CN112820888B - Preparation method of fuel cell catalyst with monatomic and nanocrystalline composite structure - Google Patents
Preparation method of fuel cell catalyst with monatomic and nanocrystalline composite structure Download PDFInfo
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- CN112820888B CN112820888B CN202110294493.4A CN202110294493A CN112820888B CN 112820888 B CN112820888 B CN 112820888B CN 202110294493 A CN202110294493 A CN 202110294493A CN 112820888 B CN112820888 B CN 112820888B
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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
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
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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
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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
- Y02E60/50—Fuel cells
Abstract
The invention discloses a preparation method of a fuel cell catalyst with a monatomic and nanocrystalline composite structure, which comprises the following steps: mixing an ammonia water solution, conductive carbon black and an ethanol water solution to obtain a first mixed solution; dissolving nitrogen-containing organic molecules and first transition metal salt in an ethanol water solution to obtain a second mixed solution; and mixing the first mixed solution and the second mixed solution, reacting for a preset time, adding a metal platinum salt and a second transition metal salt, evaporating to dryness, sintering at a preset temperature, and carrying out acid pickling and drying to obtain the fuel cell catalyst with the monatomic and nanocrystalline composite structure. The preparation method is simple and easy to implement and good in repeatability, and the fuel cell catalyst with the monoatomic and nanocrystalline composite structure prepared by the method has excellent catalytic activity and stability.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method of a fuel cell catalyst with a monatomic and nanocrystalline composite structure.
Background
In the face of environmental pollution and energy crisis caused by excessive consumption of fossil fuels, the search for more sustainable and renewable energy sources has become one of the most important challenges today. Hydrogen energy is considered as the ultimate energy source for humans, and Proton Exchange Membrane Fuel Cells (PEMFCs) are the main form of hydrogen energy utilization. PEMFCs are highly efficient power generation devices that utilize electrochemical reactions to convert H2/O2The chemical energy in the process is directly converted into electric energy, is not limited by the Carnot cycle effect, and has the characteristics of high energy conversion efficiency, low operation temperature, no pollution and the like. However, the reduction reaction of oxygen molecules on the cathode is slow, and a large amount of noble metal Pt catalyst is needed to improve the reaction speed and efficiency. Platinum group metal catalystsThe agent has sufficient catalytic activity for both hydrogen oxidation and oxygen reduction, and catalytic reactions at both the cathode and anode of the PEMFC do not depart from platinum-based catalysts. Thus, platinum carbon has heretofore remained the most commercially used catalyst. Due to the high price and low resources of platinum, there is a great deal of effort to design advanced platinum-based catalysts to improve the utilization of platinum.
Although many researches report methods for synthesizing a cathode catalyst of a proton exchange membrane fuel cell, most of the methods have complex synthesis steps and poor repeatability, and are difficult to realize industrial application, so that no fuel cell catalyst meeting the commercial application standard is reported in China. At present, the means for improving the utilization rate of the platinum-based catalyst mainly comprises two methods of reasonably controlling the size of the platinum nanocrystal and alloying the platinum nanocrystal, and Pt nanoparticles synthesized by simply controlling the size of the platinum-based nanoparticles are easy to migrate and agglomerate on the surface of a carrier, so that the stability and the catalytic activity of a fuel cell are reduced; alloying of platinum is an effective method for increasing the intrinsic activity of the catalyst and reducing the amount of platinum used, for example, by alloying Pt with Fe, Co, Ni, etc. The monatomic catalysts (SACs) have the maximum atom utilization rate and unique performance as a new field of catalytic scientific development in recent years, and have great potential in the aspects of reasonably utilizing precious metal resources and realizing economic benefits. Therefore, the development of a simple, effective, good-repeatability and high-universality synthesis method has very important significance in improving the activity of the catalyst and effectively inhibiting the agglomeration and inactivation of the nanocrystal by utilizing the composite structure of the monoatomic metal and the nanocrystal and reducing the dosage of the noble metal Pt.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a fuel cell catalyst with a composite structure of a single atom and a nanocrystal, in order to prepare a catalyst with high catalytic activity, good stability and low platinum consumption.
