CN117594833A - Performance recovery method for fuel cell system without external humidification - Google Patents

Performance recovery method for fuel cell system without external humidification Download PDF

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Publication number
CN117594833A
CN117594833A CN202311637786.3A CN202311637786A CN117594833A CN 117594833 A CN117594833 A CN 117594833A CN 202311637786 A CN202311637786 A CN 202311637786A CN 117594833 A CN117594833 A CN 117594833A
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China
Prior art keywords
fuel cell
cell system
stopping
load
low temperature
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CN202311637786.3A
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Chinese (zh)
Inventor
吕平
孙昕
许有伟
刘雪婷
邢丹敏
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Sunrise Power Co Ltd
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Sunrise Power Co Ltd
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Priority to CN202311637786.3A priority Critical patent/CN117594833A/en
Publication of CN117594833A publication Critical patent/CN117594833A/en
Pending legal-status Critical Current

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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
    • H01M8/04007Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H01M8/04029Heat exchange using liquids
    • 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
    • H01M8/04007Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H01M8/04067Heat exchange or temperature measuring elements, thermal insulation, e.g. heat pipes, heat pumps, fins
    • H01M8/04074Heat exchange unit structures specially adapted for fuel cell
    • 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
    • H01M8/04082Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04119Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
    • H01M8/04126Humidifying
    • 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
    • H01M8/04082Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201Reactant storage and supply, e.g. means for feeding, pipes
    • 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
    • H01M8/04701Temperature
    • H01M8/04723Temperature of the coolant
    • 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 provides a performance recovery method of an externally-humidification-free fuel cell system, which specifically comprises the following steps: step 1: setting the temperature of the high-low temperature test chamber to be 5-10 ℃, and placing the fuel cell system in the high-low temperature test chamber; step 2: starting a fuel cell system, introducing hydrogen to the anode side of a galvanic pile, introducing air to the cathode side, starting a cooling liquid to circularly maintain the temperature of the galvanic pile, and operating for 5-10min under the conditions of applying a certain current density load and controlling the rotating speed r=5000 r/min of a reflux pump; step by stepStep 3: stopping the fuel cell system without purging in the stopping process, and standing the fuel cell system for 3-5min after stopping; step 4: repeating the steps 2-3, wherein the load applied for the first time is 50mA/cm 2 And (2) lifting the load by 50-200mA/cm when repeating the step (2) every time later 2 Until the fuel cell system can be loaded to 500mA/cm 2 And then the high-low temperature test chamber can be restored to room temperature for activation. The invention solves the problem that the system performance recovery of the fuel cell system without external humidification cannot be realized through external humidification after the purging is over-dry.

