CN116219475A - Anode catalyst slurry for hydrogen production by water electrolysis of proton exchange membrane, membrane electrode and application - Google Patents

Anode catalyst slurry for hydrogen production by water electrolysis of proton exchange membrane, membrane electrode and application Download PDF

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CN116219475A
CN116219475A CN202310156067.3A CN202310156067A CN116219475A CN 116219475 A CN116219475 A CN 116219475A CN 202310156067 A CN202310156067 A CN 202310156067A CN 116219475 A CN116219475 A CN 116219475A
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catalyst slurry
catalyst
proton exchange
iridium
exchange membrane
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王功名
王依帆
黄婷
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention provides anode catalyst slurry for hydrogen production by water electrolysis of a proton exchange membrane, a membrane electrode and application thereof. The anode catalyst slurry comprises a core-shell catalyst of iridium supported metal oxide, a dispersing agent, a binder and a solvent. Wherein the core-shell catalyst is modified with-NH on the surface 2 and/or-SH metal oxide as the inner core and iridium nanoparticles as the outer shell. The invention takes the iridium-supported low iridium catalyst of metal oxide as a main body, can improve the utilization rate of noble metal iridium, reduce the economic cost, and is matched with a binder with a specific proportion,The solvent and the dispersing agent are prepared into catalyst slurry, and the catalyst slurry is uniformly distributed on the proton exchange membrane by an ultrasonic spraying method, so that more electrochemical active surfaces can be exposed, the catalyst slurry is better contacted with the gas diffusion layer, moisture, electrons and heat are effectively transferred, and the final water electrolysis device has good catalytic activity.

Description

Anode catalyst slurry for hydrogen production by water electrolysis of proton exchange membrane, membrane electrode and application
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to anode catalyst slurry for producing hydrogen by water electrolysis of a proton exchange membrane, a membrane electrode and application thereof.
Background
Proton Exchange Membrane Water Electrolysis (PEMWE) becomes a core technology of future hydrogen economy by virtue of high power density and excellent loading capacity, and provides a new strategy for sustainable hydrogen production in a large-scale energy storage environment. The most important element in PEMWE is a Membrane Electrode Assembly (MEA), which mainly consists of a proton exchange membrane positioned in the middle, a cathode catalytic layer, an anode catalytic layer, a polar plate and a gas diffusion layer positioned outside the two catalytic layers, wherein the cathode catalytic layer, the anode catalytic layer and the polar plate are positioned on two sides of the proton exchange membrane and are in close contact with the proton exchange membrane. When the water electrolysis device works, the water generates and releases oxygen under the catalysis of the anode catalyst, and generates and releases hydrogen under the catalysis of the cathode catalyst. The anode catalytic layer of the water electrolysis device is provided with a selected catalyst material and a state of catalyst slurry, which have important influences on the microstructure of the formed catalytic layer.
The anode catalyst layer is prepared by mixing anode catalyst with some additives to prepare catalyst slurry, and coating and transferring the catalyst slurry onto a proton exchange membrane, wherein the main methods include a knife coating method, an ultrasonic spraying method, a screen printing method, a sputtering method or an electrochemical deposition method. The ultrasonic spraying method has the advantages of saving the catalyst consumption, high catalyst dispersity and uniform catalyst arrangement, is widely used for preparing the catalyst layer, is simple to operate, has high automation degree, and is suitable for batch production of the MEA. However, the state of the catalyst slurry used in the ultrasonic spraying method directly affects the dispersion of the catalyst layer, thereby affecting the performance of the water electrolysis apparatus.
Disclosure of Invention
In view of the above, the invention aims to provide anode catalyst slurry, a membrane electrode and application for producing hydrogen by electrolyzing water through a proton exchange membrane. The anode catalyst slurry adopts a specific low iridium catalyst as a main body, and is matched with a binder, a solvent and a dispersing agent in a specific proportion, and the catalyst can be uniformly distributed on a proton exchange membrane by an ultrasonic spraying method, so that the finally obtained water electrolysis device has good catalytic activity.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an anode catalyst slurry for producing hydrogen by water electrolysis of a proton exchange membrane, comprising a core-shell catalyst of iridium supported metal oxide, a dispersant, a binder and a solvent.
