CN111446458A - Cathode catalyst for fuel cell - Google Patents
Cathode catalyst for fuel cell Download PDFInfo
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- CN111446458A CN111446458A CN202010320797.9A CN202010320797A CN111446458A CN 111446458 A CN111446458 A CN 111446458A CN 202010320797 A CN202010320797 A CN 202010320797A CN 111446458 A CN111446458 A CN 111446458A
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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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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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
- H01M4/88—Processes of manufacture
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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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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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
- 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
- Y02E60/50—Fuel cells
Abstract
The invention claims a cathode catalyst for a fuel cell and a preparation method thereof. The cathode catalyst is of a core-shell structure and comprises a conductive core positioned in the center of the core, an intermediate carrier layer coated on the periphery of the conductive core and a catalyst layer on the outermost layer; wherein the conductive core is selected from carbon, a non-carbon conductor, or a combination thereof, and the intermediate support layer is composed of a metal oxide. The cathode catalyst utilizes the metal oxide intermediate carrier layer to protect the conducting layer from oxidation corrosion on one hand, thereby prolonging the service life of the catalyst; on the other hand, the catalytic layer nano particles on the surface of the carrier layer are effectively dispersed by controlling the spinous shape of the surface of the carrier layer in the middle of the metal oxide, so that the using amount of the catalytic layer nano particles is reduced, and the problem of catalytic performance attenuation caused by migration and agglomeration on the carrier is solved.
Description
Technical Field
The invention belongs to the technical field of chemistry, and particularly relates to a hydrogen fuel cell, in particular to a noble metal hydrogen fuel cell composite structure cathode catalyst.
Background
A fuel cell is a chemical device that directly converts chemical energy of fuel into electrical energy, and is also called an electrochemical generator. It is a fourth power generation technology following hydroelectric power generation, thermal power generation and atomic power generation. The fuel cell is high in efficiency because the gibbs free energy in the chemical energy of the fuel is partially converted into electric energy through electrochemical reaction without being limited by the carnot cycle effect.
While hydrogen fuel cells have received much attention for their characteristics of being operable at lower temperatures and being environmentally friendly, Polymer Electrolyte Fuel Cells (PEFCs) have also received much attention as one of the representatives of hydrogen fuel cells.
The catalysts used in PEFC are mainly Pt-based catalysts, and Pt as a rare metal greatly increases the cost of PEFC catalysts. Currently, the major work in advancing the commercial application of PEFC is focused on reducing Pt loading and increasing the catalytic activity of Pt-based catalysts.
In particular, in the cathode electrocatalyst of the prior art, the catalyst metal is usually directly dispersed in the carrier, and Oxygen Reduction Reaction (ORR) occurs in the PEFC cathode to generate oxygen-containing substances with strong oxidizability, which finally leads to the generation of CO and CO in the Pt/C composite electrode material under the action of the oxygen-containing substances2On the other hand, the dropping of the catalytic active Pt particles is caused, and the performance of the battery is reduced. The present invention is directed to solving the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to solve the technical problem of providing a fuel cell aiming at the defects of a Pt/C composite electrode material in the prior art.
In order to solve the technical problem, the invention provides a cathode catalyst for a fuel cell, which is of a core-shell structure and comprises a conductive core positioned in the center of the core, an intermediate carrier layer coated on the periphery of the conductive core and a catalyst layer on the outermost layer; wherein the conductive core is selected from carbon, non-carbon conductive or a combination thereof, and the intermediate support layer is composed of a metal oxide, more preferably, the intermediate support layer is a doped metal oxide.
In the preferred technical scheme of the invention, the outer surface of the conductive oxide of the middle carrier layer is in a spinous process shape, so that the catalytic layer nano particles on the surface of the carrier layer can be effectively dispersed, the consumption of catalytic metal is reduced, and the problem of catalytic performance attenuation caused by migration and agglomeration of the catalytic metal on the carrier is solved.
In the preferable technical scheme of the invention, the mass percentage of the conductive core in the catalyst is 10-99%, the mass percentage of the intermediate carrier layer in the catalyst is 0.1-70%, and the mass percentage of the catalytic layer in the catalyst is 0.01-20%. More preferably, the mass ratio of the conductive core is 65-99%, the mass ratio of the intermediate carrier layer is 0.1-30%, and the mass ratio of the catalytic layer is 0.01-5%.
