CN112436165A - Activation testing method for high-temperature proton exchange membrane fuel cell stack - Google Patents
Activation testing method for high-temperature proton exchange membrane fuel cell stack Download PDFInfo
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- CN112436165A CN112436165A CN202011176180.0A CN202011176180A CN112436165A CN 112436165 A CN112436165 A CN 112436165A CN 202011176180 A CN202011176180 A CN 202011176180A CN 112436165 A CN112436165 A CN 112436165A
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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
- H01M8/04544—Voltage
- H01M8/04559—Voltage 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
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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
- H01M8/0432—Temperature; Ambient temperature
- H01M8/04365—Temperature; Ambient temperature of other components of a fuel cell or 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
- H01M8/04604—Power, energy, capacity or load
- H01M8/04619—Power, energy, capacity or load of fuel cell stacks
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- 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
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Abstract
The invention relates to an activation test method of a high-temperature proton exchange membrane fuel cell stack, which comprises the steps of installing the assembled high-temperature proton exchange membrane fuel cell stack in a high-temperature fuel cell system; starting a high-temperature fuel cell system, and activating a high-temperature proton exchange membrane fuel cell stack; and after the activation is finished, closing the high-temperature fuel cell system. The activation test method of the high-temperature proton exchange membrane fuel cell stack is suitable for the activation of the high-temperature proton exchange membrane fuel cell stack with the working temperature of 120-200 ℃, and the activation of the high-temperature proton exchange membrane fuel cell stack is directly completed in a high-temperature fuel cell system by adopting on-line hydrogen production, so that the link of building an activation test platform can be omitted; and the reformed gas generated by the high-temperature reforming of the methanol aqueous solution is used as the activation fuel, so that the activation efficiency is improved, the activation time is shortened, the consumption of hydrogen is reduced, and the activation cost is reduced compared with the case that pure hydrogen is used as the activation fuel.
Description
Technical Field
The invention relates to the technical field of activation test, in particular to an activation test method for a high-temperature proton exchange membrane fuel cell stack.
Background
Proton exchange membrane fuel cells can be divided into low-temperature and high-temperature proton exchange membrane fuel cells according to different use temperatures. The former is usually used at a temperature not exceeding 100 ℃ and the proton conducting medium is water, while the latter is used at a temperature ranging from 100 to 200 ℃ and the proton conducting medium is usually a non-aqueous protic solvent. The high-temperature proton exchange membrane fuel cell has the advantages of high electrochemical reaction activity, no water management system, simple heat management system, high CO tolerance and the like, and has wide application prospect in the industries of automobiles, energy generation, aerospace, household power supplies and the like. The high-temperature proton exchange membrane fuel cell can use methanol aqueous solution as fuel in the system due to high CO tolerance, and reformed gas generated by on-line reforming is directly introduced into the electric pile without a special CO removal process. The system is simplified, and the methanol water solution which is wide in source and convenient to carry is used as fuel, so that the purification and storage processes of hydrogen are omitted.
After the high-temperature proton exchange membrane fuel cell stack is assembled and molded, the performance of the high-temperature proton exchange membrane fuel cell stack needs to be activated to ensure that the performance of the stack reaches the optimal state for use, and meanwhile, the performance of the stack is detected to meet the delivery requirement. The activation test process of the existing high-temperature proton exchange membrane fuel cell stack generally uses pure hydrogen as fuel, and the high-temperature proton exchange membrane fuel cell stack runs for a long time in a constant current discharge mode until the performance of the fuel cell stack reaches a stable state, and the activation time is usually 50-100 hours. For a high-temperature fuel cell stack using reformed gas as fuel, because pure hydrogen is used for activation, an activation test platform needs to be additionally built, on one hand, building the activation test platform and using a large number of hydrogen cylinders needs large-area occupation, and on the other hand, the investment of equipment and the consumption of pure hydrogen fuel cause higher cost of stack activation.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to solve the problems in the background technology, the activation test method of the high-temperature proton exchange membrane fuel cell stack is provided, is suitable for the activation of the high-temperature proton exchange membrane fuel cell stack with the working temperature of 120-200 ℃, and can save the link of building an activation test platform because the activation of the high-temperature proton exchange membrane fuel cell stack is directly completed in a high-temperature fuel cell system by adopting on-line hydrogen production; and the reformed gas generated by the high-temperature reforming of the methanol aqueous solution is used as the activation fuel, so that the activation efficiency is improved, the activation time is shortened, the consumption of hydrogen is reduced, and the activation cost is reduced compared with the case that pure hydrogen is used as the activation fuel.
