CN114420945A - Anode catalyst slurry and preparation method thereof, water electrolysis membrane electrode and preparation method thereof - Google Patents
Anode catalyst slurry and preparation method thereof, water electrolysis membrane electrode and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 144
- 239000012528 membrane Substances 0.000 title claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000002002 slurry Substances 0.000 title claims abstract description 70
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000007613 slurry method Methods 0.000 title description 2
- 239000011347 resin Substances 0.000 claims abstract description 45
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000007787 solid Substances 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 238000000227 grinding Methods 0.000 claims abstract description 27
- 239000013067 intermediate product Substances 0.000 claims abstract description 27
- 238000000498 ball milling Methods 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 9
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 9
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical group [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 6
- 229920000557 Nafion® Polymers 0.000 claims description 5
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 claims description 3
- DZQBLSOLVRLASG-UHFFFAOYSA-N iridium;methane Chemical compound C.[Ir] DZQBLSOLVRLASG-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000002245 particle Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
An anode catalyst slurry and a preparation method thereof, a water electrolysis membrane electrode and a preparation method thereof belong to the technical field of new energy. The preparation method of the anode catalyst slurry comprises the following steps: s1, mixing the catalyst, a part of solvent and a perfluorinated sulfonic acid resin solution, and grinding for the first time to obtain an intermediate product with the viscosity of more than 5000mpa.s and the solid content of the catalyst of 15-25 wt%. And S2, adding the rest solvent into the intermediate product, and grinding for the second time to obtain anode catalyst slurry with the viscosity of 500-1000 mpa.s and the solid content of the catalyst of 3-6 wt%. Wherein, the first grinding includes: sanding for at least 1h under the condition that the rotating speed is 1000-2000 rpm; or, the ball milling is carried out for at least 10 hours under the condition that the rotating speed is 500-600 rpm, and the anode catalyst slurry with low solid content and high viscosity can be prepared on the premise of not introducing additional additives.
Description
Technical Field
The application relates to the technical field of new energy, in particular to anode catalyst slurry and a preparation method thereof, a water electrolysis membrane electrode and a preparation method thereof.
Background
The impact of water electrolysis bubbles and circulating water flow can cause the anode catalyst layer to fall off from the water electrolysis membrane electrode, so that the performance of the water electrolysis membrane electrode is attenuated, the service life of the water electrolysis membrane electrode is shortened, and the bonding force between the catalyst layers is enhanced, which is an effective scheme for effectively solving the problems.
The existing preparation process of anode catalyst slurry has low slurry viscosity and is not suitable for a coating process. To increase the viscosity of the slurry, it is common practice to: (1) on the premise that the raw materials selected by the slurry are not changed, the solid content of the slurry is improved to improve the viscosity, and the pure improvement of the solid content can influence the dispersion effect and the coating effect of the catalyst, cannot meet the requirements of the coating process, and is easy to cause the problems of agglomeration, sedimentation and the like, so that the surface coating of the catalyst layer is not uniform. (2) The method of introducing additional additives, such as a stabilizer, into the raw materials ensures the dispersion effect and greatly improves the solid content and viscosity of the slurry.
Therefore, how to provide a slurry with low solid content and high viscosity without introducing additional additives is a technical problem which needs to be solved urgently by the technical personnel in the field.
Disclosure of Invention
The application provides anode catalyst slurry and a preparation method thereof, a water electrolysis membrane electrode and a preparation method thereof, which can prepare low-solid-content high-viscosity slurry on the premise of not introducing additional additives.
The embodiment of the application is realized as follows:
in a first aspect, the present application provides a method of preparing an anode catalyst slurry, comprising the steps of:
s1, mixing the catalyst, a part of solvent and a perfluorinated sulfonic acid resin solution, and grinding for the first time to obtain an intermediate product with the viscosity of more than 5000mpa.s and the solid content of the catalyst of 15-25 wt%.
And S2, adding the rest solvent into the intermediate product, and grinding for the second time to obtain anode catalyst slurry with the viscosity of 500-1000 mpa.s and the solid content of the catalyst of 3-6 wt%.
