CN111600047A - Activation method of proton exchange membrane fuel cell stack - Google Patents
Activation method of proton exchange membrane fuel cell stack Download PDFInfo
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- CN111600047A CN111600047A CN202010479849.7A CN202010479849A CN111600047A CN 111600047 A CN111600047 A CN 111600047A CN 202010479849 A CN202010479849 A CN 202010479849A CN 111600047 A CN111600047 A CN 111600047A
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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
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
- H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
- H01M8/04126—Humidifying
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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
- H01M8/04223—Auxiliary 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
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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
Abstract
The invention discloses an activation method of a proton exchange membrane fuel cell stack. It includes: s1 heat engine: the initial temperature is room temperature, the reactor temperature is 40-85 ℃, humidifying gas is introduced into the cathode and the anode, and the temperature is 5-20 ℃ higher than the reactor temperature but not higher than 90 ℃; s2 current activation: s21 from 0 to X1Step-shaped loading density of X is more than or equal to 1001≤400mA/cm2(ii) a The stack temperature is 40-60 ℃; s22 from X1To less than or equal to 2000mA/cm2Step-shaped loading of the electric density; s23 step-shaped lowering of load density to X3，100≤X3≤400mA/cm2(ii) a S24 step-shaped lowering of the load density to 0; in S22-S24, the back pressure of the cathode and the anode is 0-50 KPa and is not 0; the S3 voltage is activated. The invention can carry out pre-humidification on the galvanic pile by effectively controlling the parameters of current activation; the activation process has low cost and operates under high current, thereby improving the activation efficiency and shortening the activation time.
Description
Technical Field
The invention relates to an activation method of a proton exchange membrane fuel cell stack.
Background
A fuel cell stack is a power generation device composed of a plurality of single cells connected in series by converting chemical energy possessed by fuel into electrical energy. After the fuel cell stack is assembled and molded, the performance of the fuel cell stack needs to be activated to ensure that the performance of the fuel cell stack reaches the optimal state for use, and meanwhile, whether the fuel cell stack meets the delivery requirement can be detected, so that the delivered fuel cell stack has good performance. The electric pile is not activated, the performance of the electric pile can not be fully exerted, and the whole electric pile can not be used due to low single-section performance. The activation of the galvanic pile before use can not only fully exert the performance of the galvanic pile, but also can be used for checking the galvanic pile product. Therefore, activation of the stack before use and installation are essential steps for the industrialization of fuel cell stacks.
An appropriate activation method can play a role in accelerating the study on the performance of the stack, improving the performance of the stack and saving the cost for the test of the proton exchange membrane fuel cell stack.
There are two types of current activation processes, forced activation (including constant-current forced activation and variable-current forced activation) and natural activation. Forced activation (including constant current forced activation and variable current forced activation) is superior to natural activation; in the forced activation process, the variable flow forced activation is superior to the constant flow forced activation; moreover, the time for the variable flow forced activation is greatly shortened compared with the constant flow forced activation and the constant flow natural activation.
Disclosure of Invention
The invention aims to overcome the defects of long time consumption, high cost and low activation efficiency of an activation method of a proton exchange membrane fuel cell stack in the prior art, and provides the activation method of the proton exchange membrane fuel cell stack.
The invention solves the technical problems through the following technical scheme.
