CN114836767A - Preparation method of catalyst slurry for hydrogen production by PEM (proton exchange membrane) electrolysis of water and preparation method of membrane electrode of catalyst slurry - Google Patents
Preparation method of catalyst slurry for hydrogen production by PEM (proton exchange membrane) electrolysis of water and preparation method of membrane electrode of catalyst slurry Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000001257 hydrogen Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 37
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- 238000000034 method Methods 0.000 claims abstract description 12
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- 239000002184 metal Substances 0.000 claims description 14
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- 239000004696 Poly ether ether ketone Substances 0.000 claims description 7
- 239000004693 Polybenzimidazole Substances 0.000 claims description 7
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- 229920002480 polybenzimidazole Polymers 0.000 claims description 7
- 229920002530 polyetherether ketone Polymers 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002390 adhesive tape Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
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- 239000004697 Polyetherimide Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920006260 polyaryletherketone Polymers 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 229920001601 polyetherimide Polymers 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000003892 spreading Methods 0.000 claims description 4
- 230000007480 spreading Effects 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 4
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000003011 anion exchange membrane Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
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- 241000282414 Homo sapiens Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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Classifications
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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
- 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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
- C25B11/053—Electrodes comprising one or more electrocatalytic coatings on a substrate characterised by multilayer electrocatalytic coatings
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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
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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
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a preparation method of catalyst slurry for hydrogen production by PEM (proton exchange membrane) electrolysis and a preparation method of a membrane electrode thereof. Mixing a proton-electron conductor, a binder, Pt/C powder with platinum mass concentration of 20-60% and a solvent, and dispersing uniformly under ultrasound to prepare cathode catalyst slurry; mixing a proton-electron conductor, a binder, iridium dioxide powder or an iridium dioxide/carbon black mixture and a solvent, and uniformly dispersing under ultrasound to prepare anode catalyst slurry. The introduced proton-electron conductor increases the proton transmission sites in the hydrogen production reaction by water electrolysis, accelerates the transmission of protons and electrons, and can improve the performance of the catalyst layer on the premise of reducing the catalyst consumption of the catalyst layer. The catalyst slurry is uniformly coated on the bottom film of the membrane electrode by using air gun spraying, spin coating by a spin coater or blade coating by a glass rod, and the method has the advantages of simple process and easy operation.
Description
Technical Field
The invention relates to the field of membrane electrode preparation, in particular to a preparation method of catalyst slurry for hydrogen production by PEM (proton exchange membrane) electrolysis and a preparation method of a membrane electrode thereof.
Background
With the rapid development of social industrialization, the energy crisis problem facing human beings is increasingly prominent. At present, most of energy supply still comes from traditional fossil fuel, and the environmental pollution that comes with itProblems have also become a focus of social attention. In order to solve energy and environmental problems, researchers have looked at emerging clean energy sources, such as solar, wind, tidal and hydrogen. Among them, hydrogen energy (H) 2 ) The fuel has the advantages of high energy density, small molecular mass, only water as a combustion product and the like, and is considered to be an ideal carrier for future energy storage and supply. At present, the technology for preparing the elemental hydrogen mainly comprises hydrogen production by fossil energy reforming, hydrogen production by industrial byproduct gas and hydrogen production by water electrolysis. The hydrogen production by electrolyzing water has the advantages of simple raw materials, no greenhouse gas emission, high hydrogen production efficiency, high product purity and the like, and is considered as the development direction of the future energy industry.
The water electrolysis hydrogen production technology mainly comprises the steps of hydrogen production by using alkaline electrolyte (AWE), water electrolysis by using Proton Exchange Membrane (PEM), water electrolysis by using solid polymer Anion Exchange Membrane (AEM) and water electrolysis by using Solid Oxide (SOE). Among them, AWE is the earliest industrialized water electrolysis technology, has been experienced in several decades of applications and is the most mature; SOE water electrolysis technology is in a preliminary demonstration stage; AEM water electrolysis studies were just started. From the technical point of view, the PEM water electrolysis technology has the advantages of high current density, small volume of an electrolysis bath, flexible operation, contribution to quick load change, good matching with wind power and photovoltaic power (large fluctuation and randomness of power generation), and is considered as a development trend of 5-10 years in the future.
