CN115000466A - Long-time storage method of fuel cell - Google Patents
Long-time storage method of fuel cell Download PDFInfo
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- CN115000466A CN115000466A CN202210749803.1A CN202210749803A CN115000466A CN 115000466 A CN115000466 A CN 115000466A CN 202210749803 A CN202210749803 A CN 202210749803A CN 115000466 A CN115000466 A CN 115000466A
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- fuel cell
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/043—Processes for controlling fuel cells or fuel cell systems applied during specific periods
- H01M8/04303—Processes for controlling fuel cells or fuel cell systems applied during specific periods applied during shut-down
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- 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
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Abstract
The invention provides a long-time storage method of a fuel cell, which comprises the following steps: performing cold purging after the fuel cell is shut down; after cold purging, introducing nitrogen with gas pressure P into an air cavity of the fuel cell and introducing hydrogen with gas pressure P into a hydrogen cavity, wherein the gas pressure P is set to be higher than the current atmospheric pressure P 0 (ii) a Detecting the oxygen concentration at the outlet of the air cavity, stopping introducing the nitrogen and the hydrogen when the oxygen concentration is less than or equal to a preset reference concentration a%, and placing the fuel cell in a cell storage bank for long-time storage. Based on the nitrogen and hydrogen sealing mode, platinum oxidation caused by a large amount of air entering the galvanic pile is avoided, and the problem of irreversible attenuation of the fuel cell caused by platinum oxidation is avoided. Meanwhile, under the action of pressure difference, outside air cannot permeate into the fuel cell, so that catalyst oxidation cannot be caused, and the problem of long-term degradation of a fuel cell stack cannot occur.
Description
Technical Field
The invention relates to the technical field of fuel cell storage, in particular to a long-time storage method of a fuel cell.
Background
As a new energy automobile, a fuel cell automobile has the characteristics of no pollution and zero emission, and is increasingly paid more attention by people.
The fuel cell can be stored for a long time before and after being sent to a client, and the resin ionomers in the proton exchange membrane and the catalyst layer of the fuel cell stored by adopting a common long-time storage method can be dried gradually, and the hydrophobic chain segment and the hydrophilic chain segment which are originally separated from each other can be fused in the drying process. This results in, on the one hand, drying of the proton exchange membrane itself and difficulty in transferring protons, and on the other hand, the resin ionomer in the catalyst layer cannot transfer protons, and cannot transfer air and generated water. Thus, as storage times increase, the degree of oxidation of the surface platinum increases, and the resin ionomer in the proton exchange membrane and catalytic layers becomes drier until the originally phase separated structure is completely lost. This leads to a difficult activation process and a long activation time.
In order to solve the above problems, the conventional fuel cell long-term storage method is: after the fuel cell is shut down, the fuel cell is air purged to reduce the residual water content in the fuel cell, and then stored for a long time. When the fuel cell is stored by adopting the long-time storage method, excessive air can enter the fuel cell along with the increase of storage time to cause irreversible degradation of partial performance of the fuel cell.
Disclosure of Invention
The present invention has been made to solve the above-mentioned problems, and provides a long-term storage method of a fuel cell having an air chamber inlet and an air chamber outlet, and a hydrogen chamber having a hydrogen chamber inlet. The long-time storage method comprises the following steps: performing cold purging after the fuel cell is shut down; after the cold purging of the fuel cell, introducing nitrogen with gas pressure P into an air cavity of the fuel cell through an air cavity inlet, and introducing hydrogen with gas pressure P into a hydrogen cavity of the fuel cell through a hydrogen cavity inlet, wherein the gas pressure P is set to be greater than the current atmospheric pressure P of the environment where the fuel cell is located 0 (ii) a Detecting the oxygen concentration at the air cavity outlet of the fuel cell, stopping introducing nitrogen into the air cavity of the fuel cell and stopping introducing hydrogen into the hydrogen cavity of the fuel cell when the oxygen concentration is less than or equal to a preset reference concentration a%The fuel cell is placed in a cell storage tank for long-term storage.
