CN114204056B - Anti-counter electrode optimization design membrane electrode assembly structure and optimization method - Google Patents
Anti-counter electrode optimization design membrane electrode assembly structure and optimization method Download PDFInfo
- Publication number
- CN114204056B CN114204056B CN202111513354.2A CN202111513354A CN114204056B CN 114204056 B CN114204056 B CN 114204056B CN 202111513354 A CN202111513354 A CN 202111513354A CN 114204056 B CN114204056 B CN 114204056B
- Authority
- CN
- China
- Prior art keywords
- layer
- anode
- catalyst
- electrode assembly
- membrane electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- 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
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8814—Temporary supports, e.g. decal
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material 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
- 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]
-
- 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 application belongs to the technical field of fuel cells, and particularly relates to a membrane electrode assembly with anti-reflection optimal design and an optimal design method for the assembly. The membrane electrode assembly comprises four main structures of an anode gas diffusion layer, an anode catalytic layer, a proton exchange layer, a cathode catalytic layer and a cathode gas diffusion layer, wherein an anode transition layer is added between the anode gas diffusion layer and the anode catalytic layer to enhance the anti-counter effect. The application can greatly improve the anti-reverse-polarity capability of the fuel cell and greatly prolong the actual service life of the fuel cell.
Description
Technical Field
The application relates to the technical field of fuel cells, in particular to a membrane electrode assembly structure with anti-counter electrode optimal design.
Background
Currently, the energy sources mainly relied on by human activities come from non-renewable energy sources such as petroleum, coal, natural gas, nuclear energy and the like, and the energy sources have limited reserves and can pollute the environment in the use process. In order to solve the problems of energy and environment, countries around the world are actively searching for clean, efficient and sustainable novel energy. The fuel cell is a device for directly converting chemical energy into electric energy, and has the characteristics of cleanness, quietness and high efficiency. The Proton Exchange Membrane Fuel Cell (PEMFC) is a high-efficiency electrochemical power generation device, can convert chemical energy of hydrogen and oxygen into electric energy, and simultaneously generates water, so that zero emission is realized, and therefore, the proton exchange membrane fuel cell is considered as one of the most promising energy devices in the 21 st century. In particular in the transportation field, PEMFCs are considered as the most likely new energy devices for large-scale applications replacing traditional internal combustion engines. The forda fuel cell car Mirai in 2016 has begun to be marketed, and recently it has also built nationwide hydrogen energy filling stations in combination with 11 enterprise projects such as daily output, honda, etc.; the international well-known enterprises such as ford automobiles and german russian are actively developing new fuel cell automobile technologies.
The proton exchange membrane type fuel cell may have a phenomenon of partial fuel supply shortage during start-stop, load cycle and ice melting cycle, and at this time, the anode cannot provide enough electrons to the cathode, and the anode can provide electrons and H+ through carbon corrosion, platinum oxidation or electrolysis of water so as to compensate the problem of insufficient electrons and H+ generated at the anode. Wherein the reaction chemical equation of the electrolyzed water is shown in the following formula (1):
2H 2 O＝4H + +O 2 +4e - (1)
the reaction chemistry equations for carbon corrosion are shown in the following formulas (2) and (3):
C+2H 2 O＝CO 2 +4H + +4e - (2)
C+H 2 O＝CO+2H + +4e - (3)
wherein the electrolytic water reaction absorbs heat and the carbon corrosion reaction releases heat. When the anode hydrogen supply is insufficient, the formulas (2) and (3) of the carbon corrosion reaction occur first because the reaction potential of the formulas (2) and (3) is relatively low in thermodynamics, the reaction potential of the formula (3) is only 0.2V, and the theoretical reaction potential of the formula (1) is 1.23V, but the reaction kinetics of the formulas (2) and (3) at the lower potential are slow. When the fuel cell is insufficient and the reaction of the formula (1) is not easy to occur, the reaction of the formula (2) and the formula (3) can raise the anode voltage, so that the output voltage of the fuel cell is opposite to the anode voltage, carbon corrosion of an anode component of the MEA, catalyst agglomeration and even damage of a bipolar plate are caused, and the accumulated heat can easily cause small holes in a proton exchange membrane of the MEA, so that gas short circuit is caused, and even catastrophic damage is caused.
