CN112415395A - Device and method for evaluating fuel cell stack start-stop durability - Google Patents

Device and method for evaluating fuel cell stack start-stop durability Download PDF

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Publication number
CN112415395A
CN112415395A CN202011411837.7A CN202011411837A CN112415395A CN 112415395 A CN112415395 A CN 112415395A CN 202011411837 A CN202011411837 A CN 202011411837A CN 112415395 A CN112415395 A CN 112415395A
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cell stack
air
way valve
cathode
bypass
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斯蒂芬妮·梅根·吉拉德
姚汛
纪志星
尹盼森
多纳特·米歇尔·莱昂·约瑟夫·高德洛
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Shanghai Yunliang New Energy Technology Co ltd
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Shanghai Yunliang New Energy Technology Co ltd
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    • 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]
    • G01R31/378Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC] specially adapted for the type of battery or accumulator
    • 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

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  • General Physics & Mathematics (AREA)
  • Fuel Cell (AREA)

Abstract

The invention provides a device and a method for evaluating the starting and stopping durability of a fuel cell stack, which comprises the following steps: the anode pipeline comprises a hydrogen pipe, an air main pipeline, a first bypass and an anode exhaust pipe, wherein the air main pipeline is connected with the first pipeline and the first bypass through a first three-way valve; the anode exhaust pipe is used for being communicated with an anode outlet of the cell stack, and a third stop valve is arranged on the anode exhaust pipe; the cathode pipeline comprises a second pipeline, a second bypass and a cathode exhaust pipe, the cathode air inlet pipe is connected with the second pipeline and the second bypass through a second three-way valve, and the second pipeline is used for being communicated with a cathode inlet of the cell stack; the cathode exhaust pipe is used for being communicated with a cathode outlet of the cell stack, and the second bypass and the cathode exhaust pipe are communicated with the main exhaust pipe through a third three-way valve. The invention ensures that the gas switching speeds of the anode and the cathode of the cell stack are approximately the same, and improves the accuracy of the test of the starting and stopping durability of the cell stack.

Description

Device and method for evaluating fuel cell stack start-stop durability
Technical Field
The invention relates to the technical field of fuel cells, in particular to a device and a method for evaluating the starting and stopping durability of a fuel cell stack.
Background
Start-up and shut-down are among the most frequent conditions encountered during the life cycle of a fuel cell. The start-stop durability is one of the key characteristics of the fuel cell stack, and since an oxyhydrogen interface is formed on an anode side in the starting process to cause carbon corrosion on a cathode side, the stack is degraded, the method and the device for quickly evaluating the start-stop durability of the fuel cell stack are very important.
Chinese patents CN201156078Y and CN101158711B disclose methods and devices for evaluating start-stop durability, respectively, in which air is directly introduced into an anode inlet and on-off control is performed through an electromagnetic valve. The technology has the main defects that the structure is too simple, and the process of directly switching hydrogen by using air is greatly different from the process of stopping the fuel cell in the actual process; and during switching, if the switching speeds of the cathode and anode are not uniform, OCV positive or negative voltage may be formed. Chinese patent CN111082108A improves the device based on the former patent, and mainly adds gas treatment and monitoring modules, such as temperature and humidity control and CO2Detecting the concentration; however, the patent does not improve the gas switching state on both sides of the galvanic pile from the fundamental of start-stop acceleration test, and still has the problems of slow switching speed or inconsistent switching speeds on both sides of the cathode and the anode.
Therefore, an apparatus and a method for evaluating the start-stop durability of a fuel cell stack are needed, which can achieve the consistent switching speed of the cathode and the anode.
Disclosure of Invention
In view of the above drawbacks of the prior art, an object of the present invention is to provide an apparatus and a method for evaluating the start-stop durability of a fuel cell stack, which solve the problem of inconsistent switching speeds of both sides of a cathode and an anode during a start-stop durability test of the fuel cell stack in the prior art.
