CN113629276A - Method for accelerated testing of membrane electrode durability of proton exchange membrane fuel cell - Google Patents

Method for accelerated testing of membrane electrode durability of proton exchange membrane fuel cell Download PDF

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Publication number
CN113629276A
CN113629276A CN202110868536.5A CN202110868536A CN113629276A CN 113629276 A CN113629276 A CN 113629276A CN 202110868536 A CN202110868536 A CN 202110868536A CN 113629276 A CN113629276 A CN 113629276A
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China
Prior art keywords
proton exchange
anode
fuel cell
exchange membrane
durability
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Pending
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CN202110868536.5A
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Chinese (zh)
Inventor
窦美玲
王琨
李宁
王峰
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Priority to CN202110868536.5A priority Critical patent/CN113629276A/en
Publication of CN113629276A publication Critical patent/CN113629276A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04223Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01RMEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/382Arrangements for monitoring battery or accumulator variables, e.g. SoC
    • G01R31/3835Arrangements for monitoring battery or accumulator variables, e.g. SoC involving only voltage measurements
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04223Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
    • H01M8/04225Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells during start-up
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04223Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
    • H01M8/04228Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells during shut-down
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04223Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
    • H01M8/04238Depolarisation
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/04537Electric variables
    • H01M8/04544Voltage
    • H01M8/04552Voltage of the individual fuel cell
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Abstract

The invention relates to an accelerated test method for the durability of a membrane electrode of a proton exchange membrane fuel cell, which is used for simulating the starting/stopping process of an unprotected proton exchange membrane fuel cell by forcibly generating a hydrogen-air interface through the gas pressure difference on the two sides of a cathode and an anode. The specific method comprises the following steps: after the cell is stopped, the hydrogen is stopped to be led to the anode, a certain back pressure is arranged at the outlet of the cathode side of the cell, at the moment, air at the cathode side permeates to the anode through a proton exchange membrane under the action of the pressure difference between the two sides of the cathode and the anode, a hydrogen-air interface is generated at the anode side, the starting/stopping process is simulated, and the durability of the membrane electrode of the fuel cell can be evaluated.

Description

Method for accelerated testing of membrane electrode durability of proton exchange membrane fuel cell
Technical Field
The invention relates to the field of fuel cells, in particular to an accelerated test method for the durability of a membrane electrode of a proton exchange membrane fuel cell, which is used for evaluating the durability of the membrane electrode of the proton exchange membrane fuel cell in the starting/stopping process.
Background
The proton exchange membrane fuel cell is a power generation device, and the product is environment-friendly and pollution-free water without emission of gases such as carbon dioxide and sulfur dioxide, so that the proton exchange membrane fuel cell is widely concerned by researchers. However, the insufficient durability of the fuel cell severely restricts the large-scale commercialization thereof, and a rapid and effective evaluation method for the durability of the membrane electrode is still lacking.
Under frequent dynamic working conditions, such as frequent start-stop, rapid load change and other unsteady-state operations, the key materials are attenuated, and the service life of the fuel cell is shortened. Especially, in the starting/stopping process, ambient air invades into the cell, hydrogen and air exist at the anode side at the same time at the starting/stopping moment of the fuel cell to form a hydrogen-air interface, so that high potential of a cathode is generated, the instantaneous local potential is as high as 1.6V, at the moment, the corrosion of a catalyst carbon carrier is aggravated, catalyst particles are caused to fall off and agglomerate from the carrier, the number of effective catalytic active sites is reduced, and the performance of the cell is reduced.
At present, a method of forming a hydrogen-air interface on an anode side by diffusing air in an environment to the anode is often adopted to study the attenuation behavior of a membrane electrode of a fuel cell in the starting/stopping process. The method is not easy to control the air content at the anode side, and is easy to introduce impurities existing in the ambient air, thereby having adverse effects on experimental results.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for testing the durability accelerated attenuation of a membrane electrode of a proton exchange membrane fuel cell.
More specifically, the method for testing the durability of the membrane electrode of the proton exchange membrane fuel cell comprises the following steps:
(1) assembling the membrane electrode into a single cell, and respectively introducing hydrogen and air into the anode and the cathode to activate the single cell;
(2) after activation is completed, carrying out initial polarization curve test on the single cell;
(3) after the performance test is finished, stopping supplying air to the anode side, continuously supplying air to the cathode side, and setting a certain back pressure on the cathode side of the single cell to enable the air on the cathode side to permeate to the anode side through the proton exchange membrane under the action of differential pressure and generate a hydrogen-air interface on the anode side;
(4) after the back pressure is set, the battery heating device is closed, after the temperature of the battery is naturally cooled from the working temperature, the battery heating device is started again, the temperature is raised to the working temperature again, and the process is a one-time starting/stopping process;
(5) after several starting/stopping processes, when the voltage of the battery is attenuated by more than 10%, the service life of the battery is considered to reach the limit, the battery is activated again, and then the polarization curve test is carried out.
In the embodiment of the invention, a pressure difference exists between the anode side and the cathode side of the single cell, and the gas on the cathode side permeates to the anode side through the proton exchange membrane, wherein the pressure difference is 5-50 kPa.
In the embodiment of the invention, the working temperature is 50-80 ℃, and the temperature is naturally cooled to 15-35 ℃.
The invention also provides an accelerated test method for the durability of the membrane electrode of the proton exchange membrane fuel cell, which is used for simulating the influence of a hydrogen-air interface formed in the unprotected starting/stopping process on the durability of the membrane electrode.
Compared with the prior art, the invention has the following advantages:
the invention provides a reliable method for accelerating the test of the durability of a fuel cell membrane electrode in the starting/stopping process, wherein the hydrogen is stopped to be led to an anode after a cell stops, a certain back pressure is arranged at the outlet of the cathode side of the cell, air at the cathode side permeates to the anode through a proton exchange membrane under the action of the pressure difference between the two sides of the cathode and the anode, a hydrogen-air interface is generated at the anode side, the starting/stopping process is simulated, and the durability of the fuel cell membrane electrode can be evaluated.
The invention provides a simple and rapid accelerated testing method for the durability of a membrane electrode of a proton exchange membrane fuel cell, which aims at the attenuation of the membrane electrode in the starting/stopping process. And constructing a hydrogen-air interface on the anode side through the pressure difference between the two sides of the cathode and the anode, and testing the performance of the polarization curve of the cell before and after testing to quickly evaluate the durability of the membrane electrode. The method of the invention can provide reliable data for the failure mechanism analysis of the membrane electrode of the fuel cell in the starting/stopping process.
The accelerated test method for the durability of the membrane electrode of the fuel cell can simulate the unprotected starting/stopping process, effectively shortens the durability test time, and avoids the influence of impurities possibly existing in the ambient air on the experimental result.
The invention can be widely applied to the field of proton exchange membrane fuel cells.
Drawings
The following figures are some embodiments of the invention, other figures of which may be obtained by those skilled in the art without inventive effort.
FIG. 1 is a graph showing the polarization curves of a single cell before and after a start-up/shut-down cycle test when the cathode-anode differential pressure is 10 kPa;
FIG. 2 is a graph showing the cell polarization curves before and after the start-up/shut-down cycle test when the cathode-anode differential pressure is 25 kPa.
Detailed Description
The invention is further elucidated with reference to the figures and examples. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without inventive step, are within the scope of the present invention.
Unless specifically stated otherwise, the relative arrangement of the components and steps, experimental parameters set forth in the following examples do not limit the scope of the invention. Techniques, methods, and apparatus known to those skilled in the relevant art are not discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, all specific parameter values should be construed as exemplary only and not as limiting. Thus, other examples of embodiments may have different values.
Example 1
After a membrane electrode consisting of a cathode gas diffusion layer, a cathode catalyst layer, a proton exchange membrane, a cathode catalyst layer and a cathode gas diffusion layer is assembled into a single cell, hydrogen and air are respectively introduced into an anode and a cathode, the flow rates of the hydrogen and the air are set to be 200 mL/min and 800 mL/min, the single cell is activated at 80 ℃, and after the activation is completed, the initial polarization curve of the single cell is tested.
After the test, the flow rate of the anode reaction gas is adjusted to 0, the back pressure is set to 0, the flow rate of the cathode side reaction gas is adjusted to 500 mL/min, the back pressure is set to 10 kPa, and the pressure difference between the two sides of the cathode and the anode is 10 kPa, so that the air on the cathode side permeates to the anode side through the proton exchange membrane under the action of the pressure difference, and a hydrogen-air interface is generated on the anode side. And then, closing the battery heating system, and after the temperature is naturally reduced from 80 ℃ to 35 ℃, re-opening the battery heating system, normally raising the temperature to 80 ℃, and simulating start/stop circulation. After several times of simulated starting/stopping, the battery is activated again, and after the activation is completed, the battery performance test is carried out. The results of the polarization curves show (fig. 1) that the voltage drop at the rated current density reaches 7.2% after 60 start/stop cycles of the battery.
Example 2
The operating conditions were the same as in example 1 except that the pressure at the outlet of the cathode side was adjusted to 25 kPa in step (4), the back pressure of the anode side was still set to 0, and the pressure difference across the cathode and anode was kept at 25 kPa. The results of the polarization curves show (fig. 2), after the battery is subjected to 20 start/stop cycles, the voltage drop under the rated current density reaches 19.1%, and therefore, the evaluation time of the durability of the membrane electrode can be obviously shortened by increasing the pressure difference between the cathode and the anode.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (5)

1. A method for testing the durability and the accelerated attenuation of a membrane electrode of a proton exchange membrane fuel cell is characterized in that gas pressure difference is arranged on two sides of a cathode and an anode of the fuel cell, air on the cathode side permeates to the anode through a proton exchange membrane under the action of the pressure difference, a hydrogen-air interface is generated on the anode, and the durability of the membrane electrode in the starting/stopping process is evaluated by testing a cell polarization curve before and after starting/stopping.
2. The accelerated test method for the membrane electrode durability of the proton exchange membrane fuel cell according to claim 1, which is characterized by comprising the following steps:
(1) assembling the membrane electrode into a single cell, and respectively introducing hydrogen and air into the anode and the cathode to activate the single cell;
(2) after activation is completed, carrying out initial polarization curve test on the single cell;
(3) after the performance test is finished, stopping supplying air to the anode side, continuously supplying air to the cathode side, and setting a certain back pressure on the cathode side of the single cell to enable the air on the cathode side to permeate to the anode side through the proton exchange membrane under the action of differential pressure and generate a hydrogen-air interface on the anode side;
(4) after the back pressure is set, the battery heating device is closed, after the temperature of the battery is naturally cooled from the working temperature, the battery heating device is started again, the temperature is raised to the working temperature again, and the process is a one-time starting/stopping process;
(5) after several starting/stopping processes, when the voltage of the battery is attenuated by more than 10%, the service life of the battery is considered to reach the limit, the battery is activated again, and then the polarization curve test is carried out.
3. The accelerated test method for the durability of the membrane electrode of the proton exchange membrane fuel cell according to claim 2, characterized in that a pressure difference exists between the anode side and the cathode side of the single cell, so that gas on the cathode side permeates to the anode side through the proton exchange membrane, and the pressure difference is 5-50 kPa.
4. The accelerated test method for the durability of the membrane electrode assembly of the proton exchange membrane fuel cell according to claim 2, wherein the working temperature is 50-80 ℃, and the temperature is naturally cooled to 15-35 ℃.
5. The accelerated test method for the membrane electrode durability of the proton exchange membrane fuel cell according to any one of claims 2 to 4, which is used for simulating the influence of a hydrogen-air interface formed during unprotected start-up/shut-down on the membrane electrode durability.
CN202110868536.5A 2021-07-30 2021-07-30 Method for accelerated testing of membrane electrode durability of proton exchange membrane fuel cell Pending CN113629276A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114221001A (en) * 2021-11-18 2022-03-22 四川大学 Preparation of membrane electrode for fuel cell and method for accelerating evaluation of durability of membrane electrode
CN115000468A (en) * 2022-06-10 2022-09-02 潍柴动力股份有限公司 Method for testing durability of fuel cell stack under accelerated start-stop working condition
CN116558999A (en) * 2023-07-07 2023-08-08 韵量燃料电池(广东)有限公司 Method and system for testing cross pressure cycle life of fuel cell stack

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Publication number Priority date Publication date Assignee Title
CN107039668A (en) * 2017-03-31 2017-08-11 武汉理工大学 A kind of gas diffusion layer of proton exchange membrane fuel cell durability accelerated test method
CN208955114U (en) * 2018-12-17 2019-06-07 南京攀峰赛奥能源科技有限公司 A kind of fuel battery test system
CN110530954A (en) * 2019-08-28 2019-12-03 上海交通大学 A kind of non-precious metal catalyst membrane electrode durability test method
CN110850320A (en) * 2019-11-18 2020-02-28 湖南省计量检测研究院 Durability test method for hydrogen fuel cell
CN111103545A (en) * 2019-12-27 2020-05-05 浙江锋源氢能科技有限公司 Fuel cell membrane electrode performance testing method
KR20200074539A (en) * 2018-12-17 2020-06-25 주식회사 엘지화학 Durability testing method and device for membrane electrode assembly of fuel cell
CN112763392A (en) * 2020-12-30 2021-05-07 新源动力股份有限公司 Method for accelerating evaluation of durability of proton exchange membrane for fuel cell

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107039668A (en) * 2017-03-31 2017-08-11 武汉理工大学 A kind of gas diffusion layer of proton exchange membrane fuel cell durability accelerated test method
CN208955114U (en) * 2018-12-17 2019-06-07 南京攀峰赛奥能源科技有限公司 A kind of fuel battery test system
KR20200074539A (en) * 2018-12-17 2020-06-25 주식회사 엘지화학 Durability testing method and device for membrane electrode assembly of fuel cell
CN110530954A (en) * 2019-08-28 2019-12-03 上海交通大学 A kind of non-precious metal catalyst membrane electrode durability test method
CN110850320A (en) * 2019-11-18 2020-02-28 湖南省计量检测研究院 Durability test method for hydrogen fuel cell
CN111103545A (en) * 2019-12-27 2020-05-05 浙江锋源氢能科技有限公司 Fuel cell membrane electrode performance testing method
CN112763392A (en) * 2020-12-30 2021-05-07 新源动力股份有限公司 Method for accelerating evaluation of durability of proton exchange membrane for fuel cell

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114221001A (en) * 2021-11-18 2022-03-22 四川大学 Preparation of membrane electrode for fuel cell and method for accelerating evaluation of durability of membrane electrode
CN115000468A (en) * 2022-06-10 2022-09-02 潍柴动力股份有限公司 Method for testing durability of fuel cell stack under accelerated start-stop working condition
CN116558999A (en) * 2023-07-07 2023-08-08 韵量燃料电池(广东)有限公司 Method and system for testing cross pressure cycle life of fuel cell stack
CN116558999B (en) * 2023-07-07 2023-09-26 韵量燃料电池(广东)有限公司 Method and system for testing cross pressure cycle life of fuel cell stack

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