CN113690451B - Anti-reverse-electrode gas diffusion layer and preparation method and application thereof - Google Patents

Anti-reverse-electrode gas diffusion layer and preparation method and application thereof Download PDF

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CN113690451B
CN113690451B CN202110872004.9A CN202110872004A CN113690451B CN 113690451 B CN113690451 B CN 113690451B CN 202110872004 A CN202110872004 A CN 202110872004A CN 113690451 B CN113690451 B CN 113690451B
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gas diffusion
diffusion layer
layer
water electrolysis
catalyst containing
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CN113690451A (en
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周江峰
王智捷
张泽
高佳武
赵航
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Dongfeng Motor Corp
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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
    • H01M4/88—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
    • H01M4/8605—Porous electrodes
    • 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]
    • 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
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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 particularly relates to an anti-counter electrode gas diffusion layer and a preparation method and application thereof, belonging to the technical field of fuel cells, wherein the method comprises the following steps: adding a first water electrolysis catalyst into the first dispersion liquid for dispersion, and then adding a first water repellent to obtain an impregnation solution; placing the substrate layer in an impregnation solution for impregnation operation, and then drying and roasting to obtain a pretreated substrate layer; the impregnation operation comprises at least one impregnation; obtaining microporous layer slurry; covering the microporous layer slurry on one side of the pretreated substrate layer to obtain a blank; carrying out heat treatment on the blank to obtain a counter electrode resistant gas diffusion layer; the gas diffusion layer has certain anti-reversal capability so as to ensure that the gas diffusion layer has good stability in the reversal process, and the battery has good performance before and after reversal.

Description

Anti-reverse-electrode gas diffusion layer and preparation method and application thereof
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a gas diffusion layer with an anti-reverse electrode and a preparation method and application thereof.
Background
Currently, the conservation of automobiles in the world is continuously increasing, while traditional fuel-powered automobiles rely heavily on fuel and are increasingly polluting the environment, with approximately 17% of carbon dioxide emissions from automobiles and trucks. Because the proton exchange membrane fuel cell takes hydrogen as fuel, pollutants such as SO can not be generated X 、NO X 、CO、CO 2 And the like, thus providing a new solution to the environmental problems and energy problems generated by automobiles.
The membrane electrode assembly is the most core part of the proton exchange membrane fuel cell, is the core assembly for generating current of the fuel cell, is known as the heart of the fuel cell and is the core place for generating electrochemical reaction, and the performance of the cell is determined by the quality of the membrane electrode. The membrane electrode assembly is generally composed of a proton exchange membrane, an anode catalytic layer, a cathode catalytic layer, an anode gas diffusion layer, and a cathode gas diffusion layer.
The gas diffusion layer is composed of a substrate layer and a microporous layer and mainly has the functions of transferring reaction gas into the catalyst layer, discharging water generated by reaction in time, supporting the catalyst layer, dissipating heat generated by reaction in time and transferring electrons. The deterioration of the gas diffusion layer, which is the main site for gas and water transport, is one of the important factors affecting the lifetime of the pem fuel cell.
When the vehicle fuel cell is used, the situation of hydrogen shortage can be found, so that a reverse pole accident is caused, the occurrence of the reverse pole accident can generate extremely high anode potential at the anode of the cell, so that an anode catalyst layer and a gas diffusion layer are inevitably subjected to electrochemical corrosion, the gas diffusion layer is degraded, and finally the performance of the cell is greatly reduced.
Disclosure of Invention
The application aims to provide a gas diffusion layer with anti-reversal pole, a preparation method and application thereof, so that the anti-reversal pole capacity of the gas diffusion layer is improved, the gas diffusion layer is ensured to have good stability in the process of reversal pole, and the battery has good performance before and after reversal pole.
The embodiment of the invention provides a preparation method of a counter-electrode-resistant gas diffusion layer, which comprises the following steps:
adding a first water electrolysis catalyst into the first dispersion liquid for dispersion, and then adding a first water repellent to obtain an impregnation solution;
placing the substrate layer in the dipping solution for dipping operation, and then drying and roasting to obtain a pretreated substrate layer; the impregnation operation comprises at least one impregnation;
obtaining microporous layer slurry;
covering the microporous layer slurry on one side of the pretreated substrate layer to obtain a blank;
and carrying out heat treatment on the green body to obtain the anti-counter electrode gas diffusion layer.
