CN111129508B - Transition metal doped platinum-carbon catalyst and preparation method and application thereof - Google Patents

Transition metal doped platinum-carbon catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN111129508B
CN111129508B CN201911304498.XA CN201911304498A CN111129508B CN 111129508 B CN111129508 B CN 111129508B CN 201911304498 A CN201911304498 A CN 201911304498A CN 111129508 B CN111129508 B CN 111129508B
Authority
CN
China
Prior art keywords
platinum
transition metal
carbon
catalyst
doped
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911304498.XA
Other languages
Chinese (zh)
Other versions
CN111129508A (en
Inventor
于力娜
朱云
唐柳
朱雅男
张克金
杨帅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FAW Jiefang Automotive Co Ltd
Original Assignee
FAW Jiefang Automotive Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by FAW Jiefang Automotive Co Ltd filed Critical FAW Jiefang Automotive Co Ltd
Priority to CN201911304498.XA priority Critical patent/CN111129508B/en
Publication of CN111129508A publication Critical patent/CN111129508A/en
Application granted granted Critical
Publication of CN111129508B publication Critical patent/CN111129508B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • 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

Abstract

The invention relates to a transition metal doped platinum-carbon catalyst, a preparation method and application thereof. The method comprises the following steps: (1) mixing a carbon material, a precursor solution of platinum and a transition metal salt to obtain a mixed solution; (2) mixing the obtained mixed solution with a reducing agent, separating and drying to obtain a precursor material; (3) carrying out heat treatment on the obtained precursor material to obtain transition metal doped platinum-based nanoparticles; (4) mixing the obtained transition metal doped platinum-based nanoparticles with a perfluorosulfonic acid solution, separating and drying to obtain the catalyst; wherein, the steps (1), (2), (3) and (4) are all carried out under the protection of inert atmosphere. The transition metal in the catalyst improves the structural stability, catalytic activity and durability, and a continuous proton conducting surface network is formed by coating the perfluorosulfonic acid membrane, so that the proton transfer speed is improved, the current density is improved, and the service life of the membrane electrode is prolonged.