To protect the anode catalytic layer, it is common in the industry to add an electrolyzed water reaction catalyst (e.g., irO2, ruO2, tiO 2) to the anode to promote the electrolyzed water reaction of formula (1), where the rapid reaction of formula (1) can greatly mitigate anode carbon corrosion, thereby reducing the locally generated heat of reaction. For example, in the membrane electrode and the preparation method thereof and the fuel cell disclosed in the Chinese patent 112534613A, the water electrolysis catalyst is arranged on one side of the anode catalyst layer, which is close to the anode diffusion layer, so that carbon corrosion can be reduced when the counter electrode occurs, and the water electrolysis catalyst is used for electrolyzing water on one side, which is close to the anode diffusion layer, so that proton flow can be provided for the proton exchange membrane, and the carbon corrosion at the hydrogen oxidation catalyst can be reduced, and the counter electrode tolerance time can be prolonged. However, in practice, the structure only reduces the occurrence of carbon corrosion and prolongs the time of counter-electrode tolerance to a certain extent, and the water electrolysis catalyst is gradually decomposed and reacted in a short time, and finally the problem of carbon corrosion still faces, so that the anode component of the fuel cell is corroded, and the delay process does not actually reach a sufficient ideal time length, in other words, the service life of the cell is very limited by the structure, and the service life of the fuel cell is difficult to be breakthrough-prolonged under the thinking limit of the mode in the industry. Moreover, when the fuel cell is in reverse polarity due to insufficient fuel supply caused by severe operating conditions such as start-up and stop, load cycle, ice melting cycle and the like, the reaction of the water electrolysis catalyst has certain difficulty, so that the corrosion of the fuel cell assembly is further increased.
Disclosure of Invention
The application aims to provide a membrane electrode assembly structure with anti-counter electrode optimal design, so that corrosion of a fuel cell assembly is prevented to a great extent, and the service life of the fuel cell assembly is prolonged.
In order to solve the technical problems, the application adopts the following technical scheme: the utility model provides an anti-antipole optimal design membrane electrode assembly structure, includes positive pole gas diffusion layer, positive pole catalytic layer, proton exchange layer, negative pole catalytic layer and the negative pole gas diffusion layer of arranging in proper order, be equipped with positive pole transition layer between positive pole gas diffusion layer and the positive pole catalytic layer, positive pole transition layer is including setting up the sacrificial anode graphite layer on positive pole catalytic layer surface and setting up the oxygen evolution reaction catalytic layer between sacrificial anode graphite layer and positive pole gas diffusion layer, the sacrificial anode graphite layer is the mixture of graphitized carbon dust and Nafion solution, oxygen evolution reaction catalytic layer is the mixture of electrolysis water catalyst, antioxidation catalyst carrier and Nafion solution.
Wherein the electrolyzed water catalyst is IrO 2 、RuO 2 、TiO 2 、Ir x Sn 1 -xO 2 One or more of PtIr, irRu.
Wherein the particle size of the electrolyzed water catalyst is 2-5nm; the loading of the electrolyzed water catalyst is 0.01-0.1mg/cm 2 。
Preferably, the oxygen evolution reaction catalytic layer is formed by doctor blade coating, screen printing, roller coating, spraying or depositing a mixture of an electrolytic water catalyst, an oxidation resistant catalyst carrier and a Nafion solution on the surface of the conductive microporous structure layer body.
Further, an anode gas inlet and an anode gas outlet are respectively formed on the upper surface and the lower surface of the oxygen evolution reaction catalytic layer, and the concentration of the electrolyzed water catalyst in the oxygen evolution reaction catalytic layer is unevenly distributed; in general, the concentration distribution of the electrolyzed water catalyst in the oxygen evolution reaction catalyst layer is gradually decreased in the direction from the anode gas inlet to the anode gas outlet, but the gradient difference calculation of the adjacent zones follows the following formula:
E＝(E 1 ·X+E 2 ·Y)/[(X+Y)·N](formula 1);
E 1，2 ＝0.18·2n X，Y n.beta.of formula 2;
wherein E is a weighted concentration, E 1 For the calculated X-direction concentration, E 2 For the calculated concentration in the Y direction, X or Y is the coordinate distance of the partition from the partition zero point, E 1 Or E is 2 The formula of (2) is shown in formula (2), N is the total partition number, n X，Y Sequencing the subareas in the X/Y axis direction occupied by the whole oxygen evolution reaction catalytic layer; beta is a correction coefficient of 35.97 when the catalyst component is a single component, and 21.038 when the catalyst component is not unique.