Preferably, the core-shell catalyst takes metal oxide as an inner core and metal iridium nano particles as an outer shell. Preferably, the metal oxide comprises any one or more of titanium dioxide, niobium pentoxide, tantalum oxide, tungsten oxide or tin oxide.
Preferably, the metal oxide surface is modified with a functional group comprising-NH 2 and/or-SH.
Preferably, the mass ratio of the solvent to the core-shell catalyst to the dispersant to the binder is 1 (0.01-0.05): 0.01 (0.01-1: 0.05).
Preferably, the dispersant is selected from polyethylene glycol octyl phenyl ether.
Preferably, the binder is selected from any one or more of perfluorosulfonic acid resin, polytetrafluoroethylene or polyvinylidene fluoride-hexafluoropropylene copolymer.
Preferably, the solvent is selected from any one or more of isopropanol, ethanol, nitrogen-methylpyrrolidone, nitrogen-dimethylformamide, dimethyl sulfoxide or glycerol.
In a second aspect, the invention provides a membrane electrode for producing hydrogen by water electrolysis of a proton exchange membrane, comprising an anode catalytic layer, a cathode catalytic layer and a proton exchange membrane positioned between the anode catalytic layer and the cathode catalytic layer. The anode catalytic layer is prepared from the anode catalyst slurry in the technical scheme through an ultrasonic spraying method.
Preferably, the proton exchange membrane is selected from a Nafion membrane or a Gore membrane.
In a third aspect, the present invention provides a method for preparing a membrane electrode, comprising the steps of:
and respectively spraying anode catalyst slurry and cathode catalyst slurry on two sides of the proton exchange membrane by adopting an ultrasonic spraying method to obtain the membrane electrode.
Preferably, the anode catalyst slurry comprises a core-shell catalyst of iridium supported metal oxide, a dispersant, a binder, and a solvent. The core-shell catalyst takes metal oxide as an inner core and metal iridium nano particles as an outer shell, wherein the metal oxide comprises any one or more of titanium dioxide, niobium pentoxide, tantalum oxide, tungsten oxide or tin oxide.
Preferably, the cathode catalyst slurry includes a Pt/C catalyst, a dispersant, a binder, and a solvent.
Preferably, the discharge flow rate of the ultrasonic spraying is 0.5-1.0 mL/min.
Preferably, the spraying amount of the anode catalyst slurry is 0.3-0.8 mg/cm 2 ；
Preferably, the spraying amount of the cathode catalyst slurry is 0.2-0.4 mg/cm 2 。
In a fourth aspect, the invention provides a device for producing hydrogen by water electrolysis through a proton exchange membrane, which comprises a membrane electrode related in the technical scheme.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an anode catalyst slurry for hydrogen production by water electrolysis of a proton exchange membrane, which takes a low iridium catalyst of iridium-supported metal oxide as a main body, can improve the utilization rate of noble metal iridium and reduce the economic cost, is prepared into catalyst slurry by matching with a binder, a solvent and a dispersing agent in a specific proportion, and uniformly distributes the catalyst slurry on the proton exchange membrane by an ultrasonic spraying method, so that more electrochemical active surfaces can be exposed, and the catalyst slurry is better contacted with a gas diffusion layer, effectively transfers moisture, electrons and heat, and ensures that a final water electrolysis device has good catalytic activity.
Drawings
FIG. 1 is a TEM image of the low iridium catalyst obtained in preparation example 1;
FIG. 2 is a graph showing comparison of electrolytic water curves of the membrane electrodes obtained in examples 1 to 2 and comparative example 1.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to improve the catalytic performance of a proton exchange membrane water electrolysis hydrogen production device in the prior art and further improve the hydrogen production efficiency, the invention provides anode catalyst slurry for producing hydrogen by using the proton exchange membrane water electrolysis, which comprises a core-shell catalyst of iridium supported metal oxide, a dispersing agent, a binder and a solvent.
