CN111244480B - Carbon-supported palladium-based alloy fuel cell membrane electrode and preparation method thereof - Google Patents

Carbon-supported palladium-based alloy fuel cell membrane electrode and preparation method thereof Download PDF

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CN111244480B
CN111244480B CN202010069555.7A CN202010069555A CN111244480B CN 111244480 B CN111244480 B CN 111244480B CN 202010069555 A CN202010069555 A CN 202010069555A CN 111244480 B CN111244480 B CN 111244480B
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palladium
based alloy
carbon
fuel cell
membrane electrode
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CN111244480A (en
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李恒毅
陈宣良
何孝定
周文
萨百晟
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Fujian Zhuoyi Energy Technology Development Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—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
    • 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
    • H01M4/881—Electrolytic membranes
    • 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
    • H01M4/886—Powder spraying, e.g. wet or dry powder spraying, plasma spraying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention relates to the technical field of fuel cells, in particular to a carbon-supported palladium-based alloy fuel cell membrane electrode and a preparation method thereof. The multi-walled carbon nanotube or single-walled carbon nanotube carrier loaded with palladium-based alloy is used as a first catalytic layer, the multi-walled carbon nanotube or single-walled carbon nanotube carrier loaded with platinum catalyst is used as a second catalytic layer, and the multi-walled carbon nanotube or single-walled carbon nanotube carrier is respectively sprayed on two surfaces of a proton exchange membrane to prepare the membrane electrode of the proton exchange membrane fuel cell. The membrane electrode of the proton exchange membrane fuel cell obtained by the invention can be used as a cathode and an anode, thereby greatly reducing the identification workload in the subsequent production process of the electrode (cell) stack combination of the membrane electrode group and improving the production efficiency. And the palladium-based alloy catalyst is used as a catalyst layer, so that the cost of the membrane electrode of the proton exchange membrane fuel cell is greatly reduced, and the palladium-based alloy catalyst has wide application prospects in methanol fuel cells and small portable hydrogen fuel cells.

Description

Carbon-supported palladium-based alloy fuel cell membrane electrode and preparation method thereof
Technical Field
The invention relates to the technical field of fuel cells, in particular to a carbon-supported palladium-based alloy fuel cell membrane electrode and a preparation method thereof.
Background
Fuel cells are devices that directly convert chemical energy into electrical energy, and are considered to be the most promising renewable energy source to replace conventional fossil fuels because of their advantages of high energy conversion efficiency, environmental friendliness, high energy density, and the like. At present, the catalytic layer of the fuel cell key material membrane electrode is mainly platinum or its alloy nanometer catalyst. However, platinum resources are scarce and expensive, and the adoption of a non-platinum catalyst with high catalytic activity and high stability as a catalytic layer of a membrane electrode is a key for realizing the commercialization of a fuel cell. Currently, non-platinum catalyst materials include non-platinum noble metals, chalcogen metal catalysts, transition metal nitrogen-containing compounds, and the like.
The high cost and the service life of the platinum-based catalyst are two major factors that limit the large scale application of the platinum-based catalyst to fuel cells. The first is that the cost of platinum is too high. The platinum is low in reserve and expensive, and the cost accounts for about 30-45% of the total cost. Therefore, reducing the amount of platinum or increasing the utilization rate of platinum, and developing a non-platinum catalyst instead of platinum, while maintaining relatively high catalytic activity, are one of the problems that are urgently needed to be solved. The dosage of platinum at the cathode end in the test of fuel cell vehicles by the U.S. department of energy reaches 0.4mg/cm 2These catalysts still have short lifetimes, substantially less than 5000 hours, which are not practical. How to reduce the amount of platinum used at the cathode end to less than 0.1mg/cm without sacrificing performance and life2Therefore, reducing the cost of the battery is a major issue in the current research on catalysts. The aim currently put forward in China is to ensure that the carrying capacity (cathode + anode) of platinum on the electrodes in the membrane electrode assembly is less than 0.125mg/cm2And the power density of the galvanic pile formed by the membrane electrode assembly can reach 8kW/g Pt, so that if 8g Pt is used in one vehicle, the efficiency of the vehicle can be similar to that of the vehicle using the internal combustion engine at present. Secondly, the problems of short service life and poisoning resistance of the platinum-based catalyst are difficult to solve. In the process of hydrogen production, due to the existence of impurities such as carbon oxides, sulfur oxides or nitrogen oxides, platinum is easy to be poisoned to cause activity reduction; the redox reaction generated at the cathode of the PEMFC has high overpotential, most metals are unstable in aqueous solution, oxygen or a plurality of oxygen-containing ions are easily adsorbed on the surface of an electrode or an oxide film is generated, and platinum is easily oxidized to reduce the activity.
