Ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode and preparation method thereof
By covering the catalyst layer in the AEM electrolytic hydrogen production membrane electrode and distributing anionic nanorods, the transmission resistance problem caused by the random structure is solved, the performance and applicability of the electrode are improved, and the efficient and low-cost hydrogen production effect is achieved.
Patent Information
- Application Number
- CN202510156642.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-13
- Publication Date
- 2025-05-09
AI Technical Summary
The random structure of the existing AEM electrolytic hydrogen-making membrane electrode leads to large transmission resistance of electrons and ions, reducing the overall performance of the electrolytic cell. The traditional self-supporting electrode is not conducive to large-scale production and is not suitable for powder catalysts.
By covering the anode catalyst and cathode catalyst coating layers on both sides of the anion exchange membrane substrate, and evenly distributing several anion nanorods in the two layers, the composition and ratio of the cathode catalyst and anode catalyst coating solution were optimized, and membrane electrodes were prepared using porous templates and ultrasonic spraying technology.
The high-speed channel for ion transport in the membrane electrode is realized, the anion conduction efficiency and the active area of the catalytic layer are improved, the amount of catalyst is used, and the mechanical properties of the membrane are maintained, which is suitable for large-scale production.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of hydrogen production membrane electrodes, and in particular to an ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode and a preparation method thereof. Background Art
[0002] In the field of hydrogen production from renewable energy, countries around the world have proposed the concepts of renewable energy sources, power-to-gas and other renewable energy hydrogen production conversions and actively carried out demonstration projects. In order to promote the industrialization of large-scale renewable energy hydrogen production, solve the bottlenecks of low efficiency and high cost of current hydrogen production technology, and promote the practical application of large-scale renewable energy hydrogen production technology, anion exchange membrane (AEM) hydrogen production technology has attracted widespread attention due to its low cost, high efficiency and matching with fluctuating energy. In the AEM electrolyzer, the membrane electrode assembly is the core component of the electrolyzer. The membrane electrode assembly consists of an anion exchange membrane in the middle, anode and cathode catalyst layers on both sides of the membrane, and a gas diffusion layer (GDL) located outside the catalyst layer. AEM anode GDL mostly uses nickel foam and nickel felt, while AEM cathode GDL mostly uses nickel foam, nickel felt and carbon paper.
[0003] The random structure of the membrane electrode prepared for AEM water electrolysis brings huge resistance to the transmission of electrons and substances (ions, gases and liquids), thereby reducing the overall performance of the electrolyzer. In contrast, the ordered membrane electrode can achieve an orderly distribution of materials such as catalysts and ion conductors in the catalyst layer, expand the three-phase reaction interface, reduce mass transfer resistance, and improve catalyst utilization. In practical applications, the catalyst layer is required to have good thermal stability, chemical stability, sufficient mechanical strength, and high ionic conductivity. The trade-off between the conductivity and mechanical stability of the catalyst layer mainly depends on the ion exchange capacity (IEC), the type of functional groups, and the microstructure of the membrane. The increase in IEC produces a better hydrated hydroxyl transport network, but at the same time leads to excessive water swelling, resulting in an unstable catalyst coating structure. Traditionally, the use of ionomers with a relatively low proportion of cationic functional groups can reduce the swelling rate, but at the same time reduce the ionic conductivity in the catalyst layer. Although the integrated membrane electrode technology can improve the ionic conductivity in the catalyst layer, the self-supporting electrode is not conducive to large-scale production, and this technology is not suitable for powder catalysts. Summary of the invention
[0004] In order to improve the above technical problems, the present application provides an ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode and a preparation method thereof.
[0005] An ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode adopts the following technical solution: An ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode, comprising: Anion exchange membrane matrix; An anode catalyst coating layer, wherein the anode catalyst coating layer is coated on one side of the anion exchange membrane substrate after spraying with an anode catalyst coating liquid; A cathode catalyst coating layer, wherein the cathode catalyst coating layer is coated on one side of the anion exchange membrane substrate after spraying a cathode catalyst coating liquid; The anode catalyst coating layer and the cathode catalyst coating layer are both coated with a plurality of anion nanorods.