The core-shell catalyst takes metal oxide as an inner core and metal iridium nano particles as an outer shell, wherein the metal oxide comprises any one or more of titanium dioxide, niobium pentoxide, tantalum oxide, tungsten oxide or tin oxide. The surface of the metal oxide is modified with functional groups, and the functional groups comprise-NH 2 and/or-SH. The invention is realized by using-NH 2 and/or-SH, so that the metal oxide and the metal iridium are coordinated, thereby obtaining the catalyst with the core-shell structure. The mass ratio of the metal oxide to the iridium nanoparticle is 1 (0.6-1.5). The particle diameter of the iridium nanoparticle is 4-8 nm, preferably 5-6 nm.
In some embodiments of the invention, the core-shell catalyst may be prepared according to the following method:
mixing metal oxide with a functional group modified on the surface, an iridium source, a solvent and a surfactant, performing solvothermal reaction in an inert atmosphere at 80-120 ℃, and performing heat treatment on the obtained product in the inert atmosphere at 200-500 ℃ to obtain the core-shell catalyst.
Wherein the metal oxide with the surface modified with the functional group is prepared by reacting the metal oxide with molecules containing the functional group for 8-36 hours at the temperature of 60-130 ℃. The metal oxide is prepared by the technical methodThe contents of the above are not repeated here, and the molecule containing functional groups mainly comprises-NH 2 and/or-SH, may be selected from any one or more of urea, thioglycollic acid, thiourea or 3-mercaptobenzoic acid. In the present invention, the ratio of the metal oxide to the molecule containing a functional group is 1 (10 to 20). In some embodiments of the present invention, after the reaction is completed, the product obtained by the reaction is preferably further subjected to washing, centrifugation and drying. The washed reagent includes anhydrous ethanol and water, which may be any one or more of deionized water, distilled water, or ultrapure water. The centrifugation is carried out according to a conventional method, and the rotational speed of the centrifugation is not particularly limited in the present invention. The drying can be any of the conventional drying modes, and the product after centrifugation is preferably dried for 4-12 hours at 40-80 ℃.
After introducing functional groups on the surface of the metal oxide, according to the invention, mixing the metal oxide with the functional groups modified on the surface, an iridium source, a solvent and a surfactant, performing solvothermal reaction in an inert atmosphere at 80-120 ℃, and performing heat treatment on the obtained product in the inert atmosphere at 200-500 ℃ to obtain the core-shell catalyst. The iridium source is selected from any one or more of iridium chloride, iridium acetylacetonate, iridium chloride, potassium chloride, sodium chloride or iridium acetate; the solvent is selected from any one or more of ethanol, glycol or isopropanol; the surfactant is used for dispersing the metal oxide to prevent agglomeration of the metal oxide to form a large particle form, and can be selected from any one or more of cetyltrimethylammonium bromide, ethylenediamine tetraacetic acid or polyvinylpyrrolidone. In some embodiments of the invention, according to the mass ratio of the iridium source to the surfactant of 10 (0-1), the mass ratio of the iridium source to the solvent of 0.1 (1-2), mixing the metal oxide with the surface modified with the functional groups, the iridium source, the solvent and the surfactant, performing solvothermal reaction for 4-8 hours in an inert atmosphere at 80-120 ℃, and then reacting the obtained product in a tubular furnace at 200-500 ℃ for 2-4 hours to obtain the core-shell catalyst with the mass ratio of the metal oxide to the iridium of 1 (0.6-1.5). The inert atmosphere is an atmosphere well known to those skilled in the art, and nitrogen is preferred in the present invention.
In some embodiments of the present invention, after the solvothermal reaction described above is completed, it is preferred that the resulting product is further subjected to washing, centrifugation and drying, followed by further high temperature treatment in a tube furnace under an inert atmosphere. The washed reagent includes anhydrous ethanol and water, which may be any one or more of deionized water, distilled water, or ultrapure water. The centrifugation is carried out according to a conventional method, and the rotational speed of the centrifugation is not particularly limited in the present invention. The drying can be any of the conventional drying modes, and the product after centrifugation is preferably dried for 4-12 hours at 40-80 ℃.
The preparation method of the core-shell catalyst is simple and feasible, does not need expensive equipment, and is convenient for realizing industrialized or industrialized production.
