CN114188551A - 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 - Google Patents

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 Download PDF

Info

Publication number
CN114188551A
CN114188551A CN202111337137.2A CN202111337137A CN114188551A CN 114188551 A CN114188551 A CN 114188551A CN 202111337137 A CN202111337137 A CN 202111337137A CN 114188551 A CN114188551 A CN 114188551A
Authority
CN
China
Prior art keywords
platinum
gas diffusion
diffusion layer
catalyst
palladium
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.)
Pending
Application number
CN202111337137.2A
Other languages
Chinese (zh)
Inventor
苏华能
李金龙
张玮琦
马强
徐谦
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.)
Jiangsu University
Original Assignee
Jiangsu University
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 Jiangsu University filed Critical Jiangsu University
Priority to CN202111337137.2A priority Critical patent/CN114188551A/en
Publication of CN114188551A publication Critical patent/CN114188551A/en
Pending legal-status Critical Current

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
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8807—Gas diffusion layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • 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
    • 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 cells, relates to a catalyst, and particularly relates to a preparation method of a platinum-palladium alloy catalyst growing on a gas diffusion layer in situ, which comprises the following steps: firstly, performing hydrophobic treatment on a base material, coating mixed slurry of carbon powder and polytetrafluoroethylene dispersion liquid, and calcining to obtain a gas diffusion layer; and (2) coating to obtain a gas diffusion layer containing a platinum layer, then placing the platinum layer upwards, sequentially adding water, precursors of platinum and palladium, a reducing agent and a surfactant, standing to ensure that the catalyst is reduced and grows on the platinum layer, uniformly dropwise adding a proton conductor solution, standing and drying to obtain the catalyst. The invention also applies the prepared catalyst to the electrode material of the proton exchange membrane fuel cell. The invention optimizes the complex process of the traditional electrode preparation, reduces the manufacturing cost, combines the gas diffusion layer and the catalyst layer into a whole, enhances the interaction between the gas diffusion layer and the catalyst layer and reduces the contact resistance; thereby improving the electrochemical reaction rate, the energy conversion rate, the catalyst utilization rate and the durability of the fuel cell.

