing proton conductors such as phosphoric acid) demonstrates good proton conductivity and excellent antioxidant stability even without humidification. This effectively solves the problem of the amount of impregnation affecting conductivity and mechanical strength, and also effectively alleviates the problem of phosphoric acid loss. In this invention, the proton exchange membrane and the catalyst layer binder in the membrane electrode use the same functional groups and polymer framework, which is beneficial for ion conduction, thereby reducing interfacial resistance and improving conductivity.

[0074] 5. The unique structure of the dual-effect polymer exchange membrane of this invention can adsorb OH- or protons, thereby gaining the ability to conduct OH- or protons respectively. It can prepare a polymer membrane with dual functions, that is, by introducing different soaking solutions into the stack, anion exchange membrane and proton exchange membrane can be directly prepared. Furthermore, anion exchange membrane electrode and proton exchange membrane electrode can be directly prepared in one step, eliminating the need to disassemble the stack to replace the membrane electrode. This effectively achieves a "low-cost, high-efficiency, and non-destructive" preparation and operation mode. By flexibly switching acid and alkaline conditions, the function of fuel cells or electrolyzers can be performed more quickly, safely, and with high performance.

[0075] 6. Functionalized graphene oxide can overcome the limitation of the number of proton conductors adsorbed, not only providing a large number of active sites and improving conductivity, but also effectively avoiding problems such as increased membrane resistance caused by the addition of graphene after functionalization modification; it can also effectively increase the content of basic groups such as imidazole and increase the compatibility of graphene with polymers, so that graphene oxide inorganic materials can be added into the membrane in a timely manner, thereby obtaining better film-forming performance and conductivity.

[0076] 7. The membrane electrode prepared by this invention uses inexpensive materials and has a simple preparation method. Attached Figure Description

[0077] Figure 1 This is a structural diagram of the membrane components in Example 1; Detailed Implementation

[0078] The present invention will be further described in detail below with reference to the accompanying drawings.

[0079] Example 1

[0080] First, a dual-effect exchange membrane is prepared:

[0081] S1. Add 0.02 mol of biphenyl and 0.013 mol of 4-acetylpyridine to 200 mL of dichloromethane and cool to 5 °C. Add 0.9 mol of trifluoroacetic acid dropwise, followed by 0.1 mol of trifluoromethanesulfonic acid. After the addition is complete, return to room temperature and react for 2 h. Pour the reaction solution into an aqueous methanol solution to precipitate a white solid. Wash the white solid with potassium carbonate solution at 50 °C, then wash with deionized water until neutral, and dry to obtain an arylpyridine polymer.

[0082] 0.01 mol of arylpyridine polymer was dissolved in 1000 mL of DMSO, and 0.012 mol of iodomethane was added. The mixture was heated to 50 °C and reacted for 100 h. The resulting solution was poured into a mixed solution of diethyl ether and isopropanol to precipitate a solid. The solid was washed once with deionized water and dried to obtain the quaternized arylpyridine polymer, with the following structural formula: Figure 1 a.

[0083] S2. 0.01 mol of graphene oxide was sonicated in 75 ml of NaOH solution at room temperature for 1 h to open the epoxy groups. Then, 0.02 mol of 1-methyl-3-(3-aminopropyl)-3-chloroimidazolium was added and the mixture was heated to 30 °C and stirred for 5 h. The alkalinity was then neutralized with dilute hydrochloric acid, and the mixture was washed several times with ethanol and deionized water to obtain the imidazolium-functionalized graphene oxide. This process involves attaching imidazolium groups to the epoxy groups of graphene oxide through ring-opening, and the structural formula is as follows: Figure 1 b.

[0084] S3. Prepare solution one by mixing 1g of quaternized arylpyridine polymer and 5ml of NMP; prepare solution two by mixing 1g of imidazole-functionalized graphene oxide and 20ml of NMP. Mix solution one and solution two evenly to form a film-forming slurry. Then, prepare a double-effect exchange membrane with a wet thickness of 40μm by casting film forming process. Finally, dry the membrane to obtain the finished double-effect exchange membrane.

[0085] Fabrication of dual-effect film electrodes:

[0086] S4. Preparation of anode anti-reverse electrode catalyst slurry: Weigh 0.1g of Ru, 3g of Pt / C, 2.1g of the quaternized arylpyridine polymer prepared in S1, 0.1g of imidazole functionalized graphene oxide prepared in S2, and 40g of a mixed solvent of deionized water and ethanol, and mix thoroughly for later use.

[0087] S5. Preparation of cathode catalyst slurry: Weigh 0.3g of MnO, 3g of Pt / C, 2.1g of the quaternized arylpyridine polymer prepared by S1, 0.1g of imidazole functionalized graphene oxide prepared by S2, and 40g of a mixed solvent of deionized water and ethanol, and mix thoroughly for later use.

[0088] S6. The cathode catalyst slurry and the anode anti-reverse electrode slurry are coated on both sides of the double-effect exchange membrane in step S3 by coating or spraying, and then dried to obtain a standby double-effect membrane electrode.

[0089] S7. The dual-effect membrane electrode prepared in S6 is soaked in 0.1 mol / L NaOH solution for 12 h to exchange all anions into hydroxide ions. After drying, an anion exchange membrane electrode is obtained.

[0090] The dual-effect membrane electrode prepared by S6 was soaked in a 0.1 mol / L phosphoric acid solution for 12 h to adsorb acid, and then dried to obtain a proton exchange membrane electrode.

[0091] Example 2

[0092] S1. Add 0.02 mol of p-terphenyl and 0.06 mol of 4-acetylpyridine to 200 mL of dichloromethane and cool to -20 °C. Add 0.6 mol of trichloroacetic acid dropwise, followed by 1.2 mol of trinitrobenzenesulfonic acid. After the addition is complete, return to room temperature and react for 72 h. Pour the reaction solution into an aqueous methanol solution to precipitate a white solid. Wash the white solid with potassium carbonate solution at 50 °C, then wash with deionized water until neutral, and dry to obtain the arylpyridine polymer.