Wherein, the first grinding includes: sanding for at least 1h under the condition that the rotating speed is 1000-2000 rpm; or ball milling for at least 10h under the condition that the rotating speed is 500-600 rpm.
According to the preparation method of the anode catalyst slurry, the branched chain of the perfluorosulfonic acid resin is fully extended through the first long-time grinding, the perfluorosulfonic acid resin is coated on the surface of the catalyst, and part of the perfluorosulfonic acid resin is dispersed in the solvent in the step S1, so that in the subsequent step S2, the intermediate product is uniformly dispersed in the rest solvent through the second grinding, and the anode catalyst slurry with high viscosity and low solid content can be obtained after the intermediate product is diluted by the rest solvent. When the low-solid-content high-viscosity slurry prepared by the preparation method is applied to a water electrolysis membrane electrode, when the anode catalyst slurry is coated on the anode side of a proton exchange membrane and dried, free perfluorosulfonic acid resin and perfluorosulfonic acid resin coating the catalyst are crosslinked along with solvent evaporation, so that the binding force between catalyst particles is enhanced, and the binding force between a catalyst layer and the proton exchange membrane is further enhanced. Optionally, the first grinding comprises: sanding for 1-3 h under the condition that the rotating speed is 1000-2000 rpm; or ball milling is carried out for at least 10-20 h under the condition that the rotating speed is 500-600 rpm. In some optional embodiments, the second grinding comprises: sanding for 20-40 min under the condition that the rotating speed is 1000-2000 rpm; or ball milling for 20-40 min under the condition that the rotating speed is 500-600 rpm.
In some alternative embodiments, in step S1, the weight ratio of catalyst to X is 1: (0.2 to 1).
In some alternative embodiments, the catalyst is an iridium-based catalyst including at least one of an iridium carbon catalyst, an iridium ruthenium catalyst, and an iridium oxide catalyst.
In some alternative embodiments, the solvent is a mixture of water and an alcohol solvent.
Optionally, the alcohol solvent is at least one of ethanol, n-propanol, isopropanol, and ethylene glycol.
Optionally, the mass ratio of water to the alcohol solvent is 1:0.5 to 1.
In some optional embodiments, the concentration of the perfluorosulfonic acid resin in the perfluorosulfonic acid resin solution is 5 to 30 wt%, and the concentration of the perfluorosulfonic acid resin may be optionally 10 to 30 wt%.
Optionally, the perfluorinated sulfonic acid resin solution is at least one of dupont Nafion resin, solvay D79 series resin, asahi nitroxide IC100 resin, asahi nitroxide IC154 resin.
In a second aspect, the present application provides an anode catalyst slurry suitable for a water electrolysis membrane electrode, which is prepared by the preparation method provided by the first aspect of the present application.
Compared with the existing anode catalyst slurry, the anode catalyst slurry provided by the application has the advantages that on the basis of unchanged raw materials, only through the improvement of the preparation method, the high-viscosity low-solid-content slurry with the viscosity of 500-1000 mpa.s and the solid content of 3-6 wt% can be obtained, the slurry is conveniently and uniformly coated on a proton exchange membrane, and after the slurry is coated on the proton exchange membrane and dried, the binding force among catalyst particles can be effectively enhanced, and the occurrence probability that an anode catalyst layer falls off from a water electrolysis membrane electrode due to the impact of water electrolysis bubbles and circulating water flow is reduced.
In a third aspect, the present application provides a water electrolysis membrane electrode comprising a proton exchange membrane and an anode catalyst layer formed on the anode side of the proton exchange membrane, wherein the anode catalyst layer is made from the anode catalyst slurry provided in the second aspect of the present application.
Under the above conditions, the anode catalyst layer is prepared from the anode catalyst slurry provided by the second aspect of the present application, so that the binding force between catalyst particles and the binding force between the catalyst layer and the proton exchange membrane can be effectively enhanced.
In a fourth aspect, the present application provides a method for preparing a water electrolysis membrane electrode, comprising: the anode catalyst slurry provided by the second aspect of the present application is applied to the anode side of a proton exchange membrane and dried.
The preparation method of the water electrolysis membrane electrode is simple and convenient to operate, and by improving the anode catalyst slurry, the binding force between catalyst particles can be effectively enhanced, and the probability of falling off of the anode catalyst layer from the water electrolysis membrane electrode caused by impact of water electrolysis bubbles and circulating water flow is reduced.