Further, the cold purging is performed after the fuel cell is shut down, and the method comprises the following steps: cooling the fuel cell after shutdown until the temperature of the fuel cell is reduced to a preset temperature threshold T1; performing constant current purging on the fuel cell by using a current I1, detecting the voltage U1 of the fuel cell in real time in the purging process, and stopping constant current purging if the voltage U1 of the fuel cell is detected to be smaller than a set voltage U0; and performing constant potential purging on the fuel cell by using a voltage U2, detecting the internal resistance R of the fuel cell in real time in the purging process, and stopping constant potential purging if the internal resistance R of the fuel cell is detected to be larger than the set storage requirement internal resistance R0.
Further, the time for constant current purging of the fuel cell with the current I1 is t1, the time for constant potential purging of the fuel cell with the voltage U2 is t2, the total time for cold purging of the fuel cell is t = t1+ t2, and,a preset time threshold for cold purging of the fuel cell.
further, the preset reference concentration a% is less than 3%.
Further, the preset reference concentration a% is 0.
Further, before performing cold purge after the fuel cell is shut down, the long-term storage method further includes: and detecting the performance of the fuel cell after the fuel cell is started, and acquiring the performance index of the fuel cell before storage.
Further, the persistent storage method further includes: taking out the fuel cell after long-term storage from the cell storage bank; after starting up the fuel cell after long-time storage, carrying out performance detection and acquiring a performance index of the fuel cell after storage; and comparing the performance index of the fuel cell before storage with the performance index of the fuel cell after storage.
Further, the performance index is a cell voltage of the fuel cell.
The invention has the following beneficial effects:
in the long-time storage method of the fuel cell, because the nitrogen is introduced into the air cavity of the fuel cell after cold purging, the hydrogen is introduced into the hydrogen cavity of the fuel cell, and then the subsequent sealing of the fuel cell is carried out, the platinum oxidation caused by the large amount of air entering the electric pile of the fuel cell is avoided based on the nitrogen and hydrogen sealing mode, and the problem of irreversible attenuation of the fuel cell caused by the platinum oxidation is avoided. Meanwhile, because the gas pressure of the nitrogen in the air cavity of the fuel cell and the gas pressure of the hydrogen in the hydrogen cavity are both greater than the current atmospheric pressure of the environment where the fuel cell is located, under the action of the pressure difference, even if the sealing performance of the stack of the fuel cell is poor, the external air cannot permeate into the interior of the fuel cell through the air cavity and the hydrogen cavity (even if a small amount of external air permeates into the interior of the stack, the external air can be consumed by the hydrogen), and further the catalyst oxidation cannot be caused, and the stack of the fuel cell cannot be subjected to long-term degradation.
This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify key features or essential features of the disclosure, nor is it intended to be used to limit the scope of the disclosure.
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The foregoing and other objects, features and advantages of the disclosure will be apparent from the following more particular descriptions of exemplary embodiments of the disclosure as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts throughout the exemplary embodiments of the disclosure.
Fig. 1 shows a flow chart of a long term storage method of a fuel cell of the present invention.
Detailed Description
Embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The term "include" and variations thereof as used herein is meant to be inclusive in an open-ended manner, i.e., "including but not limited to". Unless specifically stated otherwise, the term "or" means "and/or". The term "based on" means "based at least in part on". The terms "one example embodiment" and "one embodiment" mean "at least one example embodiment". The term "another embodiment" means "at least one additional embodiment". The terms "first," "second," and the like may refer to different or the same object. Other explicit and implicit definitions are also possible below.
The fuel cell has an air chamber having an air chamber inlet and an air chamber outlet, and a hydrogen chamber having a hydrogen chamber inlet and a hydrogen chamber outlet. Referring to fig. 1, the long term storage method of a fuel cell of the present invention includes steps S1-S4.
S1, performing cold purging after the fuel cell is shut down; s2, after the fuel cell is subjected to cold purging, introducing nitrogen with the gas pressure of P into the air cavity of the fuel cell through the air cavity inlet, and introducing hydrogen with the gas pressure of P into the hydrogen cavity of the fuel cell through the hydrogen cavity inlet, wherein the gas pressure P is set to be larger than the current atmospheric pressure P of the environment where the fuel cell is located 0 (e.g. current atmospheric pressure P 0 =10 kpa); s3, detecting the oxygen concentration at the air cavity outlet of the fuel cell, and stopping feeding the fuel cell when the oxygen concentration is less than or equal to a preset reference concentration a%Introducing nitrogen into the air cavity, stopping introducing hydrogen into the hydrogen cavity of the fuel cell, and S4, placing the fuel cell in the cell storage bank for long-time storage.
