CN111916775B - Platinum-based alloy catalyst for fuel cell and preparation method thereof - Google Patents
Platinum-based alloy catalyst for fuel cell and preparation method thereof Download PDFInfo
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- CN111916775B CN111916775B CN202010807009.9A CN202010807009A CN111916775B CN 111916775 B CN111916775 B CN 111916775B CN 202010807009 A CN202010807009 A CN 202010807009A CN 111916775 B CN111916775 B CN 111916775B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- 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 belongs to the technical field of fuel cell catalysts, and particularly relates to a fuel cell platinum-based alloy catalyst and a preparation method thereof, wherein a transition metal organic framework material is prepared firstly, a platinum metal precursor and the transition metal organic framework material are mixed and ball-milled, then a reducing atmosphere is introduced for a reduction thermal reaction, and then an inorganic acid is used for pickling, so that the problems of low Pt atom utilization rate, easy agglomeration and environmental pollution are effectively solved.
Description
Technical Field
The invention belongs to the technical field of fuel cell catalysts, and particularly relates to a fuel cell platinum-based alloy catalyst and a preparation method thereof.
Background
The fuel cell is a high-efficiency energy conversion device free from Carnot cycle, chemical energy in fuel can be converted into electric energy at high conversion efficiency as long as fuel is provided, but the fuel cell cannot be popularized and applied on a large scale so far, the main reason at present is that the overpotential is reduced and catalytic reaction is accelerated by seriously depending on the use of noble metal materials such as platinum and the like, and noble metal catalysts face resource scarcity, are high in price, are poor in long-term cycle stability, and the development and application of the fuel cell are hindered by a complex preparation process. In order to reduce the cost of the fuel cell catalyst, people select to use a transition metal to replace part of the Pt metal so as to reduce the dosage of the Pt metal, and simultaneously, due to the addition of the transition metal, the catalytic performance of the Pt-based alloy catalyst can be greatly improved under the surface stress action and the atomic synergistic action between the Pt and the transition metal, but researches find that the oxygen reduction catalytic activity of the transition metal oxygen group compound is slightly insufficient.
The current preparation of Pt-based alloy catalysts mainly adopts a solvothermal method, and the process is complicated and harmful to the environment. Chinese patent CN103285880B discloses a method for preparing ternary alloy catalyst by adopting solvothermal reduction methodThe method reduces three elements of Co, Ru and Pt in a three-step reduction mode by adopting a reducing agent NaBH4The method has strong reducibility, belongs to dangerous goods and is not suitable for mass production application, and in addition, the ethylene glycol used by the method is used as an organic solvent and a reducing agent, so that the catalyst cannot realize mass production and can damage the environment. Chinese patent CN108987760A discloses a method for preparing a platinum-cobalt alloy catalyst by forming an organic complex in an organic solvent through Pt salt and Co salt, distributing Co element around crystal grains through a magnetic field to form an alloy, and finally performing heat treatment. Chinese patent CN111224116A discloses a catalyst for fuel cell and a preparation method thereof, the catalyst is an aza carbon-based catalytic material M-NC containing one or more metals, which directly and fully mixes a carbon source material, a nitrogen source material, a structure guide material and a metal precursor material, then carries out preliminary heat treatment, grinds into a powdery catalyst precursor material by ball milling or disc milling, and then carries out pyrolysis in inert gas or reducing atmosphere to obtain the catalyst. The method directly mixes the precursors (carbon source, nitrogen source and metal), and the catalyst precursor material obtained by the method is easy to cause metal agglomeration and even active site deletion in the ball milling and heat treatment processes, and is uncontrollable for the phase structure of the catalyst, thereby being not beneficial to the performance improvement of the catalyst. China CN111048793A discloses a preparation method of a platinum-based octahedral catalyst, which comprises mixing a precursor solution with a carbon carrier, and then performing ball milling and impregnation to obtain a mixed slurry, wherein the precursor solution is obtained by dissolving acetylacetone transition metal salt in dimethyl sulfoxide, the acetylacetone transition metal salt contains at least two transition metal salts, and one of the transition metal salts is platinum acetylacetonate; pre-freezing the mixed slurry, and then carrying out vacuum freeze drying to obtain freeze-dried powder; mixing the lyophilized powderAnd carrying out reduction heat treatment under the reducing gas atmosphere, wherein the reducing gas comprises carbon monoxide. The above method also easily causes inevitable agglomeration of metals during ball milling, and the agglomeration of metals during heat treatment is more serious.
In short, the current preparation process of the fuel cell Pt-based alloy catalyst has the problems of low yield, failure to realize 100 percent utilization rate of Pt atoms, organic solvent pollution, high cost or difficult industrial production; in addition, because the transition metal is directly used as a precursor for ball milling, serious metal agglomeration can be caused, the activity of the catalyst is reduced, and the popularization and the application of the fuel cell are seriously restricted.
Disclosure of Invention
The invention provides a fuel cell platinum-based alloy catalyst and a preparation method thereof aiming at the defects of the prior art.
The method is realized by the following technical scheme:
the first purpose of the invention is to provide a fuel cell platinum-based alloy catalyst, which is prepared by firstly reacting transition metal salt with 2-methylimidazole to prepare a transition metal organic framework material, then mixing and ball-milling a platinum metal precursor and the transition metal organic framework material, introducing reducing atmosphere to carry out reduction thermal reaction, and then carrying out acid washing with inorganic acid.
The transition metal salt is one of cobalt nitrate, basic cobalt carbonate, cobalt sulfate, cobalt chloride, cobalt bromide, nickel sulfate, nickel chloride and nickel nitrate.
The molar ratio of the transition metal salt to the 2-methylimidazole is 1: (0.1-6); preferably 1: (1-5); still more preferably 1: (3-4).
The platinum metal precursor is one of acetylacetone platinum, potassium chloroplatinate, dinitroso diammine platinum and dichloro diammine platinum.
The molar ratio of the platinum metal precursor to the transition metal organic framework material is 1: (0.05-4); preferably 1: (0.5-3); still more preferably 1: (1-2).
The process conditions of the mixed ball milling are as follows: the time is 3-10h, the rotating speed is 150-: 1.
the reducing atmosphere is one of the following three gases: 1) hydrogen gas; 2) h2A mixed gas of/Ar; 3) h2/N2Mixing the gas; wherein the hydrogen content is more than or equal to 2 percent; preferably, the hydrogen accounts for 4-50%; still more preferably 5 to 10%.
The heat treatment comprises the following process conditions: the temperature is 400 ℃ and 1000 ℃, and the time is 30-180 min.
The inorganic acid is one of perchloric acid, sulfuric acid, hydrochloric acid, nitric acid and the like.
The concentration of the inorganic acid is 0.05-5 mol/L; preferably 0.1 to 3 mol/L; further preferably 0.5 to 2 mol/L.
The second purpose of the invention is to provide a preparation method of the platinum-based alloy catalyst for the fuel cell, which comprises the following steps:
(1) putting transition metal salt and 2-methylimidazole into deionized water according to a molar ratio, stirring and reacting for 8 hours at room temperature, filtering and drying in vacuum to obtain a transition metal organic framework material;
(2) ball-milling and mixing the Pt metal precursor and the transition metal organic framework material for 3-10h under the conditions of the rotation speed of 150-300 r/min and the ball-to-material ratio (5-12):1 according to the mol ratio to obtain PtM/C composite powder;
(3) placing the PtM/C composite powder in a high-temperature tube furnace, and carrying out heat treatment for 30-180min under the conditions of 400-1000 ℃ in a reducing atmosphere to obtain a PtM alloy carbon material;
(4) fully grinding the PtM alloy carbon material, placing the material in inorganic acid with the concentration of 0.05-5mol/L, etching at 80 ℃, filtering, washing with deionized water to be neutral, and obtaining the precipitate which is PtxMy-a catalyst C.
Has the advantages that:
the method combines the ball milling method and the gas phase reduction method, effectively solves the problems of low Pt atom utilization rate and environmental pollution, and simultaneously avoids metal agglomeration, especially avoids the phenomenon of the surface agglomeration of single atom metal sites due to the addition of the transition metal organic framework. The invention has simple manufacturing process, is environment-friendly, has the Pt atom utilization rate as high as 100 percent, is suitable for batch production, and avoids the use and the discharge of organic solvents.
