CN111146447B - Alloy catalyst with multi-dimensional pore channel structure and preparation method and application thereof - Google Patents

Alloy catalyst with multi-dimensional pore channel structure and preparation method and application thereof Download PDF

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CN111146447B
CN111146447B CN201911273325.6A CN201911273325A CN111146447B CN 111146447 B CN111146447 B CN 111146447B CN 201911273325 A CN201911273325 A CN 201911273325A CN 111146447 B CN111146447 B CN 111146447B
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solution
composite material
alloy catalyst
transition metal
combination
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CN111146447A (en
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于力娜
朱云
朱雅男
张克金
唐柳
杨帅
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FAW Jiefang Automotive Co Ltd
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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
    • 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
    • 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
    • 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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    • 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

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Abstract

The invention relates to an alloy catalyst with a multidimensional pore channel structure, a preparation method and application thereof, wherein the method takes polymer powder and transition metal salt as raw materials, a one-dimensional material is obtained after spinning as a substrate, then the alloy catalyst is obtained through carbonization, chemical bath deposition and fusion, alloy nano particles formed by noble metal and transition metal are uniformly distributed on the surface of the alloy catalyst, and a carrier of the alloy catalyst is a one-dimensional nano carbon material with rich pore channels; when the noble metal is Pt, after 30000 circles of accelerated durability, the electrochemical active area of the alloy catalyst prepared by the method can reach more than 3.5 times of that of a commercial platinum-carbon catalyst, and the alloy catalyst has high stability, and when a monocell is assembled for testing, the open-circuit voltage can reach 1.03V and the current density can reach 3400mA/cm under the conditions that the temperature is 75 ℃ and the humidity is 60% RH2@0.65V, peak power up to 2.2W/cm2。

Description

Alloy catalyst with multi-dimensional pore channel structure and preparation method and application thereof
Technical Field
The invention belongs to the field of fuel cells, and relates to an alloy catalyst with a multi-dimensional pore channel structure, and a preparation method and application thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have the characteristics of high energy conversion efficiency, low-temperature quick start, low noise, no pollution and the like, and are considered to be very suitable as power energy sources of green new energy automobiles. The proton exchange membrane fuel cell consists of a catalyst, a proton exchange membrane, a gas diffusion layer and a bipolar plate. The working principle is that hydrogen separates proton and electron at anode, proton passes through proton exchange membrane to cathode, and electron is connected to cathodeThrough an external circuit to the cathode, and when the electrons reach the cathode, the electrons react with the protons and the introduced O2Under the action of a cathode catalyst, combining to generate water, wherein the specific electrode reaction is as follows:
anode H2→2H++2e-；
Cathode 1/2O2+2H++2e-→H2O；
The total reaction formula is H2+1/2O2→H2O；
Since proton exchange membrane fuel cells use hydrogen and air as the fuel and water as the product, fuel cell technology is considered to be the ultimate goal of new energy development. The ambient temperature at which the fuel cell operates is 40-95 deg.c, and therefore, it is necessary to use a highly active noble metal Pt as the catalyst active component. However, due to the characteristics of small amount of stored metal Pt, high price, easy poisoning, etc., the development of a low platinum catalyst with high activity and high durability is the focus of research at present.
At present, in the Pt/C catalyst commonly used by the proton exchange membrane fuel cell, the Pt loading amount on the anode side generally needs 0.05-0.1mg/cm2Can meet the requirement of the fuel cell, and the Pt loading capacity on the cathode side needs 0.15-0.30mg/cm2(ii) a The cost proportion of the Pt/C catalyst in the fuel cell stack is 35-50%.
Therefore, the improvement of the performance of the Pt-based catalyst and the reduction of the platinum amount for the cathode oxygen reduction catalyst, and the improvement of the catalytic activity of the material have great significance for reducing the cost of the PEMFCs and popularizing and using the PEMFCs.
Disclosure of Invention
The invention aims to provide an alloy catalyst with a multi-dimensional pore channel structure and a preparation method and application thereof, the method takes polymer powder and transition metal salt as raw materials, a one-dimensional material is obtained after spinning as a substrate, then carbonization, chemical bath deposition and fusion are carried out to obtain the alloy catalyst with the multi-dimensional pore channel structure, alloy nano particles of noble metal and transition metal are uniformly distributed on the surface of the alloy catalyst, a carrier of the alloy catalyst is a one-dimensional nano carbon material with rich pore channels, and when the noble metal is Pt, 30000 circles of accelerated durability testsThen, the electrochemical active area of the alloy catalyst prepared by the method is more than 3.5 times that of a commercial platinum-carbon catalyst, the alloy catalyst has high stability, and when a single cell is assembled for testing, the open-circuit voltage can reach 1.03V and the current density can reach 3400mA/cm under the conditions that the temperature is 75 ℃ and the humidity is 60 percent RH2@0.65V, peak power up to 2.2W/cm2(ii) a The method is suitable for urban logistics vehicles and urban buses.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing an alloy catalyst with a multi-dimensional pore channel structure, wherein the method comprises the following steps:
(1) mixing polymer powder, a solvent and transition metal salt, and then spinning and carbonizing to obtain a composite material of transition metal particles and carbon fibers;
(2) and (2) mixing the composite material obtained in the step (1), a stabilizer, a noble metal precursor solution and a reducing agent, and carrying out solid-liquid separation and fusion to obtain the alloy catalyst.
