CN114142044A - Carbon coating method of platinum-carbon catalyst - Google Patents
Carbon coating method of platinum-carbon catalyst Download PDFInfo
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- CN114142044A CN114142044A CN202111318143.3A CN202111318143A CN114142044A CN 114142044 A CN114142044 A CN 114142044A CN 202111318143 A CN202111318143 A CN 202111318143A CN 114142044 A CN114142044 A CN 114142044A
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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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8892—Impregnation or coating of the catalyst layer, e.g. by an ionomer
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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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
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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
- H01M4/923—Compounds thereof with non-metallic elements
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- 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
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Abstract
The invention provides a carbon coating method of a platinum-carbon catalyst for a commercial fuel cell, the carbon-coated platinum-carbon catalyst can effectively improve the cycle stability of the platinum-carbon catalyst due to the existence of a surface carbon layer, the carbon coating method is simple and suitable for batch production, and the carbon-coated platinum-carbon catalyst can still show excellent oxygen reduction catalytic performance. The preparation method comprises the steps of firstly blending a certain amount of oleylamine, oleic acid and a platinum-carbon catalyst, realizing the anchoring of a ligand on platinum particles through coordination, and then completing the preparation of the carbon-coated platinum-carbon catalyst through the means of ligand pre-crosslinking, carbonization, urea nitrogen-doping activation and the like. In the invention, the surface carbon layer formed by the ligand plays a role in blocking on one hand, and avoids the deactivation of the catalyst caused by the direct contact of platinum particles and sulfonic acid groups in the ionic polymer when the platinum particles are directly exposed in a reaction environment; on the other hand, the carbon layer can play a role of stabilizing the platinum component, and prevent the platinum component from being dissolved out of the carrier or adjacent platinum atoms from being fused with each other during a long cycle.
Description
Technical Field
The invention belongs to the field of materials and electrochemistry, in particular relates to a method for preparing a novel carbon-coated platinum-carbon catalyst to realize high stability, and particularly relates to a carbon-coated method which is simple, suitable for batch production and capable of maintaining the activity of the catalyst and effectively improving the cycle stability.
Background
With the increasing world population and the increasing exhaustion of traditional fossil energy, environmental problems become more serious, and the demand of new clean energy for human beings is also increasing. In the field of batteries, a fuel cell is an ideal electrochemical power generation device, and theoretically, chemical energy can be directly converted into electric energy continuously as long as a fuel and an oxidant are continuously supplied, and thus there is no upper limit to the theoretical capacity of the fuel cell. Unlike traditional cell, the waste produced by fuel cell is water, carbon dioxide and other non-toxic and harmless matter, and has no environmental pollution. Therefore, fuel cells are becoming more and more important to be paid attention to governments and research institutes of various countries as a power generation device with high energy conversion rate and environmental friendliness.
In a fuel cell, the two half-reactions occurring at the cathode and anode can be split. However, the electrochemical polarization of the reduction reaction of oxygen on the cathode is severe, the reaction rate is slow, and is lower than the oxidation reaction rate on the anode by more than six orders of magnitude, which is a bottleneck problem limiting the development of proton exchange membrane fuel cells. The key to realizing the large-scale application of the fuel cell is to develop the electrode catalyst with high efficiency and strong stability. Research has found that platinum-based catalysts can exhibit good oxygen reduction catalytic activity, and thus are widely used in existing commercial catalyst products.
However, most of the platinum-based catalysts used in commercial applications directly support platinum metal nanoparticles on a carbon support, so that platinum particles directly exposed to an electrochemical reaction environment can exhibit high-efficiency oxygen reduction catalytic activity, but cannot maintain good long-cycle stability. The main reason is that such platinum particles do not adhere strongly to the carbon support, and dissolution and fusion of adjacent platinum particles occur during a long cycle. In addition, while directly exposing the catalytically active sites, it inevitably comes into contact with some of the deactivators present in the environment, causing loss of active sites. For example, sulfonic acid groups contained in the ionic polymer binder Nafion, which is commonly used in commercial fuel cells, interact with platinum particles, thereby greatly reducing the catalytic activity. Carbon coating is a very effective means of stabilizing platinum particles. The carbon-coated protective layer is preferably designed to allow oxygen and water to pass through and contact the catalytic sites, and to prevent the passage of deactivating agents, i.e., the carbon layer requires carbon pores of a suitable pore size, so that the coating method of the carbon layer is critical.