[0006] Through the above technical scheme, the present application is through the anion exchange membrane substrate on both sides are coated with anode catalyst coating layer and cathode catalyst coating layer, and these two layers are coated with a number of anion nanorods. Anion nanorods provide a high-speed channel for ion transmission in the membrane electrode. The present invention grows ordered nano proton conductors on both sides of the membrane electrode, which greatly improves the anion conduction efficiency, while not affecting the mechanical properties of the membrane. Suitable ion channels, and at the same time, effectively increase the active area of the catalyst layer, can greatly reduce the amount of catalyst used.
[0007] Furthermore, the cathode catalyst coating solution includes the following substances in parts by weight: 2-4 parts of cathode catalyst; 100-200 parts of anionic nanorods; 200-400 parts of isopropyl alcohol; The mass ratio of the anion nanorods to the cathode catalyst is 3:7.
[0008] Through the above technical solution, the present application optimizes the specific composition and ratio of the cathode catalyst coating liquid, and can provide sufficient active sites to catalyze the hydrogen generation reaction through an appropriate amount of cathode catalyst. The addition of anionic nanorod solution not only provides additional active centers, but also enhances the adhesion of the catalyst, making it more firmly fixed on the anion exchange membrane. Isopropanol as a solvent helps to adjust the viscosity of the solution and ensure the uniform distribution of the liquid during the spraying process. The present application improves the electron transfer efficiency through the nanorods in the anionic nanorod solution.
[0009] Furthermore, the cathode catalyst includes any one of a Pt-based cathode catalyst, a Ru-based cathode catalyst, and a Ni-based cathode catalyst, and the cathode catalyst loading on the cathode catalyst coating layer is 0.5-0.8 mg / cm 2 .
[0010] Through the above technical scheme, the present application selects Pt-based cathode catalysts, Ru-based cathode catalysts, and Ni-based cathode catalysts, and optimizes their loading on the cathode catalyst coating layer, while effectively reducing costs and providing sufficient active sites. In addition, the metal elements in the cathode catalyst can effectively activate the hydrogen-oxygen bonds in the water molecules, reduce the reaction activation energy, and accelerate the generation of hydrogen. The carbon carrier provides a large specific surface area and good electrical conductivity, which is conducive to the rapid transfer of electrons and the diffusion of reactants. The selection of loading is based on theoretical calculations and experimental verification, ensuring the optimal distribution of the catalyst on the electrode surface, thereby achieving efficient electrochemical reactions. Appropriate control of the loading also helps to prevent the aggregation of catalyst particles and maintain their dispersibility and activity.
[0011] Furthermore, the anode catalyst coating solution includes the following substances in parts by weight: 2-4 parts of anode catalyst; 100-200 parts of anionic nanorods; 200-400 parts of isopropyl alcohol; The mass ratio of the anion nanorods to the anode catalyst is 3:17.
[0012] Through the above technical solution, the present application optimizes the specific composition and ratio of the cathode catalyst coating liquid, which helps to form more active interfaces and promote the dissociation of water molecules and the precipitation of oxygen. Anionic nanorods, as a conductive material, can improve the conductivity of the catalyst layer, reduce the charge transfer resistance, and improve the reaction efficiency. At the same time, the appropriate amount of solvent (isopropanol) ensures the fluidity of the coating liquid, facilitates the subsequent spraying process, and finally achieves a uniform and dense catalyst coating layer.
[0013] Furthermore, the anode catalyst comprises any one of NiFe oxide, hydroxide, and oxyhydroxide anode materials, and the loading of the anode catalyst on the anode catalyst coating layer is 1-3 mg / cm 2 .
[0014] Through the above technical scheme, the present application optimizes the loading of the anode catalyst on the anode catalyst coating layer, which not only ensures sufficient catalytic activity, but also avoids the cost increase caused by excessive use of catalysts. At the same time, elements such as nickel and iron in NiFe oxide, hydroxide, and hydroxy oxide anode materials can effectively activate the oxygen-hydrogen bonds in water molecules, reduce the reaction activation energy, and accelerate the generation of oxygen. Its layered structure provides a large specific surface area and abundant active sites, which is conducive to the adsorption and desorption of reaction intermediates. The selection of loading is based on theoretical calculations and experimental verification, which ensures the optimal distribution of the catalyst on the electrode surface, thereby achieving efficient electrochemical reactions.