The metal oxide of the middle carrier layer is tin oxide; more preferably, the doped tin oxide is doped tin oxide, and the doping element is selected from one or more of tantalum, antimony and indium. Preferably, the doping element is present in an amount of 0.1 to 10% by mole based on the total mole of the metal elements of the oxide.
In a preferred technical scheme of the invention, the catalytic layer is selected from simple substance platinum, simple substance palladium or simple substance ruthenium metal particles or alloy particles containing one or more than two metals.
In the preferred technical scheme of the invention, the catalyst layer is a composite metal core-shell particle, namely, the inner core is selected from one or more of cobalt, iron, nickel, copper and chromium, and the outer layer is selected from one or more of precious metals such as platinum, palladium, ruthenium and the like; preferably, the mass of the noble metal in the alloy composite structure is 1 to 40%.
In the preferred technical scheme of the invention, the catalyst particles are preferably nano metal nanoparticles, and the size of the particles is 0.1-10 nm.
The conductive core is selected from one or more of graphene, conductive oxide, carbon nano tube and Ketjen black, and preferably the Ketjen black.
The present invention also provides a method of preparing a cathode catalyst for a fuel cell, comprising the steps of:
a-1, adding metal salt of an intermediate carrier layer into an aqueous solution, dissolving, then immersing into a material of a conductive core, adjusting the pH value to 7-10, carrying out hydrothermal reaction at 80-120 ℃, carrying out suction filtration, washing, drying and precipitating to form a composite carrier for later use;
b-1, preparing an organic reducing agent/water mixed solvent containing metal ions of the catalyst layer, uniformly stirring, adjusting the pH value to be more than 12, adding the composite carrier of A-1, carrying out reflux reaction at the temperature of 140 ℃, filtering, washing and drying after the reaction is finished. Wherein, the metal ions of the catalytic layer are selected from one or more of platinum, palladium or ruthenium.
Yet another method of preparing a cathode catalyst for a fuel cell, comprising the steps of:
a-2, adding metal salt of an intermediate carrier layer into an aqueous solution, dissolving, then immersing into a material of a conductive core, adjusting the pH value to 7-10, carrying out hydrothermal reaction at 80-120 ℃, carrying out suction filtration, washing, drying and precipitating to form a composite carrier for later use;
b-2, adding soluble cobalt, iron, nickel, copper and chromium metal salts into a mixed solvent of an organic reducing agent/water, uniformly stirring, adjusting the pH value to be more than 12, adding the composite carrier of A-2, carrying out reflux reaction at 140 ℃, filtering and washing after the reaction is finished to obtain composite particles for later use;
and C-2, adding soluble platinum, palladium and ruthenium metal salts into a mixed solvent of an organic reducing agent/water, uniformly stirring, adding the composite particles prepared in the step B-2, reacting at 20-80 ℃ for 1-8h, filtering and washing after the reaction is finished, and finally drying.
In the preparation method, the metal salt of the intermediate carrier layer is selected from stannous chloride, and further comprises one or more of soluble salts such as tantalum, antimony, indium and the like.
In the preparation method, the organic reducing agent is selected from one or more of organic reducing agents containing hydroxyl, aldehyde and phenolic hydroxyl, and preferably contains hydroxyl; more preferably, it is selected from ethylene glycol, glycerol or ethanol. Preferably, the water-alcohol solvent has a water volume ratio of 25 to 50%.
In the step A-1 or A-2, the addition amount of the conductive core material is 0.5-5% of the mass of the solution, and the mass fraction of the metal salt solute in the solution is 2.5-25%.
In the process of the present invention, the pH adjusting solution includes, but is not limited to, ammonia, urea, hexamethylenetetramine.
In the method, the metal salt of the intermediate carrier layer is selected from stannous chloride and one or more of tantalum chloride, antimony chloride and indium chloride soluble salt.
The metal salt of the intermediate carrier layer is soluble metal tin salt and also comprises possible doped metal salt; can be represented by the formula (A)xSn1-x)O2Stoichiometric calculations are carried out, a represents one of Ta, Sb, In, preferably Ta, and X represents the content of doping metal with a value of 0 to 0.1, preferably a doping content of 10% (mole percent).
In the method, the organic reducing agent is selected from one or more of organic reducing agents containing hydroxyl, aldehyde group and phenolic hydroxyl; more preferably, the hydroxyl-containing reducing agent is selected from one or more of ethylene glycol, glycerol or ethanol.