The membrane electrode is the most main reaction site in the PEM water electrolysis hydrogen production device, is the core component of the PEM water electrolysis cell, directly influences the hydrogen production efficiency of the electrolytic cell, and determines the safety and stable performance of the electrolysis reaction. The manufacturing process is classified into a GDE method and a CCM method depending on whether a gas diffusion layer is used. The former uses gas diffusion layer, after the catalyst is dried and formed, the gas diffusion layer electrode is obtained, then the membrane electrode is obtained by hot pressing with two sides of the proton exchange membrane; the latter does not use gas diffusion layer, directly and uniformly plates the prepared catalyst on the surface of proton exchange membrane to form catalyst covering layer, and drying and forming so as to obtain the membrane electrode. The membrane electrode prepared by the CCM method has higher catalyst utilization rate, and can establish a better ionomer/catalyst interface (three-phase interface), so that the CCM method is widely applied at present.
The proton exchange membrane used in the CCM method must have relatively high proton conductivity and low electron conductivity; better swelling resistance; low permeability to gases; has better chemical stability and mechanical stability under the running environment of the PEM water electrolyzer. At this stage, Nafion series proton exchange membranes manufactured by DuPont, USA, are generally used. The catalytic layer formed by the catalyst in the CCM method is the real site for reaction in the membrane electrode of the PEM water electrolyzer, namely electrochemical reaction occurs on the surface of the catalyst, so that the composition of the catalyst slurry influences the hydrogen production efficiency of the electrolyzer. In addition, the coating method of the catalyst slurry and the proton exchange membrane is a competitive development subject for scholars at home and abroad.
Disclosure of Invention
The invention aims to provide a preparation method of catalyst slurry for hydrogen production by PEM (proton exchange membrane) electrolysis of water, which is simple and easy to realize industrial production.
In order to achieve the purpose, the preparation method of the catalyst slurry for hydrogen production by PEM electrolysis comprises the following steps:
1) preparing cathode catalyst slurry: mixing a proton-electron conductor, a binder, Pt/C powder with platinum mass concentration of 20-60% and a solvent, and dispersing uniformly under ultrasound to prepare cathode catalyst slurry;
2) preparing anode catalyst slurry: mixing a proton-electron conductor, a binder, iridium dioxide powder or an iridium dioxide/carbon black mixture and a solvent, and uniformly dispersing under ultrasound to prepare anode catalyst slurry.
According to the invention, the proton-electron conductor is poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), i.e. PEDOT-PSS.
According to the invention, the binder is one of 0.5-20% by mass of Nafion solution, polybenzimidazole solution, sulfonated polysulfone solution, sulfonated polyether sulfone solution, sulfonated polyether imide solution, sulfonated polyether ether ketone solution and sulfonated polyaryletherketone solution.
According to the invention, the solvent is a mixture of an alcohol and deionized water.
Further, the alcohol is one or a mixture of two of ethanol, ethylene glycol and isopropanol.
Further, the volume ratio of the deionized water to the alcohol in the mixture is 1: 5 to 20.
According to the invention, the proton-electron conductor in the step 1) accounts for 1-30% of the mass concentration of the platinum in the Pt/C powder of 20-60%.
According to the invention, the binder in the step 1) accounts for 10-40% of the mass of the Pt/C powder with the platinum mass concentration of 20-60%.
According to the invention, the condition of ultrasonic dispersion in the step 1) is ice water bath, and the time is 30-90 min.
According to the invention, the proton-electron conductor in the step 2) accounts for 1-30% of the mass of the iridium dioxide powder or the iridium dioxide/carbon black mixture.