Disclosure of Invention
In view of the above technical problems in the background art, it is desirable to provide a membrane electrode for a carbon-supported palladium-based alloy fuel cell and a method for preparing the same, wherein the membrane electrode for a carbon-supported palladium-based alloy fuel cell at least needs to have the problems of low cost, long catalyst life and low catalyst poisoning; the preparation method has the advantages of easily obtained raw materials, simple process and simple and convenient operation.
In order to achieve the above object, in a first aspect of the present invention, the inventors provide a palladium-on-carbon-based alloy fuel cell membrane electrode, including a first catalytic layer, a proton exchange membrane, and a second catalytic layer connected in sequence, where the first catalytic layer includes a carrier and a palladium-based alloy supported on an outer surface and/or an inner portion of the carrier, and a mass fraction of the palladium-based alloy is 15 to 60% based on a mass of the first catalytic layer; the second catalytic layer comprises the carrier and a platinum catalyst loaded on the outer surface and/or inside of the carrier, and the mass fraction of the platinum catalyst is 20-60% based on the mass of the second catalytic layer.
In a second aspect of the present invention, the inventors provide a method for preparing a membrane electrode for a palladium-on-carbon-based alloy fuel cell, comprising the steps of:
preparing slurry: respectively adding a first catalytic layer material and a second catalytic layer material into deionized water and an ethanol solution, adding a perfluorosulfonic acid polymer solution, and fully mixing to obtain a first catalytic layer slurry and a second catalytic layer slurry;
spraying: respectively spraying the first catalyst layer slurry and the second catalyst layer slurry on two surfaces of a proton exchange membrane to obtain a sprayed proton exchange membrane;
Drying: drying the sprayed proton exchange membrane to obtain the carbon-supported palladium-based alloy fuel cell membrane electrode, wherein the first catalytic layer is made of a material comprising a carrier and a palladium-based alloy loaded on the outer surface and/or the inner part of the carrier, and the palladium-based alloy is selected from PdxCuy、PdxCoyOr PdxNiyWherein, 1 is<x<5，1<y<5; the second catalytic layer materialThe catalyst comprises the carrier and a platinum catalyst loaded on the outer surface and/or the inner part of the carrier, wherein the carrier is a multi-wall carbon nanotube or a single-wall carbon nanotube.
Different from the prior art, the technical scheme at least has the following beneficial effects:
the invention adopts the multi-walled carbon nanotube or single-walled carbon nanotube carrier loaded with palladium-based alloy as the first catalytic layer, the multi-walled carbon nanotube or single-walled carbon nanotube carrier loaded with platinum catalyst as the second catalytic layer, and the first catalytic layer and the second catalytic layer are respectively sprayed on the two surfaces of the proton exchange membrane to prepare the membrane electrode of the proton exchange membrane fuel cell. The most important point is that the membrane electrode of the proton exchange membrane fuel cell obtained by the method can be used as a cathode and an anode, so that the identification workload in the process of the combined production of the electrode (cell) stack of the subsequent membrane electrode group is greatly reduced, the assembly error is avoided, and the production efficiency is improved. And the palladium-based alloy catalyst is used as a catalyst layer, so that the cost of the membrane electrode of the proton exchange membrane fuel cell is greatly reduced, and the palladium-based alloy catalyst has wide application prospects in methanol fuel cells and small portable hydrogen fuel cells.