Description

Performance recovery method for fuel cell system without external humidification
Technical Field
The invention relates to the technical field of fuel cells, in particular to a performance recovery method of an externally-humidification-free fuel cell system.
Background
The proton exchange membrane fuel cell is a clean and efficient energy conversion device, and has the advantages of low working temperature, high dynamic response speed, no noise and the like, so that the proton exchange membrane fuel cell has been widely paid attention to the field of vehicles in recent years. Under the application scene of passenger cars, in order to consider the volume and cost of the system, more and more system manufacturers replace the external humidification of the air side by adopting a hydrogen backflow mode, the water generated in the reaction process of the fuel cell is utilized to carry out self-humidification on the electric pile, the technical scheme can not only reduce the volume of the system and reduce the cost, but also improve the hydrogen utilization rate, but also can cause the electric pile to blow out to dry under the condition of initial installation or certain improper use of the system to cause the system to run abnormally, the phenomenon of low voltage single protection or low total voltage protection is loaded under severe conditions, and then emergency shutdown is triggered.
Disclosure of Invention
According to the technical problem that the performance recovery of the system cannot be realized through external humidification after the purging of the non-external humidification fuel cell system is over-dry, the non-external humidification fuel cell system which cannot normally run due to the purging of the non-external humidification fuel cell system is placed in a high-low temperature test box, the environmental temperature is reduced, and the generated water is redistributed to realize the wetting of a membrane electrode so as to realize the performance recovery of the system under the low-temperature environment for multiple times, intermittent and small current loading; reducing the ambient temperature and the temperature of the fuel cell system can increase the relative humidity of the stack inlet air on the one hand and reduce the removal rate of the reaction-generated water on the other hand, and in addition, the reaction-generated water is redistributed in the membrane electrode by intermittent small current density loading to sufficiently wet the membrane electrode.
The invention adopts the following technical means:
a performance recovery method of a fuel cell system without external humidification specifically comprises the following steps:
step 1: setting the temperature of the high-low temperature test box to be 5-10 ℃, and placing the fuel cell system in the high-low temperature test box to cool the temperature of the cooling liquid outlet of the electric pile to be 5-10 ℃;
step 2: starting a fuel cell system, introducing hydrogen to the anode side of a galvanic pile, introducing air to the cathode side, starting a cooling liquid to circularly maintain the temperature of the galvanic pile, and operating for 5-10min under the conditions of applying a certain current density load and controlling the rotating speed r=5000 r/min of a reflux pump;
step 3: stopping the fuel cell system without purging in the stopping process, and standing the fuel cell system for 3-5min after stopping;
step 4: repeating the steps 2-3, wherein the load applied for the first time is 50mA/cm 2 And (2) lifting the load by 50-200mA/cm when repeating the step (2) every time later 2 Until the fuel cell system can be loaded to 500mA/cm 2 And then the high-low temperature test chamber can be restored to room temperature for activation, and the performance recovery of the fuel cell system is completed.
Further, when the operation of step 2 is performed for the first time, the air metering ratio of the fuel cell system is 2 to 3, the back pressure is 30 to 50kPa, and the hydrogen pressure is 50 to 70kPa.
Further, 100mA/cm was applied in the second repetition of the operation of step 2 2 The load, the air metering ratio of the fuel cell system is 2-3, the back pressure is 40-60kPa, and the hydrogen pressure is 60-80kPa.
Further, in step 4, the steps 2 to 3 are repeated twice.
Compared with the prior art, the invention has the following advantages:
1. the performance recovery method of the non-external humidification fuel cell system provided by the invention can effectively solve the problem that the non-external humidification fuel cell system cannot operate due to dry blowing through a low-temperature, repeated, intermittent and low-current repeated loading method, can greatly shorten the performance recovery time, does not need to repeatedly disassemble and assemble a galvanic pile in the system, saves a great amount of time cost and labor cost, and improves the production efficiency.
2. The performance recovery method of the non-external humidification fuel cell system provided by the invention has important application value for solving similar problems encountered by the non-external humidification fuel cell system in actual loading application, and can realize in-situ rapid performance recovery under the actual application scene without repairing the system after returning to a factory.
For the above reasons, the invention can be widely popularized in the field of fuel cells.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, 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 the drawings without inventive effort to a person skilled in the art.
FIG. 1 is a flow chart of a method for performance recovery of an externally humidified fuel cell system according to the present invention.
Fig. 2 is a voltage distribution diagram at the time of restarting loading after the pile is purged.
FIG. 3 is a graph showing voltage distribution after multiple, intermittent, small current loading of the system after cooling in a cold box.
Fig. 4 is a graph showing the initial state and the voltage distribution after performance recovery of the fuel cell system in example 1.
Fig. 5 is a graph showing initial voltage distribution of example 1 and comparative example 1.
FIG. 6 is a graph showing the voltage distribution for each run in comparative example 2.
Fig. 7 is a graph showing voltage distribution of example 1 and comparative examples 1 and 2.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in figure 1, the invention provides a performance recovery method of an externally-humidification-free fuel cell system, which mainly solves the problem that the proton transmission capacity of a membrane electrode is limited and cannot be normally used due to the fact that the system is purged, and the method comprises the steps of placing the system in a high-low temperature test box, redistributing water generated by reaction through repeated intermittent and small current loading after the temperature is reduced to a given condition, gradually wetting the membrane electrode, and realizing performance recovery after repeated times;
the method specifically comprises the following steps:
step 1: setting the temperature of the high-low temperature test box to be 5-10 ℃, and placing the fuel cell system in the high-low temperature test box to cool the temperature of the cooling liquid outlet of the electric pile to be 5-10 ℃;
step 2: starting a fuel cell system, introducing hydrogen to the anode side of a galvanic pile, introducing air to the cathode side, starting a cooling liquid to circularly maintain the temperature of the galvanic pile, and operating for 5-10min under the conditions of applying a certain current density load and controlling the rotating speed r=5000 r/min of a reflux pump;
step 3: stopping the fuel cell system without purging in the stopping process, and standing the fuel cell system for 3-5min after stopping;
step 4: repeating the steps 2-3, wherein the load applied for the first time is 50mA/cm 2 And (2) lifting the load by 50-200mA/cm when repeating the step (2) every time later 2 The specific value is determined according to the consistency of the voltage of the loading process until the fuel cell system can be loaded to 500mA/cm 2 And then the high-low temperature test chamber can be restored to room temperature for activation, and the performance recovery of the fuel cell system is completed.