[0093] 0.01 mol of arylpyridine polymer was dissolved in 10 mL of N-methylpyrrolidone, and 0.1 mol of bromoethane was added. The mixture was heated to 200 °C and reacted for 100 h. The resulting solution was poured into a mixed solution of diethyl ether and isopropanol to precipitate a solid. The solid was washed three times with deionized water and dried to obtain the quaternized arylpyridine polymer.

[0094] S2. 0.01 mol of graphene oxide was ultrasonically treated in 75 ml of KOH solution at room temperature for 1 h to open the epoxy groups. Then, 0.02 mol of aminopropyl-3-methylimidazolium tetrafluoroborate was added and heated to 80 °C and stirred for 40 h. The alkalinity was then neutralized with dilute hydrochloric acid and washed several times with ethanol and deionized water to obtain the imidazole-functionalized graphene oxide, which is to attach imidazole groups to the epoxy groups of graphene oxide.

[0095] S3. Prepare Solution 1 by mixing 1g of quaternized arylpyridine polymer and 100ml of N-methylpyrrolidone. Prepare Solution 2 by mixing 1g of imidazole-functionalized graphene oxide and 200g of N-methylpyrrolidone. Mix Solution 1 and Solution 2 thoroughly to form a film-forming slurry. Then, prepare a double-effect exchange membrane with a wet thickness of 350μm using a casting process. Finally, dry the membrane to obtain the finished double-effect exchange membrane.

[0096] Fabrication of dual-effect film electrodes:

[0097] S4. Preparation of anode anti-reverse electrode catalyst slurry: Weigh 2g of Ru, 10g of Pt / C, 7g of quaternized arylpyridine polymer prepared by S1, 2g of imidazole functionalized graphene oxide prepared by S2, and 70d of a mixed solvent of deionized water and ethanol, and mix thoroughly for later use.

[0098] S5. Preparation of cathode catalyst slurry: Weigh 2g of MnO, 10g of iridium black, 7g of the quaternized arylpyridine polymer prepared in S1, 2g of imidazole functionalized graphene oxide prepared in S2, and 70g of a mixed solvent of deionized water and ethanol, and mix thoroughly for later use.

[0099] S6. The cathode catalyst slurry and the anode anti-reverse electrode slurry are coated on both sides of the double-effect exchange membrane in step S3 by coating or spraying, and then dried to obtain a ready-to-use double-effect membrane electrode.

[0100] S7. The dual-effect membrane electrode prepared in S6 is soaked in 10 mol / L NaOH solution for 12 h to exchange all anions into hydroxide ions. After drying, an anion exchange membrane electrode is obtained.

[0101] The dual-effect membrane electrode prepared by S6 was immersed in a 10 mol / L phosphoric acid solution for 100 h to adsorb the acid, and then dried to obtain a proton exchange membrane electrode.

[0102] Example 3

[0103] S1. Add 0.01 mol of p-terphenyl, 0.02 mol of m-terphenyl, and 0.015 mol of 4-acetylpyridine to 300 mL of dichloromethane and cool to 0 °C. Add 0.3 mol of trifluoroacetic acid dropwise, followed by 0.312 mol of trinitrobenzenesulfonic acid. After the addition is complete, return to room temperature and react for 10 h. Pour the reaction solution into a methanol aqueous solution to precipitate a white solid. Wash the white solid with potassium carbonate solution at 50 °C, then wash with deionized water until neutral, and dry to obtain an arylpyridine polymer.

[0104] 0.01 mol of arylpyridine polymer was dissolved in 85 mL of N,N-dimethylformamide, and 0.04 mol of bromohexane was added. The mixture was heated to 120 °C and reacted for 50 minutes. The resulting solution was poured into a mixture of diethyl ether and isopropanol to precipitate a solid. The solid was washed twice with deionized water and dried to obtain the quaternized arylpyridine polymer.

[0105] S2. 0.01 mol of graphene oxide was ultrasonically treated in 75 ml of KOH solution at room temperature for 1 h to open the epoxy groups. Then, 0.02 mol of aminopropyl-3-methylimidazolium tetrafluoroborate was added and heated to 80 °C and stirred for 40 h. The alkalinity was then neutralized with dilute hydrochloric acid and washed several times with ethanol and deionized water to obtain the imidazole-functionalized graphene oxide, which is to attach imidazole groups to the epoxy groups of graphene oxide.

[0106] S3. Prepare Solution 1 by mixing 1g of quaternized arylpyridine polymer and 100ml of NMP. Prepare Solution 2 by mixing 1g of imidazole-functionalized graphene oxide and 100ml of NMP. Mix Solution 1 and Solution 2 thoroughly to form a film-forming slurry. Then, use a casting process to prepare a dual-effect exchange membrane with a wet thickness of 150μm. Finally, dry the membrane to obtain the finished dual-effect exchange membrane. Preparation of the dual-effect membrane electrode:

[0107] S4. Preparation of anode anti-reverse electrode catalyst slurry: Weigh 0.26g Ru, 4g Pt / C, 5g of quaternized arylpyridine polymer prepared by S1, 0.8g of imidazole functionalized graphene oxide prepared by S2, and 50g of a mixed solvent of deionized water and ethanol, and mix thoroughly for later use.

[0108] S5. Preparation of cathode catalyst slurry: Weigh 0.6g of CeO2, 8g of iridium oxide, 5g of the quaternized arylpyridine polymer prepared in S1, 1g of imidazole-functionalized graphene oxide prepared in S2, and 50g of a mixed solvent of deionized water and ethanol, and mix thoroughly for later use.

