CN111525158A - Method and device for detecting physical state of air-cooled hydrogen fuel cell - Google Patents
Method and device for detecting physical state of air-cooled hydrogen fuel cell Download PDFInfo
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- 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
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
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- H01M8/00—Fuel cells; Manufacture thereof
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- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
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- 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
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/04537—Electric variables
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- H01M8/04552—Voltage of the individual fuel cell
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- 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
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/04537—Electric variables
- H01M8/04544—Voltage
- H01M8/04559—Voltage of fuel cell stacks
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- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/04537—Electric variables
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- H01M8/04567—Voltage of auxiliary devices, e.g. batteries, capacitors
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- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
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- H—ELECTRICITY
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- 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
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/04537—Electric variables
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- H01M8/04582—Current of the individual fuel cell
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- H—ELECTRICITY
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- 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
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/04537—Electric variables
- H01M8/04574—Current
- H01M8/04589—Current of fuel cell stacks
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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
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/04537—Electric variables
- H01M8/04574—Current
- H01M8/04597—Current of auxiliary devices, e.g. batteries, capacitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a method and a device for detecting the physical state of an air-cooled hydrogen fuel cell, wherein the air-cooled hydrogen fuel cell to be detected is arranged in a detection box, the detection box is in a high-purity nitrogen environment, moist and hot hydrogen is continuously introduced into the anode of the air-cooled hydrogen fuel cell to be detected, the voltage consumed by an electronic load is adopted until the highest monocell voltage is less than 0.1V, then the anode and the cathode of a pile are respectively connected with a constant current power supply for charging, then the anode and the cathode of the pile are respectively connected with the cathode and the anode of the pile for charging, simultaneously the voltage response is continuously recorded in real time, and the equivalent hydrogen permeation current density, the double electric layer capacitance, the electrochemical active area and the ohmic internal resistance can be respectively obtained through a series of mathematical processing. The invention is suitable for air-cooled hydrogen fuel cell monocells or galvanic piles, and has simple and reliable method and simple and practical device.
Description
Technical Field
The invention relates to the technical field of fuel cell detection, in particular to a method and a device for detecting the physical state of an air-cooled hydrogen fuel cell.
Background
The performance of the hydrogen fuel cell is closely related to the physical state of the hydrogen fuel cell, and the physical state of the hydrogen fuel cell is mainly reflected by indexes such as equivalent hydrogen permeation current density, double electric layer capacitance, electrochemical active area, ohmic internal resistance and the like. The equivalent hydrogen permeation current density mainly reflects the hydrogen permeability of the proton exchange membrane, the larger the hydrogen permeability is, the poorer the performance of the hydrogen fuel cell is, and the closer the proton exchange membrane is to the end of the service life or the larger the defect exists; the electric double layer capacitance mainly reflects the capacitive characteristics of the fuel cell, namely the instant response capability of the hydrogen fuel cell, and can indirectly reflect the overall connection state of conductive paths between the catalyst and the catalyst carrier, between the catalyst carriers, between the catalyst layer and the gas diffusion layer and other conductive materials; the electrochemical active area is directly related to the performance of the fuel cell, and directly reflects the specific surface area of the catalyst which can participate in the reaction; the ohm internal resistance is an intuitive physical state index of the hydrogen fuel cell and can reflect the hydration degree of the membrane electrode and the contact state between contact parts of each component.
The existing fuel cell physical state detection methods mainly comprise cyclic voltammetry, linear potential scanning and the like, mainly adopt voltage excitation and current response investigation, are only suitable for single cell detection, and are not suitable for detection of a galvanic pile formed by connecting a plurality of single cells in series; the detection of the equivalent hydrogen permeation current density by a micro-flow meter is not suitable for a plurality of single cells connected in parallel with the gas circuit, and the equivalent hydrogen permeation current density of each single cell cannot be quantitatively represented; the measurement of the ohmic internal resistance by the alternating current impedance method also needs a special alternating current impedance instrument.
In the related prior art, the on-site detection method and the detection device for the membrane electrode condition of the fuel cell stack are only suitable for the water-cooled hydrogen fuel cell stack with a closed cathode and an enclosed anode, but not suitable for the unactivated stack, and the stack is not forcibly restored to the same initial state before charging every time in the detection step, so that the detection error is large; at present, a method and a device for rapidly detecting physical state indexes of an air-cooled hydrogen fuel cell which is suitable for an open cathode type and is not only activated or not activated are lacked.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to provide a method and a device for detecting the physical state of an air-cooled hydrogen fuel cell, which can obtain a plurality of physical state indexes through simple operation and different data processing methods.
A method for detecting the physical state of an air-cooled hydrogen fuel cell comprises the following steps:
(1) placing an air-cooled hydrogen fuel cell to be detected in a detection box, continuously introducing damp and hot high-purity hydrogen into an anode gas path, respectively connecting a cell anode (hydrogen electrode) and a cell cathode (air electrode) with leads, and leading the leads out of the detection box through the wall of the detection box; sealing the detection box door, opening a gas outlet at the top and a gas inlet at the bottom of the detection box, continuously introducing high-purity nitrogen into the gas inlet, and directly discharging the gas outlet;
(2) connecting a lead led out by the air-cooled hydrogen fuel cell to be tested with an external electronic load, and consuming the voltage of a single cell with the highest voltage to be less than 0.1V through the electronic load;
(3) connecting an anode lead and a cathode lead led out by the air-cooled hydrogen fuel cell to be tested with the anode and the cathode of an external constant current power supply respectively, turning on the constant current power supply, continuously charging for a period of time at constant current density, and then turning off the constant current power supply;
(4) connecting an anode lead and a cathode lead led out from the air-cooled hydrogen fuel cell to be detected with the cathode and the anode of an external constant current power supply respectively, starting the constant current power supply, charging the air-cooled hydrogen fuel cell to be detected with constant current density, continuously collecting the voltage of each single cell by using a voltage inspector, recording the voltage of each single cell in real time by using a data processing computer until the voltage of one single cell with the lowest voltage is more than or equal to 0.45V, stopping charging, and finishing the first data collection;
(5) repeating the steps (3) and (4) to finish the second and third data acquisition, wherein the current magnitude or the current density magnitude used in the step (4) is different in the three data acquisition processes;
(6) according to the relation between the voltage and the time in each charging process of any single battery obtained in the steps (4) and (5), drawing a voltage-time (V-t) relation curve, solving a first derivative of the curve to obtain a voltage change rate-time (dV/dt-t) relation curve, and further converting to obtain a voltage change rate-voltage (dV/dt-V) relation curve as the time and the voltage are in one-to-one correspondence;
(7) taking the voltage change rate (dV/dt) of each voltage change rate-voltage (dV/dt-V) relation curve obtained by three times of data acquisition (namely under three times of different charging current densities) at 0.4Vi,i＝1,2,3Plotting the charging current density-voltage rate of change (I)CdV/dt) curve, then linear fitting to obtain a straight line at ICThe intercept on the axis (charging current density) is the equivalent hydrogen permeation current density I of the corresponding single cellH；
(8) According to step (7) obtained IHPlotting the charging transient capacitance-voltage ((I)C-IH) dt/dV-V) curve, corresponding to the charge transient capacitance (I) at 0.4VC-IH) dt/dV value is the electric double layer capacitance C of the corresponding celldl(ii) a According to this curve, the electric double layer capacitance (C) is subtracted from the charge transient capacitanceTo-Cdl) Performing integral operation in the range of 0.1-0.4V to obtain the hydrogen desorption electric quantity Q of the corresponding single celld；；
(9) According to the formula ECSA ═ Qd/(qPt×LPt) The electrochemically active area ECSA of the corresponding single cell can be calculated, wherein qPtRepresents the electric quantity L required by the surface of the clean and smooth platinum electrode per unit area to completely cover a monolayer of hydrogen atomsPtRepresents the platinum loading of the membrane electrode;
(10) according to the voltage linear transition V and the charging current density I at the moment when the constant-current charging is started in the step (4)CThe ohmic internal resistance R of the corresponding single cell can be obtainedO＝V/IC。
The device for realizing the detection method comprises a detection box (1), a constant current power supply (2), an ammeter (3), an electronic load (4), a multi-channel voltage polling device (5), a data processing computer (6), a hydrogen humidifying heater (7) and an air-cooled hydrogen fuel cell (8) to be detected, wherein the detection box comprises a box body (9), a detection box door (10), a lead outlet (11), a hydrogen pipeline inlet and outlet (12), a top air outlet (13) and a bottom air inlet (14);
all the steps in the method can be manually operated and process data, and can also be controlled by a computer program to operate and automatically process data by a computer;
in the detection method, in the step (1), the hydrogen introduced into the anode (hydrogen) gas path is humidified and heated hydrogen;
in the detection method, in the step (1), high-purity nitrogen is continuously introduced into an air inlet of a detection box, and positive pressure is kept in the detection box;
the lead outlet, the hydrogen pipeline inlet and outlet and the detection box door on the detection box wall of the device are all provided with sealing rings, sealing glue or sealing strips or other sealing materials for ensuring the air tightness; a manual valve or an electromagnetic valve is arranged at both the air outlet at the top and the air inlet at the bottom of the detection box;
the detection method and the device are suitable for detecting the physical state of the air-cooled hydrogen fuel cell monomer or the galvanic pile, and can simultaneously obtain four physical state indexes of equivalent hydrogen permeation current density, double electric layer capacitance, electrochemical activity area and ohmic internal resistance of each single cell in the galvanic pile by simple charge-discharge operation and voltage signal data processing no matter whether the single cell is activated or not; compared with the existing closest method, the method is more rigorous, has wider application range and more accurate and credible result, and fills the gap in the technical field of the detection of the physical state of the air-cooled hydrogen fuel cell.
Drawings
FIG. 1 is a schematic view of an embodiment of the detection device of the present invention.
FIG. 2 is a schematic view of the voltage-time (V-t) relationship in step (6) of the detection method of the present invention.
FIG. 3 is a graph showing the voltage rate of change-voltage (dV/dt-V) relationship in step (6) of the detection method of the present invention.
FIG. 4 shows the charging current density-voltage change rate (I) in step (7) of the detection method of the present inventionC-dV/dt) curve.
FIG. 5 shows the charge transient capacitance-voltage ((I) in step (8) of the detection method of the present inventionC-IH) dt/dV-V) curve.
Fig. 6 is a schematic diagram of the voltage linear transition V at the charging instant in step (10) of the detection method according to the present invention.
Claims (5)
1. A method and a device for detecting the physical state of an air-cooled hydrogen fuel cell are characterized in that: the method comprises the following steps:
(1) placing an air-cooled hydrogen fuel cell to be detected in a detection box, continuously introducing damp and hot high-purity hydrogen into an anode gas path, respectively connecting a cell anode (hydrogen electrode) and a cell cathode (air electrode) with leads, and leading the leads out of the detection box through the wall of the detection box; sealing the detection box door, opening a gas outlet at the top and a gas inlet at the bottom of the detection box, continuously introducing high-purity nitrogen into the gas inlet, and directly discharging the gas outlet;
(2) connecting a lead led out by the air-cooled hydrogen fuel cell to be tested with an external electronic load, and consuming the voltage of a single cell with the highest voltage to be less than 0.1V through the electronic load;
(3) connecting an anode lead and a cathode lead led out by the air-cooled hydrogen fuel cell to be tested with the anode and the cathode of an external constant current power supply respectively, turning on the constant current power supply, continuously charging for a period of time at constant current density, and then turning off the constant current power supply;
(4) connecting an anode lead and a cathode lead led out from the air-cooled hydrogen fuel cell to be detected with the cathode and the anode of an external constant current power supply respectively, starting the constant current power supply, charging the air-cooled hydrogen fuel cell to be detected with constant current density, continuously collecting the voltage of each single cell by using a voltage inspector, recording the voltage of each single cell in real time by using a data processing computer until the voltage of one single cell with the lowest voltage is more than or equal to 0.45V, stopping charging, and finishing the first data collection;
(5) repeating the steps (3) and (4) to finish the second and third data acquisition, wherein the current magnitude or the current density magnitude used in the step (4) is different in the three data acquisition processes;
(6) according to the relation between the voltage and the time in each charging process of any single battery obtained in the steps (4) and (5), drawing a voltage-time (V-t) relation curve, solving a first derivative of the curve to obtain a voltage change rate-time (dV/dt-t) relation curve, and further converting to obtain a voltage change rate-voltage (dV/dt-V) relation curve as the time and the voltage are in one-to-one correspondence;
(7) taking the voltage change rate-voltage (dV/dt-V) relation curve obtained by three times of data acquisition (namely under three times of different charging current densities)Rate of Voltage Change at 0.4V (dV/dt)i,i＝1,2,3Plotting the charging current density-voltage rate of change (I)CdV/dt) curve, then linear fitting to obtain a straight line at ICThe intercept on the axis (charging current density) is the equivalent hydrogen permeation current density I of the corresponding single cellH；
(8) According to step (7) obtained IHPlotting the charging transient capacitance-voltage ((I)C-IH) dt/dV-V) curve, corresponding to the charge transient capacitance (I) at 0.4VC-IH) dt/dV value is the electric double layer capacitance C of the corresponding celldl(ii) a According to this curve, the electric double layer capacitance (C) is subtracted from the charge transient capacitanceTo-Cdl) Performing integral operation in the range of 0.1-0.4V to obtain the hydrogen desorption electric quantity Q of the corresponding single celld；
(9) According to the formula ECSA ═ Qd/(qPt×LPt) The electrochemically active area ECSA of the corresponding single cell can be calculated, wherein qPtRepresents the electric quantity L required by the surface of the clean and smooth platinum electrode per unit area to completely cover a monolayer of hydrogen atomsPtRepresents the platinum loading of the membrane electrode;
(10) according to the voltage linear transition V and the charging current density I at the moment when the constant-current charging is started in the step (4)CThe ohmic internal resistance R of the corresponding single cell can be obtainedO＝V/IC，
The device comprises a detection box (1), a constant current power supply (2), an ammeter (3), an electronic load (4), a multi-channel voltage inspection device (5), a data processing computer (6), a hydrogen humidifying heater (7) and an air-cooled hydrogen fuel cell (8) to be detected, wherein the detection box comprises a box body (9), a detection box door (10), a lead outlet (11), a hydrogen pipeline inlet and outlet (12), a top air outlet (13) and a bottom air inlet (14).
2. The detection method according to claim 1, characterized in that: all the steps can be manually operated and data can be manually processed, and the operation can be controlled by a computer program and the data can be automatically processed by a computer.
3. The detection method according to claim 1, characterized in that: in the step (1), the hydrogen introduced into the anode (hydrogen) gas path is humidified and heated hydrogen.
4. The detection method according to claim 1, characterized in that: in the step (1), high-purity nitrogen is continuously introduced into an air inlet of the detection box, and positive pressure is kept in the detection box.
5. The apparatus of claim 1, wherein: the lead outlet, the hydrogen pipeline inlet and outlet and the detection box door on the detection box wall are provided with sealing rings, sealing glue or sealing strips or other sealing materials for ensuring the air tightness; and a manual valve or an electromagnetic valve is arranged at the air outlet at the top and the air inlet at the bottom of the detection box.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112886037A (en) * | 2021-02-02 | 2021-06-01 | 清华大学 | Multi-membrane electrode multi-parameter synchronous detection method and device for fuel cell stack |
| CN113782786A (en) * | 2021-08-25 | 2021-12-10 | 同济大学 | Fuel cell stack hydrogen permeation current in-situ detection method and device |
| CN114373967A (en) * | 2021-12-06 | 2022-04-19 | 同济大学 | Method for measuring hydrogen permeation quantity of fuel cell stack |
| US11933858B2 (en) | 2021-02-02 | 2024-03-19 | Tsinghua University | Method and apparatus for simultaneous detection of a plurality of parameters of a plurality of membrane electrode assemblies of fuel cell stack |
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2020
- 2020-06-04 CN CN202010488405.XA patent/CN111525158A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112886037A (en) * | 2021-02-02 | 2021-06-01 | 清华大学 | Multi-membrane electrode multi-parameter synchronous detection method and device for fuel cell stack |
| US11933858B2 (en) | 2021-02-02 | 2024-03-19 | Tsinghua University | Method and apparatus for simultaneous detection of a plurality of parameters of a plurality of membrane electrode assemblies of fuel cell stack |
| CN113782786A (en) * | 2021-08-25 | 2021-12-10 | 同济大学 | Fuel cell stack hydrogen permeation current in-situ detection method and device |
| CN113782786B (en) * | 2021-08-25 | 2023-07-04 | 同济大学 | In-situ detection method and device for hydrogen permeation current of fuel cell stack |
| CN114373967A (en) * | 2021-12-06 | 2022-04-19 | 同济大学 | Method for measuring hydrogen permeation quantity of fuel cell stack |
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