Drawings
FIG. 1 is a fuel cell polarization curve of the membrane electrode obtained in example 1 measured under hydrogen-oxygen conditions, at a fuel humidity of 20%, without back pressure, and at 80 ℃;
FIG. 2 is a polarization curve of the fuel cell measured at 80 ℃ under hydrogen-oxygen conditions with the membrane electrode obtained in example 2 and with a fuel humidity of 20% and no back pressure;
FIG. 3 is a polarization curve of the fuel cell measured at 80 ℃ under hydrogen-oxygen conditions with the membrane electrode obtained in example 3 and with a fuel humidity of 20% and no back pressure;
FIG. 4 is a polarization curve of the fuel cell measured at 80 ℃ under hydrogen-oxygen conditions with 20% fuel humidity and no back pressure for the membrane electrode obtained in example 4;
FIG. 5 is a polarization curve of the fuel cell measured at 80 ℃ under hydrogen-oxygen conditions with 20% fuel humidity and no back pressure for the membrane electrode obtained in example 5.
Detailed Description
The following describes in detail a membrane electrode for a palladium-on-carbon-based alloy fuel cell according to the first aspect of the present invention and a method for producing a membrane electrode for a palladium-on-carbon-based alloy fuel cell according to the second aspect of the present invention.
A description will first be given of a membrane electrode for a palladium-on-carbon-based alloy fuel cell according to the first aspect of the invention. A palladium-on-carbon-based alloy fuel cell membrane electrode comprises a first catalytic layer, a proton exchange membrane and a second catalytic layer which are sequentially connected, wherein the first catalytic layer comprises a carrier and a palladium-based alloy loaded on the outer surface and/or the inner part of the carrier, and the mass fraction of the palladium-based alloy is 15-60% by taking the mass of the first catalytic layer as a reference; the second catalytic layer comprises the carrier and a platinum catalyst loaded on the outer surface and/or inside of the carrier, and the mass fraction of the platinum catalyst is 20-60% based on the mass of the second catalytic layer.
The fuel cell is a Proton Exchange Membrane Fuel Cell (PEMFC), and a single cell of the PEMFC consists of an anode, a cathode and a proton exchange membrane, wherein the anode is a place for oxidizing hydrogen fuel, the cathode is a place for reducing an oxidant, both electrodes contain a catalyst for accelerating electrochemical reaction of the electrodes, and the proton exchange membrane is used for transferring H+Medium of (2), allowing only H+By, H2The lost electrons pass through the wire. The proton exchange membrane fuel cell is equivalent to a direct current power supply when working, wherein the anode is the negative pole of the power supply, and the cathode is the positive pole of the power supply. The carbon-supported palladium-based alloy fuel cell membrane electrode provided by the invention is as follows: two opposite surfaces of the proton exchange membrane are respectively sprayed with a first catalytic layer of carbon-supported palladium-based alloy and a second catalytic layer of carbon-supported platinum-based alloy to obtain membrane electrodes.
Preferably, the palladium-based alloy of the present invention is selected from PdxCuy、PdxCoyOr PdxNiyWherein, 1 is<x<5，1<y<5. The palladium-based alloy used in the present invention is mainly an alloy of palladium and copper, cobalt, nickel, and may be, for example, but not limited to, PdCu, Pd2Cu、Pd3Cu、PdCo、Pd2Co、Pd3Co、PdNi、Pd2Ni or Pd3Ni。
In a more preferred embodiment, the palladium-based alloy is Pd2Co。
Preferably, the palladium loading capacity of the membrane electrode of the carbon-supported palladium-based alloy fuel cell is 0.1-0.4mg/cm 2。
Preferably, the platinum loading of the membrane electrode of the carbon-supported palladium-based alloy fuel cell is 0.1-0.2mg/cm2。
Preferably, the carrier of the present invention is a multi-walled carbon nanotube or a single-walled carbon nanotube. More preferably, the multi-walled or single-walled carbon nanotubes are Vulcan XC72, Vulcan XC72R or BP 2000.
Next, a method for preparing a membrane electrode for a carbon-supported palladium-based alloy fuel cell according to a second aspect of the present invention will be described.