[0109] S6. The cathode catalyst slurry and the anode anti-reverse electrode slurry are coated on both sides of the double-effect exchange membrane in step S3 by coating or spraying, and then dried to obtain a ready-to-use double-effect membrane electrode.

[0110] S7. Soak the membrane prepared in S6 in 5 mol / L NaOH solution for 50 h to exchange all anions into hydroxide ions. After drying, an anion exchange membrane electrode is obtained.

[0111] The membrane prepared by S6 was soaked in a 5 mol / L phosphoric acid solution for 50 h to adsorb the acid, and then dried to obtain a proton exchange membrane electrode.

[0112] Comparative Example 1

[0113] S1. Add 0.02 mol of biphenyl and 0.02 mol of 4-acetylpyridine to 200 mL of dichloromethane and cool to 5 °C. Add 0.1 mol of trifluoroacetic acid dropwise, followed by 0.1 mol of trifluoromethanesulfonic acid. After the addition is complete, return to room temperature and react for 2 h. Pour the reaction solution into an aqueous methanol solution to precipitate a white solid. Wash the white solid with potassium carbonate solution at 50 °C, then wash with deionized water until neutral, and dry to obtain an arylpyridine polymer.

[0114] Dissolve 0.01 mol of arylpyridine polymer in 1000 ml of DMSO, add 0.01 mol of iodomethane, heat to 50 °C, and react for 100 h. Pour the reacted solution into a mixed solution of diethyl ether and isopropanol to precipitate a solid. Wash the solid once with deionized water and dry to obtain the quaternized arylpyridine polymer.

[0115] S2. Prepare a membrane slurry by mixing 1g of quaternized arylpyridine polymer and 5ml of NMP. Then, prepare a double-effect exchange membrane with a wet thickness of 40μm by casting. Finally, dry the membrane to obtain the finished double-effect exchange membrane.

[0116] Fabrication of dual-effect film electrodes:

[0117] S3. Preparation of anode anti-reverse electrode catalyst slurry: Weigh 0.1g of Ru, 3g of Pt / C, 2.1g of the quaternized arylpyridine polymer prepared by S1, and 40g of a mixed solvent of deionized water and ethanol, stir and mix thoroughly for later use.

[0118] S4. Preparation of cathode catalyst slurry: Weigh 0.3g of MnO, 3g of Pt / C, 2.1g of the quaternized arylpyridine polymer prepared by S1, and 40g of a mixed solvent of deionized water and ethanol, and mix thoroughly for later use.

[0119] S5. The cathode catalyst slurry and the anode anti-reverse electrode slurry are coated on both sides of the double-effect exchange membrane in step 4) by coating or spraying, and then dried to obtain a ready-to-use double-effect membrane electrode.

[0120] S6. The dual-effect membrane electrode prepared in S5 is soaked in 0.1 mol / L NaOH solution for 12 h to exchange all anions into hydroxide ions. After drying, an anion exchange membrane electrode is obtained.

[0121] The dual-effect membrane electrode prepared by S5 was soaked in 0.1 mol / L phosphoric acid solution for 12 h to adsorb acid, and then dried to obtain a proton exchange membrane electrode.

[0122] Comparative Example 2

[0123] S1. Add 0.02 mol of biphenyl and 0.02 mol of 4-acetylpyridine to 200 mL of dichloromethane and cool to 5 °C. Add 0.1 mol of trifluoroacetic acid dropwise, followed by 0.1 mol of trifluoromethanesulfonic acid. After the addition is complete, return to room temperature and react for 2 h. Pour the reaction solution into an aqueous methanol solution to precipitate a white solid. Wash the white solid with potassium carbonate solution at 50 °C, then wash with deionized water until neutral, and dry to obtain an arylpyridine polymer.

[0124] Dissolve 0.01 mol of arylpyridine polymer in 1000 ml of DMSO, add 0.01 mol of iodomethane, heat to 50 °C, and react for 100 h. Pour the reacted solution into a mixed solution of diethyl ether and isopropanol to precipitate a solid. Wash the solid once with deionized water and dry to obtain the quaternized arylpyridine polymer.

[0125] S2. Prepare solution one by mixing 1g of quaternized arylpyridine polymer and 5ml of NMP; prepare solution two by mixing 1g of graphene oxide and 20ml of NMP. Mix solution one and solution two evenly to form a film-forming slurry. Then, prepare a double-effect exchange membrane with a wet thickness of 40μm by casting film forming process. Finally, dry the membrane to obtain the finished double-effect exchange membrane.

[0126] Fabrication of dual-effect film electrodes:

[0127] S3. Preparation of anode anti-reverse electrode catalyst slurry: Weigh 0.1g Ru, 3g Pt / C, 2.1g of the quaternized arylpyridine polymer prepared by S1, 0.1g graphene oxide, and 40g of a mixed solvent of deionized water and ethanol, and mix thoroughly for later use.

[0128] S4. Preparation of cathode catalyst slurry: Weigh 0.3g of MnO, 3g of Pt / C, 2.1g of the quaternized arylpyridine polymer prepared by S1, 0.1g of graphene oxide, and 40g of a mixed solvent of deionized water and ethanol, and mix thoroughly for later use.

[0129] S5. The dual-effect membrane electrode prepared in S4 is soaked in 0.1 mol / L NaOH solution for 12 h to exchange all anions into hydroxide ions. After drying, an anion exchange membrane electrode is obtained.

[0130] The dual-effect membrane electrode prepared by S4 was soaked in a 0.1 mol / L phosphoric acid solution for 12 h to adsorb the acid, and then dried to obtain a proton exchange membrane electrode.

[0131] Comparative Example 3

[0132] S1. Add 0.02 mol of biphenyl and 0.02 mol of 4-acetylpyridine to 200 mL of dichloromethane and cool to 5 °C. Add 0.1 mol of trifluoroacetic acid dropwise, followed by 0.1 mol of trifluoromethanesulfonic acid. After the addition is complete, return to room temperature and react for 2 h. Pour the reaction solution into an aqueous methanol solution to precipitate a white solid. Wash the white solid with potassium carbonate solution at 50 °C, then wash with deionized water until neutral, and dry to obtain an arylpyridine polymer.