In the invention, the dispersing agent is a nonionic surfactant, and can be specifically selected from polyethylene glycol octyl phenyl ether. The binder is selected from any one or more of perfluorosulfonic acid resin, polytetrafluoroethylene or polyvinylidene fluoride-hexafluoropropylene copolymer. The solvent is selected from any one or more of isopropanol, ethanol, nitrogen-methyl pyrrolidone, nitrogen-dimethylformamide, dimethyl sulfoxide or glycerol.
The dispersion condition of the anode catalytic layer prepared from the anode catalyst slurry is mainly influenced by the proportion of each component. According to researches, the addition amount of the solvent is too high, so that the slurry is thinner, the later sedimentation phenomenon is obvious, the spray nozzle is easy to block in the subsequent process of preparing the catalyst layer by adopting an ultrasonic spraying method, and the addition amount is too small, and the slurry is too thick, so that the spraying is uneven, therefore, in some embodiments of the invention, the mass ratio of the solvent to the core-shell catalyst is 1 (0.01-0.08), and preferably 1 (0.01-0.05). Too little of the dispersant may cause uneven dispersion of the slurry, and too much may adversely affect the catalytic performance, so that in some embodiments of the present invention, the mass ratio of the solvent to the dispersant is 1 (0.01 to 0.08), preferably 1 (0.01 to 0.05). The addition of the binder in an excessive amount may cause a coating effect on the catalyst, resulting in a reduction in the effective catalytic area of the catalyst, while the addition in an excessive amount may cause poor adhesion of the catalyst to the proton exchange membrane, affecting proton transfer between the catalyst layer and the proton exchange membrane, and thus, in some embodiments of the present invention, the mass ratio of the core-shell catalyst to the binder component is determined to be (1 to 8): 1, preferably (1 to 5): 1. According to the invention, the mass ratio of the solvent to the core-shell catalyst to the dispersing agent to the binder is 1 (0.01-0.05) (0.01-1:0.05), and the solid content of the obtained slurry is 1-10%, so that the core-shell catalyst can be uniformly dispersed in the mixed solution of the solvent, the binder and the dispersing agent, is not easy to settle, and can be uniformly sprayed on the surface of the proton exchange membrane in the follow-up process.
The anode catalyst slurry for hydrogen production by water electrolysis of the proton exchange membrane provided by the invention takes the low iridium catalyst of iridium-supported titanium dioxide as a main body, and is matched with the binder, the solvent and the dispersing agent in the specific proportion, so that the obtained slurry is uniformly dispersed and has moderate viscosity, and is conveniently and uniformly distributed on the proton exchange membrane by an ultrasonic spraying method to obtain a membrane electrode, more electrochemical active surfaces can be exposed, and the membrane electrode can be better contacted with a gas diffusion layer, so that moisture, electrons and heat can be effectively transferred, and a final water electrolysis device has good catalytic activity.
The invention also provides a cathode catalyst slurry comprising a Pt/C catalyst, a dispersant, a binder and a solvent. Wherein, the Pt/C catalyst is commercial Pt/C, and is generally commercially available. The specific selection of the dispersing agent, the binder and the solvent is described in the relevant content in the technical scheme, and will not be described in detail herein. As described in the above technical scheme, the dispersion state of the cathode catalyst layer prepared from the final slurry is affected by the amount of the dispersant, the binder and the solvent, and the mass ratio of the solvent to the Pt/C catalyst is determined to be 1 (0.01-0.08), preferably 1 (0.01-0.05), the mass ratio of the solvent to the dispersant is determined to be 1 (0.01-0.08), preferably 1 (0.01-0.05), and the mass ratio of the binder to the Pt/C catalyst is determined to be 1 (0.1-0.7), preferably 1 (0.1-0.5) through continuous experimental exploration. According to the invention, the mass ratio of the solvent to the Pt/C catalyst to the dispersing agent to the binder is 1 (0.01-0.05) (0.1) and the obtained slurry is mixed, so that the solid content of the obtained slurry is 1-10%, the Pt/C catalyst can be uniformly dispersed in the mixed solution of the solvent, the binder and the dispersing agent, the Pt/C catalyst is not easy to settle, and the uniform ultrasonic spraying can be performed on the surface of the proton exchange membrane in the follow-up process.
The anode catalyst slurry and the cathode catalyst slurry are obtained by uniformly mixing a low iridium catalyst (or Pt/C catalyst), a binder, a solvent and a dispersing agent. In some embodiments of the invention, the anode catalyst slurry is prepared by the following method:
ball milling and mixing the low iridium catalyst (or Pt/C catalyst), the binder, the solvent and the dispersing agent, and then ultrasonic mixing and dispersing uniformly.
According to the invention, the low iridium catalyst (or Pt/C catalyst), the binder, the solvent and the dispersing agent are ball-milled and mixed, then ultrasonic mixing and uniform dispersion are carried out, and finally the anode catalyst slurry is obtained by defoaming treatment. The specific choices and proportional relationships of the low iridium catalyst (or Pt/C catalyst), the binder, the solvent and the dispersant are described in the above technical schemes, and will not be described in detail herein. In some embodiments of the invention, after placing the low iridium catalyst (or Pt/C catalyst), binder, solvent and dispersant in a ball mill in proportion, the resulting slurry is ultrasonically dispersed in a temperature-controlled ultrasonic disperser at a temperature of 0-5 ℃ and a frequency of 30Hz for 0.5-2 hours.
The preparation method of the catalyst slurry provided by the invention is simple, does not need expensive instruments and equipment, can be used after ultrasonic dispersion is uniform, is convenient to operate, and is favorable for realizing industrialization or industrialized production.
After the preparation of the anode catalyst slurry and the cathode catalyst slurry is finished, the anode catalyst slurry and the cathode catalyst slurry can be used for manufacturing a membrane electrode. The membrane electrode comprises a proton exchange membrane positioned at the middle and two sides of the proton exchange membrane and is connected withAn anode catalytic layer and a cathode catalytic layer which are closely contacted with the proton exchange membrane. The proton exchange membrane can be a commercial Nafion membrane or a Gore membrane, and is a common commercial product. The preparation method of the membrane electrode is simple, and the anode catalyst slurry and the cathode catalyst slurry are respectively sprayed on the surface of the solid proton exchange membrane by an ultrasonic spraying method, so that the membrane electrode can be obtained. In some embodiments of the invention, the proton exchange membrane is placed on an electrical heating plate and secured using the negative pressure of an air compressor. Wherein the temperature of the electric heating plate is 100-120 ℃. And then uniformly spraying cathode catalyst slurry and anode catalyst slurry on two sides of the proton exchange membrane by using ultrasonic spraying equipment at a discharge flow rate of 0.5-1.0 mL/min to obtain the membrane electrode. In some embodiments of the invention, the anode catalyst slurry is sprayed in an amount of 0.3 to 0.8mg/cm 2 Preferably 0.5mg/cm 2 The spraying amount of the cathode catalyst slurry is 0.2-0.4 mg/cm 2 Preferably 0.2mg/cm 2 。
The invention also provides a device for producing hydrogen by water electrolysis of the proton exchange membrane, which comprises the membrane electrode. The electrolytic water properties were tested at 60℃and found to be at a current density of 2A/cm 2 The electrolysis voltage is not more than 2V, which indicates that the water electrolysis performance is good and the energy consumption is low.
In order to further illustrate the present invention, the following examples are provided. The experimental materials used in the following examples of the present invention are commercially available or prepared according to conventional preparation methods well known to those skilled in the art.
Preparation example 1
The preparation example provides a low iridium catalyst, which is prepared by the following steps:
adding 500mg of titanium dioxide into 1M 100mL of urea aqueous solution, uniformly dispersing by ultrasonic, heating and stirring for 36h at 70 ℃ in a water bath, washing the obtained product by deionized water and absolute ethyl alcohol, centrifuging, and drying in a vacuum oven at 50 ℃ for 6h to obtain the titanium dioxide carrier with the amino groups modified on the surface. 50mg of the surface-modified titanium dioxide support material were added to chloroiridiumIn a mixed solution of acid, ethanol and polyvinylpyrrolidone (PVP) (the mass ratio of PVP to chloroiridic acid is 0.4:10, and the mass ratio of ethanol to chloroiridic acid is 10:1), uniformly dispersing by ultrasonic, and controlling the mass ratio of metallic iridium to titanium dioxide, namely m (Ir): m (TiO) 2 ) Solvent-thermal reaction for 8h in an oil bath at 80 ℃ under nitrogen atmosphere, then centrifugation after washing with deionized water and absolute ethanol, drying for 6h in a vacuum oven at 50 ℃, high-temperature heat treatment at 300 ℃ under inert atmosphere, and treatment for 2h to obtain the low iridium catalyst.
TEM images of the low iridium catalyst are shown in FIG. 1, and it can be seen that the low iridium catalyst has a smaller size, a diameter of about 5-6 nm, and uniform dispersion.
Example 1
The embodiment provides a membrane electrode for PEM water electrolysis hydrogen production, which is prepared by the following steps:
(1) 50mL of a mixed solution of polyethylene glycol octyl phenyl ether and an isopropanol water solution (the mass ratio of an isopropanol solvent to the polyethylene glycol octyl phenyl ether is 1:0.02; the volume ratio of deionized water to isopropanol is 1:1) is taken, then 1.5g of the low iridium catalyst obtained in preparation example 1 and 0.5g of 5wt% Nafion solution are weighed, added into the mixed solution, put into a ball mill, and then dispersed uniformly by ultrasonic for 1h to obtain anode catalyst slurry;
(2) 50mL of a mixed solution of polyethylene glycol octyl phenyl ether and an isopropanol water solution (the mass ratio of an isopropanol solvent to the polyethylene glycol octyl phenyl ether is 1:0.02, the volume ratio of deionized water to isopropanol is 1:3), then 0.5g of 40wt% commercial Pt/C catalyst and 1g of 5wt% Nafion solution are weighed, added into the mixed solution, put into a ball mill, and then dispersed for 1h uniformly by ultrasound to obtain cathode catalyst slurry;
(3) An N115 type proton exchange membrane with the area of 5cm multiplied by 5cm is placed on an electric heating plate at the temperature of 100 ℃ and is fixed by utilizing the negative pressure of an air compressor. Then using ultrasonic spraying equipment to make the discharge flow rate be 0.5mL/min according to cathode catalyst slurry 0.2mg/cm 2 Anode catalyst slurry 0.5mg/cm 2 Uniformly spraying cathode and anode catalyst slurry on two sides of a proton exchange membrane,and obtaining the membrane electrode.
Example 2
The embodiment provides a membrane electrode for PEM water electrolysis hydrogen production, which is prepared by the following steps:
(1) 50mL of a mixed solution of polyethylene glycol octyl phenyl ether and an isopropanol water solution (the mass ratio of an isopropanol solvent to the polyethylene glycol octyl phenyl ether is 1:0.02, the volume ratio of deionized water to isopropanol is 1:3) is taken, 1.5g of the low iridium catalyst obtained in preparation example 1 and 0.5g of 5wt% Nafion solution are weighed and added into the mixed solution, a ball mill is arranged, and then the mixed solution is subjected to ultrasonic dispersion for 1 hour to obtain anode catalyst slurry;
(2) 50mL of a mixed solution of polyethylene glycol octyl phenyl ether and an isopropanol water solution (the mass ratio of an isopropanol solvent to the polyethylene glycol octyl phenyl ether is 1:0.02, the volume ratio of deionized water to isopropanol is 1:3), then 0.5g of a 20wt% commercial Pt/C catalyst and 1g of a 5wt% Nafion solution are weighed, added into the mixed solution, placed into a ball mill, and then evenly dispersed for 1h by ultrasonic treatment to obtain cathode catalyst slurry;
(3) An N115 type proton exchange membrane with the area of 5cm multiplied by 5cm is placed on an electric heating plate at the temperature of 100 ℃ and is fixed by utilizing the negative pressure of an air compressor. Then using ultrasonic spraying equipment to make the discharge flow rate be 0.5mL/min according to cathode catalyst slurry 0.2mg/cm 2 Anode catalyst slurry 0.5mg/cm 2 And (3) uniformly spraying cathode and anode catalyst slurry on two sides of the proton exchange membrane to obtain the membrane electrode.
Comparative example 1
This comparative example provides a membrane electrode for PEM electrolyzed water hydrogen production differing from example 1 only in the equivalent replacement of the low iridium catalyst from preparation 1 with 75wt% commercial IrO 2 The solid catalyst, remaining parameters and steps were identical to those of example 1.
The membrane electrode assemblies obtained in examples 1 to 2 and comparative example 1 were subjected to electrolytic water performance test, and the test results are shown in table 1 and fig. 1 below:
TABLE 1
Group of 2A/cm 2 Electrolysis voltage (V)
Example 1 1.982
Example 2 1.995
Comparative example 1 2.228
Fig. 2 is an electrolytic water curve of the membrane electrode obtained in examples 1 to 2 and comparative example 1, and it can be seen from the combination of table 1 and fig. 1 that the electrolytic voltage of the membrane electrode provided by the present invention in the electrolytic water cell is lower than that of the membrane electrode assembly obtained in comparative example, indicating that the energy consumption required for the membrane electrode provided by the present invention is lower under the condition of producing the same volume of hydrogen.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. An anode catalyst slurry for producing hydrogen by water electrolysis of a proton exchange membrane is characterized by comprising a core-shell catalyst of iridium supported metal oxide, a dispersing agent, a binder and a solvent;
the core-shell catalyst takes metal oxide as a core and metal iridium nano particles as shells;
the metal oxide comprises any one or more of titanium dioxide, niobium pentoxide, tantalum oxide, tungsten oxide or tin oxide;
the surface of the metal oxide is modified with functional groups, and the functional groups comprise-NH 2 and/or-SH;
the mass ratio of the solvent to the core-shell catalyst to the dispersant to the binder is 1 (0.01-0.05) (0.01).
2. The anode catalyst slurry of claim 1, wherein the dispersant is selected from the group consisting of polyethylene glycol octyl phenyl ether;
the binder is selected from any one or more of perfluorosulfonic acid resin, polytetrafluoroethylene or polyvinylidene fluoride-hexafluoropropylene copolymer;
the solvent is selected from any one or more of isopropanol, ethanol, nitrogen-methyl pyrrolidone, nitrogen-dimethylformamide, dimethyl sulfoxide or glycerol.
3. The membrane electrode for producing hydrogen by electrolyzing water through a proton exchange membrane is characterized by comprising an anode catalytic layer, a cathode catalytic layer and a proton exchange membrane positioned between the anode catalytic layer and the cathode catalytic layer;
the anode catalytic layer is prepared from the anode catalyst slurry according to claim 1 or 2 by an ultrasonic spraying method.
4. A membrane electrode according to claim 3, wherein the proton exchange membrane is selected from Nafion or Gore membranes.
5. The preparation method of the membrane electrode is characterized by comprising the following steps of:
and respectively spraying anode catalyst slurry and cathode catalyst slurry on two sides of the proton exchange membrane by adopting an ultrasonic spraying method to obtain the membrane electrode.
6. The method of preparing according to claim 5, wherein the anode catalyst slurry comprises a core-shell catalyst of iridium-supported metal oxide, a dispersant, a binder, and a solvent;
the core-shell catalyst takes metal oxide as a core and metal iridium nano particles as shells;
the metal oxide comprises any one or more of titanium dioxide, niobium pentoxide, tantalum oxide, tungsten oxide or tin oxide.
7. The method of preparing according to claim 5, wherein the cathode catalyst slurry comprises a Pt/C catalyst, a dispersant, a binder, and a solvent.
8. The method according to claim 5, wherein the discharge flow rate of the ultrasonic spraying is 0.5-1.0 mL/min.
9. The method according to claim 5, wherein the anode catalyst slurry is sprayed in an amount of 0.3 to 0.8mg/cm 2 ；
The spraying amount of the cathode catalyst slurry is 0.2-0.4 mg/cm 2 。
10. A device for producing hydrogen by water electrolysis through a proton exchange membrane, comprising the membrane electrode according to claim 3 or 4 or the membrane electrode produced by the production method according to any one of claims 5 to 9.
CN202310156067.3A 2023-02-20 2023-02-20 Anode catalyst slurry for hydrogen production by water electrolysis of proton exchange membrane, membrane electrode and application Pending CN116219475A (en)

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