In some optional embodiments, the coating loading of the anode catalyst slurry on one side of the proton exchange membrane is 0.5-1 mg/cm2。
Optionally, the coating manner is slot coating.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The application provides anode catalyst slurry with high viscosity and low solid content, which is suitable for a water electrolysis membrane electrode. It should be noted that the solid content in the present application refers to the solid content of the catalyst.
The viscosity of the anode catalyst slurry is 500-1000 mpa.s, the solid content of the anode catalyst slurry is 3-6 wt%, the anode catalyst slurry is low in solid content and can be coated uniformly easily, the problems of agglomeration, sedimentation and the like are avoided, meanwhile, the viscosity of the anode catalyst slurry is 500-1000 mpa.s, the problem of glue overflow after coating can be avoided, meanwhile, in the process of preparing the water electrolysis membrane electrode, the anode catalyst slurry is coated on a proton exchange membrane and dried, the binding force among catalyst particles can be effectively enhanced, and the probability of occurrence that the anode catalyst layer falls off from the water electrolysis membrane electrode due to impact of water electrolysis bubbles and circulating water flow is reduced.
The anode catalyst slurry is prepared by the following preparation method:
s1, mixing the catalyst, a part of solvent and a perfluorinated sulfonic acid resin solution, and grinding for the first time to obtain an intermediate product with the viscosity of more than 5000mpa.s and the solid content of the catalyst of 15-25 wt%.
The catalyst is a catalyst which can be used in an anode catalyst layer of the water electrolysis membrane electrode, and the catalyst is usually an oxygen evolution catalyst, so in some optional embodiments provided by the application, the catalyst is an iridium-based catalyst which is a catalyst loaded with doped or undoped active metal iridium or iridium oxide on a carrier, and the iridium-based catalyst has high catalytic activity and can effectively improve the performance of the water electrolysis membrane electrode.
Optionally, the iridium-based catalyst comprises at least one of an iridium carbon catalyst, an iridium ruthenium catalyst, and an iridium oxide catalyst.
The solvent is used as a dispersing agent, and is optionally mixed with water and an alcohol solvent; to avoid introducing impurities, the water is deionized water.
Optionally, the mass ratio of water to the alcohol solvent is 1: 0.5-1, for example, the mass ratio of water to the alcohol solvent is 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, or 1:1, and the like, under the configuration, the solvent has good dispersion effect on the catalyst.
Optionally, the alcohol solvent is at least one of ethanol, n-propanol, isopropanol and ethylene glycol, and the alcohol solvent has a low boiling point and is convenient for subsequent removal.
The perfluorinated sulfonic acid resin solution can be directly purchased from the market, and can also be prepared by dissolving perfluorinated sulfonic acid resin in an organic solvent.
Optionally, in the perfluorinated sulfonic acid resin solution, the concentration of the perfluorinated sulfonic acid resin is 5-30 wt%; for example, the concentration of perfluorosulfonic acid resin is 5 wt%, 7 wt%, 10 wt%, 13 wt%, 15 wt%, 20 wt%, 23 wt%, 25 wt%, or 30 wt%, etc.
Wherein the concentration of the perfluorinated sulfonic acid resin can be selected to be 10-30 wt%.
Among these, perfluorosulfonic acid resin solutions include, but are not limited to, DuPont Nafion, 3M, Asahi Glass, Asahi Kasei, Solvay, and the like.
Optionally, the perfluorinated sulfonic acid resin solution is at least one of dupont Nafion resin, solvay D79 series resin, asahi nitroxide IC100 resin, asahi nitroxide IC154 resin.
Alternatively, in step S1, taking the dry weight of the perfluorosulfonic acid resin solution as X, the weight ratio of the catalyst to X is 1: (0.2-1), for example, the weight ratio of the catalyst to X is 1: 0.2, 1:0.4, 1:0.5, 1:0.7, 1:0.9, 1:1, etc.
The mixing method of the catalyst, the partial solvent and the perfluorosulfonic acid resin solution includes, but is not limited to, stirring and mixing, and may be ultrasonic mixing or shear mixing using an emulsifier or the like.