[0133] S2. Prepare solution one by mixing 1g of arylpyridine polymer and 5ml of NMP; prepare solution two by mixing 1g of graphene oxide and 20ml of NMP. Mix solution one and solution two evenly to form a film-forming slurry. Then, prepare a double-effect exchange membrane with a wet thickness of 40μm by casting film formation process. Finally, dry the membrane to obtain the finished double-effect exchange membrane.

[0134] Fabrication of dual-effect film electrodes:

[0135] S3. Preparation of anode anti-reverse electrode catalyst slurry: Weigh 0.1g Ru, 3g Pt / C, 2.1g arylpyridine polymer prepared by S1, 0.1g graphene oxide, and 40g of a mixed solvent of deionized water and ethanol, stir and mix thoroughly for later use.

[0136] Preparation of cathode catalyst slurry: Weigh 0.3g of MnO, 3g of Pt / C, 2.1g of S1 to prepare arylpyridine polymer, 0.1g of graphene oxide and 40g of a mixed solvent of deionized water and ethanol, stir and mix thoroughly for later use.

[0137] S4. The cathode catalyst slurry and the anode anti-reverse electrode slurry are coated on both sides of the double-effect exchange membrane in step 4) by coating or spraying, and then dried to obtain a ready-to-use double-effect membrane electrode.

[0138] S5. The dual-effect membrane electrode prepared in S4 is soaked in 0.1 mol / L NaOH solution for 12 h to exchange all anions into hydroxide ions. After drying, an anion exchange membrane electrode is obtained.

[0139] The dual-effect membrane electrode prepared by S5 was soaked in 0.1 mol / L phosphoric acid solution for 12 h to adsorb acid, and then dried to obtain a proton exchange membrane electrode.

[0140] Comparative Example 4

[0141] First, a dual-effect exchange membrane is prepared:

[0142] S1. Add 0.02 mol of biphenyl and 0.02 mol of 4-acetylpyridine to 200 mL of dichloromethane and cool to 5 °C. Add 0.1 mol of trifluoroacetic acid dropwise, followed by 0.1 mol of trifluoromethanesulfonic acid. After the addition is complete, return to room temperature and react for 2 h. Pour the reaction solution into an aqueous methanol solution to precipitate a white solid. Wash the white solid with potassium carbonate solution at 50 °C, then wash with deionized water until neutral, and dry to obtain an arylpyridine polymer.

[0143] Dissolve 0.01 mol of arylpyridine polymer in 1000 ml of DMSO, add 0.01 mol of iodomethane, heat to 50 °C, and react for 100 h. Pour the reacted solution into a mixed solution of diethyl ether and isopropanol to precipitate a solid. Wash the solid once with deionized water and dry to obtain the quaternized arylpyridine polymer.

[0144] S2. 0.01 mol of graphene oxide was sonicated in 75 ml of NaOH solution at room temperature for 1 h to open the epoxy groups. Then, 0.02 mol of 1-methyl-3-(3-aminopropyl)-3-chloroimidazolium was added and heated to 30 °C and stirred for 5 h. The alkalinity was then neutralized with dilute hydrochloric acid and washed several times with ethanol and deionized water to obtain the imidazolium-functionalized graphene oxide, which is to attach imidazolium groups to the epoxy groups of graphene oxide.

[0145] S3. Prepare Solution 1 by mixing 1g of quaternized arylpyridine polymer and 5ml of NMP; prepare Solution 2 by mixing 1g of imidazole-functionalized graphene oxide and 20ml of NMP. Mix Solutions 1 and 2 thoroughly to form a film-forming slurry. Then, use a casting process to prepare a double-effect exchange membrane with a wet thickness of 40μm. Finally, dry the membrane to obtain the finished double-effect exchange membrane. Preparation of the double-effect membrane electrode:

[0146] S4. Preparation of anode anti-reverse electrode catalyst slurry: Weigh 0.26g Ru, 4g Pt / C, 5g perfluorosulfonic acid resin, 0.8g imidazole functionalized graphene oxide prepared in S2, and 50g of a mixed solvent of deionized water and ethanol. Mix thoroughly and set aside. The mass ratio of the added compound Ru: catalyst Pt / C: perfluorosulfonic acid resin: imidazole functionalized graphene oxide: ethanol dilution solvent is 1:10:2.8:2:50.

[0147] S5. Preparation of cathode catalyst slurry: Weigh 0.6g of CeO2, 8g of iridium oxide, 5g of perfluorosulfonic acid resin, 1g of imidazole functionalized graphene oxide prepared by S2, and 50g of a mixed solvent of deionized water and ethanol, and mix thoroughly for later use.

[0148] S6. The cathode catalyst slurry and the anode anti-reverse electrode slurry are coated on both sides of the double-effect exchange membrane in step 4) by coating or spraying, and then dried to obtain a ready-to-use double-effect membrane electrode.

[0149] S7. The dual-effect membrane electrode prepared in S6 is soaked in 0.1 mol / L NaOH solution for 12 h to exchange all anions into hydroxide ions. After drying, an anion exchange membrane electrode is obtained.

[0150] The dual-effect membrane electrode prepared by S6 was soaked in a 0.1 mol / L phosphoric acid solution for 12 h to adsorb acid, and then dried to obtain a proton exchange membrane electrode.