Disclosure of Invention
The invention provides a carbon coating method of a platinum-carbon catalyst, which comprises the following specific technical steps: firstly, a certain amount of oleylamine and oleic acid are used as ligands to be blended with a platinum-carbon catalyst, anchoring on platinum particles is realized through coordination, and then the preparation of the carbon-coated platinum-carbon catalyst is completed through means of ligand pre-crosslinking, carbonization, urea pyrolysis, nitrogen doping activation and the like.
The method comprises the following specific steps:
(1) mixing the platinum-carbon catalyst with oleic acid and oleylamine, adding a proper amount of isopropanol, stirring for 6-24 hours, and centrifuging to obtain the platinum-carbon catalyst modified by oleic acid and oleylamine;
(2) carrying out pre-crosslinking treatment on the oleic acid and oleylamine modified platinum-carbon catalyst obtained in the step (1) in a tubular furnace in a nitrogen atmosphere, and then continuously heating to further carbonize a crosslinked carbon layer to obtain a carbon-coated platinum-carbon catalyst;
(3) and (3) mixing the carbon-coated platinum-carbon catalyst obtained in the step (2) with urea, and then quickly heating the mixture in a tubular furnace in the nitrogen atmosphere to carry out high-temperature nitrogen doping activation to obtain the high-stability carbon-coated platinum-carbon catalyst.
In the invention, the mass ratio of the platinum-carbon catalyst, the oleic acid and the oleylamine in the step (1) is 1:5: 5.
In the invention, the mass ratio of the platinum-carbon catalyst and the isopropanol in the step (1) is 1: 100.
In the invention, the temperature of the nitrogen atmosphere ligand pre-crosslinking in the step (2) is 350 ℃, and the time is 0.5 hour.
In the invention, the temperature of the nitrogen atmosphere carbonization in the step (2) is 500 ℃ and the time is 1 hour.
In the invention, the mass ratio of the carbon-coated platinum-carbon catalyst to the urea in the step (3) is 1: 10.
In the invention, the temperature of the nitrogen atmosphere high-temperature nitrogen doping activation in the step (3) is 600 ℃, and the time is 1 hour.
In the invention, a surface carbon layer formed by carbon coating and oleic acid and oleylamine micromolecule organic ligands is formed on the existing platinum-carbon catalyst, so that on one hand, the barrier effect is achieved, and the platinum particles are prevented from being directly exposed in a reaction environment and being directly contacted with sulfonic acid groups in an ionic polymer to cause the inactivation of the catalyst; on the other hand, the carbon layer can play a role of stabilizing the platinum component, and prevent the platinum component from being dissolved out of the carrier or adjacent platinum atoms from being fused with each other during a long cycle.
Drawings
FIG. 1 is a transmission electron micrograph of a high stability carbon-coated platinum-carbon catalyst prepared in example 1 of the present invention.
FIG. 2 is a high-resolution TEM image of the high-stability carbon-coated Pt-C catalyst prepared in example 1 of the present invention.
FIG. 3 is a graph showing a polarization current curve of the high-stability carbon-coated platinum-carbon catalyst prepared in example 1 of the present invention.
FIG. 4 is a high resolution TEM image of the high stability carbon-coated Pt-C catalyst prepared in example 2 of the present invention.
FIG. 5 is a high resolution TEM image of the high stability carbon-coated Pt-C catalyst prepared in example 2 of the present invention.
Detailed Description
Example 1:
(1) 100mg of platinum-carbon catalyst (Johnson Matthey Co., HISEPC3000, platinum content 20%) having an average platinum particle size of 5nm was taken, and mixed with 500mg of oleic acid and 500mg of oleylamine, 10g of isopropyl alcohol was added, and the mixture was stirred at room temperature for 12 hours. Then the preparation of the oleic acid and oleylamine modified platinum-carbon catalyst is completed by centrifugation;
(2) maintaining the oleic acid and oleylamine modified platinum-carbon catalyst prepared in the step (1) for 0.5 hour at 350 ℃ in a nitrogen atmosphere, and then maintaining for 1 hour at 500 ℃ in the nitrogen atmosphere to obtain a carbon-coated platinum-carbon catalyst;
(3) and (3) mixing 50mg of the carbon-coated platinum-carbon catalyst prepared in the step (2) with 500mg of urea, and maintaining the mixture at 600 ℃ in a nitrogen atmosphere for 1 hour to obtain the high-stability carbon-coated platinum-carbon catalyst.
FIG. 1 is a transmission electron microscope image of a highly stable carbon-coated Pt-C catalyst, which illustrates that the Pt particles in the Pt-C catalyst are not fused obviously after the carbon coating treatment of the present invention, and still maintain the original particle size.
