CN110911714A - Proton exchange membrane fuel cell stack activation method - Google Patents

Proton exchange membrane fuel cell stack activation method Download PDF

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Publication number
CN110911714A
CN110911714A CN201911011884.XA CN201911011884A CN110911714A CN 110911714 A CN110911714 A CN 110911714A CN 201911011884 A CN201911011884 A CN 201911011884A CN 110911714 A CN110911714 A CN 110911714A
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China
Prior art keywords
fuel cell
cell stack
exchange membrane
proton exchange
membrane fuel
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Pending
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CN201911011884.XA
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Chinese (zh)
Inventor
侯向理
裴昱
李叶涛
姚宇希
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NEKSON POWER TECHNOLOGY Co Ltd
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NEKSON POWER TECHNOLOGY Co Ltd
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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
    • 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
    • H01M8/04694Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04701Temperature
    • 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
    • H01M8/04694Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04858Electric variables
    • H01M8/04865Voltage
    • H01M8/0488Voltage of fuel cell stacks
    • 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

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

The invention discloses a proton exchange membrane fuel cell stack activation method, which comprises the following steps: checking the air tightness of the proton exchange membrane fuel cell stack; step two, introducing hydrogen into the anode of the proton exchange membrane fuel cell stack, introducing air into the cathode of the proton exchange membrane fuel cell stack, and gradually reducing the voltage of the proton exchange membrane fuel cell stack in a constant voltage mode and keeping the voltage for 5-10 min; step three, cooling the proton exchange membrane fuel cell stack; step four, repeating the step two and the step three for 3-5 times, and stopping air intake of the anode; and step five, introducing hot water into the anode of the proton exchange membrane fuel cell stack until the performance of the proton exchange membrane fuel cell stack is stable. The activation method of the proton exchange membrane fuel cell stack provided by the invention obviously reduces the activation cost, and the whole activation process can be completed within about 1 h.

Description

Proton exchange membrane fuel cell stack activation method
Technical Field
The present invention relates to the field of fuel cell technology,
in particular, the invention relates to a proton exchange membrane fuel cell stack activation method.
Background
A Proton Exchange Membrane Fuel Cell (PEMFC) is a power generation device that directly converts chemical energy stored in fuel into electrical energy without combustion. The PEMFC mainly comprises a bipolar plate, a porous transmission layer and a membrane electrode, wherein the membrane electrode comprises a proton exchange membrane and electrodes coated with catalysts on two sides, and a gas diffusion layer is arranged outside the electrodes. The membrane electrode is clamped by a graphite plate or a metal plate with a flow channel to form a single cell, and a sealing ring is arranged between the graphite plate and the gas diffusion layer to ensure the air tightness of the cell. The fuel cell stack is formed by stacking a plurality of single cells in series, adding a current collecting plate and an end plate at both ends, and assembling the stack by bolts or binding the stack.
Before the fuel cell is not used, partial molecules in the proton membrane are not regularly arranged, the hydrogen guiding capability is poor, and the proton membrane needs to be activated to open an ion channel of the proton membrane so as to improve the hydrogen guiding capability. If the membrane is put into use in a dry and water-deficient state, the membrane may crack or break down, and the fuel cell must be activated to recover the water content of the membrane. The proton exchange membrane fuel cell stack can not be directly used after being assembled, and needs to be activated first, so that the activity and the utilization rate of a catalyst in a membrane electrode are improved, and the fuel cell stack can exert the optimal working state and performance. The current common activation methods of the fuel cell comprise an electrolytic activation method and a constant-current natural activation method, and the electrolytic activation method easily causes the problems of uneven voltage distribution, unparallel activity effect, reduced membrane electrode activity and the like; the constant-current natural activation method needs to consume a large amount of hydrogen and an additional humidifying device, increases the cost and simultaneously needs a long activation time, and the activation time is usually more than 4 h.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a proton exchange membrane fuel cell stack activation method.
In order to solve the problems, the invention adopts the following technical scheme:
a proton exchange membrane fuel cell stack activation method comprises the following steps:
checking the air tightness of the proton exchange membrane fuel cell stack;
step two, introducing hydrogen into the anode of the proton exchange membrane fuel cell stack, introducing air into the cathode of the proton exchange membrane fuel cell stack, and gradually reducing the voltage of the proton exchange membrane fuel cell stack in a constant voltage mode and keeping the voltage for 5-10 min;
step three, cooling the proton exchange membrane fuel cell stack;
step four, repeating the step two and the step three for 3-5 times, and stopping air intake of the anode;
and step five, introducing hot water into the anode of the proton exchange membrane fuel cell stack until the performance of the proton exchange membrane fuel cell stack is stable.
Preferably, in the second step, the starting single-chip voltage for gradually reducing the voltage of the pem fuel cell stack is set to 0.5V.
Preferably, the voltage of the proton exchange membrane fuel cell stack is gradually reduced in a mode of 0.5V of single-chip voltage, until all the single-chip voltages are between 0.1V and 0.3V.
Preferably, in the fifth step, the temperature of the hot water is 50-70 ℃, and the time for introducing the hot water is 5-30 min.
Preferably, in the second step, the flow rate of the introduced hydrogen is 50 mlmin-1~5000 mlmin-1And the hydrogen pressure is not more than 40 Kpa.
Preferably, the temperature of the water-cooled reactor or the air-cooled reactor is adopted in the third step.
Compared with the prior art, the invention has the following technical effects:
the proton exchange membrane fuel cell stack activation method provided by the invention does not need an auxiliary humidifying device, only needs a small amount of air and hydrogen in the activation process, has less energy consumption and obviously reduces the activation cost; on the other hand, the activation can be quickly completed by selecting the activation in a low-voltage mode, the activation time is obviously reduced, and the whole activation process can be completed within about 1 h.
Drawings
FIG. 1 is an I-V curve before and after activation of a monolithic cell provided in example 1 of the present invention;
fig. 2 is an I-V curve before and after activation of 30 cells provided in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a proton exchange membrane fuel cell stack activation method, which comprises the following steps:
checking the air tightness of the proton exchange membrane fuel cell stack;
step two, introducing hydrogen into the anode of the proton exchange membrane fuel cell stack, introducing low-flow air into the cathode, and gradually reducing the voltage of the proton exchange membrane fuel cell stack in a constant-voltage mode for 5-10 min;
step three, cooling the proton exchange membrane fuel cell stack;
step four, repeating the step two and the step three for 3-5 times, and stopping air intake of the anode;
and step five, introducing hot water into the anode of the proton exchange membrane fuel cell stack until the performance of the proton exchange membrane fuel cell stack is stable.
Specifically, in the first step, the proton exchange membrane fuel cell stack is placed on a test platform, nitrogen is introduced into a cathode, hydrogen is introduced into an anode, and the air tightness of the proton exchange membrane fuel cell stack is checked.
And step two, introducing hydrogen into the anode of the proton exchange membrane fuel cell stack, introducing low-flow air into the cathode, adjusting the electronic load to a constant-voltage mode, and gradually reducing the voltage of the proton exchange membrane fuel cell stack in a single-chip voltage 0.5V mode until all single-chip voltages are between 0.1V and 0.3V. Oxidation-reduction reaction occurs in the proton exchange membrane fuel cell stack, and the activity of the catalyst is recovered; the cathode only needs to be introduced with a small amount of air, and the flow rate of the introduced air is 200 mlmin-1~20lmin-1After voltage is applied, under the action of concentration polarization, 2-3A of small current is generated in the proton exchange membrane fuel cell stack, so that the activation process is promoted.
Preferably, the hydrogen gas is introduced at a flow rate of 50 mlmin-1~5000 mlmin-1And controlling the pressure of the introduced hydrogen to be not more than 40 Kpa in order to prevent the proton exchange membrane from being damaged by overlarge hydrogen pressure.
In the activation process, due to the fact that the proton exchange membrane fuel cell stacks are different in design and structure, the conditions for voltage uniformity of the single-chip cells are different, the voltage of the single-chip cells is 0.1V-0.3V, and in addition, the phenomenon of pole reversal of the single-chip cells can be prevented by means of gradually reducing the voltage.
And after one activation process, cooling the proton exchange membrane fuel cell stack in an air cooling or water cooling mode, then repeating the activation process for 3-5 times, and introducing hot water with the temperature of 50-70 ℃ into the anode of the proton exchange membrane fuel cell stack for 5-30 min. The process is to increase the wetness of the proton exchange membrane, recover the water content of the membrane and further improve the working performance of the proton exchange membrane fuel cell stack.
The activation method of the proton exchange membrane fuel cell stack provided by the invention firstly recovers the catalytic activity of a catalyst in the proton exchange membrane fuel cell stack by gradually reducing the loading voltage, and then improves the wettability of a membrane electrode by introducing hot water into the anode of the proton exchange membrane fuel cell stack so as to activate the proton exchange membrane fuel cell stack. The activation method does not need an auxiliary humidifying device, only needs low-flow air and a small amount of hydrogen in the activation process, has less energy consumption and obviously reduces the activation cost; on the other hand, the activation can be quickly completed by selecting the activation in a low-voltage mode, the activation time is obviously reduced, and the whole activation process can be completed within about 1 h.
The following is a further description with reference to specific examples.
Example 1
The embodiment 1 of the invention provides a proton exchange membrane fuel cell stack activation method, which comprises the following steps:
checking the air tightness of the proton exchange membrane fuel cell stack;
step two, introducing hydrogen into the anode of the single proton exchange membrane fuel cell stack,the hydrogen flow rate is 5000 mlmin-1The hydrogen pressure is 4 Kpa, low-flow air is introduced into the cathode, the electronic load is adjusted to a constant-voltage mode, the voltage of the proton exchange membrane fuel cell stack is gradually reduced in a single-chip 0.5V mode until the single-chip voltage reaches 0.2V, and the voltage is kept for 5 min;
step three, after the electronic load is closed, air cooling is carried out on the proton exchange membrane fuel cell stack;
step four, the electronic load is closed after the step two and the step three are repeated for 5 times, and the anode stops air inlet;
and step five, introducing 60 ℃ hot water into the anode of the proton exchange membrane fuel cell stack for 5 min, and totally taking 55 min when the performance of the proton exchange membrane fuel cell stack is stable.
The V-I curves performed before and after activation of the monolithic pem fuel cell stack of example 1 were measured and are shown in figure 1.
Example 2
The embodiment 2 of the invention provides a proton exchange membrane fuel cell stack activation method, which comprises the following steps:
checking the air tightness of the proton exchange membrane fuel cell stack;
step two, introducing hydrogen into the anodes of the 30 proton exchange membrane fuel cell stacks at the hydrogen flow rate of 5000 mlmin-1The hydrogen pressure is 30 Kpa, low-flow air is introduced into the cathode, the electronic load is adjusted to a constant-voltage mode, the voltage of the proton exchange membrane fuel cell stack is gradually reduced in a single-chip 0.5V mode until the single-chip voltage reaches 0.2V, and the voltage is kept for 8 min;
step three, after the electronic load is closed, air cooling is carried out on the proton exchange membrane fuel cell stack;
step four, the electronic load is closed after the step two and the step three are repeated for 5 times, and the anode stops air inlet;
and step five, introducing 60 ℃ hot water into the anode of the proton exchange membrane fuel cell stack for 15 min, and taking 70 min in total when the performance of the proton exchange membrane fuel cell stack is stable.
The V-I curves of the 30 pem fuel cell stacks of example 2 before and after activation were measured and the results are shown in fig. 2.
The present invention is not limited to the above-described specific embodiments, and various modifications and variations are possible. Any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention should be included in the scope of the present invention.

Claims (6)

1. A proton exchange membrane fuel cell stack activation method is characterized by comprising the following steps:
checking the air tightness of the proton exchange membrane fuel cell stack;
step two, introducing hydrogen into the anode of the proton exchange membrane fuel cell stack, introducing air into the cathode of the proton exchange membrane fuel cell stack, and gradually reducing the voltage of the proton exchange membrane fuel cell stack in a constant voltage mode and keeping the voltage for 5-10 min;
step three, cooling the proton exchange membrane fuel cell stack;
step four, repeating the step two and the step three for 3-5 times, and stopping air intake of the anode;
and step five, introducing hot water into the anode of the proton exchange membrane fuel cell stack until the performance of the proton exchange membrane fuel cell stack is stable.
2. The pem fuel cell stack activation method of claim 1, wherein in said second step, said initial single-chip voltage for gradually decreasing pem fuel cell stack voltage is set to 0.5V.
3. The PEMFC stack activation method according to claim 2, wherein the PEMFC stack voltage is gradually decreased in a 0.5V monolithic voltage mode until all monolithic voltages are between 0.1V and 0.3V.
4. The activation method of proton exchange membrane fuel cell stack as claimed in claim 1, wherein in the fifth step, the temperature of the hot water is 50-70 ℃, and the time for introducing the hot water is 5-30 min.
5. The method of claim 1, wherein in the second step, the hydrogen is introduced at a flow rate of 50 mlmin-1~5000 mlmin-1And the hydrogen pressure is not more than 40 Kpa.
6. The activation method for proton exchange membrane fuel cell stack as claimed in any one of claims 1 to 5, wherein the cooling of water-cooled stack or air-cooled stack is adopted in the third step.
CN201911011884.XA 2019-10-23 2019-10-23 Proton exchange membrane fuel cell stack activation method Pending CN110911714A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111261900A (en) * 2020-04-28 2020-06-09 深圳市南科燃料电池有限公司 Activation method of cathode open type air-cooled fuel cell membrane electrode
CN111584901A (en) * 2020-05-12 2020-08-25 浙江高成绿能科技有限公司 Method for rapidly recovering performance of fuel cell
CN113871633A (en) * 2021-09-26 2021-12-31 合肥综合性国家科学中心能源研究院(安徽省能源实验室) Method for high-efficiency in-situ activation of membrane electrode of proton exchange membrane fuel cell
CN114024000A (en) * 2022-01-05 2022-02-08 佛山市清极能源科技有限公司 Anode activation method of proton exchange membrane fuel cell stack
CN114024001A (en) * 2022-01-05 2022-02-08 佛山市清极能源科技有限公司 Cathode activation method of proton exchange membrane fuel cell stack

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CN1794505A (en) * 2005-09-15 2006-06-28 东莞新能源电子科技有限公司 Small-sized direct methanol fuel battery stack modularization assembly its activation method
CN101132068A (en) * 2006-08-25 2008-02-27 比亚迪股份有限公司 Activation method for membrane electrode of fuel cell
CN105552405A (en) * 2016-01-28 2016-05-04 新源动力股份有限公司 Method for improving activation efficiency of fuel cell
KR101922329B1 (en) * 2017-03-02 2018-11-26 한국에너지기술연구원 Method for activating and long-term storaging of air-breathing polymer electrolyte membrane fuel cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1794505A (en) * 2005-09-15 2006-06-28 东莞新能源电子科技有限公司 Small-sized direct methanol fuel battery stack modularization assembly its activation method
CN101132068A (en) * 2006-08-25 2008-02-27 比亚迪股份有限公司 Activation method for membrane electrode of fuel cell
CN105552405A (en) * 2016-01-28 2016-05-04 新源动力股份有限公司 Method for improving activation efficiency of fuel cell
KR101922329B1 (en) * 2017-03-02 2018-11-26 한국에너지기술연구원 Method for activating and long-term storaging of air-breathing polymer electrolyte membrane fuel cell

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111261900A (en) * 2020-04-28 2020-06-09 深圳市南科燃料电池有限公司 Activation method of cathode open type air-cooled fuel cell membrane electrode
CN111584901A (en) * 2020-05-12 2020-08-25 浙江高成绿能科技有限公司 Method for rapidly recovering performance of fuel cell
CN111584901B (en) * 2020-05-12 2021-10-26 浙江高成绿能科技有限公司 Method for rapidly recovering performance of fuel cell
CN113871633A (en) * 2021-09-26 2021-12-31 合肥综合性国家科学中心能源研究院(安徽省能源实验室) Method for high-efficiency in-situ activation of membrane electrode of proton exchange membrane fuel cell
CN114024000A (en) * 2022-01-05 2022-02-08 佛山市清极能源科技有限公司 Anode activation method of proton exchange membrane fuel cell stack
CN114024001A (en) * 2022-01-05 2022-02-08 佛山市清极能源科技有限公司 Cathode activation method of proton exchange membrane fuel cell stack

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