The invention provides an activation method of a proton exchange membrane fuel cell stack, which comprises the following steps:
s1 heat engine: the initial temperature is room temperature, the stack temperature is 40-85 ℃, humidifying gas is introduced into a cathode and an anode, the humidifying gas is humidifying inert gas and/or humidifying nitrogen, and the temperature of the humidifying gas is 5-20 ℃ higher than the stack temperature but not higher than 90 ℃;
s2 current activation:
s21 heat engineThen, the proton exchange membrane fuel cell stack is loaded with current in a step shape, so that the current density is from 0 to X1mA/cm2Wherein X is not less than 1001≤400mA/cm2(ii) a The stack temperature is 40-60 ℃; the temperature of the humidifying gas of the cathode or the anode is 5-20 ℃ higher than the stack temperature in S21;
s22, after the S21 is finished, the proton exchange membrane fuel cell stack continuously loads current in a step shape, so that the current density is changed from the X1To X2Said X is2≤2000mA/cm2；
S23, after the S22 is finished, the electric pile of the proton exchange membrane fuel cell reduces the load current in a step shape, so that the current density is changed from the X2Down to X3100 is not more than X3≤400mA/cm2；
S24, after the S23 is finished, the proton exchange membrane fuel cell stack continues to reduce the load current in a step shape, so that the current density is changed from the X3Reducing to 0;
in S21, S22, S23 or S24, humidified air or humidified oxygen is introduced into the cathode, and humidified hydrogen is introduced into the anode;
in S22, S23 or S24, the stack temperature is below 80 ℃;
in S22, S23 or S24, the temperature of the humidifying gas of the cathode or the anode is 0-20 ℃ lower than the stack temperature;
in S22, S23 or S24, the back pressure between the cathode and the anode is 0-50 KPa and is not 0;
and S3, activating the voltage.
The activation method of the present invention can be applied to proton exchange membrane fuel cell stacks that are conventional in the art.
Before S1, preferably, the method further includes step S0: and (3) mounting the cell stack to be activated on a test platform, preheating and purging the cell stack, and preferably, introducing gas to purge the cathode and the anode of the cell stack. In the step S0, the cell stack to be activated needs to satisfy the airtightness test standard.
The type of gas used for purging may be conventional in the art, such as nitrogen, among others. The purging time of the gas is generally 1.5-2.5 min.
In S1, the room temperature is generally 5-35 ℃.
In S1, the stack temperature may be 55-80 ℃, preferably 60-80 ℃, such as 60 ℃, 65 ℃, 70 ℃ or 75 ℃.
In S1, the humidified gas starts to be introduced during the temperature rise of the pem fuel cell stack. For example, the introduction of the humidified gas may be started when the temperature is raised from room temperature, or the humidified gas may be introduced during the temperature raising.
In S1, the rate of temperature increase during the heat engine may be conventional in the art.
In S1, the humidified gas may be produced by a method conventional in the art, for example, the humidified gas formed after bubbling the gas from the bottom of the water bath may be passed directly to the cathode or the anode. The temperature of the humidified gas is typically adjusted by controlling the temperature of the water in the tank, for example if the water temperature is 80 ℃, the gas passes through the water and the temperature of the humidified gas formed by bubbling is also 80 ℃. In order to prevent the gas temperature from dropping, the secondary heating and heat preservation can be carried out through the test platform.
In S1, preferably, the humidifying gas is a supersaturated gas at the stack temperature.
In S1, the temperature of the humidifying gas (also called as the dew point of the humidifying gas) is generally 5-20 ℃ higher than the temperature of the stack temperature, or 8-15 ℃ higher than the temperature of the stack temperature, or 10-12 ℃ higher than the temperature of the stack temperature and not higher than 90 ℃. For example, when the stack temperature is 60 ℃, the temperature of the humidifying gas may be 65 ℃, 68 ℃, 70 ℃, 75 ℃, or 80 ℃.
In S1, the temperature of the humidified gas is preferably less than or equal to 80 ℃.
In S1, the temperature of the humidified gas is higher than the stack temperature, that is, the dew point of the humidified gas is higher than the stack temperature, and when the humidified gas is added to the cathode or the anode, the humidified gas is directly liquefied to become liquid water droplets, on one hand, a small amount of liquefied water droplets can pre-humidify and wet the whole PEM of the PEM fuel cell stack, and on the other hand, the circulated gas can also take away a part of water droplets, so as to avoid flooding.
In S1, the inert gas may be an inert gas conventional in the chemical art, such as helium and/or argon.
In S1, the stoichiometric ratio of the gas introduced into the anode or the cathode can be selected by conventional methods in the art, and is preferably (1.5-2.5), more preferably 1.8-2.2, such as 2.
In S1, the current density when gas is introduced into the anode or the cathode can be 300-400 mA/cm2E.g. 350mA/cm2。
In a preferred embodiment, the current density of the gas introduced into the anode is 300mA/cm2The stoichiometric ratio is 2. In a preferred embodiment, the current density of the cathode when gas is introduced into the cathode is 300mA/cm2The stoichiometric ratio is 2. The stoichiometric ratio and the electric density of 300-400 mA/cm known in the field can be used by those skilled in the art2The relationship (2) calculates the flow rate of the introduced gas.
In S1, the stoichiometric ratio of the gas introduced into the cathode is preferably equal to the stoichiometric ratio of the gas introduced into the anode.
At S1, the skilled person can estimate the time of the heat engine. If the temperature of the cell stack begins to rise, the humidifying nitrogen begins to be introduced, and the heat engine can be finished after the temperature rise is finished.
The operation and conditions of the step loading current in S21 or S22 may be conventional in the art, e.g., every 100mA/cm2The current density is maintained for at least 2-5 min.
In S21, when the current is applied in the step shape, X is1Can be 200mA/cm2、300mA/cm2Or 400mA/cm2。
In S21, the stack temperature is preferably 45 to 60 ℃, for example, 50 ℃, 55 ℃ or 60 ℃.
In S21, S22, S23, or S24, the temperature ramp rate of the pem fuel cell stack may be conventional in the art.
S21, S22, S23 or S24, the method for preparing the humidified gas for the cathode or the anode is conventional in the art.
In S21, S22, S23, or S24, preferably, the temperature of the humidified gas of the cathode is equal to the temperature of the humidified gas of the anode.
In S21, the temperature of the humidified gas introduced into the cathode or the anode (also called as the dew point of the humidified gas) is generally 5 to 20 ℃, or 8 to 15 ℃, or 10 to 12 ℃ higher than the temperature of the stack temperature in S21. For example, when the stack temperature of S21 is 60 ℃, the temperature of the humidified gas introduced into the cathode or the anode may be 65 ℃, 68 ℃, 70 ℃, 75 ℃ or 80 ℃.
In S21, the temperature of the humidified gas introduced into the cathode or the anode is generally 80 ℃.
In S21, S22, S23 or S24, the stoichiometry of the gas introduced into the cathode or the anode is preferably 1.5 to 2.5, more preferably 1.8 to 2.2, for example 2.
In S21 or S24, the current density of the cathode or the anode when gas is introduced can be 300-400 mA/cm2。
In a preferred embodiment, in S21 or S24, the current density of the cathode when gas is introduced is 300mA/cm2The stoichiometric ratio is 2. In a preferred embodiment, in S21 or S24, the current density of the gas passing through the anode is 300mA/cm2The stoichiometric ratio is 2. The stoichiometric ratio and the electric density of 300-400 mA/cm known in the field can be used by those skilled in the art2The amount of gas introduced was calculated from the relationship (current/effective area of cell).
In S21, S22, S23 or S24, the stoichiometric ratio of the gas introduced into the cathode is preferably equal to the stoichiometric ratio of the gas introduced into the anode.
At the temperature of the stack, the humidified gas introduced into the cathode and the anode is preferably supersaturated gas in S21.
In S22, the loading current interval may be X1To 2000mA/cm2. Said X2Can be 600-2000 mA/cm2Preferably 1200 to 1800mA/cm2For example 1500mA/cm2、1600mA/cm2、1700mA/cm2Or 1800mA/cm2. In practical operation, the larger the current density, the better the average voltage is not lower than 0.3V.
In S22, S23 or S24, the stack temperature is preferably 60 to 80 ℃, more preferably 70 to 80 ℃, for example 75 ℃.
In S22, S23 or S24, the temperature of the humidifying gas of the cathode or the anode can be 5-15 ℃, for example 10 ℃ lower than the stack temperature.
In S22, S23 or S24, the relative humidity of the humidified gas is generally equal to 100% at the temperature of the humidified gas of the cathode or the anode.
In S22 or S23, the amount of gas introduced can be calculated by a person skilled in the art from the relationship between the stoichiometric ratio and the actual current (current/cell effective area) which is well known in the art.
In S22, S23 or S24, the back pressure of the cathode and the anode is preferably 10 to 40KPa, such as 20 to 30 KPa.
In S23, when the current is decreased in the step-like manner, X is3Can be 200mA/cm2、300mA/cm2Or 400mA/cm2。
The operation and conditions of the stepped down current in S23 or S24 may be conventional in the art, e.g., every 100mA/cm2The current density is maintained for at least 2-5 min.
In S3, the operation and conditions of the voltage activation may be conventional in the art.
In S3, in the voltage activation, the stack temperature is preferably below 80 ℃, more preferably 70 to 80 ℃, for example 75 ℃.
In S3, in the voltage activation, the temperature rise rate of the pem fuel cell stack may be conventional in the art.
In S3, in the voltage activation, the cathode is generally introduced with humidified air or humidified oxygen. Humidified hydrogen is generally fed to the anode. The relative humidity of the humidified gas introduced at the cathode or at the anode is generally equal to 100% at the temperature of the humidified gas introduced at the cathode or at the anode.
In S3, during the voltage activation, the temperature of the cathode or anode humidified gas may be 0 to 20 ℃ lower than the stack temperature during the voltage activation, for example, 0 to 15 ℃ or 0 to 10 ℃.
In S3, in the voltage activation, the temperature of the cathode or anode humidified gas is preferably equal to the stack temperature in the voltage activation process.
In S3, in the voltage activation, the preparation method of the humidified gas for the cathode or the anode is conventional in the art.
In S3, in the voltage activation, it is preferable that the temperature of the humidified gas at the cathode be equal to the temperature of the humidified gas at the anode.
In S3, during the voltage activation, a constant voltage operation is generally performed.
In the constant voltage operation, the operation voltage is preferably sequentially increased from high to low.
In the constant voltage operation, the more the operating conditions, the better, 3 operating conditions can be operated at least, and 4 operating conditions can be operated preferably.
In the constant voltage operation, the operation time of each working condition is preferably 5 to 30min, more preferably 5 to 15min, for example 5 to 10 min.
In S3, the operation voltage can be 0.3-0.9V during the voltage activation.
In S3, the operating voltage during the voltage activation may be 0.3 to 0.4V, for example, 0.35V.
In S3, in the voltage activation, the operating voltage may be 0.4 to 0.7V, for example, 0.5V or 0.6V.
In S3, in the voltage activation, the operating voltage may be 0.6 to 0.8V, for example, 0.7V or 0.75V.
In S3, the operating voltage during the voltage activation may be 0.7-0.9V, such as 0.75V, 0.8V, or 0.85V.
In S3, in the voltage activation, the conditions for terminating the voltage activation may be conventional in the art, and preferably, the current is increased by up to 0.6V by less than 5% compared with the previous cycle.
In S3, in the voltage activation, when the current density is greater than or equal to 400mA/cm2What is, what isThe flow rate of the gas introduced into the cathode or the anode is calculated by the stoichiometric ratio and the actual current density. If the current density is less than 400mA/cm2The flow rate of the gas introduced into the cathode or the anode is 300-400 mA/cm through the stoichiometric ratio and the current density2And (6) performing calculation.
S3, during the voltage activation, the back pressure of the cathode and the anode may be 0 to 50KPa and is not 0; preferably 10 to 40KPa, for example 20 to 30 KPa.
In S3, in the voltage activation, the stoichiometry ratio of the gas introduced into the cathode or the anode is preferably (1.5 to 2.5), more preferably 1.8 to 2.2, for example, 2.
In the present invention, the terms involved are explained as follows (the non-mentioned terms are understood by reference to the national standard GB/T20042.1-2017):
and activating, namely, a process of operating the fuel cell under the set conditions so as to achieve the designed performance or the optimal performance.
The reactant stoichiometric ratio, also known as the excess factor, generally refers to the ratio of the actual amount of fuel or oxidant supplied to the amount of fuel or oxidant required to actually output the current (as calculated by faraday's law).
Back pressure, the pressure of the reactants that build up at the outlet of the fuel cell.
Polarization curves, the potential of the cathode, anode, or both of the fuel cell as a function of current or current density.
The phenomenon of fuel cell performance reduction caused by gas flow obstruction due to water flooding and gas channel blockage by liquid water.
Voltage stability, the degree of fluctuation with time of the dc voltage output by the stack or fuel cell system at a constant output current.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the activation process of the invention has low cost and the following excellent effects:
(1) the stack may be pre-wetted.
(2) The galvanic pile is further humidified by effectively controlling the parameters of current activation, so that the galvanic pile can be effectively prevented from flooding at low electricity density; so that the galvanic pile operates under high current, further improving the activation efficiency and shortening the activation time (only 335 min).
(3) The influence of the change of extra test conditions on the test result can be reduced, and the working efficiency and the activation efficiency of personnel can be further improved.
Drawings
Figure 1 is a plot of average voltage versus current density for the activated stack of example 1, the initial (unactivated), and the stack of comparative example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
Proton exchange membrane fuel cell stack: and cooling water flow is set according to the number of the sections of the galvanic pile (the galvanic pile is composed of a plurality of sections of bipolar plates) (a person skilled in the art can set the water flow conventionally according to the number of the sections of the galvanic pile, the pressure difference of a water outlet and an inlet and the temperature difference, generally, the water flow is increased by 1L/min every time one section of the water flow is added), and the pressure difference of the water cavity inlet and the water cavity outlet is ensured to be within.
The initial (unactivated) cell stack employed in this example may be a stack conventional in the art, consisting of 5 metal bipolar plates.
S0, the cell stack to be activated needs to meet the air tightness test standard, therefore, before the heat engine, the cell stack to be activated is generally arranged on a test platform, nitrogen is introduced to purge the cathode and the anode of the cell stack, and the purging time is generally 1.5-2.5 min.
S1, heat engine: the initial temperature is 25 ℃, and the reactor temperature is 60 ℃; when the temperature is raised from room temperature, the humidifying nitrogen is introduced into the cathode and the anodeGas; the temperature of humidifying nitrogen gas by the anode and the cathode is 80 ℃; at the temperature of the reactor, the humidifying gas is supersaturated gas; the flow is set to be 300mA/cm of electric density2The stoichiometric ratio of time to yin and yang is 2/2. And after the temperature rise is finished, finishing the heat engine.
S2, current activation:
s21, after the heat engine, humidifying air is introduced into the cathode, and humidifying hydrogen is introduced into the anode; at the temperature of the reactor, the humidifying gas is supersaturated gas; the flow of gas introduced into the cathode and the anode is set to be 300mA/cm in electric density2Time, stoichiometric ratio of yin and yang poles 2/2. The stack temperature is 60 ℃; the temperature of the humidified gas of the cathode or anode was 80 ℃.
After the constant temperature voltage is stable (open circuit, current is 0), the current is loaded to the electric pile of the proton exchange membrane fuel cell in a step shape, so that the current density is from 100 to 300mA/cm2Adding 100mA/cm each time2The electrical density was stable for 5 minutes.
S22 and S21, the stack temperature is 80 ℃, and the temperature of the cathode or anode humidifying gas is 80 ℃. The gas outlet pressure was set at 30 kPa. Humidified air is introduced into the cathode, and humidified hydrogen is introduced into the anode. The flow rate of the gas introduced into the cathode and the anode is set to be the flow rate at the actual stoichiometric ratio of the cathode to the anode of 2/2. The relative humidity of the humidified gas at the temperature of the humidified gas of the cathode and anode is generally equal to 100%.
After the temperature and the pressure are stable, continuously loading current to the proton exchange membrane fuel cell stack in a step shape to ensure that the current density is from 300 to 1600mA/cm2Adding 100mA/cm each time2The electrical density was stable for 5 minutes.
S23 and S22, the stack temperature is 80 ℃, and the temperature of the cathode or anode humidifying gas is 80 ℃. The gas outlet pressure was set at 30 kPa. Humidified air is introduced into the cathode, and humidified hydrogen is introduced into the anode. The flow rate of the gas introduced into the cathode and the anode is set to be the flow rate at the actual stoichiometric ratio of the cathode to the anode of 2/2. The relative humidity of the humidified gas at the temperature of the humidified gas of the cathode and anode is generally equal to 100%.
After the temperature and the pressure are stable, the current is reduced in a step shape by the electric pile of the proton exchange membrane fuel cell, so thatThe current density is reduced from 1600 to 400mA/cm2Every 100mA/cm of the drop2The electrical density was stable for 5 minutes.
S24 and S23, the stack temperature is 80 ℃, and the temperature of the cathode or anode humidifying gas is 80 ℃. The gas outlet pressure was set at 30 kPa. Humidified air is introduced into the cathode, and humidified hydrogen is introduced into the anode. The flow of gas introduced into the cathode and the anode is set to be 300mA/cm in electric density22/2 stoichiometric ratio of the anode and the cathode. The relative humidity of the humidified gas at the temperature of the humidified gas of the cathode and anode is generally equal to 100%.
After the temperature and the pressure are stable, the electric pile of the proton exchange membrane fuel cell continues to reduce the load current in a step shape, so that the current density is from 400mA/cm2Decrease to 0, each decrease of 100mA/cm2The electrical density was stable for 5 minutes.
S3, voltage activation: the load is changed into a constant pressure mode, the stack temperature is 80 ℃, and the temperature of the humidifying gas of the cathode or the anode is 80 ℃. The gas outlet pressure was set at 30 kPa. Humidified air is introduced into the cathode, and humidified hydrogen is introduced into the anode. The relative humidity of the humidified gas is generally equal to 100% at a temperature of the humidified gas at which the gas is fed to the cathode or anode in a stoichiometric ratio of 2/2.
Constant voltage the following 4 conditions: 0.85V-0.7V-0.6V-0.35V, and each working condition is operated for 10 minutes. And (5) circulating for several times until the current at 0.6V is improved by less than 5% than that of the previous cycle, and finishing the activation.
In voltage activation, if the current density is more than 400mA/cm2The flow rate of the gas introduced into the cathode and anode was calculated from the stoichiometric ratio and the actual current density. If the current density is less than 400m A/cm2The flow rate of the gas introduced into the cathode and anode was 300m A/cm in terms of the stoichiometric ratio and the current density2And (6) performing calculation.
In the activation process, the heat engine time of S1 is 15 minutes; the time from S21 to S24 is 160 minutes; in S3, the voltage activation is 160 minutes, the total time is 335 minutes, and the activation time is short.
Comparative example 1
Other proton exchange membrane fuel cell modules and the like were the same as in example 1 except for the specific activation operation described below.
The activation process comprises the following steps:
s1, heat engine: the reactor temperature is set to be 70 ℃, 100% humidified nitrogen and hydrogen are introduced into the cathode and the anode, and the flow is set to be 2/2 hours when the metering ratio of the cathode and the anode is 300 electric density. For 2H.
S2, converting the gas introduced into the cathode into humidified air, setting the flow rate to be 2/2, testing the polarization performance of the proton exchange membrane fuel cell for 6 times, converting the gas introduced into the cathode into humidified nitrogen again, and keeping the state for 15 min;
and S3, repeating the steps S1 and S2 for 10 times (shortening the retention time after changing the hydrogen and the nitrogen), until the polarization performance of the proton exchange membrane fuel cell is kept stable.
S4, the performance of the activated battery is shown in the figure, and the total activation time of S1-S4 is 8 h.
Figure 1 is a plot of average voltage (voltage divided by number of nodes) versus current density (current divided by effective area) for the activated stack of example 1, the initial (unactivated), and the stack of comparative example 1. As can be seen from fig. 1, the cell performance (maximum power (power equals current times voltage)) of example 1 was improved by a factor of 1.8 (relative to the initial unactivated stack).
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.
Claims (10)
1. The activation method of the proton exchange membrane fuel cell stack is characterized by comprising the following steps:
s1 heat engine: the initial temperature is room temperature, the stack temperature is 40-85 ℃, humidifying gas is introduced into a cathode and an anode, the humidifying gas is humidifying inert gas and/or humidifying nitrogen, and the temperature of the humidifying gas is 5-20 ℃ higher than the stack temperature but not higher than 90 ℃;
s2 current activation:
s21 after the heat engine, the proton exchange membrane fuel cell stack is loaded with current in a step-like manner, so that the current density is from 0 to X1mA/cm2Wherein X is not less than 1001≤400mA/cm2(ii) a The stack temperature is 40-60 ℃; the temperature of the humidifying gas of the cathode or the anode is 5-20 ℃ higher than the stack temperature in S21;
s22, after the S21 is finished, the proton exchange membrane fuel cell stack continuously loads current in a step shape, so that the current density is changed from the X1To X2Said X is2≤2000mA/cm2；
S23 after S22 is finished, the proton exchange membrane fuel cell stack carries current in a stepped manner, so that the current density is changed from the X2Down to X3100 is not more than X3≤400mA/cm2；
S24 after S23 is finished, the proton exchange membrane fuel cell stack continues to step down the current to make the current density from the X3Reducing to 0;
in S21, S22, S23 or S24, humidified air or humidified oxygen is introduced into the cathode, and humidified hydrogen is introduced into the anode; in S22, S23 or S24, the stack temperature is below 80 ℃; in S22, S23 or S24, the temperature of the humidifying gas of the cathode or the anode is 0-20 ℃ lower than the stack temperature; in S22, S23 or S24, the back pressure between the cathode and the anode is 0-50 KPa and is not 0;
and activating by the voltage of S3.
2. The method for activating the pem fuel cell stack of claim 1 wherein in S1, the stack temperature is 55-80 ℃, preferably 60-80 ℃, such as 60 ℃, 65 ℃, 70 ℃ or 75 ℃;
and/or in S1, in the temperature rising process of the proton exchange membrane fuel cell stack, starting to introduce humidifying gas;
and/or in S1, the temperature of the humidifying gas is 8-15 ℃ higher than the temperature of the stack temperature, or 10-12 ℃;
and/or, in S1, the temperature of the humidified gas is less than or equal to 80 ℃.
3. The method for activating pem fuel cell stack of claim 1 wherein in S1, the stoichiometric ratio of the gas introduced into the anode or the cathode is (1.5-2.5), preferably 1.8-2.2, such as 2;
and/or in S1, the current density when gas is introduced into the anode or the cathode is 300-400 mA/cm2；
And/or in S1, the stoichiometric ratio of the gas introduced into the cathode is equal to the stoichiometric ratio of the gas introduced into the anode.
4. The method for activating pem fuel cell stack of claim 1 wherein in S21 or S22 said step-wise applied current conditions are: per 100mA/cm2Maintaining the current density for at least 2-5 min;
and/or, in S21, the X1Is 200mA/cm2、300mA/cm2Or 400mA/cm2；
And/or, in S21, the stack temperature is 45-60 ℃, for example, 50 ℃, 55 ℃ or 60 ℃;
and/or, in S21, S22, S23 or S24, the temperature of the humidified gas of the cathode is equal to the temperature of the humidified gas of the anode;
or in S21, the temperature of the humidifying gas introduced into the cathode or the anode is 8-15 ℃ higher than the temperature of the stack in S21, or 10-12 ℃;
or in S21, the temperature of the humidified gas introduced into the cathode or the anode is less than or equal to 80 ℃.
5. The method of activating pem fuel cell stack of claim 1 wherein in S21, S22, S23 or S24, the stoichiometric ratio of gas introduced into the cathode or the anode is 1.5 to 2.5, preferably 1.8 to 2.2, such as 2;
and/or in S21 or S24, the current density when gas is introduced into the cathode or the anode is 300-400mA/cm2；
Alternatively, in S21, S22, S23 or S24, the stoichiometric ratio of the gas introduced into the cathode is equal to the stoichiometric ratio of the gas introduced into the anode.
6. The method for activating pem fuel cell stack of claim 1 wherein, in S22, said X2600 to 2000mA/cm2；
And/or in S22, S23 or S24, the stack temperature is 60-80 ℃;
and/or in S22, S23 or S24, the temperature of the humidifying gas of the cathode or the anode is 5-15 ℃ lower than the stack temperature;
and/or, in S22, S23 or S24, the relative humidity of the humidified gas is equal to 100% at the temperature of the humidified gas of the cathode or the anode;
and/or in S22, S23 or S24, the back pressure of the cathode and the anode is 10-40 KPa;
and/or, in S23, the X3Is 200mA/cm2、300mA/cm2Or 400mA/cm2；
And/or in S23 or S24, the condition of the stepped load reduction current is that: per 100mA/cm2The current density is maintained for at least 2-5 min.
7. The method for activating pem fuel cell stack of claim 6 wherein, in S22, X is2Is 1200 to 1800mA/cm2For example 1500mA/cm2、1600mA/cm2、1700mA/cm2Or 1800mA/cm2；
And/or in S22, S23 or S24, the stack temperature is 70-80 ℃, such as 75 ℃;
and/or, in S22, S23, or S24, the temperature of the cathode or anode humidified gas is 10 ℃ lower than the stack temperature;
and/or in S22, S23 or S24, the back pressure of the cathode and the anode is 20-30 KPa.
8. The method for activating the pem fuel cell stack of claim 1 wherein in S3, the stack temperature in said voltage activation is below 80 ℃, preferably 70-80 ℃, for example 75 ℃;
and/or, in S3, the relative humidity of the humidified gas introduced into the cathode or the anode is equal to 100% at the temperature of the humidified gas introduced into the cathode or the anode;
and/or in S3, in the voltage activation, the temperature of the humidifying gas of the cathode or the anode is 0-15 ℃ or 0-10 ℃ lower than the stack temperature in the voltage activation process;
or, in S3, in the voltage activation, the temperature of the cathode or anode humidified gas is equal to the stack temperature in the voltage activation process;
and/or, in S3, in the voltage activation, the temperature of the humidified gas of the cathode is equal to the temperature of the humidified gas of the anode.
9. The method for activating a pem fuel cell stack according to claim 1 wherein in S3, during said voltage activation, a constant voltage operation is performed;
in the constant voltage operation, the operation voltage is preferably carried out from large to small in sequence;
in the constant voltage operation, the operation time of each working condition is preferably 5-30 min, more preferably 5-15 min, such as 5-10 min;
in S3, in the voltage activation, the operation voltage is preferably 0.3-0.9V, 0.3-0.4V, 0.4-0.7V, 0.6-0.8V or 0.7-0.9V.
10. The method for activating a pem fuel cell stack according to claim 1 wherein in S3, the conditions for terminating voltage activation are as follows: the current is improved by less than 5 percent than that of the previous round under the condition of 0.6V;
and/or in S3, the back pressure of the cathode and the anode is 0-50 KPa and is not 0 in the voltage activation; preferably 10 to 40KPa, for example 20 to 30 KPa;
and/or in S3, the stoichiometric ratio of the gas introduced into the cathode or the anode in the voltage activation is (1.5-2.5), preferably 1.8-2.2, such as 2.
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| CN113097538A (en) * | 2021-04-13 | 2021-07-09 | 金华氢途科技有限公司 | Rapid activation method for fuel cell |
| CN113224353A (en) * | 2021-05-08 | 2021-08-06 | 张家口市氢能科技有限公司 | Quick activation method and device for hydrogen fuel cell |
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| CN113363535A (en) * | 2021-05-19 | 2021-09-07 | 海卓动力(上海)能源科技有限公司 | Rapid activation method for proton exchange membrane fuel cell |
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