The preparation method of the alloy catalyst comprises the steps of taking polymer powder and transition metal salt as raw materials, obtaining a one-dimensional substrate material containing abundant transition metal particle structures by adopting a method of combining spinning and carbonization treatment, then carrying out chemical bath precipitation, enabling the substrate material to interact with a noble metal precursor and a reducing agent, forming uniformly distributed noble metal nanoparticles on the surface of the substrate material, and then carrying out high-temperature heat treatment to enable the transition metal particles to be melted out of the substrate material and to be fused with the noble metal nanoparticles, thus obtaining alloy nanoparticles of noble metal and transition metal; meanwhile, after the transition metal particles are melted out, a multidimensional pore channel structure is formed in the substrate material, so that the alloy catalyst with the multidimensional pore channel structure is obtained.
The method skillfully utilizes the process of melting and transferring the transition metal crystal to form the alloy by high-temperature heat treatment, and a large number of pore channels are formed in the carbon fiber substrate material, so that the specific surface area and the proton transfer rate of the alloy catalyst are greatly improved; meanwhile, the noble metal component and the transition metal component change the geometric structure and the d-electron layer structure of the noble metal alloy in an alloy construction mode, and obviously inhibit the adsorption of oxygen-containing groups and promote the generation of active sites, thereby achieving the purpose of improving the activity of the catalyst.
Preferably, the mass ratio of the polymer powder and the transition metal salt in step (1) is (0.073-0.09): 0.003-0.019), such as 0.08:0.018, 0.085:0.01 or 0.088:0.006, etc.
Preferably, the mass ratio of the polymer powder, the solvent and the transition metal salt in step (1) is (0.073-0.09): (0.875-0.918): 0.003-0.019), such as 0.08:0.9:0.018, 0.085:0.909:0.01 or 0.088:0.915:0.006, etc.
Preferably, the polymer powder in step (1) includes any one of polyacrylonitrile, polyvinylpyrrolidone, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, or polyurethane, or a combination of at least two thereof, and the combination illustratively includes a combination of polyacrylonitrile and polyvinylpyrrolidone, a combination of polyvinyl alcohol and polymethyl methacrylate, or a combination of polyacrylic acid and polyurethane, or the like.
Preferably, the solvent in step (1) comprises any one of ethanol, water, acetone, N-dimethylformamide or isopropanol, or a combination of at least two thereof, and the combination illustratively comprises a combination of ethanol and water, a combination of acetone and N, N-dimethylformamide or a combination of isopropanol and ethanol, or the like.
Preferably, the transition metal salt in step (1) includes any one of iron salt, cobalt salt, nickel salt or copper salt or a combination of at least two of them, and the combination illustratively includes a combination of iron salt and cobalt salt, a combination of nickel salt and copper salt, a combination of cobalt salt and nickel salt or a combination of copper salt and iron salt, and the like.
Preferably, the iron salt comprises ferric chloride and/or ferric nitrate.
Preferably, the cobalt salt includes any one of cobalt acetate, cobalt chloride or cobalt nitrate or a combination of at least two thereof, and the combination illustratively includes a combination of cobalt acetate and cobalt chloride, a combination of cobalt nitrate and cobalt acetate, a combination of cobalt chloride and cobalt nitrate, or the like.
Preferably, the nickel salt includes any one of nickel chloride, nickel nitrate or nickel acetate or a combination of at least two thereof, which illustratively includes a combination of nickel chloride and nickel nitrate, a combination of nickel acetate and nickel chloride, a combination of nickel nitrate and nickel acetate, or the like.
Preferably, the copper salt comprises copper chloride and/or copper nitrate.
Preferably, the method for mixing the polymer powder, the solvent and the transition metal salt according to step (1) comprises the steps of:
(a) dissolving polymer powder in a solvent to obtain a polymer solution;
(b) adding a transition metal salt into the polymer solution in the step (a), and dissolving to obtain a mixed solution.
Preferably, the dissolution process of step (a) is accompanied by heating.
Preferably, the polymer solution is cooled to room temperature before the transition metal salt is added in step (b).
Preferably, the spinning in step (1) is electrostatic spinning.
The method adopts electrostatic spinning, can obtain the nano-fiber at low cost and high efficiency, and the obtained nano-fiber as a one-dimensional nano-material has the advantages of uniform appearance, rough surface, stable and continuous structure, capability of doping various metal salts to prepare a composite material and the like. After the catalyst is used as a substrate for further modification, the obtained catalyst has the characteristics of difficult agglomeration, strong tolerance, easy modification and the like in the reaction, and when the catalyst is used in the electrocatalytic reaction process, the specific continuity of the one-dimensional structure is favorable for charge conduction, so that the reaction efficiency is improved.
The purpose of adjusting the distance between the spray head and the receiver and the voltage during electrospinning is to spread the spinning product evenly over the surface of the receiver.
Preferably, the temperature of the carbonization in step (1) is 450-700 ℃, such as 500 ℃, 550 ℃, 600 ℃ or 650 ℃, etc.
Preferably, the carbonization process in the step (1) adopts step-by-step temperature rise carbonization; namely, the temperature is firstly raised to the first temperature for pretreatment, and then the temperature is continuously raised to the carbonization temperature for carbonization.
Preferably, the first temperature is 200-.
Preferably, the incubation time for the carbonization is 0.5-3h, such as 1h, 1.5h, 2h or 2.5h, etc.
Preferably, the temperature rise rate of the carbonization is 0.5-2 ℃/min, such as 0.8 ℃/min, 1 ℃/min, 1.3 ℃/min, 1.5 ℃/min, 1.8 ℃/min, or the like.
Preferably, the carbonization is performed under an inert atmosphere.
Preferably, the inert atmosphere comprises any one of nitrogen, argon or helium or a combination of at least two thereof, which illustratively comprises a combination of nitrogen and argon, a combination of nitrogen and helium, or a combination of argon and helium, and the like.
Preferably, the mass ratio of the composite material to the reducing agent in the step (2) is (0.232-0.851): (0.148-0.767), such as 0.3:0.7, 0.5:0.5 or 0.8: 0.3.