The invention provides a preparation method of a fuel cell catalyst with a monatomic and nanocrystalline composite structure, which comprises the following steps: mixing an ammonia water solution, conductive carbon black and an ethanol water solution to obtain a first mixed solution; dissolving nitrogen-containing organic molecules and first transition metal salt in an ethanol water solution to obtain a second mixed solution; and mixing the first mixed solution and the second mixed solution, reacting for a preset time, adding a metal platinum salt and a second transition metal salt, evaporating to dryness, sintering at a preset temperature, and carrying out acid pickling and drying to obtain the fuel cell catalyst with the monatomic and nanocrystalline composite structure.
In some embodiments, the conductive carbon black comprises at least one of: vulcan XC-72, Vulcan XC-72R, BP2000, Ketjen black and acetylene black.
In some embodiments, the nitrogen-containing organic molecule comprises at least one of: dopamine, cyanamide, polyaniline, benzidine.
In some embodiments, the mass ratio of the nitrogen-containing organic molecule to the first transition metal salt is 10 (0.5-1).
In some embodiments, the second transition metal salt comprises at least one of: co (NO)3)2·6H2O、CoCl2·6H2O、CoSO4·7H2O、Co(acac)2。
In some embodiments, sintering under the preset temperature condition comprises: sintering under the conditions of reducing atmosphere and preset temperature.
In some embodiments, the sintering temperature under the preset temperature condition is in a range of 600-1200 ℃, and the sintering time under the preset temperature condition is in a range of 1-4 h.
In some embodiments, the reducing atmosphere comprises 5-10% H2and/Ar gas.
In some embodiments, the temperature of the acid washing is between 50 and 80 ℃, and the time period of the acid washing is between 1 and 4 hours.
The invention provides a fuel cell catalyst with a monatomic and nanocrystalline composite structure, which is prepared by the preparation method.
In some embodiments, the conductive carbon black support is modified by metal monoatomic modification, and the size of the nano crystal is in a range of 3-5 nm.
The invention provides an application of a fuel cell catalyst with a monatomic and nanocrystalline composite structure in a cathode of a hydrogen air proton exchange membrane fuel cell.
The invention provides a preparation method of a fuel cell catalyst with a composite structure of single atoms and nano crystals, which is characterized in that precious metal Pt and transition metal elements are reduced at high temperature to form nano crystals to be loaded on modified conductive carbon black, the conductive carbon black carrier can effectively inhibit the size of the nano crystals, has good dispersion effect on the nano crystals and inhibits the agglomeration of the nano crystals in an acid oxygen reduction reaction, and the preparation method is simple and easy to implement and has good repeatability.
In addition, the novel fuel cell catalyst with the monatomic and nanocrystalline composite structure provided by the invention shows excellent catalytic activity and stability in an acid oxygen reduction reaction.
Drawings
FIG. 1 is a flow chart of the preparation of a fuel cell catalyst with a composite structure of monoatomic molecules and nanocrystals according to an embodiment of the present invention;
FIG. 2 shows the monoatomic reaction product of Pt prepared in example 1 of the present invention3Transmission electron microscopy of a fuel cell catalyst of Co nanocrystalline composite structure;
FIG. 3 shows the monoatomic reaction product with Pt prepared in example 1 of the present invention3A high resolution transmission electron micrograph of a Co nanocrystalline composite structured fuel cell catalyst;
FIG. 4 shows the monoatomic reaction product with Pt prepared in example 1 of the present invention3An X-ray powder diffraction pattern of a fuel cell catalyst with a Co nanocrystalline composite structure;
FIG. 5 shows the monoatomic reaction product with Pt prepared in example 1 of the present invention3A CV change diagram of the Co nanocrystalline composite structure fuel cell catalyst in a 30000-circle stability test;
FIG. 6 shows the monoatomic reaction product with Pt prepared in example 1 of the present invention3LSV change diagram of Co nanocrystalline composite structure fuel cell catalyst in 30000-circle stability test;
FIG. 7 is a graph of LSV variation of commercial Pt/C in the 30000-cycle stability test;
FIG. 8 shows the monoatomic reaction product with Pt prepared in example 1 of the present invention3The fuel cell catalyst with the Co nanocrystalline composite structure is accelerated in a hydrogen air proton exchange membrane fuel cell by 30000 circlesPerformance change graphs before and after cyclic aging test;
FIG. 9 shows the monoatomic reaction product with Pt prepared in example 2 of the present invention3Transmission electron microscopy of a fuel cell catalyst of Ni nanocrystalline composite structure;
FIG. 10 shows the monoatomic reaction product with Pt prepared in example 2 of the present invention3An X-ray powder diffraction pattern of a fuel cell catalyst of Ni nanocrystalline composite structure;
FIG. 11 shows the monoatomic reaction product with Pt prepared in example 3 of the present invention3Transmission electron microscopy of a Co nanocrystalline composite structured fuel cell catalyst.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
Fig. 1 is a flow chart illustrating a preparation process of a fuel cell catalyst with a composite structure of a monoatomic compound and a nanocrystal according to an embodiment of the present invention. As shown in fig. 1, the present invention provides a method for preparing a fuel cell catalyst with a composite structure of a single atom and a nanocrystal, comprising: mixing an ammonia water solution, conductive carbon black and an ethanol water solution to obtain a first mixed solution; dissolving nitrogen-containing organic molecules and first transition metal salt in an ethanol water solution to obtain a second mixed solution; and mixing the first mixed solution and the second mixed solution, reacting for a preset time, adding a metal platinum salt and a second transition metal salt, evaporating to dryness, sintering at a preset temperature, and carrying out acid pickling and drying to obtain the fuel cell catalyst with the monatomic and nanocrystalline composite structure.
In operation S101, an ammonia solution, conductive carbon black, and an ethanol aqueous solution are mixed to obtain a first mixed solution.
According to an embodiment of the present invention, an aqueous ammonia solution, conductive carbon black, and an aqueous ethanol solution are mixed under magnetic stirring at normal temperature to obtain a first mixed solution.
According to the embodiment of the present invention, the aqueous ammonia solution may be a commercially available aqueous solution containing 25% to 28% ammonia.
According to an embodiment of the invention, the conductive carbon black comprises at least one of: vulcan XC-72, Vulcan XC-72R, BP2000, Ketjen black and acetylene black, wherein the Vulcan XC-72 and the Vulcan XC-72R, BP2000 are types of commonly used conductive carbon black.
According to an embodiment of the present invention, the aqueous ethanol solution may be a mixed solution of ethanol and water in a volume ratio of 1: 3.
In operation S102, a nitrogen-containing organic molecule and a first transition metal salt are dissolved in an ethanol aqueous solution to obtain a second mixed solution.
According to an embodiment of the present invention, a nitrogen-containing organic molecule and a first transition metal salt are dissolved in an ethanol aqueous solution, and subjected to ultrasonic treatment for a predetermined time period, for example, 10min, 15min, and the like, to obtain a second mixed solution.
According to an embodiment of the invention, the nitrogen-containing organic molecule comprises at least one of: dopamine, cyanamide, polyaniline, benzidine.
According to an embodiment of the present invention, the first transition metal salt may be cobalt acetylacetonate.
According to the embodiment of the invention, the mass ratio of the nitrogen-containing organic molecule to the first transition metal salt is 10 (0.5-1), and can be 10:0.5, 10:0.6, 10:0.7, 10:0.8 and 10: 1.
In operation S103, the first mixed solution and the second mixed solution are mixed and reacted for a preset time.
According to the embodiment of the invention, the first mixed solution and the second mixed solution are mixed, and the reaction is carried out for a preset time, wherein the preset time can be 2-6 hours, and can be 2 hours, 3 hours, 4 hours, 5 hours and 6 hours.
In operation S104, a metal platinum salt and a second transition metal salt are added, evaporated to dryness, and sintered under a preset temperature condition.
According to an embodiment of the present invention, the metal platinum salt may be selected from H2PtCl6·6H2O or Pt (acac)2。
According to an embodiment of the invention, the second transition metal salt comprises at least one of: co (NO)3)2·6H2O、CoCl2·6H2O、CoSO4·7H2O、Co(acac)2。
According to the embodiment of the invention, the evaporation operation is to remove the solution from the mixed solution by using a rotary evaporator, wherein the rotary evaporation temperature can be selected to be 40-60 ℃.
According to an embodiment of the present invention, the sintering under the preset temperature condition includes: sintering under the conditions of reducing atmosphere and preset temperature.
According to the embodiment of the invention, the sintering temperature under the preset temperature condition is 600-1200 ℃, optionally 600 ℃, 800 ℃, 1000 ℃, 1100 ℃ and 1200 ℃, and the sintering time under the preset temperature condition is 1-4 hours, optionally 1 hour, 1.5 hours, 2 hours, 3 hours and 4 hours.
According to the embodiment of the invention, the reducing atmosphere comprises 5-10% of H2A gas of Ar, wherein H2The volume ratio of the/Ar is selected from 5%, 6%, 8%, 9% and 10%.
In operation S105, the fuel cell catalyst having the composite structure of the monoatomic ions and the nanocrystals is obtained through acid washing and drying.
According to an embodiment of the present invention, the acid washing may be performed in a sulfuric acid solution.
According to an embodiment of the present invention, the concentration of the sulfuric acid solution used for acid washing may be 0.1 mol/L.
According to the embodiment of the invention, the temperature range of acid washing is 50-80 ℃, optionally 50 ℃, 60 ℃, 65 ℃, 70 ℃ and 80 ℃, and the time range of acid washing is 1-4 h, optionally 1h, 1.5h, 2h, 3h and 4 h.
The invention provides a fuel cell catalyst with a monatomic and nanocrystalline composite structure, which is prepared by the preparation method.
In some embodiments, the conductive carbon black support is modified by metal monoatomic modification, and the size of the nano crystal is in a range of 3-5 nm.
The invention provides an application of a fuel cell catalyst with a monatomic and nanocrystalline composite structure in a cathode of a hydrogen air proton exchange membrane fuel cell.
The invention loads metal platinum salt and transition metal salt on a modified conductive carbon black carrier through high-temperature reduction to obtain the fuel cell catalyst with a composite structure of single atoms and nano crystals. The preparation method is simple and easy to implement, the modified conductive carbon black carrier can effectively inhibit the size of the nanocrystalline, has a good dispersing effect on the nanocrystalline, and inhibits the nanocrystalline from agglomerating in an acid oxygen reduction reaction, meanwhile, the monoatomic active center on the modified conductive carbon black carrier can expose more catalytic active sites, has certain catalytic activity, and can also enhance the interaction between nanocrystalline particles and the conductive carbon black carrier. When the fuel cell catalyst with the monatomic and nanocrystalline composite structure provided by the invention is used for a cathode of a proton exchange membrane fuel cell, excellent catalytic activity and stability are shown.
According to the embodiment of the invention, the prepared fuel cell catalyst with the monatomic and nanocrystalline composite structure is subjected to electrochemical performance test. Weighing 4mg of the prepared catalyst, dispersing the catalyst in 0.49ml of water, 0.49ml of ethanol and 20 mul of 5% Nafion solution, and ultrasonically mixing the catalyst and the solution uniformly to obtain catalyst slurry; dropping 10 mul of slurry on a platinum carbon electrode with the diameter of 5mm by a liquid transfer gun, and naturally airing; and (4) placing the sample in an electrochemical workstation, and testing to obtain a cyclic voltammetry Curve (CV) and a linear sweep voltammetry curve (LSV). Wherein, CV test conditions are as follows: at 0.1M HClO4In solution, N is introduced2Saturation, scan rate 50mV/s, range from 0.05V to 1.05V (vs RHE).
According to the embodiment of the invention, the prepared fuel cell catalyst with the monatomic and nanocrystalline composite structure is subjected to a stability test, wherein the stability test conditions are as follows: at 0.1M HClO4In solution, introducing O2Saturation, scan rate of 100mV/s, range of 0.6V-1.1V (vs RHE), and number of scan cycles of 30000 cycles.
According to the embodiment of the invention, the prepared fuel cell catalyst with the monatomic and nanocrystalline composite structure is used for preparing the membrane electrode of the proton exchange membrane fuel cell, wherein the preparation process comprises the following steps: taking the prepared catalyst, adding a certain amount of deionized water, 5% perfluorosulfonic acid-polytetrafluoroethylene copolymer (Nafion) and isopropanol serving as dispersing agents, and preparing catalyst slurry after uniformly mixing through ultrasonic treatment. And uniformly spraying the uniformly mixed catalyst slurry onto a Nafion211 proton exchange membrane in a pneumatic spraying manner, and carrying out hot pressing on the catalyst slurry and carbon paper to obtain the membrane electrode for testing.
According to the embodiment of the invention, in the process of preparing the membrane electrode of the proton exchange membrane fuel cell, the mass ratio of the catalyst, the deionized water, the 5% Nafion and the isopropanol can be 1:12:12: 11.
To more clearly illustrate the features of the practice of the present invention, the invention will be further illustrated in connection with an example of a method of making a fuel cell catalyst having a composite structure of monatomic and nanocrystalline.
Example 1
(1) Mixing 4ml of ammonia water solution, 300mg of BP2000 and 130ml of ethanol water solution, stirring for 30min by magnetic force, and uniformly mixing to obtain a first mixed solution.
(2) 300mg of dopamine and 30mg of cobalt acetylacetonate were weighed and dissolved in 10ml of an aqueous ethanol solution to obtain a second mixed solution.
(3) Mixing the first mixed solution and the second mixed solution, reacting for 4h, and adding 0.338gH2PtCl6·6H2O、0.063g Co(NO3)2·6H2And dispersing the O in the mixed solution, uniformly mixing by using a magnetic stirrer, removing the solvent by rotary evaporation, and transferring the obtained mixture to an oven to be dried to obtain a precursor.
(4) Putting the obtained precursor into a porcelain boat, putting the porcelain boat into a tube furnace, and introducing 5% H2Heating the tube furnace to 900 ℃ at the speed of 5 ℃/min by using Ar gas, and preserving heat for 3 hours; naturally cooling to room temperature to obtain the powder material.
(5) Placing the obtained powder material into a round-bottom flask, adding 0.1mol/L sulfuric acid solution, placing the round-bottom flask into an oil bath, keeping the temperature for 4 hours at 80 ℃, then performing suction filtration and washing, washing to be neutral, and drying to obtain the monatomic and Pt3A fuel cell catalyst with a Co nanocrystalline composite structure.
FIG. 2 shows the monoatomic reaction product of Pt prepared in example 1 of the present invention3Transmission electron microscopy of a Co nanocrystalline composite structured fuel cell catalyst. As shown in FIG. 2, Pt3Co nanocrystals are uniformly dispersed on a conductive carbon black carrier.
FIG. 3 shows the monoatomic reaction product with Pt prepared in example 1 of the present invention3High resolution transmission electron microscopy of Co nanocrystalline composite structured fuel cell catalysts. As shown in FIG. 3, Pt3The size of the Co nanocrystal is 3-5 nm, the existence of a monoatomic atom can be observed near the nanocrystal, the fact that the monoatomic atom and the nanocrystal coexist in the catalyst is shown, and even at the high temperature of 900 ℃, the monoatomic modified conductive carbon black carrier can still effectively load and limit Pt3Size of Co nanocrystals.
FIG. 4 shows the monoatomic reaction product with Pt prepared in example 1 of the present invention3X-ray powder diffraction pattern of Co nanocrystalline composite structured fuel cell catalyst. As shown in FIG. 4, a monoatomic modified BP2000 conductive carbon black-loaded Pt3The Co nanocrystalline catalyst showed significant pure Pt3Diffraction peaks of Co nanocrystals.
FIG. 5 shows the monoatomic reaction product with Pt prepared in example 1 of the present invention3CV change chart of the Co nanocrystalline composite structure fuel cell catalyst in 30000-circle stability test. As shown in FIG. 5, the CV curves before and after the stability test were not changed much, and the electrochemical active area was slightly reduced, indicating that the monoatomic modification of conductive carbon black supports loaded with Pt3The Co nanocrystalline fuel cell catalyst has good stability.
FIG. 6 shows the monoatomic reaction product with Pt prepared in example 1 of the present invention3LSV change diagram of Co nanocrystalline composite structure fuel cell catalyst in 30000-circle stability test. As shown in FIG. 6, the half-wave potential was reduced by only 5mV before and after the stability test, indicating that the monoatomic species was bound to Pt3The fuel cell catalyst with the Co nanocrystalline composite structure has excellent stability.