A preparation method of a carbon-supported palladium-based alloy fuel cell membrane electrode comprises the following steps:
preparing slurry: respectively adding a first catalytic layer material and a second catalytic layer material into deionized water and an ethanol solution, adding a perfluorosulfonic acid polymer solution, and fully mixing to obtain a first catalytic layer slurry and a second catalytic layer slurry;
spraying: respectively spraying the first catalyst layer slurry and the second catalyst layer slurry on two surfaces of a proton exchange membrane to obtain a sprayed proton exchange membrane;
drying: drying the sprayed proton exchange membrane to obtain the carbon-supported palladium-based alloy fuel cell membrane electrode, wherein the first catalytic layer is made of a material comprising a carrier and a palladium-based alloy loaded on the outer surface and/or the inner part of the carrier, and the palladium-based alloy is selected from Pd xCuy、PdxCoyOr PdxNiyWherein, 1 is<x<5，1<y<5, for example, in various embodiments, the palladium-based alloy is PdCo, Pd2Co or Pd3Co, in a more preferred embodiment, the palladium-based alloy is Pd2Co; the second catalytic layer material comprises the carrier and a catalyst layer loaded on the outer surface of the carrierAnd/or an internal platinum catalyst, wherein the carrier is a multi-wall carbon nanotube or a single-wall carbon nanotube.
Preferably, the mass ratio of the first catalytic layer material to the perfluorosulfonic acid polymer solution is (50-95): 50-5; the mass ratio of the second catalytic layer material to the perfluorosulfonic acid polymer solution is (50-95) to (50-5).
Preferably, the deionized water and the ethanol solution of the invention are prepared from the following components in a volume ratio of (10-50): (90-50) mixing deionized water and ethanol.
To explain technical contents, structural features, and objects and effects of the technical solutions in detail, the following detailed description is given with reference to the accompanying drawings in conjunction with the embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application.
The perfluorosulfonic acid polymer solution used in the embodiment of the present invention is Nafion-212 solution manufactured by dupont, and in different embodiments, the solution may also be selected from Nafion-112, Nafion-115, Nafion-117, Nafion-211, and the like. The Vulcan XC72, Vulcan XC72R and BP2000 employed in the present invention were purchased from Cabot.
Pd used in the invention2The preparation method of Co/C is as follows:
adding a certain amount of carbon black and cobalt acetate into an ethanol solution to form a mixed solution, carrying out ultrasonic treatment for 10-60 min, and stirring for 10-60 min. Reducing cobalt acetate by using an alkaline solution (5-10 ml) of sodium borohydride at 80 ℃, and keeping the temperature for 0.5-1 h. Adding the potassium chloropalladate ethanol solution into the mixed solution, enabling the volume ratio of the potassium chloropalladate ethanol solution to the cobalt acetate ethanol solution to be 20:10, and preserving heat for 3-5 hours at 80 ℃. Centrifuging, and drying in a drying oven for 24h to obtain carbon-supported Pd2Co/C catalyst.
Carbon-supported PdCo catalyst and carbon-supported Pd3Preparation method of Co catalyst and carbon-supported Pd2The difference of the preparation method of the Co catalyst is that the volume ratio of the potassium chloropalladate ethanol solution to the cobalt acetate ethanol solution is respectively adjusted to 10:10 and 30: 10.
The polarization curve of the fuel cell in the invention is measured by the membrane electrode under the hydrogen-oxygen atmosphere, the fuel humidity is 20%, no back pressure is generated, and the temperature is 80 ℃.