Further, when the fuel cell system is operated at a current density load in step 2, the air metering ratio, the back pressure and the hydrogen pressure are determined in accordance with the prescribed operating conditions of the fuel cell system.
Further, when the operation of step 2 is performed for the first time, the air metering ratio of the fuel cell system is 2 to 3, the back pressure is 30 to 50kPa, and the hydrogen pressure is 50 to 70kPa.
Further, 100mA/cm was applied in the second repetition of the operation of step 2 2 The load, the air metering ratio of the fuel cell system is 2-3, the back pressure is 40-60kPa, and the hydrogen pressure is 60-80kPa.
Further, in step 4, the steps 2 to 3 are repeated twice.
As shown in FIG. 2, which shows the voltage distribution when loading is started again after the stack is purged to dryness, it can be seen that 50mA/cm is loaded 2 The voltage of the rear multiple batteries is lower than 0.8V (the inspection is 2 sections and 1 section), and normal loading operation cannot be performed; the voltage distribution of the system after being cooled in the low-temperature box for a plurality of times, intermittently and with small current is shown as figure 3, and the system is loaded with 50mA/cm after being cooled in the low-temperature box 2 The voltage distribution of (2) is shown as a curve 1 in fig. 3, and it can be seen that the pile performance is still worse under the condition, but the pile performance is improved compared with the initial state, the pile can continuously and stably run, the curve 2 and the curve 3 are respectively the voltage distribution when the pile is reloaded after the pile is stood for the 2 nd time and the 3 rd time, the performance and the consistency of the pile can be continuously improved, and the pile is continuously improved in the low-temperature loopThe performance of the battery is obviously improved after the battery is subjected to multiple times of small current loading and standing under the condition, which indicates that the state of water in the battery is redistributed, and the membrane electrode of the battery is continuously wetted.
The performance recovery method of the fuel cell system without external humidification provided by the invention can effectively solve the problem of incapability of normal operation caused by excessive dry purging in the operation process of the system by using the modes of low temperature, multiple times, intermittent and small current loading, and adopts low-temperature operation conditions, so that on one hand, the relative humidity of intake air can be improved, and on the other hand, the saturated vapor pressure of water is reduced, so that more water generated by the reaction is stored in a galvanic pile; the adoption of the multiple, intermittent and small-current loading method can prevent the cell damage caused by excessive dry loading of the galvanic pile, and can redistribute water generated by the reaction in the membrane electrode, improve the hydrothermal state in the cell and gradually wet the membrane electrode.
Example 1
The embodiment utilizes an externally-humidification-free fuel cell system with the rated power of 60Kw, the system adopts a hydrogen reflux mode to carry out self humidification, a cell stack is 370 metal plate cell stacks, and the fuel cell stack is purged for 10min at the water temperature of 70 ℃ to enable the cell stack to reach a drier working state; the embodiment adopts the performance recovery method of the fuel cell system without external humidification, and specifically comprises the following steps:
step 1: placing the fuel cell system in a high-low temperature test box and cooling the temperature of a cooling liquid outlet of the electric pile to 5 ℃;
step 2: introducing hydrogen and air into the anode and cathode of the galvanic pile respectively, and loading 50mA/cm 2 The operation condition refers to the system parameters under the electric density point, the rotation speed of the reflux pump is regulated to the maximum rotation speed, and the reflux pump is operated for 10min under the condition;
step 3: stopping the fuel cell system, keeping the fuel cell system stand for 5min after stopping without purging in the stopping process;
step 4: the steps 2 and 3 are repeated twice.
Loading 50mA/cm after the above steps are completed 2 The voltage distribution after the initial state and performance recovery of the galvanic pile is shown in fig. 4, and it can be seen that the method provided by the embodimentThe performance recovery effect of the system is obvious.
In order to facilitate a comparison of the performance recovery effect of the method according to the invention, the voltage profiles are compared below under different conditions with the same loading density.
Comparative example 1
Using the same fuel cell system and test conditions as in example 1, performance recovery was performed as follows:
step 1: placing the fuel cell system in a high-low temperature test box and cooling the temperature of a cooling liquid outlet of the electric pile to 5 ℃;
step 2: introducing hydrogen and air into the anode and cathode of the galvanic pile respectively, and loading 50mA/cm 2 The operating conditions were referenced to the system parameters at this electrical density point and the reflux pump speed was adjusted to the maximum speed to run the fuel cell system for 30 minutes.
The voltage distribution of the cell stack in the initial state of the fuel cell system and the voltage distribution of the cell stack after the recovery of the fuel cell system by the methods of example 1 and comparative example 1 are shown in fig. 5, it can be seen that the average voltage of the cell stack is not significantly improved after the performance recovery by the method of comparative example 1, which indicates that the hydrothermal state in the cell stack is not significantly improved by the method, the membrane electrode is still dry, and the proton transmission channel is not opened; the recovery of the system performance using example 1 was significant compared to comparative example 1, the water generated during the cell reaction was redistributed and the membrane electrode was gradually wetted, increasing by 60% compared to the initial average voltage.
Comparative example 2
Using the same fuel cell system and test conditions as in example 1, performance recovery was performed as follows:
step 1: under the normal operating temperature condition of the fuel cell system, hydrogen and air are respectively introduced into the anode and the cathode of the electric pile, and 50mA/cm is loaded 2 The operation condition refers to the system parameters under the electric density point, and the rotation speed of the reflux pump is regulated to the maximum rotation speed, so that the fuel cell system operates for 10min;
step 2: stopping the fuel cell system, and standing the fuel cell system for 5min after stopping;
step 3: the steps 2 and 3 are repeated twice.
After the above steps are completed, the initial state of the fuel cell system is compared with the voltage distribution of the electric pile when the fuel cell system is operated again after each shutdown, and the result is shown in fig. 6, it can be seen that the performance of the cell is not improved after three tests by adopting the method of multiple, intermittent and small current loading at the normal operation temperature described in comparative example 2, and the voltage consistency is poor, which indicates that the water content in the membrane electrode is further reduced by adopting the method, and the water generated by the reaction is carried out of the cell by the gas under the small current, so that the water distribution of the membrane electrode cannot be improved.
As shown in fig. 7, the voltage distribution of the fuel cell system is compared with that of the stacks treated by the methods of example 1, comparative example 1 and comparative example 2 in the initial state, and it can be seen that the stack performance can be effectively recovered by using the method for loading multiple intermittent small currents in the low-temperature environment according to the present invention.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced with equivalents; such modifications and substitutions do not depart from the spirit of the technical solutions according to the embodiments of the present invention.

Claims (4)

1. A method for recovering performance of a fuel cell system without external humidification, comprising the steps of:
step 1: setting the temperature of the high-low temperature test box to be 5-10 ℃, and placing the fuel cell system in the high-low temperature test box to cool the temperature of the cooling liquid outlet of the electric pile to be 5-10 ℃;
step 2: starting a fuel cell system, introducing hydrogen to the anode side of a galvanic pile, introducing air to the cathode side, starting a cooling liquid to circularly maintain the temperature of the galvanic pile, and operating for 5-10min under the conditions of applying a certain current density load and controlling the rotating speed r=5000 r/min of a reflux pump;
step 3: stopping the fuel cell system without purging in the stopping process, and standing the fuel cell system for 3-5min after stopping;
step 4: repeating the steps 2-3, wherein the load applied for the first time is 50mA/cm 2 And (2) lifting the load by 50-200mA/cm when repeating the step (2) every time later 2 Until the fuel cell system can be loaded to 500mA/cm 2 And then the high-low temperature test chamber can be restored to room temperature for activation, and the performance recovery of the fuel cell system is completed.
2. The method for recovering performance of a fuel cell system without external humidification according to claim 1, wherein the fuel cell system has an air metering ratio of 2 to 3, a back pressure of 30 to 50kPa, and a hydrogen pressure of 50 to 70kPa when the step 2 operation is performed for the first time.
3. The method for recovering performance of a non-externally humidified fuel cell system according to claim 1, wherein 100mA/cm is applied when the operation of step 2 is repeated for the second time 2 The load, the air metering ratio of the fuel cell system is 2-3, the back pressure is 40-60kPa, and the hydrogen pressure is 60-80kPa.
4. The performance recovery method of an externally humidified less fuel cell system according to claim 1, wherein in step 4, steps 2 to 3 are repeated twice.
CN202311637786.3A 2023-12-01 2023-12-01 Performance recovery method for fuel cell system without external humidification Pending CN117594833A (en)

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Application Number Priority Date Filing Date Title
CN202311637786.3A CN117594833A (en) 2023-12-01 2023-12-01 Performance recovery method for fuel cell system without external humidification

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311637786.3A CN117594833A (en) 2023-12-01 2023-12-01 Performance recovery method for fuel cell system without external humidification

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CN117594833A true CN117594833A (en) 2024-02-23

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