In the long-time storage method of the fuel cell, nitrogen is introduced into the air cavity of the fuel cell after cold purging, hydrogen is introduced into the hydrogen cavity of the fuel cell, and then the subsequent sealing of the fuel cell is performed, so that platinum oxidation caused by the fact that a large amount of air enters the stack of the fuel cell is avoided based on the nitrogen and hydrogen sealing mode, and the problem of irreversible attenuation of the fuel cell caused by platinum oxidation is avoided. Meanwhile, because the gas pressure of the nitrogen in the air cavity of the fuel cell and the gas pressure of the hydrogen in the hydrogen cavity are both greater than the current atmospheric pressure of the environment where the fuel cell is located, under the action of the pressure difference, even if the sealing performance of the stack of the fuel cell is poor, the external air cannot permeate into the interior of the fuel cell through the air cavity and the hydrogen cavity (even if a small amount of external air permeates into the interior of the stack, the external air can be consumed by the hydrogen), and further the catalyst oxidation cannot be caused, and the stack of the fuel cell cannot be subjected to long-term degradation.
In one embodiment, in step S1, the cold purge is performed after the fuel cell is shut down, specifically including steps S11-S13.
And S11, cooling the fuel cell after shutdown (cooling can be performed through a fan) until the temperature of the fuel cell is reduced to a preset temperature threshold T1. The preset temperature threshold T1 is an ideal purge temperature of the fuel cell calibrated by multiple experiments, and if the temperature of the fuel cell is greater than the preset temperature threshold T1, the temperature of the fuel cell is decreased to the preset temperature threshold T1, and after subsequent constant current purge and constant potential purge, the purge of the fuel cell is too dry, and the fuel cell cannot be started after long-term storage.
And S12, performing constant current purging (namely performing air purging) on the fuel cell by using the current I1, detecting the voltage U1 of the fuel cell in real time in the purging process, and stopping the constant current purging if the detected voltage U1 of the fuel cell is smaller than the set voltage U0. The constant current purging is adopted, so that the high potential of the galvanic pile is limited on the premise that the galvanic pile of the fuel cell produces water as little as possible, the corrosion of the catalyst caused by the high potential of the fuel cell can be avoided, the corrosion degree of the catalyst in the purging process is reduced, the service life of the fuel cell is prolonged, and the performance of the fuel cell is improved.
And S13, performing constant potential purging (namely air purging) on the fuel cell by using the voltage U2, detecting the internal resistance R of the fuel cell in real time in the purging process, and stopping the constant potential purging if the internal resistance R of the fuel cell is detected to be larger than the set storage requirement internal resistance R0. After the fuel cell is purged by constant current, because the dry-out performance of the fuel cell stack is reduced, the fuel cell stack is further purged by constant potential, the current point can be reduced on the premise of limiting high potential until the internal resistance R of the fuel cell is greater than the set storage demand internal resistance R0, and therefore the fuel cell can be conveniently stored in any environment.
In one embodiment, in step S1, when the time for constant current purging of the fuel cell with the current I1 is t1 and the time for constant potential purging of the fuel cell with the voltage U2 is t2, the total time for cold purging of the fuel cell is t = t1+ t2, and,a preset time threshold for cold purging of the fuel cell. Here, a preset time threshold valueRefers to the ideal purge time of the fuel cell calibrated by multiple experiments. In thatMeanwhile, on the premise of ensuring that the internal resistance R of the fuel cell can be larger than the set storage requirement internal resistance R0, in order to improve the performance of the fuel cell after long-term storage, the constant current purging time t1 can be properly prolonged, and the constant current can be shortenedTime t2 for the bit purge.
In one embodiment, in step S1,therefore, the problem of performance reduction of the fuel cell caused by overlong constant potential purging time t2 can be avoided as much as possible. Conversely, in order to shorten the time t2 for the constant potential purge, the air flow rate during the constant current purge may be increased as appropriate. Preferably, the first and second electrodes are formed of a metal,at this time, the constant current purge time t1 and the constant potential purge time t2 are passed, so that the performance of the fuel cell after long-term storage can be optimized.
In one embodiment, in step S3, the preset reference concentration a% is 3%, that is, when the oxygen concentration at the air chamber outlet of the fuel cell is less than or equal to 3%, it indicates that a small amount of air still exists in the air chamber of the fuel cell, but since the 3% of air hardly causes platinum oxidation, the influence on the fuel cell is small and can be ignored.