Description

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
Technical Field
The invention belongs to the technical field of fuel cells, relates to a catalyst, and particularly relates to a preparation method of a platinum-palladium alloy catalyst growing on a gas diffusion layer in situ and application of the platinum-palladium alloy catalyst to a fuel cell electrode.
Background
The use of fossil fuels emits a large amount of harmful gases, causing serious environmental pollution, and its reserves are being reduced and are not renewable. Proton Exchange Membrane Fuel Cell (PEMFC) is a high-efficient hydrogen energy conversion device, can store the chemical energy in hydrogen fuel and oxidizing agent and directly convert into the electric energy through the way of electrochemical reaction, have green, high specific energy, the characteristic of the quick start of low temperature and high steady operation, can apply to many fields such as new energy automobile, field movement power supply and silent power supply, etc., regard as the promising alternative scheme in the aspect of raising energy efficiency and reducing the greenhouse gas emission, it is the ideal power source to substitute the internal-combustion engine, have received extensive attention and research in recent years.
In a proton exchange membrane fuel cell, a gas diffusion electrode is a core component, and plays an important role in determining the performance of the cell. The technical indexes of the MEA for the vehicle in 2020 are proposed by the United states department of energy (DOE) to be as follows: the cost is less than $14kW-1The durability requirement reaches 5000h, and the power density reaches 1W cm under rated power-2. According to the requirement, the total dosage of the noble metal Pt is less than 0.125mg cm-2The current density at 0.9V should reach 0.44A cm-2。
The gas diffusion electrode is composed of a Gas Diffusion Layer (GDL) and a Catalytic Layer (CL), which is a main site of a hydrogen oxidation reaction and an oxygen reduction reaction, and has a great influence on the performance and durability of the proton exchange membrane fuel cell. The catalyst used in the catalyst layer is mainly a noble metal platinum-based material, and accounts for most of the cost of the proton exchange membrane fuel cell. Thus, the preparation of the catalytic layer and catalyst determines not only the performance of the proton exchange membrane fuel cell, but also its cost. For catalytic layers, two key technical challenges exist to be solved: (1) the activity and stability of the catalytic layer during the whole cell operation process; (2) the cost of manufacture of the catalyst and catalyst layer. The current method of preparing catalytic layers is to prepare catalyst inks using commercial Pt/C and PtCo/C catalysts and then spray the inks onto gas diffusion layers or onto proton exchange membranes. Both of these methods are complex and require careful process control. Meanwhile, commercial Pt/C and PtCo/C catalysts undergo oswald ripening during operation, resulting in shedding of carbon carriers and aggregation of Pt particles, which seriously affect the activity and durability of the catalysts, thereby reducing the performance and lifetime of PEMFCs. Improving the performance of the Pt catalyst and optimizing the manufacturing process of the catalyst layer are the keys of improving the performance of the battery and reducing the cost.
From the angle of intrinsic activity of the catalyst, the activity and stability of the catalyst are improved by changing a carrier, preparing a multi-element alloy catalyst, controlling the morphology and the like, the use amount of the noble metal catalyst is reduced, the performance of the battery can be effectively improved, and the cost of the catalyst is reduced. Gong art et al (CN202110407889.5) discloses a preparation method of a three-dimensional porous platinum catalyst, which comprises the following steps: a) reacting ZnCl2Or mixing LiCl and NaCl or KCl, adding into deionized water to prepare a saturated solution, adding an organic carbon source, an organic nitrogen source and a transition metal salt, and drying to obtain a precursor; b) heating, carbonizing and cooling the precursor to obtain a carbon material; c) adding a carbon material into an inorganic acid, stirring, washing to be neutral, and drying to obtain a black powdery three-dimensional porous carbon material; d) dispersing the porous carbon material in deionized water, adding a platinum-containing precursor, mixing and dispersing, adding a reducing agent, washing after reaction, and drying in vacuum to obtain a black powdery catalyst. The technology is prepared by the processes of repeated dissolution, drying, calcination, washing and the like, and the preparation process is very complicated and takes a long time. Liao Shijun et al (CN202110369424.5) provide a low platinum core-shell structure catalyst and a preparation method and a doping modification method thereof, firstly, a carbon nano tube is ultrasonically dispersed in an absolute ethanol solution, then a titanium precursor and acetic acid are added into the absolute ethanol solution, and nano particles of the carbon nano tube loaded with titanium oxide are prepared by a hydrothermal method; then, carrying out nitridation treatment on the obtained precursor in the reducing atmosphere of ammonia gas to obtain a precursor of the carbon nano tube loaded with titanium nitride; and finally, amplifying by using a self-designed electrolytic cell through a constant current continuous electrodeposition method to prepare the TiN @ Pt/NCNT material. The invention greatly reduces the cost of the fuel cell catalyst and is beneficial to accelerating the fuel cellThe commercialization process is complicated, and the waste liquid after electrodeposition contains a large amount of platinum precursor and needs to be subjected to subsequent treatment and recovery.