In order to solve the above technical problem, the present invention provides an apparatus for evaluating start-stop durability of a fuel cell stack, comprising:
the anode pipeline comprises a hydrogen pipe, an air main pipeline, a first bypass and an anode exhaust pipe, wherein the air main pipeline is connected with the first pipeline and the first bypass through a first three-way valve; the anode exhaust pipe is used for being communicated with an anode outlet of the cell stack, and a third stop valve is arranged on the anode exhaust pipe;
the cathode pipeline comprises a second pipeline, a second bypass and a cathode exhaust pipe, the cathode air inlet pipe is connected with the second pipeline and the second bypass through a second three-way valve, and the second pipeline is used for being communicated with a cathode inlet of the cell stack; the cathode exhaust pipe is used for being communicated with a cathode outlet of the cell stack, and the second bypass and the cathode exhaust pipe are communicated with the main exhaust pipe through a third three-way valve;
and the control system is connected with the first three-way valve, the second three-way valve, the third three-way valve, the first stop valve, the second stop valve and the third stop valve and controls the actions of the valves.
Preferably, a one-way valve is arranged on the first pipeline and located between the first three-way valve and the anode inlet.
Preferably, a check valve is arranged on the hydrogen pipe, and the check valve is located between the first stop valve and the anode inlet.
Preferably, an air flow meter is arranged on the air main path.
The invention also provides a method for evaluating the start-stop durability of the fuel cell stack, which adopts the device for evaluating the start-stop durability of the fuel cell stack and comprises the following steps:
1) stopping the fuel cell stack, discharging and consuming oxygen on the cathode side of the stack until the voltage is reduced to 0V;
2) opening a second stop valve, and synchronously adjusting a second three-way valve and a third three-way valve to discharge air at a first preset flow rate through an air main path and a first bypass, and discharge air at a second preset flow rate through a cathode air inlet pipe, a second bypass and a main exhaust pipe, wherein the first preset flow rate is different from the second preset flow rate;
3) synchronously adjusting the first three-way valve, the second three-way valve and the third three-way valve, closing the second stop valve, opening the third stop valve, enabling air in an air main path to enter the cell stack through the first pipeline, enabling air at the cathode to enter the cell stack through the cathode air inlet pipe, and waiting for a preset time;
4) monitoring cell voltages of the cell stack and zeroing all parameters;
5) adjusting the first three-way valve to enable the main air path to be communicated with the first bypass, opening the first stop valve, starting the cell stack, and enabling the cell stack to run to a performance operation judgment point;
6) and judging whether the performance of the cell stack reaches the specified performance attenuation value, if so, calculating the starting and stopping durability of the cell stack, otherwise, repeating the steps 1) -5) until the performance of the cell stack reaches the specified performance attenuation value.
Preferably, the calibration process of the second preset flow and the first preset flow is as follows:
a, normally shutting down and discharging a cell stack, and maintaining the cell stack in a hydrogen/hydrogen state for a certain time;
b, sending air with a first flow value into a first bypass, and sending air with a second flow value into a second bypass, wherein the first flow value is the maximum flow of the air main path, and is the first preset flow; the second flow value is less than the first flow value;
c, synchronously adjusting the first three-way valve, the second three-way valve and the third three-way valve, closing the second stop valve, opening the third stop valve, enabling air in the air main path to enter the cell stack through the first pipeline, enabling air at the cathode to enter the cell stack through the cathode air inlet pipe, and waiting for a certain time;
d, monitoring the voltage of the battery electric pile, repeating the steps A-C according to the voltage condition, if the voltage is positive voltage, increasing the size of the second flow value, and if negative voltage occurs, reducing the size of the second flow value; until no voltage is generated in the cell stack,
the current second flow value is a second preset flow.
Preferably, the preset time is 1-2 min.
Preferably, all of the parameters include the air flow rate in the air main path, the air temperature and the dew point of the air.