The preparation method of the cathode catalyst for a fuel cell of the present invention comprises the steps of:
A. preparation of the conductive layer and the intermediate carrier layer substrate:
dissolving soluble metal tin salt and doped metal salt in deionized water according to chemical formula (A)xSn1-x)O2And performing stoichiometric calculation, wherein A represents one of Ta, Sb and In, and preferably Ta. X represents the content of doping metal and has a value of 0 to 0.1, preferably a doping content of 10% (mole percent); the mass fraction of the metal salt in the soluble metal salt solution is 2.5-25%, preferably 20%, the conductive material with the mass fraction of 0.5-5% is added into the metal salt solution and continuously stirred and dispersed, and the conductive material can be carbon nano tubes, metal oxides, ketjen black, graphene and the like, preferably ketjen black, and the mass fraction is preferably 5%. After dispersion, adding one of ammonia water, urea and hexamethylenetetramine into the solution, adjusting the pH value to 7-10, placing the adjusted solution into a sealed polytetrafluoroethylene tank, carrying out hydrothermal reaction at 80-120 ℃ for 8-24h, filtering after the reaction is finished, repeatedly washing insoluble substances by deionized water, and drying at 50-100 ℃;
B. and (3) loading precious metal on the catalytic layer:
ethylene glycol, glycerol or ethanol is used as a reducing agent,preferably ethanol, in an ethanol/water system, e.g. taking a certain amount of H2PtCl6Dissolving in ethanol, adding into a certain amount of deionized water, fully dissolving, adjusting pH to above 12 with ammonia water, adding a certain amount of the matrix prepared in step A, ultrasonically dispersing for 30-60min, heating to 100-2Drying at medium 80 deg.C for 2h to obtain soluble Pt salt solution with mass fraction of 0.1-10%, preferably 10%, and water volume of 25-50%, preferably 25% in ethanol/water system.
In a preferred embodiment, the step B may be replaced by: b' catalytic layer noble metal alloy or composite structure load:
adopting a reducing solvent such as ethylene glycol, glycerol, ethanol and the like, dissolving metal salt such as soluble cobalt, iron, nickel, copper, chromium salt and the like, adding the substrate material in an amount of 0.1-5% of the mass of the solution, and reacting at the temperature of 200 ℃ for 4-12h, wherein the mass fraction of solute soluble metal salt in the solution is 0.1-10%; the displacement reaction solution is a solution containing one or more of palladium, platinum and ruthenium ions, the mass of the composite particles is 0.5-5% of the mass of the displacement reaction solution, the mass fraction of the noble metal in the displacement solution is 0.01-1%, and the reaction is carried out for 1-8h at the temperature of 20-80 ℃.
The metal oxide is used as a carrier of the catalyst instead of carbon, so that the stability of the battery can be improved, and the service life of the battery can be prolonged. The invention aims at controlling the growth morphology of the substrate of the intermediate carrier layer (AxSn1-x) O2(A is a doping element) of the metal oxide, reducing the Pt content on the load substrate and reducing the cathode cost on the basis of ensuring the catalytic activity.
The invention has the beneficial effects that: the cathode catalyst utilizes the metal oxide intermediate carrier layer to protect the conducting layer from oxidation corrosion on one hand, thereby prolonging the service life of the catalyst; on the other hand, the catalytic layer nano particles on the surface of the carrier layer are effectively dispersed by controlling the spinous shape of the surface of the carrier layer in the middle of the metal oxide, so that the using amount of the catalytic layer nano particles is reduced, and the problem of catalytic performance attenuation caused by migration and agglomeration on the carrier is solved; and because the preparation method has simple process, the investment cost can be effectively saved, and the mass production can be quickly formed.
Drawings
Fig. 1 is a method for preparing a cathode catalyst according to an embodiment of the present invention.
Fig. 2 is a method for preparing a cathode catalyst according to still another embodiment of the present invention.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes and are not intended to limit the scope of the present invention. The conditions used in the examples may be further adjusted according to the conditions of the particular manufacturer, and the conditions not specified are generally the conditions in routine experiments.
Introduction and summary
The present invention is illustrated by way of example and not by way of limitation. It should be noted that references to "an" or "one" embodiment in this disclosure are not necessarily to the same embodiment, but to at least one.
Various aspects of the invention are described below. It will be apparent, however, to one skilled in the art that the present invention may be practiced according to only some or all aspects of the present invention. For purposes of explanation, specific numbers, materials and configurations are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced without specific details. In other instances, well-known features are omitted or simplified in order not to obscure the present invention.