The technical scheme adopted by the invention for solving the technical problems is as follows: an activation test method for a high-temperature proton exchange membrane fuel cell stack comprises the following steps: s1, starting the high-temperature fuel cell system, when the temperature of the high-temperature proton exchange membrane fuel cell stack rises to 110-160 ℃, introducing reformed gas into the anode of the high-temperature proton exchange membrane fuel cell stack, introducing dry air into the cathode of the high-temperature proton exchange membrane fuel cell stack, and gradually loading current through a direct current load until the current density reaches 0.1A/cm2(ii) a S2, when the temperature of the high-temperature proton exchange membrane fuel cell stack rises to 120-200 ℃, gradually loading current through a direct current load until the current density reaches 0.2-0.3A/cm2And continuously running for 0.5-1 h under the current density in a constant current discharge mode; s3, gradually loading current through the direct current load until the current density reaches 0.4-0.6A/cm2And continuously running for 0.5-1 h under the current density in a constant current discharge mode; s4, detecting the voltage or output power of the high-temperature proton exchange membrane fuel cell stack, if the voltage is lower than the preset voltage or the output power is lower than the preset power, repeating the step S2 and the step S3 in sequence, otherwise, completing activation; and S5, after the activation is completed, closing the high-temperature fuel cell system.
Further, in the above technical solution, before S1, the assembled high-temperature pem fuel cell stack needs to be installed in a high-temperature fuel cell system.
Specifically, in the above technical solution, the method for installing the assembled high temperature pem fuel cell stack in the high temperature fuel cell system includes connecting the high temperature pem fuel cell stack in the high temperature fuel cell system with the reformed gas, air and coolant channels, and connecting the high temperature pem fuel cell stack with the dc load.
Further, in the above technical solution, the reformed gas is generated by high-temperature reforming of a methanol aqueous solution.
Further, in the above technical solution: the molar ratio of methanol to water in the methanol aqueous solution is 1: 1-1: 2.
further, in the above technical solution, the coolant in the coolant channel is an organic liquid with a boiling point higher than the operating temperature of the high-temperature pem fuel cell stack.
Further, in the above technical solution, the stoichiometric ratio of the reformed gas is 1.1 to 2.5.
Further, in the technical scheme, the stoichiometric ratio of the air is 1.1-5.
Specifically, in the above technical solution, the method for shutting down the high temperature fuel cell system after the activation of S5 is completed includes the following steps: s11, gradually reducing the load current to 0 ampere through the direct current load, and then closing the supply of the methanol water solution; and S22, after cooling, continuously blowing the cathode of the high-temperature proton exchange membrane fuel cell stack for 30-60 min by using air, and then closing the high-temperature fuel cell system.