Preferably, the oxidation resistant catalyst support is a corrosion resistant non-carbon support and/or carbon support.
Wherein the non-carbon carrier is TRO, snO 2 、TiO 2 、Ta 2 O 5 、Nb 2 O 5 One of them.
Wherein the carbon support is a carbide or nitride; or the carbon support is highly graphitized carbon black or graphene or carbon nanotubes.
In fact, in the foregoing technical solution, an optimization design method of a membrane electrode assembly has been implied, and the core of the optimization design method includes the following two key steps, which should be determined sequentially, so that the anti-counter electrode performance of the membrane electrode assembly is optimized, and the two key steps are respectively: (1) Selecting an electrolyzed water catalyst and an oxidation-resistant catalyst carrier; (2) The proper number of subareas is selected according to the size of the membrane electrode assembly, and the concentration of the catalyst for the electrolysis water in the subareas is determined according to a calculation method. Of course, this method is mainly applicable to the membrane electrode assembly having the aforementioned structure.
The application has the beneficial effects that: the anode gas diffusion layer and the anode catalytic layer are arranged, the anode transition layer comprises an oxygen evolution reaction catalytic layer and a sacrificial anode graphite layer, so that an electrolytic water catalyst in the oxygen evolution reaction catalytic layer can generate an electrolytic water reaction to relieve the carbon corrosion phenomenon of a fuel cell component caused by insufficient anode fuel supply under extreme operation working conditions of the fuel cell, and the sacrificial anode graphite layer can generate a slow carbon corrosion reaction along with the electrolytic water reaction under the electrolytic water reaction potential due to the fact that the thermodynamic reaction potential of the electrolytic water is higher than the carbon corrosion reaction potential, and is used as a sacrificial material to face the unavoidable carbon corrosion reaction, and the carbon corrosion reaction which originally should occur on the anode material is firstly performed on the sacrificial anode graphite layer, so that the anode material is saved to the greatest extent, the corrosion speed of the anode material is reduced to the greatest extent, and the purpose of prolonging the service life of the fuel cell is achieved.
Drawings
FIG. 1 is a schematic diagram of the overall structure of an embodiment of the present application;
FIG. 2 is a schematic diagram showing the concentration gradient distribution of the electrolyzed water catalyst in the oxygen evolution reaction catalyst layer in the example;
fig. 3 is a schematic diagram showing experimental results of the counter electrode test performed on the membrane electrode assemblies prepared in example 2 and comparative example 1;
fig. 4 is a schematic view showing the partitioning of the oxygen evolution reaction catalyst layer 7 of the membrane electrode assembly in the example;
FIG. 5 shows the humidity distribution of each partition on the catalytic layer 7 of oxygen evolution reaction detected in the normal operation state of the membrane electrode assembly;
FIG. 6 shows the humidity distribution of each partition on the catalytic layer 7 of oxygen evolution reaction detected in the counter electrode state of the membrane electrode assembly;
FIG. 7 is a schematic diagram of a membrane electrode assembly manufacturing process and key process;
fig. 8 is a schematic view showing calculation points of catalyst concentration in a certain partition of the oxygen evolution reaction catalyst layer.
The reference numerals are:
1-anode gas diffusion layer 2-anode catalytic layer
3-proton exchange layer 4-cathode catalytic layer
5-cathode gas diffusion layer 6-sacrificial anode graphite layer
7-oxygen evolution reaction catalytic layer.
Detailed Description
The application will be further described with reference to examples and drawings, to which reference is made, but which are not intended to limit the scope of the application.