As described above, the apparatus and method for evaluating the start-stop durability of a fuel cell stack according to the present invention have the following advantageous effects: the adoption all is provided with the bypass in anode line and cathode line, first bypass and second bypass promptly, when starting to stop the durability test with this realization, can be before switching over the pile from hydrogen/hydrogen state fast to empty/empty state, let in the air of certain flow simultaneously earlier and arrange to the export through first bypass and second bypass, then switch first three-way valve simultaneously, the position of second three-way valve, make the gas of certain velocity of flow enter into the positive pole and the negative pole of pile simultaneously, ensure that the gas switching speed of pile positive pole, negative pole both sides is close the same, with this normal use that simulates the pile more accurately, improve the accuracy that the durability test was stopped to the pile opens and stops.
Drawings
Fig. 1 is a schematic diagram of an apparatus for evaluating the start-stop durability of a fuel cell stack according to the present invention.
Fig. 2 is a schematic diagram of bypass air intake in an apparatus for evaluating the start-stop durability of a fuel cell stack.
Fig. 3 is a schematic diagram showing the simultaneous air supply to the cathode and anode of the fuel cell stack.
Fig. 4 is a schematic diagram showing the intake of air at the time of normal start-up of the fuel cell stack.
Fig. 5 is a flow chart illustrating a method for evaluating the start-stop durability of a fuel cell stack according to the present invention.
Description of the element reference numerals
1 cell stack
2 air flow meter
3 first three-way valve
4. 6 one-way valve
5 first stop valve
7 second three-way valve
8 third stop valve
9 third three-way valve
10 second stop valve
11 first pipeline
12 first bypass
13 second three-way valve
14 second bypass
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
It should be understood that the structures, ratios, sizes, and the like shown in the drawings are only used for matching the disclosure of the present disclosure, and are not used for limiting the conditions that the present disclosure can be implemented, so that the present disclosure is not limited to the technical essence, and any structural modifications, ratio changes, or size adjustments should still fall within the scope of the present disclosure without affecting the efficacy and the achievable purpose of the present disclosure. In addition, the terms "upper", "lower", "left", "right", "middle" and "one" used in the present specification are for clarity of description, and are not intended to limit the scope of the present invention, and the relative relationship between the terms and the terms is not to be construed as a scope of the present invention.
As shown in fig. 1, the present invention provides an apparatus for evaluating the start-stop durability of a fuel cell stack, comprising:
the anode pipeline comprises a hydrogen pipe, an air main pipeline, a first pipeline 11, a first bypass 12 and an anode exhaust pipe, wherein the air main pipeline is connected with the first pipeline 11 and the first bypass 12 through a first three-way valve 3, the first pipeline 11 and the hydrogen pipe are both used for being communicated with an anode inlet of the cell stack 1, the hydrogen pipe is provided with a first stop valve 5, and the first bypass 12 is provided with a second stop valve 10; the anode exhaust pipe is used for being communicated with an anode outlet of the cell stack, and a third stop valve 8 is arranged on the anode exhaust pipe; the cathode pipeline comprises a second pipeline 13, a second bypass 14 and a cathode exhaust pipe, the cathode intake pipe is connected with the second pipeline 13 and the second bypass 14 through a second three-way valve 7, and the second pipeline 13 is used for being communicated with a cathode inlet of the cell stack 1; the cathode exhaust pipe is used for being communicated with a cathode outlet of the cell stack 1, and the second bypass 14 and the cathode exhaust pipe are communicated with the main exhaust pipe through a third three-way valve 9;
and a control system connected to the first three-way valve 3, the second three-way valve 7, the third three-way valve 9, the first stop valve 5, the second stop valve 10, and the third stop valve 8, for controlling the operation of the valves.
According to the invention, the bypasses, namely the first bypass 11 and the second bypass 14 are arranged in the anode pipeline and the cathode pipeline, so that when the start-stop durability test is carried out, before the cell stack 1 is rapidly switched from a hydrogen/hydrogen state to an empty/empty state, air with a certain flow is simultaneously introduced to an outlet through the first bypass 11 and the second bypass 14, and then the positions of the first three-way valve 3 and the second three-way valve 7 are simultaneously switched, so that the gas with a certain flow rate simultaneously enters the anode and the cathode of the cell stack 1, the gas switching speeds of the anode and the cathode of the cell stack are ensured to be approximately the same, the normal use of the cell stack 1 is more accurately simulated, and the accuracy of the start-stop durability test of the cell stack is improved.