According to the invention, the binder in the step 2) accounts for 10-40% of the mass of the iridium dioxide powder or the iridium dioxide/carbon black mixture.
According to the invention, the iridium dioxide powder in step 2) has a mass concentration of 85% or 95%.
According to the invention, in the iridium dioxide/carbon black mixture in the step 2), the iridium dioxide powder accounts for 40-80% of the mass of the mixture.
According to the invention, the condition of ultrasonic dispersion in the step 2) is ice water bath, and the time is 120-180 min.
The invention also aims to provide a preparation method of the membrane electrode for hydrogen production by PEM (proton exchange membrane) electrolysis of water, which comprises the following steps:
1) preparing cathode catalyst slurry: mixing a proton-electron conductor, a binder, Pt/C powder with the platinum mass concentration of 20-40% and a solvent, and uniformly dispersing under ultrasound to prepare cathode catalyst slurry;
2) preparing anode catalyst slurry: mixing a proton-electron conductor, a binder, iridium dioxide powder or an iridium dioxide/carbon black mixture and a solvent, and uniformly dispersing under ultrasound to prepare anode catalyst slurry;
3) pretreating a commercial Nafion membrane or a proton exchange membrane to prepare a bottom membrane of a membrane electrode;
4) fixing the periphery of the bottom membrane prepared in the step 3) on the surface of a flat support by using a metal frame with a groove in the middle;
5) coating the cathode catalyst slurry prepared in the step 1) on the surface of the base membrane prepared in the step 4), turning the base membrane to the other side, fixing the base membrane on the surface of the flat support by using a metal frame, and coating the anode catalyst slurry prepared in the step 2) on the other side of the base membrane to obtain the membrane electrode for hydrogen production by PEM (proton exchange membrane) electrolyzed water.
According to the invention, the commercial Nafion membrane in the step 3) is Nafion115 or Nafion 117.
According to the invention, the proton exchange membrane in the step 3) is one of polybenzimidazole, sulfonated polysulfone, sulfonated polyethersulfone, sulfonated polyetherimide, sulfonated polyetheretherketone and sulfonated polyaryletherketone.
According to the invention, the Nafion membrane pretreatment mode in the step 3) is as follows: sequentially passing a Nafion membrane through H with the mass concentration of 2-5% 2 O 2 The aqueous solution is subjected to heat treatment at 60-80 ℃ for 30-60 min, washed by deionized water, and then subjected to heat treatment at 60-80 ℃ for 30-60 min by using 0.5-1 mol/L sulfuric acid aqueous solution, and washed by deionized water and then subjected to heat treatment at 60-80 ℃ for 30-60 min by using deionized water.
According to the invention, the pretreatment mode of the proton exchange membrane in the step 3) is as follows: and soaking the membrane in 1-3 mol/L acid water solution for 2-7 days.
Further, the acid is one of sulfuric acid, hydrochloric acid, formic acid, methanesulfonic acid, and phosphoric acid.
According to the invention, the flat support in step 4) is a glass plate or an aluminum plate.
According to the invention, the coating mode in the step 5) is air gun spraying, spin coating by a spin coater or blade coating by a glass rod.
Further, the air gun spraying step is as follows: placing the flat support prepared in the step 4) on a hot table, and uniformly spraying the cathode catalyst slurry prepared in the step 1) on the surface of a bottom membrane by using an air gun; and putting the other side of the bottom film in a metal frame in an upward mode, fixing the bottom film in a flat support, and uniformly spraying the anode catalyst slurry prepared in the step 2) on the other side of the bottom film by using an air gun.
Furthermore, the temperature of the hot table is 30-80 ℃.
Furthermore, the spraying times are 1-5 times.
