Multi-membrane electrode multi-parameter synchronous detection method and device for fuel cell stack

文档序号:535816 发布日期:2021-06-01 浏览:34次 中文

阅读说明:本技术 燃料电池堆多片膜电极多参数同步检测方法和装置 (Multi-membrane electrode multi-parameter synchronous detection method and device for fuel cell stack ) 是由 裴普成 任棚 陈东方 于 2021-02-02 设计创作,主要内容包括:本申请提出一种燃料电池堆多片膜电极多参数同步检测方法和装置,涉及质子交换膜燃料电池堆技术领域,其中,方法包括:在燃料电池堆阳极供给氢气、阴极供给惰性气体,控制燃料电池堆温度、气体流量、气体背压和气体湿度分别维持对应的预设数值,燃料电池堆中的各片燃料电池维持在稳定浓差电势;向燃料电池堆施加多次不同的电压激励或微电流激励,采集整堆电流信号和各片燃料电池的电压信号;根据燃料电池激励-响应公式解析各片燃料电池膜电极的氢渗透电流、催化剂活性面积、双电层电容和短路电阻。本申请对电流或电压激励的形式无限定,极大地提升了膜电极参数测试的准确度和精度,也可极大地降低测试设备的成本。(The application provides a fuel cell stack multi-membrane electrode multi-parameter synchronous detection method and a device, which relate to the technical field of proton exchange membrane fuel cell stacks, wherein the method comprises the following steps: supplying hydrogen to the anode of the fuel cell stack, supplying inert gas to the cathode of the fuel cell stack, controlling the temperature, the gas flow, the gas back pressure and the gas humidity of the fuel cell stack to respectively maintain corresponding preset values, and maintaining each fuel cell in the fuel cell stack at a stable concentration potential; applying different voltage excitations or micro-current excitations for a plurality of times to the fuel cell stack, and collecting the current signal of the whole stack and the voltage signal of each fuel cell; and analyzing the hydrogen permeation current, the catalyst active area, the double electric layer capacitance and the short-circuit resistance of the membrane electrode of each fuel cell according to a fuel cell excitation-response formula. The method has no limitation on the current or voltage excitation form, greatly improves the accuracy and precision of the membrane electrode parameter test, and can also greatly reduce the cost of test equipment.)

1. A multi-membrane electrode multi-parameter synchronous detection method for a fuel cell stack is characterized by comprising the following steps:

supplying hydrogen to the anode of the fuel cell stack, supplying inert gas to the cathode of the fuel cell stack, controlling the temperature, the gas flow, the gas back pressure and the gas humidity of the fuel cell stack to respectively maintain corresponding preset values, and maintaining each fuel cell in the fuel cell stack at a stable concentration potential;

applying different voltage excitation or micro-current excitation for multiple times to the fuel cell stack, and collecting a current signal of the whole stack and a voltage signal of each fuel cell, wherein the initial point of each excitation application is recorded as a time zero point, and each single stable concentration potential is recorded as a single initial voltage;

analyzing hydrogen permeation current, catalyst active area, double electric layer capacitance and short-circuit resistance of each fuel cell membrane electrode according to a fuel cell excitation-response formula; wherein the fuel cell excitation-response equation is:

wherein ichFor real-time excitation current density or real-time response current density when voltage is excited, iHIs hydrogen permeation current density, QCata.For real-time adsorption and desorption of the total amount of charge on the surface of the catalyst, CdlIs double electric layer capacitor, U is single-chip real-time voltage, U0Monolithic threshold voltage, R, for a single excitationeT is the time for the short circuit resistance.

2. The method of claim 1,

the voltage excitation control is that the voltage of the fuel cell stack rises from a stable value to a limit value; wherein the limit value of the stack voltage is determined according to the single fuel cell with the highest response voltage, wherein the response voltage is less than a safe voltage threshold value.

3. The method of claim 1, wherein the microcurrent excitation comprises: constant current excitation and non-constant current excitation;

the end point of the micro-current excitation applied excitation is determined according to the single fuel cell with the highest response voltage, wherein the response voltage is smaller than a safe voltage threshold;

when a high-precision power supply is used for programming current excitation, the programming current is used as the whole stack of measured current.

4. The method of claim 1, wherein in performing the plurality of excitations, the excitations are performed at preset time intervals; wherein the preset time interval is determined according to the voltage drop of all the single fuel cells to the concentration potential after the previous excitation is completed and the preset time is maintained.

5. The method of claim 1, wherein when the short circuit resistance is greater than a preset resistance value or simplified processing is performed ignoring the effect of the short circuit resistance, the fuel cell excitation-response equation is converted to:

wherein ichFor real-time excitation current density or real-time response current density when voltage is excited, iHIs hydrogen permeation current density, QCataTotal amount of adsorbed and desorbed charge on the surface of the catalyst in real time, CdlIs double electric layer capacitor, U is single-chip real-time voltage, U0The monolithic start voltage for a single excitation, t is the time.

6. The method of any of claims 1-5, wherein the data for each individual fuel cell is analyzed individually, setting an initial analysis voltage window to [ U [1,U2]And the voltage window corresponds to a voltage interval after hydrogen desorption is completed and before oxygen adsorption begins, all data in the voltage window range are processed, and the voltage window is set as follows:

when the analysis is performed by using the formula (1), Y is equal to a0+a1X1+a2X2+a3X3Performing ternary linear regression, analyzing to obtain various coefficients, and obtaining the multi-parameter of the membrane electrode of the fuel cell:

when the analysis is performed by using the formula (2), Y is a0+a1X1+a2X2Performing binary linear regression, and analyzing to obtain the membrane electrode multi-parameter:

iH=a0,QCata.-H=a1,Cdl=a2 (5)

wherein Q isCata.-HFor the total amount of hydrogen desorption charge, the active area of the catalyst can be analyzed through the amount of hydrogen desorption charge:

wherein, gamma isCata.The amount of charge, L, required for the hydrogen adsorption of the catalyst surface to completely cover a monolayerCata.Is the measured electrode catalyst loading;

when the formula (1) is used for analysis, the total quantity of the absorbed and desorbed charges on the surface of the real-time catalyst in the full voltage range under all excitation conditions is reversely solved:

when the formula (2) is used for analysis, the total quantity of the absorbed and desorbed charges on the surface of the real-time catalyst in the full voltage range under all excitation conditions is reversely solved:

checking in said voltage window [ U ]1,U2]Inner QCata.Whether a preset condition is met or not, if not, adjusting a voltage window, and repeatedly analyzing until the preset condition is met, wherein the preset condition is that all Q's in the voltage window are metCata.The standard deviation of the data is less than the limit.

7. A fuel cell stack multi-membrane electrode multi-parameter synchronous detection device is characterized by comprising:

the fuel cell system comprises a setting module, a control module and a control module, wherein the setting module is used for supplying hydrogen at the anode of a fuel cell stack and inert gas at the cathode of the fuel cell stack, controlling the temperature, the gas flow, the gas back pressure and the gas humidity of the fuel cell stack to respectively maintain corresponding preset values, and maintaining each fuel cell in the fuel cell stack at a stable concentration potential;

the control module is used for applying different voltage excitation or micro-current excitation for a plurality of times to the fuel cell stack, collecting a current signal of the whole stack and a voltage signal of each fuel cell, wherein the initial point of each excitation application is recorded as a time zero point, and each single-chip concentration potential is recorded as a single-chip initial voltage;

the analysis module is used for analyzing the hydrogen permeation current, the catalyst active area, the double electric layer capacitance and the short-circuit resistance of each fuel cell membrane electrode according to a fuel cell excitation-response formula; wherein the fuel cell excitation-response equation is:

wherein ichFor real-time excitation current density or real-time response current density when voltage is excited, iHIs hydrogen permeation current density, QCata.For real-time adsorption and desorption of the total amount of charge on the surface of the catalyst, CdlIs double electric layer capacitor, U is single-chip real-time voltage, U0Monolithic threshold voltage, R, for a single excitationeT is the time for the short circuit resistance.

8. The apparatus of claim 7, further comprising:

the control module is used for controlling the voltage excitation to increase the voltage of the fuel cell stack from a stable value to a limit value; wherein the limit value of the stack voltage is determined according to the single fuel cell with the highest response voltage, wherein the response voltage is less than a safe voltage threshold value;

the microcurrent excitation comprises: the constant current excitation and non-constant current excitation determining module is used for determining the end point of excitation application of the micro current excitation according to the single fuel cell with the highest response voltage, wherein the response voltage is smaller than a safe voltage threshold; when a high-precision power supply is used for programming current excitation, the programming current is used as the whole stack of measured current.

9. The apparatus of claim 7, further comprising:

the excitation module is used for exciting according to a preset time interval in the process of exciting for multiple times; wherein the preset time interval is determined according to the voltage drop of all the single fuel cells to the concentration potential after the previous excitation is completed and the preset time is maintained.

10. The apparatus of any of claims 7-9, further comprising:

when the short-circuit resistance is larger than a preset resistance value or the influence of the short-circuit resistance is ignored for simplification processing, the fuel cell excitation-response formula is converted into:

wherein ichFor real-time excitation current density or real-time response current density when voltage is excited, iHIs hydrogen permeation current density, QCata.For real-time adsorption and desorption of the total amount of charge on the surface of the catalyst, CdlIs double electric layer capacitor, U is single-chip real-time voltage, U0The starting voltage of a single excitation single chip, and t is time;

analyzing the data of each single fuel cell individually, and setting an initial analysis voltage window as U1,U2]The voltage window corresponds to the voltage interval after hydrogen desorption is completed and before oxygen adsorption begins, and all data in the voltage window range are processed and setDetermining:

a first analysis module for performing analysis using the formula (1) according to the formula (a) given by Y0+a1X1+a2X2+a3X3Performing ternary linear regression, analyzing to obtain various coefficients, and obtaining the multi-parameter of the membrane electrode of the fuel cell:

a second analysis module for performing analysis using the formula (2) according to the formula (a) given by Y0+a1X1+a2X2Performing binary linear regression, and analyzing to obtain the membrane electrode multi-parameter:

iH=a0,QCata.-H=a1,Cdl=a2 (5)

wherein Q isCata.-HFor the total amount of hydrogen desorption charge, the active area of the catalyst can be analyzed through the amount of hydrogen desorption charge:

wherein, gamma isCataThe amount of charge, L, required to adsorb hydrogen, which is a monolayer completely covering the catalyst surfaceCataIs the measured electrode catalyst loading;

when the first analysis module uses the formula (1) to analyze, the total amount of the absorbed and desorbed charges on the surface of the real-time catalyst in the full voltage range under all excitation conditions is reversely solved:

when the second analysis module analyzes by using the formula (2), the total amount of the absorbed and desorbed charges on the surface of the real-time catalyst in the full voltage range under all excitation conditions is reversely solved:

a checking module for checking in the voltage window [ U ]1,U2]Inner QCata.Whether a preset condition is met or not;

an adjusting module, configured to adjust a voltage window if the voltage window is not satisfied, and repeatedly analyze the voltage window until the preset condition is satisfied, where the preset condition is that all Q's in the voltage window are satisfiedCata.The standard deviation of the data is less than the limit.

Technical Field

The application relates to the technical field of fuel cells, in particular to a multi-membrane electrode multi-parameter synchronous detection method and device for a fuel cell stack.

Background

Proton exchange membrane fuel cells are relatively ideal vehicle-mounted power sources and are receiving wide attention. With the gradual increase of the power requirement of the fuel cell stack, the number of the membrane electrodes of a single stack of the fuel cell is increased to hundreds of pieces, and the influence of the consistency of the membrane electrode on the performance and the durability of the stack is increasingly prominent. Membrane electrode batch testing and parameter evaluation are critical to consistency screening. The traditional parameters for evaluating the quality of the membrane electrode generally comprise the active area of a catalyst and the hydrogen permeation current. The traditional electrochemical test method can only test a single fuel cell generally, for example, the cyclic voltammetry can only test the catalyst active area of a single fuel cell membrane electrode, and the linear potential scanning method can only test the hydrogen permeation current of a single fuel cell membrane electrode. In recent years, a constant-current charging analysis method for synchronously testing parameters of a plurality of membrane electrodes of a galvanic pile has been developed, but strict high-precision constant current and high-frequency voltage sampling are required, an incomplete analysis model causes intrinsic errors in parameter analysis, the analysis process is complicated, and error conduction is easily caused. Therefore, the existing membrane electrode multi-parameter detection method has extremely high equipment requirement and poor stability of measurement and analysis results.

Disclosure of Invention

The present application is directed to solving, at least to some extent, one of the technical problems in the related art.

Therefore, the first objective of the present application is to provide a multi-membrane electrode multi-parameter synchronous detection method for a fuel cell stack, which solves various disadvantages of the existing methods, has no limitation on the current or voltage excitation form, has extremely low requirement on voltage sampling frequency, complete analysis model and extremely high stability of the analysis process, and greatly improves the membrane electrode parameter testing precision.

The second objective of the present application is to provide a multi-membrane electrode multi-parameter synchronous detection device for a fuel cell stack.

In order to achieve the above object, a first embodiment of the present application provides a multi-parameter synchronous detection method for multiple membrane electrodes of a fuel cell stack, including:

supplying hydrogen at the anode of the fuel cell stack and supplying inert gas at the cathode of the fuel cell stack, controlling the temperature, the gas flow, the gas back pressure and the gas humidity of the fuel cell stack to respectively maintain corresponding preset values, and maintaining each fuel cell in the fuel cell stack at a stable concentration potential;

applying different voltage excitation or micro-current excitation for multiple times to the fuel cell stack, and collecting a current signal of the whole stack and a voltage signal of each fuel cell, wherein the initial point of each excitation application is recorded as a time zero point, and each single stable concentration potential is recorded as a single initial voltage;

analyzing hydrogen permeation current, catalyst active area, double electric layer capacitance and short-circuit resistance of each fuel cell membrane electrode according to a fuel cell excitation-response formula; wherein the fuel cell excitation-response equation is:

wherein ichFor real-time excitation current density or real-time response current density when voltage is excited, iHIs hydrogen permeation current density, QCataTotal amount of adsorbed and desorbed charge on the surface of the catalyst in real time, CdlIs double electric layer capacitor, U is single-chip real-time voltage, U0Monolithic threshold voltage, R, for a single excitationeT is the time for the short circuit resistance.

According to the multi-membrane electrode multi-parameter synchronous detection method for the fuel cell stack, hydrogen is supplied to the anode of the fuel cell stack, inert gas is supplied to the cathode of the fuel cell stack, the temperature, the gas flow, the gas back pressure and the gas humidity of the fuel cell stack are controlled to respectively maintain corresponding preset values, and each fuel cell in the fuel cell stack is maintained at a stable concentration potential; applying different voltage excitation or micro-current excitation for multiple times to the fuel cell stack, and collecting a current signal of the whole stack and a voltage signal of each fuel cell, wherein the initial point of each excitation application is recorded as a time zero point, and each single stable concentration potential is recorded as a single initial voltage; and analyzing the hydrogen permeation current, the catalyst active area, the double electric layer capacitance and the short-circuit resistance of the membrane electrode of each fuel cell according to a fuel cell excitation-response formula. The method has no limitation on the current or voltage excitation form, extremely low requirement on voltage sampling frequency, complete analysis model and extremely high stability of the analysis process, greatly improves the accuracy and precision of membrane electrode parameter test, and can also greatly reduce the cost of test equipment.

Optionally, in one embodiment of the present application, the inert gas includes, but is not limited to, one of nitrogen, helium, and argon, and if the cathode is supplied with air, it is necessary to discharge to consume oxygen under dead-end or cathode gas circulation conditions, thereby providing an inert gas environment for the cathode.

Alternatively, in one embodiment of the present application, the voltage excitation control is a rise in stack voltage of the fuel cell stack from a steady value to a limit value; wherein the limit value of the stack voltage is determined according to the single fuel cell with the highest response voltage, wherein the response voltage is less than a safe voltage threshold value.

Optionally, in one embodiment of the present application, the micro-current excitation comprises: constant current excitation and non-constant current excitation;

the end point of the micro-current excitation applied excitation is determined according to the single fuel cell with the highest response voltage, wherein the response voltage is smaller than a safe voltage threshold;

when a high-precision power supply is used for programming current excitation, the programming current is used as the whole stack of measured current.

Optionally, in an embodiment of the present application, the plurality of different voltage excitations or trickle excitations are different in the rate of rise of the excitation voltage or in the value of the excitation current.

Optionally, in an embodiment of the present application, during the multiple times of excitation, excitation is performed at preset time intervals; wherein the preset time interval is determined according to the voltage drop of all the single fuel cells to the concentration potential after the previous excitation is completed and the preset time is maintained.

Alternatively, in one embodiment of the present application, when the short-circuit resistance is greater than a preset resistance value or simplified processing is performed ignoring the effect of the short-circuit resistance, the fuel cell excitation-response equation is converted into:

wherein ichFor real-time excitation current density or real-time response current density when voltage is excited, iHIs hydrogen permeation current density, QCata.For real-time adsorption and desorption of the total amount of charge on the surface of the catalyst, CdlIs double electric layer capacitor, U is single-chip real-time voltage, U0The monolithic start voltage for a single excitation, t is the time.

Alternatively, in one embodiment of the present application, the data of each monolithic fuel cell is analyzed separately, and the initial analysis voltage window is set to [ U1,U2]And the voltage window corresponds to a voltage interval after hydrogen desorption is completed and before oxygen adsorption begins, all data in the voltage window range are processed, and the voltage window is set as follows:

when the analysis is performed by using the formula (1), Y is equal to a0+a1X1+a2X2+a3X3Performing ternary linear regression, analyzing to obtain various coefficients, and obtaining the multi-parameter of the membrane electrode of the fuel cell:

when the analysis is performed by using the formula (2), Y is a0+a1X1+a2X2Performing binary linear regression, and analyzing to obtain the membrane electrode multi-parameter:

iH=a0,QCata.-H=a1,Cdl=a2 (5)

wherein Q isCata.-HFor the total amount of hydrogen desorption charge, the active area of the catalyst can be analyzed through the amount of hydrogen desorption charge:

wherein, gamma isCata.The amount of charge, L, required for the hydrogen adsorption of the catalyst surface to completely cover a monolayerCata.Is the measured electrode catalyst loading.

Optionally, in an embodiment of the present application, the method further includes:

when the formula (1) is used for analysis, the total quantity of the absorbed and desorbed charges on the surface of the real-time catalyst in the full voltage range under all excitation conditions is reversely solved:

when the formula (2) is used for analysis, the total quantity of the absorbed and desorbed charges on the surface of the real-time catalyst in the full voltage range under all excitation conditions is reversely solved:

checking in said voltage window [ U ]1,U2]Inner QCata.Whether a preset condition is met or not, if not, adjusting a voltage window, and repeatedly analyzing until the preset condition is met, wherein the preset condition is that all Q's in the voltage window are metCata.The standard deviation of the data is less than the limit.

In order to achieve the above object, a second aspect of the present application provides a multi-membrane electrode multi-parameter synchronous detection device for a fuel cell stack, comprising:

the fuel cell system comprises a setting module, a control module and a control module, wherein the setting module is used for supplying hydrogen at the anode of a fuel cell stack and inert gas at the cathode of the fuel cell stack, controlling the temperature, the gas flow, the gas back pressure and the gas humidity of the fuel cell stack to respectively maintain corresponding preset values, and maintaining each fuel cell in the fuel cell stack at a stable concentration potential;

the control module is used for applying different voltage excitation or micro-current excitation for a plurality of times to the fuel cell stack, collecting a current signal of the whole stack and a voltage signal of each fuel cell, wherein the initial point of each excitation application is recorded as a time zero point, and each single-chip concentration potential is recorded as a single-chip initial voltage;

the analysis module is used for analyzing the hydrogen permeation current, the catalyst active area, the double electric layer capacitance and the short-circuit resistance of each fuel cell membrane electrode according to a fuel cell excitation-response formula; wherein the fuel cell excitation-response equation is:

wherein ichFor real-time excitation current density or real-time response current density when voltage is excited, iHIs hydrogen permeation current density, QCata.For real-time adsorption and desorption of the total amount of charge on the surface of the catalyst, CdlIs double electric layer capacitor, U is single-chip real-time voltage, U0Monolithic threshold voltage, R, for a single excitationeT is the time for the short circuit resistance.

According to the multi-membrane electrode multi-parameter synchronous detection device for the fuel cell stack, hydrogen is supplied to the anode of the fuel cell stack, inert gas is supplied to the cathode of the fuel cell stack, the temperature, the gas flow, the gas back pressure and the gas humidity of the fuel cell stack are controlled to respectively maintain corresponding preset values, and each fuel cell in the fuel cell stack is maintained at a stable concentration potential; applying different voltage excitation or micro-current excitation for multiple times to the fuel cell stack, and collecting a current signal of the whole stack and a voltage signal of each fuel cell, wherein the initial point of each excitation application is recorded as a time zero point, and each single stable concentration potential is recorded as a single initial voltage; and analyzing the hydrogen permeation current, the catalyst active area, the double electric layer capacitance and the short-circuit resistance of the membrane electrode of each fuel cell according to a fuel cell excitation-response formula. The method has no limitation on the current or voltage excitation form, extremely low requirement on voltage sampling frequency, complete analysis model and extremely high stability of the analysis process, greatly improves the accuracy and precision of membrane electrode parameter test, and can also greatly reduce the cost of test equipment.

Optionally, in an embodiment of the present application, the apparatus further includes:

the control module is used for controlling the voltage excitation to increase the voltage of the fuel cell stack from a stable value to a limit value; wherein the limit value of the stack voltage is determined according to the single fuel cell with the highest response voltage, wherein the response voltage is less than a safe voltage threshold value;

the microcurrent excitation comprises: the constant current excitation and non-constant current excitation determining module is used for determining the end point of excitation application of the micro current excitation according to the single fuel cell with the highest response voltage, wherein the response voltage is smaller than a safe voltage threshold; when a high-precision power supply is used for programming current excitation, the programming current is used as the whole stack of measured current.

Optionally, in an embodiment of the present application, the apparatus further includes:

the excitation module is used for exciting according to a preset time interval in the process of exciting for multiple times; wherein the preset time interval is determined according to the voltage drop of all the single fuel cells to the concentration potential after the previous excitation is completed and the preset time is maintained.

Optionally, in an embodiment of the present application, the apparatus further includes:

when the short-circuit resistance is larger than a preset resistance value or the influence of the short-circuit resistance is ignored for simplification processing, the fuel cell excitation-response formula is converted into:

wherein ichFor real-time excitation current density or real-time response current density when voltage is excited, iHIs hydrogen permeation current density, QCata.For real-time adsorption and desorption of the total amount of charge on the surface of the catalyst, CdlIs double electric layer capacitor, U is single-chip real-time voltage, U0The starting voltage of a single excitation single chip, and t is time;

analyzing the data of each single fuel cell individually, and setting an initial analysis voltage window as U1,U2]And the voltage window corresponds to a voltage interval after hydrogen desorption is completed and before oxygen adsorption begins, all data in the voltage window range are processed, and the voltage window is set as follows:

a first analysis module for performing analysis using the formula (1) according to the formula (a) given by Y0+a1X1+a2X2+a3X3Performing ternary linear regression, analyzing to obtain various coefficients, and obtaining the multi-parameter of the membrane electrode of the fuel cell:

a second analysis module for performing analysis using the formula (2) according to the formula (a) given by Y0+a1X1+a2X2Performing binary linear regression, and analyzing to obtain the membrane electrode multi-parameter:

iH=a0,QCata.-H=a1,Cdl=a2 (5)

wherein Q isCata.-HFor the total amount of hydrogen desorption charge, the active area of the catalyst can be analyzed through the amount of hydrogen desorption charge:

wherein, gamma isCata.The amount of charge, L, required for the hydrogen adsorption of the catalyst surface to completely cover a monolayerCata.Is the measured electrode catalyst loading;

when the first analysis module uses the formula (1) to analyze, the total amount of the absorbed and desorbed charges on the surface of the real-time catalyst in the full voltage range under all excitation conditions is reversely solved:

when the second analysis module analyzes by using the formula (2), the total amount of the absorbed and desorbed charges on the surface of the real-time catalyst in the full voltage range under all excitation conditions is reversely solved:

a checking module for checking in the voltage window [ U ]1,U2]Inner QCata.Whether a preset condition is met or not;

an adjusting module, configured to adjust a voltage window if the voltage window is not satisfied, and repeatedly analyze the voltage window until the preset condition is satisfied, where the preset condition is that all Q's in the voltage window are satisfiedCata.The standard deviation of the data is less than the limit.

Additional aspects and advantages of the present application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the present application.

Drawings

The foregoing and/or additional aspects and advantages of the present application will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:

fig. 1 is a schematic flowchart of a multi-parameter synchronous detection method for multiple membrane electrodes of a fuel cell stack according to an embodiment of the present disclosure;

FIG. 2 is a flowchart of a multi-membrane electrode multi-parameter synchronous detection method for a fuel cell stack according to an embodiment of the present disclosure;

FIG. 3 is a graph of excitation-voltage response for multi-parameter measurement of membrane electrodes according to an embodiment of the present application;

FIG. 4 is a reverse decomposition chart of the total amount of adsorbed and desorbed charges on the surface of the real-time catalyst in the full voltage range under all excitation conditions of the embodiment of the present application;

fig. 5 is a schematic structural diagram of a multi-membrane electrode multi-parameter synchronous detection device of a fuel cell stack according to an embodiment of the present disclosure.

Detailed Description

Reference will now be made in detail to embodiments of the present application, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are exemplary and intended to be used for explaining the present application and should not be construed as limiting the present application.

The fuel cell stack multi-membrane electrode multi-parameter synchronous detection method and device according to the embodiments of the present application are described below with reference to the accompanying drawings.

Fig. 1 is a schematic flowchart of a multi-parameter synchronous detection method for multiple membrane electrodes of a fuel cell stack according to an embodiment of the present disclosure.

As shown in fig. 1, the method for synchronously detecting multiple parameters of multiple membrane electrodes of a fuel cell stack comprises the following steps:

step 101, supplying hydrogen to the anode of the fuel cell stack and supplying inert gas to the cathode of the fuel cell stack, controlling the temperature, the gas flow rate, the gas back pressure and the gas humidity of the fuel cell stack to respectively maintain corresponding preset values, and maintaining each fuel cell in the fuel cell stack at a stable concentration potential.

And 102, applying different voltage excitation or micro-current excitation for a plurality of times to the fuel cell stack, and collecting a current signal of the whole stack and a voltage signal of each fuel cell, wherein the initial point of each excitation application is recorded as a time zero point, and each single stable concentration potential is recorded as a single initial voltage.

And 103, analyzing the hydrogen permeation current, the catalyst active area, the electric double layer capacitance and the short-circuit resistance of the membrane electrode of each fuel cell according to a fuel cell excitation-response formula.

Wherein the fuel cell excitation-response formula is:

wherein ichFor real-time excitation current density or real-time response current density when voltage is excited, iHIs hydrogen permeation current density, QCata.For real-time adsorption and desorption of the total amount of charge on the surface of the catalyst, CdlIs double electric layer capacitor, U is single-chip real-time voltage, U0Monolithic threshold voltage, R, for a single excitationeT is the time for the short circuit resistance.

In the embodiment of the present application, the inert gas includes but is not limited to one of nitrogen, helium and argon, and if the cathode is supplied with air, it is necessary to discharge and consume oxygen under the condition of dead end or cathode gas circulation, so as to provide an inert gas environment for the cathode.

In the embodiment of the application, the voltage excitation control is that the stack voltage of the fuel cell stack is increased from a stable value to a limit value; the limit value of the stack voltage is determined according to the single fuel cell with the highest response voltage, wherein the response voltage is smaller than the safe voltage threshold value.

In an embodiment of the present application, the microcurrent excitation comprises: constant current excitation and non-constant current excitation; determining the end point of excitation application of the micro-current excitation according to the single fuel cell with the highest response voltage, wherein the response voltage is less than a safe voltage threshold; when a high-precision power supply is used for programming current excitation, the programming current is used as the whole stack of measured current.

In the present embodiment, the plurality of different voltage excitations or trickle excitations are different in the rate of rise of the excitation voltage or the value of the excitation current.

In the embodiment of the application, in the process of carrying out excitation for multiple times, excitation is carried out according to a preset time interval; wherein the preset time interval is determined according to the voltage drop of all the single fuel cells to the stable concentration difference potential after the previous excitation is completed and the preset time is maintained.

In the embodiment of the present application, when the short-circuit resistance is greater than the preset resistance value, the fuel cell excitation-response formula is converted into:

wherein ichFor real-time excitation current density or real-time response current density when voltage is excited, iHIs hydrogen permeation current density, QCata.For real-time adsorption and desorption of the total amount of charge on the surface of the catalyst, CdlIs double electric layer capacitor, U is single-chip real-time voltage, U0The monolithic start voltage for a single excitation, t is the time.

In the embodiment of the present application, the data of each single fuel cell is analyzed individually, and the initial analysis voltage window is set as [ U ]1,U2]And after the hydrogen desorption is finished and before the oxygen adsorption is started, processing all data in the voltage window range, and setting:

when the analysis is performed by using the formula (1), Y is equal to a0+a1X1+a2X2+a3X3Performing ternary linear regression, analyzing to obtain various coefficients, and obtaining the multi-parameter of the membrane electrode of the fuel cell:

when the analysis is performed by using the formula (2), Y is a0+a1X1+a2X2Performing binary linear regression, and analyzing to obtain the membrane electrode multi-parameter:

iH=a0,QCata.-H=a1,Cdl=a2 (5)

wherein Q isCata.-HFor the total amount of hydrogen desorption charge, the active area of the catalyst can be analyzed through the amount of hydrogen desorption charge:

wherein, gamma isCata.The amount of charge, L, required for the hydrogen adsorption of the catalyst surface to completely cover a monolayerCata.Is the measured electrode catalyst loading.

In the embodiment of the application, when the formula (1) is used for analysis, the total amount of the absorbed and desorbed charges on the surface of the real-time catalyst in the full voltage range under all excitation conditions is reversely solved:

when the formula (2) is used for analysis, the total quantity of the absorbed and desorbed charges on the surface of the real-time catalyst in the full voltage range under all excitation conditions is reversely solved:

checking in a voltage window U1,U2]Inner QCata.Whether a preset condition is met or not, if not, adjusting a voltage window, and repeatedly analyzing until the preset condition is met, wherein the preset condition is that all Q's in the voltage window are Q' sCata.The standard deviation of the data is less than the limit.

Specifically, (1) gas supply and working condition control, namely supplying hydrogen to the anode of the fuel cell stack, supplying inert gas to the cathode of the fuel cell stack, controlling the temperature, the gas back pressure and the gas humidity of the fuel cell stack to be stable, and waiting for each fuel cell to reach and maintain stable concentration potential. The inert gas can be selected from nitrogen, helium or argon.

Further, if the cathode is supplied with air, it is necessary to discharge the cathode under dead-end or cathode gas circulation conditions to consume oxygen, thereby providing an inert gas environment for the cathode.

Specifically, (2) excitation is applied and response signals are collected, namely, an external power supply is used for applying voltage excitation or micro-current excitation to the fuel cell stack, the current signal of the whole stack and the voltage signal of each fuel cell are collected, the initial point of each excitation application is recorded as a time zero point, the stable single-chip concentration difference potential is recorded as a single-chip initial voltage, and multiple times of differentiated excitation is needed in the membrane electrode parameter measurement process each time. The difference is represented in the rate of rise of the excitation voltage or in the value of the excitation current. In the process of carrying out excitation for multiple times, waiting for the completion of the previous excitation, the reduction of all single-chip voltages to the concentration potential and the stabilization for a period of time, and then applying the next excitation.

Further, the voltage excitation is used for controlling the voltage of the electric pile to rise from a stable value to a limit value, the limit value of the voltage of the electric pile is determined according to the single chip with the highest response voltage, and the response voltage of the single chip cannot exceed a safety threshold value. The micro-current excitation comprises constant current excitation and non-constant current excitation, and the excitation application end point is determined according to the single chip with the highest response voltage which must not exceed the safety threshold. When a high-precision power supply is used for programming current excitation, the programming current can be used as the whole stack of measured current; when a common power supply is used for excitation, the whole pile of real-time current must be measured.

Specifically, (3) parameter analysis: and analyzing the hydrogen permeation current, the catalyst active area, the electric double layer capacitance and the short-circuit resistance of each membrane electrode according to a fuel cell excitation-response formula.

As an example of a scenario, a flowchart of a multi-membrane electrode multi-parameter synchronous detection method for a fuel cell stack according to an embodiment of the present invention is specifically described in conjunction with a multi-parameter test for a stack membrane electrode including 7 fuel cells, as shown in fig. 2. The testing and analyzing process is divided into three steps:

(1) gas supply and condition control: and supplying hydrogen to the anode of the fuel cell stack and supplying inert gas to the cathode, wherein the inert gas is nitrogen in the embodiment, the hydrogen flow is 4SLPM, the nitrogen flow is 15.8SLPM, the temperature of the fuel cell stack is controlled to be 50 ℃, the gas back pressure is 0.2bar, and the relative humidity of the gas is 100%, and waiting for each fuel cell to reach and maintain a stable concentration potential.

(2) Applying excitation and acquiring response signals: the method comprises the steps of applying voltage excitation or micro-current excitation to a fuel cell stack by using an external power supply, collecting a whole stack current signal and each fuel cell voltage signal, recording the initial point of each excitation application as a time zero point, recording a stable single-chip concentration difference potential as a single-chip initial voltage, and carrying out multiple differential excitation in the membrane electrode parameter measurement process each time. The difference is represented in the rate of rise of the excitation voltage or in the value of the excitation current. In the process of carrying out excitation for multiple times, waiting for the completion of the previous excitation, the reduction of all single-chip voltages to the concentration potential and the stabilization for a period of time, and then applying the next excitation. The voltage excitation is used for controlling the voltage of the electric pile to rise from a stable value to a limit value, the limit value of the voltage of the electric pile is determined according to the single chip with the highest response voltage, and the response voltage of the single chip cannot exceed a safety threshold value. The micro-current excitation comprises constant current excitation and non-constant current excitation, and the excitation application end point is determined according to the single chip with the highest response voltage which must not exceed the safety threshold. When a high-precision power supply is used for programming current excitation, the programming current can be used as the whole stack of measured current; when a common power supply is used for excitation, the whole pile of real-time current must be measured.

In the embodiment, a high-precision power supply is adopted to apply constant current excitation, and the current density of multiple times of excitation is respectively 6 mA-cm-2、7mA·cm-2、8mA·cm-2、9mA·cm-2、10mA·cm-2The excitation is terminated when the maximum voltage of the single chip reaches a safety threshold of 0.8V. And (3) collecting the voltage of the fuel cell single chip by using a data acquisition system, wherein the voltage sampling frequency is 100 Hz. The excitation-voltage response of the first monolithic in the stack is shown in figure 3.

(3) Parameter analysis: and analyzing the hydrogen permeation current, the catalyst active area, the electric double layer capacitance and the short-circuit resistance of each membrane electrode according to a fuel cell excitation-response formula.

The full stimulus-response equation is:

when simplification processing is carried out or the short-circuit resistance is too large, the electronic short-circuit term can be ignored, and a simplified excitation-response formula is adopted, wherein the simplified excitation-response formula is as follows:

in the formula ichFor real-time excitation current density or real-time response current density when voltage is excited, iHIs hydrogen permeation current density, QCata.For real-time catalyst surface adsorption and desorption of total amount of charge (involving hydrogen desorption and oxygen adsorption), CdlIs double electric layer capacitor, U is single-chip real-time voltage, U0Monolithic threshold voltage, R, for a single excitationeT is the time for the short circuit resistance.

In this embodiment, the complete excitation-response formula is used to develop the resolution. Firstly, setting an initial analysis voltage window to be [0.4V,0.6V ], wherein the voltage window corresponds to a voltage interval after the hydrogen desorption is finished and before the oxygen adsorption is started, processing all data in the voltage window range, and setting:

according to Y ═ a0+a1X1+a2X2+a3X3And (5) performing ternary linear regression, and analyzing to obtain each coefficient, thereby obtaining the membrane electrode multi-parameter. The analysis result of the first slice is:

iH=a0=4.13mA·cm-2,Qcata.-H=a1=46.95mC·cm-2

in the formula, QCata.-HFor the total amount of hydrogen desorption charge, the active area of the catalyst can be analyzed through the amount of hydrogen desorption charge:

in the formula, gammaCata.The amount of charge, L, required for the hydrogen adsorption of the catalyst surface to completely cover a monolayerCata.Is the measured electrode catalyst loading.

After the solution is completed, the analysis result needs to be subjected to inverse solution verification. When a complete excitation-response formula is used for analysis, the total quantity of the absorbed and desorbed charges on the surface of the real-time catalyst in a full voltage range under all excitation conditions needs to be reversely solved:

checking in a voltage window of 0.4V,0.6V]Inner QCata.If the platform phenomenon is not strict, the voltage window needs to be adjusted, repeated analysis is carried out until the verification requirement is met, and the verification requirement is that all Q values in the adjusted voltage windowCata.The standard deviation of the data was below the limit.

In this example, the inverse decomposition chart of the total amount of adsorbed and desorbed charges on the surface of the real-time catalyst in the full voltage range of the first monolithic chip under all excitation conditions is shown in FIG. 4, and the inverse decomposition result is shown in the voltage window [0.4V,0.6V ]]Inner QCata.Exhibits a strict plateau phenomenon and all Q's within a voltage windowCata.The standard deviation of the data was below the limit. And finishing the testing and analyzing process, wherein the obtained analyzing result is the finally obtained membrane electrode parameter.

According to the multi-membrane electrode multi-parameter synchronous detection method for the fuel cell stack, hydrogen is supplied to the anode of the fuel cell stack, inert gas is supplied to the cathode of the fuel cell stack, the temperature, the gas back pressure and the gas humidity of the fuel cell stack are controlled to respectively maintain corresponding preset values, and each fuel cell in the fuel cell stack is maintained at a stable concentration potential; applying different voltage excitation or micro-current excitation for multiple times to the fuel cell stack, and collecting a current signal of the whole stack and a voltage signal of each fuel cell, wherein the initial point of each excitation application is recorded as a time zero point, and each single stable concentration potential is recorded as a single initial voltage; and analyzing the hydrogen permeation current, the catalyst active area, the double electric layer capacitance and the short-circuit resistance of the membrane electrode of each fuel cell according to a fuel cell excitation-response formula. The method and the device for synchronously detecting the hydrogen permeation current, the catalyst active area, the double electric layer capacitance and the short-circuit resistance of the multi-membrane electrode of the electric pile basically solve various defects of membrane electrode parameter measurement, have no limitation on the current or voltage excitation form, have extremely low requirement on voltage sampling frequency, complete analysis model and extremely high stability of the analysis process, and greatly improve the accuracy and precision of membrane electrode parameter test.

In order to implement the above embodiments, the present application further provides a multi-parameter synchronous detection apparatus for a plurality of membrane electrodes of a fuel cell stack.

Fig. 5 is a schematic structural diagram of a multi-membrane electrode multi-parameter synchronous detection device of a fuel cell stack according to an embodiment of the present disclosure.

As shown in fig. 5, the multi-membrane electrode multi-parameter synchronous detection device for a fuel cell stack comprises: a setup module 510, a control module 520, and an analysis module 530.

The setting module 510 is configured to supply hydrogen at an anode of a fuel cell stack and supply an inert gas at a cathode of the fuel cell stack, control the temperature, the gas flow rate, the gas backpressure, and the gas humidity of the fuel cell stack to respectively maintain corresponding preset values, and control each fuel cell in the fuel cell stack to maintain a stable concentration potential.

And the control module 520 is used for applying different voltage excitation or micro-current excitation for multiple times to the fuel cell stack, and acquiring a current signal of the whole stack and a voltage signal of each fuel cell, wherein the initial point of application of each excitation is recorded as a time zero point, and the concentration difference potential of each single gas flow is recorded as a single initial voltage.

The analysis module 530 is used for analyzing the hydrogen permeation current, the catalyst active area, the electric double layer capacitance and the short-circuit resistance of each fuel cell membrane electrode according to the fuel cell excitation-response formula; wherein the fuel cell excitation-response equation is:

wherein ichFor real-time excitation current density or real-time response current density when voltage is excited, iHIs hydrogen permeation current density, QCata.For real-time catalysisTotal amount of adsorbed and desorbed charge on the surface of the agent, CdlIs double electric layer capacitor, U is single-chip real-time voltage, U0Monolithic threshold voltage, R, for a single excitationeT is the time for the short circuit resistance.

According to the multi-membrane electrode multi-parameter synchronous detection device for the fuel cell stack, hydrogen is supplied to the anode of the fuel cell stack, inert gas is supplied to the cathode of the fuel cell stack, the temperature, the gas flow, the gas back pressure and the gas humidity of the fuel cell stack are controlled to respectively maintain corresponding preset values, and each fuel cell in the fuel cell stack is maintained at a stable concentration potential; applying different voltage excitation or micro-current excitation for multiple times to the fuel cell stack, and collecting a current signal of the whole stack and a voltage signal of each fuel cell, wherein the initial point of each excitation application is recorded as a time zero point, and each single stable concentration potential is recorded as a single initial voltage; and analyzing the hydrogen permeation current, the catalyst active area, the double electric layer capacitance and the short-circuit resistance of the membrane electrode of each fuel cell according to a fuel cell excitation-response formula. Therefore, the hydrogen permeation current, the catalyst active area, the double electric layer capacitance and the short-circuit resistance of the multi-membrane electrode of the pile are synchronously detected, various defects of membrane electrode parameter measurement are basically overcome, the current or voltage excitation form is not limited, the requirement on voltage sampling frequency is extremely low, an analysis model is complete, the stability of an analysis process is extremely high, and the accuracy and precision of membrane electrode parameter measurement are greatly improved.

In an embodiment of the present application, the apparatus further includes: the control module is used for controlling the voltage excitation to increase the voltage of the fuel cell stack from a stable value to a limit value; wherein the limit value of the stack voltage is determined according to the single fuel cell with the highest response voltage, wherein the response voltage is less than a safe voltage threshold value; the microcurrent excitation comprises: the constant current excitation and non-constant current excitation determining module is used for determining the end point of excitation application of the micro current excitation according to the single fuel cell with the highest response voltage, wherein the response voltage is smaller than a safe voltage threshold; when a high-precision power supply is used for programming current excitation, the programming current is used as the whole stack of measured current.

In an embodiment of the present application, the apparatus further includes: the excitation module is used for exciting according to a preset time interval in the process of exciting for multiple times; wherein the preset time interval is determined according to the voltage drop of all the single fuel cells to the concentration potential after the previous excitation is completed and the preset time is maintained.

In an embodiment of the present application, the apparatus further includes: when the short-circuit resistance is larger than a preset resistance value or the influence of the short-circuit resistance is ignored for simplification processing, the fuel cell excitation-response formula is converted into:

wherein ichFor real-time excitation current density or real-time response current density when voltage is excited, iHIs hydrogen permeation current density, QCata.For real-time adsorption and desorption of the total amount of charge on the surface of the catalyst, CdlIs double electric layer capacitor, U is single-chip real-time voltage, U0The starting voltage of a single excitation single chip, and t is time; analyzing the data of each single fuel cell individually, and setting an initial analysis voltage window as U1,U2]And the voltage window corresponds to a voltage interval after hydrogen desorption is completed and before oxygen adsorption begins, all data in the voltage window range are processed, and the voltage window is set as follows:

a first analysis module for performing analysis using the formula (1) according to the formula (a) given by Y0+a1X1+a2X2+a3X3Performing ternary linear regression, analyzing to obtain various coefficients, and obtaining the multi-parameter of the membrane electrode of the fuel cell:

a second analysis module for performing analysis using the formula (2) according to the formula (a) given by Y0+a1X1+a2X2Performing binary linear regression, and analyzing to obtain the membrane electrode multi-parameter:

iH=a0,QCata.-H=a1,Cdl=a2 (5)

wherein Q isCata.-HFor the total amount of hydrogen desorption charge, the active area of the catalyst can be analyzed through the amount of hydrogen desorption charge:

wherein, gamma isCata.The amount of charge, L, required for the hydrogen adsorption of the catalyst surface to completely cover a monolayerCata.Is the measured electrode catalyst loading;

when the first analysis module uses the formula (1) to analyze, the total amount of the absorbed and desorbed charges on the surface of the real-time catalyst in the full voltage range under all excitation conditions is reversely solved:

when the second analysis module analyzes by using the formula (2), the total amount of the absorbed and desorbed charges on the surface of the real-time catalyst in the full voltage range under all excitation conditions is reversely solved:

a checking module for checking in the voltage window [ U ]1,U2]Inner QCata.Whether a preset condition is met or not;

an adjusting module, configured to adjust the voltage window if the voltage window is not satisfied, and repeat the analysis until the preset condition is satisfied, where the preset condition isAll Q's within the voltage windowCata.The standard deviation of the data is less than the limit.

It should be noted that the explanation of the embodiment of the multi-membrane electrode multi-parameter synchronous detection method for a fuel cell stack is also applicable to the multi-membrane electrode multi-parameter synchronous detection apparatus for a fuel cell stack in this embodiment, and details are not repeated here.

In the description herein, reference to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.

Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present application, "plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.

Any process or method descriptions in flow charts or otherwise described herein may be understood as representing modules, segments, or portions of code which include one or more executable instructions for implementing steps of a custom logic function or process, and alternate implementations are included within the scope of the preferred embodiment of the present application in which functions may be executed out of order from that shown or discussed, including substantially concurrently or in reverse order, depending on the functionality involved, as would be understood by those reasonably skilled in the art of the present application.

The logic and/or steps represented in the flowcharts or otherwise described herein, e.g., an ordered listing of executable instructions that can be considered to implement logical functions, can be embodied in any computer-readable medium for use by or in connection with an instruction execution system, apparatus, or device, such as a computer-based system, processor-containing system, or other system that can fetch the instructions from the instruction execution system, apparatus, or device and execute the instructions. For the purposes of this description, a "computer-readable medium" can be any means that can contain, store, communicate, propagate, or transport the program for use by or in connection with the instruction execution system, apparatus, or device. More specific examples (a non-exhaustive list) of the computer-readable medium would include the following: an electrical connection (electronic device) having one or more wires, a portable computer diskette (magnetic device), a Random Access Memory (RAM), a read-only memory (ROM), an erasable programmable read-only memory (EPROM or flash memory), an optical fiber device, and a portable compact disc read-only memory (CDROM). Additionally, the computer-readable medium could even be paper or another suitable medium upon which the program is printed, as the program can be electronically captured, via for instance optical scanning of the paper or other medium, then compiled, interpreted or otherwise processed in a suitable manner if necessary, and then stored in a computer memory.

It should be understood that portions of the present application may be implemented in hardware, software, firmware, or a combination thereof. In the above embodiments, the various steps or methods may be implemented in software or firmware stored in memory and executed by a suitable instruction execution system. If implemented in hardware, as in another embodiment, any one or combination of the following techniques, which are known in the art, may be used: a discrete logic circuit having a logic gate circuit for implementing a logic function on a data signal, an application specific integrated circuit having an appropriate combinational logic gate circuit, a Programmable Gate Array (PGA), a Field Programmable Gate Array (FPGA), or the like.

It will be understood by those skilled in the art that all or part of the steps carried by the method for implementing the above embodiments may be implemented by hardware related to instructions of a program, which may be stored in a computer readable storage medium, and when the program is executed, the program includes one or a combination of the steps of the method embodiments.

In addition, functional units in the embodiments of the present application may be integrated into one processing module, or each unit may exist alone physically, or two or more units are integrated into one module. The integrated module can be realized in a hardware mode, and can also be realized in a software functional module mode. The integrated module, if implemented in the form of a software functional module and sold or used as a stand-alone product, may also be stored in a computer readable storage medium.

The storage medium mentioned above may be a read-only memory, a magnetic or optical disk, etc. Although embodiments of the present application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present application, and that variations, modifications, substitutions and alterations may be made to the above embodiments by those of ordinary skill in the art within the scope of the present application.

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