FIG. 7 is a graph of LSV change in a 30000-cycle stability test for commercial Pt/C. As shown in fig. 7, the half-wave potential was reduced by 67mV before and after the stability test. As can be seen from the combination of FIGS. 6 and 7, the monoatomic ions and Pt3The catalytic activity and stability of the fuel cell catalyst with the Co nanocrystalline composite structure are obviously superior to those of commercial Pt/C.
FIG. 8 shows the monoatomic reaction product with Pt prepared in example 1 of the present invention3Co nanocrystalline composite structure fuel cell catalyst in hydrogen air spaceAnd (3) performance change graphs before and after 30000-turn accelerated cycle aging tests in the proton exchange membrane fuel cell. Monoatomic with Pt3When the fuel cell catalyst with the Co nanocrystalline composite structure is applied to the cathode of a hydrogen air proton exchange membrane fuel cell, the Pt loading capacity of the cathode is 0.15mgPt/cm2Under the condition of (1), the current density under 0.8V can reach 334mA/cm2The highest power density can reach 988mW/cm2In addition, the stability of the catalyst passes the accelerated cyclic aging test standard in related industries, the catalyst still shows excellent catalytic activity after 30000 circles of accelerated tests, and the test results show that the prepared monoatomic catalyst and Pt are3The fuel cell catalyst with the Co nanocrystalline composite structure has excellent catalytic activity and stability.
Example 2
(1) Mixing 4ml of ammonia water solution, 300mg of BP2000 and 130ml of ethanol water solution, stirring for 30min by magnetic force, and uniformly mixing to obtain a first mixed solution.
(2) 300mg of dopamine and 30mg of cobalt acetylacetonate were weighed and dissolved in 10ml of an aqueous ethanol solution to obtain a second mixed solution.
(3) Mixing the first mixed solution and the second mixed solution, reacting for 4h, and adding 0.338gH2PtCl6·6H2O、0.05gNiCl2·6H2And dispersing the O in the mixed solution, uniformly mixing by using a magnetic stirrer, removing the solvent by rotary evaporation, and transferring the obtained mixture to an oven to be dried to obtain a precursor.
(4) Putting the obtained precursor into a porcelain boat, putting the porcelain boat into a tube furnace, and introducing 8% H2Heating the tube furnace to 900 ℃ at the speed of 5 ℃/min by using Ar gas, and preserving heat for 3 hours; naturally cooling to room temperature to obtain the powder material.
(5) Placing the obtained powder material into a round-bottom flask, adding 0.1mol/L sulfuric acid solution, placing the round-bottom flask into an oil bath, keeping the temperature for 4 hours at 80 ℃, then performing suction filtration and washing, washing to be neutral, and drying to obtain the monatomic and Pt3A fuel cell catalyst with a Ni nanocrystalline composite structure.
FIG. 9 shows a monoatomic reaction with Pt according to example 2 of the present invention3Transmission electron microscopy of a fuel cell catalyst with Ni nanocrystalline composite structure. As shown in fig. 9, Pt3The Ni nanocrystalline is uniformly dispersed on the conductive carbon black modified by the monoatomic atom.
FIG. 10 shows the monoatomic reaction product with Pt prepared in example 2 of the present invention3X-ray powder diffraction pattern of a fuel cell catalyst of Ni nanocrystalline composite structure. As shown in FIG. 10, the monoatomic modified BP2000 conductive carbon Black-Supported Pt3The Ni nanocrystalline catalyst showed significant pure Pt3Diffraction peaks of Ni nanocrystals.
Example 3
(1) Mixing 4ml of ammonia water solution, 300mg of Vulcan XC-72R and 130ml of ethanol water solution, stirring for 30min by magnetic force, and uniformly mixing to obtain a first mixed solution.
(2) 300mg of dopamine and 30mg of cobalt acetylacetonate were weighed and dissolved in 10ml of an aqueous ethanol solution to obtain a second mixed solution.
(3) Mixing the first mixed solution and the second mixed solution, reacting for 4h, and adding 0.338gH2PtCl6·6H2O、0.063gCo(NO3)2·6H2And dispersing the O in the mixed solution, uniformly mixing by using a magnetic stirrer, removing the solvent by rotary evaporation, and transferring the obtained mixture to an oven to be dried to obtain a precursor.
(4) Putting the obtained precursor into a porcelain boat, putting the porcelain boat into a tube furnace, and introducing 10% H2Heating the tube furnace to 900 ℃ at the speed of 5 ℃/min by using Ar gas, and preserving heat for 3 hours; naturally cooling to room temperature to obtain the powder material.
(5) Placing the obtained powder material into a round-bottom flask, adding 0.1mol/L sulfuric acid solution, placing the round-bottom flask into an oil bath, keeping the temperature for 4 hours at 80 ℃, then performing suction filtration and washing, washing to be neutral, and drying to obtain the monatomic and Pt3A fuel cell catalyst with a Co nanocrystalline composite structure.
FIG. 11 shows a monoatomic reaction product with Pt according to example 3 of the present invention3Transmission electron microscopy of a Co nanocrystalline composite structured fuel cell catalyst. As shown in FIG. 11, the nanocrystals were uniformly dispersed on the monoatomic-modified conductive carbon black, andthe particles are small, about 5 nm. The conductive carbon black Vulcan XC-72R of other brands can be modified to have better capability of loading nano crystals and controlling the size of the nano crystals.
The invention provides a preparation method of a fuel cell catalyst with a composite structure of single atoms and nano crystals, which is characterized in that precious metal Pt and transition metal elements are reduced at high temperature to form nano crystals to be loaded on modified conductive carbon black, the conductive carbon black carrier can effectively inhibit the size of the nano crystals, has good dispersion effect on the nano crystals and inhibits the agglomeration of the nano crystals in an acid oxygen reduction reaction, and the preparation method is simple and easy to implement and has good repeatability. In addition, the fuel cell catalyst with the monatomic and nanocrystalline composite structure provided by the invention shows excellent catalytic activity and stability in an acid oxygen reduction reaction.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a fuel cell catalyst with a monatomic and nanocrystalline composite structure is characterized by comprising the following steps:
mixing an ammonia water solution, conductive carbon black and an ethanol water solution to obtain a first mixed solution;
dissolving nitrogen-containing organic molecules and first transition metal salt in the ethanol water solution to obtain a second mixed solution;
mixing the first mixed solution and the second mixed solution, reacting for a preset time, adding a metal platinum salt and a second transition metal salt, evaporating to dryness, sintering at a preset temperature, and carrying out acid pickling and drying to obtain a fuel cell catalyst with a monatomic and nanocrystalline composite structure;
wherein the nitrogen-containing organic molecule comprises at least one of: dopamine, cyanamide, polyaniline, benzidine.
2. The method of claim 1, wherein the conductive carbon black comprises at least one of: vulcan XC-72, Vulcan XC-72R, BP2000, Ketjen black and acetylene black.
3. The method according to claim 1, wherein the mass ratio of the nitrogen-containing organic molecule to the first transition metal salt is 10 (0.5 to 1).
4. The method of claim 1, wherein the second transition metal salt comprises at least one of: co (NO)3)2·6H2O、CoCl2·6H2O、CoSO4·7H2O、Co(acac)2。
5. The method according to claim 1, wherein the sintering under the preset temperature condition comprises: and sintering under the reducing atmosphere and the preset temperature condition.
6. The method according to claim 5, wherein the sintering temperature under the preset temperature condition is 600-1200 ℃, the sintering time under the preset temperature condition is 1-4H, and the reducing atmosphere comprises 5-10% of H2and/Ar gas.
7. The method as claimed in claim 1, wherein the temperature of the acid washing is in the range of 50 to 80 ℃ and the time period of the acid washing is in the range of 1 to 4 hours.
8. A fuel cell catalyst with a monatomic and nanocrystalline composite structure obtained by the production method according to any one of claims 1 to 7.
9. The fuel cell catalyst with the monatomic and nanocrystalline composite structure according to claim 8, wherein the conductive carbon black support is modified with a metal monatomic, and the size of the nanocrystals is in the range of 3 to 5 nm.
10. The use of the fuel cell catalyst of the composite structure of monoatomic and nanocrystalline according to claim 8 in a cathode of a hydrogen air proton exchange membrane fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202110294493.4A CN112820888B (en) | 2021-03-19 | 2021-03-19 | Preparation method of fuel cell catalyst with monatomic and nanocrystalline composite structure |
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