CN113540536B - Method and device for humidifying galvanic pile and electronic equipment - Google Patents

Method and device for humidifying galvanic pile and electronic equipment Download PDF

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CN113540536B
CN113540536B CN202110726750.7A CN202110726750A CN113540536B CN 113540536 B CN113540536 B CN 113540536B CN 202110726750 A CN202110726750 A CN 202110726750A CN 113540536 B CN113540536 B CN 113540536B
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cathode
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electric pile
air humidity
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CN113540536A (en
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王卫杰
冀转
丛志龙
贺挺
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CRRC Suzhou Hydrogen Power Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04828—Humidity; Water content
    • H01M8/04835—Humidity; Water content of fuel cell reactants
    • 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
    • H01M8/04149—Humidifying by diffusion, e.g. making use of membranes
    • 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
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Abstract

The invention provides a method and a device for humidifying a galvanic pile and electronic equipment, wherein the method comprises the following steps: controlling the operation of the target galvanic pile, and calculating the cathode humidifying water quantity and the anode humidifying water quantity of the target galvanic pile based on the operation parameters during the operation of the target galvanic pile; determining the membrane reverse osmosis amount of a proton exchange membrane in a target electric pile; respectively calculating cathode inlet air humidity and anode inlet air humidity of the target galvanic pile according to cathode humidifying water quantity, anode humidifying water quantity and membrane reverse osmosis quantity; the target stack is humidified based on the cathode intake air humidity and the anode intake air humidity. The invention can more reasonably humidify the galvanic pile.

Description

Method and device for humidifying galvanic pile and electronic equipment
Technical Field
The invention relates to the technical field of galvanic piles, in particular to a galvanic pile humidifying method and device and electronic equipment.
Background
In the operation process of the fuel cell, the water content in the galvanic pile directly influences the performance of the galvanic pile, when the humidifying water content in the galvanic pile is lower, the proton exchange membrane is in a dry state, the proton conductivity is reduced, but when the humidifying water content is higher, the cell flooding condition can be caused, so the appropriate humidifying water content is beneficial to enabling the galvanic pile to work in the optimal humidity state, and the service life of the galvanic pile can be prolonged to a certain extent. In the humidification method for the galvanic pile provided by the related technology, when the galvanic pile is humidified in an operation state, the humidity of the galvanic pile in the operation state is determined according to the sensitivity of the membrane electrode to the humidity in the membrane electrode testing process or the sensitivity test of the galvanic pile under each current density is carried out according to the principle that the larger the discharge current is, the more the water generated by the reaction is, the larger the reverse osmosis water amount is and the lower the gas humidification amount is, and finally the suitable humidity range of the galvanic pile under different electrical densities is obtained. However, this method is somewhat blind, and requires a lot of tests to compare the performance of the stack, which is time-consuming and labor-consuming.
Disclosure of Invention
In view of the above, the present invention provides a method and an apparatus for humidifying a cell stack, and an electronic device, which can humidify the cell stack more reasonably.
In a first aspect, an embodiment of the present invention provides a stack humidification method, including: controlling the operation of a target electric pile, and calculating the cathode humidification water demand and the anode humidification water demand of the target electric pile based on the operation parameters during the operation of the target electric pile; determining the membrane reverse osmosis amount of a proton exchange membrane in the target electric pile; respectively calculating cathode inlet air humidity and anode inlet air humidity of the target galvanic pile according to the cathode humidifying water quantity, the anode humidifying water quantity and the membrane reverse osmosis quantity; humidifying the target stack based on the cathode inlet air humidity and the anode inlet air humidity.
In one embodiment, the step of calculating the cathode humidification water demand and the anode humidification water demand of the target stack based on the operation parameters during the operation of the target stack includes: under the condition that a proton exchange membrane in the target electric pile is in a saturated state, based on the operation parameters during the operation of the target electric pile, calculating the cathode humidifying water quantity of the target electric pile according to the following formula:
Figure BDA0003138987900000021
Wherein the operation parameters comprise the operation current of the target electric pile, the cathode gas supply pressure and the number of single cells; m is a unit ofH2OinAirinThe amount of humidification water is required for the cathode,
Figure BDA0003138987900000022
is the stoichiometric ratio of oxygen at the cathode,
Figure BDA0003138987900000023
is the volume ratio of oxygen to air, MH2OIs the molar mass of water, F is the Afugardro constant, pvs,TIs the saturated vapor pressure, p, at the operating temperature of the target stackcaFor the cathode supply pressure, I for the operating current, ncellIs the number of the single cells.
In one embodiment, the step of calculating the cathode humidification water demand and the anode humidification water demand of the target stack based on the operation parameters during the operation of the target stack further includes: under the condition that a proton exchange membrane in the target electric pile is in a saturated state, determining the relation between the anode humidification quantity and the anode relative humidity according to the following formula based on the operation parameters during the operation of the target electric pile:
Figure BDA0003138987900000024
wherein the operating parameter further comprises an anode gas supply pressure of the target stack; m isH2OinH2inThe amount of humidification water required for the anode, SH2Is the stoichiometric ratio of oxygen at the anode, panThe pressure of the gas supplied to the anode,
Figure BDA0003138987900000025
is the inlet air humidity of the anode.
In one embodiment, the step of determining the membrane reverse osmosis amount of the proton exchange membrane in the target stack comprises: under the condition that the proton exchange membrane in the target electric pile is in a saturated state, calculating the membrane reverse osmosis quantity of the proton exchange membrane according to the following formula:
Figure BDA0003138987900000031
Wherein m isH2O-ROIs the reverse osmosis quantity of the membrane, xiDIs the electromigration coefficient, beta constant.
In one embodiment, the step of calculating the cathode inlet air humidity and the anode inlet air humidity of the target stack according to the cathode humidification water demand amount, the anode humidification water demand amount, and the membrane reverse osmosis amount includes: determining the cathode water supplement amount of the target electric pile when a proton exchange membrane in the target electric pile is in a saturated state based on the difference value of the cathode humidifying water amount and the membrane reverse osmosis amount; determining cathode inlet air humidity of the target electric pile when a proton exchange membrane in the target electric pile is in a non-saturated state based on the cathode water supplement amount; the cathode inlet air humidity
Figure BDA0003138987900000032
The expression of (c) is as follows:
Figure BDA0003138987900000033
in one embodiment, the step of calculating the cathode inlet air humidity and the anode inlet air humidity of the target stack according to the cathode humidification water demand amount, the anode humidification water demand amount, and the membrane reverse osmosis amount, respectively, further includes: determining the anode water replenishing quantity of the target electric pile when a proton exchange membrane in the target electric pile is in a saturated state based on the relation between the anode humidifying water quantity and the membrane reverse osmosis quantity; determining the anode inlet air humidity of the target electric pile when a proton exchange membrane in the target electric pile is in a non-saturated state based on the anode water supplement amount; the inlet air humidity of the anode
Figure BDA0003138987900000034
The expression of (c) is as follows:
Figure BDA0003138987900000035
in one embodiment, the step of controlling the operation of the target stack includes: controlling the operating temperature of the target electric pile to rise to a first designated temperature; when the operating temperature reaches the first designated temperature, introducing a first designated gas with a first metering amount and a second designated gas with a second metering amount into the target electric pile, controlling the gas temperatures of the first designated gas and the second designated gas to rise to the first designated temperature, and controlling the target electric pile to operate based on a first operating current; controlling the operating temperature to rise to a second specified temperature; controlling the inlet pressure of the first specified gas to rise to a first specified pressure and controlling the inlet pressure of the second specified gas to rise to a second specified pressure when the gas temperature reaches the first specified temperature; controlling the target stack to operate for a first specified time period based on a second operating current.
In a second aspect, an embodiment of the present invention further provides a stack humidifying device, including: the humidifying water quantity calculating module is used for controlling the operation of a target galvanic pile and calculating the cathode humidifying water quantity and the anode humidifying water quantity of the target galvanic pile based on the operation parameters during the operation of the target galvanic pile; the membrane reverse osmosis amount determining module is used for determining the membrane reverse osmosis amount of a proton exchange membrane in the target electric pile; the inlet air humidity calculation module is used for respectively calculating the cathode inlet air humidity and the anode inlet air humidity of the target electric pile according to the cathode humidifying water quantity, the anode humidifying water quantity and the membrane reverse osmosis quantity; and the humidifying module is used for humidifying the target electric pile based on the cathode inlet air humidity and the anode inlet air humidity.
In a third aspect, an embodiment of the present invention further provides an electronic device, which includes a processor and a memory, where the memory stores computer-executable instructions that can be executed by the processor, and the processor executes the computer-executable instructions to implement any one of the methods provided in the first aspect.
In a fourth aspect, embodiments of the present invention also provide a computer-readable storage medium storing computer-executable instructions that, when invoked and executed by a processor, cause the processor to implement any one of the methods provided in the first aspect.
According to the method, the device and the electronic equipment for humidifying the galvanic pile, provided by the embodiment of the invention, the operation of the target galvanic pile is controlled, the cathode humidifying water quantity and the anode humidifying water quantity of the target galvanic pile are calculated based on the operation parameters during the operation of the target galvanic pile, the membrane reverse osmosis quantity of a proton exchange membrane in the target galvanic pile is determined, and then the cathode inlet air humidity and the anode inlet air humidity of the target galvanic pile are respectively calculated according to the cathode humidifying water quantity, the anode humidifying water quantity and the membrane reverse osmosis quantity, so that the target galvanic pile is humidified based on the cathode inlet air humidity and the anode inlet air humidity. The method respectively calculates the cathode inlet air humidity and the anode inlet air humidity based on the cathode humidifying water quantity, the anode humidifying water quantity and the membrane reverse osmosis quantity during the operation of the target galvanic pile, and humidifies the target galvanic pile based on the cathode inlet air humidity and the anode inlet air humidity.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic flow chart of a method for humidifying a stack according to an embodiment of the present invention;
fig. 2 is a schematic flow chart illustrating a process for controlling the operation of a target stack according to an embodiment of the present invention;
fig. 3 is a schematic structural diagram of a cell stack humidifying device according to an embodiment of the present invention;
Fig. 4 is a schematic structural diagram of an electronic device according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
At present, in a humidification method for a galvanic pile provided by the related art, when the galvanic pile humidifies gas in an operating state, a principle that the larger the discharge current is, the lower the gas humidification amount is followed, because the larger the discharge current is, the more water is generated in a cathode reaction, and a proton exchange membrane pair has a certain reverse osmosis capacity, the reverse osmosis performance of water is related to the concentration gradient of water at two sides of the membrane, the higher the concentration of water at one side is, the faster the reverse osmosis rate is, that is, the larger the reverse osmosis water amount per unit time is, the prior art only humidifies gas according to the principle, does not humidify gas quantitatively, has a certain blindness, and lacks a certain theoretical humidification amount guidance. In addition, in the method for performing the humidity sensitivity test on the electric pile, reference is often needed according to the sensitivity test data of the membrane electrode, and a large number of tests are designed to perform the performance comparison of the electric pile under different current densities or within a current density interval, so as to determine the appropriate inlet air humidity under the current density or within the current density interval. The work is heavy in the process, the time period is long, and certain theoretical humidification quantity guidance is lacked, so that the waste of manpower and material resources is caused. Based on the method, the device and the electronic equipment, the galvanic pile is humidified more reasonably.
To facilitate understanding of the present embodiment, first, a detailed description is given of a stack humidification method disclosed in the present embodiment, referring to a schematic flow chart of the stack humidification method shown in fig. 1, where the method mainly includes the following steps S102 to S108:
and S102, controlling the operation of the target galvanic pile, and calculating the cathode humidifying water quantity and the anode humidifying water quantity of the target galvanic pile based on the operation parameters during the operation of the target galvanic pile. Wherein the operation parameters include operation current, cathode gas supply pressure, anode gas supply pressure, the number of single cells, and the like. In one embodiment, it is assumed that the proton exchange membrane in the target stack is in a saturated state, and the cathode humidification water demand and the anode humidification water demand of the target stack are calculated based on the operation parameters under the condition.
And step S104, determining the membrane reverse osmosis amount of the proton exchange membrane in the target electric pile. Among them, the proton exchange membrane may be simply referred to as a membrane. In one embodiment, the reverse osmosis of water depends on the water concentration on both sides of the proton exchange membrane, the diffusion coefficient of water passing through the proton exchange membrane and the membrane thickness, and the water transport in the proton exchange membrane can be regarded as a whole, i.e. the reverse osmosis of water can be regarded as a part of electroosmotic migration.
And S106, respectively calculating the cathode inlet air humidity and the anode inlet air humidity of the target galvanic pile according to the cathode humidifying water quantity, the anode humidifying water quantity and the membrane reverse osmosis quantity. In one embodiment, the amount of humidification water required for different current densities is calculated, and the amount of reverse osmosis of the membrane is combined according to the relation between the amount of humidification water and the intake air humidity, so that the intake air humidity under the amount of humidification water is reversely deduced.
Step S108, humidifying the target stack based on the cathode intake air humidity and the anode intake air humidity. In one embodiment, after determining the cathode intake air humidity and the anode intake air humidity, the temperature of the humidification tank may be determined based on the cathode intake air humidity and the anode intake air humidity, so that the target stack is humidified at the temperature by the humidification tank.
According to the galvanic pile humidifying method provided by the embodiment of the invention, the cathode inlet air humidity and the anode inlet air humidity are respectively calculated based on the cathode humidifying water quantity, the anode humidifying water quantity and the membrane reverse osmosis quantity during the operation period of the target galvanic pile, and the target galvanic pile is humidified based on the cathode inlet air humidity and the anode inlet air humidity.
In practical application, since the gases are humidified basically in a bubbling method on the test bench, the humidity of the inlet air is controlled by adjusting the temperature (dew point temperature) of the humidification tank, that is, the gases enter the stack through the humidification tank with saturated vapor at the temperature (dew point temperature), the operating temperature in the stack can be referred to as the ambient temperature of the gases at the time, according to the definition of relative humidity (that is, inlet air humidity):
Figure BDA0003138987900000071
wherein, the first and the second end of the pipe are connected with each other,
Figure BDA0003138987900000072
is the relative humidity, PdpIs the saturated vapour pressure of water at the dew point temperature, PvsIs the saturated vapor pressure of water at ambient temperature.
Since the operating temperature of the stack is known, when humidifying the gas, only the dew point temperature of the humidification needs to be controlled. Therefore, in the actual test process, it is difficult to directly give a certain amount of humidification water to the reaction gases (including hydrogen and air), and in practice, the amount of humidification of the reaction gases is achieved by controlling the relative humidity of the reaction gases. Based on this, the embodiment of the invention determines the relative humidity of the anode and cathode inlet air by reversely deducing the thinking, that is, the relative humidity under the humidification water amount is reversely deduced according to the relation between the humidification water amount and the relative humidity by calculating the humidification water amount required under different current densities, and then the temperature of the humidification tank is determined.
For convenience of understanding, the embodiment of the present invention provides an implementation manner of controlling the operation of the target stack, and referring to a schematic flow chart of controlling the operation of the target stack shown in fig. 2, see the following steps S202 to S210:
in step S202, the operating temperature of the target stack is controlled to be increased to a first designated temperature. Illustratively, the first designated temperature is 60 ℃, and in one embodiment, the temperature of the stack may be raised to 60 ℃ by heating cooling water, during which the hydrogen and air circuits are purged with a quantity of nitrogen.
Step S204, when the operation temperature reaches a first designated temperature, introducing a first designated gas with a first measurement and a second designated gas with a second measurement into the target electric pile, controlling the gas temperatures of the first designated gas and the second designated gas to rise to the first designated temperature, and controlling the target electric pile based on the first designated temperatureThe running current runs. Wherein the first specified gas is hydrogen, the second specified gas is air, the first measurement is hydrogen metering ratio of 1.5, the second measurement is air metering ratio of 2.0, and the first operating current is 0.02A/cm2. In one embodiment, after the temperature of the galvanic pile rises to 60 ℃, hydrogen and air are respectively introduced according to the air input of the hydrogen metering ratio of 1.5 and the air metering ratio of 2.0, the temperature is controlled to be 60 ℃, meanwhile, the operation temperature of the target galvanic pile is increased to 75 ℃, a certain humidity is provided for the target galvanic pile in the process, the membrane is prevented from being dried and damaged, in addition, the temperature of the gas is increased, and simultaneously, the load current is pulled to 0.02A/cm 2。
In step S206, the operating temperature is controlled to increase to a second designated temperature. Wherein the second specified temperature may be 75 ℃.
In step S208, when the gas temperature reaches the first designated temperature, the intake pressure of the first designated gas is controlled to be raised to the first designated pressure, and the intake pressure of the second designated gas is controlled to be raised to the second designated pressure. Wherein the first specified pressure may be 30kPa and the second specified pressure may be 10 kPa. In one embodiment, the hydrogen feed pressure is raised to 30kPa (gauge) and the air feed pressure is raised to 10kPa (gauge) as the hydrogen and air are heated to 60 ℃.
In step S210, the control target stack operates for a first specified time period based on the second operating current. Wherein the second operation current may be 0.1A/cm2The first specified duration is 30min, e.g., at 0.1A/cm2The operation is carried out for 30 min.
For the sake of understanding, the embodiment of the present invention takes the calculation of the cathode inlet air humidity as an example, and the above steps S102 to S106 are described, in the process of stack load, the larger the discharge current is, the more water is generated in the cathode reaction, the more water is reverse-permeated from the cathode to the anode due to the influence of the water concentration gradient, and the less water needs to be humidified as the current density increases in order to maintain the saturation balance of the membrane. Therefore, when the membrane is in a saturated equilibrium state, the humidity in the stack is in an ideal state, wherein when the humidification water content in the stack is low, the proton exchange membrane is in a dry state, the proton conductivity is reduced, but when the humidification water content is high, the battery is flooded.
The water content in the membrane is constant when the membrane is in saturation, during the operation of the cell stack, the water in the membrane in saturation can be regarded as the sum of the humidified water amount and the reverse osmosis water amount generated by the cathode reaction, and according to the data, the water content in the membrane in saturation is equal to the saturated water vapor amount under the condition, so the formula is obtained: the amount of humidification water needed by the cathode is equal to the amount of saturated water vapor under a certain condition-the reverse osmosis amount of water generated by the reaction.
In practical application, the water content of air entering the reactor and the inlet air humidity of the cathode
Figure BDA0003138987900000091
Operating current I, number of cells ncellCathode gas supply pressure pcaAnd saturated vapor pressure p under the condition of target electric pile operating temperaturevs,TThe relationship of (a) to (b) is as follows:
Figure BDA0003138987900000092
mH2OinAirinhumidification water amount (g.s) is needed for the cathode-1)，
Figure BDA0003138987900000093
Is the stoichiometric ratio of oxygen at the cathode,
Figure BDA0003138987900000094
the volume ratio of oxygen to air (0.21), MH2OThe molar mass of water (18 g. mol)-1) F is the Afugardro constant (96485℃ mol)-1)，pvs,TIs the saturated vapor pressure, p, at the target stack operating temperaturecaThe cathode gas supply pressure (kPa), I the operating current, ncellIs the number of single cells.
In addition, the saturated vapor pressure pvs,TThe calculation formula of (a) is as follows:
Pvs,T＝eaT-1+b+cT+dT2+eT3+fln(T)；
wherein, a is-5800.2206; 1.3914993; c-0.048640239; d is 0.41764768 × 10-4; e-0.1445209310-4; 6.5459673; t-stack operating temperature, in units (K).
In practical application, when
Figure BDA0003138987900000101
When the water content λ of the film is 14, the film is in a saturated state in the case of vapor absorption, i.e., a vapor equilibrium film. Based on this, under the condition that the proton exchange membrane in the target electric pile is in a saturated state, the cathode humidifying water quantity of the target electric pile is as follows:
Figure BDA0003138987900000102
in addition, the calculation formula of the reverse osmosis amount of the membrane is as follows:
Figure BDA0003138987900000103
wherein m isH2O-ROIs the reverse osmosis quantity of the membrane, xiDIs the electromigration coefficient, β constant. When lambda is 1, the electroosmotic migration coefficient is 0.9, and the information shows that when lambda is 1.4 ≦ 14, the electroosmotic migration coefficient is 1, and when xiDWhen the pure water transport amount of the membrane is 0, beta is 1, and the reverse osmosis amount of the membrane is equal to the water amount transferred by electroosmosis, and the water saturation state is still maintained. On the basis, the calculation formula of the reverse osmosis amount of the membrane is as follows:
Figure BDA0003138987900000104
in one embodiment, the mask may be based on a maskAnd calculating the cathode inlet air humidity of the target electric pile according to the humidification water amount needed by the cathode and the membrane reverse osmosis amount, wherein in a specific embodiment, the cathode water supplement amount of the target electric pile can be determined when the proton exchange membrane in the target electric pile is in a saturated state based on the difference value of the humidification water amount needed by the cathode and the membrane reverse osmosis amount. Specifically, cathode water supplement amount m H2OhumcaAs follows:
Figure BDA0003138987900000111
after finishing, the amount of cathode make-up water m shown below was obtainedH2Ohumca：
Figure BDA0003138987900000112
Based on the cathode make-up water amount as shown above, the cathode intake air humidity of the target stack under the condition that the proton exchange membrane in the target stack is in the unsaturated state can be determined based on the cathode make-up water amount. In one specific embodiment, the cathode inlet air humidity under different conditions can be known by combining the above formula (1-1)
Figure BDA0003138987900000113
Comprises the following steps:
Figure BDA0003138987900000114
similarly, the inlet air humidity of the anode is calculated
Figure BDA0003138987900000115
Can be seen in the cathode inlet air humidity
Figure BDA0003138987900000116
The calculation process of (2). In practical application, the water content of hydrogen entering the reactor and the inlet air humidity of the anode
Figure BDA0003138987900000117
Operating current I, number of cells ncellAnode gas supply pressure panAnd saturated vapor pressure p under the condition of target electric pile operating temperaturevs,TThe relationship of (a) to (b) is as follows:
Figure BDA0003138987900000118
wherein m isH2OinH2inThe amount of humidification water required for the anode, SH2Is the stoichiometric ratio of hydrogen at the anode, panThe anode was supplied with air pressure.
In one embodiment, the anode replenishment quantity of the target stack under the condition that the proton exchange membrane in the target stack is in a saturated state can be determined based on the relationship between the anode humidification water quantity and the membrane reverse osmosis quantity, that is, the anode replenishment water quantity is equal to the electroosmotic migration water quantity, wherein the anode replenishment quantity m is obtained from the above formula (1-3) H2OhumanComprises the following steps:
Figure BDA0003138987900000119
based on the cathode make-up water amount as shown above, the anode inlet air humidity of the target stack under the condition that the proton exchange membrane in the target stack is in the unsaturated state can be determined based on the anode make-up water amount. In a specific embodiment, the humidity of the inlet air of the anode under different conditions can be known by combining the above formulas (1-8)
Figure BDA0003138987900000121
Comprises the following steps:
Figure BDA0003138987900000122
in specific implementation, the relative humidity of hydrogen and air under different currents is respectively calculated according to the formulas (1-7) and (1-10), so that the working condition of inlet air humidity in the process of electric pile load pulling is determined.
According to the embodiment of the invention, the relative humidity (humidification quantity) of the cathode and anode inlet air required by the cathode and anode theory is obtained through a series of theoretical calculations, a certain theoretical reference value is provided for the inlet air humidity of the galvanic pile, and the humidification quantity of the gas of the galvanic pile is adjusted on the basis. It should be noted that the time required to bring the membrane to saturation varies due to the differences in thickness of the different membranes.
In summary, since the proton conductivity of the proton exchange membrane mainly depends on the structure of the membrane and the water content of the membrane, and the maximum water content of the membrane mainly depends on the state of water for balancing the membrane (i.e. the water saturation of the membrane), theoretically, only the membrane needs to be in a water saturation state when humidifying the stack. In practical applications, the water content when the film reaches a water saturation state in a state of vapor-phase water absorption is 14, and the relative humidity is 1. Based on the theory, the embodiment of the invention obtains the humidification quantity required by the cathode and anode theory through a series of theoretical calculations, provides a certain theoretical reference value for the inlet air humidity of the galvanic pile, and adjusts the humidification quantity of the gas of the galvanic pile on the basis, thereby greatly shortening the test period and reducing the workload.
With respect to the cell stack humidification method provided in the foregoing embodiment, an embodiment of the present invention provides a cell stack humidification device, referring to a schematic structural diagram of a cell stack humidification device shown in fig. 3, where the device mainly includes the following components:
a humidifying water amount calculation module 302 for controlling the operation of the target stack and calculating the cathode humidifying water amount and the anode humidifying water amount of the target stack based on the operation parameters during the operation of the target stack;
a membrane reverse osmosis amount determination module 304 for determining a membrane reverse osmosis amount of a proton exchange membrane in the target stack;
the inlet air humidity calculation module 306 is used for respectively calculating the cathode inlet air humidity and the anode inlet air humidity of the target galvanic pile according to the cathode humidifying water quantity, the anode humidifying water quantity and the membrane reverse osmosis quantity;
and a humidifying module 308 for humidifying the target stack based on the cathode inlet air humidity and the anode inlet air humidity.
The galvanic pile humidifying device provided by the embodiment of the invention respectively calculates the cathode inlet air humidity and the anode inlet air humidity based on the cathode humidifying water quantity, the anode humidifying water quantity and the membrane reverse osmosis quantity during the operation of the target galvanic pile, and humidifies the target galvanic pile based on the cathode inlet air humidity and the anode inlet air humidity.
In one embodiment, the humidification water demand calculation module 302 is further configured to: under the condition that a proton exchange membrane in the target electric pile is in a saturated state, based on the operation parameters during the operation of the target electric pile, calculating the cathode humidifying water quantity of the target electric pile according to the following formula:
Figure BDA0003138987900000131
the operation parameters comprise the operation current of the target electric pile, the cathode gas supply pressure and the number of single cells; m is a unit ofH2OinAirinThe cathode needs the humidification water amount,
Figure BDA0003138987900000132
is the stoichiometric ratio of oxygen at the cathode,
Figure BDA0003138987900000133
is the volume ratio of oxygen to air, MH2OIs the molar mass of water, F is the Afugardro constant, pvs,TIs the saturated vapor pressure, p, at the target stack operating temperaturecaThe cathode is supplied with air pressure, I is the running current, ncellIs the number of single cells.
In one embodiment, the humidification water demand calculation module 302 is further configured to: under the condition that a proton exchange membrane in a target electric pile is in a saturated state, determining the relation between the anode water adding amount and the anode relative humidity according to the following formula based on the operation parameters during the operation of the target electric pile:
Figure BDA0003138987900000134
wherein the operation parameters further comprise anode gas supply pressure of the target stack; m isH2OinH2inThe amount of humidification water required for the anode, SH2Is the stoichiometric ratio of oxygen at the anode，panThe pressure of the gas supplied to the anode,
Figure BDA0003138987900000141
Is the inlet air humidity of the anode.
In one embodiment, the membrane reverse osmosis amount determination module 304 is further configured to: under the condition that the proton exchange membrane in the target electric pile is in a saturated state, calculating the membrane reverse osmosis quantity of the proton exchange membrane according to the following formula:
Figure BDA0003138987900000142
wherein m isH2O-ROIs the reverse osmosis quantity of the membrane, xiDIs the electromigration coefficient, β constant.
In one embodiment, the intake air humidity calculation module 306 is further configured to: determining the cathode water supplement amount of the target galvanic pile when the proton exchange membrane in the target galvanic pile is in a saturated state based on the difference value between the cathode humidifying water amount and the membrane reverse osmosis amount; determining cathode inlet air humidity of the target electric pile when a proton exchange membrane in the target electric pile is in a non-saturated state based on cathode water supplement amount; cathode inlet air humidity
Figure BDA0003138987900000143
The expression of (a) is as follows:
Figure BDA0003138987900000144
in one embodiment, the intake air humidity calculation module 306 is further configured to: determining the anode water supply amount of the target galvanic pile when the proton exchange membrane in the target galvanic pile is in a saturated state based on the equal relation between the anode humidifying water amount and the membrane reverse osmosis amount; determining the anode inlet air humidity of the target electric pile when the proton exchange membrane in the target electric pile is in the unsaturated state based on the anode water supplement amount; humidity of anode inlet air
Figure BDA0003138987900000145
The expression of (c) is as follows:
Figure BDA0003138987900000146
in one embodiment, the humidification water demand calculation module 302 is further configured to: controlling the operating temperature of the target electric pile to rise to a first designated temperature; when the operation temperature reaches a first designated temperature, introducing a first designated gas with a first metering amount and a second designated gas with a second metering amount into the target electric pile, controlling the gas temperatures of the first designated gas and the second designated gas to rise to the first designated temperature, and controlling the target electric pile to operate based on a first operation current; controlling the operating temperature to rise to a second specified temperature; when the gas temperature reaches a first designated temperature, controlling the inlet pressure of a first designated gas to rise to a first designated pressure, and controlling the inlet pressure of a second designated gas to rise to a second designated pressure; the control target stack is operated for a first specified time period based on the second operating current.
The device provided by the embodiment of the present invention has the same implementation principle and technical effect as the method embodiments, and for the sake of brief description, reference may be made to the corresponding contents in the method embodiments without reference to the device embodiments.
The embodiment of the invention provides electronic equipment, which particularly comprises a processor and a storage device; the storage means has stored thereon a computer program which, when executed by the processor, performs the method of any of the above described embodiments.
Fig. 4 is a schematic structural diagram of an electronic device 100 according to an embodiment of the present invention, where the electronic device 100 includes: a processor 40, a memory 41, a bus 42 and a communication interface 43, wherein the processor 40, the communication interface 43 and the memory 41 are connected through the bus 42; the processor 40 is arranged to execute executable modules, such as computer programs, stored in the memory 41.
The Memory 41 may include a high-speed Random Access Memory (RAM) and may also include a non-volatile Memory (non-volatile Memory), such as at least one disk Memory. The communication connection between the network element of the system and at least one other network element is realized through at least one communication interface 43 (which may be wired or wireless), and the internet, a wide area network, a local network, a metropolitan area network, etc. may be used.
The bus 42 may be an ISA bus, PCI bus, EISA bus, or the like. The bus may be divided into an address bus, a data bus, a control bus, etc. For ease of illustration, only one double-headed arrow is shown in FIG. 4, but that does not indicate only one bus or one type of bus.
The memory 41 is used for storing a program, the processor 40 executes the program after receiving an execution instruction, and the method executed by the apparatus defined by the flow process disclosed in any of the foregoing embodiments of the present invention may be applied to the processor 40, or implemented by the processor 40.
The processor 40 may be an integrated circuit chip having signal processing capabilities. In implementation, the steps of the above method may be performed by instructions in the form of hardware integrated logic circuits or software in the processor 40. The Processor 40 may be a general-purpose Processor, and includes a Central Processing Unit (CPU), a Network Processor (NP), and the like; the device can also be a Digital Signal Processor (DSP), an Application Specific Integrated Circuit (ASIC), a Field-Programmable Gate Array (FPGA) or other Programmable logic device, a discrete Gate or transistor logic device, or a discrete hardware component. The various methods, steps and logic blocks disclosed in the embodiments of the present invention may be implemented or performed. A general purpose processor may be a microprocessor or the processor may be any conventional processor or the like. The steps of the method disclosed in connection with the embodiments of the present invention may be directly implemented by a hardware decoding processor, or implemented by a combination of hardware and software modules in the decoding processor. The software module may be located in ram, flash memory, rom, prom, or eprom, registers, etc. storage media as is well known in the art. The storage medium is located in a memory 41, and the processor 40 reads the information in the memory 41 and completes the steps of the method in combination with the hardware thereof.
The computer program product of the readable storage medium provided in the embodiment of the present invention includes a computer readable storage medium storing a program code, where instructions included in the program code may be used to execute the method described in the foregoing method embodiment, and specific implementation may refer to the foregoing method embodiment, which is not described herein again.
The functions, if implemented in the form of software functional units and sold or used as a stand-alone product, may be stored in a computer readable storage medium. Based on such understanding, the technical solution of the present invention may be embodied in the form of a software product, which is stored in a storage medium and includes instructions for causing a computer device (which may be a personal computer, a server, or a network device) to execute all or part of the steps of the method according to the embodiments of the present invention. And the aforementioned storage medium includes: various media capable of storing program codes, such as a usb disk, a removable hard disk, a Read-Only Memory (ROM), a Random Access Memory (RAM), a magnetic disk, or an optical disk.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that the following descriptions are only illustrative and not restrictive, and that the scope of the present invention is not limited to the above embodiments: those skilled in the art can still make modifications or changes to the embodiments described in the foregoing embodiments, or make equivalent substitutions for some features, within the scope of the disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the embodiments of the present invention, and they should be construed as being included therein. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (5)

1. A method for humidifying a galvanic pile is characterized by comprising the following steps:
controlling the operation of a target galvanic pile, and calculating the cathode humidifying water quantity and the anode humidifying water quantity of the target galvanic pile based on the operation parameters during the operation of the target galvanic pile;
determining the membrane reverse osmosis amount of a proton exchange membrane in the target electric pile;
Respectively calculating cathode inlet air humidity and anode inlet air humidity of the target galvanic pile according to the cathode humidifying water quantity, the anode humidifying water quantity and the membrane reverse osmosis quantity;
humidifying the target stack based on the cathode inlet air humidity and the anode inlet air humidity;
the step of calculating the cathode humidification water demand and the anode humidification water demand of the target stack based on the operation parameters during the operation of the target stack includes:
under the condition that a proton exchange membrane in the target electric pile is in a saturated state, based on the operation parameters during the operation of the target electric pile, calculating the cathode humidifying water quantity of the target electric pile according to the following formula:
Figure 11820DEST_PATH_IMAGE001
；
wherein the operation parameters comprise the operation current of the target stack, the cathode gas supply pressure and the number of single cells;
Figure 484389DEST_PATH_IMAGE002
the amount of humidification water is required for the cathode,
Figure 597839DEST_PATH_IMAGE003
is the stoichiometric ratio of oxygen at the cathode,
Figure 460753DEST_PATH_IMAGE004
the volume ratio of oxygen to air is,
Figure 685061DEST_PATH_IMAGE005
is the molar mass of water, F is the Afugardro constant,
Figure 746557DEST_PATH_IMAGE006
is the saturated vapor pressure at the target stack operating temperature,
Figure 30908DEST_PATH_IMAGE007
the cathode gas supply pressure, I is the operating current,
Figure 879653DEST_PATH_IMAGE008
is the number of the single batteries;
the step of calculating the cathode humidification water demand and the anode humidification water demand of the target stack based on the operation parameters during the operation of the target stack further includes:
Under the condition that a proton exchange membrane in the target electric pile is in a saturated state, determining the relation between the anode humidification quantity and the anode relative humidity according to the following formula based on the operation parameters during the operation of the target electric pile:
Figure 907652DEST_PATH_IMAGE009
；
wherein the operating parameter further comprises an anode gas supply pressure of the target stack;
Figure 89235DEST_PATH_IMAGE010
the amount of humidification water is required for the anode,
Figure 278908DEST_PATH_IMAGE011
is the stoichiometric ratio of oxygen at the anode,
Figure 116414DEST_PATH_IMAGE012
the pressure of the gas supplied to the anode,
Figure 682524DEST_PATH_IMAGE013
is the inlet air humidity of the anode;
the step of determining the membrane reverse osmosis amount of the proton exchange membrane in the target stack comprises the following steps:
under the condition that the proton exchange membrane in the target electric pile is in a saturated state, calculating the membrane reverse osmosis quantity of the proton exchange membrane according to the following formula:
Figure 984193DEST_PATH_IMAGE014
；
wherein the content of the first and second substances,
Figure 344767DEST_PATH_IMAGE015
the amount of reverse osmosis of the membrane is,
Figure 669569DEST_PATH_IMAGE016
as a function of the electromigration coefficient,
Figure 39370DEST_PATH_IMAGE017
is a constant;
the step of calculating the cathode inlet air humidity and the anode inlet air humidity of the target galvanic pile respectively according to the cathode humidifying water quantity, the anode humidifying water quantity and the membrane reverse osmosis quantity comprises the following steps:
determining the cathode water supplement amount of the target electric pile when a proton exchange membrane in the target electric pile is in a saturated state based on the difference value of the cathode humidifying water amount and the membrane reverse osmosis amount;
Determining cathode inlet air humidity of the target electric pile when a proton exchange membrane in the target electric pile is in a non-saturated state based on the cathode water supplement amount;
the cathode inlet air humidity
Figure 929966DEST_PATH_IMAGE018
The expression of (c) is as follows:
Figure 727021DEST_PATH_IMAGE019
；
the step of calculating the cathode inlet air humidity and the anode inlet air humidity of the target stack according to the cathode humidifying water quantity, the anode humidifying water quantity and the membrane reverse osmosis quantity further comprises:
determining the anode water replenishing quantity of the target electric pile when a proton exchange membrane in the target electric pile is in a saturated state based on the relation between the anode humidifying water quantity and the membrane reverse osmosis quantity;
determining the anode inlet air humidity of the target electric pile when a proton exchange membrane in the target electric pile is in a non-saturated state based on the anode water supplement amount;
the inlet air humidity of the anode
Figure 273540DEST_PATH_IMAGE020
The expression of (a) is as follows:
Figure 447032DEST_PATH_IMAGE021
。
2. the method of claim 1, wherein the step of controlling the operation of the target stack comprises:
controlling the operating temperature of the target electric pile to rise to a first designated temperature;
when the operating temperature reaches the first designated temperature, introducing a first designated gas with a first metering amount and a second designated gas with a second metering amount into the target electric pile, controlling the gas temperatures of the first designated gas and the second designated gas to rise to the first designated temperature, and controlling the target electric pile to operate based on a first operating current;
Controlling the operating temperature to rise to a second specified temperature;
controlling the inlet pressure of the first specified gas to rise to a first specified pressure and controlling the inlet pressure of the second specified gas to rise to a second specified pressure when the gas temperature reaches the first specified temperature;
and controlling the target stack to operate for a first specified time period based on the second operating current.
3. A stack humidification device, comprising:
the humidifying water quantity calculating module is used for controlling the operation of a target galvanic pile and calculating the cathode humidifying water quantity and the anode humidifying water quantity of the target galvanic pile based on the operation parameters during the operation of the target galvanic pile;
the membrane reverse osmosis amount determining module is used for determining the membrane reverse osmosis amount of a proton exchange membrane in the target electric pile;
the inlet air humidity calculation module is used for respectively calculating the cathode inlet air humidity and the anode inlet air humidity of the target electric pile according to the cathode humidifying water quantity, the anode humidifying water quantity and the membrane reverse osmosis quantity;
a humidification module for humidifying the target stack based on the cathode inlet air humidity and the anode inlet air humidity;
the humidifying water amount calculation module is also used for:
Under the condition that a proton exchange membrane in the target electric pile is in a saturated state, based on the operation parameters of the target electric pile during the operation period, calculating the cathode humidification water demand of the target electric pile according to the following formula:
Figure 457713DEST_PATH_IMAGE001
；
wherein the operation parameters comprise the operation current of the target electric pile, the cathode gas supply pressure and the number of single cells;
Figure 861888DEST_PATH_IMAGE002
the amount of humidification water is required for the cathode,
Figure 958020DEST_PATH_IMAGE003
is the stoichiometric ratio of oxygen at the cathode,
Figure 669624DEST_PATH_IMAGE004
the volume ratio of oxygen to air is,
Figure 534811DEST_PATH_IMAGE005
is the molar mass of water, F is the Afugardro constant,
Figure 611352DEST_PATH_IMAGE022
is the saturated vapor pressure at the target stack operating temperature,
Figure 194780DEST_PATH_IMAGE007
the cathode gas supply pressure, I is the operating current,
Figure 444496DEST_PATH_IMAGE023
is the number of the single batteries;
the humidifying water amount calculation module is also used for:
under the condition that a proton exchange membrane in the target electric pile is in a saturated state, determining the relation between the anode humidification quantity and the anode relative humidity according to the following formula based on the operation parameters during the operation of the target electric pile:
Figure 429769DEST_PATH_IMAGE024
；
wherein the operating parameter further comprises an anode gas supply pressure of the target stack;
Figure 677211DEST_PATH_IMAGE025
the amount of humidification water is required for the anode,
Figure 747935DEST_PATH_IMAGE026
is the stoichiometric ratio of oxygen at the anode,
Figure 801342DEST_PATH_IMAGE027
the pressure of the gas supplied to the anode,
Figure 578805DEST_PATH_IMAGE028
Is the inlet air humidity of the anode;
the membrane reverse osmosis amount determination module is further configured to:
under the condition that the proton exchange membrane in the target electric pile is in a saturated state, calculating the membrane reverse osmosis quantity of the proton exchange membrane according to the following formula:
Figure 59465DEST_PATH_IMAGE029
；
wherein, the first and the second end of the pipe are connected with each other,
Figure 351906DEST_PATH_IMAGE030
the amount of reverse osmosis of the membrane is,
Figure 645222DEST_PATH_IMAGE031
to be the electromigration coefficient, of the material,
Figure 339508DEST_PATH_IMAGE032
is a constant;
the intake air humidity calculation module is further configured to:
determining the cathode water supplement amount of the target electric pile when a proton exchange membrane in the target electric pile is in a saturated state based on the difference value of the cathode humidifying water amount and the membrane reverse osmosis amount;
determining cathode inlet air humidity of the target electric pile when a proton exchange membrane in the target electric pile is in a non-saturated state based on the cathode water replenishing quantity;
the cathode inlet air humidity
Figure 991069DEST_PATH_IMAGE033
The expression of (a) is as follows:
Figure 36386DEST_PATH_IMAGE034
；
the intake air humidity calculation module is further configured to:
determining the anode water replenishing quantity of the target electric pile when a proton exchange membrane in the target electric pile is in a saturated state based on the relation between the anode humidifying water quantity and the membrane reverse osmosis quantity;
determining the anode inlet air humidity of the target electric pile when a proton exchange membrane in the target electric pile is in a non-saturated state based on the anode water supplement amount;
The inlet air humidity of the anode
Figure 369278DEST_PATH_IMAGE035
The expression of (c) is as follows:
Figure 918071DEST_PATH_IMAGE036
。
4. an electronic device comprising a processor and a memory, the memory storing computer-executable instructions executable by the processor, the processor executing the computer-executable instructions to implement the method of any of claims 1 to 2.
5. A computer-readable storage medium having computer-executable instructions stored thereon which, when invoked and executed by a processor, cause the processor to implement the method of any of claims 1 to 2.
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CN106249161A (en) * 2016-08-11 2016-12-21 上海交通大学 Proton Exchange Membrane Fuel Cells monocell test device under dry hydrogen test condition
CN207977405U (en) * 2018-03-13 2018-10-16 南京攀峰赛奥能源科技有限公司 One proton exchanging film fuel battery air humidifying device

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CN102800876A (en) * 2012-09-06 2012-11-28 江苏冰城电材股份有限公司 Self-humidifying fuel cell
CN106249161A (en) * 2016-08-11 2016-12-21 上海交通大学 Proton Exchange Membrane Fuel Cells monocell test device under dry hydrogen test condition
CN207977405U (en) * 2018-03-13 2018-10-16 南京攀峰赛奥能源科技有限公司 One proton exchanging film fuel battery air humidifying device

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