[0015] In the second aspect, the present application provides a method for preparing an ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode, using the following technical scheme: A method for preparing an ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode comprises the following preparation steps: The porous template is placed in a reaction device, vacuumed and an anion exchange resin solution is added, filtered to fill the holes of the porous template with the ion exchange resin, and vacuum dried to prepare a template material; the template material is placed in a dissolving solution, heated and kept warm, and an anion nanorod solution is collected; After the anion nanorod solution is prepared into a cathode catalyst coating liquid and an anode catalyst coating liquid according to a formula, the cathode catalyst coating liquid and the anode catalyst coating liquid are ultrasonically sprayed onto both sides of an anion exchange membrane substrate respectively, thereby preparing an ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode.
[0016] Through the above technical scheme, the present application uses a porous template to provide an ideal growth environment for anion exchange resin, and adopts a negative pressure suction method to form an orderly arranged nanorod structure in the pores. This structure not only increases the specific surface area of the electrode, but also improves the electron transfer efficiency through the conductivity of the nanorods. During the collection process of the anion nanorod solution, the heating and heat preservation treatment promote the cross-linking reaction of the resin molecular chain to form a stable nanorod structure. The ultrasonic spraying technology uses high-frequency vibration to atomize the liquid into tiny particles, ensuring the uniform distribution of the catalyst on the membrane, thereby achieving efficient electrochemical reaction.
[0017] At the same time, the ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode used in the present application, due to the limitation of the smaller diameter of the nanowires, changes the anion transmission channel from the anisotropy in the plane and the vertical plane to the isotropy along the direction of the nanowires, and as the diameter of the nanowires gradually decreases, this isotropic effect is further enhanced, which is more conducive to the transmission of anions in the catalytic layer and reduces the limitation of anion conductivity on the improvement of membrane electrode performance.
[0018] Furthermore, the porous template is an aluminum oxide porous template, and the dissolving solution is a potassium hydroxide solution.
[0019] Furthermore, a method for preparing an ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode also includes a porous template pretreatment step, and the porous template pretreatment step adopts the following technical scheme: The porous template is washed with ethanol, and then the surface of the template is treated with a sodium dodecyl sulfate solution, and vacuum dried to complete the porous template pretreatment step.
[0020] The technical solution of this application first removes organic pollutants on the surface of the template through physical cleaning by ethanol washing, thereby ensuring its surface cleanliness. The anion groups in the sodium dodecyl sulfate solution can interact with the hydroxyl groups on the surface of the alumina to form a hydrophobic film, which improves the wettability and adsorption properties of the template. The vacuum drying treatment accelerates the evaporation of water by reducing the ambient pressure, ensuring the complete drying of the template. These pretreatment steps work together to provide good conditions for the uniform filling and curing of the anion exchange resin, thereby improving the quality and performance of the membrane electrode.
[0021] Furthermore, the anion exchange resin solution includes any one of a quaternary ammonium polysulfone ionomer resin solution, a polyarylpiperidine ionomer resin solution, a polynorbornene ionomer resin solution, and a polybenzimidazole ionomer resin solution.
[0022] Through the above technical solution, the polyarylpiperidine anion exchange resin used in this application achieves selective conduction by exchanging ions with OH⁻ ions through the quaternary ammonium groups on its molecular chain. The high ion exchange capacity and low resistance characteristics of this resin also make it perform well in the process of hydrogen production by electrolysis of water. These characteristics work together to ensure the high efficiency and stability of the membrane electrode.
[0023] Furthermore, the diameter of a single anion exchange resin in the anion nanorod solution is 350-450 nm, and the length is 35-60 μm.
[0024] Through the above technical solution, the present application optimizes the specific size of the anion nanorods, maximizes the surface area and conductivity of the nanorods, and thus improves the catalytic performance and conductive performance of the electrode. The diameter and length of the nanorods have an important influence on their performance. The smaller diameter gives the nanorods a higher specific surface area, increases the number of active sites, and promotes the adsorption and conversion of reactants. The longer length helps to form a continuous conductive channel, reduces the charge transfer resistance, and improves the electron transfer efficiency. This size design not only enhances the activity of the catalyst, but also improves the overall conductivity of the membrane electrode, thereby improving the efficiency of hydrogen production by water electrolysis.