Further, the spin coating of the spin coater comprises the following steps: placing the flat support prepared in the step 4) on an adsorption table of a spin coater, laying a layer of cathode catalyst slurry prepared in the step 1) and dripping the cathode catalyst slurry on the surface of a basement membrane, starting the spin coater, uniformly coating the cathode catalyst slurry on the surface of the basement membrane, and drying the basement membrane; and then placing the other side of the base membrane facing upwards in a metal frame, fixing the base membrane in a flat support, placing the base membrane on an adsorption table of a spin coater, flatly laying the anode catalyst slurry prepared in the step 2) layer by layer and dripping the anode catalyst slurry on the other side of the base membrane, starting the spin coater, uniformly coating the anode catalyst slurry on the other side of the base membrane, and then drying the base membrane.
Furthermore, the spin coating is carried out at a rotation speed of 1000-3000 kilorevolutions per minute for 5-20 s for 1-3 times.
Furthermore, the drying temperature is 30-80 ℃.
Further, the glass rod is subjected to blade coating, and the steps are as follows: adhering two sides of the bottom film prepared in the step 3) to a flat support by using a transparent adhesive tape, uniformly coating the cathode catalyst slurry prepared in the step 1) on the surface of the bottom film by using a glass rod, and immediately placing the bottom film in an oven for drying; adhering the other side of the basement membrane to a flat support by using a transparent adhesive tape, uniformly coating the positive catalyst slurry prepared in the step 2) on the other side of the basement membrane by using a glass rod, and immediately placing the basement membrane in an oven for drying.
Furthermore, the drying temperature is 30-80 ℃.
Compared with the prior art, the invention has the following advantages:
1) the proton-electron conductor is used as the main component of the catalyst slurry, increases the proton transmission sites in the hydrogen production reaction by water electrolysis, accelerates the transmission of protons and electrons, and can improve the performance of the catalyst layer on the premise of reducing the catalyst consumption of the catalyst layer;
2) the invention uses the hydrophilic solution as the binder of the membrane electrode basement membrane and the catalyst, which is beneficial to the binding of the catalyst and the membrane electrode basement membrane, reduces the interface resistance and improves the conductivity of the catalyst, thereby greatly improving the service performance of the membrane electrode;
3) the catalyst slurry is uniformly coated on the basement membrane of the membrane electrode by using air gun spraying, spin coating by a spin coater or blade coating by a glass rod, and the method has the advantages of simple process and easy operation.
Detailed Description
The present invention will be further described with reference to examples.
Example 1
1) Preparing a bottom film of the membrane electrode: a Nafion115 membrane (10 cm. times.10 cm) was placed at 60 ℃ in 5% H 2 O 2 Treating in water solution for 60min, repeatedly washing the membrane with deionized water, and treating the membrane in 80 deg.C deionized water for 30 min; then treating the mixture for 30min in 0.5mol/L sulfuric acid aqueous solution at the temperature of 80 ℃; repeatedly washing the membrane with deionized water, treating the membrane in 80 deg.C deionized water for 30min, taking out, and naturally cooling to obtain the bottom membrane of the membrane electrode;
2) preparing cathode catalyst slurry: weighing 50mg of Pt/C powder with the platinum mass concentration of 20%, stirring and mixing 50mL of deionized water and 250mL of ethanol to form a solution, and ultrasonically dispersing the solution in an ice-water bath for 20 min; then adding 0.5mg of PEDOT-PSS and 100mg of Nafion solution with the mass concentration of 5 percent into the solution, and performing ultrasonic dispersion for 10min in ice water bath to obtain cathode catalyst slurry;
3) preparing anode catalyst slurry: weighing 100mg of iridium dioxide powder with the mass concentration of 95%, 100mL of deionized water and 500mL of ethylene glycol, stirring and mixing to obtain a solution, and ultrasonically dispersing the solution in an ice water bath for 60 min; then 10mg of PEDOT-PSS and 400mg of Nafion solution with the mass concentration of 5 percent are added into the solution, and then the mixture is subjected to ultrasonic dispersion for 60min in ice water bath to obtain anode catalyst slurry;
4) preparing a membrane electrode: placing the bottom film prepared in the step 1) in a metal frame with a groove in the middle, and fixing the bottom film on the surface of a glass plate; placing the glass plate on a hot table at 40 ℃, pouring the cathode catalyst slurry prepared in the step 2) into an air gun tank, uniformly spraying the cathode catalyst slurry on the surface of the basement membrane by using an air gun, and finishing spraying the cathode catalyst slurry after 3 times of spraying; turning the bottom film to the other side, placing the bottom film in a metal frame with a groove in the middle, and fixing the bottom film on the surface of the glass plate; and (3) pouring the anode catalyst slurry prepared in the step 3) into a tank body of an air gun, uniformly spraying the anode catalyst slurry on the other surface of the bottom membrane by using the air gun, and finishing spraying the anode catalyst slurry after 3 times of spraying, thus obtaining the membrane electrode for hydrogen production by PEM (proton exchange membrane) electrolyzed water.
