CN108963301B - Method for cold starting proton exchange membrane fuel cell and fuel cell power generation system - Google Patents
Method for cold starting proton exchange membrane fuel cell and fuel cell power generation system Download PDFInfo
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- CN108963301B CN108963301B CN201710353112.9A CN201710353112A CN108963301B CN 108963301 B CN108963301 B CN 108963301B CN 201710353112 A CN201710353112 A CN 201710353112A CN 108963301 B CN108963301 B CN 108963301B
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- 239000000446 fuel Substances 0.000 title claims abstract description 154
- 239000012528 membrane Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000010248 power generation Methods 0.000 title claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 86
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000001257 hydrogen Substances 0.000 claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 54
- 239000001301 oxygen Substances 0.000 claims description 33
- 229910052760 oxygen Inorganic materials 0.000 claims description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000004891 communication Methods 0.000 claims description 21
- 238000001514 detection method Methods 0.000 claims description 20
- 230000008859 change Effects 0.000 claims description 14
- 239000012530 fluid Substances 0.000 claims description 13
- 238000012546 transfer Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 210000004027 cell Anatomy 0.000 description 125
- 238000003411 electrode reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
- H01M8/04225—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells during start-up
-
- 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
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04014—Heat exchange using gaseous fluids; Heat exchange by combustion of reactants
- H01M8/04022—Heating by combustion
-
- 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
-
- 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
- H01M8/04634—Other electric variables, e.g. resistance or impedance
- H01M8/04649—Other electric variables, e.g. resistance or impedance of fuel cell stacks
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- 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 application discloses a method for cold starting a proton exchange membrane fuel cell, comprising: when the proton exchange membrane fuel cell can not be started normally, preparing to enter a cold start program, and comprising the following steps: step a: providing hydrogen gas to a gas inlet of an anode of the pem fuel cell and excess air to a gas inlet of a cathode; step b: providing hydrogen to a gas inlet of the cathode; step c: detecting whether an exit condition occurs or not, and if so, ending the cold start program; if not, returning to execute the step a; the exit condition is selected from at least one of the conditions that the internal temperature of the proton exchange membrane fuel cell is greater than zero and the resistance value of the proton exchange membrane fuel cell is close to the resistance value of the proton exchange membrane fuel cell in the ice-free state at zero. The application also discloses a fuel cell power generation system.
Description
Technical Field
The present application relates to a method for cold starting a proton exchange membrane fuel cell and a fuel cell power generation system.
Background
Proton exchange membrane fuel cells have great promise as a clean, efficient energy conversion device. The problem of low-temperature start-up of a pem fuel cell is critical to its suitability for low-temperature environments. In order to improve the cold start capability of the pem fuel cell, the general strategy includes the following ways: firstly, a fuel cell component material with low specific heat capacity is selected, so that the heat required by the fuel cell is reduced when the temperature is raised to the same temperature; secondly, when the fuel cell is stopped, residual moisture in the fuel cell is blown away or removed by other means as much as possible, so that the moisture only exists in the proton exchange membrane in a non-freezable water state; and thirdly, the fuel cell is operated at low electrical efficiency during starting, so that most energy is converted into heat to heat the fuel cell.
Although the above measures can significantly improve the cold start characteristics of the pem fuel cell, the above measures still cannot satisfy the cold start requirement when the temperature is extremely low (e.g., as low as-30 degrees). At this time, a rapid heating method is required.
The current rapid heating methods mainly comprise an external heating method, such as a method of catalytic combustion heating by using external hydrogen; a method of heating by compressed air; there are methods of using an external battery to supply electrical heating; such as a method of heating by using electricity generated by the fuel cell itself; the external heating method and the fuel cell self-power generation heating method not only require separate addition of additional equipment, but also fail to satisfy the requirement of rapidly raising the temperature of the fuel cell within several seconds. In addition, internal heating methods can also be adopted, such as direct internal contact reaction of hydrogen and oxygen, and hydrogen loaded in the cathode of the fuel cell is the heat generated by the hydrogen-oxygen reaction of the cathode side of the fuel cell. However, the mixing reaction of hydrogen and oxygen (air) is easy to cause explosion, so how to effectively control the concentration of hydrogen and oxygen, and not to reduce the heating effect while ensuring the safety is always a difficult point of the internal heating method.
Therefore, an effective method for cold starting a pem fuel cell that enables the pem fuel cell to start smoothly and achieve normal current output even in a relatively low temperature operating environment is needed. There is also a need for a fuel cell power generation system.
Disclosure of Invention
It is an object of the present application to provide a method for cold starting a proton exchange membrane fuel cell.
It is another object of the present application to provide a fuel cell power generation system.
A method for cold starting a proton exchange membrane fuel cell of the present application, comprising:
when the proton exchange membrane fuel cell can not be started normally, preparing to enter a cold start program, and comprising the following steps:
step a: providing hydrogen gas to a gas inlet of an anode of the pem fuel cell and excess air to a gas inlet of a cathode;
step b: providing hydrogen to a gas inlet of the cathode;
step c: detecting whether an exit condition occurs or not, and if so, ending the cold start program; if not, returning to execute the step a;
the exit condition is selected from at least one of the conditions that the internal temperature of the proton exchange membrane fuel cell is greater than zero and the resistance value of the proton exchange membrane fuel cell is close to the resistance value of the proton exchange membrane fuel cell in an internal ice-free state at zero.