Embodiment 1 a method for preparing a carbon-supported palladium-based alloy fuel cell membrane electrode
(1) Adding a carbon-supported platinum catalyst with the mass fraction of 20% of platinum and the carrier Vulcan-XC72R into a mixed solution of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 10:90), adding a platinum catalyst and a Nafion-212 solution with the mass fraction of 5%, magnetically stirring for 1 hour, ultrasonically dispersing for 1 hour, and preparing carbon-supported platinum catalytic slurry, so that the mass ratio of the carbon-supported platinum to the Nafion in the suspension is 60: 40;
(2) And (2) uniformly spraying the carbon-supported platinum catalytic slurry obtained in the step (1) on one surface of a Nafion-212 membrane by using an ultrasonic spraying instrument to prepare a cathode catalytic layer, and drying in a vacuum drying oven. The spraying time is 30 minutes, the temperature is 85 ℃, and the platinum loading capacity is 0.1mg/cm2；
(3) Palladium-based alloy catalyst (Pd)2Co/C, the carrier is BP2000) is added into a mixed solution of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 10:90), then Nafion solution with the mass fraction of 5 percent is added, magnetic stirring is carried out for 1 hour, ultrasonic dispersion is carried out for 1 hour, and palladium-based alloy catalytic slurry is prepared, so that the mass ratio of the palladium on carbon to the Nafion in the suspension is 60: 40;
(4) and (4) uniformly spraying the palladium-based alloy catalytic slurry obtained in the step (3) on the other surface of the Nafion-212 membrane by using an ultrasonic spraying instrument to prepare an anode catalytic layer, and drying in a vacuum drying oven to obtain the complete membrane electrode. The spraying time is 60 minutes, the temperature is 85 ℃, and the loading capacity of the metal palladium is 0.1mg/cm2。
Referring to fig. 1, the membrane electrode of the pd-on-carbon based alloy fuel cell obtained in this example has a corresponding current density of 2603mA cm at a voltage of 0.4V-2Maximum power density of 331.5mW cm-2。
EXAMPLE 2 preparation of another carbon-supported Palladium-based alloy Fuel cell Membrane electrode
(1) Adding a carbon-supported platinum catalyst with platinum mass percent of 60% and Vulcan-XC72 as a carrier into a mixed solution of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 10:90), adding a platinum catalyst and 5% of Nafion-212 solution, magnetically stirring for 1 hour, ultrasonically dispersing for 1 hour, and preparing carbon-supported platinum catalytic slurry, so that the mass ratio of the carbon-supported platinum to the Nafion in the suspension is 50: 50;
(2) And (2) uniformly spraying the carbon-supported platinum catalytic slurry obtained in the step (1) on one surface of a Nafion-212 membrane by using an ultrasonic spraying instrument to prepare a cathode catalytic layer, and drying in a vacuum drying oven. The spraying time is 30 minutes, the temperature is 85 ℃, and the platinum loading capacity is 0.125mg/cm2；
(3) Palladium-based alloy catalyst (Pd)2Co/C, the carrier is BP2000) is added into a mixed solution of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 10:90), then Nafion solution with the mass fraction of 5 percent is added, magnetic stirring is carried out for 1 hour, ultrasonic dispersion is carried out for 1 hour, and palladium-based alloy catalytic slurry is prepared, so that the mass ratio of the palladium on carbon to the Nafion in the suspension is 60: 40;
(4) and (4) uniformly spraying the palladium-based alloy catalytic slurry obtained in the step (3) on the other surface of the Nafion-212 membrane by using an ultrasonic spraying instrument to prepare an anode catalytic layer, and drying in a vacuum drying oven to obtain a complete membrane electrode. The spraying time is 60 minutes, the temperature is 85 ℃, and the metal palladium loading capacity is 0.2mg/cm2。
Referring to fig. 2, the membrane electrode of the pd-on-carbon based alloy fuel cell obtained in this example has a current density of 3670mA cm at a voltage of 0.4V-2Maximum power density of 422mW cm-2。
EXAMPLE 3 preparation of another carbon-supported Palladium-based alloy Fuel cell Membrane electrode
(1) Adding a carbon-supported platinum catalyst with platinum mass percent of 50% and Vulcan-XC72 as a carrier into a mixed solution of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 20:80), adding a platinum catalyst and 5% of Nafion-212 solution, magnetically stirring for 1 hour, ultrasonically dispersing for 1 hour, and preparing carbon-supported platinum catalytic slurry, so that the mass ratio of the carbon-supported platinum to the Nafion in the suspension is 65: 35;
(2) And (3) uniformly spraying the carbon-supported platinum catalytic slurry obtained in the step (1) on one surface of a Nafion-212 membrane by using an ultrasonic spraying instrument to prepare a cathode catalytic layer, and drying in a vacuum drying oven. The spraying time is 30 minutes, the temperature is 85 ℃, and the platinum loading capacity is 0.125mg/cm2；