It should be noted that spatially relative terms, such as "on" … …, "" on "… … surfaces," "over" and the like, may be used herein for ease of description to describe one device or feature's spatial location relative to another device or feature as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as "above" or "on" other devices or structures would then be oriented "below" or "under" the other devices or structures. Thus, the exemplary term "on … …" may include both orientations of "on … …" and "under … …". The device may also be positioned in other different ways (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
The application is to optimize the anti-reverse performance of the fuel cell, mainly study from two angles of structure and electrolyzed water catalyst distribution, on one hand, the application creatively proposes to design an anode transition layer between an anode gas diffusion layer and an anode catalytic layer, wherein the anode transition layer comprises a sacrificial anode graphite layer and an oxygen evolution reaction catalytic layer; on the other hand, the application provides the idea of designing the concentration of the click water catalyst in a blocking way, and the following experiences are obtained by performing curve fitting through empirical data:
in general, the concentration distribution of the electrolyzed water catalyst in the oxygen evolution reaction catalyst layer is gradually decreased in the direction from the anode gas inlet to the anode gas outlet, but the gradient difference calculation of the adjacent zones follows the following formula:
E＝(E 1 ·X+E 2 ·Y)/[(X+Y)·N](formula 1);
E 1.2 ＝0.18·2n X，Y n.beta.of formula 2;
wherein E is a weighted concentration, E 1 For the calculated X-direction concentration, E 2 For the calculated concentration in the Y direction, X or Y is the coordinate distance of the partition from the partition zero point, E 1 Or E is 2 The formula of (2) is shown in formula (2), N is the total partition number, n X，Y Sequencing the subareas in the X/Y axis direction occupied by the whole oxygen evolution reaction catalytic layer; beta is a correction coefficient of 35.97 when the catalyst component is a single component, and 21.038 when the catalyst component is not unique.
The membrane battery component structure designed by the application is shown in figure 1, and comprises an anode gas diffusion layer 1, an anode catalytic layer 2, a proton exchange layer 3, a cathode catalytic layer 4 and a cathode gas diffusion layer 5, wherein an anode transition layer is arranged between the anode gas diffusion layer 1 and the anode catalytic layer 2, the anode transition layer comprises a sacrificial anode graphite layer 6 arranged on the surface of the anode catalytic layer 2 and an oxygen evolution reaction catalytic layer 7 arranged between the sacrificial anode graphite layer 6 and the anode gas diffusion layer 1, the sacrificial anode graphite layer 6 is a mixture of highly graphitized carbon powder and Nafion solution, and the oxygen evolution reaction catalytic layer 7 is a mixture of an electrolyzed water catalyst, an antioxidant catalyst carrier and Nafion solution. The anode gas diffusion layer 1, the anode transition layer, the anode catalytic layer 2, the proton exchange layer 3, the cathode catalytic layer 4 and the cathode gas diffusion layer 5 can be sequentially laminated and hot pressed, and the anode transition layer, the anode catalytic layer 2, the proton exchange layer 3 and the cathode catalytic layer 4 form a membrane electrode (CCM).
Wherein the electrolyzed water catalyst is IrO 2 、RuO 2 、TiO 2 、Ir x Sn 1 -xO 2 One or more of PtIr, irRu. The particle size of the electrolyzed water catalyst is 2-200nm; the loading of the electrolyzed water catalyst is 0.01-0.1mg/cm 2 The thickness of the oxygen evolution reaction catalytic layer 7 is 1-20um.
Wherein the oxygen evolution reaction catalytic layer 7 is formed by a mixture of an electrolyzed water catalyst, an antioxidant catalyst carrier and a Nafion solution through knife coating or screen printing or roller coating or spraying or depositing on the surface of the conductive microporous structure layer body, and fig. 7 is a manufacturing flow of the whole anti-electrode membrane cell assembly for reference.
The Nafion solution is a perfluorinated sulfonic acid polymer solution, and mainly plays a role in conducting protons, the protons which are not generated in the reaction of the anode catalytic layer are conducted to the anode catalytic layer and then are conducted to the cathode through the proton exchange membrane, and the Nafion solution is used as a coating and a carrier of the catalyst, and the catalytic layer of the catalyst is thinner, so that the material transmission resistance and the electrode resistance can be reduced, and the proton conducting catalyst has a positive effect on the proton conduction.
The sacrificial anode graphite layer 6 is a mixture of highly graphitized carbon powder and Nafion solution, wherein the highly graphitized carbon powder is actually carbon material with a graphite structure formed by heat treatment of amorphous carbon material at high temperature to make phase transition, and the sacrificial anode graphite layer 6 prepared from the mixture of the carbon material and Nafion solution can be used as a more ideal transition structure to bear the influence of carbon corrosion.
In the technical scheme, the oxidation-resistant catalyst carrier is a corrosion-resistant non-carbon carrier and/or a carbon carrier. Wherein the non-carbon carrier is TRO, snO 2 、TiO 2 、Ta 2 O 5 、Nb 2 O 5 One of them. And the carbon support is carbide or nitride; or the carbon support is highly graphitized carbon black or graphene or carbon nanotubes.