Description

Transition metal doped platinum-carbon catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of new energy fuel cells, in particular to a transition metal doped platinum-carbon catalyst and a preparation method and application thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have been the subject of intensive research in the field of new energy, are one of the most promising fuel cell automobile commercialization schemes, and are now the technology of competitive development in many developed countries. The principle of the method is that chemical energy is directly converted into electric energy by utilizing the reaction of hydrogen and oxygen, and the method has the advantages of high energy conversion efficiency, quick low-temperature start, no pollution, good durability, high specific power and the like, so the method is considered to be one of the best green energy sources in the 20 th century.
The platinum-based catalyst is an ideal catalyst system required by a hydrogen fuel cell system at present, has better catalytic activity at 60-90 ℃, but due to the characteristics of less storage amount of Pt metal, high price, easy poisoning and the like, in order to make the proton exchange membrane fuel cell commercially feasible in large-scale market application, the development of a platinum catalyst with high activity, high durability and lower platinum content is needed as a research focus.
CN106972181A discloses a Pt-based nanowire cathode catalyst for a vehicle-mounted fuel cell and a preparation method thereof, the Pt-based nanowire cathode catalyst comprises a carbon carrier and an active component loaded on the carbon carrier, wherein the active component is a Pt nanowire or a PtM alloy nanowire, wherein M is a transition metal selected from one of elements in group B and group IIIV of the periodic table of elements; the cathode catalyst is prepared by reducing a liquid phase such as a template-free method or a template method and the like to prepare a Pt nanowire or a PtM alloy nanowire, and then loading a main active component on a carbon carrier with high conductivity. Compared with the prior art, the Pt-based nanowire cathode catalyst provided by the invention has the advantages of simple preparation method, uniform nanowire structure, high activity, good durability and the like. However, the catalyst provided by the invention has a low proton transfer speed in the application process, and further influences the current density and the service life of the fuel cell.
The optimization of the utilization rate of the catalyst provides a way for reducing the platinum loading capacity, and CN103579639A discloses a cathode catalyst for a fuel cell and a preparation method thereof, wherein the catalyst is a hollow shell type carbon-loaded Pt-based nano catalyst, and Pt or an alloy consisting of Pt and transition metal is used as the activityComponent of the general formula Pt or PtMxWherein, M is Ag, Au, Ru, Rh, Pd, Os or Ir, x is more than or equal to 0.05 and less than or equal to 0.95, the particle size of the catalyst is 10-100nm, and the thickness of the shell wall is 1-20 nm. The prepared catalyst has high utilization rate of the Pt-based component, and compared with the traditional carbon-supported Pt-based nanoparticle catalyst, the catalyst provided by the invention has the advantages that on the premise of ensuring the effective Pt-based active component on the surface, the Pt-based component which does not participate in the reaction in the traditional nanoparticle is omitted, and the utilization rate of the Pt-based component is improved; meanwhile, the empty shell structure induces the Pt-based component to generate lattice distortion, an electronic regulation effect is generated, and the Pt-based component participating in catalytic reaction has high catalytic activity, but the catalyst provided by the invention has the advantages of unstable structure, poor durability, complex preparation method and difficult industrialization.
Platinum loading has heretofore received relatively little attention as compared to producing bimetallic catalysts with higher catalytic activity. The utilization degree of the catalyst is closely related to the structure-related characteristics of the catalyst layer, the catalyst layer is usually composed of a small amount of polymer Nafion and Pt/C or Pt-alloy/C particles, and proton conductive chains are formed on the surfaces of the carbon carriers loaded with the platinum nano particles, wherein the polymer Nafion plays the role of a binder on one hand to firmly adhere the catalyst to a proton membrane, and provides a conductive transportation path for H protons on the anode side on the other hand. The catalyst layer works on the principle that hydrogen separates out protons and electrons at the anode, the protons pass through the proton exchange membrane to the cathode, the electrons reach the cathode through an external circuit, and when the electrons reach the cathode, the electrons, the protons and the introduced O2Under the action of cathode catalyst, combining to generate water, and specifically performing electrode reaction as follows:
anode H2→2H+2e- (1)
Cathode 1/2O2+2H+2e-→H2O (2)
The total reaction formula is H2+1/2O2→H2O (3)
However, the distribution of polymer Nafion in the catalytic layer on the surface of Pt/C or Pt-alloy/C is discontinuous, so that the transfer rate of H proton is slow, oxygen on the cathode side, electrons in an external circuit are caused, and the redox reaction of the reaction (2) is slow in less proton H, so that the current density and the durability of the membrane electrode are poor.
Based on the analysis of the prior art, how to develop a catalyst with lower platinum loading, stable structure, higher catalytic activity and better durability, and the preparation method is simple to operate, easy to control and batch, which is a problem to be solved at present.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a transition metal doped platinum-carbon catalyst and a preparation method and application thereof. The catalyst has a stable structure and excellent catalytic activity and durability; the perfluorosulfonic acid membrane is coated on the surfaces of the carbon carrier and the doped platinum-based nanoparticles, so that the proton transfer speed is obviously improved, the current density is improved, and the service life of the membrane electrode is prolonged. In addition, the preparation method has the characteristics of simple operation, easy control, easy batch production and high practical application value.
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 a transition metal doped platinum-carbon catalyst, comprising the steps of:
(1) mixing a carbon material, a precursor solution of platinum and a transition metal salt to obtain a mixed solution;
(2) mixing the mixed solution obtained in the step (1) with a reducing agent, separating and drying to obtain a precursor material;
(3) carrying out heat treatment on the precursor material obtained in the step (2) to obtain transition metal doped platinum-based nanoparticles;
(4) mixing the transition metal doped platinum-based nanoparticles obtained in the step (3) with a perfluorosulfonic acid solution, separating and drying to obtain the transition metal doped platinum-carbon catalyst;
wherein, the steps (1), (2), (3) and (4) are all carried out under the protection of inert atmosphere.
The preparation method provided by the invention is characterized in that a carbon material is used as a substrate, a large amount of metal ions are deposited on the surface of the carbon material in an ionic interaction-electrostatic adsorption mode, then the ionic adsorption and a rapid reduction process are combined under the action of a reducing agent, and transition metal doped platinum-based nanoparticles are efficiently and rapidly formed on the surface of the carbon material. The transition metal atoms are doped into the crystal lattice of the platinum, so that the distance between the platinum atoms in the formed nano-crystal is changed, the generation of active sites is facilitated, the catalytic activity of the material is improved, and meanwhile, the transition metal is easily attached to the position, which is easy to be eroded, of the edge or the top of the nano-crystal lattice after being introduced, so that the effects of stabilizing the material and resisting corrosion are achieved, and the catalytic performance and the durability are improved. Then, the proton conducting polymer perfluorosulfonic acid is covered on the surface of the metal doped platinum-based nano particle to form a continuous proton conducting surface network, so that the proton transfer speed is obviously improved, and the current density and the service life of the membrane electrode are greatly improved. The preparation method has the characteristics of simple operation, easy control, easy batch production and high practical application value.
Preferably, the carbon material is dispersed in step (1) before mixing.
Preferably, the dispersing mode is that the carbon material is mixed with a solvent, and the mixture is dispersed uniformly by ultrasonic.
In the present invention, the solvent for the dispersed carbon material is not particularly limited, and may be a solvent such as deionized water, ultrapure water, or ethanol, and any of those commonly used by those skilled in the art may be used in the present invention.
Preferably, after dispersion, inert gas is introduced until saturation, and oxygen is removed therefrom.
Preferably, the carbon material in step (1) comprises any one or a combination of at least two of ketjen black, Vulcan XC-72R, carbon nanotubes, carbon nanospheres, biomass carbon material, carbon fibers, mesoporous carbon or graphene material, preferably any one or a combination of at least two of ketjen black, Vulcan XC-72, carbon nanotubes or carbon nanospheres, wherein a typical but non-limiting combination: ketjen black and carbon nanospheres, Vulcan XC-72 and Vulcan XC-72R, carbon nanotubes and carbon fibers, biomass carbon materials and mesoporous carbon, carbon nanotubes and graphene materials, and the like.
Preferably, the carbon nanotubes comprise any one or a combination of at least two of single-walled carbon nanotubes, multi-walled carbon nanotubes, doped single-walled carbon nanotubes, or doped multi-walled carbon nanotubes, wherein a typical but non-limiting combination: single-walled carbon nanotubes and doped single-walled carbon nanotubes, multi-walled carbon nanotubes and doped multi-walled carbon nanotubes, single-walled carbon nanotubes and multi-walled carbon nanotubes, and the like.
Preferably, the graphene material comprises any one of graphene, graphene oxide, reduced graphene oxide, graphene foam or doped graphene or a combination of at least two thereof, wherein a typical but non-limiting combination: graphene and graphene oxide, graphene and graphene foam, reduced graphene oxide, doped graphene, and the like.
Preferably, the precursor of platinum in step (1) comprises any one of chloroplatinic acid, potassium tetrachloroplatinate, potassium hexachloroplatinate or platinum nitrate or a combination of at least two thereof, wherein a typical but non-limiting combination is: chloroplatinic acid and platinum nitrate, potassium tetrachloroplatinate and potassium hexachloroplatinate, and the like.
Preferably, the transition metal salt in step (1) comprises any one or a combination of at least two of chloride, nitrate, acetate, thiomolybdate or tungstate of iron, cobalt, nickel, copper, molybdenum or tungsten, preferably any one or a combination of at least two of iron chloride, iron nitrate, cobalt acetate, cobalt nitrate, cobalt chloride, nickel nitrate, nickel chloride, nickel acetate, copper nitrate, copper chloride, ammonium thiomolybdate, ammonium tungstate or sodium tungstate, wherein the typical but non-limiting combination is: ferric chloride and cobalt chloride, cobalt acetate and nickel chloride, nickel acetate and copper chloride, ferric nitrate and nickel acetate, nickel nitrate and ammonium thiomolybdate, sodium tungstate and nickel nitrate, and the like.
Preferably, the mass ratio of carbon, platinum and transition metal in the carbon material, platinum precursor solution and transition metal salt in step (1) is 1 (0.5-1.5): (0.01-0.3), and may be, for example, 1:0.5:0.01, 1:0.5:0.05, 1:0.5:0.1, 1:0.5:0.3, 1:0.8:0.04, 1:0.8:0.2, 1:1:0.01, 1:1:0.05, 1:1:0.1, 1:1:0.3, 1:1.2:0.04, 1:1.2:0.2, 1:1.5:0.01, 1:1.5:0.05, 1:1.5:0.1 or 1:1.5:0.3, etc., preferably 1: 0.8-1.2: 0.04.
Preferably, the reducing agent in step (2) is a strong reducing agent.
Preferably, the reducing agent in step (2) comprises any one of sodium borohydride, hydroxylamine hydrochloride or potassium borohydride or a combination of at least two thereof, wherein the typical but non-limiting combination is: sodium and potassium borohydride, hydroxylamine hydrochloride, potassium borohydride and the like.
Preferably, the drying in step (2) is by any one or a combination of at least two of forced air drying, vacuum drying or freeze drying, wherein a typical but non-limiting combination is: freeze drying and vacuum drying, freeze drying and forced air drying, etc.; the freeze-drying can maintain the stability of the material, so that the material is not decomposed and deteriorated.
Preferably, the mass ratio of platinum to the reducing agent in the mixed solution in the step (2) is 1 (1.5-6), and may be, for example, 1:1.5, 1:1.8, 1:2, 1:3, 1:4, 1:5, 1:6, or the like, preferably 1 (2-5).
Preferably, the temperature of the heat treatment in step (3) is 300-.
Preferably, the time of the heat treatment in the step (3) is 0.5 to 2h, for example, 0.5h, 1h, 1.5h or 2h, etc.