Preferably, the mass ratio of the composite material, the noble metal element in the noble metal precursor solution and the reducing agent in step (2) is (0.232-0.851): (0.15-0.28): (0.148-0.767), such as 0.3:0.27:0.7, 0.5:0.2:0.5 or 0.8:0.16: 0.3.
Preferably, the stabilizer in step (2) comprises any one of glycine-sodium hydroxide buffer solution, sodium carbonate-sodium bicarbonate buffer solution, borax-sodium hydroxide buffer solution, urea solution or hexamethylenetetramine solution.
Preferably, the reducing agent in step (2) includes any one of sodium borohydride, ascorbic acid or hydrazine hydrate or a combination of at least two of them, and the combination illustratively includes a combination of sodium borohydride and ascorbic acid, a combination of hydrazine hydrate and sodium borohydride, a combination of ascorbic acid and hydrazine hydrate, and the like.
Preferably, the noble metal precursor solution of step (2) includes a metal platinum precursor.
Preferably, the metal platinum precursor includes any one of chloroplatinic acid, potassium tetrachloroplatinate, potassium hexachloroplatinate, platinum nitrate, or a tetraammineplatinum solution, or a combination of at least two thereof, which exemplarily includes a combination of a chloroplatinic acid solution and a potassium tetrachloroplatinate solution, a combination of a potassium hexachloroplatinate solution and a platinum nitrate solution, or a combination of a tetraammineplatinum solution and a platinum nitrate solution, and the like.
Preferably, the solid-liquid separation in step (2) further comprises washing.
Preferably, the washing liquid of the washing is water.
Preferably, the end point of the wash is to the point where the eluate is neutral.
Preferably, after the washing, drying is further included before the fusing.
Preferably, the temperature for the fusion in step (2) is 800-1000 ℃, such as 850 ℃, 900 ℃ or 950 ℃ and the like.
The fusion temperature is 800-1000 ℃, which is beneficial to the fusion and migration of transition metal in the composite material of transition metal particles and carbon fibers and is fused with noble metal nanoparticles to form alloy nanoparticles, and when the temperature is less than 800 ℃, the reaction can not occur; when the temperature is > 1000 ℃, particles are formed too large.
Preferably, the fusion time in step (2) is 0.5-3h, such as 1h, 1.5h, 2h or 2.5h, etc.
Preferably, the process of fusing in step (2) is performed under an inert atmosphere.
Preferably, the step (2) further comprises cooling after the fusion.
Preferably, the end point of the cooling temperature reduction is to room temperature.
Preferably, the method for mixing the composite material obtained in the step (1), the stabilizer, the noble metal precursor solution and the reducing agent in the step (2) comprises the following steps:
(a') dispersing the composite material obtained in the step (1) in a stabilizer to obtain a dispersion liquid of the composite material;
(b ') adding the noble metal precursor solution to the dispersion liquid in the step (a'), and mixing;
(c ') adding a reducing agent to the product of step (b') to effect a reaction.
According to the method, the composite material is dispersed in the stabilizer, the stabilizer is favorable for obtaining a mixed solution with good dispersibility and more uniformity, then the noble metal precursor solution is added, so that the noble metal precursor is adsorbed on the surface of the composite material, and then the reducing agent is added for reaction, so that the noble metal precursor adsorbed on the surface of the composite material is reduced to form the noble metal nano-particles.
Preferably, the mixing time in step (b') is 2-15h, such as 3h, 5h, 8h, 10h or 12h, etc., preferably 5-10 h.
Preferably, the reaction in step (c') is carried out for a time of 0.5 to 10h, such as 1h, 3h, 5h, 7h or 9h, etc., preferably 2 to 4 h.
Preferably, the reaction in step (c') is carried out with stirring.
As a preferred technical scheme of the invention, the preparation method of the alloy catalyst with the multidimensional pore channel structure comprises the following steps:
(1') dissolving the polymer powder in a solvent to obtain a polymer solution;
(2 ') adding a transition metal salt to the polymer solution in the step (1') and dissolving to obtain a mixed solution of polymer powder and the transition metal salt;
(3 ') carrying out electrostatic spinning on the mixed solution in the step (2'), and then carbonizing the product of electrostatic spinning at the temperature of 450-700 ℃ for 0.5-3h to obtain the composite material of the transition metal particles and the carbon fibers;
(4 ') dispersing the composite material obtained in the step (3') in a stabilizer to obtain a dispersion liquid of the composite material;
(5 ') adding a noble metal precursor solution into the dispersion liquid of the composite material obtained in the step (4'), stirring, adding a reducing agent, reacting, carrying out solid-liquid separation, washing, drying, fusing for 0.5-3h at the temperature of 800-1000 ℃ under an inert atmosphere, and then cooling to room temperature under the inert atmosphere to obtain the alloy catalyst.
In a second aspect, the invention provides an alloy catalyst with a multi-dimensional pore channel structure prepared by the method in the first aspect.
In a third aspect, the invention provides the use of the alloy catalyst of the multi-dimensional pore channel structure according to the second aspect, for a proton exchange membrane fuel cell.
Preferably, the alloy catalyst is used in the cathode of a proton exchange membrane fuel cell.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method skillfully utilizes the process of high-temperature heat treatment of transition metal crystal fusion migration and noble metal nano particles to form alloy, and a large number of pore channels are formed in the one-dimensional carbon fiber substrate material, so that the specific surface area and the proton migration rate of the alloy catalyst are greatly improved;
(2) according to the method, the alloy nanoparticles formed by the transition metal crystals and the noble metal nanoparticles in the fusion process change the geometric structure and the d-electron layer structure of the noble metal alloy, and obviously inhibit the adsorption of oxygen-containing groups and promote the generation of active sites, so that the aim of improving the activity of the catalyst is fulfilled.
Drawings
FIG. 1 is a LSV test curve of an alloy catalyst and a commercial platinum-carbon catalyst obtained in example 1 of the present invention tested after 30000 times of durability;
fig. 2 is an I-V test curve and a current density-power density test curve of an assembled battery obtained from the alloy catalyst obtained in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The reagents additionally used in the embodiments of the present invention are as follows:
glycine-sodium hydroxide buffer solution: diluting 50ml of 0.2M glycine +12ml of 0.2M sodium hydroxide with water to 100 ml;
sodium carbonate-sodium bicarbonate buffer solution: 1mL of 0.1M Na2CO3 solution + 9mL of 0.1M NaHCO3 solution;
borax-sodium hydroxide buffer solution: 50ml of 0.05M borax and 6ml of 0.2M NaOH are diluted to 200 ml by adding water
Hexamethylenetetramine solution: 0.2g of hexamethylenetetramine in 50mL of water;
urea solution: 0.2g urea plus 50mL water.
Example 1
The preparation method of the alloy catalyst with the multidimensional pore channel structure comprises the following steps:
(1') weighing 0.5g of polyacrylonitrile powder in 5g N, N-dimethylformamide, and dissolving the polyacrylonitrile powder in the N-dimethylformamide under heating at 80 ℃ to obtain a polymer solution;
(2 ') cooling the polymer solution obtained in the step (1') to room temperature, and then adding 0.018g of nickel nitrate, and sufficiently stirring to completely dissolve the nickel nitrate;
(3 ') pumping the mixed solution in the step (2') into a spinning nozzle, adjusting the distance and voltage between the nozzle and a receiver to uniformly disperse the obtained composite fiber on the surface of the receiver, taking down a fiber film after spinning is carried out for 10 hours, transferring the fiber film into a tubular furnace, heating to 250 ℃ at the speed of 2 ℃/min under the nitrogen atmosphere for staying for 2 hours, then continuously heating to 450 ℃ at the speed of 2 ℃/min for staying for 3 hours, and then cooling to room temperature under the nitrogen atmosphere to obtain a nickel and carbon nanofiber composite material, and taking out for later use;
(4 ') dispersing 0.2g of the nickel and carbon nanofiber composite material obtained in the step (3') in 50mL of glycine-sodium hydroxide buffer solution, and performing ultrasonic treatment for 30min to uniformly disperse the composite material to obtain a dispersion liquid of the composite material;
(5 ') adding 1.3mL of chloroplatinic acid solution having a platinum element content of 0.10g/mL to the dispersion of the composite material obtained in step (4'), stirring for 5 hours, and then adding 0.5mL of 0.1g/mL NaBH4Solution (0.1 g/mL herein refers to NaBH in 1mL of solution4The mass of the platinum nanoparticles is 0.1g), carrying out reaction to quickly reduce platinum ions adsorbed on the composite material to generate platinum nanoparticles, continuously stirring for 2 hours at room temperature, carrying out suction filtration, washing with water until eluate is neutral, placing in a vacuum oven for drying at 100 ℃, then transferring to a tubular furnace, heating at a rate of 2 ℃/min, fusing for 3 hours at 800 ℃ in a nitrogen atmosphere, and then cooling to room temperature in the nitrogen atmosphere to obtain the alloy catalyst.
Example 2
The preparation method of the alloy catalyst with the multidimensional pore channel structure comprises the following steps:
(1') weighing 1g of polyvinylpyrrolidone powder in 12g of ethanol, and stirring for dissolving to obtain a polymer solution;
(2 ') adding 0.255g of cobalt nitrate into the polymer solution obtained in the step (1'), and fully stirring to completely dissolve the cobalt nitrate;
(3 ') pumping the mixed solution in the step (2') into a spinning nozzle, adjusting the distance and voltage between the nozzle and a receiver to uniformly disperse the obtained composite fiber on the surface of the receiver, taking down a fiber film after spinning is carried out for 10 hours, transferring the fiber film into a tubular furnace, heating to 250 ℃ at the speed of 0.5 ℃/min under the argon atmosphere for staying for 2 hours, then continuously heating to 700 ℃ at the speed of 0.5 ℃/min for staying for 0.5 hour, then cooling to room temperature under the argon atmosphere to obtain a cobalt and carbon nanofiber composite material, and taking out for later use;
(4 ') dispersing 0.2g of the cobalt and carbon nanofiber composite material obtained in the step (3') in 50mL of sodium carbonate-sodium bicarbonate buffer solution, and performing ultrasonic treatment for 36min to uniformly disperse the cobalt and carbon nanofiber composite material to obtain a dispersion liquid of the composite material;
(5 ') adding 2.4mL of potassium tetrachloroplatinate solution with the platinum element content of 0.10g/mL into the dispersion liquid of the composite material obtained in the step (4'), stirring for 8 hours, adding 6.6mL of 0.1g/mL ascorbic acid solution, continuing stirring for 2 hours at room temperature, performing suction filtration to obtain a solid, washing until the eluate is neutral, placing the eluate in a vacuum oven at 100 ℃ for drying for 8 hours, then transferring the eluate into a tubular furnace, heating at the rate of 2 ℃/min, fusing for 0.5 hour at 1000 ℃ under the helium atmosphere, and then cooling to room temperature under the helium atmosphere to obtain the alloy catalyst.
Example 3
The preparation method of the alloy catalyst with the multidimensional pore channel structure comprises the following steps:
(1') weighing 0.8g of polyvinyl alcohol powder in 10g of deionized water, and stirring for dissolving to obtain a polymer solution;
(2 ') adding 0.157g of ferric nitrate to the polymer solution obtained in the step (1'), and sufficiently stirring to completely dissolve the ferric nitrate;
(3 ') pumping the mixed solution in the step (2') into a spinning nozzle, adjusting the distance and voltage between the nozzle and a receiver to uniformly disperse the obtained composite fiber on the surface of the receiver, taking down a fiber film after spinning is carried out for 10 hours, transferring the fiber film into a tubular furnace, heating to 300 ℃ at the speed of 2 ℃/min under the nitrogen atmosphere for 2 hours, continuing heating to 600 ℃ at the speed of 2 ℃/min for 1 hour, cooling to room temperature under the helium atmosphere to obtain an iron and carbon nanofiber composite material, and taking out for later use;
(4 ') dispersing 0.2g of the iron and carbon nanofiber composite obtained in the step (3') in 50mL of borax-sodium hydroxide buffer solution, and performing ultrasonic treatment for 36min to uniformly disperse the iron and carbon nanofiber composite to obtain a dispersion liquid of the composite;
(5 ') adding 1.8mL of potassium hexachloroplatinate solution with the platinum element content of 0.10g/mL into the dispersion liquid of the composite material obtained in the step (4'), stirring for 8 hours, adding 1.4mL of 0.1g/mL hydrazine hydrate solution, continuing stirring for 2 hours at room temperature, performing suction filtration to obtain a solid, washing until the eluate is neutral, placing the eluate in a vacuum oven at 100 ℃ for drying for 8 hours, then transferring the eluate into a tubular furnace, heating at the rate of 2 ℃/min, fusing for 0.5 hour at 1000 ℃ under the helium atmosphere, and then cooling to room temperature under the helium atmosphere to obtain the alloy catalyst.
Example 4
The preparation method of the alloy catalyst with the multidimensional pore channel structure comprises the following steps:
(1') weighing 1.0g of polymethyl methacrylate powder in 10g of acetone, and stirring to dissolve to obtain a polymer solution;
(2 ') adding 0.0442g of copper nitrate to the polymer solution obtained in the step (1'), and sufficiently stirring to completely dissolve the copper nitrate;
(3 ') pumping the mixed solution in the step (2') into a spinning nozzle, adjusting the distance and voltage between the nozzle and a receiver to uniformly disperse the obtained composite fiber on the surface of the receiver, taking down a fiber film after spinning is carried out for 10 hours, transferring the fiber film into a tubular furnace, heating to 300 ℃ at the speed of 2 ℃/min under the argon atmosphere for staying for 2 hours, then continuously heating to 700 ℃ at the speed of 1 ℃/min for staying for 0.5 hour, and then cooling to room temperature under the argon atmosphere to obtain the copper and carbon nanofiber composite material, and taking out for later use;
(4 ') dispersing 0.2g of the copper and carbon nanofiber composite material obtained in the step (3') in 50mL of urea solution, and performing ultrasonic treatment for 50min to uniformly disperse the copper and carbon nanofiber composite material to obtain a dispersion liquid of the composite material;
(5 ') adding 1.8mL of platinum nitrate solution with the platinum element content of 0.10g/mL into the dispersion liquid of the composite material obtained in the step (4'), stirring for 10 hours, adding 350 mu L of 0.1g/mL sodium borohydride solution, continuing stirring for 4 hours at room temperature, performing suction filtration to obtain a solid, washing with water until the eluate is neutral, placing in a vacuum oven for drying for 8 hours at 90 ℃, then transferring into a tubular furnace, heating at the rate of 2 ℃/min, fusing for 1 hour at 900 ℃ under the nitrogen atmosphere, and then cooling to room temperature under the nitrogen atmosphere to obtain the alloy catalyst.
Example 5
The preparation method of the alloy catalyst with the multidimensional pore channel structure comprises the following steps:
(1') weighing 1.0g of polyurethane powder in a mixed solution of 5g of acetone and 5g N, N-dimethylformamide, and stirring to dissolve the polyurethane powder to obtain a polymer solution;
(2 ') adding 0.047g of nickel acetate to the polymer solution obtained in the step (1'), and sufficiently stirring to completely dissolve the nickel acetate;
(3 ') pumping the mixed solution in the step (2') into a spinning nozzle, adjusting the distance and voltage between the nozzle and a receiver to uniformly disperse the obtained composite fiber on the surface of the receiver, taking down a fiber film after spinning is carried out for 10 hours, transferring the fiber film into a tubular furnace, heating to 250 ℃ at the speed of 2 ℃/min under the argon atmosphere for staying for 2 hours, then continuously heating to 700 ℃ at the speed of 1 ℃/min for staying for 0.5 hour, and then cooling to room temperature under the argon atmosphere to obtain a nickel and carbon nanofiber composite material, and taking out for later use;
(4 ') dispersing 0.2g of the nickel and carbon nanofiber composite material obtained in the step (3') in 50mL of hexamethylenetetramine solution, and performing ultrasonic treatment for 60min to uniformly disperse the nickel and carbon nanofiber composite material to obtain a dispersion liquid of the composite material;
(5 ') adding 1.6mL of chloroplatinic acid solution with the platinum element content of 0.10g/mL into the dispersion liquid of the composite material obtained in the step (4'), stirring for 10 hours, adding 630 mu L of 0.1g/mL sodium borohydride solution, continuing stirring for 4 hours at room temperature, carrying out suction filtration to obtain a solid, washing with water until the eluate is neutral, placing in a vacuum oven for drying for 8 hours at 90 ℃, then transferring into a tubular furnace, heating at the rate of 2 ℃/min, fusing for 1 hour at 900 ℃ under the nitrogen atmosphere, and then cooling to room temperature under the nitrogen atmosphere to obtain the alloy catalyst.
Example 6
The preparation method of the alloy catalyst with the multidimensional pore channel structure comprises the following steps:
(1') weighing 0.8g of polyvinylpyrrolidone powder in 10g of isopropanol, and stirring for dissolving to obtain a polymer solution;
(2 ') adding 0.090g of nickel chloride into the polymer solution obtained in the step (1'), and fully stirring to completely dissolve the nickel chloride;
(3 ') pumping the mixed solution in the step (2') into a spinning nozzle, adjusting the distance and voltage between the nozzle and a receiver to uniformly disperse the obtained composite fiber on the surface of the receiver, taking down a fiber film after spinning is carried out for 10 hours, transferring the fiber film into a tubular furnace, heating to 250 ℃ at the speed of 2 ℃/min under the argon atmosphere for staying for 2 hours, then continuously heating to 700 ℃ at the speed of 1 ℃/min for staying for 0.5 hour, and then cooling to room temperature under the argon atmosphere to obtain a nickel and carbon nanofiber composite material, and taking out for later use;
(4 ') dispersing 0.2g of the nickel and carbon nanofiber composite material obtained in the step (3') in 50mL of hexamethylenetetramine solution, and performing ultrasonic treatment for 60min to uniformly disperse the nickel and carbon nanofiber composite material to obtain a dispersion liquid of the composite material;
(5 ') adding 1.6mL of chloroplatinic acid solution with the platinum element content of 0.10g/mL into the dispersion liquid of the composite material obtained in the step (4'), stirring for 10 hours, adding 1mL of 0.1g/mL sodium borohydride solution, continuing stirring for 4 hours at room temperature, performing suction filtration to obtain a solid, washing with water until the eluate is neutral, placing in a vacuum oven for drying at 90 ℃ for 8 hours, then transferring into a tubular furnace, heating at the rate of 2 ℃/min, fusing for 1 hour at 900 ℃ under the nitrogen atmosphere, and then cooling to room temperature under the nitrogen atmosphere to obtain the alloy catalyst.
Example 7
The preparation method of the alloy catalyst with the multidimensional pore channel structure comprises the following steps:
(1') weighing 0.8g of polyacrylonitrile powder in 10g of N, N-dimethylformamide, heating, stirring and dissolving to obtain a polymer solution;
(2 ') adding 0.123g of ferric chloride to the polymer solution obtained in the step (1'), and sufficiently stirring to completely dissolve the ferric chloride;
(3 ') pumping the mixed solution in the step (2') into a spinning nozzle, adjusting the distance and voltage between the nozzle and a receiver to uniformly disperse the obtained composite fiber on the surface of the receiver, taking down a fiber film after spinning is carried out for 10 hours, transferring the fiber film into a tubular furnace, heating to 250 ℃ at the speed of 2 ℃/min under the argon atmosphere for staying for 2 hours, then continuously heating to 700 ℃ at the speed of 1 ℃/min for staying for 0.5 hour, and then cooling to room temperature under the argon atmosphere to obtain the iron and carbon nanofiber composite material, and taking out for later use;
(4 ') dispersing 0.2g of the iron and carbon nanofiber composite obtained in the step (3') in 50mL of glycine-sodium hydroxide buffer solution, and performing ultrasonic treatment for 60min to uniformly disperse the iron and carbon nanofiber composite to obtain a dispersion liquid of the composite;
(5 ') adding 1.6mL of chloroplatinic acid solution with the platinum element content of 0.10g/mL into the dispersion liquid of the composite material obtained in the step (4'), stirring for 10 hours, adding 1mL of 0.1g/mL sodium borohydride solution, continuing stirring for 4 hours at room temperature, performing suction filtration to obtain a solid, washing with water until the eluate is neutral, placing in a vacuum oven for drying at 90 ℃ for 8 hours, then transferring into a tubular furnace, heating at the rate of 2 ℃/min, fusing for 1 hour at 900 ℃ under the nitrogen atmosphere, and then cooling to room temperature under the nitrogen atmosphere to obtain the alloy catalyst.
Example 8
The preparation method of the alloy catalyst with the multidimensional pore channel structure comprises the following steps:
(1') weighing 0.4g of polyacrylonitrile and 0.4g of polyvinylpyrrolidone powder in 10g of N, N-dimethylformamide, and heating, stirring and dissolving to obtain a polymer solution;
(2 ') adding 0.064g of cobalt acetate and 0.047g of cobalt chloride to the polymer solution obtained in the step (1'), and sufficiently stirring the mixture to completely dissolve the cobalt acetate and the cobalt chloride;
(3 ') pumping the mixed solution in the step (2') into a spinning nozzle, adjusting the distance and voltage between the nozzle and a receiver to uniformly disperse the obtained composite fiber on the surface of the receiver, taking down a fiber film after spinning is carried out for 10 hours, transferring the fiber film into a tubular furnace, heating to 250 ℃ at the speed of 2 ℃/min under the argon atmosphere for staying for 2 hours, then continuously heating to 700 ℃ at the speed of 1 ℃/min for staying for 0.5 hour, and then cooling to room temperature under the argon atmosphere to obtain the cobalt and carbon nanofiber composite material, and taking out for later use;
(4 ') dispersing 0.2g of the cobalt and carbon nanofiber composite material obtained in the step (3') in 50mL of glycine-sodium hydroxide buffer solution, and performing ultrasonic treatment for 60min to uniformly disperse the cobalt and carbon nanofiber composite material to obtain a dispersion liquid of the composite material;
(5 ') adding 1.6mL of chloroplatinic acid solution with the platinum element content of 0.10g/mL into the dispersion liquid of the composite material obtained in the step (4'), stirring for 10 hours, adding 1mL of 0.1g/mL sodium borohydride solution, continuing stirring for 4 hours at room temperature, performing suction filtration to obtain a solid, washing with water until the eluate is neutral, placing in a vacuum oven for drying at 90 ℃ for 8 hours, then transferring into a tubular furnace, heating at the rate of 2 ℃/min, fusing for 1 hour at 900 ℃ under the nitrogen atmosphere, and then cooling to room temperature under the nitrogen atmosphere to obtain the alloy catalyst.
Comparative example 1
This comparative example differs from example 1 in that no nickel nitrate was added in step (2') and the other conditions were exactly the same as in example 1.
Comparative example 2
This comparative example differs from example 1 in that the fusion temperature in step (5') was replaced with 700 ℃ and the other conditions were exactly the same as in example 1.
And (3) performance testing:
the alloy catalyst obtained in example 1 and a commercial Pt/C catalyst were subjected to a durability test under the following conditions: at 0.1M HClO4The solution is dripped on a glassy carbon electrode head of a Pine rotating disc electrode in the United states, a durable 30000-circle cycle resistance experiment is carried out at 0.6V-1.2V, the test result is shown in figure 1, and as can be seen from figure 1, the alloy catalyst obtained in example 1 shows better durable performance, and the durable performance is obviously better than that of a commercial Pt/C catalyst;
the alloy catalyst obtained in the example 1 has excellent durability, the mass activity attenuation of the catalyst after 30000 cycles of CV is only 30%, which is far lower than the technical index required by the United states department of energy (DOE), and the alloy catalyst has better ORR performance.
The catalysts obtained in examples 1 to 8 and comparative examples 1 to 2 and a commercial platinum carbon catalyst were subjected to a mass activity test on a rotating disk electrode, and the test results are shown in table 1;
area of glassy carbon electrode (0.196 cm)2). The mass of the Pt dripped on the glassy carbon electrode tip is 0.005 mg.
Quality activity test method: and carrying out LSV test on the material in 0.1M perchloric acid solution, setting a voltage window to be 0.05-1.03V, sweeping speed to be 5mV/s, and sampling point interval to be 1 mV. After obtaining the LSV curve, the mass activity (m) was calculated using the following formulaA)：
Figure BDA0002314835160000161
Wherein jkThe current density (mA/cm) was set to 0.9V2) (ii) a j is the limiting current density (mA/cm)2)；LptThe loading amount of platinum (mg) is 0.005mg of the loading amount of Pt dripped on the glassy carbon electrode head, S is the area of the glassy carbon electrode and is 0.196cm2。
30000 circles Activity test method: the material was subjected to an accelerated CV test in a 0.1M perchloric acid solution at a voltage of 0.6-1.2V, oxygen saturation, a sweep rate of 200mV/S, and 30000 cycles. Mass activity decay was calculated by testing LSV curves before and after 30000 cycles of testing.
The mass activities (after 30000 cycles of accelerated durability) of the alloy catalysts obtained in examples 1 to 8 of the present invention, the catalysts obtained in comparative examples 1 to 2, and the commercial Pt/C catalyst (Manchu 9100, Pt/C) are shown in Table 1;
TABLE 1
Figure BDA0002314835160000171
As can be seen from the data in the above table, the mass activity after 30000 cycles of accelerated aging of the alloy catalyst obtained in example 1 was 127mA/mgpt@0.90V, is commercializedThe Pt/C catalyst has 3.5 times of mass activity and shows better durability.
The alloy catalyst prepared in example 1 was subjected to membrane electrode preparation: weighing 0.12g of the catalyst prepared in the example 1, adding 0.8mL of water for soaking, adding 57mL of isopropanol and 23mL of ethanol, ultrasonically stirring for 20min, then adding 1350 mu L of 5% Nafion solution, continuously ultrasonically stirring for 60min, shearing and stirring for 30min under the protection of nitrogen, and crushing cells for 10 min; CCM is prepared by ultrasonic spraying, a proton membrane is Goll enhanced type 18 mu m, and the Pt loading capacity of an anode is 0.10mg/cm2Cathode at 0.4mg/cm2The carbon paper is SGL 29BC, and the effective area of the membrane electrode is 5 multiplied by 10cm2And edge sealing is carried out on the single cell, and single cell manufacturing is carried out.
Among them, the test cell temperature was 75 ℃, the humidification temperature was 70 ℃, the relative humidity was 60% RH, and the stoichiometric ratio hydrogen/air was 1.2/2.5, and the test results are shown in fig. 2, and it can be seen from fig. 2 that the membrane electrode prepared in example 1 has good power characteristics, and the current density can reach 3400mA/cm2@0.65V, peak power density as high as 2.2W/cm2。
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (38)

1. The preparation method of the alloy catalyst with the multi-dimensional pore channel structure is characterized by comprising the following steps of:
(1) mixing polymer powder, a solvent and transition metal salt, and then spinning and carbonizing to obtain a composite material of transition metal particles and carbon fibers;
(2) mixing the composite material obtained in the step (1), a stabilizer, a noble metal precursor solution and a reducing agent, and carrying out solid-liquid separation and fusion to obtain the alloy catalyst;
the fusion temperature in the step (2) is 800-1000 ℃, the fusion time is 0.5-3h, and the fusion process is carried out in an inert atmosphere;
the mass ratio of the polymer powder, the solvent and the transition metal salt in the step (1) is (0.073-0.09): (0.875-0.918): 0.003-0.019);
the mass ratio of the composite material to the noble metal element and the reducing agent in the noble metal precursor solution in the step (2) is (0.232-0.851): (0.15-0.28): (0.148-0.767);
and (3) the stabilizer in the step (2) comprises any one of glycine-sodium hydroxide buffer solution, sodium carbonate-sodium bicarbonate buffer solution, borax-sodium hydroxide buffer solution, urea solution or hexamethylenetetramine solution.