Optionally, in the impregnation, the time of single impregnation is 20min to 30min.
Optionally, the drying temperature is 60-80 ℃.
Optionally, the roasting temperature is 300-400 ℃.
Optionally, the content of the first water repellent in the pretreated substrate layer is 1wt% to 15wt%.
Optionally, the loading amount of the first water electrolysis catalyst in the pre-treatment substrate layer is 1 μ g/cm 2 -20μg/cm 2 。
Optionally, the first water electrolysis catalyst comprises: at least one of a nanometer material catalyst containing an iridium simple substance, a nanometer material catalyst containing an iridium simple substance oxide, a nanometer material catalyst containing an iridium simple substance hydroxide, a nanometer material catalyst containing a ruthenium simple substance oxide and a nanometer material catalyst containing a ruthenium simple substance hydroxide.
Optionally, the first dispersion comprises at least one of ethanol, isopropanol, ethylene glycol, and hexafluoroisopropanol.
Optionally, the first water repellent comprises at least one of polytetrafluoroethylene, polyvinylidene fluoride and a copolymer of tetrafluoroethylene and ethylene.
Optionally, the substrate layer comprises one of a carbon paper or a carbon cloth.
Optionally, the obtaining of the microporous layer slurry specifically includes:
and mixing a second water electrolysis catalyst, conductive carbon black and a second water repellent in a second dispersion liquid to obtain microporous layer slurry.
Optionally, the mass ratio of the conductive carbon black to the second water electrolysis catalyst is 50:1-250:1; the mass ratio of the conductive carbon black to the second dispersion liquid is 1:5-1:10; the mass ratio of the conductive carbon black to the second water repellent is 4:1-10:1.
optionally, the content of the second water repellent in the microporous layer of the anti-reverse gas diffusion layer is 10wt% to 30wt%.
Optionally, the total loading of the first water electrolysis catalyst and the second water electrolysis catalyst in the anti-counter electrode gas diffusion layer is 10 μ g/cm 2 -50μg/cm 2 。
Optionally, conductive carbon black in the anti-counter electrode gas diffusion layerThe loading capacity is 1.0mg/cm 2 -2.5mg/cm 2 。
Optionally, the second water electrolysis catalyst comprises: at least one of a nano-material catalyst containing an elementary substance of iridium, a nano-material catalyst containing an elementary substance oxide of iridium, a nano-material catalyst containing an elementary substance hydroxide of iridium, a nano-material catalyst containing an elementary substance of ruthenium, a nano-material catalyst containing an elementary substance oxide of ruthenium and a nano-material catalyst containing an elementary substance hydroxide of ruthenium.
Optionally, the conductive carbon Black comprises at least one of acetylene Black, vulcan XC-72, black pearls, carbon nanotubes, and graphene powder.
Optionally, the second hydrophobic agent comprises at least one of polytetrafluoroethylene, polyvinylidene fluoride and a copolymer of tetrafluoroethylene and ethylene.
Optionally, the second dispersion comprises at least one of ethanol, isopropanol, ethylene glycol, and hexafluoroisopropanol.
Based on the same inventive concept, the embodiment of the invention also provides the anti-reverse-pole gas diffusion layer, and the anti-reverse-pole gas diffusion layer is prepared by the preparation method of the anti-reverse-pole gas diffusion layer.
Based on the same inventive concept, the embodiment of the invention also provides an application of the anti-reverse-pole gas diffusion layer, and the application comprises the application of the anti-reverse-pole gas diffusion layer to the preparation of a proton exchange membrane fuel cell.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the preparation method of the anti-reverse-electrode gas diffusion layer provided by the embodiment of the invention comprises the following steps: adding a first water electrolysis catalyst into the first dispersion liquid for dispersion, and then adding a first water repellent to obtain an impregnation solution; placing the substrate layer in the dipping solution for dipping operation, and then drying and roasting to obtain a pretreated substrate layer; the impregnation operation comprises at least one impregnation; obtaining microporous layer slurry; covering the microporous layer slurry on one side of the pretreated substrate layer to obtain a blank; carrying out heat treatment on the blank to obtain a counter electrode resistant gas diffusion layer; by adding the water electrolysis agent into the substrate layer, the gas diffusion layer mainly generates water electrolysis reaction, effectively inhibits the carbon corrosion reaction of the gas diffusion layer, and still has good gas transmission and water drainage capacity, so that the gas diffusion layer has certain anti-polarity capacity to ensure that the gas diffusion layer has good stability in the counter-polarity process, and the battery has good performance before and after counter-polarity.
The above description is only an overview of the technical solutions of the present invention, and the present invention can be implemented in accordance with the content of the description so as to make the technical means of the present invention more clearly understood, and the above and other objects, features, and advantages of the present invention will be more clearly understood.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a flow chart of a method provided by an embodiment of the present invention;
fig. 2 is a graph showing polarization curves of gas diffusion layers provided in examples of the present invention and comparative examples before and after the reversal of the polarization on a membrane electrode.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are illustrative of the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
according to an exemplary embodiment of the present invention, there is provided a method of preparing a counter-electrode-resistant gas diffusion layer, the method including:
s1, adding a first water electrolysis catalyst into first dispersion liquid for dispersion, and then adding a first water repellent to obtain an impregnation solution;
specifically, the first water electrolysis catalyst may be selected from: at least one of a nano-material catalyst containing an elementary substance of iridium, a nano-material catalyst containing an elementary substance oxide of iridium, a nano-material catalyst containing an elementary substance hydroxide of iridium, a nano-material catalyst containing an elementary substance of ruthenium, a nano-material catalyst containing an elementary substance oxide of ruthenium and a nano-material catalyst containing an elementary substance hydroxide of ruthenium. It should be noted that the above list of the first water electrolysis catalyst is only used to illustrate that the method can be implemented, and is not intended to limit the present invention, and in other embodiments, a person skilled in the art can select other similar catalysts according to the actual situation.
The mechanism for improving the anti-reversal capability by adopting the first water electrolysis catalyst to treat the substrate layer is that the water electrolysis agent is added into the substrate layer, so that the substrate layer mainly generates water electrolysis reaction under high potential, the carbon corrosion reaction of the substrate layer is effectively inhibited, and the substrate layer still has good air transmission and water drainage capability, so that the substrate layer has certain anti-reversal capability.
Specifically, the first dispersion may be selected from at least one of ethanol, isopropanol, ethylene glycol, and hexafluoroisopropanol; it should be noted that the above list of the first dispersion is only to illustrate that the method can be implemented, and is not to limit the present invention, and in other embodiments, a person skilled in the art can select other similar dispersions according to actual situations.
Specifically, the first water repellent may be selected from at least one of polytetrafluoroethylene, polyvinylidene fluoride, and a copolymer of tetrafluoroethylene and ethylene; it should be noted that the above list of first water repellent is only to illustrate that the method can be implemented, and is not to limit the present invention, and in other embodiments, those skilled in the art can select other similar water repellent according to the actual situation.
Specifically, the substrate layer comprises one of carbon paper or carbon cloth; it should be noted that the above list of substrate layers is only to illustrate that the method can be implemented and is not intended to limit the invention, and in other embodiments, a person skilled in the art can select other, similar substrate layers according to the actual situation.
S2, placing the substrate layer into the dipping solution for dipping operation, and then drying and roasting to obtain a pretreated substrate layer; the dipping operation at least comprises one-time dipping, and the time of the single dipping is 20min-30min; the drying temperature is 60-80 ℃; the roasting temperature is 300-400 ℃;
the time of single impregnation is controlled to be 20min-30min, the time is excessively large, the strength of the carbon paper is damaged by long-time impregnation, and the expected effect cannot be achieved by excessively small adverse effect.
The drying temperature is controlled to be 60-80 ℃, the adverse effect of excessively large temperature is that the water evaporation rate is too high, so that the distribution is not uniform, and the adverse effect of excessively small temperature is that the drying cannot be carried out in a short time.
The roasting temperature is controlled to be 300-400 ℃, and the roasting cannot be fully carried out due to the adverse effect of excessively low temperature.
As an alternative embodiment, the first hydrophobic agent is present in the pre-treated base layer in an amount of 1wt% to 15wt%.
The content of the first water repellent in the pretreated substrate layer is controlled to be 1-15 wt%, the adverse effect of overlarge content of the water repellent is that the conductivity of the gas diffusion layer is reduced due to overhigh content of the water repellent, and the adverse effect of undersize causes that the hydrophobicity of the gas diffusion layer is insufficient and water in the battery cannot be discharged in time.
As an alternative embodiment, the loading of the first water electrolysis catalyst in the pre-treated substrate layer is 1 μ g/cm 2 -20μg/cm 2 。
Controlling the loading capacity of the first water electrolysis catalyst in the pre-treated substrate layer to be 1 mu g/cm 2 -20μg/cm 2 An adverse effect of too large a loading amount is to cause a decrease in conductivity of the gas diffusion layer, and an adverse effect of too small is to decrease the water electrolysis capacity of the gas diffusion layer at high potential.
S3, obtaining microporous layer slurry;
as an alternative embodiment, the second water electrolysis catalyst, the conductive carbon black and the second water repellent are mixed in the second dispersion to obtain the microporous layer slurry.
Specifically, the second water electrolysis catalyst may be selected from: at least one of a nano-material catalyst containing an elementary substance of iridium, a nano-material catalyst containing an elementary substance oxide of iridium, a nano-material catalyst containing an elementary substance hydroxide of iridium, a nano-material catalyst containing an elementary substance of ruthenium, a nano-material catalyst containing an elementary substance oxide of ruthenium and a nano-material catalyst containing an elementary substance hydroxide of ruthenium. It should be noted that the above list of the second water electrolysis catalyst is only used to illustrate that the method can be implemented, and is not intended to limit the invention.
The mechanism for improving the anti-reversal capability by adopting the second water electrolysis catalyst as the raw material of the microporous layer slurry is that a water electrolysis agent is added into the microporous layer, so that the microporous layer mainly generates water electrolysis reaction under high potential, the carbon corrosion reaction of the microporous layer is effectively inhibited, and the microporous layer still has good air transmission and water drainage capability, so that the microporous layer has certain anti-reversal capability.
Specifically, the conductive carbon Black may be selected from at least one of acetylene Black, vulcan XC-72, black pearls, carbon nanotubes, and graphene powder; it should be noted that the above list of conductive carbon blacks is only illustrative of the method that can be practiced and is not intended to limit the invention, and in other embodiments, other, similar conductive carbon blacks may be selected by one skilled in the art as is practical.
Specifically, the second dispersion may be selected from at least one of ethanol, isopropanol, ethylene glycol, and hexafluoroisopropanol; it should be noted that the above list of the second dispersion is only to illustrate that the method can be implemented, and is not to limit the present invention, and in other embodiments, a person skilled in the art can select other similar dispersions according to actual situations.
Specifically, the second water repellent may be at least one selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, and a copolymer of tetrafluoroethylene and ethylene; it should be noted that the above list of second water repellent is only to illustrate that the method can be implemented, and is not to limit the present invention, and in other embodiments, those skilled in the art can select other similar water repellent according to the actual situation.
As an alternative embodiment, the mass ratio of the conductive carbon black and the second water electrolysis catalyst is 50:1-250:1; the mass ratio of the conductive carbon black to the second dispersion liquid is 1:5-1:10; the mass ratio of the conductive carbon black to the second water repellent is 4:1-10:1.
controlling the mass ratio of the conductive carbon black to the second water electrolysis catalyst to be 50:1-250:1, an adverse effect of excessively large mass ratio is to reduce the water electrolysis capacity of the gas diffusion layer at high potential, and an adverse effect of excessively small mass ratio is to cause a decrease in conductivity of the gas diffusion layer.
Controlling the mass ratio of the conductive carbon black to the second dispersion liquid to be 1:5-1:10, the adverse effect of this mass ratio being too small is that the slurry is not homogeneous.
Controlling the mass ratio of the conductive carbon black to the second water repellent to be 4:1-10:1, an adverse effect of excessively large mass ratio is to reduce the water electrolysis capacity of the gas diffusion layer at high potential, and an adverse effect of excessively small mass ratio is to cause a decrease in conductivity of the gas diffusion layer.
S4, covering the microporous layer slurry on one side of the pretreatment substrate layer to obtain a blank;
and S5, carrying out heat treatment on the blank to obtain the anti-reverse-electrode gas diffusion layer.
As an alternative embodiment, the content of the second water repellent in the microporous layer of the anti-reverse gas diffusion layer is 10wt% to 30wt%.
The reason for controlling the content of the second water repellent in the microporous layer of the anti-reverse gas diffusion layer to be 10wt% -30wt% is that the conductivity of the gas diffusion layer is reduced due to the excessively high content of the water repellent; the water repellent content is too low, resulting in insufficient hydrophobicity of the gas diffusion layer.
As an alternative embodiment, the total loading of the first water electrolysis catalyst and the second water electrolysis catalyst in the anti-counter electrode gas diffusion layer is 10 μ g/cm 2 -50μg/cm 2 。
Controlling the total loading of the first water electrolysis catalyst and the second water electrolysis catalyst in the anti-counter electrode gas diffusion layer to be 10 mu g/cm 2 -50μg/cm 2 The adverse effect of excessively large loading is that the conductivity of the gas diffusion layer is reduced; an unduly small adverse effect is a reduction in the water electrolysis capacity of the gas diffusion layer at high potentials.
As an alternative embodiment, the conductive carbon black loading in the anti-reverse gas diffusion layer is 1.0mg/cm 2 -2.5mg/cm 2 。
According to another exemplary embodiment of the present invention, there is also provided a counter-electrode-resistant gas diffusion layer prepared by the method of preparing a counter-electrode-resistant gas diffusion layer as provided above.
According to another exemplary embodiment of the present invention, there is also provided a use of an anti-back-electrode gas diffusion layer, the use comprising the use of an anti-back-electrode gas diffusion layer as provided above for the preparation of a proton exchange membrane fuel cell.
The gas diffusion layer against counter electrode of the present application, and the preparation method and application thereof will be described in detail below with reference to examples, comparative examples, and experimental data.
Example 1
A preparation method of a gas diffusion layer for resisting a counter electrode for a proton exchange membrane fuel cell comprises the following steps:
(1) Pretreatment of a basal layer: adding iridium oxide into isopropanol for dispersion, then adding polytetrafluoroethylene emulsion into the isopropanol to obtain a mixed solution, placing carbon paper into the mixed solution for impregnation for 30min, drying the carbon paper at 60 ℃, and performing multiple impregnation until the iridium oxide loading reaches 15ug/cm 2 Then, roasting at 300 ℃ to obtain pretreated carbon paper, wherein the content of polytetrafluoroethylene in the carbon paper is 5%;
(2) Preparing microporous layer slurry: mixing isopropanol with water, and adding oxigen to obtain slurry A; mixing ethanol with water, and adding Vulcan XC-72 carbon powder to obtain slurry B; respectively carrying out magnetic stirring and ultrasonic treatment on the slurry A and the slurry B; mixing the dispersed slurry A and the slurry B, adding 60% of polytetrafluoroethylene emulsion into the mixture, magnetically stirring the mixture, and performing ball milling and mixing to obtain uniform microporous layer slurry;
(3) Preparation of a gas diffusion layer: the microporous layer slurry obtained in the step (2) is coated on the carbon paper pretreated in the step (1) by scraping until the carbon powder loading capacity reaches 2.5mg/cm 2 The oxidation loading amount reaches 20ug/cm 2 (ii) a Drying in an oven at 60 deg.C for 2h, and calcining at 350 deg.C for 4h to obtain the gas diffusion layer with PTFE content of 20%.
Example 2
A preparation method of a gas diffusion layer for resisting a counter electrode of a proton exchange membrane fuel cell comprises the following steps:
(1) Base layer pretreatment: adding iridium oxide into isopropanol for dispersion, then adding polytetrafluoroethylene emulsion into the isopropanol to obtain a mixed solution, placing carbon paper into the mixed solution for impregnation for 30min, drying the carbon paper at 60 ℃, and performing multiple impregnation until the iridium oxide loading reaches 5ug/cm 2 Then, roasting at 300 ℃ to obtain pretreated carbon paper, wherein the content of polytetrafluoroethylene in the carbon paper is 5%;
(2) Preparing microporous layer slurry: mixing isopropanol with water, and adding oxigen to obtain slurry A; mixing ethanol with water, and adding Vulcan XC-72 carbon powder to obtain slurry B; respectively carrying out magnetic stirring and ultrasonic treatment on the slurry A and the slurry B; mixing the dispersed slurry A and the slurry B, adding 60% of polytetrafluoroethylene emulsion into the mixture, magnetically stirring the mixture, and performing ball milling and mixing to obtain uniform microporous layer slurry;
(3) Preparation of a gas diffusion layer: the microporous layer slurry obtained in the step (2) is coated on the carbon paper pretreated in the step (1) by scraping until the carbon powder loading capacity reaches 2.5mg/cm 2 The oxidation loading amount reaches 20ug/cm 2 (ii) a Drying in an oven at 60 deg.C for 2h, and calcining at 350 deg.C for 4h to obtain gas diffusion layer with PTFE content of 20%.
Example 3
A preparation method of a gas diffusion layer for resisting a counter electrode for a proton exchange membrane fuel cell comprises the following steps:
(1) Base layer pretreatment: adding iridium oxide into isopropanol for dispersion, adding polytetrafluoroethylene emulsion into the isopropanol to obtain a mixed solution, placing carbon paper into the mixed solution for soaking for 30min, drying the carbon paper at 60 ℃, and soaking for multiple times until the iridium oxide loading capacity reaches 2.5ug/cm 2 Then, roasting at 300 ℃ to obtain pretreated carbon paper, wherein the content of polytetrafluoroethylene in the carbon paper is 5%;
(2) Preparing microporous layer slurry: mixing isopropanol with water, and adding oxigen to obtain slurry A; mixing ethanol with water, and adding Vulcan XC-72 carbon powder to obtain slurry B; respectively carrying out magnetic stirring and ultrasonic treatment on the slurry A and the slurry B; mixing the dispersed slurry A and the slurry B, adding 60% of polytetrafluoroethylene emulsion into the mixture, magnetically stirring the mixture, and performing ball milling and mixing to obtain uniform microporous layer slurry;
(3) Preparation of a gas diffusion layer: the microporous layer slurry obtained in the step (2) is coated on the carbon paper pretreated in the step (1) by scraping until the carbon powder loading capacity reaches 2.5mg/cm 2 The oxidation loading amount reaches 20ug/cm 2 (ii) a Drying in an oven at 60 deg.C for 2 hr, and baking at 350 deg.CAnd (4) sintering for 4 hours to obtain the gas diffusion layer, wherein the content of PTFE in the microporous layer is 20%.
Comparative example 1
A preparation method of a gas diffusion layer for resisting a counter electrode for a proton exchange membrane fuel cell comprises the following steps:
(1) Base layer pretreatment: adding polytetrafluoroethylene emulsion into isopropanol to obtain a mixed solution, placing the carbon paper into the mixed solution for soaking for 30min, drying the carbon paper at 60 ℃, soaking for multiple times until the content of polytetrafluoroethylene in the carbon paper is 5%, and then placing the carbon paper at 300 ℃ for roasting to obtain pretreated carbon paper;
(2) Preparing microporous layer slurry: mixing isopropanol, ethanol and water, and then adding Vulcan XC-72 carbon powder into the mixture to obtain mixed slurry; magnetically stirring and ultrasonically treating the mixed slurry; adding 60% of polytetrafluoroethylene emulsion, magnetically stirring, and performing ball milling and mixing to obtain uniform microporous layer slurry;
(3) Preparation of a gas diffusion layer: the microporous layer slurry obtained in the step (2) is coated on the carbon paper pretreated in the step (1) by scraping until the carbon powder loading capacity reaches 2.5mg/cm 2 (ii) a Drying in an oven at 60 deg.C for 2h, and calcining at 350 deg.C for 4h to obtain the gas diffusion layer with PTFE content of 20%.
Comparative example 2
A preparation method of a gas diffusion layer for resisting a counter electrode of a proton exchange membrane fuel cell comprises the following steps:
(1) Base layer pretreatment: adding polytetrafluoroethylene emulsion into isopropanol to obtain a mixed solution, placing the carbon paper into the mixed solution for soaking for 30min, drying the carbon paper at 60 ℃, soaking for multiple times until the content of polytetrafluoroethylene in the carbon paper is 5%, and then placing the carbon paper at 300 ℃ for roasting to obtain pretreated carbon paper;
(2) Preparing microporous layer slurry: mixing isopropanol with water, and adding oxirane into the mixture to obtain slurry A; mixing ethanol with water, and adding Vulcan XC-72 carbon powder to obtain slurry B; respectively carrying out magnetic stirring and ultrasonic treatment on the slurry A and the slurry B; mixing the dispersed slurry A and the slurry B, adding 60% of polytetrafluoroethylene emulsion, magnetically stirring, and performing ball milling mixing to obtain uniform microporous layer slurry;
(3) Preparation of a gas diffusion layer: the microporous layer slurry obtained in the step (2) is coated on the carbon paper pretreated in the step (1) by scraping until the carbon powder loading capacity reaches 2.5mg/cm 2 The oxidation loading amount reaches 20ug/cm 2 (ii) a Drying in an oven at 60 deg.C for 2h, and calcining at 350 deg.C for 4h to obtain the gas diffusion layer with PTFE content of 20%.
Examples of the experiments
The gas diffusion layers prepared in examples 1 to 3 and comparative examples 1 to 2 were tested under the following test conditions: cell temperature 80 ℃, anode 100% RH, anode gas hydrogen, anode flow 210cc/min, anode excess coefficient 1.5, anode back pressure 150kPa; the cathode was 100% RH, the cathode gas was air, the cathode flow rate was 500cc/ml, the cathode excess factor was 2.5, and the cathode back pressure was 150kPa; the test results are shown in fig. 2.
It can be obtained from the figure that the current density is 2000mA/cm 2 At a current density of (a) of (b),
the voltage of example 1 is 0.6V, which is degraded by only 5.4% relative to 0.634V before the reverse polarity;
the voltage of example 2 is 0.595V, which is reduced by only 6.2% compared to 0.634V before the reversal;
the voltage of example 3 is 0.589V, which is reduced by only 7.1% compared with 0.634V before the reverse pole;
and at 2000mA/cm 2 At a current density of (a) of (b),
the voltage of comparative example 1 was 0.577V, which is 9% degraded with respect to 0.634V before the reversal;
the voltage of comparative example 2 was 0.556V, which was 12.3% degenerated with respect to 0.634V before the reversal.
In conclusion, the gas diffusion layer manufactured by the method provided in the examples of the present application has a remarkable anti-reverse polarity capability compared to the gas diffusion layer manufactured by the comparative example.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
(1) According to the method provided by the embodiment of the invention, the water electrolysis agent is added into the microporous layer, and the water electrolysis agent is added into the substrate layer, so that the gas diffusion layer mainly generates water electrolysis reaction, the carbon corrosion reaction of the gas diffusion layer is effectively inhibited, and the gas diffusion layer still has good gas transmission and water drainage capabilities, so that the gas diffusion layer has a certain anti-reversal capability;
(2) The gas diffusion layer provided by the embodiment of the invention has strong anti-reversal capability, has good stability in the reversal process, and has good performance before and after the reversal of the prepared battery.
Finally, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (9)

1. A method of preparing a counter-electrode-resistant gas diffusion layer, the method comprising:
adding a first water electrolysis catalyst into the first dispersion liquid for dispersion, and then adding a first water repellent to obtain an impregnation solution;
placing the substrate layer in the dipping solution for dipping operation, and then dryingDrying and roasting to obtain a pretreated substrate layer; the dipping operation at least comprises one-time dipping, and the time of the single dipping is 20min-30min; the loading capacity of the first water electrolysis catalyst in the pretreatment substrate layer is 1 mu g/cm 2 -20μg/cm 2 ；
Mixing a second water electrolysis catalyst, conductive carbon black and a second water repellent in a second dispersion liquid to obtain microporous layer slurry;
covering the microporous layer slurry on one side of the pretreated substrate layer to obtain a blank;
carrying out heat treatment on the blank to obtain a counter electrode resistant gas diffusion layer, wherein the total loading amount of the first water electrolysis catalyst and the second water electrolysis catalyst in the counter electrode resistant gas diffusion layer is 10 mu g/cm 2 -50μg/cm 2 。
2. The method for preparing a gas diffusion layer against a counter electrode according to claim 1, wherein the temperature of the drying is 60 ℃ to 80 ℃; the roasting temperature is 300-400 ℃; the content of the first water repellent in the pretreated substrate layer is 1wt% -15wt%.
3. The method of producing a counter-electrode-resistant gas diffusion layer according to claim 1, wherein the first water electrolysis catalyst comprises: at least one of a nanometer material catalyst containing an iridium simple substance, a nanometer material catalyst containing an iridium simple substance oxide, a nanometer material catalyst containing an iridium simple substance hydroxide, a nanometer material catalyst containing a ruthenium simple substance oxide and a nanometer material catalyst containing a ruthenium simple substance hydroxide.
4. The method of manufacturing a gas diffusion layer against reverse electrode according to claim 1, wherein the first dispersion liquid includes at least one of ethanol, isopropanol, ethylene glycol, and hexafluoroisopropanol;
the first water repellent comprises at least one of polytetrafluoroethylene, polyvinylidene fluoride and a copolymer of tetrafluoroethylene and ethylene;
the substrate layer includes one of a carbon paper or a carbon cloth.
5. The method for producing a gas diffusion layer against a counter electrode according to claim 1, characterized in that the mass ratio of the conductive carbon black and the second water electrolysis catalyst is 50:1-250:1; the mass ratio of the conductive carbon black to the second dispersion liquid is 1:5-1:10; the mass ratio of the conductive carbon black to the second water repellent is 4:1-10:1.
6. the method for preparing the gas diffusion layer with the anti-reverse polarity of claim 1, wherein the content of the second water repellent in the microporous layer of the gas diffusion layer with the anti-reverse polarity is 10wt% to 30wt%; the conductive carbon black loading amount in the anti-reverse electrode gas diffusion layer is 1.0mg/cm 2 -2.5mg/cm 2 。
7. The method of producing a counter-electrode-resistant gas diffusion layer according to claim 1, wherein the second water electrolysis catalyst comprises: at least one of a nano-material catalyst containing an iridium simple substance, a nano-material catalyst containing an iridium simple substance oxide, a nano-material catalyst containing an iridium simple substance hydroxide, a nano-material catalyst containing a ruthenium simple substance oxide and a nano-material catalyst containing a ruthenium simple substance hydroxide;
the conductive carbon Black comprises at least one of acetylene Black, vulcan XC-72, black pearls, carbon nanotubes and graphene powder;
the second water repellent comprises at least one of polytetrafluoroethylene, polyvinylidene fluoride and a copolymer of tetrafluoroethylene and ethylene;
the second dispersion includes at least one of ethanol, isopropanol, ethylene glycol, and hexafluoroisopropanol.
8. A gas diffusion layer against counter electrode, characterized in that it is prepared by the method of preparing a gas diffusion layer against counter electrode according to any one of claims 1 to 7.
9. Use of a gas diffusion layer against a counter electrode according to claim 8 for the preparation of a proton exchange membrane fuel cell.
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