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Preparation method for graphene-coated metal nanometer particle catalyst and application of graphene-coated metal nanometer particle catalyst

A technology coated with metal nanoparticles and graphene, applied in chemical instruments and methods, physical/chemical process catalysts, nanotechnology, etc., can solve the problems of poor stability of Pt-based electrocatalysts, easy agglomeration of metal nanoparticles, and low degree of graphitization and other problems, to achieve the effects of large-scale production, simple and effective operation method, and high electrocatalytic activity

Inactive Publication Date: 2015-09-23
DALIAN UNIV OF TECH
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  • Abstract
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  • Application Information

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Problems solved by technology

However, the commercialization of low-temperature fuel cells still faces certain challenges, one of which is the slow kinetics of the cathode oxygen reduction (ORR) process.
At present, carbon-supported platinum and platinum alloy catalysts are the best performance and most widely used oxygen reduction catalysts for fuel cells, but Pt-based electrocatalysts are poor in stability and high in price, which limits the large-scale commercialization of fuel cells, so the development has high Catalysts with catalytic activity and stability, corrosion resistance and low cost have important practical significance and application value
[0003] Metal-nitrogen-carbon materials are considered to be the most promising non-precious metal ORR electrocatalysts, but there are still some problems: unreasonable structures or easy agglomeration make metal-nitrogen-carbon materials unevenly dispersed, which limits the catalytic performance. The loading of active metal-nitrogen-carbon materials reduces the overall nitrogen density of the material and reduces the metal utilization rate (generally only 2-5%); the degree of graphitization is low and the conductivity is poor; the small specific surface area makes ORR The mass transfer efficiency is low; more importantly, the active sites of ordinary metal-nitrogen-carbon materials are easily corroded in the electrolyte solution, thereby reducing the catalytic activity and life of the catalyst
However, the preparation method has poor reproducibility, metal nanoparticles are easy to agglomerate, and have poor catalytic performance for ORR.

Method used

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  • Preparation method for graphene-coated metal nanometer particle catalyst and application of graphene-coated metal nanometer particle catalyst

Examples

Experimental program
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Effect test

Embodiment 1

[0036] Example 1: Fe 8% -N 0.5 -CNT-E 2 -24-600(Fe 8% Refers to the mass content of Fe in the material is 8%, N 0.5 Refers to the quality of nitrogen source melamine is 0.5 times that of carboxylated carbon nanotubes, E 2 Means that the mass of ethylenediaminetetraacetic acid disodium salt is twice that of iron salt, 24 means that the hydrothermal reaction time is 24h, and 600 means that the calcination temperature is 600℃)

[0037] Take 0.1000g of carboxylated carbon nanotubes, 0.0386g of ferric chloride and 0.0500g of melamine and add them to a mixed solution of 30mL of water and ethanol, sonicate for 30min to make the dispersion uniform, then magnetically stir at 50℃ for 2h, and then take 0.0772g of ethylenediamine Tetraacetic acid disodium salt and 10 mL of methanol were added to the above mixed solution and hydrothermally reacted at 150℃ for 24h, washed, filtered, and dried under vacuum at 80℃ to obtain composite Fe 8% -N 0.5 -CNTEDTA-24;

[0038] Put the above materials in N 2...

Embodiment 2

[0039] Example 2: Fe 8% -N 1 -CNT-E 2 -24-600(Fe 8% Refers to the mass content of Fe in the material is 8%, N 1 Means that the quality of nitrogen source melamine is twice that of carboxylated carbon nanotubes, E 2 Means that the mass of ethylenediaminetetraacetic acid disodium salt is twice that of iron salt, 24 means that the hydrothermal reaction time is 24h, and 600 means that the calcination temperature is 600℃)

[0040] Add 0.1000g carboxylated carbon nanotubes, 0.0386g ferric chloride and 0.1000g melamine to a mixed solution of 30mL water and ethanol, sonicate for 30min to make the dispersion uniform, then magnetically stir at 50℃ for 2h, then take 0.0772g ethylenediamine Tetraacetic acid disodium salt and 10 mL of methanol were added to the above mixed solution and hydrothermally reacted at 150℃ for 24h, washed, filtered, and dried under vacuum at 80℃ to obtain composite Fe 8% -N 1 -CNTEDTA-24;

[0041] Put the above materials in N 2 3℃ min under the atmosphere -1 The rate o...

Embodiment 3

[0042] Example 3: Fe 8% -N 1.25 -CNT-E 2 -24-600(Fe 8% Refers to the mass content of Fe in the material is 8%, N 1.25 Refers to the quality of nitrogen source melamine is 1.25 times that of carboxylated carbon nanotubes, E 2 Means that the mass of ethylenediaminetetraacetic acid disodium salt is twice that of iron salt, 24 means hydrothermal time reaction is 24h, 600 means calcination temperature is 600℃)

[0043] Take 0.1000g of carboxylated carbon nanotubes, 0.0386g of ferric chloride and 0.1250g of melamine into a mixed solution of 30mL of water and ethanol, sonicate for 30min to make the dispersion uniform, then magnetically stir at 50℃ for 2h, and then take 0.0772g of ethylenediamine Tetraacetic acid disodium salt and 10 mL of methanol were added to the above mixed solution and hydrothermally reacted at 150℃ for 24h, washed, filtered, and dried under vacuum at 80℃ to obtain composite Fe 8% -N 1.25 -CNTEDTA-24;

[0044] Put the above materials in N 2 3℃ min under the atmosphere ...

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Abstract

The invention relates to a preparation method for a graphene-coated iron-loaded and nitrogen-loaded active site catalyst on a carbon nano tube (CNT); sources of raw materials used for the method are extensive; carbon source and nitrogen source materials are low in cost; the sample yield is high; the production cost of a fuel cell is helped to be reduced; the content of Fe and N in the prepared catalyst is controllable, and meanwhile, bigger specific surface area is kept so as to overcome the problem that metal nanometer particles are easy to aggregate in the past. The preparation method comprises the following steps: (1) supporting Fe and N to the surface of the carbon nano tube to obtain Fe-N-CNT; (2) synthetizing a composite material, formed by coating the surface of the Fe-N-CNT with graphene precursors, by a hydrothermal method; (3) calcining the composite material to obtain Fe-N-CNT&GN. Compared with a traditional fuel cell cathode Pt / C catalyst, the catalyst prepared by the method disclosed by the invention is low in cost, relatively higher in catalytic activity, high in stability, high in methanol tolerance, and has a good commercial application prospect.

Description

Technical field [0001] The invention belongs to the technical field of energy materials and electrochemistry, and relates to a method for preparing an electrocatalyst applied to a fuel cell cathode oxygen reduction reaction, and in particular to a metal nanoparticle catalyst coated on carbon nanotubes with graphene Preparation. Background technique [0002] Problems such as the exhaustion of fossil resources and environmental degradation have intensified, and the development and utilization of clean and renewable energy has become a global focus of attention. Low-temperature fuel cell is an electrochemical reaction device that directly converts the chemical energy of fuel into electrical energy. It has the characteristics of simple structure, high theoretical energy density, and environmental protection. It has become a hot spot for domestic and foreign scholars in recent years. However, the commercialization of low-temperature fuel cells still faces certain challenges, one of w...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J21/18B01J27/24B01J35/10B82Y30/00H01M4/90
CPCY02E60/50
Inventor 李光兰刘彩娣程光春
Owner DALIAN UNIV OF TECH
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