(3) Palladium-based alloy catalyst (Pd)2Co/C, the carrier is BP2000) is added into a mixed solution of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 20:80), Nafion solution with the mass fraction of 5 percent is added, magnetic stirring is carried out for 1 hour, ultrasonic dispersion is carried out for 1 hour, and palladium-based alloy catalytic slurry is prepared, so that the mass ratio of carbon-supported platinum to Nafion in the suspension is 70: 30;
(4) and (4) uniformly spraying the palladium-based alloy catalytic slurry obtained in the step (3) on the other surface of the Nafion-212 membrane by using an ultrasonic spraying instrument to prepare an anode catalytic layer, and drying in a vacuum drying oven to obtain the complete membrane electrode. The spraying time is 60 minutes, the temperature is 85 ℃, and the loading capacity of the metal palladium is 0.15mg/cm2。
Referring to fig. 3, the current density of the membrane electrode of the carbon-supported palladium-based alloy fuel cell obtained in this embodiment is 3603mA cm at a voltage of 0.4V-2The maximum power density is 421.75mW cm-2。
EXAMPLE 4 preparation of another carbon-supported Palladium-based alloy Fuel cell Membrane electrode
(1) Adding a carbon-supported platinum catalyst with platinum mass percent of 40% and Vulcan-XC72 as a carrier into a mixed solution of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 10:90), adding a platinum catalyst and 5% of Nafion-212 solution, magnetically stirring for 1 hour, ultrasonically dispersing for 1 hour, and preparing carbon-supported platinum catalytic slurry, so that the mass ratio of the carbon-supported platinum to the Nafion in the suspension is 70: 30;
(2) And (2) uniformly spraying the carbon-supported platinum catalytic slurry obtained in the step (1) on one surface of a Nafion-212 membrane by using an ultrasonic spraying instrument to prepare a cathode catalytic layer, and drying in a vacuum drying oven. The spraying time is 30 minutes, the temperature is 85 ℃, and the platinum loading capacity is 0.2mg/cm2；
(3) Palladium-based alloy catalyst (Pd)2Co/C, the carrier is BP2000) is added into a mixed solution of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 10:90), then Nafion solution with the mass fraction of 5 percent is added, magnetic stirring is carried out for 1 hour, ultrasonic dispersion is carried out for 1 hour, and palladium-based alloy catalytic slurry is prepared, so that the mass ratio of the palladium on carbon to the Nafion in the suspension is 70: 30;
(4) and (4) uniformly spraying the palladium-based alloy catalytic slurry obtained in the step (3) on the other surface of the Nafion-212 membrane by using an ultrasonic spraying instrument to prepare an anode catalytic layer, and drying in a vacuum drying oven to obtain the complete membrane electrode. The spraying time is 60 minutes, the temperature is 85 ℃, and the loading capacity of the metal palladium is 0.25mg/cm2。
Referring to fig. 4, the current density of the membrane electrode of the pd-on-carbon-based alloy fuel cell obtained in this embodiment is 3204mA cm when the voltage is 0.4V-2The maximum power density is 418.75mW cm-2。
EXAMPLE 5 preparation of another carbon-supported Palladium-based alloy Fuel cell Membrane electrode
(1) Adding a carbon-supported platinum catalyst with platinum mass percent of 30% and Vulcan-XC72 as a carrier into a mixed solution of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 10:90), adding a platinum catalyst and 5% of Nafion-212 solution, magnetically stirring for 1 hour, ultrasonically dispersing for 1 hour, and preparing carbon-supported platinum catalytic slurry, so that the mass ratio of the carbon-supported platinum to the Nafion in the suspension is 95: 5;
(2) and (3) uniformly spraying the carbon-supported platinum catalytic slurry obtained in the step (1) on one surface of a Nafion-212 membrane by using an ultrasonic spraying instrument to prepare a cathode catalytic layer, and drying in a vacuum drying oven. The spraying time is 30 minutes, the temperature is 85 ℃, and the platinum loading capacity is 0.2mg/cm2；
(3) Palladium-based alloy catalyst (Pd)2Co/C, the carrier is BP2000) is added into a mixed solution of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 10:90), then Nafion solution with the mass fraction of 5 percent is added, magnetic stirring is carried out for 1 hour, ultrasonic dispersion is carried out for 1 hour, and palladium-based alloy catalytic slurry is prepared, so that the mass ratio of the palladium on carbon to the Nafion in the suspension is 95: 5;