[0025] In summary, this application has the following beneficial effects: First, the present invention is to coat the two sides of the anion exchange membrane substrate with an anode catalyst coating layer and a cathode catalyst coating layer, and both layers are coated with a number of anion nanorods. The anion nanorods provide a high-speed channel for ion transport in the membrane electrode. The present invention greatly improves the anion conduction efficiency by growing ordered nano proton conductors on both sides of the membrane electrode, while not affecting the mechanical properties of the membrane. Suitable ion channels, and at the same time, effectively increase the active area of the catalyst layer, which can greatly reduce the amount of catalyst used.
[0026] Second, the porous template used in this application provides an ideal growth environment for the anion exchange resin, so that it forms an orderly arranged nanorod structure in the pores. This structure not only increases the specific surface area of the electrode, but also improves the electron transfer efficiency through the conductivity of the nanorods. During the collection process of the anion nanorod solution, the heating and heat preservation treatment promote the cross-linking reaction of the resin molecular chain to form a stable nanorod structure. The ultrasonic spraying technology uses high-frequency vibration to atomize the liquid into tiny particles, ensuring the uniform distribution of the catalyst on the membrane, thereby achieving efficient electrochemical reaction.
[0027] At the same time, the ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode used in the present application, due to the limitation of the smaller diameter of the nanowires, changes the anion transmission channel from the anisotropy in the plane and the vertical plane to the isotropy along the direction of the nanowires, and as the diameter of the nanowires gradually decreases, this isotropic effect is further enhanced, which is more conducive to the transmission of anions in the catalytic layer and reduces the limitation of anion conductivity on the improvement of membrane electrode performance.
[0028] Third, the present application optimizes the specific composition and ratio of the cathode catalyst coating liquid and the anode catalyst coating liquid. The appropriate amount of cathode catalyst and anode catalyst can provide sufficient active sites to catalyze the hydrogen generation reaction. The addition of the anion nanorod solution not only provides additional active centers, but also enhances the adhesion of the catalyst, making it more firmly fixed on the anion exchange membrane. Isopropanol as a solvent helps to adjust the viscosity of the solution and ensure the uniform distribution of the liquid during the spraying process. The present application improves the electron transfer efficiency through the nanorods in the anion nanorod solution. BRIEF DESCRIPTION OF THE DRAWINGS
[0029] Figure 1 Schematic diagram of the traditional catalyst layer structure; Figure 2 This is a schematic diagram of the structure of the ion-ordered catalyst layer in Example 1 of the present application. DETAILED DESCRIPTION
[0030] The present application is further described in detail below with reference to the embodiments.
[0031] In the examples of the present application, the raw materials and instruments used are as follows, but not limited thereto: The present application is further described in detail below with reference to the embodiments.
[0032] Example 1 The porous alumina template with a pore size of 400 nm, a thickness of 50 μm, and a diameter of 50 mm was cleaned with ethanol, and then the template was surface treated with a 1% mass fraction of sodium dodecyl sulfate solution, and the template was placed in a culture dish with the pores facing upward. The culture dish was placed in a vacuum drying oven and dried at 50°C for later use.
[0033] Place the treated alumina template on a glass sand core suction bottle, start the vacuum pump to make the suction bottle in a negative pressure state, and use a pipette to add 2ml of 5% polyaryl piperidine anion exchange resin solution. After repeatedly adding the solution for 5 times, the pores in the alumina template are filled with anion exchange resin. After taking out the alumina template, put it in a vacuum drying oven and dry it at 50℃ for 10h.
[0034] The alumina template was placed in 2 ml of 6 mol / L KOH solution, then kept in an oven at 60 degrees for 2 hours and taken out. The alumina template was completely dissolved, and several single anionic nanorods with a diameter of 400 nm and a length of 50 μm were collected and retained in the solution to prepare an anionic nanorod solution.
[0035] 10 mg of Pt / C cathode catalyst was mixed with 0.5 ml of anion nanorod solution and 1 ml of isopropanol in an ice bath for 1 h, and then ultrasonically sprayed on the surface of the anion exchange membrane. The Pt loading was 0.5 mg / cm 2 The mass ratio of anion exchange resin to catalyst is 30:70, and the loading of cathode catalyst on the cathode catalyst coating layer is 0.5 mg / cm 2 .