In order to ensure the stability of the gas flow and avoid the occurrence of backflow, in this embodiment, the first pipeline 11 is provided with a check valve 4, and the check valve 4 is located between the first three-way valve 3 and the anode inlet of the cell stack 1. The hydrogen pipe is provided with a one-way valve 6, and the one-way valve 6 is positioned between the first stop valve 5 and the anode inlet of the cell stack 1.
In order to better control the air intake flow and improve the accuracy of the test, the air flow meter 2 is arranged on the air main path in the embodiment, so that the air intake flow of the air is determined, and the adjustment and the calculation are convenient.
The invention also provides a method for evaluating the start-stop durability of the fuel cell stack, which adopts the device for evaluating the start-stop durability of the fuel cell stack to connect the cell stack to be tested into the device, and comprises the following steps: as shown in figure 5 of the drawings,
1) the cell stack 1 is shut down, and oxygen on the cathode side of the cell stack is consumed by discharging until the voltage is reduced to 0V; in which the cell stack 1 is in the hydrogen/hydrogen state;
2) opening the second stop valve 10, and synchronously adjusting the second three-way valve 13 and the third three-way valve 9 to discharge the air at a first preset flow rate through the main air path and the first bypass 12, that is, the air at the first preset flow rate (also called anode air) flows through the intake route s1 in fig. 2; the air is exhausted through the cathode intake pipe, the second bypass 14 and the main exhaust pipe at a second preset flow rate, that is, the air at the second preset flow rate (also called cathode air) flows according to the intake route s2 in fig. 2, and the first preset flow rate and the second preset flow rate are different;
3) synchronously adjusting the first three-way valve 3, the second three-way valve 13 and the third three-way valve 9, closing the second stop valve 10, and opening the third stop valve 8, so that the air in the air main path enters the cell stack 1 through the first pipeline 11 (see an air inlet line s3 in fig. 3), the air in the cathode enters the cell stack 1 through a cathode air inlet pipe (see an air inlet line s4 in fig. 3), and then waiting for a preset time, wherein the preset time is 1-2min in the embodiment; simultaneously introducing air to a cathode and an anode of a cell stack to rapidly switch the cell stack to an empty/empty state, setting the temperature of cooling water of the cell stack 1 to be 25 ℃, the dew point of the air to be 23 ℃ and the temperature to be 30 ℃, and waiting for 5min to enable each parameter to reach a corresponding set value;
4) monitoring the cell voltage of the cell stack 1 and zeroing all parameters; all parameters include air flow, air temperature and air dew point in the air main path;
5) adjusting the first three-way valve 3 to communicate the main air path with the first bypass 12, opening the first cut-off valve 5, and starting the cell stack 1, as shown in fig. 4, first introducing hydrogen to the anode, i.e., the anode inlet line s5, and then introducing air to the cathode, i.e., the cathode inlet line s 6; the cell stack 1 is operated to a performance operation judgment point; the performance operation determination point in this embodiment is a working point known to those skilled in the art, that is, the time when the current of the fuel cell is loaded to be unchanged, and the performance of the fuel cell is stable in the subsequent period of time;
6) and judging whether the performance of the cell stack reaches a specified performance attenuation value (the performance attenuation value in the embodiment is generally 10% of the maximum output voltage and is 20% of the maximum output voltage at most), if so, calculating the start-stop durability of the cell stack, otherwise, repeating the steps 1) -5) until the performance of the cell stack reaches the specified performance attenuation value.
Before the method is carried out, flow matching can be carried out, namely the calibration process of the second preset flow and the first preset flow is as follows:
a, normally shutting down and discharging a cell stack 1, and maintaining the cell stack 1 in a hydrogen/hydrogen state for a certain time;
b, sending air with a first flow value into a first bypass 12, and sending air with a second flow value into a second bypass 14, wherein the first flow value is the maximum flow of the air main path, namely a first preset flow; the second flow value is less than the first flow value;
c, synchronously adjusting the first three-way valve 3, the second three-way valve 7 and the third three-way valve 9, closing the second stop valve 10, opening the third stop valve 8, enabling air in an air main path to enter the cell stack 1 through the first pipeline 11, enabling air at the cathode to enter the cell stack 1 through a cathode air inlet pipe, and then waiting for a certain time;
d, monitoring the voltage of the cell stack 1, repeating the steps A-C according to the voltage condition, if the voltage is positive, increasing the size of the second flow value, and if negative voltage occurs, reducing the size of the second flow value; until no voltage is generated in the cell stack 1, the current second flow value is a second preset flow.
According to the embodiment, through the flow matching, the performance evaluation is not influenced by other interference factors in an experiment, and the evaluation accuracy is improved.
In this example, a fuel cell stack including 20 membrane electrodes is subjected to a start-stop durability test, and the specific working steps are as follows:
1) the cell stack 1 is shut down, after discharging according to normal shutdown, the pressure of hydrogen is set to be 50kPa, after the voltage is reduced to 0V, the first three-way valve 3, the second three-way valve 7 and the third three-way valve 9 are all in bypass states, namely are respectively communicated with the first bypass 11 and the second bypass 14, the first stop valve 5 and the third stop valve 8 are in closed states, and the cell stack is maintained in a hydrogen/hydrogen state for one minute;
2) the second stop valve 10 is opened, the first preset flow and the second preset flow are matched through the calibration process, in this embodiment, the matched air flow 50NLPM (i.e., the first preset flow) is set to enter the first bypass 11, and the air flow 30NLPM (i.e., the second preset flow) enters the second bypass 14, until the gas flow is stable; setting the temperature of cooling water of the galvanic pile to be 25 ℃, the dew point of air to be 23 ℃ and the temperature to be 30 ℃, and waiting for 5min to enable each parameter to reach a corresponding set value;
3) simultaneously switching a first three-way valve 3, a second three-way valve 13 and a third three-way valve 9 to the air inlet state of the cell stack 1, closing a second stop valve 10, and opening a third stop valve 8, so that the air of the anode instantly flows through the cell stack from a first bypass 12 to a first pipeline 11, the air of the cathode instantly flows through the cell stack from a second bypass 14 to a second pipeline 13, and then waiting for 1 min;
4) the set air flow rate was 0, and both the temperature and the dew point were set to 0.
5) Switching the first three-way valve 3 to a bypass state, opening the first stop valve 5, and starting the fuel cell stack according to a strategy of firstly introducing hydrogen to the anode and then introducing air to the cathode; after the average voltage reached 0.9V, the stack was slowly loaded to 2A/cm2 according to a pull-load strategy, at which current density the corresponding operating conditions were as in table 1 below.
Figure BDA0002817629650000061
Figure BDA0002817629650000071
TABLE 1
6) And repeating the steps 1) to 5) until the performance of the cell stack is reduced to 90% of the initial performance. The stack dropped from an initial average voltage of 0.6V to 0.54V over 2000 start-stop cycles. I.e. indicating a start-stop durability of the cell stack of 200 times.
Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (8)

1. An apparatus for evaluating start-stop durability of a fuel cell stack, comprising:
the anode pipeline comprises a hydrogen pipe, an air main pipeline, a first bypass and an anode exhaust pipe, wherein the air main pipeline is connected with the first pipeline and the first bypass through a first three-way valve; the anode exhaust pipe is used for being communicated with an anode outlet of the cell stack, and a third stop valve is arranged on the anode exhaust pipe;
the cathode pipeline comprises a second pipeline, a second bypass and a cathode exhaust pipe, the cathode air inlet pipe is connected with the second pipeline and the second bypass through a second three-way valve, and the second pipeline is used for being communicated with a cathode inlet of the cell stack; the cathode exhaust pipe is used for being communicated with a cathode outlet of the cell stack, and the second bypass and the cathode exhaust pipe are communicated with the main exhaust pipe through a third three-way valve;
and the control system is connected with the first three-way valve, the second three-way valve, the third three-way valve, the first stop valve, the second stop valve and the third stop valve and controls the actions of the valves.
2. The apparatus for evaluating the start-stop durability of a fuel cell stack according to claim 1, characterized in that: and a one-way valve is arranged on the first pipeline and is positioned between the first three-way valve and the anode inlet.
3. The apparatus for evaluating the start-stop durability of a fuel cell stack according to claim 1, characterized in that: the hydrogen pipe is provided with a one-way valve, and the one-way valve is positioned between the first stop valve and the anode inlet.
4. The apparatus for evaluating the start-stop durability of a fuel cell stack according to claim 1, characterized in that: and an air flow meter is arranged on the air main path.
5. A method for evaluating the start-stop durability of a fuel cell stack is characterized by comprising the following steps: the device for evaluating the start-stop durability of the fuel cell stack according to any one of claims 1 to 4 is adopted, and comprises the following steps:
1) stopping the fuel cell stack, discharging and consuming oxygen on the cathode side of the stack until the voltage is reduced to 0V;
2) opening a second stop valve, and synchronously adjusting a second three-way valve and a third three-way valve to discharge air at a first preset flow rate through an air main path and a first bypass, and discharge air at a second preset flow rate through a cathode air inlet pipe, a second bypass and a main exhaust pipe, wherein the first preset flow rate is different from the second preset flow rate;
3) synchronously adjusting the first three-way valve, the second three-way valve and the third three-way valve, closing the second stop valve, opening the third stop valve, enabling air in an air main path to enter the cell stack through the first pipeline, enabling air at the cathode to enter the cell stack through the cathode air inlet pipe, and waiting for a preset time;
4) monitoring cell voltages of the cell stack and zeroing all parameters;
5) adjusting the first three-way valve to enable the main air path to be communicated with the first bypass, opening the first stop valve, starting the cell stack, and enabling the cell stack to run to a performance operation judgment point;
6) and judging whether the performance of the cell stack reaches the specified performance attenuation value, if so, calculating the starting and stopping durability of the cell stack, otherwise, repeating the steps 1) -5) until the performance of the cell stack reaches the specified performance attenuation value.
6. The method for evaluating the start-stop durability of a fuel cell stack according to claim 5, characterized in that: the calibration process of the second preset flow and the first preset flow is as follows:
a, normally shutting down and discharging a cell stack, and maintaining the cell stack in a hydrogen/hydrogen state for a certain time;
b, sending air with a first flow value into a first bypass, and sending air with a second flow value into a second bypass, wherein the first flow value is the maximum flow of the air main path, and is the first preset flow; the second flow value is less than the first flow value;
c, synchronously adjusting the first three-way valve, the second three-way valve and the third three-way valve, closing the second stop valve, opening the third stop valve, enabling air in the air main path to enter the cell stack through the first pipeline, enabling air at the cathode to enter the cell stack through the cathode air inlet pipe, and waiting for a certain time;
d, monitoring the voltage of the battery electric pile, repeating the steps A-C according to the voltage condition, if the voltage is positive voltage, increasing the size of the second flow value, and if negative voltage occurs, reducing the size of the second flow value; until no voltage is generated in the battery electric pile, the current second flow value is the second preset flow.
7. The method for evaluating the start-stop durability of a fuel cell stack according to claim 5, characterized in that: the preset time is 1-2 min.
8. The method for evaluating the start-stop durability of a fuel cell stack according to claim 5, characterized in that: all of the parameters include the air flow rate in the air main, the air temperature and the dew point of the air.
CN202011411837.7A 2020-12-04 2020-12-04 Device and method for evaluating fuel cell stack start-stop durability Pending CN112415395A (en)

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