The Pt/C catalyst is prepared by a general immersion reduction method, wherein the initial potential of the catalyst is 0.922V vs RHE, the half-wave potential is 0.758V vs RHE, and the limiting current density is 5.61mA/cm2The loading amount is 300 mu g/cm2Apparent ECSA of 56m2(ii)/g; the catalyst doped with nickel or cobalt in the application obviously improves the electrochemical performance.
Drawings
FIG. 1 is a linear sweep voltammogram of the PtCo-C catalyst of example 1;
FIG. 2 is a cyclic voltammogram of the PtCo-C catalyst of example 1;
FIG. 3 is a nitrogen desorption curve for the PtCo-C catalyst of example 1;
FIG. 4 is an SEM photograph of the PtCo-C catalyst of example 1;
FIG. 5 is a linear sweep voltammogram of the PtNi-C catalyst of example 2;
FIG. 6 is a cyclic voltammogram of the PtNi-C catalyst of example 3;
FIG. 7 is a nitrogen desorption curve for the PtNi-C catalyst of example 3;
FIG. 8 is an SEM photograph of the PtNi-C catalyst of example 1.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
A fuel cell platinum-based alloy catalyst is prepared by the following steps:
preparation of Co-based metal-organic framework materials: dissolving 2.91g (10mmol) of cobalt nitrate hexahydrate and 3.28g (40mmol) of 2-methylimidazole in 50ml of deionized water, stirring for 8 hours at room temperature, filtering to obtain a filter cake, and then drying in vacuum overnight;
preparation of PtCoC composite powder: weighing 3.93g (10mmol) of platinum acetylacetonate and 4.55g (10mmol) of Co-based metal organic framework material, mixing, placing the mixture in an alumina ball mill, and ball-milling for 4 hours under the conditions that the ball-material ratio is 10: 1 and the rotating speed is 200 r/min;
preparation of PtCo alloy carbon material: placing PtCoC composite powder in a tube furnace, heating to 700 ℃, and introducing reducing atmosphere H2Carrying out heat treatment for 120min under the condition of/Ar mixed gas to obtain a PtCo alloy carbon material; wherein, H in the reducing atmosphere2The proportion is 5 percent;
preparation of PtCo-C catalyst: after the PtM alloy carbon material was sufficiently ground, it was placed at 0.5M H ℃ at 80 DEG C2SO4Washing with acid for 12h, cooling to room temperature, filtering, and washing with deionized water to neutrality to obtain precipitate as PtCo-C catalyst;
in this embodiment, a Cyclic Voltammetry (CV) is used to test the electrochemical area and the corresponding peak size of the redox peak position of the PtCo-C catalyst, and a Linear Sweep Voltammetry (LSV) is used to test the polarization current, the initial potential, the half-wave potential, and the like of the PtCo-C catalyst;
FIG. 1 is a linear sweep voltammogram of a PtCo-C catalyst in a three-electrode system, with a loading of 20 μ g/cm calculated as Pt2As can be seen from fig. 1: the PtCo-C catalyst has an initial potential of 0.93V vs RHE, a half-wave potential of 0.71V vs RHE, and a limiting current density of 7.5mA/cm2；
FIG. 2 shows PtCo-C catalyst at 0.5M H at 25 deg.C2SO4Cyclic voltammetry test curve at 0.05V scan rate in solution, with a loading of 20 μ g/cm calculated as Pt2As can be seen from fig. 2: the apparent ECSA of the catalyst was 65m2/g。
FIG. 3 is a nitrogen desorption curve for the PtCo-C catalyst, as can be seen from FIG. 3: the specific surface area of the catalyst is 954m2/g。
Example 2
A fuel cell platinum-based alloy catalyst is prepared by the following steps:
preparation of Ni-based metal-organic framework material: 2.90g (10mmol) of nickel nitrate hexahydrate and 3.28g (40mmol) of 2-methylimidazole are dissolved in 50ml of deionized water, stirred at room temperature for 8 hours, filtered to obtain a filter cake, and then dried overnight under vacuum.