[0151] Comparative Example 5

[0152] First, a dual-effect exchange membrane is prepared:

[0153] S1. Add 0.02 mol of biphenyl and 0.02 mol of 4-acetylpyridine to 200 mL of dichloromethane and cool to 5 °C. Add 0.1 mol of trifluoroacetic acid dropwise, followed by 0.1 mol of trifluoromethanesulfonic acid. After the addition is complete, return to room temperature and react for 2 h. Pour the reaction solution into an aqueous methanol solution to precipitate a white solid. Wash the white solid with potassium carbonate solution at 50 °C, then wash with deionized water until neutral, and dry to obtain an arylpyridine polymer.

[0154] Dissolve 0.01 mol of arylpyridine polymer in 1000 ml of DMSO, add 0.01 mol of iodomethane, heat to 50 °C, and react for 100 h. Pour the reacted solution into a mixed solution of diethyl ether and isopropanol to precipitate a solid. Wash the solid once with deionized water and dry to obtain the quaternized arylpyridine polymer.

[0155] S2. 0.01 mol of graphene oxide was sonicated in 75 ml of NaOH solution at room temperature for 1 h to open the epoxy groups. Then, 0.02 mol of 1-methyl-3-(3-aminopropyl)-3-chloroimidazolium was added and heated to 30 °C and stirred for 5 h. The alkalinity was then neutralized with dilute hydrochloric acid and washed several times with ethanol and deionized water to obtain the imidazolium-functionalized graphene oxide, which is to attach imidazolium groups to the epoxy groups of graphene oxide.

[0156] S3. Prepare Solution 1 by mixing 1g of quaternized arylpyridine polymer and 5ml of NMP; prepare Solution 2 by mixing 1g of imidazole-functionalized graphene oxide and 20ml of NMP. Mix Solutions 1 and 2 thoroughly to form a film-forming slurry. Then, use a casting process to prepare a double-effect exchange membrane with a wet thickness of 40μm. Finally, dry the membrane to obtain the finished double-effect exchange membrane. Preparation of the double-effect membrane electrode:

[0157] S4. Preparation of anode anti-reverse electrode catalyst slurry: Weigh 0.26g Ru, 4g Pt / C, 5g arylpyridine polymer prepared in S1, 0g imidazole functionalized graphene oxide prepared in S2, and 50g of a mixed solvent of deionized water and ethanol. Mix thoroughly and set aside. The mass ratio of the added compound Ru: catalyst Pt / C: perfluorosulfonic acid resin: imidazole functionalized graphene oxide: ethanol diluent is 1:10:2.8:2:50.

[0158] S5. Preparation of cathode catalyst slurry: Weigh 0.6g of CeO2, 8g of iridium oxide, 5g of the arylpyridine polymer prepared in S1, 0g of the imidazole-functionalized graphene oxide prepared in S2, and 50g of a mixed solvent of deionized water and ethanol. Stir and mix thoroughly for later use. S6. Coat both sides of the double-effect exchange membrane in step 4) with cathode catalyst slurry and anode anti-reverse electrode slurry by coating or spraying, and dry to obtain a ready-to-use double-effect membrane electrode.

[0159] S6. The dual-effect membrane electrode prepared in S5 is soaked in 0.1 mol / L NaOH solution for 12 h to exchange all anions into hydroxide ions. After drying, an anion exchange membrane electrode is obtained.

[0160] The dual-effect membrane electrode prepared by S5 was soaked in 0.1 mol / L phosphoric acid solution for 12 h to adsorb acid, and then dried to obtain a proton exchange membrane electrode.

[0161] Comparative Example 6

[0162] First, a dual-effect exchange membrane is prepared:

[0163] S1. Add 0.02 mol of biphenyl and 0.02 mol of 4-acetylpyridine to 200 mL of dichloromethane and cool to 5 °C. Add 0.1 mol of trifluoroacetic acid dropwise, followed by 0.1 mol of trifluoromethanesulfonic acid. After the addition is complete, return to room temperature and react for 2 h. Pour the reaction solution into an aqueous methanol solution to precipitate a white solid. Wash the white solid with potassium carbonate solution at 50 °C, then wash with deionized water until neutral, and dry to obtain an arylpyridine polymer.

[0164] Dissolve 0.01 mol of arylpyridine polymer in 1000 ml of DMSO, add 0.01 mol of iodomethane, heat to 50 °C, and react for 100 h. Pour the reacted solution into a mixed solution of diethyl ether and isopropanol to precipitate a solid. Wash the solid once with deionized water and dry to obtain the quaternized arylpyridine polymer.

[0165] S2. 0.01 mol of graphene oxide was sonicated in 75 ml of NaOH solution at room temperature for 1 h to open the epoxy groups. Then, 0.02 mol of 1-methyl-3-(3-aminopropyl)-3-chloroimidazolium was added and heated to 30 °C and stirred for 5 h. The alkalinity was then neutralized with dilute hydrochloric acid and washed several times with ethanol and deionized water to obtain the imidazolium-functionalized graphene oxide, which is to attach imidazolium groups to the epoxy groups of graphene oxide.

[0166] S3. Prepare Solution 1 by mixing 1g of quaternized arylpyridine polymer and 5ml of NMP; prepare Solution 2 by mixing 1g of imidazole-functionalized graphene oxide and 20ml of NMP. Mix Solutions 1 and 2 thoroughly to form a film-forming slurry. Then, use a casting process to prepare a dual-effect exchange membrane with a wet thickness of 30μm. Finally, dry the membrane to obtain the finished dual-effect exchange membrane. Preparation of the dual-effect membrane electrode:

[0167] S4. Preparation of anode anti-reverse electrode catalyst slurry: Weigh 0.26g Ru, 4g Pt / C, 0g arylpyridine polymer prepared in S1, 0.8g imidazole functionalized graphene oxide prepared in S2, and 50g of a mixed solvent of deionized water and ethanol. Mix thoroughly and set aside. The mass ratio of the added compound Ru: catalyst Pt / C: perfluorosulfonic acid resin: imidazole functionalized graphene oxide: ethanol diluent is 1:10:2.8:2:50.