The manufacturing process of the catalytic layer is optimized, and the cell performance is further improved by developing a new catalytic layer preparation process. The institute of chemical and physical research (CN201611022937.4) of the Chinese academy of sciences, the institute of chemical and physical sciences, has invented a method for preparing the catalyst layer of single atomic layer of platinum for fuel cell of proton exchange membrane directly, this catalyst layer passes the electrostatic spinning technology, prepare Pd/C catalyst layer directly at first, then in three electrode systems, adopt the method of the deposition of underpotential to deposit the monoatomic Cu on Pd/C catalyst layer, then replace and get Pt of the monoatomic layer, prepare Pd/C @ Pt finallyMLAnd a catalytic layer. Pd/C @ PtMLThe catalyst layer is used as a cathode, and the loading is Pd 0.15mg cm-2，Pt 0.02mg cm-2The maximum power density of a single cell is 0.56W cm-2(H2Air) better than commercial cathode Pt loading of 0.09mg cm-2The catalyst layer of (1). Single cell accelerated decay tests were conducted on both catalytic layers and Pd/C @ Pt was foundMLThe catalytic layer has better stability. Zhengshi et al (CN201911051563.2) invented a catalyst layer of proton exchange membrane fuel cell and its preparation method, the catalyst layer is three layers, the first layer is a mixed layer of Pt/C catalyst and polyvinylidene fluoride hexafluoropropylene copolymer adhesive, the second layer is a mixed layer of Pt/CNTs catalyst and Nafion adhesive, and the third layer is a mixed layer of Pt/C catalyst and PBI ionomer adhesive. The invention divides the catalyst layer into three layers, increases the contact resistance of the catalyst layer and reduces the material transmission. However, most of the Pt catalysts in the catalyst layer are deposited on the surface of the carrier in the form of spherical particles, many active sites are hidden under the surface, and thus the Pt catalysts cannot play a role in catalysis, and in the long-term operation process of the battery, the Pt catalysts may agglomerate or fall off, which seriously affects the performance and durability of the battery.
In view of the above prior art, the inventors have devised a method for preparing an electrode in which a catalyst is grown in situ on a microporous layer having an ordered structure. The platinum-palladium alloy catalyst grown in situ on the gas diffusion layer shows a polygonal rhombus shape, can effectively improve the specific surface area, exposes more active sites, has higher stability than nanoparticles, and greatly improves the catalytic efficiency. In addition, the catalyst directly grows on the gas diffusion layer in situ, so that the interaction force between the catalyst layer and the gas diffusion layer is greatly enhanced, and the transmission resistance between the gas diffusion layer and the catalyst layer is reduced. The electrode has low transmission resistance, excellent electrochemical activity and catalyst stability, can effectively improve the performance of the fuel cell, and develops a new direction for the research of the fuel cell.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a fuel cell electrode with a polygonal rhombus platinum-palladium alloy catalyst in-situ grown on a gas diffusion layer, so that the electrochemical surface area is increased, the activity and the stability of the catalyst are improved, and the performance of the fuel cell is effectively improved.
The specific technical scheme is as follows:
a preparation method of a platinum-palladium alloy catalyst growing on a gas diffusion layer in situ comprises the following steps:
(1) washing the cut carbon paper or carbon cloth in boiling acetone, taking out, soaking in a polytetrafluoroethylene dispersion liquid for full soaking, drying at 70 ℃ for 2h, sintering at 300-450 ℃ for 15-60 min, preferably at 370 ℃ for 30min, and performing hydrophobic treatment, wherein the content of polytetrafluoroethylene is 10-15 wt.% of that of the carbon paper or carbon cloth;
(2) adding the carbon powder and the polytetrafluoroethylene dispersion liquid which are subjected to acid treatment into isopropanol to be subjected to ultrasonic dispersion to form uniform slurry, then uniformly spraying the slurry on one side of carbon paper or carbon cloth subjected to hydrophobic treatment, drying the carbon paper or carbon cloth at 70 ℃ for 2 hours, and sintering the carbon paper or carbon cloth at 300-450 ℃ for 15-60 min, preferably at 370 ℃ for 30min to obtain a gas diffusion layer; wherein the mass-volume ratio of the carbon powder to the polytetrafluoroethylene dispersion to the isopropanol is 15-20 mg: 2-5 mg: 2-10 mL, preferably 17mg:3mg:5mL, and the carbon powder loading capacity is 2-2.5 mg cm-2；
(3) Uniformly dispersing Pt/C and Nafion in isopropanol, uniformly spraying the mixture on the surface of a gas diffusion layer, and drying at 70 ℃ for 2h to obtain the gas diffusion layer containing a platinum layer, whereinThe mass-volume ratio of Pt/C to Nafion to isopropanol is 5-10 mg: 2-5 mg: 2-10 mL, preferably 7mg:3mg:5mL, and the loading amount of platinum in the platinum layer is 0.005-0.01 mg cm-2；
(4) Placing a gas diffusion layer containing a platinum layer at the bottom of a container, enabling the platinum layer to face upwards, sequentially adding water, a platinum and palladium precursor, a reducing agent and a surfactant, standing, enabling a catalyst to be reduced and grown on the platinum layer, taking out after complete reaction, washing with water, and drying at 70 ℃ for 2 hours to obtain a platinum-palladium alloy catalyst layer, wherein the molar volume ratio of the platinum and palladium precursor, the reducing agent, the surfactant and the water is 1-2 mmol: 2-4 mmol: 5-20 mL, preferably 1mmol:3mmol:2mmol:10 mL; then uniformly dripping 0.1-0.5 mg cm of catalyst layer on the surface of the catalyst layer-2Standing the proton conductor solution for 12 hours to uniformly distribute the proton conductor in the catalyst layer, and then drying the proton conductor solution for 2 hours at 70 ℃ to obtain the platinum-palladium alloy catalyst growing on the gas diffusion layer in situ.
In a preferred embodiment of the present invention, the platinum precursor in step (4) is any one of chloroplatinic acid, potassium chloroplatinate, platinum chloride, platinum acetylacetonate, and sodium chloroplatinate, preferably chloroplatinic acid; the palladium precursor is any one of palladium chloride, sodium tetrachloropalladate, palladium acetylacetonate or potassium chloropalladate, and palladium chloride is preferred.
In a preferred embodiment of the invention, in the precursor of platinum and palladium in the step (4), the molar ratio of platinum to palladium is 3: 1-1: 3.
In a preferred embodiment of the present invention, the surfactant in step (4) is any one of cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, polyvinylpyrrolidone, or poloxamer.
In the preferred embodiment of the present invention, the reducing agent in step (4) is any one of formic acid, ascorbic acid, sodium citrate or lysine, preferably formic acid.
In the invention, a catalyst seed layer is prepared on the gas diffusion layer, the seed layer is a trace platinum layer, besides the platinum layer prepared by the method, the gas diffusion layer can be placed in a diluted platinum precursor solution, and a reducing agent is added to form the platinum layer on the surface; or dripping a small amount of platinum precursor solution on the surface of the gas diffusion layer, and then carrying out thermal reduction in a hydrogen-argon mixed gas to form a platinum layer; or electrodepositing a platinum layer on the surface of the gas diffusion layer by an electrodeposition technology; alternatively, a platinum layer or the like is formed on the surface of the gas diffusion layer by magnetron sputtering.