The thickness of the sacrificial anode graphite layer is 2-5 um, the size of carbon powder particles is 20-50 um, the model is XC-72 or S560 or S770, and the sacrificial anode graphite layer can be added on the membrane electrode by a knife coating method or a spraying method.
Experimental comparisons of one set of examples with one set of comparative examples are provided below.
Example 1
The membrane electrode assembly structure used in example 1 comprises an anode gas diffusion layer 1, an anode catalytic layer 2, a proton exchange layer 3, a cathode catalytic layer 4, and a cathode gas diffusion layer 5, wherein the anode transition layer comprises a sacrificial anode graphite layer 6 arranged on the surface of the anode catalytic layer 2 and an oxygen evolution reaction catalytic layer 7 arranged between the sacrificial anode graphite layer 6 and the anode gas diffusion layer 1, the sacrificial anode graphite layer 6 is a mixture of highly graphitized carbon powder and Nafion solution, and the oxygen evolution reaction catalytic layer 7 is a mixture of an electrolyzed water catalyst, an antioxidant catalyst carrier and Nafion solution. The anode gas diffusion layer 1, the anode transition layer, the anode catalytic layer 2, the proton exchange layer 3, the cathode catalytic layer 4 and the cathode gas diffusion layer 5 are sequentially overlapped and hot pressed.
The length of the whole battery is 90cm, the width is 40cm, the thickness of the oxygen evolution reaction catalytic layer 7 is 20um in 36 intervals, and the water electrolysis catalyst is selected as TiO 2 Is 0.1mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The concentration distribution of the electrolyzed water catalyst in the oxygen evolution reaction catalyst layer 7 was 0.1mg/cm from the anode gas inlet 2 0.01mg/cm at the anode gas outlet 2 I.e. the overall trend of the concentration of electrolyzed water catalyst decreases from inlet to outlet, but the concentration of electrolyzed water catalyst in each zoneThe difference is calculated using the formula described above.
Comparative example 1
The structure of this comparative example remained substantially the same as that of example 2, and only the difference between it and example 2 was: the concentration of the electrolyzed water catalyst in the oxygen evolution reaction catalyst layer 7 of the present comparative example was uniformly distributed (i.e., the electrolyzed water catalyst having the same concentration was used).
Experimental test
The membrane electrode assemblies prepared in example 1 and comparative example 1 were assembled into single cells, respectively, and sample 1 and sample 2 were obtained at a current density of 0.2A/cm 2 The counter electrode test is carried out, the corresponding battery voltage and the counter electrode resistance time change are observed to be compared, and the test result is shown in figure 3.
It is evident from FIG. 3 that the same loading of IrO 2 The counter electrode test is carried out after the gradient design of the concentration distribution, the counter electrode tolerance time of the battery is prolonged by approximately 2000 seconds, and is more than half an hour, the counter electrode resistance of the membrane electrode is greatly improved, so that the battery damage frequency in the actual use process of the fuel battery can be greatly reduced, and the service life of the fuel battery is greatly prolonged.
According to the anti-reverse pole optimal design membrane electrode assembly structure provided by the embodiment, the electrolytic water reaction can be generated through the electrolytic water catalyst in the oxygen evolution reaction catalytic layer 7 so as to relieve the carbon corrosion phenomenon of the fuel cell assembly caused by insufficient anode fuel supply under the extreme operation working condition of the fuel cell, and moreover, the thermodynamic reaction potential of the electrolytic water is higher than the carbon corrosion reaction potential, so that the sacrificial anode graphite layer 6 can generate slow carbon corrosion reaction along with the electrolytic water reaction under the electrolytic water reaction potential, and the sacrificial anode graphite layer is used as a sacrificial material to face the unavoidable carbon corrosion reaction, so that the carbon corrosion reaction which originally occurs on the anode material is firstly performed on the sacrificial anode graphite layer, thereby protecting the anode material to the greatest extent, reducing the corrosion speed of the anode material to the greatest extent, and prolonging the service life of the fuel cell.
More importantly, by optimizing the design of the oxygen evolution reaction catalytic layer 7, the concentration distribution of the electrolyzed water catalyst is gradually reduced from the anode gas inlet to the anode gas outlet, and the electrolyzed water catalyst with the same concentration is maintained, and the optimized design mode of the concentration distribution has longer voltage-resistant reversal time than that of the electrolyzed water catalyst with conventional gradient distribution and uniform distribution, so that the structure is more reasonable, and the specific reasons for generating the advantages can be referred to a set of tests given below.
The membrane electrode assembly prepared in example 1 was taken, the oxygen evolution reaction catalytic layer 7 was partitioned, the structure of the partitioned structure obtained was shown in fig. 4, then a single cell was prepared for testing, and in the use process, after hydrogen and air containing a certain moisture were introduced, the humidity distribution rule of each partition on the oxygen evolution reaction catalytic layer 7 was detected, so that the results shown in fig. 5 and 6 could be obtained. As can be seen from fig. 5, the humidity distribution rule of the fuel cell is gradually decreased from the anode gas inlet to the anode gas outlet during normal operation of the fuel cell, and as can be seen from fig. 6 (the operating state in which the counter-electrode phenomenon occurs), the humidity distribution rule after the counter-electrode is gradually increased from the anode gas inlet to the anode gas outlet.
Then, according to the humidity distribution rule, the concentration distribution of the electrolyzed water catalyst on the oxygen evolution reaction catalytic layer 7 can be designed to be in a form that the anode gas inlet is more and the anode gas outlet is less so as to achieve a state matched with the humidity distribution rule, so that more sufficient reaction is formed at the anode gas inlet, the anode performs the hydrogen oxidation reaction with the input hydrogen as much as possible, and electrons are output, and the phenomenon that the output electrons are insufficient due to insufficient hydrogen oxidation reaction of the anode under extreme conditions is avoided as much as possible, so that the anode potential is higher than the counter electrode phenomenon of the cathode. The anti-counter electrode effect formed in this way can optimize the structure of the current membrane electrode assembly, and achieve the effect of obviously prolonging the service life of the fuel cell, thereby having very good application prospect.
The foregoing embodiments are preferred embodiments of the present application, and in addition, the present application may be implemented in other ways, and any obvious substitution is within the scope of the present application without departing from the concept of the present application.
In order to facilitate understanding of the improvements of the present application over the prior art, some of the figures and descriptions of the present application have been simplified and some other elements have been omitted for clarity, as will be appreciated by those of ordinary skill in the art.
Claims (8)
1. The utility model provides an anti antipole optimal design membrane electrode assembly structure, includes positive pole gas diffusion layer (1), positive pole catalytic layer (2), proton exchange layer (3), negative pole catalytic layer (4) and negative pole gas diffusion layer (5) that arrange in proper order, its characterized in that: an anode transition layer is arranged between the anode gas diffusion layer (1) and the anode catalytic layer (2), the anode transition layer comprises a sacrificial anode graphite layer (6) arranged on the surface of the anode catalytic layer (2) and an oxygen evolution reaction catalytic layer (7) arranged between the sacrificial anode graphite layer (6) and the anode gas diffusion layer (1), the sacrificial anode graphite layer (6) is a mixture of graphitized carbon powder and Nafion solution, and the oxygen evolution reaction catalytic layer (7) is a mixture of an electrolyzed water catalyst, an antioxidant catalyst carrier and Nafion solution;
the upper surface and the lower surface of the oxygen evolution reaction catalytic layer (7) respectively form an anode gas inlet and an anode gas outlet, and the concentration of the electrolyzed water catalyst in the oxygen evolution reaction catalytic layer (7) is unevenly distributed;
the concentration distribution of the electrolyzed water catalyst in the oxygen evolution reaction catalyst layer is gradually decreased in the direction from the anode gas inlet to the anode gas outlet, but the concentration distribution calculation in any zone follows the following formula:
E=(E 1 ·X+E 2 ·Y)/[(X+Y)·N](formula 1);
E 1,2 =0.18·2n X,Y n.beta.of formula 2;
wherein E is the calculated concentration, E 1 For the calculated X-direction concentration, E 2 For the calculated concentration in the Y direction, X or Y is the coordinate distance of the partition from the partition zero point，E 1 Or E is 2 The formula of (2) is shown in formula (2), N is the total partition number, n X,Y Sequencing the partitions in the X or Y axis direction occupied by the whole oxygen evolution reaction catalytic layer; beta is a correction coefficient of 35.97 when the catalyst component is a single component, and 21.038 when the catalyst component is not unique.
2. The anti-counter electrode optimizing design membrane electrode assembly structure according to claim 1, characterized in that: the electrolyzed water catalyst is IrO 2 、RuO 2 、TiO 2 、Ir x Sn 1 -xO 2 One or more of PtIr, irRu.