2. The method of claim 1, wherein the polymer powder in step (1) comprises any one of polyacrylonitrile, polyvinylpyrrolidone, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, or polyurethane, or a combination of at least two thereof.
3. The method of claim 1, wherein the solvent in step (1) comprises any one of ethanol, water, acetone, N-dimethylformamide, or isopropanol, or a combination of at least two thereof.
4. The method of claim 1, wherein the transition metal salt in step (1) comprises any one of iron, cobalt, nickel or copper salts or a combination of at least two thereof.
5. The method of claim 4, wherein the iron salt comprises ferric chloride and/or ferric nitrate.
6. The method of claim 4, wherein the cobalt salt comprises any one of cobalt acetate, cobalt chloride, or cobalt nitrate, or a combination of at least two thereof.
7. The method of claim 4, wherein the nickel salt comprises any one of nickel chloride, nickel nitrate, or nickel acetate, or a combination of at least two thereof.
8. The method of claim 4, wherein the copper salt comprises copper chloride and/or copper nitrate.
9. The method of claim 1, wherein the method of mixing the polymer powder, the solvent, and the transition metal salt of step (1) comprises the steps of:
(a) dissolving polymer powder in a solvent to obtain a polymer solution;
(b) adding a transition metal salt into the polymer solution in the step (a), and dissolving to obtain a mixed solution.
10. The method of claim 9, wherein the dissolving process of step (a) is accompanied by heating.
11. The method of claim 9, wherein the polymer solution is cooled to room temperature prior to adding the transition metal salt in step (b).
12. The method of claim 1, wherein the spinning of step (1) is electrospinning.
13. The method as claimed in claim 1, wherein the carbonization temperature in step (1) is 450-700 ℃.
14. The method of claim 1, wherein the carbonization is carried out for a holding time of 0.5 to 3 hours.
15. The method according to claim 1, wherein the temperature increase rate of the carbonization is 0.5 to 2 ℃/min.
16. The method of claim 1, wherein the carbonizing is performed under an inert atmosphere.
17. The method of claim 16, wherein the inert atmosphere comprises any one of nitrogen, argon, or helium, or a combination of at least two thereof.
18. The method of claim 1, wherein the mass ratio of the composite material to the reducing agent in step (2) is (0.232-0.851): (0.148-0.767).
19. The method of claim 1, wherein the reducing agent of step (2) comprises any one of sodium borohydride, ascorbic acid or hydrazine hydrate or a combination of at least two thereof.
20. The method of claim 1, wherein the noble metal precursor solution of step (2) comprises a metallic platinum precursor.
21. The method of claim 20, wherein the metallic platinum precursor comprises any one of chloroplatinic acid, potassium tetrachloroplatinate, potassium hexachloroplatinate, platinum nitrate, or a tetraammineplatinum solution, or a combination of at least two thereof.
22. The method of claim 1, wherein step (2) further comprises washing after the solid-liquid separation.
23. The method of claim 22, wherein the wash liquid of the wash is water.
24. The method of claim 22, wherein the eluate to the end of the wash is neutral.
25. The method of claim 22, wherein after the washing, and prior to the fusing, further comprising oven drying.
26. The method of claim 1, wherein said fusing of step (2) further comprises cooling.
27. The method of claim 26, wherein the end of the cooling down to room temperature.
28. The method of claim 27, wherein the cooling is performed under an inert atmosphere.
29. The method of claim 1, wherein the step (2) of mixing the composite material obtained in step (1), the stabilizer, the noble metal precursor solution and the reducing agent comprises the steps of:
(a') dispersing the composite material obtained in the step (1) in a stabilizer to obtain a dispersion liquid of the composite material;
(b ') adding the noble metal precursor solution to the dispersion liquid in the step (a'), and mixing;
(c ') adding a reducing agent to the product of step (b') to effect a reaction.
30. The method of claim 29, wherein the mixing in step (b') is for a time of 2 to 15 hours.
31. The method of claim 30, wherein the mixing in step (b') is for a period of 5 to 10 hours.
32. The process of claim 29, wherein the reaction in step (c') is carried out for a period of time of from 0.5 to 10 hours.
33. The process of claim 32, wherein the reaction in step (c') is carried out for a period of time of from 2 to 4 hours.
34. The process of claim 29 wherein the reaction in step (c') is carried out with agitation.
35. The method of claim 1, wherein the method comprises the steps of:
(1') dissolving the polymer powder in a solvent to obtain a polymer solution;
(2 ') adding a transition metal salt to the polymer solution in the step (1') and dissolving to obtain a mixed solution of polymer powder and the transition metal salt;
(3 ') carrying out electrostatic spinning on the mixed solution in the step (2'), and then carbonizing the product of electrostatic spinning at the temperature of 450-700 ℃ for 0.5-3h to obtain the composite material of the transition metal particles and the carbon fibers;
(4 ') dispersing the composite material obtained in the step (3') in a stabilizer to obtain a dispersion liquid of the composite material;
(5 ') adding a noble metal precursor solution into the dispersion liquid of the composite material obtained in the step (4'), stirring, adding a reducing agent, reacting, carrying out solid-liquid separation, washing, drying, fusing for 0.5-3h at the temperature of 800-1000 ℃ under an inert atmosphere, and then cooling to room temperature under the inert atmosphere to obtain the alloy catalyst.
36. A multi-dimensional channel structured alloy catalyst prepared by the method of any one of claims 1 to 35.
37. Use of the alloy catalyst with a multi-dimensional cell channel structure according to claim 36, wherein the alloy catalyst is used in a proton exchange membrane fuel cell.
38. Use of the multi-dimensional channel structured alloy catalyst according to claim 37, wherein the alloy catalyst is used in a cathode of a proton exchange membrane fuel cell.
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