Preferably, the transition metal doped platinum-based nanoparticles of step (4) are dispersed before mixing.
Preferably, the dispersant comprises any one or a combination of at least two of ethanol, isopropanol, n-octanol, or acetone, with typical but not limiting combinations: ethanol and isopropanol, ethanol and n-octanol, isopropanol and acetone.
Preferably, the mass ratio of the dispersant to the transition metal doped platinum-based nanoparticles is (100-.
Preferably, the mass fraction of the perfluorosulfonic acid solution in step (4) is 5%, and the perfluorosulfonic acid solution is purchased from dupont, usa and has the model number D520.
The perfluorinated sulfonic acid solution covers the surface of the metal-doped platinum-based nanoparticle through the preparation method to form a face-to-face continuous conduction H proton network, so that the proton transfer speed is obviously improved, the current density and the service life of a membrane electrode are greatly improved, the perfluorinated sulfonic acid solution plays the same role as the perfluorinated sulfonic acid solution if the concentration of the perfluorinated sulfonic acid solution is only changed, and the perfluorinated sulfonic acid solution also belongs to the protection scope of the invention.
Preferably, the mass ratio of the perfluorosulfonic acid to the transition metal-doped platinum-based nanoparticles in step (4) is 0.001-0.005:1, and may be, for example, 0.001:1, 0.002:1, 0.003:1, 0.004:1, or 0.005:1, etc.
Preferably, the drying in step (4) is performed by any one or a combination of at least two of oven drying, vacuum drying or freeze drying in an inert atmosphere, wherein the typical but non-limiting combination is: freeze drying and vacuum drying, freeze drying and oven drying in inert atmosphere, preferably vacuum drying.
Preferably, the manner of separation in step (2) and step (4) independently comprises any one or a combination of at least two of suction filtration, centrifugation or filtration, wherein a typical but non-limiting combination: centrifuging and filtering, centrifuging and filtering. For example, suction filtration may be used in step (2), and suction filtration, centrifugation, or filtration may be used in step (4).
Preferably, the mixing manner in step (1), step (2) and step (4) is independently stirring and/or ultrasound, for example, step (1) adopts stirring, step (2) can adopt stirring and ultrasound, and step (4) can adopt stirring and ultrasound.
Preferably, the gas of the inert atmosphere in steps (1), (2), (3) and (4) independently comprises any one of nitrogen, argon or helium or a combination of at least two thereof, wherein a typical but non-limiting combination is: nitrogen and argon, argon and helium, and the like; the independent means that the inert atmosphere gases used in the steps (1) to (4) are independent from each other and do not affect each other, for example, nitrogen is used in the step (1), nitrogen, argon, helium and the like can be used in the step (2), and similarly, nitrogen, argon, helium and the like can be used in the step (3), and nitrogen, argon and helium can be used in the step (4).
Preferably, the preparation method comprises the following steps:
(1) adding water into a carbon material, performing ultrasonic treatment, introducing inert gas to saturation to obtain a carbon material dispersion liquid, adding a platinum precursor solution and a transition metal salt into the carbon material dispersion liquid under the protection of inert atmosphere, stirring, and controlling the mass ratio of carbon, platinum and transition metal in the carbon material, the platinum precursor solution and the transition metal salt to be 1 (0.5-1.5) to (0.01-0.3) to obtain a mixed solution;
(2) rapidly adding a reducing agent into the mixed solution obtained in the step (1) under the protection of inert atmosphere, stirring vigorously, controlling the mass ratio of platinum to the reducing agent in the mixed solution to be 1 (1.5-6), carrying out suction filtration on a reaction product, washing the reaction product to be neutral by using deionized water, and transferring the reaction product to a refrigerator for drying to obtain a precursor material;
(3) under the protection of inert atmosphere, treating the precursor material obtained in the step (2) at the temperature of 300-700 ℃ for 0.5-2h, and then cooling to room temperature under the protection of inert atmosphere to obtain transition metal doped platinum-based nanoparticles;
(4) adding the transition metal doped platinum-based nanoparticles obtained in the step (3) into a dispersing agent under the protection of inert atmosphere, stirring, controlling the mass ratio of the dispersing agent to the transition metal doped platinum-based nanoparticles to be (100- & ltSUB & gt 200) & gt 1, adding a perfluorinated sulfonic acid solution with the mass fraction of 5%, controlling the mass ratio of the perfluorinated sulfonic acid to the transition metal doped platinum-based nanoparticles to be 0.001-0.005:1, performing ultrasonic crushing, performing microwave radiation for 3-20min, performing solid-liquid separation, and then placing in a vacuum oven for drying to obtain the transition metal doped platinum-carbon catalyst.
In the present invention, the time of the ultrasonic treatment is not particularly limited, and it is sufficient to mix the dispersion uniformly.
In a second aspect, the present invention provides a transition metal doped platinum-carbon catalyst prepared by the preparation method of the first aspect, wherein the catalyst comprises a carbon carrier, doped platinum-based nanoparticles loaded on the carbon carrier, and a perfluorosulfonic acid film, the doped platinum-based nanoparticles are formed by doping a transition metal into a platinum lattice, and the perfluorosulfonic acid film is coated on the surfaces of the carbon carrier and the doped platinum-based nanoparticles.
According to the transition metal doped platinum-carbon catalyst provided by the invention, atoms of the transition metal exist in the crystal lattice of platinum and are attached to the position, which is easy to erode, of the edge or the top of the nano crystal lattice, and the atoms of the transition metal entering the crystal lattice change the distance between platinum atoms in the nano crystal, so that the generation of active sites is facilitated, and the catalytic activity of the catalyst is improved; the transition metal atoms at the position where the edges or the vertexes of the nano crystal lattices are easy to erode improve the structural stability and the corrosion resistance of the catalyst, so that the catalytic activity and the durability of the catalyst are improved; in addition, the proton conducting polymer perfluorosulfonic acid membrane covers the surface of the transition metal doped platinum-based nano particle to form a face-to-face continuous conducting H proton network instead of intermittent H proton transmission, so that the proton transmission speed can be obviously improved, and the current density and the service life of the membrane electrode are greatly prolonged.
Preferably, the carbon support comprises any one of or a combination of at least two of ketjen black, Vulcan XC-72R, carbon nanotubes, carbon nanospheres, biomass carbon material, carbon fibers, mesoporous carbon, or graphene material.
Preferably, the transition metal comprises any one of iron, cobalt, nickel, copper, molybdenum or tungsten or a combination of at least two thereof, with typical but non-limiting combinations: iron and cobalt, nickel and iron, iron and tungsten, molybdenum and nickel, nickel and copper, and the like.
Preferably, the mass fraction of platinum is 40-55%, for example, 40%, 45%, 50%, 55%, or the like, based on 100% by mass of the catalyst.
Preferably, the mass fraction of the transition metal is 2 to 10%, for example, 2%, 4%, 6%, 8%, 10%, or the like, based on 100% by mass of the catalyst.
Preferably, the thickness of the perfluorosulfonic acid membrane is 0.01 to 0.2. mu.m, and may be, for example, 0.01. mu.m, 0.02. mu.m, 0.05. mu.m, 0.1. mu.m, 0.15. mu.m, 0.18. mu.m, 0.2. mu.m, or the like.
In a third aspect, the present invention provides a fuel cell comprising a transition metal doped platinum carbon catalyst as described in the second aspect above.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method provided by the invention, a large number of metal ions are deposited on the surface of the carbon material in an ionic interaction-electrostatic adsorption mode, ion adsorption and a very-fast reduction process are combined under the action of a strong reducing agent, transition metal doped platinum-based nanoparticles are efficiently and rapidly formed on the surface of the carbon material, and then a proton conducting polymer perfluorosulfonic acid membrane is coated on the surface of the transition metal doped platinum-based nanoparticles to form a continuous proton conducting surface network;
(2) according to the transition metal doped platinum-carbon catalyst provided by the invention, the structural stability, catalytic activity and durability of the catalyst are improved by introducing transition metal atoms; the proton transfer rate is improved through the continuous coating of the proton conduction polymer perfluorosulfonic acid membrane, so that the current density is improved, and the service life is prolonged;
(3) the fuel cell provided by the invention has the advantages of high energy conversion efficiency, good durability, long service life and the like, and has wide application prospect.
Drawings
FIG. 1 is a LSV test curve of the catalyst obtained in example 1.
FIG. 2 is an I-V test curve of a membrane electrode prepared with the catalyst obtained in example 1.
Fig. 3 is an LSV test curve of the catalyst obtained in comparative example 1.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings by way of specific embodiments, and the specific embodiments of the present invention are described in detail below to achieve the intended technical effects.
Example 1
The embodiment provides a preparation method of a transition metal doped platinum-carbon catalyst, which comprises the following steps:
(1) weighing 0.05g of Ketjen black in a reaction container, adding 20mL of water, placing the mixed solution in an ultrasonic crushing and homogenizing machine for continuous ultrasonic treatment for 10min to obtain a uniform solution, continuously introducing nitrogen into the uniform solution, and carrying out the next reaction after 30 min;
(2) adding 400 mu L of chloroplatinic acid solution containing 0.1g/mL of platinum, 50 mu L of ferric chloride solution containing 0.1g/mL of iron and 50 mu L of cobalt chloride solution containing 0.1g/mL of cobalt into the mixed solution prepared in the step (1), and continuously stirring for 1h under the protection of nitrogen to enable ions to be fully adsorbed to the surface of the Ketjen black;
(3) weighing 0.1g of sodium borohydride, quickly adding the sodium borohydride into the mixed solution obtained in the step (2) under the protection of nitrogen, quickly reducing ions, continuously and violently stirring for 10 hours, then carrying out suction filtration on a product, washing the product to be neutral by deionized water, and transferring the product to a vacuum oven for drying for 5 hours at the temperature of 100 ℃;
(4) transferring the precursor material obtained in the step (3) to a tubular furnace, fusing for 2h at 400 ℃ under the protection of nitrogen, and then taking out after the temperature is reduced to room temperature under the protection of nitrogen to obtain iron-cobalt doped platinum-based nanoparticles;
(5) and (3) adding 10g of ethanol into 0.06g of the iron-cobalt-doped platinum-based nanoparticles obtained in the step (4), stirring for 45min, adding 1.2mg of a perfluorinated sulfonic acid solution with the mass fraction of 5%, performing ultrasonic crushing for 30min under the protection of nitrogen, performing microwave radiation for 20min, performing centrifugal separation until the separation solution is neutral, placing the mixture in a vacuum oven for drying at 70 ℃ for 10h, and then grinding to obtain the iron-cobalt-doped platinum-carbon catalyst.
In the iron-cobalt doped platinum-carbon catalyst prepared in this example, the mass fraction of platinum is 40%, the total mass fraction of cobalt and iron is 10%, and the thickness of the perfluorosulfonic acid film is 0.01 μm.
The iron-cobalt doped platinum-carbon catalyst prepared in this example was subjected to LSV testing, and the test curve is shown in fig. 1. The parameters of the test method are set as follows: the scanning voltage is 0.1-1.25V, the scanning speed is 5mV/s, the rotating speed is 1600 revolutions, and the mass of the iron-cobalt doped platinum-carbon catalyst dripped by the glassy carbon electrode tip is 0.005mg and the area is 0.196cm under the condition of introducing oxygen2. It was calculated that the initial mass activity of 0.9V was 135mA/mg, and after 30000 cycles of CV test, the initial mass activity of 0.9V was 85mA/mg, and it was seen that the mass activity was attenuated by 37% (DOE requirement 40%), thereby illustrating that the iron-cobalt-doped platinum-carbon catalyst prepared in example 1 had excellent catalytic performance and durability.
The iron-cobalt doped platinum-carbon catalyst prepared in this example was used to prepare a single cell, and the preparation method was: weighing 0.12g of the catalyst prepared in the embodiment, adding 0.6mL of water for soaking, adding 50mL of isopropanol and 30mL of ethanol, carrying out ultrasonic treatment for 20min, adding 1000 mu L of 5% perfluorosulfonic acid solution in mass fraction, continuing ultrasonic treatment for 30min, carrying out shearing stirring for 120min under the protection of nitrogen, and crushing cells for 10 min; CCM is prepared by ultrasonic spraying, a proton membrane is Goll enhanced 15 mu m, and the Pt loading capacity of an anode is 0.10mg/cm2Cathode at 0.40mg/cm2The carbon paper is SGL 28BC, 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.
The test cell temperature was 75 ℃, the humidification temperature was 70 ℃, the relative humidity was 60% RH, the stoichiometric ratio hydrogen/air was 1.2/2.5, and the back pressure was 0.1Mpa, and the test curve is shown in fig. 2. As can be seen from FIG. 2, the single cell prepared by the embodiment has good power characteristics, and when the voltage is 0.8V, the current density can reach 600mA/cm2(ii) a When the voltage is 0.6V, the current density can reach 2300mA/cm2The peak power density is as high as 1400mW/cm2。
Example 2
The embodiment provides a preparation method of a transition metal doped platinum-carbon catalyst, which comprises the following steps:
1) weighing 0.048g of Vulcan XC-72 in a reaction container, adding 15mL of water into the reaction container, placing the mixed solution into an ultrasonic homogenizer for uniform dispersion, continuously carrying out ultrasonic treatment for 60min to obtain a uniform solution, continuously introducing argon into the uniform solution, and carrying out the next reaction after 45 min;
(2) adding 500 mu L of potassium tetrachloroplatinate solution containing 0.1g/mL of platinum, 10 mu L of nickel chloride solution containing 0.1g/mL of nickel and 10 mu L of copper chloride solution containing 0.1g/mL of copper into the mixed solution prepared in the step (1), and continuously stirring for 6 hours under the protection of argon gas to enable ions to be fully adsorbed to the surface of Vulcan XC-72;
(3) weighing 0.3g of hydroxylamine hydrochloride, quickly adding the hydroxylamine hydrochloride into the mixed solution obtained in the step (2) of violent stirring under the protection of inert gas to quickly reduce ions, continuously and violently stirring for 2 hours, carrying out suction filtration on a product, washing the product with water for three times, and transferring the product to a vacuum oven for drying for 6 hours at the temperature of 90 ℃;
(4) transferring the product obtained in the step (3) to a tubular furnace, fusing for 0.5h at 600 ℃ under the protection of argon, and then taking out after the temperature is reduced to room temperature under the protection of argon to obtain nickel-copper doped platinum-based nanoparticles;
(5) adding 8g of isopropanol into 0.06g of the nickel-copper doped platinum-based nanoparticles obtained in the step (4), stirring for 30min, adding 6mg of 5% perfluorinated sulfonic acid solution, performing ultrasonic crushing for 25min under the protection of helium, performing microwave radiation for 5min, performing filter pressing washing to neutrality, placing in a vacuum oven, drying for 24h at 65 ℃, and grinding to obtain the nickel-copper doped platinum-carbon catalyst.
In the nickel-copper doped platinum-carbon catalyst prepared in this example, the mass fraction of platinum is 50%, the total mass fraction of nickel and copper is 2%, and the thickness of the perfluorosulfonic acid film is 0.2 μm.
Example 3
The embodiment provides a preparation method of a transition metal doped platinum-carbon catalyst, which comprises the following steps:
(1) weighing 0.049g of carbon nanotube in a reaction container, adding 20mL of water, placing the mixed solution in an ultrasonic homogenizer for uniform dispersion, continuously performing ultrasonic treatment for 30min to obtain a uniform solution, continuously introducing helium gas into the uniform solution, and performing the next reaction after 30 min;
(2) adding 450 mu L of potassium hexachloroplatinate solution containing 0.1g/mL platinum, 30 mu L of cobalt nitrate solution containing 0.1g/mL cobalt and 30 mu L of ammonium thiomolybdate solution containing 0.1g/mL molybdenum into the mixed solution prepared in the step (1), and continuously stirring for 3h under the protection of inert gas to enable ions to be fully adsorbed to the surface of the carbon nano tube;
(3) weighing 0.15g of potassium borohydride, quickly adding the potassium borohydride into the mixed solution obtained in the step (2) under the protection of helium gas to quickly reduce ions, continuously stirring the solution vigorously for 5 hours, filtering the product, washing the product with water for three times, and transferring the product to a vacuum oven to be dried for 8 hours at the temperature of 100 ℃;
(4) transferring the precursor material obtained in the step (3) to a tube furnace, fusing for 1h at 500 ℃ under the protection of helium, and taking out after the temperature is reduced to room temperature under the protection of helium to obtain cobalt-molybdenum doped platinum-based nanoparticles;
(5) and (3) adding 10g of n-octanol into 0.06g of the cobalt-molybdenum doped platinum-based nanoparticles obtained in the step (4), stirring for 30min, adding 4mg of perfluorinated sulfonic acid solution with the mass fraction of 5%, ultrasonically crushing for 30min under the protection of argon, performing microwave radiation for 10min, performing suction filtration and washing to neutrality, placing in a vacuum oven, drying for 8h at 75 ℃, and grinding to obtain the cobalt-molybdenum doped platinum-carbon catalyst.
In the cobalt molybdenum doped platinum-carbon catalyst prepared in this example, the mass fraction of platinum is 45%, the total mass fraction of cobalt and molybdenum is 6%, and the thickness of the perfluorosulfonic acid film is 0.11 μm.
Example 4
The embodiment provides a preparation method of a transition metal doped platinum-carbon catalyst, which comprises the following steps:
(1) weighing 0.049g of carbon nanospheres in a reaction container, adding 20mL of water into the reaction container, placing the mixed solution in an ultrasonic homogenizer for uniform dispersion, continuously performing ultrasonic treatment for 20min to obtain a uniform solution, continuously introducing nitrogen into the uniform solution, and performing the next reaction after 30 min;
(2) adding 450 mu L of platinum nitrate solution containing platinum 0.1g/mL, 30 mu L of ferric nitrate solution containing iron 0.1g/mL and 30 mu L of ammonium tungstate solution containing tungsten 0.1g/mL into the mixed solution prepared in the step (1), and continuously stirring for 5 hours under the protection of inert gas to enable ions to be fully adsorbed to the surfaces of the carbon nanospheres;
(3) weighing 0.2g of sodium borohydride, quickly adding the sodium borohydride into the mixed solution obtained in the step (2) of violent stirring under the protection of nitrogen to quickly reduce ions, continuously and violently stirring for 5 hours, filtering the product, washing the product with water for three times, and transferring the product to a vacuum oven to be dried for 8 hours at 100 ℃;
(4) transferring the product obtained in the step (3) to a tubular furnace, fusing for 1h at 450 ℃ under the protection of nitrogen, and taking out after the temperature is reduced to room temperature under the protection of nitrogen to obtain iron-tungsten doped platinum-based nanoparticles;
5) and (3) adding 10g of isopropanol into 0.06g of the iron-tungsten doped platinum-based nanoparticles obtained in the step (4), stirring for 30min, adding 5mg of a perfluorinated sulfonic acid solution with the mass fraction of 5%, ultrasonically crushing for 30min under the protection of argon, performing microwave radiation for 10min, performing suction filtration and washing to neutrality, placing in a vacuum oven, drying for 8h at 75 ℃, and grinding to obtain the iron-tungsten doped platinum-carbon catalyst.
In the iron-tungsten doped platinum-carbon catalyst prepared in this example, the mass fraction of platinum is 45%, the total mass fraction of iron and tungsten is 6%, and the thickness of the perfluorosulfonic acid film is 0.17 μm.
Example 5
The embodiment provides a preparation method of a transition metal doped platinum-carbon catalyst, which comprises the following steps:
(1) weighing 0.049g of carbon nanospheres in a reaction container, adding 25mL of water into the reaction container, placing the mixed solution in an ultrasonic homogenizer for uniform dispersion, continuously performing ultrasonic treatment for 20min to obtain a uniform solution, continuously introducing nitrogen into the uniform solution, and performing the next reaction after 30 min;
(2) adding 500 mu L of platinum nitrate solution containing 0.1g/mL of platinum, 30 mu L of ferric chloride solution containing 0.1g/mL of iron and 30 mu L of sodium tungstate solution containing 0.1g/mL of tungsten into the mixed solution prepared in the step (1), and continuously stirring for 5 hours under the protection of inert gas to enable ions to be fully adsorbed to the surfaces of the carbon nanospheres;
(3) weighing 0.2g of sodium borohydride, quickly adding the sodium borohydride into the mixed solution obtained in the step (2) of violent stirring under the protection of argon gas to quickly reduce ions, continuously and violently stirring for 5 hours, filtering the product, washing the product with water for three times, and transferring the product to a vacuum oven to be dried for 8 hours at 100 ℃;
(4) transferring the precursor material obtained in the step (3) to a tubular furnace, fusing for 1h at 450 ℃ under the protection of nitrogen, and then taking out after the temperature is reduced to room temperature under the protection of nitrogen to obtain iron-tungsten doped platinum-based nanoparticles;
(5) adding 6g of ethanol and 4g of isopropanol into 0.06g of the iron-tungsten doped platinum-based nanoparticles obtained in the step (4), stirring for 30min, adding 4mg of a perfluorinated sulfonic acid solution with the mass fraction of 5%, ultrasonically crushing for 30min under the protection of argon, performing microwave radiation for 10min, performing centrifugal separation until the filtrate is neutral, placing the filtrate in a vacuum oven, drying for 8h at 75 ℃, and grinding to obtain the iron-tungsten doped platinum-carbon catalyst.
In the iron-tungsten doped platinum-carbon catalyst prepared in this example, the mass fraction of platinum is 45%, the total mass fraction of iron and tungsten is 6%, and the thickness of the perfluorosulfonic acid film is 0.12 μm.
Example 6
The embodiment provides a preparation method of a transition metal doped platinum-carbon catalyst, which comprises the following steps:
(1) weighing 0.048g of Vulcan XC-72 in a reaction container, adding 12mL of water into the reaction container, placing the mixed solution into an ultrasonic homogenizer for uniform dispersion, continuously carrying out ultrasonic treatment for 45min to obtain a uniform solution, continuously introducing argon into the uniform solution, and carrying out the next reaction after 45 min;
(2) adding 500 mu L of potassium tetrachloroplatinate solution containing 0.1g/mL of platinum, 15 mu L of nickel chloride solution containing 0.1g/mL of nickel and 10 mu L of copper nitrate solution containing 0.1g/mL of copper into the mixed solution prepared in the step (1), and continuously stirring for 6 hours under the protection of argon gas to enable ions to be fully adsorbed to the surface of Vulcan XC-72;
(3) weighing 0.25g of hydroxylamine hydrochloride, quickly adding the hydroxylamine hydrochloride into the mixed solution obtained in the step (2) of violent stirring under the protection of inert gas to quickly reduce ions, continuously and violently stirring for 2 hours, carrying out suction filtration on a product, washing the product with water for three times, and transferring the product to a vacuum oven for drying for 6 hours at the temperature of 90 ℃;
(4) transferring the precursor material obtained in the step (3) to a tube furnace, fusing for 1h at 500 ℃ under the protection of argon, and then taking out after the temperature is reduced to room temperature under the protection of argon to obtain nickel-copper doped platinum-based nanoparticles;
(5) adding 6g of ethanol into 0.06g of the nickel-copper doped platinum-based nanoparticles obtained in the step (4), stirring for 30min, adding 3mg of a perfluorinated sulfonic acid solution with the mass fraction of 5%, ultrasonically crushing for 30min under the protection of argon, performing microwave radiation for 10min, performing suction filtration and washing to neutrality, placing in a vacuum oven, drying for 12h at 65 ℃, and then grinding to obtain the nickel-copper doped platinum-carbon catalyst.
In the nickel-copper doped platinum-carbon catalyst prepared in this example, the mass fraction of platinum is 50%, the total mass fraction of nickel and copper is 2%, and the thickness of the perfluorosulfonic acid film is 0.093 μm.
Example 7
The embodiment provides a preparation method of a transition metal doped platinum-carbon catalyst, which comprises the following steps:
(1) weighing 0.048g of Vulcan XC-72 in a reaction container, adding 20mL of water into the reaction container, placing the mixed solution into an ultrasonic homogenizer for uniform dispersion, continuously carrying out ultrasonic treatment for 30min to obtain a uniform solution, continuously introducing argon into the uniform solution, and carrying out the next reaction after 45 min;
(2) adding 520 mu L of potassium tetrachloroplatinate solution containing 0.1g/mL of platinum, 30 mu L of nickel acetate solution containing 0.1g/mL of nickel and 25 mu L of copper chloride solution containing 0.1g/mL of copper into the mixed solution prepared in the step (1), and continuously stirring for 6 hours under the protection of argon gas to enable ions to be fully adsorbed to the surface of Vulcan XC-72;