Various operations will be described as multiple discrete steps in turn, and in a manner that is most helpful in understanding the present invention; however, the description in order should not be construed as to imply that these operations are necessarily order dependent.
Various embodiments will be described in terms of typical classes of reactants. It will be apparent to those skilled in the art that the present invention may be practiced using any number of different types of reactants, not just those provided herein for purposes of illustration. Furthermore, it will also be apparent that the invention is not limited to any particular hybrid example.
Example 1 preparation of hydrogen fuel cell catalyst 1
(1) Preparing an aqueous solution with solutes of stannous chloride and tantalum chloride, wherein the tantalum accounts for 3 mol percent of the total metal ions, the mass fraction of the solute is 8.3%, adding 5g of Ketjen black into 200g of the aqueous solution, uniformly stirring, adding ammonia water to adjust the pH of the aqueous solution to 9, placing the adjusted solution into a sealed polytetrafluoroethylene tank, carrying out hydrothermal reaction at 120 ℃ for 8 hours, carrying out suction filtration-deionized water washing for multiple times after the reaction is finished, wherein the composite base material contains 39.6% of carbon and 60.4% of oxide;
(2) make solute as H2PtCl6Adding ammonia water to adjust the pH value to 12, adding 100g of the solution into 5g of the composite substrate material, condensing and refluxing for 4 hours at 140 ℃, cooling to room temperature after the reaction is finished, and performing suction filtration-deionized water washing for multiple times, wherein the catalyst composite particles contain 14.2% of platinum, 34.0% of doped tin oxide and 51.8% of carbon.
Example 2 hydrogen fuel cell catalyst 2 preparation
(1) Preparing an aqueous solution with solutes of stannous chloride and tantalum chloride, wherein the tantalum accounts for 3 mol percent of the total metal ions, the mass fraction of the solute is 5.3%, taking 100g of the solution, adding 5g of Ketjen black, uniformly stirring, adding ammonia water to adjust the pH of the solution to 9, placing the adjusted solution in a sealed polytetrafluoroethylene tank, carrying out hydrothermal reaction at 100 ℃ for 12 hours, carrying out suction filtration-deionized water washing for multiple times after the reaction is finished, and then, containing 50.1% of carbon and 49.9% of oxide in the composite base material;
(2) the solute is nitre H2PtCl6Adding 100g of the ethanol-water solution (the volume ratio of water to ethanol is 1:3, and the mass fraction of platinum is 10%) into 5g of the composite substrate material prepared according to the step (1), carrying out condensation reflux reaction for 6 hours at 100 ℃, and carrying out suction filtration-deionized water washing for multiple times after the reaction is finished, wherein at the moment, the composite particles of the catalyst contain 9.5% of platinum, 45.2% of doped tin oxide and 45.3% of carbon.
Example 3 hydrogen fuel cell catalyst 3 preparation
(1) Preparing an aqueous solution with solutes of stannous chloride and tantalum chloride, wherein the tantalum accounts for 3 mol percent of the total metal ions, the mass fraction of the solute is 8.3%, adding 5g of Keqin black into 200g of the aqueous solution, uniformly stirring, adding ammonia water to adjust the pH value of the aqueous solution to 10, transferring the aqueous solution into a reaction kettle, reacting at 80 ℃ for 12 hours, performing suction filtration-deionized water washing for multiple times after the reaction is finished, and drying for later use, wherein at the moment, the composite base material contains 59.6% of carbon and 60.4% of oxide;
(2) preparing glycol/water solution (cobalt chloride mass fraction is 4%) with cobalt chloride as solute, adding 5g of the composite substrate material prepared according to the step (1) into 100g of the solution, reacting for 6h at 120 ℃, and performing suction filtration-deionized water washing for multiple times after the reaction is finished. At the moment, the composite particles of the catalyst contain 16.7 percent of cobalt, 50.3 percent of doped tin oxide and 33 percent of carbon;
(3) configuration containing H2PtCl6And (3) adding 100g of the solution into 5g of the composite particles prepared in the step (2) in the ethylene glycol/water solution (with the platinum content being 0.5%), condensing and refluxing for 4 hours at 140 ℃, cooling to room temperature after the reaction is finished, and performing suction filtration-deionized water washing for multiple times. At this time, the catalyst composite particles contained 2.9% of platinum, 16.2% of cobalt, 48.8% of doped tin oxide and 32.0% of carbon.
Example 4 hydrogen fuel cell catalyst 4 preparation
(1) Preparing an aqueous solution with solutes of stannous chloride and tantalum chloride, wherein the tantalum accounts for 3 mol percent of the total metal ions, the mass fraction of the solutes is 5.3%, taking 100g of the solution, adding 5g of Keqin black, stirring uniformly, adding hexamethylenetetramine to adjust the pH of the solution to 8, transferring the solution into a reaction kettle, reacting for 8 hours at 100 ℃, performing suction filtration-deionized water washing for multiple times after the reaction is finished, and drying for later use. At the moment, the composite base material contains 50.1% of carbon and 49.9% of oxide;
(2) preparing ethylene glycol/water solution (the mass fraction of ferric chloride is 4.83%) with ferric chloride as solute, adding 5g of the composite substrate material prepared according to the step (1) into 100g of the solution, carrying out condensation reflux reaction for 6h at 120 ℃, and carrying out suction filtration-deionized water washing for multiple times after the reaction is finished. At the moment, the catalyst composite particles contain 16.7 percent of iron, 41.8 percent of doped tin oxide and 41.8 percent of carbon;
(3) configuration containing H2PtCl6And (3) adding 100g of the solution into 5g of the composite particles prepared in the step (2) to react for 4 hours at 140 ℃, and performing suction filtration and deionized water washing for multiple times after the reaction is finished. In this case, the catalyst composite particles contained 2.8% of platinum, 16.2% of cobalt, 40.5% of doped tin oxide and 40.5% of carbon.
Comparative example
TEC10E50E (TKK) catalyst produced by noble metal group in the field is used as a contrast material.
Battery assembly
(1) 10.62g of an ionic polymer solution DE521CS (5%), 1g of a catalyst material and 6g of deionized water were mixed by ball milling to obtain a coating slurry;
(2) the coating slurry is sprayed on a DuPont NR211 type polymeric diaphragm by a spraying device, and the loading of noble metal on the diaphragm is 0.15mg/cm2Drying to obtain membrane electrode, and collecting 5X5cm2And (4) electrode area, and assembling the membrane electrode into a cell for testing.
Battery testing
(1) The test conditions are that hydrogen is 100Nm L/min and normal pressure, the dew point of the cathode and the anode is 40 ℃, RH is 100 percent, and the operation temperature is 40 ℃.
(2) Measuring a polarization curve, and calculating the catalytic activity mass activity according to the test result;
(3) cyclic voltammetry testing: scanning range: 0.075-1.0V; sweeping speed: 20 mV/s; the execution was repeated 5000 times, and the number of executions when the electrochemical active area became 50% of the original area was measured.
Test results
Remarks are: https:// www.kistec.com, as tested by national institute of Industrial and technology integration, Shenchuan, Japan
When the hydrogen fuel cell composite structure cathode catalyst is assembled into a full cell for testing, the load capacity of noble metal is not higher than 0.2mg/cm2Catalytic activity is not less than 1.1A/cm2(0.6V), mass activity is not less than 80A/g (corresponding to noble metal mass, 0.9V), and repeated circulation is carried outThe electrochemical active area is not less than 50% after the ampere test is carried out for 3000-4500 times.
The result shows that when the cathode catalyst is assembled into a full cell for testing, the noble metal loading is not higher than 0.2mg/cm2, the catalytic activity is not lower than 1.1A/cm2(0.6V), the mass activity is not lower than 80A/g (corresponding to the mass of the noble metal, 0.9V), and the electrochemical active area is not lower than 50% after repeated cyclic voltammetry testing for 3000-4500 times.
The above-described specific embodiments are merely preferred embodiments of the present invention, and it should be noted that, for those skilled in the art, various modifications or substitutions can be made without departing from the principle of the present invention, and these modifications or substitutions should also be regarded as the protection scope of the present invention.
Claims (15)
1. The cathode catalyst for the fuel cell is characterized by being of a core-shell structure and comprising a conductive core positioned in the center of the core, an intermediate carrier layer coated on the periphery of the conductive core and a catalyst layer on the outermost layer; wherein the conductive core is selected from carbon, a non-carbon conductor, or a combination thereof, and the intermediate support layer is composed of a metal oxide.
2. The cathode catalyst according to claim 1, wherein the outer surface of the conductive oxide of the intermediate support layer is spinous.
3. The cathode catalyst according to claim 1 or 2, wherein the metal oxide of the intermediate support layer is tin oxide.
4. Cathode catalyst according to claim 1 or 2, characterized in that the intermediate support layer is a doped metal oxide.
5. The cathode catalyst according to claim 1 or 2, wherein the metal oxide of the intermediate support layer is doped tin oxide, and the doping element is one or more selected from tantalum, antimony and indium.
6. The cathode catalyst according to claim 1 or 2, wherein the catalytic layer is selected from elemental platinum, elemental palladium, or elemental ruthenium metal particles, or alloy particles containing one or more metals.
7. The cathode catalyst according to claim 1 or 2, wherein the catalytic layer is a composite metal core-shell particle, i.e. the inner core is selected from one or more of cobalt, iron, nickel, copper and chromium, and the outer layer is selected from one or more of platinum, palladium and ruthenium.
8. The cathode catalyst according to claim 1 or 2, wherein the conductive core is selected from one or more of graphene, conductive oxide, carbon nanotube, and ketjen black, and preferably ketjen black.
9. The cathode catalyst according to claim 1 or 2, wherein the conductive core is 10 to 99% by mass in the catalyst, the intermediate support layer is 0.1 to 70% by mass in the catalyst, and the catalytic layer is 0.01 to 20% by mass in the catalyst.
10. A method of preparing a cathode catalyst for a fuel cell, comprising the steps of:
a-1, adding metal salt of an intermediate carrier layer into an aqueous solution, dissolving, then immersing into a material of a conductive core, adjusting the pH value to 7-10, carrying out hydrothermal reaction at 80-120 ℃, carrying out suction filtration, washing, drying and precipitating to form a composite carrier for later use;
b-1, preparing an organic reducing agent/water mixed solvent containing metal ions of the catalyst layer, uniformly stirring, adjusting the pH value to be more than 12, adding the composite carrier of A-1, carrying out reflux reaction at the temperature of 140 ℃, filtering, washing and drying after the reaction is finished.
11. The method of claim 10, wherein the metal ions of the catalytic layer are selected from one or more of platinum, palladium, or ruthenium.
12. A method of preparing a cathode catalyst for a fuel cell, comprising the steps of:
a-2, adding metal salt of an intermediate carrier layer into an aqueous solution, dissolving, then immersing into a material of a conductive core, adjusting the pH value to 7-10, carrying out hydrothermal reaction at 80-120 ℃, carrying out suction filtration, washing, drying and precipitating to form a composite carrier for later use;
b-2, adding soluble cobalt, iron, nickel, copper and chromium metal salts into a mixed solvent of an organic reducing agent/water, uniformly stirring, adjusting the pH value to be more than 12, adding the composite carrier of A-2, carrying out reflux reaction at 140 ℃, filtering and washing after the reaction is finished to obtain composite particles for later use;
and C-2, adding soluble platinum, palladium and ruthenium metal salts into a mixed solvent of an organic reducing agent/water, uniformly stirring, adding the composite particles prepared in the step B-2, reacting at 20-80 ℃ for 1-8h, filtering and washing after the reaction is finished, and finally drying.
13. The method according to any one of claims 10 to 13, wherein the metal salt of the intermediate support layer is selected from stannous chloride and further comprises one or more of tantalum, antimony and indium soluble salts.
14. The method as claimed in any one of claims 10 to 13, wherein the organic reducing agent is selected from one or more of organic reducing agents containing hydroxyl group, aldehyde group, phenolic hydroxyl group.
15. The method according to any one of claims 10 to 13, wherein the organic reducing agent is selected from the group consisting of hydroxyl-containing reducing agents.
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| CN115188978A (en) * | 2022-08-05 | 2022-10-14 | 中国科学技术大学 | Preparation method and application of supported polycrystalline surface defect high-entropy alloy catalyst |
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Address after: 215000 2 / F, building 1, No. 178, Tayun Road, Yuexi street, Wuzhong Economic Development Zone, Suzhou City, Jiangsu Province Patentee after: SUZHOU SMART ADVANCED COATING TECHNOLOGIES Co.,Ltd. Address before: 215122 room 1617-1624, floor 16, building 1, Jinsha Business Plaza, No. 6, Weihua Road, Suzhou Industrial Park, Jiangsu Province Patentee before: SUZHOU SMART ADVANCED COATING TECHNOLOGIES Co.,Ltd. |