Preferably, in step S3, the preset reference concentration a% is 0, which corresponds to the air chamber being completely filled with nitrogen gas without any air, so that the irreversible degradation of the fuel cell due to platinum oxidation is not caused.
In one embodiment, referring to fig. 1, before performing the cold purge after the shutdown of the fuel cell, the long term storage method further includes: and S0, detecting the performance of the fuel cell after the fuel cell is started and acquiring the performance index of the fuel cell before storage. Based on the performance index of the fuel cell before storage, the performance difference of the fuel cell before and after long-time storage can be verified, and then various parameters related to the long-time storage method process can be adjusted conveniently.
In one embodiment, referring to fig. 1, the persistent storage method further includes: s5, taking out the fuel cell after long-term storage from the cell storage bank; s6, performing performance detection after starting the fuel cell after long-time storage, and acquiring the performance index of the fuel cell after storage; and S7, comparing the performance index difference between the fuel cell before storage and the fuel cell after storage. Based on the performance index difference before and after the storage of the fuel cell, the method can directly verify that the performance of the fuel cell is not changed greatly after the fuel cell is stored for a long time by the method.
In one embodiment, the performance indicator before and after long storage of the fuel cell is the cell voltage of the fuel cell.
Having described embodiments of the present disclosure, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terms used herein were chosen in order to best explain the principles of the embodiments, the practical application, or technical improvements to the techniques in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (10)
1. A method of long storage of a fuel cell having an air chamber with an air chamber inlet and an air chamber outlet, and a hydrogen chamber with a hydrogen chamber inlet, the method comprising:
performing cold purging after the fuel cell is shut down;
after the cold purging of the fuel cell, introducing nitrogen with gas pressure P into an air cavity of the fuel cell through an air cavity inlet, and introducing hydrogen with gas pressure P into a hydrogen cavity of the fuel cell through a hydrogen cavity inlet, wherein the gas pressure P is set to be greater than the current atmospheric pressure P of the environment where the fuel cell is located 0 ;
Detecting the oxygen concentration at the outlet of the air cavity of the fuel cell, and stopping introducing nitrogen into the air cavity of the fuel cell and hydrogen into the hydrogen cavity of the fuel cell when the oxygen concentration is less than or equal to a preset reference concentration a%;
and placing the fuel cell in a cell storage tank for long-time storage.
2. The long-term storage method of a fuel cell according to claim 1, wherein cold purging is performed after the fuel cell is shut down, comprising the steps of:
cooling the fuel cell after shutdown until the temperature of the fuel cell is reduced to a preset temperature threshold T1;
performing constant current purging on the fuel cell by using a current I1, detecting the voltage U1 of the fuel cell in real time in the purging process, and stopping constant current purging if the voltage U1 of the fuel cell is detected to be smaller than a set voltage U0;
and performing constant potential purging on the fuel cell by using a voltage U2, detecting the internal resistance R of the fuel cell in real time in the purging process, and stopping constant potential purging if the internal resistance R of the fuel cell is detected to be larger than the set storage requirement internal resistance R0.
3. The method of claim 2, wherein the constant current purging of the fuel cell with current I1 is performed for a time t1, the constant potential purging of the fuel cell with voltage U2 is performed for a time t2, the total cold purging time of the fuel cell is t = t1+ t2, and,a preset time threshold for cold purging of the fuel cell.
6. the long term storage method for a fuel cell according to claim 1, wherein the preset reference concentration a% is less than 3%.
7. The long term storage method for a fuel cell according to claim 6, wherein the preset reference concentration a% is 0.
8. The long term storage method for a fuel cell according to claim 1, wherein before performing cold purge after the fuel cell is shut down, the long term storage method further comprises: and detecting the performance of the fuel cell after the fuel cell is started, and acquiring the performance index of the fuel cell before storage.
9. The long term storage method of a fuel cell according to claim 8, further comprising:
taking out the fuel cell after long-term storage from the cell storage bank;
after starting up the fuel cell after long-time storage, carrying out performance detection and acquiring a performance index of the fuel cell after storage;
and comparing the performance index of the fuel cell before storage with the performance index of the fuel cell after storage.
10. The method of claim 9, wherein the performance indicator is a monolithic voltage of the fuel cell.
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