Example 2
1) Preparing a bottom film of the membrane electrode: a Nafion117 membrane (10 cm. times.10 cm) was placed at 80 ℃ in 3% H 2 O 2 Treating in water solution for 40min, repeatedly washing the membrane with deionized water, and treating the membrane in deionized water at 60 deg.C for 30 min; then treating the mixture for 30min in 1mol/L sulfuric acid aqueous solution at the temperature of 80 ℃; repeatedly washing the membrane with deionized water, treating the membrane in 80 deg.C deionized water for 30min, taking out, and naturally cooling to obtain the bottom membrane of the membrane electrode;
2) preparing cathode catalyst slurry: weighing 75mg of Pt/C powder with the platinum mass concentration of 40%, 75mL of deionized water and 750mL of isopropanol, stirring and mixing to obtain a solution, and ultrasonically dispersing the solution for 30min in an ice-water bath; then adding 7.5mg of PEDOT-PSS and 750mg of Nafion solution with the mass concentration of 20 percent into the solution, and then carrying out ultrasonic dispersion for 30min in ice water bath to obtain cathode catalyst slurry;
3) preparing anode catalyst slurry: weighing 80mg of iridium dioxide powder with the mass concentration of 95%, 120g of carbon black, 200mL of deionized water and 1600mL of ethanol, stirring and mixing to obtain a solution, and ultrasonically dispersing the solution in an ice water bath for 120 min; then adding 60mg of PEDOT-PSS and 200mg of Nafion solution with the mass concentration of 20% into the solution, and performing ultrasonic dispersion for 60min in an ice water bath to obtain anode catalyst slurry;
4) preparing a membrane electrode: placing the basement membrane prepared in the step 1) in a metal frame with a groove in the middle, fixing the basement membrane on the surface of an aluminum sheet, and placing the aluminum sheet on an adsorption table of a spin coater; spreading the cathode catalyst slurry prepared in the step 2) to be a layer and dripping the cathode catalyst slurry on the surface of the basement membrane, starting a spin coater (the rotating speed is 3000 kilorevolutions per minute, the time is 5 s), uniformly coating the cathode catalyst slurry on the surface of the basement membrane, and then putting the basement membrane in a 50 ℃ oven to be dried for 5 min; repeating the above steps for 2 times, namely spreading cathode catalyst slurry on the surface of the basement membrane, spin-coating and drying; placing the other side of the bottom film upwards in a metal frame, fixing the bottom film on the surface of an aluminum sheet, placing the aluminum sheet on an adsorption table of a spin coater, flatly laying the anode catalyst slurry prepared in the step 3) layer by layer and dripping the anode catalyst slurry on the surface of the bottom film, starting the spin coater (the rotating speed is 2500 kilorevolutions per minute, the time is 10 s), uniformly coating the anode catalyst slurry on the other side of the bottom film, and then placing the bottom film in a 50 ℃ oven to be dried for 5 min; and repeating the steps for 2 times, namely spreading anode catalyst slurry on the other surface of the basement membrane, spin-coating and drying to obtain the membrane electrode for hydrogen production by PEM (proton exchange membrane) electrolyzed water.