Wherein, the first grinding includes: sanding for at least 1h under the condition that the rotating speed is 1000-2000 rpm; or ball milling is carried out for at least 10 hours under the condition that the rotating speed is 500-600 rpm, wherein in the application and the embodiment, the material ball ratio is 0.85, the grinding balls D50 are 0.6-1.5 mu m, and the grinding balls D90 are 2.5-3.5 mu m.
Optionally, the first grinding comprises: sanding for 1-3 h under the condition that the rotating speed is 1000-2000 rpm; or ball milling is carried out for at least 10-20 h under the condition that the rotating speed is 500-600 rpm. Specifically, for example, the first grinding is performed by sanding for 1h, 1.5h, 2h, 2.5h, 3h, etc. at a rotation speed of 1000rpm, 1200rpm, 1400rpm, 1500rpm, 1700rpm, 1800 rpm, or 2000 rpm; alternatively, the first milling is ball milling at 500rpm, 520rpm, 530rpm, 550rpm, 570rpm, 580rpm, 590rpm or 600rpm for 10h, 12h, 15h, 16h, 18h or 20h, etc.
Under the grinding condition, the branched chain of the perfluorosulfonic acid resin can be fully extended, the perfluorosulfonic acid resin is coated on the surface of the catalyst, and part of the perfluorosulfonic acid resin is dispersed in the solvent in the step S1, so that in the subsequent step S2, the intermediate product is uniformly dispersed in the rest solvent by using the second grinding, the intermediate product is diluted by using the rest solvent, the anode catalyst slurry with high viscosity and low solid content can be obtained, and the free perfluorosulfonic acid resin and the perfluorosulfonic acid resin coating the catalyst are crosslinked along with the evaporation of the solvent, so that the binding force between catalyst particles is enhanced, and the binding force between the catalyst layer and the proton exchange membrane is further enhanced.
And S2, adding the rest solvent into the intermediate product, and grinding for the second time to obtain anode catalyst slurry with the viscosity of 500-1000 mpa.s and the solid content of the catalyst of 3-6 wt%.
And adding the rest solvent into the intermediate product, and uniformly diluting the intermediate product by using second grinding to reduce the viscosity and the solid content of the catalyst, wherein the total amount of the solvent added in the step S1 and the step S2 is 15-30 times of the mass of the catalyst, and the amount of the solvent added in the step S1 and the step S2 can be adjusted according to the solid content, which is not limited herein.
Optionally, the second grinding comprises: sanding for 20-40 min under the condition that the rotating speed is 1000-2000 rpm; or ball milling for 20-40 min under the condition that the rotating speed is 500-600 rpm. Specifically, for example, the second grinding is performed by sanding at 1000rpm, 1200rpm, 1400rpm, 1500rpm, 1700rpm, 1800 rpm, or 2000rpm for 20min, 25min, 30min, 35min, 37min, or 40min, etc.; alternatively, the second milling is performed by ball milling at 500rpm, 520rpm, 530rpm, 550rpm, 570rpm, 580rpm, 590rpm or 600rpm for 20min, 25min, 30min, 35min, 37min or 40min, etc. The second ball milling under the above conditions can sufficiently mix the intermediate product with the remaining solvent, so that the catalyst is uniformly dispersed in the anode catalyst slurry.
In summary, the anode catalyst slurry with a viscosity of 500-1000 mpa.s and a solid content of 3-6 wt% can be prepared by the steps of S1 and S2.
The application provides a water electrolysis membrane electrode, which comprises a proton exchange membrane and an anode catalyst layer formed on the anode side of the proton exchange membrane, wherein the anode catalyst layer is prepared from the anode catalyst slurry provided by the application, and the binding force between catalyst particles and the binding force between the catalyst layer and the proton exchange membrane can be effectively enhanced.
The application provides a preparation method of a water electrolysis membrane electrode, which comprises the following steps: coating the anode catalyst slurry provided by the application on the anode side of a proton exchange membrane, and drying; an anode catalyst layer was obtained.