(3) weighing 0.25g of hydroxylamine hydrochloride, quickly adding the hydroxylamine hydrochloride into the mixed solution obtained in the step (2) of violent stirring under the protection of inert gas to quickly reduce ions, continuously and violently stirring for 5 hours, carrying out suction filtration on a product, washing the product with water for three times, and transferring the product to a vacuum oven for drying for 6 hours at the temperature of 90 ℃;
(4) transferring the precursor material obtained in the step (3) to a tube furnace, fusing for 0.5h at 600 ℃ under the protection of argon, and then taking out after the temperature is reduced to room temperature under the protection of argon to obtain nickel-copper doped platinum-based nanoparticles;
(5) adding 5g of n-octanol and 6g of isopropanol into 0.06g of nickel-copper doped platinum-based nanoparticles obtained in the step (4), stirring for 30min, adding 4mg of perfluorinated sulfonic acid solution with the mass fraction of 5%, ultrasonically crushing for 30min under the protection of argon, performing microwave radiation for 10min, performing suction filtration washing to neutrality, placing in a vacuum oven, drying for 8h at 75 ℃, and grinding to obtain the nickel-copper doped platinum-carbon catalyst.
In the nickel-copper doped platinum-carbon catalyst prepared in this example, the mass fraction of platinum is 50%, the total mass fraction of nickel and copper is 2%, and the thickness of the perfluorosulfonic acid film is 0.12 μm.
Example 8
The embodiment provides a preparation method of a transition metal doped platinum-carbon catalyst, which comprises the following steps:
(1) weighing 0.05g of Ketjen black in a reaction container, adding 20mL of water, uniformly dispersing the mixed solution in an ultrasonic crushing and homogenizing machine, continuously performing ultrasonic treatment for 10min to obtain a uniform solution, continuously introducing nitrogen into the uniform solution, and performing the next reaction after 30 min;
(2) 550 mu L of chloroplatinic acid solution containing 0.1g/mL of platinum, 40 mu L of ferric chloride solution containing 0.1g/mL of iron and 60 mu L of cobalt acetate solution containing 0.1g/mL of cobalt are added into the mixed solution prepared in the step (1), and stirring is continued for 1h under the protection of nitrogen so that ions are fully adsorbed to the surface of the Ketjen black;
(3) weighing 0.1g of potassium borohydride, quickly adding the potassium borohydride into the mixed solution obtained in the step (2) of violent stirring under the protection of argon gas to quickly reduce ions, continuously and violently stirring for 8 hours, then carrying out suction filtration on a product, washing the product to be neutral by using deionized water, and transferring the product to a vacuum oven to be dried for 6 hours at the temperature of 100 ℃;
(4) transferring the precursor material obtained in the step (3) to a tubular furnace, fusing for 0.5h at 500 ℃ under the protection of nitrogen, and taking out after the temperature is reduced to room temperature under the protection of nitrogen to obtain iron-cobalt doped platinum-based nanoparticles;
(5) and (3) adding 10g of isopropanol into 0.06g of the iron-cobalt doped platinum-based nanoparticles obtained in the step (4), stirring for 30min, adding 4mg of a perfluorinated sulfonic acid solution with the mass fraction of 5%, ultrasonically crushing for 30min under the protection of argon, performing microwave radiation for 10min, performing suction filtration and washing to neutrality, placing in a vacuum oven, drying for 8h at 75 ℃, and grinding to obtain the iron-cobalt doped platinum-carbon catalyst.
In the iron-cobalt doped platinum-carbon catalyst prepared in this example, the mass fraction of platinum is 40%, the total mass fraction of iron and cobalt is 10%, and the thickness of the perfluorosulfonic acid film is 0.1 μm.
Example 9
The embodiment provides a preparation method of a transition metal doped platinum-carbon catalyst, which comprises the following steps:
(1) weighing 0.05g of Ketjen black in a reaction container, adding 20mL of water, uniformly dispersing the mixed solution in an ultrasonic crushing and homogenizing machine, continuously performing ultrasonic treatment for 10min to obtain a uniform solution, continuously introducing nitrogen into the uniform solution, and performing the next reaction after 30 min;
(2) adding 450 mu L of chloroplatinic acid solution containing 0.1g/mL of platinum, 20 mu L of ferric chloride solution containing 0.1g/mL of iron and 60 mu L of cobalt nitrate solution containing 0.1g/mL of cobalt into the mixed solution prepared in the step (1), and continuously stirring for 1h under the protection of nitrogen to enable ions to be fully adsorbed to the surface of the Ketjen black;
(3) weighing 0.1g of sodium borohydride, quickly adding the sodium borohydride into the mixed solution obtained in the step (2) of violent stirring under the protection of helium gas to quickly reduce ions, continuously and violently stirring for 6 hours, then carrying out suction filtration on a product, washing the product to be neutral by using deionized water, and transferring the product to a vacuum oven to be dried for 7 hours at 90 ℃;
(4) transferring the precursor material obtained in the step (3) to a tubular furnace, fusing for 1h at 500 ℃ under the protection of nitrogen, and taking out after the temperature is reduced to room temperature under the protection of nitrogen to obtain iron-cobalt doped platinum-based nanoparticles;
(5) adding 12g of ethanol into 0.06g of the iron-cobalt doped platinum-based nanoparticles obtained in the step (4), stirring for 30min, adding 6mg of a perfluorinated sulfonic acid solution with the mass fraction of 5%, performing ultrasonic crushing for 30min under the protection of nitrogen, performing microwave radiation for 10min, performing suction filtration and washing to neutrality, placing in a vacuum oven, drying for 10h at 75 ℃, and grinding to obtain the iron-cobalt doped platinum-carbon catalyst.
In the iron-cobalt doped platinum-carbon catalyst prepared in this example, the mass fraction of platinum is 40%, the total mass fraction of iron and cobalt is 10%, and the thickness of the perfluorosulfonic acid film is 0.18 μm.
Example 10
The embodiment provides a preparation method of a transition metal doped platinum-carbon catalyst, which comprises the following steps:
(1) weighing 0.045g of graphene in a reaction container, adding 12mL of water into the reaction container, placing the mixed solution in an ultrasonic homogenizer for uniform dispersion, continuously performing ultrasonic treatment for 45min to obtain a uniform solution, continuously introducing argon into the uniform solution, and performing the next reaction after 45 min;
(2) adding 500 mu L of potassium tetrachloroplatinate solution containing 0.1g/mL of platinum and 30 mu L of cobalt chloride solution containing 0.1g/mL of cobalt into the mixed solution prepared in the step (1), and continuously stirring for 6h under the protection of argon to enable ions to be fully adsorbed to the surface of the graphene;
(3) weighing 0.25g of hydroxylamine hydrochloride, quickly adding the hydroxylamine hydrochloride into the mixed solution obtained in the step (2) of violent stirring under the protection of inert gas to quickly reduce ions, continuously and violently stirring for 2 hours, carrying out suction filtration on a product, washing the product with water for three times, and transferring the product to a vacuum oven for drying for 6 hours at the temperature of 90 ℃;
(4) transferring the precursor material obtained in the step (3) to a tube furnace, fusing for 1h at 500 ℃ under the protection of argon, and then taking out after the temperature is reduced to room temperature under the protection of argon to obtain cobalt-doped platinum-based nanoparticles;
(5) adding 9g of n-octanol into 0.06g of cobalt-doped platinum-based nanoparticles obtained in the step (4), stirring for 30min, adding 3mg of perfluorinated sulfonic acid solution with the mass fraction of 5%, ultrasonically crushing for 30min under the protection of argon, performing microwave radiation for 10min, performing suction filtration and washing to neutrality, placing in a vacuum oven, drying for 12h at 65 ℃, and grinding to obtain the cobalt-doped platinum-carbon catalyst.
In the cobalt-doped platinum-carbon catalyst prepared in this example, the mass fraction of platinum was 50%, the mass fraction of cobalt was 3%, and the thickness of the perfluorosulfonic acid film was 0.09 μm.
Comparative example 1
Compared with the example 1, the difference is that the transition metal doped platinum carbon catalyst provided by the comparative example does not coat the perfluorosulfonic acid membrane, and the specific steps are as follows:
(1) 0.05g of Ketjen black is weighed into a reaction vessel, 20mL of water is added into the reaction vessel, and then the mixed solution is placed into an ultrasonic crushing and homogenizing machine for continuous ultrasonic treatment for 10min to obtain a uniform solution. Then continuously introducing nitrogen into the reaction kettle, and carrying out the next reaction after 30 min;
(2) adding 400 mu L of chloroplatinic acid solution containing 0.1g/mL of platinum, 50 mu L of ferric chloride solution containing 0.1g/mL of iron and 50 mu L of cobalt chloride solution containing 0.1g/mL of cobalt into the mixed solution prepared in the step (1), and continuously stirring for 1h under the protection of nitrogen to enable ions to be fully adsorbed to the surface of the Ketjen black;
(3) weighing 0.1g of sodium borohydride, quickly adding the sodium borohydride into the mixed solution obtained in the step (2) of violent stirring under the protection of nitrogen to quickly reduce ions, continuously and violently stirring for 10 hours, then carrying out suction filtration on a product, washing the product to be neutral by using deionized water, and transferring the product to a vacuum oven to be dried for 5 hours at the temperature of 100 ℃;
(4) and (4) transferring the precursor material obtained in the step (3) to a tubular furnace, fusing for 2h at 400 ℃ under the protection of nitrogen, and taking out after the temperature is reduced to room temperature under the protection of nitrogen to obtain the iron-cobalt doped platinum-carbon catalyst.
The iron-cobalt doped platinum-carbon catalyst prepared in the comparative example was subjected to LSV testing, the parameter settings of the testing method were the same as those of example 1, and the test curve is shown in fig. 3. The initial mass activity at 0.9V was calculated to be 105mA/mg, the mass activity after 30000 cycles of CV was calculated to be 46mA/mg, and the mass activity attenuation was calculated to be 56.6%, thus indicating that the iron-cobalt doped platinum-carbon catalyst prepared in comparative example 1 had a mass activity attenuation higher than DOE requirements.
Performance evaluation of transition metal doped platinum carbon catalysts:
the catalysts prepared in the above examples and comparative examples were subjected to an LSV test with the test method parameters set to: the scanning voltage is 0.1-1.25V, the scanning speed is 5mV/s, the rotating speed is 1600 r, the mass of the catalyst dripped by the glassy carbon electrode head is 0.005mg, and the area is 0.196cm2。
Results of the initial mass activity test are shown in table 1. the test results are shown in table 1.
TABLE 1
Figure BDA0002322711930000211
Note: the mass activity @0.9V in the table is: at a voltage of 0.9V, the mass activity of the catalyst.
The following points can be seen from table 1:
(1) it can be seen from the comprehensive examples 1-10 that, in the examples 1-10, the platinum-carbon catalyst is prepared by doping the transition metal and coating the perfluorosulfonic acid membrane, and the initial mass activity of the platinum-carbon catalyst is 135-188mA/mg at the voltage of 0.9V;
(2) by combining example 1 with comparative example 1, it can be seen that the platinum-carbon catalyst prepared by example 1 using iron-cobalt doping and a perfluorosulfonic acid membrane coating has an initial mass activity of 106mA/mg at a voltage of 0.9V, which is significantly lower than that of the platinum-carbon catalyst prepared by example 1, compared to the platinum-carbon catalyst prepared by comparative example using only iron-cobalt doping, and thus the platinum-carbon catalyst prepared by example 1 has higher catalytic activity.
In conclusion, the transition metal atoms entering the crystal lattice change the distance between the platinum atoms in the nanocrystal due to the introduction of the transition metal, so that the generation of active sites is facilitated, and the catalytic activity of the catalyst is improved; transition metal atoms at the position where the edges or the vertexes of the nano crystal lattice are easy to erode improve the structural stability and the corrosion resistance of the catalyst; the perfluorinated sulfonic acid membrane is coated to form a face-to-face continuous H proton conduction network, so that the proton transfer speed is obviously improved, and the durability and the catalytic activity of the platinum-carbon catalyst are further improved. The preparation method provided by the invention is simple to operate, easy to control, easy to batch and high in practical application value.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (33)

1. A preparation method of a transition metal doped platinum-carbon catalyst is characterized by comprising the following steps:
(1) mixing a carbon material, a precursor solution of platinum and a transition metal salt to obtain a mixed solution;
(2) mixing the mixed solution obtained in the step (1) with a reducing agent, separating and drying to obtain a precursor material;
(3) carrying out heat treatment on the precursor material obtained in the step (2) to obtain transition metal doped platinum-based nanoparticles;
(4) mixing the transition metal doped platinum-based nanoparticles obtained in the step (3) with a perfluorosulfonic acid solution, separating and drying to obtain the transition metal doped platinum-carbon catalyst;
the reducing agent in the step (2) comprises any one or the combination of at least two of sodium borohydride, hydroxylamine hydrochloride or potassium borohydride;
the temperature of the heat treatment in the step (3) is 300-700 ℃, and the time of the heat treatment is 0.5-2 h;
wherein, the steps (1), (2), (3) and (4) are all carried out under the protection of inert atmosphere.
2. The production method according to claim 1, wherein the carbon material is dispersed in step (1) before mixing.
3. The method according to claim 2, wherein the carbon material is dispersed by mixing the carbon material with a solvent and ultrasonically dispersing the mixture uniformly.
4. The method according to claim 2, wherein the inert gas is introduced to the reaction vessel to saturate the reaction vessel after the dispersion.
5. The method according to claim 1, wherein the carbon material in step (1) comprises any one or a combination of at least two of ketjen black, Vulcan XC-72R, carbon nanotube, carbon nanosphere, biomass carbon material, carbon fiber, mesoporous carbon, or graphene material.
6. The method according to claim 5, wherein the carbon material in step (1) is any one or a combination of at least two of Ketjen black, Vulcan XC-72, carbon nanotubes, or carbon nanospheres.
7. The method of claim 5 or 6, wherein the carbon nanotubes comprise any one or a combination of at least two of single-walled carbon nanotubes, multi-walled carbon nanotubes, doped single-walled carbon nanotubes, or doped multi-walled carbon nanotubes.
8. The preparation method according to claim 5, wherein the graphene material comprises any one of graphene, graphene oxide, reduced graphene oxide, graphene foam or doped graphene or a combination of at least two of the above.
9. The production method according to claim 1, wherein the precursor of platinum in step (1) contains any one of chloroplatinic acid, potassium tetrachloroplatinate, potassium hexachloroplatinate or platinum nitrate or a combination of at least two thereof.
10. The method according to claim 1, wherein the transition metal salt in step (1) comprises any one of chloride, nitrate, acetate, thiomolybdate, or tungstate of iron, cobalt, nickel, copper, molybdenum, or tungsten, or a combination of at least two thereof.
11. The method according to claim 10, wherein the transition metal salt in step (1) is any one or a combination of at least two of ferric chloride, ferric nitrate, cobalt acetate, cobalt nitrate, cobalt chloride, nickel nitrate, nickel chloride, nickel acetate, copper nitrate, copper chloride, ammonium thiomolybdate, ammonium tungstate and sodium tungstate.
12. The method according to claim 1, wherein the mass ratio of carbon, platinum and transition metal in the carbon material, platinum precursor solution and transition metal salt in step (1) is 1 (0.5-1.5) to (0.01-0.3).
13. The method according to claim 12, wherein the mass ratio of carbon, platinum and transition metal in the carbon material, platinum precursor solution and transition metal salt in step (1) is 1 (0.8-1.2) to (0.04-0.2).
14. The method according to claim 1, wherein the drying in step (2) is carried out by any one or a combination of at least two of forced air drying, vacuum drying and freeze drying.
15. The production method according to claim 1, wherein the mass ratio of platinum to the reducing agent in the mixed solution in the step (2) is 1 (1.5-6).
16. The production method according to claim 15, wherein the mass ratio of platinum to the reducing agent in the mixed solution in the step (2) is 1 (2-5).
17. The method as claimed in claim 1, wherein the temperature of the heat treatment in the step (3) is 400-600 ℃.
18. The method of claim 1, wherein the transition metal doped platinum-based nanoparticles are dispersed in the step (4) before mixing.
19. The production method according to claim 18, wherein the dispersant for dispersion comprises any one of ethanol, isopropanol or n-octanol, or a combination of at least two thereof.
20. The method as claimed in claim 19, wherein the mass ratio of the dispersant to the transition metal-doped platinum-based nanoparticles is (100- & 200): 1.
21. The method as recited in claim 20, wherein the mass ratio of the dispersant to the transition metal-doped platinum-based nanoparticles is (130-185): 1.
22. The production method according to claim 1, wherein the mass fraction of the perfluorosulfonic acid solution in the step (4) is 5%.
23. The production method according to claim 1, wherein the mass ratio of the perfluorosulfonic acid to the transition metal-doped platinum-based nanoparticles in step (4) is 0.001 to 0.005: 1.
24. The method according to claim 1, wherein the drying in step (4) is performed by any one or a combination of at least two of drying in an inert atmosphere, vacuum drying, and freeze drying.
25. The method according to claim 24, wherein the drying in step (4) is carried out under vacuum.
26. The method according to claim 1, wherein the separation in steps (2) and (4) independently comprises any one or a combination of at least two of suction filtration, centrifugation, or filtration.
27. The method according to claim 1, wherein the mixing in step (1), step (2) and step (4) is independently stirring and/or sonication.
28. The method according to claim 1, wherein the gas of the inert atmosphere in steps (1), (2), (3) and (4) independently comprises any one of nitrogen, argon or helium or a combination of at least two thereof.
29. The method of claim 1, comprising the steps of:
(1) adding water into a carbon material, performing ultrasonic treatment, introducing inert gas to saturation to obtain a carbon material dispersion liquid, adding a platinum precursor solution and a transition metal salt into the carbon material dispersion liquid under the protection of inert atmosphere, stirring, and controlling the mass ratio of carbon, platinum and transition metal in the carbon material, the platinum precursor solution and the transition metal salt to be 1 (0.5-1.5) to (0.01-0.3) to obtain a mixed solution;
(2) rapidly adding a reducing agent into the mixed solution obtained in the step (1) under the protection of inert atmosphere, stirring vigorously, controlling the mass ratio of platinum to the reducing agent in the mixed solution to be 1 (1.5-6), carrying out suction filtration on a reaction product, washing the reaction product to be neutral by using deionized water, and transferring the reaction product to a refrigerator for drying to obtain a precursor material;
(3) under the protection of inert atmosphere, treating the precursor material obtained in the step (2) at the temperature of 300-700 ℃ for 0.5-2h, and then cooling to room temperature under the protection of inert atmosphere to obtain transition metal doped platinum-based nanoparticles;
(4) adding the transition metal doped platinum-based nanoparticles obtained in the step (3) into a dispersing agent under the protection of inert atmosphere, stirring, controlling the mass ratio of the dispersing agent to the transition metal doped platinum-based nanoparticles to be (100- & ltSUB & gt 200) & gt 1, adding a perfluorinated sulfonic acid solution with the mass fraction of 5%, controlling the mass ratio of the perfluorinated sulfonic acid to the transition metal doped platinum-based nanoparticles to be 0.001-0.005:1, performing ultrasonic crushing, performing microwave radiation for 3-20min, performing solid-liquid separation, and then placing in a vacuum oven for drying to obtain the transition metal doped platinum-carbon catalyst.
30. The transition metal-doped platinum-carbon catalyst prepared by the preparation method according to any one of claims 1 to 29, wherein the catalyst comprises a carbon carrier, doped platinum-based nanoparticles supported on the carbon carrier, the doped platinum-based nanoparticles being formed by doping a transition metal into a crystal lattice of platinum, and a perfluorosulfonic acid film coated on the surfaces of the carbon carrier and the doped platinum-based nanoparticles;
the mass fraction of the platinum is 40-55% based on 100% of the mass of the catalyst;
the mass fraction of the transition metal is 2-10% based on 100% of the mass of the catalyst;
the thickness of the perfluorosulfonic acid membrane is 0.01-0.2 μm.
31. The catalyst of claim 30 wherein the carbon support comprises any one or a combination of at least two of ketjen black, Vulcan XC-72R, carbon nanotubes, carbon nanospheres, biomass carbon material, carbon fibers, mesoporous carbon, or graphene material.
32. The catalyst of claim 30, wherein the transition metal comprises any one of iron, cobalt, nickel, copper, molybdenum, or tungsten, or a combination of at least two thereof.
33. A fuel cell comprising a transition metal doped platinum carbon catalyst as claimed in any one of claims 30 to 32.
CN201911304498.XA 2019-12-17 2019-12-17 Transition metal doped platinum-carbon catalyst and preparation method and application thereof Active CN111129508B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911304498.XA CN111129508B (en) 2019-12-17 2019-12-17 Transition metal doped platinum-carbon catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911304498.XA CN111129508B (en) 2019-12-17 2019-12-17 Transition metal doped platinum-carbon catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN111129508A CN111129508A (en) 2020-05-08
CN111129508B true CN111129508B (en) 2021-07-02