(4) and (4) uniformly spraying the palladium-based alloy catalytic slurry obtained in the step (3) on the other surface of the Nafion-212 membrane by using an ultrasonic spraying instrument to prepare an anode catalytic layer, and drying in a vacuum drying oven to obtain the complete membrane electrode. The spraying time is 60 minutes, the temperature is 85 ℃, and the loading capacity of the metal palladium is 0.3mg/cm 2。
Referring to fig. 5, the voltage of the membrane electrode of the carbon-supported palladium-based alloy fuel cell obtained in this embodiment is 0.The corresponding current density is 3805mA cm at 4V voltage-2Maximum power density of 490.5mW cm-2。
EXAMPLE 6 preparation of another carbon-supported Palladium-based alloy Fuel cell Membrane electrode
(1) Adding a carbon-supported platinum catalyst with platinum mass percent of 30% and Vulcan-XC72 as a carrier into a mixed solution of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 10:90), adding a platinum catalyst and 5% of Nafion-212 solution, magnetically stirring for 1 hour, ultrasonically dispersing for 1 hour, and preparing carbon-supported platinum catalytic slurry, so that the mass ratio of the carbon-supported platinum to the Nafion in the suspension is 95: 5;
(2) and (3) uniformly spraying the carbon-supported platinum catalytic slurry obtained in the step (1) on one surface of a Nafion-212 membrane by using an ultrasonic spraying instrument to prepare a cathode catalytic layer, and drying in a vacuum drying oven. The spraying time is 30 minutes, the temperature is 85 ℃, and the platinum loading capacity is 0.15mg/cm2；
(3) Palladium-based alloy catalyst (Pd)3Co, the carrier is BP2000) is added into a mixed solution of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 10:90), then Nafion solution with the mass fraction of 5 percent is added, magnetic stirring is carried out for 1 hour, ultrasonic dispersion is carried out for 1 hour, and palladium-based alloy catalytic slurry is prepared, so that the mass ratio of carbon-supported palladium to Nafion in the suspension is 95: 5;
(4) And (4) uniformly spraying the palladium-based alloy catalytic slurry obtained in the step (3) on the other surface of the Nafion-212 membrane by using an ultrasonic spraying instrument to prepare an anode catalytic layer, and drying in a vacuum drying oven to obtain a complete membrane electrode. The spraying time is 60 minutes, the temperature is 85 ℃, and the metal palladium loading capacity is 0.3mg/cm2。
The membrane electrode of the carbon-supported palladium-based alloy fuel cell obtained in the embodiment has a corresponding current density of 3609mA cm at a voltage of 0.4V-2Maximum power density of 400.5mW cm-2。
EXAMPLE 7 preparation of Another carbon-supported Palladium-based alloy Fuel cell Membrane electrode
(1) Adding a carbon-supported platinum catalyst with platinum mass percent of 30% and Vulcan-XC72 as a carrier into a mixed solution of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 10:90), adding a platinum catalyst and 5% of Nafion-212 solution, magnetically stirring for 1 hour, ultrasonically dispersing for 1 hour, and preparing carbon-supported platinum catalytic slurry, so that the mass ratio of the carbon-supported platinum to the Nafion in the suspension is 95: 5;
(2) and (3) uniformly spraying the carbon-supported platinum catalytic slurry obtained in the step (1) on one surface of a Nafion-212 membrane by using an ultrasonic spraying instrument to prepare a cathode catalytic layer, and drying in a vacuum drying oven. The spraying time is 30 minutes, the temperature is 85 ℃, and the platinum loading capacity is 0.2mg/cm 2；
(3) Adding a palladium-based alloy catalyst (PdCo, the carrier is BP2000) into a mixed solution of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 10:90), adding a Nafion solution with the mass fraction of 5%, magnetically stirring for 1 hour, and ultrasonically dispersing for 1 hour to prepare a palladium-based alloy catalytic slurry, so that the mass ratio of carbon-supported palladium to Nafion in a suspension is 95: 5;
(4) and (4) uniformly spraying the palladium-based alloy catalytic slurry obtained in the step (3) on the other surface of the Nafion-212 membrane by using an ultrasonic spraying instrument to prepare an anode catalytic layer, and drying in a vacuum drying oven to obtain a complete membrane electrode. The spraying time is 60 minutes, the temperature is 85 ℃, and the loading capacity of the metal palladium is 0.4mg/cm2。
The membrane electrode of the carbon-supported palladium-based alloy fuel cell obtained in the embodiment has a corresponding current density of 3720mAcm at a voltage of 0.4V-2The maximum power density is 432.5mW cm-2。
It should be noted that, although the above embodiments have been described herein, the invention is not limited thereto. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein, or by using equivalent structures or equivalent processes performed in the content of the present specification and the attached drawings, which are included in the scope of the present invention.

Claims (7)

1. The membrane electrode of the palladium-on-carbon-based alloy fuel cell is characterized by comprising a first catalytic layer, a proton exchange membrane and a second catalytic layer which are sequentially connected, wherein the first catalytic layer comprises a carrier and a palladium-based alloy loaded on the outer surface and/or the inner part of the carrier, and the mass fraction of the palladium-based alloy is 15-60% by taking the mass of the first catalytic layer as a reference; the second catalytic layer comprises the carrier and a platinum catalyst loaded on the outer surface and/or inside of the carrier, the mass fraction of the platinum catalyst is 20-60% by taking the mass of the second catalytic layer as a reference, and the preparation method of the membrane electrode of the carbon-supported palladium-based alloy fuel cell comprises the following steps:
preparing slurry: respectively adding a first catalytic layer material and a second catalytic layer material into deionized water and an ethanol solution, adding a perfluorosulfonic acid polymer solution, and fully mixing to obtain a first catalytic layer slurry and a second catalytic layer slurry;
spraying: respectively spraying the first catalyst layer slurry and the second catalyst layer slurry on two surfaces of a proton exchange membrane to obtain a sprayed proton exchange membrane;
drying: drying the sprayed proton exchange membrane to obtain the carbon-supported palladium-based alloy fuel cell membrane electrode, wherein the first catalytic layer comprises a carrier and a palladium-based alloy loaded on the outer surface and/or inside of the carrier, the second catalytic layer comprises the carrier and a platinum catalyst loaded on the outer surface and/or inside of the carrier, and the palladium-based alloy is selected from PdCo and Pd 2Co or Pd3One of Co.
2. The palladium on carbon-based alloy fuel cell membrane electrode of claim 1, wherein the palladium-based alloy is Pd2Co。
3. The palladium on carbon-based alloy fuel cell membrane electrode of claim 1, wherein the palladium loading of the palladium on carbon-based alloy fuel cell membrane electrode is 0.1-0.4mg/cm2。
4. The palladium on carbon-based alloy fuel cell membrane electrode of claim 1, wherein the platinum loading of the palladium on carbon-based alloy fuel cell membrane electrode is 0.1-0.2 mg/cm2。
5. The palladium on carbon-based alloy fuel cell membrane electrode of claim 1, wherein the support is a multi-walled carbon nanotube or a single-walled carbon nanotube.
6. The palladium on carbon-based alloy fuel cell membrane electrode assembly according to claim 1, wherein the mass ratio of the first catalytic layer material to the perfluorosulfonic acid type polymer solution is (50-95): (50-5); the mass ratio of the second catalytic layer material to the perfluorosulfonic acid polymer solution is (50-95) to (50-5).
7. The palladium on carbon-based alloy fuel cell membrane electrode of claim 1, wherein the deionized water and ethanol solution are formed from (10-50): (90-50) mixing deionized water and ethanol.
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