The preparation method of the water electrolysis membrane electrode further comprises the following steps: after the anode catalyst layer is formed, a Pt-containing cathode catalyst layer is formed on the other side (i.e., the cathode side) of the proton exchange membrane away from the anode catalyst layer, to obtain a water electrolysis membrane electrode. Or the preparation method of the water electrolysis membrane electrode also comprises the following steps: before the anode catalyst layer is formed, a cathode catalyst layer containing Pt is formed on the cathode side of the proton exchange membrane in advance to obtain a water electrolysis membrane electrode.
The proton exchange membrane may be made of perfluorosulfonic acid, polystyrene sulfonic acid, polytrifluorostyrenesulfonic acid, phenol resin sulfonic acid, or hydrocarbon, and specifically, for example, the proton exchange membrane is one of a Nafion proton exchange membrane and a PBI proton exchange membrane.
Alternatively, the coating loading of the anode catalyst slurry on the proton exchange membrane is 0.5mg/cm2～1mg/cm2For example, the coating loading of the anode catalyst slurry on a single side of the proton exchange membrane is 0.5mg/cm2、0.6mg/cm2、0.7mg/cm2、0.8mg/cm2、0.9mg/cm2Or 1mg/cm2And the like.
The anode catalyst slurry prepared by the method has low solid content and high viscosity, and is convenient to coat uniformly, so that the coating mode is slit coating optionally, and the coating uniformity can be further improved on the premise of high coating speed.
The anode catalyst paste and the preparation method thereof, and the water electrolyte membrane electrode and the preparation method thereof according to the present application will be described in further detail with reference to examples below.
Example 1
S1, weighing 2g of iridium oxide, 5g of deionized water, 3g of isopropanol and 3g of Dupont D2020 solution (the concentration is 20 wt%), and uniformly mixing by ultrasonic waves to obtain a mixture.
S2, the mixture is put into a ball mill, and ball milling is carried out for 18h under the condition that the rotating speed is 500rpm, so that an intermediate product with the viscosity of 5000mpa.s and the solid content of the catalyst of 15.4 wt% is obtained.
S3, adding 20g of deionized water and 20g of isopropanol into the intermediate product, and carrying out ball milling for 30min under the condition that the rotating speed is 500rpm to obtain anode catalyst slurry with the viscosity of 700mpa.s and the solid content of 3.8 wt%.
S4, obtaining an N115 membrane with a cathode catalytic layer on a cathode, coating anode catalyst slurry on one side of the N115 membrane far away from the cathode catalytic layer,the coating load was 0.5mg/cm2And then dried at 50 ℃. Wherein the cathode catalyst is Pt/C, and the coating loading is 0.5mg/cm2. Thus obtaining the water electrolysis membrane electrode.
Example 2
S1, weighing 2g of iridium oxide, 4g of deionized water, 2g of isopropanol and 4g of Dupont D2020 solution (the concentration is 20 wt%), and uniformly mixing by ultrasonic waves to obtain a mixture.
S2, the mixture is put into a sand mill and is subjected to sand milling for 1h under the condition that the rotating speed is 1000rpm, and an intermediate product with the viscosity of 5000mpa.s and the solid content of 16.7 wt% is obtained.
S3, adding 20g of deionized water and 20g of isopropanol into the intermediate product, and sanding for 30min under the condition that the rotating speed is 1000rpm to obtain anode catalyst slurry with the viscosity of 700mpa.s and the solid content of 3.8 wt%.
S4, obtaining an N117 membrane with a cathode catalytic layer on a cathode, coating anode catalyst slurry on one side of the N117 membrane far away from the cathode catalytic layer, wherein the coating loading is 0.5mg/cm2And then dried at 50 ℃. Wherein the cathode catalyst is Pt/C, and the coating loading is 0.5mg/cm2. Thus obtaining the water electrolysis membrane electrode.
Example 3
S1, weighing 2g of iridium oxide, 3g of deionized water, 3g of n-propanol and 3g of Dupont D2020 solution (the concentration is 20 wt%), and uniformly mixing by ultrasonic waves to obtain a mixture.
S2, the mixture is put into a ball mill, and ball milling is carried out for 20 hours under the condition that the rotating speed is 550rpm, so that an intermediate product with the viscosity of 5500mpa.s and the solid content of 18.2 wt% is obtained.