Preparation of ptnicb composite powder: weighing 3.93g (10mmol) of platinum acetylacetonate and 4.55g (10mmol) of Ni-based metal organic framework material, mixing, placing the mixture in an alumina ball mill, and ball-milling for 4 hours under the conditions that the ball-material ratio is 10: 1 and the rotating speed is 220 r/min;
preparation of PtNi alloy carbon material: putting PtNiC composite powder into a tube furnace, heating to 700 ℃, and introducing reducing atmosphere H2Carrying out heat treatment for 90min under the condition of/Ar mixed gas to obtain the PtNi alloy carbon material; wherein, H in the reducing atmosphere2The proportion is 3 percent;
preparation of PtNi-C catalyst: fully grinding PtNi alloy carbon material, and placing at 80 ℃ of 0.5M H2SO4Washing with acid for 12h, cooling to room temperature, filtering, and washing with deionized water to neutrality to obtain precipitate, i.e. PtNi-C catalyst;
FIG. 5 is a linear sweep voltammogram of a PtNi-C catalyst in a three-electrode system, with a loading of 20 μ g/cm calculated as Pt2As can be seen from fig. 1: the PtNi-C catalyst has an initial potential of 0.94V vs RHE, a half-wave potential of 0.72V vs RHE, and a limiting current density of 6.8mA/cm2；
FIG. 6 shows the cyclic voltammetry test curves of PtNi-C catalyst at 25 deg.C in 0.5M H2SO4 solution at 0.05V sweep rate, where the loading is 20 μ g/cm calculated as Pt2As can be seen from fig. 2: the apparent ECSA of the catalyst was 72m2/g；
FIG. 7 is a nitrogen desorption curve of the PtNi-C catalyst, as can be seen from FIG. 7: the specific surface area of the catalyst is 1024m2/g。
Claims (5)
1. A fuel cell platinum-based alloy catalyst is characterized in that transition metal salt and 2-methylimidazole are stirred in water at room temperature to react to prepare a transition metal organic framework material, a platinum metal precursor and the transition metal organic framework material are mixed and ball-milled, then a reducing atmosphere is introduced to carry out reduction thermal reaction, and then inorganic acid pickling is carried out to prepare the catalyst;
the process conditions of the mixed ball milling are as follows: the time is 3-10h, the rotating speed is 150-: 1;
the transition metal salt is one of cobalt nitrate, basic cobalt carbonate, cobalt sulfate, cobalt chloride, cobalt bromide, nickel sulfate, nickel chloride and nickel nitrate;
the molar ratio of the transition metal salt to the 2-methylimidazole is 1: (0.1-6);
the platinum metal precursor is one of acetylacetone platinum, potassium chloroplatinate, dinitroso diammine platinum and dichloro diammine platinum;
the molar ratio of the platinum metal precursor to the transition metal organic framework material is 1: (0.05-4).
2. The fuel cell platinum-based alloy catalyst according to claim 1, wherein the reducing atmosphere is one of three gases: 1) hydrogen gas; 2) H2/Ar mixed gas; 3) H2/N2 mixed gas; wherein the hydrogen content is more than or equal to 2 percent.
3. The fuel cell platinum-based alloy catalyst according to claim 1, wherein the reduction thermal reaction is carried out under process conditions of: the temperature is 400 ℃ and 1000 ℃, and the time is 30-180 min.
4. The fuel cell platinum-based alloy catalyst according to claim 1, wherein the inorganic acid is one of perchloric acid, sulfuric acid, hydrochloric acid, nitric acid, and the like.
5. The fuel cell platinum-based alloy catalyst according to claim 1, wherein the method for preparing the fuel cell platinum-based alloy catalyst comprises the steps of:
(1) putting transition metal salt and 2-methylimidazole into water according to a molar ratio, stirring and reacting for 8 hours at room temperature, and then filtering and drying in vacuum to obtain a transition metal organic framework material;
(2) ball-milling and mixing the Pt metal precursor and the transition metal organic framework material for 3-10h under the conditions of the rotation speed of 150-300 r/min and the ball-to-material ratio (5-12):1 according to the mol ratio to obtain PtM/C composite powder;
(3) placing the PtM/C composite powder in a high-temperature tube furnace, and carrying out heat treatment for 30-180min under the conditions of 400-1000 ℃ in a reducing atmosphere to obtain a PtM alloy carbon material;
(4) fully grinding the PtM alloy carbon material, placing the material in inorganic acid with the concentration of 0.05-5mol/L, etching at 80 ℃, filtering, washing with deionized water to be neutral, and obtaining precipitate, namely the PtxMy-C catalyst.
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| CN113889633B (en) * | 2021-09-23 | 2023-06-27 | 中汽创智科技有限公司 | Alloy catalyst and preparation method and application thereof |
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