Family

ID=70498319

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911304498.XA Active CN111129508B (en) 2019-12-17 2019-12-17 Transition metal doped platinum-carbon catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111129508B (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111589454A (en) * 2020-05-15 2020-08-28 无锡威孚高科技集团股份有限公司 High-temperature preparation method of binary alloy catalyst of proton exchange membrane fuel cell
CN112077334A (en) * 2020-09-03 2020-12-15 南京晓庄学院 Preparation method and application of transition metal doped ruthenium-rhodium alloy
CN113549935B (en) * 2021-05-20 2023-03-10 中国科学技术大学 Heteroatom-doped transition metal monoatomic catalyst and preparation method and application thereof
CN113398951B (en) * 2021-06-16 2022-10-28 中国科学技术大学 Intermetallic compound catalyst and method for preparing intermetallic compound catalyst by using bimetallic complex
CN113903932B (en) * 2021-08-27 2024-02-06 北京工业大学 Three-dimensional carbon structure supported platinum catalyst and preparation method thereof
CN113611877A (en) * 2021-09-06 2021-11-05 无锡威孚高科技集团股份有限公司 Multi-element alloy catalyst and preparation method and application thereof
CN114606515A (en) * 2022-01-21 2022-06-10 中国科学技术大学 Platinum monatomic catalyst, preparation method and application
CN114566662B (en) * 2022-02-28 2024-03-08 北京大学 High-entropy intermetallic compound with ordered structure, preparation method thereof and application of high-entropy intermetallic compound as cathode catalyst of fuel cell
CN115084544A (en) * 2022-06-15 2022-09-20 中汽创智科技有限公司 Alloy catalyst and preparation method and application thereof

Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1167544A (en) * 1994-10-18 1997-12-10 南加州大学 Organic fuel cell, and methods of operation thereof and manufacture of electrode thereof
CN1776945A (en) * 2004-11-20 2006-05-24 三星Sdi株式会社 Method for preparing metal catalyst and electrode
CN101411014A (en) * 2006-03-31 2009-04-15 丰田自动车株式会社 Electrode catalyst for fuel cell and method for producing the same
CN101409351A (en) * 2007-07-18 2009-04-15 丰田自动车株式会社 Electrode for fuel cell, electrolyte-dispersed solution for forming electrode, method of producing the solution, and polymer electrolyte fuel cell
CN103515622A (en) * 2013-08-02 2014-01-15 清华大学 Membrane electrode for fuel cell and preparation method thereof
CN104282919A (en) * 2007-12-28 2015-01-14 Lg化学株式会社 Electrode for fuel cell having two kinds of hydrophilicity and method for preparing the same and membrane electrode assembly and fuel cell comprising the same
CN104300158A (en) * 2013-07-15 2015-01-21 通用汽车环球科技运作有限责任公司 Using Immiscible Liquid-Liquid Systems to Control the Dealloying of Non-Noble Metals From alloy Particles Containing Noble Metals
CN105409042A (en) * 2013-05-14 2016-03-16 庄信万丰燃料电池有限公司 Catalyst
CN106159291A (en) * 2016-08-30 2016-11-23 苏州擎动动力科技有限公司 Proton Exchange Membrane Fuel Cells catalysis electrode, the battery with it and preparation method
CN106252670A (en) * 2015-06-10 2016-12-21 通用汽车环球科技运作有限责任公司 Use the electrode added with crystal seed by the nucleocapsid catalyst volume to volume manufacture to high performance fuel cell electrode
CN106784903A (en) * 2016-12-28 2017-05-31 清华大学深圳研究生院 For the platinum transition metal alloy nanometer crystal preparation method of fuel-cell catalyst
CN108530995A (en) * 2017-03-02 2018-09-14 通用汽车环球科技运作有限责任公司 Mitigate the cracking of PEMFC electrodes under low Pt load capacity
CN108543541A (en) * 2018-03-12 2018-09-18 华南理工大学 A kind of nickel cobalt phosphorus/amino carbon nano-tube catalyst and its preparation method and application
CN108630955A (en) * 2017-03-16 2018-10-09 丰田自动车株式会社 The manufacturing method and catalyst composite of catalyst ink
CN108878904A (en) * 2017-05-10 2018-11-23 丰田自动车株式会社 Fuel cell electrode catalyst layer and fuel cell
CN108914155A (en) * 2018-07-12 2018-11-30 中国科学院长春应用化学研究所 Wet reducing prepares the method that catalyst is precipitated in low platinum hydrogen
CN109065903A (en) * 2018-09-17 2018-12-21 苏州擎动动力科技有限公司 A kind of preparation method of high activity loading type octahedron ternary alloy catalyst
CN109103472A (en) * 2018-07-27 2018-12-28 武汉理工新能源有限公司 A kind of high oxygen transmission fuel cell catalyst layer and membrane electrode assembly and fuel cell
CN109167091A (en) * 2018-09-17 2019-01-08 苏州擎动动力科技有限公司 A method of membrane electrode is prepared using carbon periosteum as carrier
CN109273732A (en) * 2018-09-28 2019-01-25 中能源工程集团氢能科技有限公司 A kind of cobalt cladding carbon supported platinum catalyst and preparation method thereof with proton transport function
CN109449466A (en) * 2018-10-23 2019-03-08 山东潍氢动力科技有限公司 Preparation method, the preparation method of membrane electrode anode catalyst layer of membrane electrode
CN109713331A (en) * 2018-12-18 2019-05-03 新源动力股份有限公司 A kind of catalyst pulp, catalyst coated membranes, membrane electrode assembly and application thereof
CN109935848A (en) * 2017-12-15 2019-06-25 中国科学院大连化学物理研究所 A kind of composite catalyst and preparation method thereof
CN110474054A (en) * 2018-05-11 2019-11-19 丰田自动车株式会社 Catalyst layer and its manufacturing method