S3, adding 20g of deionized water and 20g of n-propanol into the intermediate product, and carrying out ball milling for 30min under the condition that the rotation speed is 550rpm to obtain anode catalyst slurry with the viscosity of 700mpa.s and the solid content of 3.9 wt%.
S4, obtaining an N117 membrane with a cathode catalytic layer on a cathode, coating anode catalyst slurry on one side of the N117 membrane far away from the cathode catalytic layer, wherein the coating loading is 0.5mg/cm2And then dried at 50 ℃. Wherein the cathode catalyst is Pt/C, and the coating loading is 0.5mg/cm2. Thus obtaining the water electrolysis membrane electrode.
Comparative example 1
It differs from example 1 only in that: in step S2, the mixture was put into a ball mill and ball milled at 500rpm for 4 hours to obtain an intermediate product with a viscosity of 500mpa.s and a solid content of 15.4 wt%.
S3, adding 20g of deionized water and 20g of isopropanol into the intermediate product, and carrying out ball milling for 30min under the condition that the rotating speed is 500rpm to obtain anode catalyst slurry with the viscosity of 80mpa.s and the solid content of 3.8 wt%.
Comparative example 2
It differs from example 1 only in that:
s1, weighing 2g of iridium oxide, 1g of deionized water, 0.5g of isopropanol and 3g of DuPont D2020 solution (the concentration is 20 wt%), and ultrasonically mixing uniformly to obtain a mixture.
S2, putting the mixture into a ball mill, and performing ball milling for 1h under the condition that the rotating speed is 500rpm to obtain slurry with the viscosity of 6000mpa.s and the solid content of 30.8 wt%.
S3, adding 24g of deionized water and 24g of isopropanol into the intermediate product, and carrying out ball milling for 30min under the condition that the rotating speed is 500rpm to obtain anode catalyst slurry with the viscosity of 700mpa.s and the solid content of 3.8 wt%.
Comparative example 3
It differs from example 1 only in that: s1, weighing 2g of iridium oxide, 5g of deionized water and 3g of isopropanol, and ultrasonically mixing uniformly to obtain a mixture.
S2, putting the mixture into a ball mill, carrying out ball milling for 18h under the condition that the rotation speed is 500rpm, then adding 3g of DuPont D2020 solution (the concentration is 20 wt%), carrying out ball milling and dispersing for 1h under the condition that the rotation speed is 500rpm, and obtaining an intermediate product with the viscosity of 1000mpa.s and the solid content of 15.4 wt%.
Test example 1
The water electrolysis membrane electrodes of examples 1 to 3 and comparative examples 1 to 3 were weighed as pre-test masses, then each water electrolysis membrane electrode was assembled into a single cell, the water electrolysis performance test was performed at 50 ℃ under standard atmospheric pressure for 50 hours, after the test was completed, the cell was disassembled, each water electrolysis membrane electrode after the test was weighed to obtain post-test masses, and the mass loss was calculated as mass loss (pre-test mass-post-test mass)/pre-test mass x 100%. The results are shown in Table 1.
TABLE 1 test results
| Mass/mg before test | Mass/mg after test | Mass loss/%) | |
| Example 1 | 26.52 | 25.00 | 0.075 |
| Example 2 | 26.52 | 25.00 | 0.075 |
| Example 3 | 25.52 | 25.49 | 0.118 |
| Comparative example 1 | 27.52 | 27.33 | 0.690 |
| Comparative example 2 | 27.14 | 26.99 | 0.553 |
| Comparative example 3 | 27.72 | 27.45 | 0.974 |
It is known to those skilled in the art that when the catalyst solids content in the slurry is within a certain range, the greater the viscosity, the greater the adhesion and the lower the mass loss.
As shown in table 1, the short ball milling time in step S2 of comparative example 1 resulted in a viscosity lower than that of example 1 and a significantly higher quality loss of the water electrolyte membrane electrode after the test than that of example 1, although the solid content was the same as that of example 1.
Although the solid content and viscosity of the anode catalyst slurry finally obtained in comparative example 2 are respectively the same as those of example 1, the loss of quality of the water electrolyte membrane electrode after the test is significantly higher in the actual test process than that of example 1 because the ball milling time of comparative example 2 in step S2 is shorter.