3. The anti-counter electrode optimizing design membrane electrode assembly structure according to claim 2, characterized in that: the particle size of the electrolyzed water catalyst is 2-5nm; the loading of the electrolyzed water catalyst is 0.01-0.1mg/cm 2 。
4. The anti-counter electrode optimizing design membrane electrode assembly structure according to claim 1, characterized in that: the oxygen evolution reaction catalytic layer (7) is formed by a mixture of an electrolyzed water catalyst, an antioxidant catalyst carrier and Nafion solution through knife coating, screen printing, roller coating, spraying or depositing on the surface of the conductive microporous structure layer body.
5. The anti-counter electrode optimizing design membrane electrode assembly structure according to claim 1, characterized in that: the oxidation-resistant catalyst carrier is a corrosion-resistant non-carbon carrier and/or a carbon carrier.
6. The anti-counter electrode optimizing design membrane electrode assembly structure according to claim 5, wherein: the non-carbon carrier is TRO, snO 2 、TiO 2 、Ta 2 O 5 、Nb 2 O 5 One of them.
7. The anti-counter electrode optimizing design membrane electrode assembly structure according to claim 6, wherein: the carbon carrier is carbide or nitride; or the carbon support is highly graphitized carbon black or graphene or carbon nanotubes.
8. A method for optimizing the anti-counterelectrode performance of a membrane electrode assembly, which is used for the membrane electrode assembly with the structure as claimed in claims 1 to 7, and is characterized in that: the method comprises the following two key steps, wherein the two steps are determined in sequence so as to optimize the anti-counter electrode performance of the membrane electrode assembly, and the two steps are respectively as follows: (1) Selecting an electrolyzed water catalyst and an oxidation-resistant catalyst carrier; (2) The number of the subareas is selected appropriately according to the size of the membrane electrode assembly, and the concentration of the catalyst of the electrolyzed water in the subareas is determined.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111513354.2A CN114204056B (en) | 2021-12-10 | 2021-12-10 | Anti-counter electrode optimization design membrane electrode assembly structure and optimization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111513354.2A CN114204056B (en) | 2021-12-10 | 2021-12-10 | Anti-counter electrode optimization design membrane electrode assembly structure and optimization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114204056A CN114204056A (en) | 2022-03-18 |
| CN114204056B true CN114204056B (en) | 2023-09-19 |
Family
ID=80652660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111513354.2A Active CN114204056B (en) | 2021-12-10 | 2021-12-10 | Anti-counter electrode optimization design membrane electrode assembly structure and optimization method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114204056B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7291295B2 (en) | 2019-12-31 | 2023-06-14 | コーロン インダストリーズ インク | Membrane-electrode assembly capable of improving reverse voltage durability of fuel cell, manufacturing method thereof, and fuel cell including the same |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101212054A (en) * | 2006-12-31 | 2008-07-02 | 比亚迪股份有限公司 | Fuel cell membrane electrode and its preparation method |
| JP2008293735A (en) * | 2007-05-23 | 2008-12-04 | Toyota Motor Corp | Fuel cell and fuel cell system |
| CN102522572A (en) * | 2012-01-07 | 2012-06-27 | 大连理工大学 | Manufacturing method for integrated membrane electrode of fuel cell |
| CN103367768A (en) * | 2013-07-02 | 2013-10-23 | 上海交通大学 | Method for preparing double-catalyst-layer structure of proton exchange membrane fuel cell |
| CN112103543A (en) * | 2020-10-16 | 2020-12-18 | 大连理工大学 | Gradient membrane electrode for proton exchange membrane fuel cell and preparation method thereof |
| CN112397735A (en) * | 2019-08-19 | 2021-02-23 | 罗伯特·博世有限公司 | Fuel cell electrode catalyst layer coating |
| CN112534613A (en) * | 2019-11-27 | 2021-03-19 | 苏州擎动动力科技有限公司 | Membrane electrode, preparation method thereof and fuel cell |
| CN112615033A (en) * | 2021-01-19 | 2021-04-06 | 泰州市海创新能源研究院有限公司 | Direct methanol fuel cell catalyst layer gradient membrane electrode and preparation method thereof |
