CN111600047B - Activation method of proton exchange membrane fuel cell stack - Google Patents

Activation method of proton exchange membrane fuel cell stack Download PDF

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Publication number
CN111600047B
CN111600047B CN202010479849.7A CN202010479849A CN111600047B CN 111600047 B CN111600047 B CN 111600047B CN 202010479849 A CN202010479849 A CN 202010479849A CN 111600047 B CN111600047 B CN 111600047B
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temperature
cathode
anode
fuel cell
gas
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CN111600047A (en
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郑立能
杨敏
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Shanghai Electric Group Corp
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Shanghai Electric Group Corp
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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
    • 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
    • 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, a 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 X 1 Step-shaped loading density of X is more than or equal to 100 1 ≤400mA/cm 2 (ii) a The stack temperature is 40-60 ℃; s22 from X 1 To less than or equal to 2000mA/cm 2 Step-shaped loading of the electric density; s23 step-shaped load reducing current density to X 3 ，100≤X 3 ≤400mA/cm 2 (ii) a S24, reducing the load density to 0 in a step shape; in S22-S24, the back pressure of the cathode and the anode is 0-50 KPa and is not 0; and S3, activating voltage. 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

Activation method of proton exchange membrane fuel cell stack
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 is an essential step 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-current forced activation is superior to the constant-current 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, a heat engine: the initial temperature is room temperature, the stack temperature is 40-85 ℃, humidifying gas is introduced into the cathode and the 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 shape, so that the current density is from 0 to X 1 mA/cm 2 Wherein X is not less than 100 1 ≤400mA/cm 2 (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 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 X 1 To X 2 Said X is 2 ≤2000mA/cm 2 ；
S23, after 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 X 2 Down to X 3 100 is not more than X 3 ≤400mA/cm 2 ；
S24, after the S23 is finished, the electric pile of the proton exchange membrane fuel cell continues to reduce the load current in a step shape, so that the current is denseDegree from said X 3 Reducing to 0;
in S21, S22, S23 or S24, introducing humidifying air or humidifying oxygen into the cathode, and introducing humidifying hydrogen 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 of the cathode and the anode is 0 to 50KPa, 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 purge time of the gas is generally 1.5 to 2.5min.
In S1, the room temperature is generally 5 to 35 ℃.
In S1, the stack temperature may be 55 to 80 ℃, preferably 60 to 80 ℃, such as 60 ℃, 65 ℃, 70 ℃ or 75 ℃.
In S1, the humidified gas is started 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 prepared 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 directly introduced into 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, at the stack temperature, the humidifying gas is a supersaturated gas.
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 humidifying gas is higher than the stack temperature, namely the dew point of the humidifying gas is higher than the stack temperature, and the humidifying gas is directly liquefied into liquid water drops after being added into the cathode or the anode, so that on one hand, a small amount of liquefied water drops can pre-humidify and wet the whole PEM of the proton exchange membrane fuel cell stack, and on the other hand, part of water drops can be taken away by circulating gas, and the result of flooding is avoided.
In S1, the inert gas may be an inert gas conventional in the chemical field, 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 routine methods in the art, and is preferably (1.5 to 2.5), more preferably 1.8 to 2.2, for example 2.
In S1, the current density when gas is introduced into the anode or the cathode can be 300-400 mA/cm 2 E.g. 350mA/cm 2 。
In a preferred embodiment, the current density when gas is introduced into the anode is 300mA/cm 2 The stoichiometric ratio is 2. In a preferred embodiment, the current density of the cathode when gas is introduced into the cathode is 300mA/cm 2 The stoichiometric ratio is 2. The person skilled in the art can use the stoichiometric ratio and the electric density of 300-400 mA which are well known in the field/cm 2 The flow rate of the introduced gas is calculated according to the relation (1).
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.
In S1, a person skilled in the art can estimate the time of the heat engine. If the humidifying nitrogen is introduced when the temperature of the cell stack begins to rise, the heat engine can be finished after the temperature rise is finished.
The operation and conditions of the stepped loading of current in S21 or S22 may be conventional in the art, e.g., every 100mA/cm 2 The current density is maintained for at least 2-5 min.
In S21, when the current is applied in the step shape, X is 1 Can be 200mA/cm 2 、300mA/cm 2 Or 400mA/cm 2 。
In S21, the stack temperature is preferably 45 to 60 ℃, for example, 50 ℃, 55 ℃ or 60 ℃.
In S21, S22, S23 or S24, the heating rate of the pem fuel cell stack may be conventional in the art.
In 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 referred to 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 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 not higher than 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 when gas is introduced into the cathode or the anode can be 300-400 mA/cm 2 。
In a preferred embodiment, in S21 or S24, the current density of the cathode when gas is introduced is 300mA/cm 2 The stoichiometric ratio is 2. In a preferred embodiment, in S21 or S24, the current density when gas is introduced into the anode is 300mA/cm 2 The stoichiometric ratio is 2. The stoichiometric ratio and the electric density of 300-400 mA/cm which are well known in the field can be used by the technical personnel in the field 2 The relationship of (electrical density = current/cell effective area) calculates the amount of gas introduced.
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.
In S21, preferably, at the stack temperature, the humidified gases introduced into the cathode and the anode are all supersaturated gases.
In S22, the interval of the loading current may be X 1 To 2000mA/cm 2 . Said X 2 Can be 600-2000 mA/cm 2 Preferably 1200 to 1800mA/cm 2 For example 1500mA/cm 2 、1600mA/cm 2 、1700mA/cm 2 Or 1800mA/cm 2 . In actual operation, the larger the current density, the better at an average voltage of not less 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 cathode or the anode humidified gas may be 5 to 15 ℃, for example, 10 ℃ lower than the stack temperature.
In S22, S23 or S24, the relative humidity of the humidified gas at the temperature of the humidified gas of the cathode or the anode is generally equal to 100%.
In S22 or S23, the amount of gas introduced can be calculated by those skilled in the art from the relationship between the stoichiometric ratio and the actual current (electrical density = 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, for example 20 to 30KPa.
In S23, when the current is decreased in the step shape, the X is 3 Can be 200mA/cm 2 、300mA/cm 2 Or 400mA/cm 2 。
In S23 or S24, the operation and conditions of the stepped down current may be conventional in the art, e.g., every 100mA/cm 2 The 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 80 ℃ or lower, 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, humidified air or humidified oxygen is generally introduced to the cathode. 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 humidified gas at the cathode or the anode may be lower by 0 to 20 ℃, for example, 0 to 15 ℃ or 0 to 10 ℃ than the temperature of the stack during the voltage activation.
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 10min.
In S3, in the voltage activation, the operating voltage can be 0.3-0.9V.
In S3, in the voltage activation, the operating voltage 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, in the voltage activation, the operating voltage may be 0.7 to 0.9V, for example, 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 less than 5% in the previous cycle until 0.6V.
In S3, in the voltage activation, if the current density is more than or equal to 400mA/cm 2 And the flow of the introduced gas of the cathode or the anode is calculated by the stoichiometric ratio and the actual current density. If the current density is less than 400mA/cm 2 The flow of the gas introduced into the cathode or the anode is controlled by the stoichiometric ratio and the current density of 300-400 mA/cm 2 And (4) performing calculation.
In 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 30KPa.
In S3, in the voltage activation, the stoichiometric 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 terms not mentioned 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 may be combined arbitrarily to obtain preferred embodiments of the present invention without departing from the 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 being flooded by water when the galvanic pile is low in 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 50 kPa.
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, so that before a 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 1.5-2.5min.
S1, a heat engine: the initial temperature is 25 ℃, and the reactor temperature is 60 ℃; when the temperature is increased from room temperature, humidifying nitrogen is introduced into the cathode and the anode; 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 as 300mA/cm of current density 2 The flow rate is 2/2 hour of the stoichiometric ratio of time to positive and negative poles. And after the temperature rise is finished, finishing the heat engine.
S2, current activation:
s21, after the heat engine, introducing humidified air into the cathode, and introducing humidified hydrogen 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 density 2 The flow rate of time and the stoichiometric ratio of the anode and the cathode is 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/cm 2 Adding 100mA/cm each time 2 The electrical seal was stable for 5 minutes.
And S22, after the step S21 is finished, the stack temperature is 80 ℃, and the temperature of the cathode or anode humidifying gas is 80 ℃. The gas outlet pressure was set at 30kPa. Humidified air is introduced into the cathode, and humidified hydrogen is introduced into the anode. The flow of the gas introduced into the cathode and the anode is set as the flow when the actual electricity density and the stoichiometric ratio of the cathode to the anode are 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 in a step shape to the proton exchange membrane fuel cell stack to ensure that the current density is from 300 to 1600mA/cm 2 Adding 100mA/cm each time 2 The electrical density was stable for 5 minutes.
And S23, after the step S22 is finished, the stack temperature is 80 ℃, and the temperature of the cathode or anode humidifying gas is 80 ℃. The gas outlet pressure was set at 30kPa. 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 as the flow of actual electric density and the flow of the stoichiometric ratio of the anode to the cathode to the stoichiometric ratio 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 that the current density is reduced from 1600 to 400mA/cm 2 Every 100mA/cm of the drop 2 The electrical density was stable for 5 minutes.
And S24, after the step S23 is finished, 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 30kPa. 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 density 2 And the stoichiometric ratio of the anode and the cathode is 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 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/cm 2 Decrease to 0, each decrease of 100mA/cm 2 The 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 30kPa. 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 humidified gas temperature at which the gas fed to the cathode or anode is stoichiometric to 2/2 of that of the cathode or anode.
Constant voltage the following 4 conditions: 0.85V-0.7V-0.6V-0.35V, and each working condition is operated for 10 minutes. And (4) circulating for several times until the current at 0.6V is improved by less than 5 percent compared with the current in the previous cycle, and ending the activation.
In voltage activation, if the current density is larger than 400mA/cm 2 The 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 400mA/cm 2 The flow rate of the gas introduced into the cathode and the anode was 300mA/cm in terms of the stoichiometric ratio and the current density 2 And (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 following specific activation operation.
The activation process comprises the following steps:
s1, a heat engine: the reactor temperature is set to 70 ℃, 100% humidified nitrogen and hydrogen are introduced into the cathode and the anode, and the flow is set to be 2/2 of the metering ratio of the cathode and the anode when the electricity density is 300. 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 15min;
and S3, repeating the steps S1 and S2 for 10 times (shortening the holding 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 8h.
Figure 1 is a plot of average voltage (voltage divided by number of nodes) versus current density (current divided by effective area) for the stack of example 1 after activation, the initial (not activated), 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 is improved by a factor of 1.8 (relative to the initially inactive 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 (28)

1. The activation method of the proton exchange membrane fuel cell stack is characterized by comprising the following steps:
s1, a heat engine: the initial temperature is room temperature, the stack temperature is 40-85 ℃, humidifying gas is introduced into the cathode and the 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 shape, so that the current density is from 0 to X 1 mA/cm 2 Wherein X is not less than 100 1 ≤400mA/cm 2 (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 and after S21, continuously loading current in a step shape to the proton exchange membrane fuel cell stack to enable the current density to be from the X 1 To X 2 Said X is 2 ≤2000mA/cm 2 ；
S23 and after S22, the electric pile of the proton exchange membrane fuel cell carries current in a stepped mode, so that the current density is increased from the X 2 Down to X 3 100 is not more than X 3 ≤400mA/cm 2 ；
S24, after S23 is finished, the electric pile of the proton exchange membrane fuel cell continues to step-shaped load reduction currentFrom said X to a current density 3 Reducing to 0;
in S21, S22, S23 or S24, humidifying air or humidifying oxygen is introduced into the cathode, and humidifying 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 of the cathode and the anode is 0 to 50KPa and is not 0;
and (3) activating the voltage to obtain the product.
2. The activation method of a pem fuel cell stack of claim 1, wherein in S1, said stack temperature is 55-80 ℃;
and/or in S1, starting to introduce humidifying gas in the temperature rising process of the proton exchange membrane fuel cell stack;
and/or in S1, the temperature of the humidifying gas is 8-15 ℃ higher than the temperature of the stack temperature;
and/or in S1, the temperature of the humidified gas is less than or equal to 80 ℃.
3. The activation method of a pem fuel cell stack as claimed in claim 2, wherein in S1, said stack temperature is 60-80 ℃;
and/or in S1, the temperature of the humidifying gas is 10-12 ℃ higher than the temperature of the stack temperature.
4. The method for activating a pem fuel cell stack of claim 3 wherein in S1 said stack temperature is 60 ℃, 65 ℃, 70 ℃ or 75 ℃.
5. The activation method of pem fuel cell stack of claim 1 wherein in S1, the stoichiometric ratio of the gas introduced into said anode or said cathode is 1.5-2.5;
and/or, in S1, the current density when gas is introduced into the anode or the cathode is 300-400 mA/cm 2 ；
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, and the stoichiometric ratio refers to the ratio of the actual supply amount of the fuel or the oxidant to the amount of the fuel or the oxidant required by the actual output current.
6. The method for activating a pem fuel cell stack according to claim 5 wherein the stoichiometric ratio of the gas introduced into said anode or said cathode in S1 is 1.8-2.2.
7. The method of activating pem fuel cell stack of claim 6 wherein in S1, the stoichiometric ratio of the gas introduced into said anode or said cathode is 2.
8. The method for activating pem fuel cell stack of claim 1 wherein in S21 or S22, said step-wise current application conditions are: per 100mA/cm 2 Maintaining the current density for at least 2-5 min;
and/or, in S21, the X 1 Is 200mA/cm 2 、300mA/cm 2 Or 400mA/cm 2 ；
And/or in S21, the reactor temperature is 45-60 ℃;
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 in S21, the temperature of the humidified gas introduced into the cathode or the anode is less than or equal to 80 ℃.
9. The method for activating pem fuel cell stack of claim 8 wherein, in S21, said stack temperature is 50 ℃, 55 ℃ or 60 ℃;
or in S21, the temperature of the humidifying gas introduced into the cathode or the anode is 10-12 ℃ higher than the temperature of the stack in S21.
10. The activation method for pem fuel cell stack of claim 1 wherein in S21, S22, S23 or S24, the stoichiometric ratio of the gas introduced into said cathode or said anode is 1.5-2.5;
and/or in S21 or S24, the current density when gas is introduced into the cathode or the anode is 300-400 mA/cm 2 ；
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, and the stoichiometric ratio is the ratio of the actual supply amount of the fuel or the oxidant to the amount of the fuel or the oxidant required for the actual output current.
11. The method for activating a pem fuel cell stack according to claim 10 wherein the stoichiometric ratio of the gas introduced into said cathode or said anode in S21, S22, S23 or S24 is 1.8-2.2.
12. The method of activating a pem fuel cell stack according to claim 11 wherein in S21, S22, S23 or S24, the stoichiometric ratio of the gas introduced into said cathode or said anode is 2.
13. The method of activating pem fuel cell stack of claim 1 wherein, in S22, said X 2 600 to 2000mA/cm 2 ；
And/or in S22, S23 or S24, the reactor 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 of 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 X 3 Is 200mA/cm 2 、300mA/cm 2 Or 400mA/cm 2 ；
And/or in S23 or S24, the condition of the step-shaped load reduction current is as follows: per 100mA/cm 2 The current density is maintained for at least 2-5 min.
14. The method of activating pem fuel cell stack of claim 13 wherein, in S22, said X 2 Is 1200-1800 mA/cm 2 ；
And/or in S22, S23 or S24, the stack temperature is 70-80 ℃;
and/or, in S22, S23 or S24, the temperature of the cathode or the 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.
15. The method of activating pem fuel cell stack of claim 14 wherein, in S22, said X 2 Is 1500mA/cm 2 、1600mA/cm 2 、1700mA/cm 2 Or 1800mA/cm 2 ；
And/or in S22, S23 or S24, the stack temperature is 75 ℃.
16. The activation method of a pem fuel cell stack according to claim 1 wherein in S3, in said voltage activation, the stack temperature is 80 ℃ or lower;
and/or in S3, under the temperature of the humidification gas introduced into the cathode or the anode, the relative humidity of the humidification gas introduced into the cathode or the anode is equal to 100%;
and/or in S3, in the voltage activation, the temperature of the humidifying gas of the cathode or the anode is 0-15 ℃ lower than the temperature of the reactor in the voltage activation process;
or, in S3, during the voltage activation, the temperature of the humidified gas of the cathode or the anode is equal to the stack temperature during the voltage activation;
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.
17. The method for activating the pem fuel cell stack of claim 16 wherein in S3, the stack temperature during said voltage activation is between 70 ℃ and 80 ℃;
and/or in S3, in the voltage activation, the temperature of the humidifying gas of the cathode or the anode is 0-10 ℃ lower than the stack temperature in the voltage activation process.
18. The method of activating a pem fuel cell stack of claim 17 wherein in S3, said voltage activation is performed at a stack temperature of 75 ℃.
19. 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 sequentially carried out from large to small;
the running time of each working condition is 5-30 min;
the operating voltage is 0.3-0.9V.
20. The method for activating a pem fuel cell stack of claim 19 wherein in S3, said voltage activation is performed at an operating voltage of 0.3-0.4V.
21. The method for activating a pem fuel cell stack of claim 19 wherein in S3, said voltage activation is performed at an operating voltage of 0.4-0.7V.
22. The method for activating a pem fuel cell stack of claim 19 wherein in S3, said voltage activation is performed at an operating voltage of 0.6-0.8V.
23. The method for activating a pem fuel cell stack of claim 19 wherein in S3, said voltage activation is performed at an operating voltage of 0.7-0.9V.
24. The method for activating pem fuel cell stack of claim 19 wherein in S3, said constant voltage operation is performed for 5-15 min per operating condition.
25. The method for activating pem fuel cell stack of claim 24 wherein in S3, said constant voltage operation is performed for 5-10 min per operating condition.
26. The method for activating a pem fuel cell stack according to claim 1 wherein in S3, the conditions for terminating voltage activation in said voltage activation are: the current is improved by less than 5 percent than the previous round under the condition of 0.6V;
and/or, in S3, during the voltage activation, the back pressure of the cathode and the anode is 0-50 KPa and is not 0;
and/or in S3, in the voltage activation, the stoichiometric ratio of gas introduced into the cathode or the anode is 1.5-2.5.
27. The method for activating a pem fuel cell stack of claim 26 wherein in S3, the back pressure of the cathode and anode is between 10 and 40KPa during said voltage activation;
and/or in S3, in the voltage activation, the stoichiometric ratio of gas introduced into the cathode or the anode is 1.8-2.2.
28. The method for activating pem fuel cell stack of claim 27 wherein in S3, said voltage activation has a cathode to anode backpressure of 20-30 Kpa;
and/or in S3, in the voltage activation, the stoichiometric ratio of gas introduced into the cathode or the anode is 2.
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