The invention has the beneficial effects that: the activation test method of the high-temperature proton exchange membrane fuel cell stack provided by the invention is suitable for the activation of the high-temperature proton exchange membrane fuel cell stack with the working temperature of 120-200 ℃, and the activation of the high-temperature proton exchange membrane fuel cell stack is directly completed in a high-temperature fuel cell system by adopting on-line hydrogen production, so that the link of building an activation test platform can be omitted; and the reformed gas generated by the high-temperature reforming of the methanol aqueous solution is used as the activation fuel, so that the activation efficiency is improved, the activation time is shortened, the consumption of hydrogen is reduced, and the activation cost is reduced compared with the case that pure hydrogen is used as the activation fuel.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic diagram of load current versus time during activation of a cell stack according to an embodiment of the present invention;
FIG. 2 is a graph showing the relationship between the applied voltage and the time during the activation of the cell stack according to the embodiment of the present invention;
FIG. 3 is a schematic of the loading current versus time during activation of a comparative example cell stack in accordance with the present invention;
FIG. 4 is a graph showing the relationship between the applied voltage and the time during the activation of the stack of the comparative example cell in accordance with the present invention;
FIG. 5 is a graph showing current-voltage polarization curves of the activation of the stacks of the examples and comparative examples of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention discloses an activation testing method of a high-temperature proton exchange membrane fuel cell stack, which comprises the following steps: s1, starting the high-temperature fuel cell system, when the temperature of the high-temperature proton exchange membrane fuel cell stack rises to 110-160 ℃, introducing reformed gas into the anode of the high-temperature proton exchange membrane fuel cell stack, introducing dry air into the cathode of the high-temperature proton exchange membrane fuel cell stack, and gradually loading current through a direct current load until the current density reaches 0.1A/cm2(ii) a S2, when the temperature of the high-temperature proton exchange membrane fuel cell stack rises to 120-200 ℃, gradually loading current through a direct current load until the current density reaches 0.2-0.3A/cm2And continuously running for 0.5-1 h under the current density in a constant current discharge mode; s3, gradually loading current through the direct current load until the current density reaches 0.4-0.6A/cm2And continuously running for 0.5-1 h under the current density in a constant current discharge mode; s4 testing high-temperature proton exchange membrane fuelIf the voltage or the output power of the battery cell stack is lower than the preset voltage or the output power is lower than the preset power, sequentially repeating the step S2 and the step S3, otherwise, completing activation; and S5, after the activation is completed, closing the high-temperature fuel cell system.
Before S1, the assembled high-temperature pem fuel cell stack needs to be installed in a high-temperature fuel cell system. The method for installing the assembled high-temperature proton exchange membrane fuel cell stack in the high-temperature fuel cell system comprises the steps of connecting the high-temperature proton exchange membrane fuel cell stack in the high-temperature fuel cell system with a reformed gas channel, an air channel and a cooling liquid channel, and connecting the high-temperature proton exchange membrane fuel cell stack with a direct-current load. The reformed gas is generated by high-temperature reforming of a methanol aqueous solution. The molar ratio of methanol to water in the methanol aqueous solution is 1: 1-1: 2. the cooling liquid in the cooling liquid channel is organic liquid with the boiling point higher than the working temperature of the high-temperature proton exchange membrane fuel cell stack. The stoichiometric ratio of the reformed gas is 1.1-2.5. The stoichiometric ratio of air is 1.1-5. After the activation of S5 is completed, the method for shutting down the high temperature fuel cell system includes the steps of: s11, gradually reducing the load current to 0 ampere through the direct current load, and then closing the supply of the methanol water solution; and S22, after cooling, continuously blowing the cathode of the high-temperature proton exchange membrane fuel cell stack for 30-60 min by using air, and then closing the high-temperature fuel cell system.
Examples of activation processes using the present application are as follows:
in this embodiment, taking online activation of a newly assembled 5kW high temperature pem fuel cell stack as an example, the specific activation steps are as follows: s1: the assembled 5kW high-temperature proton exchange membrane fuel cell stack is formed by connecting 100 monocells in series, and the effective area of an electrode is 180cm2(ii) a The high-temperature proton exchange membrane fuel cell stack is arranged in a high-temperature fuel cell system, is connected with a reformed gas channel, an air channel and a cooling liquid channel, and is connected with a direct-current load; s2: starting the system, when the temperature of the high-temperature proton exchange membrane fuel cell stack rises to 120 ℃, introducing reformed gas into the anode of the high-temperature proton exchange membrane fuel cell stack, wherein the stoichiometric ratio of the reformed gas to the anode is 1.2, and the cathode of the high-temperature proton exchange membrane fuel cell stackIntroducing dry air into the electrode, wherein the stoichiometric ratio of the electrode is 2, gradually loading current to 18A through a direct current load, and continuously operating in a constant current mode under the current until the temperature of the high-temperature proton exchange membrane fuel cell stack rises to 160 ℃; s3: adjusting the flow rates of the reformed gas and the air respectively to be 1.2 and 2 in stoichiometric ratio, then gradually loading the current to 36 amperes through a direct current load, and continuously operating for 0.5 hour under the current in a constant current discharge mode; adjusting the flow rates of the reformed gas and the air, wherein the stoichiometric ratio of the reformed gas and the air is 1.2 and 2 respectively, gradually loading the current to 72 amperes through a direct current load, and continuously operating for 0.5 hour under the current in a constant current discharge mode; s4: and (3) detecting the voltage or the output power of the high-temperature proton exchange membrane fuel cell stack while activating, if the voltage is lower than the preset voltage or the output power is lower than the preset power, repeating the step (3), otherwise, completing the activation of the high-temperature proton exchange membrane fuel cell stack. S5: after activation of the high-temperature proton exchange membrane fuel cell stack is completed, the load current is reduced to 0 ampere, the supply of the methanol aqueous solution is closed, the temperature is reduced, and the cathode is stopped after continuously purging for 60min by using air.
In the activation process of the examples, the applicant observed the activation process by recording the current and the voltage, and obtained a current-time relationship diagram such as fig. 1 and a voltage-time relationship diagram such as fig. 2.
The comparative examples using the existing activation method are as follows:
step 1: the assembled 5kW high-temperature proton exchange membrane fuel cell stack consists of 100 monocells connected in series, and the effective area of an electrode is 180cm2(ii) a The device is arranged on an activation platform, is connected with hydrogen, air and a cooling liquid channel, and connects a high-temperature proton exchange membrane fuel cell stack with a direct-current load; step 2: heating the high-temperature proton exchange membrane fuel cell stack, introducing hydrogen into the anode of the high-temperature proton exchange membrane fuel cell stack when the temperature of the high-temperature proton exchange membrane fuel cell stack rises to 120 ℃, wherein the stoichiometric ratio of the hydrogen to the anode is 1.2, introducing dry air into the cathode of the high-temperature proton exchange membrane fuel cell stack, the stoichiometric ratio of the hydrogen to the cathode is 2, gradually loading current to 36A through a direct-current load, slowly raising the temperature of the stack to 160 ℃, and discharging at a constant currentThe mode is continuously operated for 100 hours under the conditions of 36A and 160 ℃ or until the voltage is stably output; and step 3: and stopping the electric pile after the activation of the electric pile is finished.
In the process of carrying out the activation of the comparative example, the applicant observed the activation process by recording the current and the voltage, and obtained a current-time relationship diagram such as fig. 3 and a voltage-time relationship diagram such as fig. 4.
Comparison of examples using the activation method of the present application with comparative examples using existing activation methods:
as shown in fig. 5, it can be seen from the current-voltage polarization curve after the cell stack is activated by different methods that the methanol-water reforming on-line activation of the cell stack by changing the load can achieve the effect similar to the long-time small-current discharge activation of pure hydrogen. Namely, the galvanic pile after reforming activation and pure hydrogen activation are respectively adopted, and when 90A discharges, the power of the galvanic pile can respectively reach 5.004kW and 5.015 kW.
To sum up, the activation method of this application is applicable to the activation that operating temperature is 120 ~ 200 ℃ high temperature proton exchange membrane fuel cell pile, the method that adopts online hydrogen manufacturing directly accomplishes the activation of high temperature proton exchange membrane fuel cell pile in high temperature fuel cell system, save the link of setting up activation test platform, and adopt the reformed gas that methanol aqueous solution high temperature reforming generated as the activation fuel, compare pure hydrogen as the activation fuel, the activation efficiency has been improved, the activation time has been reduced, and then the consumption of hydrogen has been reduced, the activation cost has been reduced.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention are equivalent to or changed within the technical scope of the present invention.
Claims (9)
1. An activation test method for a high-temperature proton exchange membrane fuel cell stack is characterized by comprising the following steps: s1, starting the high-temperature fuel cell system, and waiting for the temperature of the high-temperature proton exchange membrane fuel cell stack to rise to the target temperature 1At 10-160 deg.c, reformed gas is introduced into the anode of the high temperature proton exchange film fuel cell pile, dry air is introduced into the cathode of the high temperature proton exchange film fuel cell pile, and current is loaded gradually through DC load until the current density reaches 0.1A/cm2(ii) a S2, when the temperature of the high-temperature proton exchange membrane fuel cell stack rises to 120-200 ℃, gradually loading current through a direct current load until the current density reaches 0.2-0.3A/cm2And continuously running for 0.5-1 h under the current density in a constant current discharge mode; s3, gradually loading current through the direct current load until the current density reaches 0.4-0.6A/cm2And continuously running for 0.5-1 h under the current density in a constant current discharge mode; s4, detecting the voltage or output power of the high-temperature proton exchange membrane fuel cell stack, if the voltage is lower than the preset voltage or the output power is lower than the preset power, repeating the step S2 and the step S3 in sequence, otherwise, completing activation; and S5, after the activation is completed, closing the high-temperature fuel cell system.
2. The activation testing method of a high temperature pem fuel cell stack of claim 1, wherein: before S1, the assembled high-temperature pem fuel cell stack needs to be installed in a high-temperature fuel cell system.
3. The activation testing method of a high temperature pem fuel cell stack of claim 2, wherein: the method for installing the assembled high-temperature proton exchange membrane fuel cell stack in the high-temperature fuel cell system comprises the steps of connecting the high-temperature proton exchange membrane fuel cell stack in the high-temperature fuel cell system with a reformed gas channel, an air channel and a cooling liquid channel, and connecting the high-temperature proton exchange membrane fuel cell stack with a direct-current load.
4. The activation testing method of a high temperature pem fuel cell stack of claim 3, wherein: the reformed gas is generated by high-temperature reforming of a methanol aqueous solution.
5. The activation testing method of a high temperature pem fuel cell stack of claim 4, wherein: the molar ratio of methanol to water in the methanol aqueous solution is 1: 1-1: 2.
6. the activation testing method of a high temperature pem fuel cell stack of claim 3, wherein: the cooling liquid in the cooling liquid channel is organic liquid with the boiling point higher than the working temperature of the high-temperature proton exchange membrane fuel cell stack.
7. The activation testing method of a high temperature pem fuel cell stack of claim 3, wherein: the stoichiometric ratio of the reformed gas is 1.1-2.5.
8. The activation testing method of a high temperature pem fuel cell stack of claim 3, wherein: the stoichiometric ratio of the air is 1.1-5.
9. The activation testing method of a high temperature pem fuel cell stack of claim 1, wherein: after the activation of S5 is completed, the method for shutting down the high temperature fuel cell system includes the following steps: s11, gradually reducing the load current to 0 ampere through the direct current load, and then closing the supply of the methanol water solution; and S22, after cooling, continuously blowing the cathode of the high-temperature proton exchange membrane fuel cell stack for 30-60 min by using air, and then closing the high-temperature fuel cell system.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116338261A (en) * | 2023-03-29 | 2023-06-27 | 广东佛燃科技有限公司 | Low-power high-temperature solid oxide fuel cell stack test system |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116338261A (en) * | 2023-03-29 | 2023-06-27 | 广东佛燃科技有限公司 | Low-power high-temperature solid oxide fuel cell stack test system |
| CN116338261B (en) * | 2023-03-29 | 2024-03-26 | 广东佛燃科技有限公司 | Low-power high-temperature solid oxide fuel cell stack test system |
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Application publication date: 20210302 |