The platinum-palladium catalyst prepared by the method is polygonal rhombus in shape and 100-200 nm in size.
The invention also aims to apply the prepared platinum-palladium catalyst to an electrode material of a proton exchange membrane fuel cell.
Using gas diffusion electrode as cathode, conventional Pt/C electrode as anode, separating with proton exchange membrane, hot pressing (70 deg.C, 4kg cm)-2) So as to obtain the membrane electrode with the catalyst in-situ grown on the microporous layer with the ordered structure.
Advantageous effects
According to the invention, the platinum-palladium alloy catalyst grows on the gas diffusion layer in situ, the shape of the catalyst is polygonal rhombus, and the catalyst layer uniformly grows on the gas diffusion layer. The invention optimizes the complex process of the traditional electrode preparation and reduces the manufacturing cost. The gas diffusion layer and the catalyst layer are combined into one, so that the interaction between the gas diffusion layer and the catalyst layer is greatly enhanced, and the contact resistance is effectively reduced. The prepared platinum palladium catalyst is in a polygonal rhombus shape structure, so that the electrochemical reaction area is remarkably increased, and the activity and the stability of the catalyst are enhanced. The electrode can effectively improve the electrochemical reaction rate, the energy conversion rate and the catalyst utilization rate, and improve the durability of the fuel cell.
Drawings
FIG. 1 is a flow chart of a fuel cell electrode preparation process in which the polygonal diamond platinum-palladium catalyst is grown in situ on a gas diffusion layer, wherein the flow chart includes a scanning electron microscope image of 1, the gas diffusion layer, 2, the platinum layer (sprayed Pt/C), 3, the polygonal diamond platinum-palladium catalyst layer, and 4, the polygonal diamond platinum-palladium catalyst;
FIG. 2. Performance of the electrode is plotted against bar graph (left: current density at 0.6V, right: peak power density).
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Example 1
A preparation method of a platinum-palladium alloy catalyst growing on a gas diffusion layer in situ comprises the following steps:
(1) and (3) treating the carbon paper: cutting carbon paper (Dongli-090) into 2cm × 2cm, soaking in acetone, boiling for 15-20min, removing impurities on the surface and in the pores of the carbon paper, and oven drying at 70 deg.C. Then soaking the PTFE powder in a dispersion liquid of polytetrafluoroethylene (PTFE, 12 wt.%), performing hydrophobic treatment, taking out, drying at 70 ℃ for 2h, and then placing in a muffle furnace at 370 ℃ for sintering for 30min to enable the content of PTFE to reach 15-20 wt.%;
(2) preparation of gas diffusion layer: dispersing carbon powder (Vulcan XC-72R) treated by acid and PTFE in isopropanol dispersion liquid, performing ultrasonic treatment for 30min to make the carbon powder and PTFE uniform, uniformly spraying the carbon powder and PTFE on the surface of hydrophobic carbon paper, drying at 70 ℃ for 2h, calcining at 370 ℃ for 30min, taking out, cooling, weighing and calculating to obtain carbon powder with the loading capacity of 2mg cm-2A gas diffusion layer of PTFE/C0.15;
(3) preparing a platinum layer: uniformly dispersing a small amount of Pt/C and Nafion in isopropanol, wherein the mass-volume ratio of the Pt/C to the Nafion to the isopropanol is 7mg to 3mg to 5mL, then uniformly spraying the slurry on the surface of a gas diffusion layer, drying for 2 hours at 70 ℃, and weighing and calculating to obtain the Pt loading capacity of 0.01mg cm-2A platinum layer of (a);
(4) preparing an in-situ growth platinum-palladium catalyst and an electrode: placing the gas diffusion layer obtained in the step (1) at the bottom of a reaction container, enabling a platinum layer to face upwards, adding 15mL of water into the container to completely cover the gas diffusion layer, then adding a solution of chloroplatinic acid, palladium chloride and formic acid, wherein the molar ratio of the chloroplatinic acid to the palladium chloride to the formic acid is 1:1:6, standing at room temperature for 96h, taking out the gas diffusion layer after the solution is completely transparent, washing with deionized water for 5 times, and drying at 70 ℃ for 12h to obtain the catalyst loading of 0.2mg cm-2Then evenly dripping a proton conductor Nafion solution on the surface of the catalytic layer, wherein the mass ratio of the catalyst to Nafion is1:1, standing at room temperature for more than 12h to uniformly distribute Nafion in the catalyst, and drying at 70 ℃ for 2h to obtain the electrode with the polygonal diamond platinum-palladium catalyst growing on the gas diffusion layer in situ.
Preparing a membrane electrode and assembling a battery: the conventional electrode prepared in step (2) of comparative example 1 (platinum loading 0.2mg cm)-2) Taking the polygonal diamond platinum-palladium electrode prepared in the step (2) as an anode, taking the polygonal diamond platinum-palladium electrode as a cathode, separating the polygonal diamond platinum-palladium electrode by using a Nafion 211 membrane treated by hydrogen peroxide and sulfuric acid, and carrying out hot pressing for 5min by using a hot press to obtain a membrane electrode;
and (3) testing the discharge performance: after the membrane electrode was assembled in a single cell system, a discharge test was performed. The test conditions were: the working temperature of the battery is 70 ℃, the relative humidity is 100 percent, the pressure is normal, hydrogen is introduced into the anode, oxygen is introduced into the cathode, and the flow rates are 100SCCM and 150SCCM respectively. Under the working voltage of 0.6V, the current density can reach 1.1A cm-2The maximum power density reaches 0.81W cm-2。
Example 2
The polygonal diamond platinum-palladium catalyst was prepared with a platinum to palladium atomic ratio of 3:1, other relevant parameters in the membrane electrode were the same as in example 1, and cell test conditions were the same as in example 1.
Under the working voltage of 0.6V, the current density can reach 1.0A cm-2The maximum power density reaches 0.76W cm-2。
Example 3
The polygonal diamond platinum-palladium catalyst was prepared with a platinum to palladium atomic ratio of 1:3, other relevant parameters in the membrane electrode were the same as in example 1, and the cell test conditions were the same as in example 1.
Under the working voltage of 0.6V, the current density can reach 1.1A cm-2The maximum power density reaches 0.70W cm-2。
Example 4
The loading capacity of the catalyst for preparing the polygonal diamond platinum palladium is 0.1mg cm-2Other relevant parameters in the membrane electrode were the same as in example 1, and the cell test conditions were the same as in example 1.
Under the working voltage of 0.6V, the current density can reach 1.0A cm-2The maximum power density reaches 0.76W cm-2。
Example 5
The loading capacity of the catalyst for preparing the polygonal diamond platinum palladium is 0.3mg cm-2Other relevant parameters in the membrane electrode were the same as in example 1, and the cell test conditions were the same as in example 1.
Under the working voltage of 0.6V, the current density can reach 0.7A cm-2The maximum power density reaches 0.64W cm-2。
Example 6
The precursor of the platinum-palladium alloy catalyst prepared in situ is platinum chloride and palladium chloride, the reducing agent is formic acid, the surfactant is cetyl trimethyl ammonium bromide, the molar ratio of the platinum chloride to the palladium chloride to the formic acid to the cetyl trimethyl ammonium bromide is 1:1:6:3, other relevant parameters in the membrane electrode are the same as those in the example 1, and the cell test conditions are the same as those in the example 1.
Under the working voltage of 0.6V, the current density can reach 1.2A cm-2The maximum power density reaches 0.85W cm-2。
Example 7
The precursors for preparing the platinum-palladium alloy catalyst in situ are platinum chloride and palladium chloride, the reducing agent is ascorbic acid, the molar ratio of the platinum chloride to the palladium chloride to the ascorbic acid is 1:1:3, other relevant parameters in the membrane electrode are the same as those in the embodiment 1, and the battery test conditions are the same as those in the embodiment 1.
Under the working voltage of 0.6V, the current density can reach 0.9A cm-2The maximum power density reaches 0.71W cm-2。
Example 8
The precursors of the platinum-palladium alloy catalyst prepared in situ are acetylacetone platinum and acetylacetone palladium, the reducing agent is ascorbic acid, the molar ratio of the acetylacetone platinum to the acetylacetone palladium to the ascorbic acid is 1:1:3, other relevant parameters in the membrane electrode are the same as those in the embodiment 1, and the cell test conditions are the same as those in the embodiment 1.
Under the working voltage of 0.6V, the current density can reach 1.0A cm-2The maximum power density reaches 0.74W cm-2。
Example 9
The precursors for preparing the platinum-palladium alloy catalyst in situ are acetylacetone platinum and acetylacetone palladium, the reducing agent is ascorbic acid, the surfactant is polyvinylpyrrolidone, the molar ratio of the acetylacetone platinum to the acetylacetone palladium to the ascorbic acid to the polyvinylpyrrolidone is 1:1:3:3, other relevant parameters in the membrane electrode are the same as those in the embodiment 1, and the cell test conditions are the same as those in the embodiment 1.
Under the working voltage of 0.6V, the current density can reach 1.1A cm-2The maximum power density reaches 0.79W cm-2。
Example 10
Precursors for preparing the platinum-palladium alloy catalyst in situ are potassium chloroplatinate and potassium chloropalladate, other relevant parameters in the membrane electrode are the same as those in the embodiment 1, and the cell test conditions are the same as those in the embodiment 1.
Under the working voltage of 0.6V, the current density can reach 1.0A cm-2The maximum power density reaches 0.77W cm-2。
Comparative example 1
And preparing the acidic polyelectrolyte membrane fuel cell with a conventional catalytic structure, and performing a discharge test. The fuel cell anode and cathode both use conventional electrodes and the procedure is as follows:
(1) preparation of conventional electrode: weighing a proper amount of 40 wt% of Pt/C and Nafion, dispersing the Pt/C, Nafion and the isopropanol in an isopropanol dispersion liquid, wherein the mass volume ratio of the Pt/C to the Nafion to the isopropanol is 7mg:3mg:5mL, uniformly spraying the Pt/C to the Nafion to the surface of the gas diffusion layer in the step (2) in the example 1 by ultrasonic waves, drying the mixture for 2 hours at 70 ℃, taking out the dried mixture, cooling and weighing the dried mixture to obtain the Pt catalyst loading capacity of 0.2mg cm-2A conventional electrode of (1);
(2) preparation of conventional membrane electrode and assembly of cell: taking two conventional electrodes prepared in the step (2) as a cathode and an anode of the battery respectively, separating the two conventional electrodes by using a Nafion 211 membrane treated by hydrogen peroxide and sulfuric acid, and carrying out hot pressing for 5min by using a hot press to obtain a conventional membrane electrode;
(3) and (3) testing the discharge performance: after the membrane electrode was assembled in a single cell system, a discharge test was performed. The test conditions were: the working temperature of the battery is 70 ℃, the relative humidity is 100 percent, the pressure is normal, hydrogen is introduced into the anode, oxygen is introduced into the cathode, and the flow rates are 100SCCM and 150SCCM respectively. At 0Under the working voltage of 6V, the current density can reach 0.9A cm-2The maximum power density reaches 0.72W cm-2。
Comparative example 2
A platinum catalyst was prepared with the only difference that chloroplatinic acid was added and no palladium chloride was added, and the preparation procedure was the same as in example 1. Under the working voltage of 0.6V, the current density can reach 1.0A cm-2The maximum power density reaches 0.75W cm-2。
Comparative example 3
A palladium catalyst was prepared with the only difference that only palladium chloride was added and no chloroplatinic acid was added, and the procedure was the same as in example 1. Under the working voltage of 0.6V, the current density can reach 0.8A cm-2The maximum power density reaches 0.68W cm-2。
As can be seen from the comparative example, the fuel cell electrode in which the polygonal rhombus platinum palladium catalyst is grown on the gas diffusion layer in situ has better performance, which shows that the platinum palladium alloy catalyst and the in-situ electrode preparation method have excellent promotion effects on the electrochemical reaction efficiency and the cell performance.
It should be noted that, according to the embodiments of the present invention, those skilled in the art can fully implement the full scope of the independent claims and the dependent claims, and implement the processes and methods as the above embodiments; and the invention has not been described in detail so as not to obscure the present invention. The above description is only a partial embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes that can be easily conceived by those skilled in the art within the technical scope of the present invention should be covered within the scope of the present invention.

Claims (10)

1. A preparation method of a platinum-palladium alloy catalyst growing on a gas diffusion layer in situ is characterized by comprising the following steps:
(1) washing the cut carbon paper or carbon cloth in boiling acetone, taking out, soaking in a polytetrafluoroethylene dispersion liquid for full soaking, drying at 70 ℃ for 2h, sintering at 300-450 ℃ for 15-60 min, and performing hydrophobic treatment, wherein the content of polytetrafluoroethylene is 10-15 wt% of that of the carbon paper or carbon cloth;
(2) adding the carbon powder and the polytetrafluoroethylene dispersion liquid which are subjected to acid treatment into isopropanol, performing ultrasonic dispersion to obtain uniform slurry, uniformly spraying the slurry on one side of carbon paper or carbon cloth subjected to hydrophobic treatment, drying at 70 ℃ for 2h, and sintering at 300-450 ℃ for 15-60 min to obtain a gas diffusion layer; wherein the mass-volume ratio of the carbon powder to the polytetrafluoroethylene dispersion to the isopropanol is 15-20 mg: 2-5 mg: 2-10 mL, and the carbon powder loading capacity is 2-2.5 mg cm-2；
(3) Uniformly dispersing Pt/C and Nafion in isopropanol, uniformly spraying the mixture on the surface of a gas diffusion layer, and drying at 70 ℃ for 2 hours to obtain the gas diffusion layer containing a platinum layer, wherein the mass-volume ratio of the Pt/C to the Nafion to the isopropanol is 5-10 mg: 2-5 mg: 2-10 mL, and the platinum loading amount in the platinum layer is 0.005-0.01 mg cm-2；
(4) Placing a gas diffusion layer containing a platinum layer at the bottom of a container, enabling the platinum layer to face upwards, sequentially adding water, a platinum and palladium precursor, a reducing agent and a surfactant, standing, taking out after complete reaction, washing with water, and drying at 70 ℃ for 2 hours to obtain a platinum-palladium alloy catalyst layer, wherein the molar volume ratio of the platinum and palladium precursor, the reducing agent, the surfactant and the water is 1-2 mmol: 2-4 mmol: 5-20 mL, preferably 1mmol:3mmol:2mmol:10 mL; then uniformly dripping 0.1-0.5 mg cm of catalyst layer on the surface of the catalyst layer-2Standing the proton conductor solution for 12h, and drying the proton conductor solution for 2h at 70 ℃ to obtain the platinum-palladium alloy catalyst growing on the gas diffusion layer in situ.
2. The method of preparing a platinum-palladium alloy catalyst grown in situ on a gas diffusion layer according to claim 1, wherein: sintering at 370 ℃ for 30min as described in step (1).
3. The method of preparing a platinum-palladium alloy catalyst grown in situ on a gas diffusion layer according to claim 1, wherein: the mass-volume ratio of the carbon powder, the polytetrafluoroethylene dispersion liquid and the isopropanol in the step (2) is 17mg:3mg:5 mL.
4. The method of preparing a platinum-palladium alloy catalyst grown in situ on a gas diffusion layer according to claim 1, wherein: and (3) sintering at 370 ℃ for 30min in the step (2) to obtain the gas diffusion layer.
5. The method of preparing a platinum-palladium alloy catalyst grown in situ on a gas diffusion layer according to claim 1, wherein: the mass-to-volume ratio of Pt/C to Nafion to isopropanol in step (3) was 7mg to 3mg to 5 mL.
6. The method of preparing a platinum-palladium alloy catalyst grown in situ on a gas diffusion layer according to claim 1, wherein: the platinum precursor in the step (4) is any one of chloroplatinic acid, potassium chloroplatinate, platinum chloride, platinum acetylacetonate or sodium chloroplatinite, and preferably chloroplatinic acid; the palladium precursor is any one of palladium chloride, sodium tetrachloropalladate, palladium acetylacetonate or potassium chloropalladate, and palladium chloride is preferred.
7. The method of preparing a platinum-palladium alloy catalyst grown in situ on a gas diffusion layer according to claim 1, wherein: in the platinum and palladium precursors in the step (4), the molar ratio of platinum to palladium is 3: 1-1: 3; the surfactant is any one of cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, polyvinylpyrrolidone or poloxamer; the reducing agent is any one of formic acid, ascorbic acid, sodium citrate or lysine, and formic acid is preferred.
8. A platinum palladium alloy catalyst grown in situ on a gas diffusion layer prepared according to the method of any one of claims 1 to 7.
9. The platinum palladium alloy catalyst grown in situ on a gas diffusion layer according to claim 8, wherein: the shape of the diamond is polygonal rhombus, and the size of the diamond is 100-200 nm.
10. Use of the platinum palladium alloy catalyst according to claim 8 or 9 grown in situ on a gas diffusion layer, wherein: it is applied to the electrode material of the proton exchange membrane fuel cell.
CN202111337137.2A 2021-11-12 2021-11-12 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 Pending CN114188551A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111337137.2A CN114188551A (en) 2021-11-12 2021-11-12 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