| CN113707896A (en) * | 2021-08-30 | 2021-11-26 | 武汉理工氢电科技有限公司 | Fuel cell membrane electrode, preparation method thereof and proton exchange membrane fuel cell |
-
2021
- 2021-12-10 CN CN202111513354.2A patent/CN114204056B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101212054A (en) * | 2006-12-31 | 2008-07-02 | 比亚迪股份有限公司 | Fuel cell membrane electrode and its preparation method |
| JP2008293735A (en) * | 2007-05-23 | 2008-12-04 | Toyota Motor Corp | Fuel cell and fuel cell system |
| CN102522572A (en) * | 2012-01-07 | 2012-06-27 | 大连理工大学 | Manufacturing method for integrated membrane electrode of fuel cell |
| CN103367768A (en) * | 2013-07-02 | 2013-10-23 | 上海交通大学 | Method for preparing double-catalyst-layer structure of proton exchange membrane fuel cell |
| CN112397735A (en) * | 2019-08-19 | 2021-02-23 | 罗伯特·博世有限公司 | Fuel cell electrode catalyst layer coating |
| CN112534613A (en) * | 2019-11-27 | 2021-03-19 | 苏州擎动动力科技有限公司 | Membrane electrode, preparation method thereof and fuel cell |
| CN112103543A (en) * | 2020-10-16 | 2020-12-18 | 大连理工大学 | Gradient membrane electrode for proton exchange membrane fuel cell and preparation method thereof |
| CN112615033A (en) * | 2021-01-19 | 2021-04-06 | 泰州市海创新能源研究院有限公司 | Direct methanol fuel cell catalyst layer gradient membrane electrode and preparation method thereof |
| CN113707896A (en) * | 2021-08-30 | 2021-11-26 | 武汉理工氢电科技有限公司 | Fuel cell membrane electrode, preparation method thereof and proton exchange membrane fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114204056A (en) | 2022-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | Investigations on high performance proton exchange membrane water electrolyzer | |
| Siracusano et al. | Optimization of components and assembling in a PEM electrolyzer stack | |
| Siracusano et al. | An electrochemical study of a PEM stack for water electrolysis | |
| Millet et al. | GenHyPEM: A research program on PEM water electrolysis supported by the European Commission | |
| US10889903B2 (en) | Oxygen-generating anode | |
| Ye et al. | A novel PtRuIr nanoclusters synthesized by selectively electrodepositing Ir on PtRu as highly active bifunctional electrocatalysts for oxygen evolution and reduction | |
| Lee et al. | Development of porous Pt/IrO2/carbon paper electrocatalysts with enhanced mass transport as oxygen electrodes in unitized regenerative fuel cells | |
| Chen et al. | Carbon-coated oxygen vacancies-rich Co3O4 nanoarrays grow on nickel foam as efficient bifunctional electrocatalysts for rechargeable zinc-air batteries | |
| CN103178283B (en) | Hydrogen-bromine energy storage battery structure | |
| CN102054989B (en) | Bipolar plate for proton exchange membrane fuel cell and manufacture method thereof | |
| CN103007926A (en) | Preparation method of platinum/vertical graphene composite material electrocatalyst | |
| CN114204056B (en) | Anti-counter electrode optimization design membrane electrode assembly structure and optimization method | |
| CN105047963A (en) | Novel fuel cell manufacturing method based on graphene thermoelectric management layer | |
| Nguyen et al. | Reversible fuel cells | |
| Liu et al. | Micro-protective layer for lifetime extension of solid polymer electrolyte water electrolysis | |
| Lehner et al. | Water electrolysis | |
| Xu et al. | Platinum activated IrO2/SnO2 nanocatalysts and their electrode structures for high performance proton exchange membrane water electrolysis | |
| CN112221892A (en) | Novel metal bipolar plate surface modification method | |
| Xian et al. | Research progress of the influence of wind power and photovoltaic of power fluctuation on water electrolyzer for hydrogen production | |
| KR20210027924A (en) | High efficiency unitized regenerative fuel cell based on polymer electrolyte membrane, method of operating the same, and method of manufacturing the same | |
| CN216719998U (en) | Air electrode with double-layer diffusion layer | |
| Kuehne et al. | Unitized reversible PEM fuel cells for flexible electrical energy storage | |
| CN110165241B (en) | Graphitized carbon-based corrosion-resistant microporous layer of fuel cell and preparation method thereof | |
| JP3921300B2 (en) | Hydrogen generator | |
| Rajbhandari et al. | An Assessment of Proton Exchange Membrane Water Electrolyzers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |