CN-121983602-A - Hydrogen fuel cell electrode catalyst and preparation method and application thereof

Abstract

The invention relates to the technical field of catalysts, and discloses a hydrogen fuel cell electrode catalyst, a preparation method and application thereof. The hydrogen fuel cell electrode catalyst comprises a composite carrier and Pt particles loaded on the composite carrier, wherein the composite carrier comprises graphene, a ZrO 2 layer coated on the graphene and surface layer oxides bonded on the surface of the ZrO 2 layer, and the surface layer oxides are SiO 2 and/or TiO 2 . The catalyst of the invention can realize higher electrocatalytic efficiency when used in a hydrogen fuel cell electrode, has better electrochemical stability, and can keep higher electrocatalytic efficiency in corrosive environment (such as phosphoric acid electrolyte).

Inventors

• WANG SIFAN
• LIN WENFENG
• WANG ZHIQIANG
• WANG SHUIBO
• ZHAO CHONG
• Tong Duo

Assignees

• 浙江省白马湖实验室有限公司

Dates

Publication Date

20260505

Application Date

20260408

Claims (10)

1. 1. The hydrogen fuel cell electrode catalyst is characterized by comprising a composite carrier and Pt particles loaded on the composite carrier, wherein the composite carrier comprises graphene, a ZrO 2 layer coated on the graphene and a surface oxide combined on the surface of the ZrO 2 layer, and the surface oxide is SiO 2 and/or TiO 2 .
2. 2. The hydrogen fuel cell electrode catalyst according to claim 1, wherein the surface layer oxides are SiO 2 and TiO 2 .
3. 3. A method for producing the hydrogen fuel cell electrode catalyst according to claim 1 or 2, comprising: S1, generating a ZrO 2 layer on the surface of graphene through in-situ reaction of a zirconium source; S2, generating surface layer oxide on the surface of the S1 product through in-situ reaction of a surface layer oxide source, wherein the surface layer oxide source is a silicon source and/or a titanium source; S3, generating Pt particles on the surface of the S2 product through in-situ reaction of a platinum source.
4. 4. A method of preparation according to claim 3, characterized in that: in the step S1, the mass ratio of graphene to ZrO 2 is 1:0.4-0.6 based on the complete reaction of a zirconium source; In the step S2, the mass ratio of the S1 product to the surface oxide is 1:0.8-1.1 based on the complete reaction of the surface oxide source; in the step S3, the mass ratio of the S2 product to Pt particles is 1:0.3-1.4 based on the complete reaction of the platinum source.
5. 5. A method of preparation according to claim 3, characterized in that it comprises in particular: S1, adding NaOH and a zirconium source into graphene aqueous dispersion liquid, carrying out hydrothermal reaction, adding H 2 O 2 , mixing, and separating out a product; s2, dispersing the S1 product into water, adding sodium hydroxide, adding a silicon source, reacting for 10-15 hours at 60-65 ℃ and separating out the product, or mixing a titanium source, oleic acid, oleylamine, a reaction solvent and the S1 product, reacting for 20-30 hours at 150-160 ℃ and separating out the product; and S3, mixing the S2 product with ethylene glycol, adding citrate and a platinum source, and carrying out reduction reaction at 130-150 ℃ to separate the product.
6. 6. The preparation method of the platinum alloy is characterized in that in the step S3, the mass ratio of the platinum source to the citrate is 1:9-37, the citrate is added in the form of 0.01-0.02 mol/L citrate aqueous solution, the platinum source is added in the form of 15-25 mg/mL platinum source aqueous solution, and the reduction reaction time is 5-7 h.
7. 7. The preparation method of the graphene aqueous dispersion according to claim 5, wherein in the step S1, the temperature of the hydrothermal reaction is 100-120 ℃ and the time is 5-7H, the volume ratio of H 2 O 2 to water in the graphene aqueous dispersion is 0.005-0.01:1, and the mixing temperature is 50-55 ℃ and the time is 5-6H.
8. 8. The preparation method of claim 5, wherein in step S1, the graphene aqueous dispersion liquid comprises graphene nanoplatelets, cetyltrimethylammonium bromide and water, wherein the mass-volume ratio of the graphene nanoplatelets to the water is 1 g:100-150 ml, and the mass-volume ratio of the cetyltrimethylammonium bromide to the water is 1 g:250-300 ml.
9. 9. Use of a hydrogen fuel cell electrode catalyst according to claim 1 or 2 in a hydrogen fuel cell for catalyzing a cathodic oxygen reduction reaction or an anodic hydrogen oxidation reaction in a hydrogen fuel cell.
10. 10. The use according to claim 9, wherein the hydrogen fuel cell comprises a working electrode, a counter electrode, a reference electrode and an electrolyte, wherein the working electrode is the hydrogen fuel cell electrode catalyst, the counter electrode is a carbon rod, and the electrolyte contains 0.1-0.5 mol/L HClO 4 and 0-0.2 mol/L H 3 PO 4 .

Description

Hydrogen fuel cell electrode catalyst and preparation method and application thereof Technical Field The invention relates to the technical field of catalysts, in particular to a hydrogen fuel cell electrode catalyst and a preparation method and application thereof. Background The hydrogen fuel cell has the advantages of zero emission, high energy efficiency, rapid filling, renewable fuel and the like, and is becoming one of the key energy conversion technologies. In hydrogen fuel cells, the catalyst is the "first element" that converts chemical energy into electrical energy efficiently and controllably, its activity and selectivity determine the rated efficiency and peak power of the stack, and its stability and anti-poisoning capability determine life and maintenance costs. Therefore, the catalyst is not only a technical bottleneck in the hydrogen fuel cell, but also a key lever for reducing cost and enhancing efficiency. From the aspect of electrode division, the anode bears a Hydrogen Oxidation Reaction (HOR), the eigen dynamics is extremely fast, the requirements can be met by low-load platinum (Pt) or a small amount of alloyed Pt, and more focusing on impurities such as carbon monoxide, sulfur and the like and the matching of hydrogen supply purity and water thermal management are achieved in engineering. The cathode is responsible for the Oxygen Reduction Reaction (ORR), which has a multi-electron multi-proton coupling path and a higher free energy barrier for reaction, making it a major short plate of efficiency and life, and various Pt-based catalysts and non-platinum group metals (Fe, co, ni) are now commonly used. Noble metal Pt-based catalysts are the base lines of the industrial application, but the high cost and resource scarcity of the noble metal Pt-based catalysts are difficult to meet the long-term large-scale requirements, and meanwhile, the activity degradation caused by the coupling of dissolution/migration and carrier corrosion of Pt still occurs under the extreme working condition. Patent CN119542445A discloses a topological chiral half-metal catalyst for oxygen electrocatalysis, a preparation method and application thereof, the topological chiral half-metal catalyst is a supported catalyst and comprises a carrier, an active component and a guest metal, wherein the carrier is selected from one of Vulcan XC-72R, vulcan XC-72, ketjen black and carbon nano tubes, the active component is Pt, and the guest metal is selected from one or two of Ga, al, ba, ge, bi, sb, eu, fe, cr, sr, mg. The topological chiral semi-metal catalyst has higher catalytic activity and product selectivity in the fuel cell cathode oxygen reduction reaction, but the adopted carrier is a carbon carrier, so that the electrochemical stability is poor. Disclosure of Invention The invention provides a hydrogen fuel cell electrode catalyst, a preparation method and application thereof, and aims to solve the technical problem that the existing hydrogen fuel cell electrode catalyst is poor in electrochemical stability. The catalyst of the invention can realize higher electrocatalytic efficiency when used in a hydrogen fuel cell electrode, has better electrochemical stability, and can keep higher electrocatalytic efficiency in corrosive environment (such as phosphoric acid electrolyte). The specific technical scheme of the invention is as follows: In a first aspect, the invention provides a hydrogen fuel cell electrode catalyst, which comprises a composite carrier and Pt particles loaded on the composite carrier, wherein the composite carrier comprises graphene, a ZrO 2 layer coated on the graphene and surface layer oxides bonded to the surface of the ZrO 2 layer, and the surface layer oxides are SiO 2 and/or TiO 2. ZrO 2 can be firmly combined on the surface of graphene through a C-O-Zr bond and a physical anchoring mode, and the two are matched with each other, so that the effect that graphene can endow a composite carrier with better conductivity, so that higher electrocatalytic efficiency can be realized when the catalyst is used in a hydrogen fuel cell electrode, zrO 2 has a firm crystal structure and can provide stronger anchoring sites for Pt, the characteristics can enable the Pt to relieve corrosion of the graphene, and even if part of graphene is corroded, zrO 2 can maintain the porous structure of the catalyst to a certain extent and prevent collapse of the porous structure, so that the dispersibility and accessibility of an active site are maintained, and by the adoption of the mode, the introduction of a ZrO 2 layer can improve the electrochemical stability of the catalyst, so that the catalyst can maintain higher catalytic efficiency in a corrosive environment (such as phosphoric acid electrolyte). On the basis, the electrochemical stability of the catalyst can be further improved by combining SiO 2 and/or TiO 2 on the surface of the ZrO 2 layer, specifically, the heterogeneous interface charge rearrangement ca