[0036] 20 mg NiFeOOH(F) powder anode (ACS Catal. 2021, 11 (1), 264-270) was mixed with 0.45 ml of anion nanorod solution and 1 ml of isopropanol in an ice bath for 1 h, and then ultrasonically sprayed on the other surface of the anion exchange membrane. The anode catalyst loading was 2 mg / cm 2 The mass ratio of anion exchange resin to catalyst is 15:85, and the loading of anode catalyst on the anode catalyst coating layer is 2 mg / cm 2 After spraying, a double-sided CCM membrane electrode is obtained, and the effective area of the membrane electrode is 5cm 2 .
[0037] Example 2 The porous alumina template with a pore size of 400 nm, a thickness of 50 μm, and a diameter of 50 mm was cleaned with ethanol, and then the template was surface treated with a 1% mass fraction of sodium dodecyl sulfate solution, and the template was placed in a culture dish with the pores facing upward. The culture dish was placed in a vacuum drying oven and dried at 50°C for later use.
[0038] Place the treated alumina template on a glass sand core suction bottle, start the vacuum pump to make the suction bottle in a negative pressure state, and use a pipette to add 2ml of 5% polyaryl piperidine anion exchange resin solution. After repeatedly adding the solution for 5 times, the pores in the alumina template are filled with anion exchange resin. After taking out the alumina template, put it in a vacuum drying oven and dry it at 50℃ for 10h.
[0039] The alumina template was placed in 2 ml of 6 mol / L KOH solution, then kept in an oven at 60 degrees for 2 hours and taken out. The alumina template was completely dissolved, and several single anionic nanorods with a diameter of 400 nm and a length of 50 μm were collected and retained in the solution to prepare an anionic nanorod solution.
[0040] 15 mg of Pt / C cathode catalyst was mixed with 0.75 ml of anion nanorod solution and 1.5 ml of isopropanol in an ice bath for 1 h, and then ultrasonically sprayed on the surface of the anion exchange membrane. The Pt loading was 0.75 mg / cm 2 The mass ratio of anion exchange resin to catalyst is 30:70, and the loading of cathode catalyst on the cathode catalyst coating layer is 0.65 mg / cm 2 .
[0041] 20 mg NiFeOOH(F) powder anode (ACS Catal. 2021, 11 (1), 264-270) was mixed with 0.45 ml of anion nanorod solution and 1 ml of isopropanol in an ice bath for 1 h, and then ultrasonically sprayed on the other surface of the anion exchange membrane. The anode catalyst loading was 2 mg / cm 2 The mass ratio of anion exchange resin to catalyst is 15:85, and the loading of anode catalyst on the anode catalyst coating layer is 2 mg / cm 2 After spraying, a double-sided CCM membrane electrode is obtained, and the effective area of the membrane electrode is 5cm 2 .
[0042] Example 3 The porous alumina template with a pore size of 400 nm, a thickness of 50 μm, and a diameter of 50 mm was cleaned with ethanol, and then the template was surface treated with a 1% mass fraction of sodium dodecyl sulfate solution, and the template was placed in a culture dish with the pores facing upward. The culture dish was placed in a vacuum drying oven and dried at 50°C for later use.
[0043] Place the treated alumina template on a glass sand core suction bottle, start the vacuum pump to make the suction bottle in a negative pressure state, and use a pipette to add 2ml of 5% polyaryl piperidine anion exchange resin solution. After repeatedly adding the solution for 5 times, the pores in the alumina template are filled with anion exchange resin. After taking out the alumina template, put it in a vacuum drying oven and dry it at 50℃ for 10h.
[0044] The alumina template was placed in 2 ml of 6 mol / L KOH solution, then kept in an oven at 60 degrees for 2 hours and taken out. The alumina template was completely dissolved, and several single anionic nanorods with a diameter of 400 nm and a length of 50 μm were collected and retained in the solution to prepare an anionic nanorod solution.
[0045] 20 mg of Pt / C cathode catalyst was mixed with 1 ml of anion nanorod solution and 2 ml of isopropanol in an ice bath for 1 h, and then ultrasonically sprayed on the surface of the anion exchange membrane. The Pt loading was 1 mg / cm 2 The mass ratio of anion exchange resin to catalyst is 30:70, and the loading of cathode catalyst on the cathode catalyst coating layer is 0.8 mg / cm 2 .
[0046] 20 mg NiFeOOH(F) powder anode (ACS Catal. 2021, 11 (1), 264-270) was mixed with 0.45 ml of anion nanorod solution and 1 ml of isopropanol in an ice bath for 1 h, and then ultrasonically sprayed on the other surface of the anion exchange membrane. The anode catalyst loading was 2 mg / cm 2 The mass ratio of anion exchange resin to catalyst is 15:85, and the loading of anode catalyst on the anode catalyst coating layer is 2 mg / cm 2 After spraying, a double-sided CCM membrane electrode is obtained, and the effective area of the membrane electrode is 5cm 2 .
[0047] Example 4 The porous alumina template with a pore size of 400 nm, a thickness of 50 μm, and a diameter of 50 mm was cleaned with ethanol, and then the template was surface treated with a 1% mass fraction of sodium dodecyl sulfate solution, and the template was placed in a culture dish with the pores facing upward. The culture dish was placed in a vacuum drying oven and dried at 50°C for later use.
[0048] The treated alumina template was placed on a glass sand core suction flask, the vacuum pump was started to put the suction flask in a negative pressure state, and 2 ml of a 5% by mass polynorbornene anion exchange resin solution was added using a pipette.
[0049] The conditions for filtration and drying of the filled resin are the same as those in Example 1.
[0050] The alumina template was placed in 2 ml of 5% by mass phosphoric acid solution and treated for 2 hours to corrode the alumina template, leaving the anionic nanorods in the solution.
[0051] 10 mg of RuCu / C cathode catalyst was ultrasonically dispersed with 0.5 ml of anion nanorod solution and 1 ml of isopropanol in an ice bath for 1 h, and then ultrasonically sprayed on the surface of the anion exchange membrane. The mass ratio of anion exchange resin to catalyst was 30:70, and the loading of cathode catalyst on the cathode catalyst coating layer was 1 mg / cm 2 .
[0052] 20 mg NiFeO x The powder anode was ultrasonically dispersed with 0.45 ml of anion nanorod solution and 1 ml of isopropanol in an ice bath for 1 h, and then ultrasonically sprayed on the other side of the anion exchange membrane. The mass ratio of anion exchange resin to catalyst was 15:85, and the loading of anode catalyst on the anode catalyst coating layer was 2 mg / cm 2 .
[0053] Example 5 The porous alumina template with a pore size of 400 nm, a thickness of 50 μm, and a diameter of 50 mm was cleaned with ethanol, and then the template was surface treated with a 1% mass fraction of sodium dodecyl sulfate solution, and the template was placed in a culture dish with the pores facing upward. The culture dish was placed in a vacuum drying oven and dried at 50°C for later use.
[0054] The treated alumina template was placed on a glass sand core suction flask, the vacuum pump was started to put the suction flask in a negative pressure state, and 2 ml of a 5% by mass polynorbornene anion exchange resin solution was added using a pipette.
[0055] The conditions for filtration and drying of the filled resin are the same as those in Example 1.
[0056] The alumina template was placed in 2 ml of 5% by mass phosphoric acid solution and treated for 2 hours to corrode the alumina template, leaving the anionic nanorods in the solution.
[0057] 10 mg of RuCu / C cathode catalyst was ultrasonically dispersed with 0.5 ml of anion nanorod solution and 1 ml of isopropanol in an ice bath for 1 h, and then ultrasonically sprayed on the surface of the anion exchange membrane. The mass ratio of anion exchange resin to catalyst was 30:70, and the loading of cathode catalyst on the cathode catalyst coating layer was 1 mg / cm 2 .
[0058] 30 mg NiFeO xThe powder anode was ultrasonically dispersed with 0.62 ml of anion nanorod solution and 1.5 ml of isopropanol in an ice bath for 1 h, and then ultrasonically sprayed on the other side of the anion exchange membrane. The mass ratio of anion exchange resin to catalyst was 15:85, and the loading of anode catalyst on the anode catalyst coating layer was 3 mg / cm 2 .
[0059] Example 6 The porous alumina template with a pore size of 400 nm, a thickness of 50 μm, and a diameter of 50 mm was cleaned with ethanol, and then the template was surface treated with a 1% mass fraction of sodium dodecyl sulfate solution, and the template was placed in a culture dish with the pores facing upward. The culture dish was placed in a vacuum drying oven and dried at 50°C for later use.
[0060] The treated alumina template was placed on a glass sand core suction flask, the vacuum pump was started to put the suction flask in a negative pressure state, and 2 ml of a 5% by mass polynorbornene anion exchange resin solution was added using a pipette.
[0061] The conditions for filtration and drying of the filled resin are the same as those in Example 1.
[0062] The alumina template was placed in 2 ml of 5% by mass phosphoric acid solution and treated for 2 hours to corrode the alumina template, leaving the anionic nanorods in the solution.
[0063] 10 mg of RuCu / C cathode catalyst was ultrasonically dispersed with 0.5 ml of anion nanorod solution and 2 ml of isopropanol in an ice bath for 1 h, and then ultrasonically sprayed on the surface of the anion exchange membrane. The mass ratio of anion exchange resin to catalyst was 30:70, and the loading of cathode catalyst on the cathode catalyst coating layer was 1 mg / cm 2 .
[0064] 40 mg NiFeOx powder anode was ultrasonically dispersed with 0.9 ml anion nanorod solution and 4.5 ml isopropanol in an ice bath for 1 h, and then ultrasonically sprayed on the other side of the anion exchange membrane. The mass ratio of anion exchange resin to catalyst was 15:85, and the loading of anode catalyst on the anode catalyst coating layer was 4 mg / cm 2 .
[0065] Performance Testing The performance of the electrodes prepared in Examples 1-6 was tested: The sealing gasket, anode porous transport layer (nickel foam), membrane electrode, cathode gas transport layer (carbon paper), flow channel plate and end plate are assembled in sequence to form an AEM electrolytic cell.
[0066] Test parameters: torque 3N.m, 1M KOH solution supplied to the anode, alkali solution flow rate 30ml / min, no liquid supplied to the cathode, test temperature 60℃, 0.1A / cm2, 0.5A / cm 2 and 1A / cm 2 Activate for 20 min, then start from 0.1A / cm 2 The current density was gradually increased to 2A / cm 2 , step size is 0.1A / cm 2 , hold each step for 30 s, and record the voltage value at each current density.
[0067] The details are shown in Table 1 below: Table 1 Performance test table
[0068] From the above embodiments 1-6, Figure 1 From the results in Table 1, we can find that: First, from Figure 1 It can be found that in the schematic diagram of the traditional catalyst layer structure, short and curved anionic polymers (100nm-2μm) are distributed in the catalyst layer to form hydroxide ion transmission channels. The transmission path is long and the ion conduction efficiency is low.
[0069] And from Figure 2 Schematic diagram of the ion-ordered catalyst layer structure. Long and ordered anion nanorods (35μm-60μm) are distributed in the catalyst layer to form hydroxide ion transmission channels. The transmission path is short and the ion conduction efficiency is high.
[0070] Combining Examples 1-6 and the data in Table 1 can further illustrate: The present application is to coat the two sides of the anion exchange membrane substrate with an anode catalyst coating layer and a cathode catalyst coating layer, and both layers are coated with a number of anion nanorods. The anion nanorods provide a high-speed channel for ion transmission in the membrane electrode; at the same time, the application optimizes the specific composition and ratio of the cathode catalyst coating liquid and the anode catalyst coating liquid, and can provide sufficient active sites to catalyze the hydrogen generation reaction through the appropriate amount of cathode catalyst and anode catalyst. The addition of the anion nanorod solution not only provides additional active centers, but also enhances the adhesion of the catalyst, making it more firmly fixed on the anion exchange membrane. Isopropanol as a solvent helps to adjust the viscosity of the solution and ensure the uniform distribution of the liquid during the spraying process. The present application improves the electron transfer efficiency through the nanorods in the anion nanorod solution.
[0071] The present invention has been described in detail above in conjunction with specific implementations and exemplary examples, but these descriptions cannot be understood as limiting the present invention. Those skilled in the art understand that, without departing from the spirit and scope of the present invention, a variety of equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its implementation methods, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be subject to the attached claims.
[0072] All publications, patent applications, patents and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings conventionally understood by those skilled in the art. In the event of a conflict, the definition in this specification shall prevail.
[0073] When this specification uses the prefix "well-known to those skilled in the art", "prior art" or similar terms to introduce materials, substances, methods, steps, devices or components, etc., the objects introduced by the prefix cover those commonly used in the art when this application is filed, but also include those that are not commonly used at present but will become recognized in the art as being suitable for similar purposes.
[0074] In the context of the present specification, any matters or items not mentioned are directly applicable to those known in the art without any changes except those explicitly stated.
Claims
1. An ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode, characterized in that: include: Anion exchange membrane matrix; An anode catalyst coating layer, wherein the anode catalyst coating layer is coated on one side of the anion exchange membrane substrate after spraying with an anode catalyst coating liquid; A cathode catalyst coating layer, wherein the cathode catalyst coating layer is coated on one side of the anion exchange membrane substrate after spraying a cathode catalyst coating liquid; The anode catalyst coating layer and the cathode catalyst coating layer are both coated with a plurality of anion nanorods.
2. The ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode according to claim 1, characterized in that: The cathode catalyst coating solution comprises the following materials in parts by weight: 2-4 parts of cathode catalyst; 100-200 parts of anionic nanorods; 200-400 parts of isopropyl alcohol; The mass ratio of the anion nanorods to the cathode catalyst is 3:
7.
3. The ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode according to claim 1, characterized in that: The cathode catalyst comprises any one of a Pt-based cathode catalyst, a Ru-based cathode catalyst, and a Ni-based cathode catalyst, and the loading amount of the cathode catalyst on the cathode catalyst coating layer is 0.5-0.8 mg / cm 2 .
4. The ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode according to claim 1, characterized in that: The anode catalyst coating solution comprises the following substances in parts by weight: 2-4 parts of anode catalyst; 100-200 parts of anionic nanorods; 200-400 parts of isopropyl alcohol; The mass ratio of the anion nanorods to the anode catalyst is 3:
17.
5. The ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode according to claim 4, characterized in that: The anode catalyst comprises any one of NiFe oxide, hydroxide, and hydroxy oxide anode materials, and the loading amount of the anode catalyst on the anode catalyst coating layer is 1-3 mg / cm 2 .
6. The method for preparing an ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode according to any one of claims 1 to 5, characterized in that: The method comprises the following preparation steps: The porous template is placed in a reaction device, vacuumed and an anion exchange resin solution is added, filtered to fill the holes of the porous template with the ion exchange resin, and vacuum dried to prepare a template material; the template material is placed in a dissolving solution, heated and kept warm, and an anion nanorod solution is collected; After the anion nanorod solution is prepared into a cathode catalyst coating liquid and an anode catalyst coating liquid according to a formula, the cathode catalyst coating liquid and the anode catalyst coating liquid are ultrasonically sprayed onto both sides of an anion exchange membrane substrate respectively, thereby preparing an ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode.
7. The method for preparing an ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode according to claim 6, characterized in that: The porous template is an aluminum oxide porous template, and the dissolving solution is a potassium hydroxide solution.
8. The method for preparing an ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode according to claim 7, characterized in that: The porous template pretreatment step is also included, and the porous template pretreatment step adopts the following technical scheme: The porous template is washed with ethanol, and then the surface of the template is treated with a sodium dodecyl sulfate solution, and vacuum dried to complete the porous template pretreatment step.
9. The method for preparing an ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode according to claim 6, characterized in that: The anion exchange resin solution includes any one of a quaternary ammonium polysulfone ionomer resin solution, a polyarylpiperidine ionomer resin solution, a polynorbornene ionomer resin solution, and a polybenzimidazole ionomer resin solution.
10. The method for preparing an ion-ordered anion exchange membrane water electrolysis hydrogen production membrane electrode according to claim 6, characterized in that: The diameter of a single anion exchange resin in the anion nanorod solution is 350-450 nm, and the length is 35-60 μm.