FIG. 2 is a high-resolution transmission electron microscope image of a high-stability carbon-coated Pt-C catalyst, which illustrates that a carbon layer of 1-2nm is uniformly coated on the outside of Pt particles in the Pt-C catalyst after the carbon coating treatment according to the present invention.
Fig. 3 is a plot of polarization current for a high stability carbon-coated platinum-carbon catalyst. It can be seen from the figure that after 5000 cycles of the material is coated with carbon, the performance is obviously improved, which indicates that the previous cycle plays a role in activating the catalyst. From 5000 circles to 25000 circles, the performance is basically maintained without obvious attenuation, which shows that the high-stability carbon-coated platinum-carbon catalyst after the carbon coating treatment of the invention has excellent cycle stability.
Compared to a material that has not been carbon coated: fig. 4 is a plot of polarization current for platinum-carbon catalysts that were not carbon coated. As shown, after the first 5000 cycles, no similar process of activating the carbon layer occurred. After 25000 cycles of cycling, the performance was significantly degraded and the cycling stability was very poor.
Example 2:
(1) 500mg of platinum-carbon catalyst (Premetek, U.S.A., having a platinum content of 40%) having an average platinum particle diameter of 3nm was taken and mixed with 2500mg of oleic acid and 2500mg of oleylamine, and 50g of isopropyl alcohol was added thereto and stirred at room temperature for 24 hours. Then the preparation of the oleic acid and oleylamine modified platinum-carbon catalyst is completed by centrifugation;
(2) maintaining the oleic acid and oleylamine modified platinum-carbon catalyst prepared in the step (1) for 0.5 hour at 350 ℃ in a nitrogen atmosphere, and then maintaining for 1 hour at 500 ℃ in the nitrogen atmosphere to obtain a carbon-coated platinum-carbon catalyst;
(3) and (3) mixing 50mg of the carbon-coated platinum-carbon catalyst prepared in the step (2) with 500mg of urea, and maintaining the mixture at 600 ℃ in a nitrogen atmosphere for 1 hour to obtain the high-stability carbon-coated platinum-carbon catalyst.
FIG. 5 is a high-resolution transmission electron microscope image of a high-stability carbon-coated Pt-C catalyst, which illustrates that after the carbon coating treatment of the present invention, a carbon layer of 1-2nm is uniformly coated on the outside of the Pt particles in the Pt-C catalyst having an average Pt particle size of 3nm, which proves the universality of the present invention and can effectively coat various Pt-C catalysts with carbon.
Claims (7)
1. A carbon coating method for effectively improving the circulation stability of a platinum-carbon catalyst is characterized by comprising the following specific steps:
(1) mixing the platinum-carbon catalyst with oleic acid and oleylamine, adding a proper amount of isopropanol, stirring for 6-24 hours, and centrifuging to obtain the platinum-carbon catalyst modified by oleic acid and oleylamine;
(2) sequentially pre-crosslinking and carbonizing the oleic acid and oleylamine modified platinum-carbon catalyst obtained in the step (1) in a nitrogen atmosphere to obtain a carbon-coated platinum-carbon catalyst;
(3) and (3) mixing the carbon-coated platinum-carbon catalyst obtained in the step (2) with urea, and then carrying out high-temperature nitrogen doping activation in a nitrogen atmosphere to obtain the high-stability carbon-coated platinum-carbon catalyst.
2. The carbon coating method for effectively improving the cycle stability of the platinum-carbon catalyst as claimed in claim 1, wherein the mass ratio of the platinum-carbon catalyst, the oleic acid and the oleylamine in the step (1) is 1:5: 5.
3. The carbon coating method for effectively improving the cycle stability of the platinum-carbon catalyst as claimed in claim 1, wherein the mass ratio of the platinum-carbon catalyst and the isopropanol in the step (1) is 1: 100.
4. The carbon-coating method for effectively improving the cycling stability of the platinum-carbon catalyst according to claim 1, wherein the pre-crosslinking temperature of the nitrogen atmosphere ligand in the step (2) is 350 ℃ and the time is 0.5 hour.
5. The carbon-coating method for effectively improving the cycle stability of the platinum-carbon catalyst according to claim 1, wherein the temperature of the nitrogen atmosphere carbonization in the step (2) is 500 ℃ and the time is 1 hour.
6. The carbon-coating method for effectively improving the cycle stability of the platinum-carbon catalyst according to claim 1, wherein the mass ratio of the carbon-coated platinum-carbon catalyst to urea in the step (3) is 1: 10.
7. The carbon coating method for effectively improving the cycle stability of the platinum-carbon catalyst according to claim 1, wherein the temperature of the nitrogen atmosphere high-temperature nitrogen-doping activation in the step (3) is 600 ℃ and the time is 1 hour.
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