Comparing comparative example 3 with example 1, it can be seen that the participation of perfluorosulfonic acid resin solution is required in the ball milling process of step S2, if the milling sequence is changed, the viscosity of the intermediate product is significantly reduced and is lower than that of example 1, finally the intermediate product of comparative example 3 is processed by steps S3 and S4 which are the same as those of example 1 to obtain a water electrolyte membrane electrode, and after the test, the quality loss of the water electrolyte membrane electrode of comparative example 3 is significantly higher than that of example 1.
In summary, the present application provides a method for preparing an anode catalyst slurry, which can prepare a low-solid-content high-viscosity slurry without introducing additional additives, and the low-solid-content high-viscosity slurry can effectively enhance the binding force between catalyst particles after actually preparing a water electrolysis membrane electrode, and reduce the probability of occurrence of falling-off of an anode catalyst layer from the water electrolysis membrane electrode due to impact of water electrolysis bubbles and circulating water flow.
The foregoing is merely exemplary of the present application and is not intended to limit the present application, which may be modified or varied by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A preparation method of anode catalyst slurry is characterized by comprising the following steps:
s1, mixing the catalyst, a part of solvent and a perfluorinated sulfonic acid resin solution, and grinding for the first time to obtain an intermediate product with the viscosity of more than 5000mpa.s and the solid content of the catalyst of 15-25 wt%;
s2, adding the rest solvent into the intermediate product, and grinding for the second time to obtain the anode catalyst slurry with the viscosity of 500-1000 mpa.s and the solid content of the catalyst of 3-6 wt%;
wherein the first grinding comprises: sanding for at least 1h under the condition that the rotating speed is 1000-2000 rpm; or, ball-milling for at least 10h under the condition that the rotating speed is 500-600 rpm;
optionally, the first grinding comprises: sanding for 1-3 h under the condition that the rotating speed is 1000-2000 rpm; or ball milling is carried out for at least 10-20 h under the condition that the rotating speed is 500-600 rpm.
2. The method of claim 1, wherein the second grinding comprises: sanding for 20-40 min under the condition that the rotating speed is 1000-2000 rpm; or ball milling for 20-40 min under the condition that the rotating speed is 500-600 rpm.
3. The production method according to claim 1, wherein in step S1, the weight ratio of the catalyst to X is 1: (0.2 to 1).
4. The production method according to claim 1, wherein the catalyst is an iridium-based catalyst including at least one of an iridium carbon catalyst, an iridium ruthenium catalyst, and an iridium oxide catalyst.
5. The method according to claim 1, wherein the solvent is a mixture of water and an alcohol solvent;
optionally, the alcohol solvent is at least one of ethanol, n-propanol, isopropanol and ethylene glycol;
optionally, the mass ratio of the water to the alcohol solvent is 1:0.5 to 1.
6. The preparation method according to any one of claims 1 to 5, wherein the concentration of the perfluorosulfonic acid resin in the perfluorosulfonic acid resin solution is 5 to 30 wt%, and the concentration of the perfluorosulfonic acid resin is optionally 10 to 30 wt%;
optionally, the perfluorinated sulfonic acid resin solution is at least one of dupont Nafion resin, solvay D79 series resin, asahi nitroxide IC100 resin, and asahi nitroxide IC154 resin.
7. An anode catalyst slurry suitable for a water electrolysis membrane electrode, wherein the anode catalyst slurry is prepared by the preparation method of any one of claims 1 to 6.
8. A water electrolysis membrane electrode comprising a proton exchange membrane and an anode catalyst layer formed on the anode side of the proton exchange membrane, wherein the anode catalyst layer is made from the provided anode catalyst slurry provided in claim 7.
9. A method for preparing a water electrolysis membrane electrode is characterized by comprising the following steps: the anode catalyst slurry according to claim 7 is applied to the anode side of a proton exchange membrane and dried to obtain an anode catalyst layer.
10. The preparation method of claim 9, wherein the coating loading of the anode catalyst slurry on the proton exchange membrane is 0.5-1 mg/cm2；
Optionally, the coating manner is slot coating.
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