Example 3
1) Preparing a bottom film of the membrane electrode: soaking the polybenzimidazole membrane in 3mol/L sulfuric acid aqueous solution for 5 days; taking out the membrane, and taking the membrane as a bottom membrane of the membrane electrode after the membrane is naturally dried;
2) preparing cathode catalyst slurry: weighing 34mg of Pt/C powder with the platinum mass concentration of 60%, 40mL of deionized water and 800mL of ethylene glycol, stirring and mixing to obtain a solution, and ultrasonically dispersing the solution in an ice-water bath for 40 min; then 6.8mg of PEDOT-PSS and 2.72g of polybenzimidazole/N, N-dimethylacetamide solution with the mass concentration of 0.5 percent are added into the solution, and the mixture is subjected to ultrasonic dispersion for 50min in ice water bath to obtain cathode catalyst slurry;
3) preparing anode catalyst slurry: weighing 110mg of iridium dioxide powder with the mass concentration of 85%, 100mL of deionized water and 1000mL of isopropanol, stirring and mixing to obtain a solution, and ultrasonically dispersing the solution for 120min in an ice water bath; then adding 5.5mg of PEDOT-PSS and 6.6g of polybenzimidazole/N, N-dimethylacetamide solution with the mass concentration of 0.5 percent into the solution, and performing ultrasonic dispersion for 60min in ice-water bath to obtain anode catalyst slurry;
4) preparing a membrane electrode: adhering the two sides of the bottom film prepared in the step 1) on a glass plate by using 3 layers of transparent adhesive tapes, uniformly coating the cathode catalyst slurry prepared in the step 2) on one side of the bottom film by using a glass rod, and immediately placing the bottom film in a 60 ℃ oven to be dried for 5 min; and then, the other side of the bottom film is upwards and is stuck on a glass plate by using 3 layers of transparent adhesive tapes, the positive catalyst slurry prepared in the step 3) is evenly coated on the other side of the bottom film by a glass rod, and the bottom film is immediately placed in a 60 ℃ oven to be dried for 5min, thus obtaining the membrane electrode for hydrogen production by PEM (proton exchange membrane) electrolysis.
Example 4
1) Preparing a bottom film of the membrane electrode: soaking the sulfonated polyether-ether-ketone membrane in 2mol/L phosphoric acid water solution for 7 days; taking out the membrane, and taking the membrane as a bottom membrane of the membrane electrode after the membrane is naturally dried;
2) preparing cathode catalyst slurry: weighing 100mg of Pt/C powder with the platinum mass concentration of 20%, 100mL of deionized water and 700mL of isopropanol, stirring and mixing to obtain a solution, and ultrasonically dispersing the solution for 20min in an ice-water bath; then adding 10mg of PEDOT-PSS and 4g of sulfonated polyether ether ketone/N, N-dimethylacetamide solution with the mass concentration of 1% into the solution, and performing ultrasonic dispersion for 60min in ice water bath to obtain cathode catalyst slurry;
3) preparing anode catalyst slurry: weighing 94mg of iridium dioxide powder with the mass concentration of 85%, 20mg of carbon black, 100mL of deionized water and 500mL of ethylene glycol, stirring and mixing to obtain a solution, and ultrasonically dispersing the solution in an ice water bath for 90 min; then adding 30mg of PEDOT-PSS and 1g of sulfonated polyether ether ketone/N, N-dimethylacetamide solution with the mass concentration of 1% into the solution, and performing ultrasonic dispersion for 90min in ice water bath to obtain anode catalyst slurry;
4) preparing a membrane electrode: placing the bottom film prepared in the step 1) in a metal frame with a groove in the middle, and fixing the bottom film on the surface of a glass plate; placing the glass plate on a 50 ℃ hot table, filling the cathode catalyst slurry prepared in the step 2) into an air gun tank, uniformly spraying the cathode catalyst slurry on the surface of the basement membrane by using an air gun, and finishing spraying the cathode catalyst slurry after 3 times of spraying; turning the bottom film to the other side, placing the bottom film in a metal frame with a groove in the middle, and fixing the bottom film on the surface of the glass plate; and (3) pouring the anode catalyst slurry prepared in the step 3) into a tank body of an air gun, uniformly spraying the anode catalyst slurry on the other surface of the bottom membrane by using the air gun, and finishing spraying the anode catalyst slurry after 3 times of spraying, thus obtaining the membrane electrode for hydrogen production by PEM (proton exchange membrane) electrolyzed water.
Claims (10)
1. A preparation method of catalyst slurry for hydrogen production by PEM electrolysis of water is characterized by comprising the following steps:
1) preparing cathode catalyst slurry: mixing a proton-electron conductor, a binder, Pt/C powder with platinum mass concentration of 20-60% and a solvent, and dispersing uniformly under ultrasound to prepare cathode catalyst slurry;
2) preparing anode catalyst slurry: mixing a proton-electron conductor, a binder, iridium dioxide powder or an iridium dioxide/carbon black mixture and a solvent, and uniformly dispersing under ultrasound to prepare anode catalyst slurry.
2. The method of claim 1, wherein the proton-electron conductor is poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), PEDOT-PSS; in the step 1), the proton-electron conductor accounts for 1-30% of the mass of Pt/C powder with the mass concentration of 20-60% of platinum; in the step 2), the proton-electron conductor accounts for 1-30% of the mass of the iridium dioxide powder or the iridium dioxide/carbon black mixture.
3. The preparation method according to claim 1, wherein the binder is one of a Nafion solution, a polybenzimidazole solution, a sulfonated polysulfone solution, a sulfonated polyethersulfone solution, a sulfonated polyetherimide solution, a sulfonated polyetheretherketone solution, and a sulfonated polyaryletherketone solution, the mass concentration of which is 0.5-20%.
4. The preparation method according to claim 1, wherein the binder in the step 1) accounts for 10-40% of the mass concentration of the Pt/C powder with the mass concentration of 20-60%; in the step 2), the binder accounts for 10-40% of the mass of the iridium dioxide powder or the iridium dioxide/carbon black mixture.
5. The method of claim 1, wherein the solvent is a mixture of an alcohol and deionized water; the alcohol is one or a mixture of two of ethanol, ethylene glycol and isopropanol; the volume ratio of deionized water to alcohol in the mixture is 1: 5 to 20.
6. The preparation method according to claim 1, wherein the ultrasonic dispersion in step 1) is carried out in an ice-water bath for 30-90 min; and 2) performing ultrasonic dispersion in the step 2) under the condition of ice-water bath for 120-180 min.
7. The preparation method according to claim 1, wherein the mass concentration of the iridium dioxide powder in the step 2) is 85% or 95%; in the iridium dioxide/carbon black mixture in the step 2), the iridium dioxide powder accounts for 40-80% of the mass of the mixture.
8. A preparation method of a membrane electrode for hydrogen production by PEM (proton exchange membrane) electrolysis of water comprises the following steps:
1) preparing cathode catalyst slurry: mixing a proton-electron conductor, a binder, Pt/C powder with the platinum content of 20-40% and a solvent, and dispersing uniformly under ultrasound to prepare cathode catalyst slurry;
2) preparing anode catalyst slurry: mixing a proton-electron conductor, a binder, iridium dioxide powder or an iridium dioxide/carbon black mixture and a solvent, and uniformly dispersing under ultrasound to prepare anode catalyst slurry;
3) pretreating a commercial Nafion membrane or a proton exchange membrane to prepare a bottom membrane of a membrane electrode;
4) fixing the periphery of the bottom membrane prepared in the step 3) on the surface of a flat support by using a metal frame with a groove in the middle;
5) coating the cathode catalyst slurry prepared in the step 1) on the surface of the base membrane prepared in the step 4), turning the base membrane to the other side, fixing the base membrane on the surface of the flat support by using a metal frame, and coating the anode catalyst slurry prepared in the step 2) on the other side of the base membrane to obtain the membrane electrode for hydrogen production by PEM (proton exchange membrane) electrolyzed water.