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109962246A (en) * 2017-12-14 2019-07-02 中国科学院大连化学物理研究所 The loaded low platinum nucleocapsid catalyst of one kind and its preparation and application
CN109148905A (en) * 2018-09-30 2019-01-04 北京海得利兹新技术有限公司 A kind of polymer dielectric film fuel cell high activity elctro-catalyst and preparation method thereof
CN110518257B (en) * 2019-09-03 2022-07-22 上海电气集团股份有限公司 Preparation method of carbon-supported transition metal @ Pt core-shell structure catalyst

Patent Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1167544A (en) * 1994-10-18 1997-12-10 南加州大学 Organic fuel cell, and methods of operation thereof and manufacture of electrode thereof
CN1776945A (en) * 2004-11-20 2006-05-24 三星Sdi株式会社 Method for preparing metal catalyst and electrode
CN101411014A (en) * 2006-03-31 2009-04-15 丰田自动车株式会社 Electrode catalyst for fuel cell and method for producing the same
CN101409351A (en) * 2007-07-18 2009-04-15 丰田自动车株式会社 Electrode for fuel cell, electrolyte-dispersed solution for forming electrode, method of producing the solution, and polymer electrolyte fuel cell
CN104282919A (en) * 2007-12-28 2015-01-14 Lg化学株式会社 Electrode for fuel cell having two kinds of hydrophilicity and method for preparing the same and membrane electrode assembly and fuel cell comprising the same
CN105409042A (en) * 2013-05-14 2016-03-16 庄信万丰燃料电池有限公司 Catalyst
CN104300158A (en) * 2013-07-15 2015-01-21 通用汽车环球科技运作有限责任公司 Using Immiscible Liquid-Liquid Systems to Control the Dealloying of Non-Noble Metals From alloy Particles Containing Noble Metals
CN103515622A (en) * 2013-08-02 2014-01-15 清华大学 Membrane electrode for fuel cell and preparation method thereof
CN106252670A (en) * 2015-06-10 2016-12-21 通用汽车环球科技运作有限责任公司 Use the electrode added with crystal seed by the nucleocapsid catalyst volume to volume manufacture to high performance fuel cell electrode
CN106159291A (en) * 2016-08-30 2016-11-23 苏州擎动动力科技有限公司 Proton Exchange Membrane Fuel Cells catalysis electrode, the battery with it and preparation method
CN106784903A (en) * 2016-12-28 2017-05-31 清华大学深圳研究生院 For the platinum transition metal alloy nanometer crystal preparation method of fuel-cell catalyst
CN108530995A (en) * 2017-03-02 2018-09-14 通用汽车环球科技运作有限责任公司 Mitigate the cracking of PEMFC electrodes under low Pt load capacity
CN108630955A (en) * 2017-03-16 2018-10-09 丰田自动车株式会社 The manufacturing method and catalyst composite of catalyst ink
CN108878904A (en) * 2017-05-10 2018-11-23 丰田自动车株式会社 Fuel cell electrode catalyst layer and fuel cell
CN109935848A (en) * 2017-12-15 2019-06-25 中国科学院大连化学物理研究所 A kind of composite catalyst and preparation method thereof
CN108543541A (en) * 2018-03-12 2018-09-18 华南理工大学 A kind of nickel cobalt phosphorus/amino carbon nano-tube catalyst and its preparation method and application
CN110474054A (en) * 2018-05-11 2019-11-19 丰田自动车株式会社 Catalyst layer and its manufacturing method
CN108914155A (en) * 2018-07-12 2018-11-30 中国科学院长春应用化学研究所 Wet reducing prepares the method that catalyst is precipitated in low platinum hydrogen
CN109103472A (en) * 2018-07-27 2018-12-28 武汉理工新能源有限公司 A kind of high oxygen transmission fuel cell catalyst layer and membrane electrode assembly and fuel cell
CN109065903A (en) * 2018-09-17 2018-12-21 苏州擎动动力科技有限公司 A kind of preparation method of high activity loading type octahedron ternary alloy catalyst
CN109167091A (en) * 2018-09-17 2019-01-08 苏州擎动动力科技有限公司 A method of membrane electrode is prepared using carbon periosteum as carrier
CN109273732A (en) * 2018-09-28 2019-01-25 中能源工程集团氢能科技有限公司 A kind of cobalt cladding carbon supported platinum catalyst and preparation method thereof with proton transport function
CN109449466A (en) * 2018-10-23 2019-03-08 山东潍氢动力科技有限公司 Preparation method, the preparation method of membrane electrode anode catalyst layer of membrane electrode
CN109713331A (en) * 2018-12-18 2019-05-03 新源动力股份有限公司 A kind of catalyst pulp, catalyst coated membranes, membrane electrode assembly and application thereof

Also Published As

Publication number Publication date
CN111129508A (en) 2020-05-08

Similar Documents

Publication Publication Date Title
CN111129508B (en) Transition metal doped platinum-carbon catalyst and preparation method and application thereof
Zhu et al. Recent advances on MOF derivatives for non-noble metal oxygen electrocatalysts in zinc-air batteries
Hanif et al. ZIF derived PtNiCo/NC cathode catalyst for proton exchange membrane fuel cell
KR100696463B1 (en) High concentration carbon impregnated catalyst, method for preparing the same, catalyst electrode using the same and fuel cell having the catalyst electrode
US10847811B2 (en) Catalyst particle, and electrode catalyst, electrolyte membrane-electrode assembly, and fuel cell using the same
CA3021498C (en) High activity alloy-based electrode catalyst, and membrane electrode assembly and fuel cell using high activity alloy-based electrode catalyst
CN108539206B (en) Catalysis layer full-order fuel cell electrode and membrane electrode
US20080020924A1 (en) Method of fabricating platinum alloy electrocatalysts for membrane fuel cell applications
US20070161501A1 (en) Method for making carbon nanotube-supported platinum alloy electrocatalysts
JP2007307554A (en) Supported catalyst, its manufacturing method, electrode using this, and fuel cell
Ma et al. Cobalt based non-precious electrocatalysts for oxygen reduction reaction in proton exchange membrane fuel cells
Zhou et al. Non-precious nickel-based catalysts for hydrogen oxidation reaction in alkaline electrolyte
CN108448138B (en) Preparation method of fuel cell electrode and membrane electrode with full-ordered structure of catalyst layer
JP6603396B2 (en) Carbon powder for fuel cell and catalyst, electrode catalyst layer, membrane electrode assembly and fuel cell using carbon powder for fuel cell
CN109935841A (en) A kind of fuel cell catalyst layer and preparation method thereof
CN110911700B (en) Catalyst, preparation method and application thereof
CN103401000B (en) Used in proton exchange membrane fuel cell catalyst, its preparation method and Proton Exchange Membrane Fuel Cells
KR20060052555A (en) Fuel cell, membrane-electrode assembly, and catalyst used for them and the producing method of catalyst
Seselj et al. Catalyst Development for High‐Temperature Polymer Electrolyte Membrane Fuel Cell (HT‐PEMFC) Applications
CN110993966A (en) Fuel cell electrocatalyst and preparation method thereof
Qin et al. Advances in platinum-based and platinum-free oxygen reduction reaction catalysts for cathodes in direct methanol fuel cells
Yan et al. Pt nanowire electrocatalysts for proton exchange membrane fuel cells
CN114188551A (en) Preparation method of platinum-palladium alloy catalyst growing on gas diffusion layer in situ and application of platinum-palladium alloy catalyst to fuel cell electrode
CN114335577A (en) Modified catalyst, membrane electrode, preparation method of membrane electrode and fuel cell
CN111224118A (en) Multi-element doped platinum-based catalyst and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant