CN114864968B - Anti-counter electrode catalyst for fuel cell and preparation method and application thereof - Google Patents

Anti-counter electrode catalyst for fuel cell and preparation method and application thereof Download PDF

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CN114864968B
CN114864968B CN202210354200.1A CN202210354200A CN114864968B CN 114864968 B CN114864968 B CN 114864968B CN 202210354200 A CN202210354200 A CN 202210354200A CN 114864968 B CN114864968 B CN 114864968B
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counter electrode
catalyst
metal sulfide
graphene
fuel cell
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CN114864968A (en
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高佳武
唐雪君
周江峰
王智捷
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
    • H01M4/90—Selection of catalytic material
    • 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
    • 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
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Inert Electrodes (AREA)

Abstract

The invention particularly relates to an anti-counter electrode catalyst for a fuel cell, a preparation method and application thereof, belonging to the technical field of fuel cells, wherein the raw materials of the catalyst comprise: the catalyst is a crosslinked compound of the graphene and the anti-counter electrode material; the graphene and the anti-counter electrode material are adopted for compounding, and the anti-counter electrode material can be well combined with the commercial catalyst by adding the graphene, so that the internal resistance and the contact internal resistance of the CCM cannot be reduced due to the addition of the weak conductive substance.

Description

Anti-counter electrode catalyst for fuel cell and preparation method and application thereof
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to an anti-counter electrode catalyst for a fuel cell, and a preparation method and application thereof.
Background
The proton exchange membrane fuel cell is a green cell which takes hydrogen as fuel and generates water, and has the characteristics of high power density, high energy efficiency, green environmental protection and the like. The method can be applied to the fields of aerospace, automobiles, ships and the like, and has wide application. In the automotive field, it can be used as a power source for driving an automobile. However, during the actual running process of the automobile, conditions such as abrupt start-stop, idle running, abrupt loading and unloading and the like are encountered, so that hydrogen fuel cannot be timely supplied to the MEA, the phenomenon of opposite poles of the MEA occurs, the phenomenon can cause huge loss on the performance of the MEA, and the power generation capacity and the service life of the battery are directly influenced.
The phenomenon of inversion generally causes two negative effects. The first is to make up for the lack of protons caused by the lack of fuel, and the carbon on the CCM anode can undergo oxidation reaction to provide protons, which can cause carbon corrosion and further degrade the catalyst performance. The second is that when the counter electrode phenomenon occurs, the platinum particles on the catalyst will become large sharply, which will decrease the catalytic ability of the platinum and thus the performance and life of the battery.
At present, a catalyst for water electrolysis is added at the anode of the CCM, when hydrogen fuel is in shortage, protons are provided by replacing carbon oxidation through water electrolysis, so that the aim of preventing carbon corrosion is fulfilled, and at present, a common strategy is to mix ruthenium oxide and iridium oxide with better water electrolysis performance into a CCM anode catalytic layer, and the ohmic internal resistance at the anode is increased by the means.
Disclosure of Invention
The application aims to provide a counter electrode catalyst for a fuel cell, and a preparation method and application thereof, so as to solve the problem that the counter electrode catalyst can increase internal resistance at an anode.
The applicant found during the course of the study that: the phenomenon of inversion generally causes two negative effects. The first is to make up for the lack of protons caused by the lack of fuel, and the carbon on the CCM anode can undergo oxidation reaction to provide protons, which can cause carbon corrosion and further degrade the catalyst performance. The second is that when the counter electrode phenomenon occurs, the platinum particles on the catalyst will become large sharply, which will decrease the catalytic ability of the platinum and thus the performance and life of the battery.
At present, a catalyst for water electrolysis is added at the anode of the CCM, when hydrogen fuel is in shortage, protons are provided by replacing carbon oxidation through water electrolysis, so that the aim of preventing carbon corrosion is fulfilled, and at present, a common strategy is to mix ruthenium oxide and iridium oxide with better water electrolysis performance into a CCM anode catalytic layer. Such as a proton exchange membrane fuel cell anti-reverse electrode catalyst and a preparation method thereof, as disclosed in Chinese patent application CN 112838227A. The main component of the adopted anti-counter electrode catalyst is Pt/WO 3 Mn, in which the water electrolysis capacity of WO3-Mn, i.e. HER activity, is not high and does not achieve very good resistance to carbon corrosion. In addition to that, WO 3 The introduction of Mn will greatly increase the contact resistance of CCM, resulting in a decrease in battery performance. Such as Chinese patent applicationPlease CN113871629a, a counter electrode resistant catalyst, a preparation method and application thereof, which mainly relieves the corrosion of carbon by adding iridium oxide at the CCM anode; in this method, the addition of iridium oxide increases the ohmic internal resistance at the anode of the CCM, and the power generation capability of the CCM is reduced, and the iridium element is difficult to obtain, which increases the manufacturing cost of the battery.
The embodiment of the invention provides a counter electrode resistant catalyst for a fuel cell, which comprises the following raw materials: the catalyst is a crosslinked composite of graphene and an anti-counter electrode material.
Optionally, the anti-counter electrode material includes: non-noble metal sulfides.
Optionally, the non-noble metal sulfide is nano-platelet.
Optionally, the mass ratio of the graphene to the non-noble metal sulfide is 1:1-4.
Optionally, the non-noble metal sulfide raw materials include: stannous chloride, a generator and a stripper.
Optionally, the mass ratio of the stannous chloride to the generating agent to the stripping agent is 1:4-8:2-5.
Optionally, the generator comprises a TAA.
Optionally, the stripper comprises one of PVP, N- (3-methoxypropyl) -2-pyrrolidone and pyrrolidone.
Optionally, the raw materials of the catalyst further comprise a binder.
Optionally, the mass ratio of the graphene to the binder is 1:0.01-0.05.
Optionally, the binder comprises one of Nafion solution, acrylic acid and polyurethane.
Based on the same inventive concept, the embodiment of the invention also provides a preparation method of the anti-reverse electrode catalyst for the fuel cell, which comprises the following steps:
obtaining an anti-reverse pole material;
and compounding the anti-counter electrode material and graphene to obtain the catalyst.
Optionally, the obtained anti-counter electrode material specifically includes:
mixing stannous chloride, a generating agent, a stripping agent and a dispersing solvent to obtain a mixture;
and (3) carrying out a heating reaction on the mixture to obtain the anti-counter electrode material.
Based on the same inventive concept, embodiments of the present invention also provide a membrane electrode including an anode catalytic layer containing the anti-counter electrode catalyst for a fuel cell as described above.
Based on the same inventive concept, the embodiments of the present invention also provide a fuel cell including the membrane electrode as described above.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
according to the anti-counter electrode catalyst for the fuel cell, the graphene and the anti-counter electrode material are compounded, and the anti-counter electrode material can be well combined with the commercial catalyst by adding the graphene, so that the performance of the CCM is not reduced due to the addition of weak conductive substances and the contact internal resistance of the CCM.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present invention more readily apparent.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method provided by an embodiment of the present invention;
FIG. 2 is a graph of experimental results provided by an embodiment of the present invention;
fig. 3 is a scanning electron microscope image of the catalyst provided in example 1 of the present invention.
Detailed Description
The advantages and various effects of the present invention will be more clearly apparent from the following detailed description and examples. It will be understood by those skilled in the art that these specific embodiments and examples are intended to illustrate the invention, not to limit the invention.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning 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. In case of conflict, the present specification will control.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Noun interpretation:
TEG triethylene glycol
TAA N-p-toluenesulfonyl-L-argininamide hydrochloride
DEG: diethylene glycol
TEG: triethylene glycol
PF-TEG: tetraethylene glycol
DMF: n, N-dimethylformamide
PEMFC: proton exchange membrane fuel cell
MEA: membrane electrode
CCM: catalytic layer
PVP: crosslinked polyvinylpyrrolidone
The technical scheme of the embodiment of the application aims to solve the technical problems, and the overall thought is as follows:
according to an exemplary embodiment of the present invention, there is provided a counter electrode catalyst for a fuel cell, the catalyst comprising: graphene and anti-counter electrode materials.
The graphene and the anti-counter electrode material are adopted for compounding, and the anti-counter electrode material can be well combined with the commercial catalyst by adding the graphene, so that the internal resistance and the contact internal resistance of the CCM cannot be reduced due to the addition of the weak conductive substance. Commercially available catalysts are typically platinum carbon catalysts.
Meanwhile, the applicant finds that when the counter electrode occurs, graphene on the composite material can replace carbon on a platinum carbon catalyst to generate carbon corrosion, so that damage to the catalyst is reduced, the degree of carbon corrosion is greatly reduced, and the effect of protecting a battery is further achieved.
In some embodiments, the anti-counter electrode material comprises: non-noble metal sulfides. It should be noted that, in other embodiments, those skilled in the art may use other anti-counter electrode materials as needed, which only needs to ensure that the anti-counter electrode material can replace carbon oxidation to provide protons when the hydrogen fuel is in shortage, so as to achieve the purpose of preventing carbon corrosion.
In some embodiments, the non-noble metal sulfide is nano-platelet, as shown in fig. 3, and in this embodiment, the raw materials of the non-noble metal sulfide include: stannous chloride, a generator and a stripper, in other words, the non-noble metal sulfide is tin sulfide, it should be noted that in other embodiments, one skilled in the art may select other non-noble metals to prepare the non-noble metal sulfide.
In the embodiment, the non-noble metal sulfide has higher OER activity, and the non-noble metal sulfide composite graphene replaces noble metals such as ruthenium, iridium and the like to be added to the CCM anode, so that the manufacturing cost of the anti-reverse electrode catalyst is greatly reduced.
Specifically, the mass ratio of stannous chloride, the generating agent and the stripping agent is 1:4-8:2-5, wherein the generating agent can be TAA, and the stripping agent can be at least one of PVP, N- (3-methoxypropyl) -2-pyrrolidone and pyrrolidone.
The mass ratio of stannous chloride to the generating agent is controlled to be 1:4-8, so that metal sulfide SnS can be efficiently generated 2 If the ratio is too low, snS will not be generated 2 If the ratio is too large, too much sulfur element will wrap the produced nano-sheets, making the nano-sheets difficultTo be layered. The mass ratio of stannous chloride to the generator includes, but is not limited to: 1:4, 1:5, 1:6, 1:7, 1:8, etc.
Controlling the mass ratio of stannous chloride to stripping agent to be 1:2-5 can lead the generated metal sulfide to present a nano lamellar structure, if the ratio is too small, the metal sulfide cannot form a lamellar structure, and if the ratio is too large, the separation of the metal sulfide becomes difficult. The mass ratio of stannous chloride to stripping agent includes, but is not limited to: 1:2, 1:3, 1:4, and 1:5, etc.
In some embodiments, the mass ratio of graphene to non-noble metal sulfide is 1:1-4. The mass ratio of graphene to non-noble metal sulfide includes, but is not limited to, 1: 1. 1:2, 1:3, 1:4, etc.
The mass ratio of the graphene to the non-noble metal sulfide is controlled to be 1:1-4 can obtain graphene non-noble metal sulfide with good compounding degree, if the proportion is too high, the proportion of graphene in the composite material is small, the electric conductivity of the catalyst is reduced, and the performance of the MEA is reduced. If the ratio is too low, the addition amount of the non-noble metal sulfide is small, the electrolytic water ability becomes weak, and the anti-polar ability of the catalyst becomes weak.
In general, the raw materials of the catalyst further comprise a binder, the binder is used for crosslinking graphene and the anti-counter electrode material, and the mass ratio of the graphene to the binder is 1:0.01-0.05, the mass ratio of graphene to binder including, but not limited to, 1:0.01, 1:0.02, 1:0.03, 1:0.04 and 1:0.05, etc. The specific binder can be at least one of Nafion solution, acrylic acid and polyurethane.
The mass ratio of the graphene to the binder is controlled to be 1: and 0.01-0.05 can better crosslink graphene and metal sulfide. If the ratio is too low, the two materials cannot be completely compounded, the materials are easy to fall off in the subsequent processing process, the material performance is reduced, and if the ratio is too high, the adhesive with weak conductivity will encapsulate the whole material, the conductivity of the material is reduced, the active sites of the metal sulfide are difficult to expose, the electrolytic water capacity is reduced, and the anti-counter electrode capacity is reduced.
According to another exemplary embodiment of the present invention, there is provided a method for preparing an anti-counter electrode catalyst for a fuel cell as described above, the method comprising:
s1, obtaining an anti-reverse pole material;
in some embodiments, an anti-counter electrode material is obtained, comprising in particular:
s1.1, mixing stannous chloride, a generating agent, a stripping agent and a dispersing solvent to obtain a mixture;
s1.2, heating the mixture to react to obtain the anti-reflection material.
Specifically, firstly, weighing stannous chloride, pouring the stannous chloride into a beaker, respectively adding a generating agent, a stripping agent and a dispersing solvent into the beaker, firstly stirring the mixture at room temperature for 30min, then pouring the solution into a reaction kettle, putting the reaction kettle into an oven, and setting the temperature to 180-200 ℃, wherein the temperature comprises but is not limited to: the temperature is kept at 180 ℃, 185 ℃, 190 ℃, 195 ℃ and 200 ℃ for 12-16 hours, and the temperature keeping time comprises but is not limited to: 12h, 13h, 14h, 15h, 16h, etc.; and taking out the reactant after natural cooling, and centrifuging to obtain the non-noble metal sulfide.
S2, compounding the anti-counter electrode material and graphene to obtain the catalyst.
Specifically, adding metal sulfide into graphene, continuing to carry out ultrasonic treatment, adding a binder into the solution, carrying out magnetic stirring at a rotating speed of 800r/min for 30min, and then centrifuging to obtain the graphene composite metal sulfide.
In some embodiments, the preparation of graphene comprises: firstly, 1g of expanded graphite is weighed, then DMF and deionized water are added into the graphite, and ultrasonic treatment is carried out, so that a graphene solution is obtained.
Wherein, the mass ratio of the expanded graphite to the DMF is controlled to be 1:10-18, the expanded graphite can be fully dispersed, if the mass ratio is too low, the graphite is difficult to disperse, the sheet-shaped single-layer material is difficult to obtain by subsequent ultrasonic treatment, and if the mass ratio is too high, the ultrasonic efficiency is reduced. Controlling the mass ratio of expanded graphite to DMF includes, but is not limited to: 1: 10. 1: 11. 1: 12. 1: 13. 1: 14. 1: 15. 1: 16. 1:17 and 1:18, etc.
The power of the ultrasonic wave is controlled to be 400-600W, the operation condition can well disperse the expanded graphite, if the numerical value is too low, the graphite is difficult to disperse, if the numerical value is too high, the graphite flake material is broken up by the excessively strong energy, and the structure of the graphene is damaged. The power of ultrasound includes, but is not limited to, 400W, 450W, 500W, 550W, and 600W.
In practical use, the anti-counter electrode catalyst provided by the application is generally mixed with a commercial catalyst, the commercial catalyst can adopt a catalyst with a TKK model of TECOV50E, and specifically, the mixing mass ratio of the anti-counter electrode catalyst to the commercial catalyst is 1:5-10.
According to another exemplary embodiment of the present invention, there is provided a membrane electrode including an anode catalyst layer containing the anti-counter electrode catalyst for a fuel cell as described above.
According to another exemplary embodiment of the present invention, there is provided a fuel cell including the membrane electrode as described above.
The anti-reverse electrode catalyst for fuel cells of the present application, and the preparation method and application thereof will be described in detail with reference to examples, comparative examples and experimental data.
Example 1
A method for preparing an anti-counter electrode catalyst for a fuel cell, the method comprising:
firstly, 1g of expanded graphite is weighed and added into a beaker, 12g of DMF and 20g of deionized water are added into the beaker, the solution is stirred by a key, then ultrasonic is carried out, the ultrasonic power is set to 400W, and the time is 30min.
The beaker was again taken and 1g of SnCl was added to the beaker 2 Adding 4g of TAA,3g of PVP and 30g of TEG into a beaker, stirring the solution at room temperature for 30min, pouring the solution into a reaction kettle, putting the reaction kettle into a baking oven, setting the temperature to 180 ℃, preserving heat for 12h, taking out the reactant after natural cooling, and centrifuging to obtain the metal sulfide.
1g of metal sulfide is added into a solution containing 1g of graphene, then 0.01g of Nafion solution is added into the solution, magnetic stirring is carried out, the rotating speed is 800r/min, the time is 30min, and then centrifugation is carried out, so that the graphene composite metal sulfide is obtained.
Example 2
A method for preparing an anti-counter electrode catalyst for a fuel cell, the method comprising:
firstly, 1g of expanded graphite is weighed and added into a beaker, 15g of DMF and 25g of deionized water are added into the beaker, the solution is stirred by a key, then ultrasonic is carried out, the ultrasonic power is set to 400W, and the time is 30min.
The beaker was again taken and 2g of SnCl was added to the beaker 2 10TAA,6g PVP and 80g TEG are added into a beaker, the solution is stirred for 30min at room temperature, the solution is poured into a reaction kettle, the reaction kettle is placed into a baking oven, the temperature is set to 180 ℃, the heat is preserved for 12h, and after natural cooling, the reactant is taken out and centrifuged, so that the metal sulfide is obtained.
2g of metal sulfide is added into a solution containing 1g of graphene, then 0.02g of Nafion solution is added into the solution, magnetic stirring is carried out, the rotating speed is 800r/min, the time is 30min, and then centrifugation is carried out, so that the graphene composite metal sulfide is obtained.
Example 3
A method for preparing an anti-counter electrode catalyst for a fuel cell, the method comprising:
firstly, 1g of expanded graphite is weighed and added into a beaker, 18g of DMF and 30g of deionized water are added into the beaker, the solution is stirred by a key, then ultrasonic is carried out, the ultrasonic power is set to be 600W, and the time is 30min.
The beaker was again taken and 3g of SnCl was added to the beaker 2 18g of TAA,12g of N- (3-methoxypropyl) -2-pyrrolidone and 100g of TEG are added into a beaker, the solution is stirred for 30min at room temperature, the solution is poured into a reaction kettle, the reaction kettle is placed into an oven, the temperature is set to 180 ℃, the temperature is kept for 12h, and after natural cooling, the reactant is taken out and centrifuged to obtain the metal sulfide.
3g of metal sulfide is added into a solution containing 1g of graphene, then 0.05g of polyurethane is added into the solution, magnetic stirring is performed again, the rotating speed is 800r/min, the time is 30min, and centrifugation is performed to obtain the graphene composite metal sulfide.
Example 4
A method for preparing an anti-counter electrode catalyst for a fuel cell, the method comprising:
firstly, 1g of expanded graphite is weighed and added into a beaker, 18g of DMF and 30g of deionized water are added into the beaker, the solution is stirred by a key, then ultrasonic is carried out, the ultrasonic power is set to be 600W, and the time is 30min.
The beaker was again taken and 4g of SnCl was added to the beaker 2 18g of TAA,14g of pyrrolidone and 100g of TEG are added into a beaker, the solution is stirred for 30min at room temperature, the solution is poured into a reaction kettle, the reaction kettle is placed into an oven, the temperature is set to 180 ℃, the temperature is kept for 12h, after natural cooling, the reactant is taken out, and the metal sulfide is obtained by centrifugation.
Adding 4g of metal sulfide into a solution containing 1g of graphene, adding 0.08g of acrylic acid into the solution, magnetically stirring at a rotating speed of 800r/min for 30min, and centrifuging to obtain the graphene composite metal sulfide.
Example 5
A method for preparing an anti-counter electrode catalyst for a fuel cell, the method comprising:
firstly, 1g of expanded graphite is weighed and added into a beaker, 12g of DMF and 30g of deionized water are added into the beaker, the solution is stirred by a key, then ultrasonic is carried out, the ultrasonic power is set to be 500W, and the time is 30min.
The beaker was again taken and 4g of SnCl was added to the beaker 2 18g of TAA,14g of pyrrolidone and 100g of DEG are added into a beaker, the solution is stirred for 30min at room temperature, the solution is poured into a reaction kettle, the reaction kettle is placed into a baking oven, the temperature is set to 180 ℃, the heat is preserved for 12h, after natural cooling, the reactant is taken out, and the metal sulfide is obtained by centrifugation.
Adding 4g of metal sulfide into a solution containing 1g of graphene, adding 0.12g of acrylic acid into the solution, magnetically stirring at a rotating speed of 800r/min for 30min, and centrifuging to obtain the graphene composite metal sulfide.
Experimental example
Since the results of the respective examples have similarity, the effect will be described below with the catalyst of example 1 alone.
The catalyst of example 1 was added to a commercial catalyst using TKK model TECOV50E. The mass ratio of the anti-reverse electrode catalyst to the commercial catalyst is 1:7.5. The same process is adopted to prepare a film-forming electrode and a performance test and a counter electrode test are carried out, wherein the preparation process of the film-forming electrode is as follows: firstly, 1g of catalyst is weighed into a beaker, 10g of deionized water, 30g of isopropanol and 10g of Nafion solution are added into the beaker, and the mixture is stirred uniformly. And coating the dispersed slurry on a proton membrane by adopting a spraying mode to obtain a membrane electrode, as shown in figure 2.
As can be seen from the graph, in the initial state, after adding the counter electrode catalyst, the current density of the MEA slightly decreases because the counter electrode catalyst does not contain OER active material, the OER capability of the catalyst decreases, and thus the output power of the MEA decreases, but after 10min counter electrode test, it can be seen that the performance of the MEA without adding the counter electrode catalyst decreases sharply, and the applicant analyzed the reason probably because the counter electrode causes carbon corrosion in the catalyst and platinum particles to increase, and thus the ORR capability decreases. After the anti-counter electrode catalyst is added, the output power of the MEA is not obviously reduced, because the metal sulfide is a flaky material with high OER activity, when the counter electrode condition occurs, the metal sulfide can promote the electrolysis of water to provide protons, and reduce the severity of carbon corrosion.
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 catalyst provided by the embodiment of the invention, the nonmetallic sulfide and the catalyst can be well combined through the addition of the graphene, so that the internal resistance and the contact internal resistance of the CCM cannot be reduced due to the addition of the weak conductive substance, and when the counter electrode occurs, the graphene on the composite material can replace carbon on the platinum carbon catalyst to generate carbon corrosion, so that the damage to the catalyst is reduced, the carbon corrosion degree is greatly reduced, and the effect of protecting the battery is further achieved;
(2) According to the catalyst provided by the embodiment of the invention, the non-noble metal sulfide composite graphene with high OER activity is adopted to replace noble metals such as ruthenium and iridium to be added to the CCM anode, so that the manufacturing cost of the anti-counter electrode catalyst is greatly reduced.
Finally, it is also 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. It is therefore intended that the following claims be interpreted as including the 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 modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.

Claims (6)

1. A counter electrode resistant catalyst for a fuel cell, the catalyst comprising: the catalyst is a crosslinked composite of graphene and an anti-counter electrode material, and the anti-counter electrode material comprises: the mass ratio of the graphene to the non-noble metal sulfide is 1:1-4, wherein the non-noble metal sulfide comprises the following raw materials: stannous chloride, a generating agent and a stripping agent, wherein the mass ratio of the stannous chloride to the generating agent to the stripping agent is 1:4-8:2-5, wherein the mass ratio of the graphene to the binder is 1:0.01-0.05; the generating agent comprises TAA, the stripping agent comprises PVP, N- (3-methoxypropyl) -2-pyrrolidone and one of pyrrolidone, and the binder comprises Nafion solution, acrylic acid and polyurethane; the crosslinked composite is obtained by adding non-noble metal sulfide into graphene, performing ultrasonic treatment, adding a binder into the solution, performing magnetic stirring at a rotating speed of 800r/min for 30min, and performing centrifugation.
2. The counter electrode catalyst for a fuel cell according to claim 1, wherein the non-noble metal sulfide is nano-sheet.
3. A membrane electrode comprising an anode catalytic layer containing the anti-reverse catalyst for a fuel cell according to any one of claims 1 to 2.
4. A fuel cell comprising the membrane electrode of claim 3.
5. A method for producing the anti-counter electrode catalyst for a fuel cell according to any one of claims 1 to 2, the method comprising:
obtaining the non-noble metal sulfide of the anti-counter electrode material;
adding non-noble metal sulfide into graphene, performing ultrasonic treatment, adding a binder into the solution, performing magnetic stirring at a rotating speed of 800r/min for 30min, and performing centrifugation to obtain the catalyst.
6. The method for preparing a counter electrode catalyst for a fuel cell according to claim 5, wherein the obtained counter electrode material is a non-noble metal sulfide, specifically comprising:
mixing stannous chloride, a generating agent, a stripping agent and a dispersing solvent to obtain a mixture;
and (3) carrying out a heating reaction on the mixture to obtain the non-noble metal sulfide of the anti-counter electrode material.
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