[0168] S5. Preparation of cathode catalyst slurry: Weigh 0.6g of CeO2, 8g of iridium oxide, 0g of the arylpyridine polymer prepared in S1, 0.8g of the imidazole-functionalized graphene oxide prepared in S2, and 50g of a mixed solvent of deionized water and ethanol. Stir and mix thoroughly for later use. S6. Coat both sides of the double-effect exchange membrane in step 4) with cathode catalyst slurry and anode anti-reverse electrode slurry by coating or spraying, and dry to obtain a ready-to-use double-effect membrane electrode.

[0169] S6. The cathode catalyst slurry and the anode anti-reverse electrode slurry are coated on both sides of the double-effect exchange membrane in step 4) by coating or spraying, and then dried to obtain a ready-to-use double-effect membrane electrode.

[0170] S7. The dual-effect membrane electrode prepared in S6 is soaked in 0.1 mol / L NaOH solution for 12 h to exchange all anions into hydroxide ions. After drying, an anion exchange membrane electrode is obtained.

[0171] The dual-effect membrane electrode prepared by S6 was soaked in a 0.1 mol / L phosphoric acid solution for 12 h to adsorb acid, and then dried to obtain a proton exchange membrane electrode.

[0172] Comparative Example 7

[0173] First, a dual-effect exchange membrane is prepared:

[0174] S1. Add 0.02 mol of biphenyl and 0.013 mol of 4-acetylpyridine to 200 mL of dichloromethane and cool to 5 °C. Add 0.9 mol of trifluoroacetic acid dropwise, followed by 0.1 mol of trifluoromethanesulfonic acid. After the addition is complete, return to room temperature and react for 2 h. Pour the reaction solution into an aqueous methanol solution to precipitate a white solid. Wash the white solid with potassium carbonate solution at 50 °C, then wash with deionized water until neutral, and dry to obtain an arylpyridine polymer.

[0175] S2. 0.01 mol of graphene oxide was sonicated in 75 ml of NaOH solution at room temperature for 1 h to open the epoxy groups. Then, 0.02 mol of 1-methyl-3-(3-aminopropyl)-3-chloroimidazolium was added and heated to 30 °C and stirred for 5 h. The alkalinity was then neutralized with dilute hydrochloric acid and washed several times with ethanol and deionized water to obtain the imidazolium-functionalized graphene oxide, which is to attach imidazolium groups to the epoxy groups of graphene oxide.

[0176] S3. Prepare solution one by mixing 1g of arylpyridine polymer and 5ml of NMP; prepare solution two by mixing 1g of imidazole-functionalized graphene oxide and 20ml of NMP. Mix solution one and solution two evenly to form a film-forming slurry. Then, prepare a double-effect exchange membrane with a wet thickness of 40μm by casting film forming process. Finally, dry the membrane to obtain the finished double-effect exchange membrane.

[0177] Fabrication of dual-effect film electrodes:

[0178] S4. Preparation of anode anti-reverse electrode catalyst slurry: Weigh 0.1g Ru, 3g Pt / C, 2.1g arylpyridine polymer prepared by S1, 0.1g imidazole functionalized graphene oxide prepared by S2, and 40g of a mixed solvent of deionized water and ethanol, and mix thoroughly for later use.

[0179] S5. Preparation of cathode catalyst slurry: Weigh 0.3g of MnO, 3g of Pt / C, 2.1g of arylpyridine polymer prepared by S1, 0.1g of imidazole functionalized graphene oxide prepared by S2, and 40g of a mixed solvent of deionized water and ethanol, and mix thoroughly for later use.

[0180] S6. The cathode catalyst slurry and the anode anti-reverse electrode slurry are coated on both sides of the double-effect exchange membrane in step S3 by coating or spraying, and then dried to obtain a standby double-effect membrane electrode.

[0181] S7. The dual-effect membrane electrode prepared in S6 is soaked in 0.1 mol / L NaOH solution for 12 h to exchange all anions into hydroxide ions. After drying, an anion exchange membrane electrode is obtained.

[0182] The dual-effect membrane electrode prepared by S6 was soaked in a 0.1 mol / L phosphoric acid solution for 12 h to adsorb acid, and then dried to obtain a proton exchange membrane electrode.

[0183] The acid-base retention rate, chemical stability, conductivity, tensile strength, dimensional change rate, and chemical stability of the dual-effect membrane electrodes prepared in the test examples and comparative examples were evaluated. The conductivity was tested at 120℃ and 40% humidity, and at 100℃ and 30% humidity. The tensile strength was tested using the national standard method (GB / T20042.3-2009). The hydrogen permeation current was tested using an electrochemical method.

[0184] Comparative Example 1: Without adding imidazole-functionalized graphene, multilayer films were directly formed using quaternized arylpyridine polymers. The results showed low acid or alkali adsorption and low conductivity.

[0185] Comparative Example 2: Without introducing imidazole groups into graphene oxide, graphene oxide and polymer were directly doped into a multilayer film. The results showed that although simply adding graphene oxide maintained a high acid and base adsorption capacity, it was itself a resistor with low conductivity.

[0186] In Comparative Example 3, the conductivity was reduced because the unquaternized arylpyridine polymer and graphene oxide without imidazole groups were used to prepare the film. This is because the functionalized graphene can effectively avoid the problem of increased film resistance caused by the addition of graphene, while the unfunctionalized graphene oxide does not have this advantage; the unquaternized arylpyridine polymer itself also has a low conductivity.

[0187] In Comparative Example 4, perfluorosulfonic acid was used as the stereochemical resin in the catalyst slurry. The conductivity was low because the use of a stereochemical resin different from that of the polymer could not effectively avoid the interfacial resistance caused by the material difference, resulting in poor battery performance and alkali resistance.

[0188] Comparative Example 5, which did not contain imidazole-functionalized graphene oxide in its catalyst slurry, exhibited lower electrical conductivity and battery output performance, as well as lower chemical stability. This is because imidazole-functionalized graphene oxide can form good proton / OH- transport channels with functional groups within the membrane, which is beneficial for the migration of protons or OH- in the battery environment, thereby improving electrical conductivity and chemical stability.

[0189] Comparative Example 6 shows that the catalyst slurry did not use arylpyridine polymers, resulting in poor conductivity of the catalyst layer and low membrane electrode performance. This indicates that using arylpyridine polymers with the same membrane skeleton in the catalyst slurry can effectively improve the proton and OH- conductivity of the membrane.

[0190] Comparative Example 7: During film preparation, if the arylpyridine polymer is not quaternized, there are very few adsorption sites for protons and OH- on the polymer, which seriously affects the proton conductivity and OH- conduction capacity.

[0191] The ionic conductivity of the membrane was tested, and the results are shown in the table below. The results show that after impregnation with acids and alkalis, both proton conductivity and OH- conductivity were formed. The membrane with imidazole-modified graphene oxide exhibited high conductivity, and due to its multilayer structure, the membrane showed high mechanical strength.

[0192] Table 1. Conductivity and tensile strength of the membrane

[0193]

[0194]

[0195] Table 2. Conductivity and tensile strength of the membrane

[0196]

[0197] The dual-effect membrane electrodes prepared in the embodiments and comparative examples of this invention were immersed in Fenton's reagent for durability testing, and the results are shown in the table below. The membranes without multilayer modification and containing ether linkages exhibited significantly poorer chemical resistance.

[0198] Table 3. Test of residual mass of membrane electrode.

[0199]

[0200]

[0201] The dual-effect membrane electrodes prepared in the embodiments and comparative examples of this invention were weighed after adsorbing acids and alkalis, and then immersed in pure water for a certain period of time to test the residual mass rate, thus detecting their ability to retain acids and alkalis. The conductivity retention rate before and after immersion was also tested, and the results are shown in the table below. The conductivity retention rate was poor for the electrode without multilayer modification, while the membrane with imidazole-modified graphene oxide exhibited high conductivity and good conductivity stability.

[0202] Table 4. Acid and alkali absorption capacity, acid and alkali retention capacity, and conductivity retention rate of dual-effect film electrodes.

[0203]

[0204] As shown in Table 5, the dual-effect membrane electrode designed in this invention exhibits better current density under the same voltage during water electrolysis, with current densities exceeding 2000 mA / cm² at an electrolysis voltage of 2.0V. In contrast, the comparative examples show lower performance due to the lack of corresponding methods and structures.

[0205] Table 5 Electrolytic Current Density of Membrane Electrode

[0206] Example 1 1501 2013 Example 2 1431 2132 Example 3 1578 2098 Comparative Example 1 1100 1895 Comparative Example 2 1281 1987 Comparative Example 3 1087 1675 Comparative Example 4 1035 1200 Comparative Example 5 1124 1324 Comparative Example 6 908 1023 Comparative Example 7 809 993

[0207] This specific embodiment is merely an explanation of the present invention and is not intended to limit the invention. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they are within the scope of the claims of the present invention.

Claims

1. A dual-effect membrane electrode for water electrolysis and fuel cells, characterized in that: The membrane electrode is formed by coating an anode anti-reverse electrode catalyst slurry and a cathode catalyst slurry on both sides of a double-effect exchange membrane, respectively. The dual-effect exchange membrane comprises quaternized arylpyridine polymer and imidazole-functionalized graphene oxide; The anode anti-reverse electrode catalyst slurry includes compound I, catalyst I, quaternized arylpyridine polymer, imidazole functionalized graphene oxide, and alcohol diluent. The compound I is one or more of Ru, Ir, Co, Ni, Ta, Re, Sn, Sb or their oxides; the catalyst I is 40-70 wt% Pt / C or one or two of Pt black; The cathode catalyst slurry comprises compound II, catalyst II, quaternized arylpyridine polymer, imidazole-functionalized graphene oxide, and alcohol-based diluent. The compound II is one or more combinations of MnO, MnO2, CeO2 and ZrO2; the catalyst II is one or more combinations of 40-70 wt% Pt / C, Pt Black, Iridium Black and Iridium Oxide; The quaternized arylpyridine polymer is obtained by an affinity substitution reaction between an arylpyridine polymer and a haloalkane. The imidazole-functionalized graphene oxide is obtained by attaching imidazole groups to epoxy groups on graphene oxide.

2. The dual-effect film electrode according to claim 1, characterized in that: In the anodic anti-reverse catalyst slurry, the mass ratio of compound I: catalyst I: quaternized arylpyridine polymer: imidazole functionalized graphene oxide: alcohol diluent is (0.1-2):(3-10):(2.1-7):(0.1-2):(40-70); In the cathode catalyst slurry, the mass ratio of compound II: catalyst II: quaternized arylpyridine polymer: imidazole functionalized graphene oxide: alcohol diluent is (0.3-2): (3-10): (2.1-7): (0.1-2): (40-70). The catalyst loading in the anode anti-knock catalyst slurry and the cathode catalyst slurry is 0.01 to 2.5 mg / cm 2 ; The alcohol diluents are all mixtures of deionized water and ethanol, or deionized water and isopropanol, and the mass ratio of deionized water and ethanol, or deionized water and isopropanol, is 1:0.1-5.

3. A method for preparing a dual-effect membrane electrode for water electrolysis and fuel cells according to any one of claims 1-2, characterized in that, Includes the following steps: Synthetic dual-effect exchange membrane: Step 1) The aryl hydrocarbon is copolymerized with 4-acetylpyridine to obtain an arylpyridine polymer. Then, the arylpyridine polymer is mixed with a haloalkanes to undergo a nucleophilic substitution reaction to obtain a quaternized arylpyridine polymer. Step 2) Imidazole groups are attached to the epoxy groups on the graphene oxide to obtain imidazole-functionalized graphene oxide. Step 3) The quaternized arylpyridine polymer from step 1) is dissolved in a high-boiling-point solvent to form solution one. The imidazole-functionalized graphene oxide from step 2) is dispersed in a high-boiling-point solvent to form solution two. Solution one and solution two are mixed to form a film-forming slurry. The film-forming slurry is cast into a film and dried to obtain a dual-effect exchange membrane. Fabrication of dual-effect film electrodes: Step 4) Preparation of anode anti-reverse electrode catalyst slurry: Compound I, catalyst I, quaternized arylpyridine polymer, imidazole functionalized graphene oxide and alcohol diluent are thoroughly mixed and set aside for later use; Step 5) Preparation of cathode catalyst slurry: Compound II, catalyst II, quaternized arylpyridine polymer, imidazole functionalized graphene oxide and alcohol diluent are thoroughly mixed and set aside for later use; Step 6) Coat both sides of the double-effect exchange membrane in step 3) with cathode catalyst slurry and anode anti-reverse electrode slurry respectively, and dry them to obtain a ready-to-use double-effect membrane electrode. Step 7) Immerse the spare dual-effect membrane electrode prepared in step 6) in an alkaline solution and dry it to obtain an anion exchange membrane electrode; Immerse the spare dual-effect membrane electrode prepared in step 6) in an acidic solution and dry it to obtain a proton exchange membrane electrode.

4. The preparation method according to claim 3, characterized in that: The specific steps for synthesizing the quaternized arylpyridine polymer described in step 1) are as follows: a. Add 4-acetylpyridine and aryl hydrocarbons to dichloromethane solvent, add catalyst and protonating agent at low temperature, then return to room temperature, react for one time and then purify to obtain arylpyridine polymer; b. Dissolve the arylpyridine polymer from step a in a high-boiling-point solvent, add a haloalkane and heat, react for two hours and then purify to obtain a quaternized arylpyridine polymer; the high-boiling-point solvent is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone. The molar ratio of 4-acetylpyridine to aryl hydrocarbon is (1:1.5)-(3:1); The molar ratio of the arylpyridine polymer to the haloalkane is (1:1.2)-(1:10); The aryl hydrocarbon is present in dichloromethane at a concentration of 0.1-5 mol / L; The molar ratio of 4-acetylpyridine to the catalyst is (1:3)-(1:10); The molar ratio of 4-acetylpyridine to the protonating agent is (1:3)-(1:20); The catalyst is selected from trifluoroacetic acid and trichloroacetic acid, and the protonating agent is selected from trifluoromethanesulfonic acid and trinitrobenzenesulfonic acid; The low temperature is -20 to 5°C; The reaction time is 2-72 hours. The halogenated hydrocarbon is selected from one or more of iodomethane, bromoethane, bromobutane, and bromohexane; the heating temperature is 50-200℃; The second reaction time is 2-100 hours; The arylpyridine polymer is present at a concentration of 0.01-2 mol / L in a high-boiling-point solvent.

5. The preparation method according to claim 3, characterized in that: The specific steps for synthesizing imidazole-functionalized graphene oxide described in step 2) are as follows: Graphene oxide was dispersed in alkaline solution II for 30 min to 5 h to open the epoxy group. Then, an imidazole salt with an amino side chain was added and heated and stirred. After purification, the imidazole functionalized graphene oxide was obtained, which is to attach an imidazole group to the epoxy group of graphene oxide. The alkaline solution is selected from either NaOH or KOH. The mass ratio of the graphene oxide to the volume ratio of the alkaline solution II is (1:50)-(1:200) g / mol; The molar ratio of the graphene oxide to the imidazole salt with amino groups on the side chain is (1:1)-(1:3); the heating temperature for the heating and stirring is 30-80℃; and the stirring time is 5-40h. The imidazole salt with an amino group on its side chain is selected from one or more of 1-methyl-3-(3-aminopropyl)-3-chloroimidazolium, aminopropyl-3-methylimidazolium tetrafluoroborate, 1,2-dimethyl-1H-imidazolium-1-propylamine hydrogen bromide, 1-methyl-3-imidazolium-propylamine hydrogen bromide, and 1-methyl-2-isopropyl-3-aminopropylimidazolium hydrogen bromide.

6. The preparation method according to claim 3, characterized in that: The high-boiling-point solvents mentioned in step (3) are selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone; The mass-to-volume ratio of the quaternized arylpyridine polymer to the high-boiling solvent is (1:5)-(1:100) g / ml; The mass-to-volume ratio of the imidazole-functionalized graphene oxide to the high-boiling-point solvent is (1:20)-(1:200) g / ml; The mass ratio of imidazole-functionalized graphene oxide to quaternized arylpyridine polymer is 1:1000-1:10; The wet thickness of the dual-effect exchange membrane is 40-350 μm; The drying process employs vacuum drying, with a vacuum drying temperature of 50-200℃.

7. The preparation method according to claim 3, characterized in that: The drying temperature in step (6) is 40-195℃; The alkaline solution in step (7) is selected from one or more of NaOH, Na2CO3, NaHCO3, KOH, K2CO3, and KHCO3 solutions; the acid in the acidic solution is selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, and silicotungstic acid. The concentration of the alkaline solution is 0.1-10 mol / L; The concentration of the acidic solution is 0.01-5 mol / L; The soaking time is 12-100 hours; The drying temperature is 25-80℃.

8. The preparation method according to claim 3, characterized in that: The aryl hydrocarbon is selected from any one or more of the following structures:

9. The application of the dual-effect film electrode according to claim 1, characterized in that: The dual-effect membrane electrode is used as a membrane electrode in water electrolysis and fuel cells, or applied in anhydrous systems and high-temperature proton exchange membrane fuel cells with an operating temperature of 120-200℃.

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