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111337137.2A CN114188551A (en) 2021-11-12 2021-11-12 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

Publications (1)

Publication Number Publication Date
CN114188551A true CN114188551A (en) 2022-03-15

Family

ID=80601549

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111337137.2A Pending CN114188551A (en) 2021-11-12 2021-11-12 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

Country Status (1)

Country Link
CN (1) CN114188551A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115216798A (en) * 2022-07-13 2022-10-21 大连理工大学 Anode gas diffusion layer and preparation method and application thereof

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1581548A (en) * 2004-05-14 2005-02-16 武汉理工大学 Unit combined fuel cell membrane eletrode and its preparing method
CN101083325A (en) * 2007-07-03 2007-12-05 中国科学院上海微***与信息技术研究所 Method for preparing nano-Pd or Pd platinum alloy electrocatalyst for fuel cell
US20080070777A1 (en) * 2006-09-19 2008-03-20 Jang Bor Z Process for producing fuel cell electrode, catalyst-coated membrane and membrane-electrode assembly
US20140186748A1 (en) * 2011-05-13 2014-07-03 Industry-Academic Cooperation Foundation, Yonsei University Method for producing alloy catalyst for fuel cells using silica coating
CN104716333A (en) * 2013-12-15 2015-06-17 中国科学院大连化学物理研究所 Ordered gas diffusion electrode, and production method and application thereof
WO2017101132A1 (en) * 2015-12-16 2017-06-22 中国科学院大连化学物理研究所 Ordered membrane electrode, preparation and application thereof
CN107681163A (en) * 2017-09-21 2018-02-09 上海交通大学 A kind of fuel cell membrane electrode and its preparation method and application
CN110854403A (en) * 2019-10-24 2020-02-28 江苏大学 High-temperature membrane fuel cell electrode capable of relieving loss of phosphoric acid electrolyte and preparation method thereof
CN112331858A (en) * 2020-10-30 2021-02-05 江苏大学 Fuel cell electrode with catalyst in-situ grown on ordered structure microporous layer and preparation method of membrane electrode
CN112382767A (en) * 2020-10-26 2021-02-19 江苏大学 Fuel cell electrode in-situ preparation method based on double-layer ordered structure microporous layer
CN113363507A (en) * 2020-07-21 2021-09-07 河海大学 Preparation method of titanium carbide supported platinum-palladium nanoflower electrode catalyst

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1581548A (en) * 2004-05-14 2005-02-16 武汉理工大学 Unit combined fuel cell membrane eletrode and its preparing method
US20080070777A1 (en) * 2006-09-19 2008-03-20 Jang Bor Z Process for producing fuel cell electrode, catalyst-coated membrane and membrane-electrode assembly
CN101083325A (en) * 2007-07-03 2007-12-05 中国科学院上海微***与信息技术研究所 Method for preparing nano-Pd or Pd platinum alloy electrocatalyst for fuel cell
US20140186748A1 (en) * 2011-05-13 2014-07-03 Industry-Academic Cooperation Foundation, Yonsei University Method for producing alloy catalyst for fuel cells using silica coating
CN104716333A (en) * 2013-12-15 2015-06-17 中国科学院大连化学物理研究所 Ordered gas diffusion electrode, and production method and application thereof
WO2017101132A1 (en) * 2015-12-16 2017-06-22 中国科学院大连化学物理研究所 Ordered membrane electrode, preparation and application thereof
CN107681163A (en) * 2017-09-21 2018-02-09 上海交通大学 A kind of fuel cell membrane electrode and its preparation method and application
CN110854403A (en) * 2019-10-24 2020-02-28 江苏大学 High-temperature membrane fuel cell electrode capable of relieving loss of phosphoric acid electrolyte and preparation method thereof
CN113363507A (en) * 2020-07-21 2021-09-07 河海大学 Preparation method of titanium carbide supported platinum-palladium nanoflower electrode catalyst
CN112382767A (en) * 2020-10-26 2021-02-19 江苏大学 Fuel cell electrode in-situ preparation method based on double-layer ordered structure microporous layer
CN112331858A (en) * 2020-10-30 2021-02-05 江苏大学 Fuel cell electrode with catalyst in-situ grown on ordered structure microporous layer and preparation method of membrane electrode

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
WEI SUN等: ""Improving cell performance and alleviating performance degradation by constructing a novel structure of membrane electrode assembly (MEA) of DMFCs"", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 *
朱红等: "质子交换膜燃料电池用碳纳米管载铂催化剂的研究", 《电化学》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115216798A (en) * 2022-07-13 2022-10-21 大连理工大学 Anode gas diffusion layer and preparation method and application thereof

Similar Documents

Publication Publication Date Title
JP4590937B2 (en) Electrode catalyst and method for producing the same
CN111129508B (en) Transition metal doped platinum-carbon catalyst and preparation method and application thereof
CA2591040C (en) Electrode catalyst for fuel cell
KR101270809B1 (en) Platinum alloy carbon-supported catalysts
US20220140354A1 (en) Fuel cell electrode with catalysts grown in situ on ordered structure microporous layer and method for preparing membrane electrode assembly
US20090291352A1 (en) Electrode material
KR100868756B1 (en) Pt/Ru alloy supported catalyst, manufacturing method thereof, and fuel cell using the same
CN108539206B (en) Catalysis layer full-order fuel cell electrode and membrane electrode
CN112382767B (en) Fuel cell electrode in-situ preparation method based on double-layer ordered structure microporous layer
CN111162299A (en) Method for preparing membrane electrode of low-temperature proton exchange membrane fuel cell
Sugita et al. Connected iridium nanoparticle catalysts coated onto silica with high density for oxygen evolution in polymer electrolyte water electrolysis
CN111244480B (en) Carbon-supported palladium-based alloy fuel cell membrane electrode and preparation method thereof
US9466843B2 (en) Electrode catalyst and method of preparing electrode catalyst for fuel cell, and membrane electrode assembly and fuel cell including same
Tatus-Portnoy et al. A low-loading Ru-rich anode catalyst for high-power anion exchange membrane fuel cells
KR100823505B1 (en) Catalyst for fuel cell, method of preparing same membrane-electrode assembly for fuel cell and fuel cell system femprising same
KR100561169B1 (en) Oxygen adsorbing cocatalyst containg catalyst for fuel cell, electrode for fuel cell using the same, and fuel cell containing the electrode
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
JP2005100713A (en) Electrode catalyst for fuel cell and manufacturing method thereof
CN112701308A (en) Preparation method of fuel cell catalyst with high durability
KR102108646B1 (en) Pt complex catalyst electrode with triple catalyst layers for direct methanol fuel cell and preparation method thereof
Yang et al. The application of Ir–V/C catalyst as a durable anode catalyst for a 1.5 kW proton exchange membrane fuel cell stack
CN114335577A (en) Modified catalyst, membrane electrode, preparation method of membrane electrode and fuel cell
CN110224148B (en) Pt or Au modified porous PdFe intermetallic compound and preparation method and application thereof
CN110931808A (en) Pd-WO3Anode electrocatalyst of/C proton exchange membrane fuel cell and its preparing method and use
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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20220315