9. The production method according to claim 8, wherein the commercial Nafion membrane in the step 3) is Nafion115 or Nafion 117;the proton exchange membrane in the step 3) is one of polybenzimidazole, sulfonated polysulfone, sulfonated polyether sulfone, sulfonated polyether imide, sulfonated polyether ether ketone and sulfonated polyaryletherketone; the Nafion membrane pretreatment mode in the step 3) is as follows: sequentially passing a Nafion membrane through H with the mass concentration of 2-5% 2 O 2 The aqueous solution is subjected to heat treatment at 60-80 ℃ for 30-60 min, washed by deionized water, and then subjected to heat treatment at 60-80 ℃ for 30-60 min by using 0.5-1 mol/L sulfuric acid aqueous solution, and washed by deionized water and then subjected to heat treatment at 60-80 ℃ for 30-60 min by using deionized water; the pretreatment mode of the proton exchange membrane in the step 3) is as follows: soaking the membrane in 1-3 mol/L acid water solution for 2-7 days; the acid is one of sulfuric acid, hydrochloric acid, formic acid, methanesulfonic acid and phosphoric acid; the flat support in the step 4) is a glass plate or an aluminum sheet.
10. The preparation method according to claim 8, wherein the coating manner in the step 5) is air gun spraying, spin coating by a spin coater or blade coating by a glass rod;
the air gun spraying method comprises the following steps: placing the flat support prepared in the step 4) on a hot table, and uniformly spraying the cathode catalyst slurry prepared in the step 1) on the surface of a bottom membrane by using an air gun; placing the other side of the bottom film in a metal frame in an upward mode, fixing the bottom film in a flat support, and uniformly spraying the anode catalyst slurry prepared in the step 2) on the other side of the bottom film by using an air gun;
furthermore, the temperature of the hot table is 30-80 ℃;
furthermore, the spraying times are 1-5 times;
the spin coating of the spin coater comprises the following steps: placing the flat support prepared in the step 4) on an adsorption table of a spin coater, laying a layer of cathode catalyst slurry prepared in the step 1) and dripping the cathode catalyst slurry on the surface of a basement membrane, starting the spin coater, uniformly coating the cathode catalyst slurry on the surface of the basement membrane, and drying the basement membrane; placing the other side of the base membrane upwards in a metal frame, fixing the base membrane in a flat support, placing the base membrane on an adsorption table of a spin coater, spreading the anode catalyst slurry prepared in the step 2) layer by layer and dropping the anode catalyst slurry on the other side of the base membrane, starting the spin coater, uniformly coating the anode catalyst slurry on the other side of the base membrane, and drying the base membrane;
the spin coating conditions are that the rotating speed is 1000-3000 kilorevolutions per minute, the time is 5-20 s, and the times are 1-3; the drying temperature is 30-80 ℃;
the glass rod coating method comprises the following steps: adhering two sides of the bottom film prepared in the step 3) to a flat support by using a transparent adhesive tape, uniformly coating the cathode catalyst slurry prepared in the step 1) on the surface of the bottom film by using a glass rod, and immediately placing the bottom film in an oven for drying; adhering the other side of the bottom film to a flat support by using a transparent adhesive tape, uniformly coating the positive catalyst slurry prepared in the step 2) on the other side of the bottom film by using a glass rod, and immediately placing the bottom film in an oven for drying;
the drying temperature is 30-80 ℃.
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