In step a of the present application, providing excess air to the gas inlet of the cathode means providing a stoichiometric excess of air relative to the electrode reaction of the pem fuel cell.
Alternatively, although air is preferably provided, other oxygen-containing gases or pure oxygen may be used in place of air. Other oxygen-containing gases such as gas mixtures consisting of oxygen and other gases that do not participate in or affect the electrode reactions.
In the present application, the internal temperature of the fuel cell may be monitored and measured using a temperature detection device (e.g., a thermometer) provided inside the fuel cell; the resistance value of the fuel cell can be monitored and measured using an impedance measuring device provided inside the fuel cell. Other ways of measuring temperature and resistance known to those skilled in the art may also be used in the present application.
In the present application, the resistance value of the pem fuel cell in the zero-degree internal ice-free state is directly related to the total power of the fuel cell, and the size of the electrodes, and can be determined by those skilled in the art according to the fuel cell used.
Alternatively, when at least one condition selected from the group consisting of the concentration of hydrogen at a position (at an arbitrarily selected position) in the anode, the concentration of oxygen at a position (at an arbitrarily selected position) in the cathode, and the voltage of the pem fuel cell does not change with time, the implementation of step a is stopped and the implementation of step b is started.
Optionally, a time for performing the step a each time is preset, and when the time is reached, the step a is stopped and the step b is started.
Alternatively, when at least one of the oxygen concentration at a position (arbitrarily selected one position) within the cathode and the voltage of the pem fuel cell does not change with time, the implementation of step b is stopped and the implementation of step c is started.
Presetting time for implementing the step b each time, and stopping implementing the step b and starting implementing the step c when the time is up.
In the present application, the time for performing step a or step b may be preset according to the total power of the battery, the flow rate of the gas introduced, the stoichiometric ratio of the electrode reaction, and other conditions.
In the present application, a concentration sensor may be employed to measure the gas concentration; a voltage measuring device may be employed to measure the battery voltage. Other ways of measuring concentration and cell voltage known to those skilled in the art may also be used in the present application.
Optionally, in step b, the method further comprises stopping supplying air to the gas inlet of the cathode; or continue to provide air to the gas inlet of the cathode.
Optionally, in step b, the method further comprises stopping the supply of air to the gas inlet of the cathode.
Optionally, in step b, the method further comprises stopping the supply of hydrogen to the gas inlet of the anode, or continuing the supply of hydrogen to the gas inlet of the anode.
Optionally, in step b, the method further comprises stopping the supply of hydrogen to the gas inlet of the anode.
Optionally, an auxiliary heating step is added before step a, between step a and step b or after step b. Battery-assisted heating methods commonly used in the art may be suitably employed in the present application, such as by heating a coolant flowing through the battery, disposing a heating resistor element within the battery, and the like.
Optionally, when step a and/or step b are/is performed, the gas outlet of the anode and the gas outlet of the cathode may be closed or not.
Optionally, the time for each implementation of step a is less than 3 seconds.
Optionally, the time for each implementation of step b is less than 3 seconds.
The present application provides a fuel cell power generation system including:
a pem fuel cell stack comprised of a plurality of pem fuel cells, said pem fuel cell stack comprising an anode, a cathode, a pem and a bipolar plate (optionally including other conventional components of the pem fuel cell stack);
the detection device is used for detecting the internal temperature of the proton exchange membrane fuel cell stack and/or the resistance value of the proton exchange membrane fuel cell stack;
a first delivery line having one end in communication with a hydrogen source and another end in fluid communication with a gas inlet of an anode of the pem fuel cell stack;
a second delivery line having one end in communication with an air source and the other end in fluid communication with a gas inlet of a cathode of the pem fuel cell stack;
a third delivery line in fluid communication with the first delivery line and the second delivery line; and
a control system electrically connected to the PEMFC stack, the first transfer line, the second transfer line and the third transfer line;
when the control system judges that the proton exchange membrane fuel cell stack cannot be normally started and prepares to enter a cold start program according to the detection value of the detection device, the control system executes the opening and/or closing of the first conveying pipeline, the second conveying pipeline and the third conveying pipeline;
when the control system judges that an exit condition occurs according to the detection value of the detection device, the control system stops executing the opening and/or closing of the first conveying pipeline, the second conveying pipeline and the third conveying pipeline, and the cold start program is ended;
the exit condition is selected from at least one of the conditions that the internal temperature of the proton exchange membrane fuel cell is greater than zero and the resistance value of the proton exchange membrane fuel cell is close to the resistance value of the proton exchange membrane fuel cell in an internal ice-free state at zero.
In the present application, the third conveying pipeline is in fluid communication with the first conveying pipeline and the second conveying pipeline, which means that the third conveying pipeline may be disposed between the first conveying pipeline and the second conveying pipeline, and both ends of the third conveying pipeline share a part of pipelines with the first conveying pipeline and the second conveying pipeline respectively; alternatively, however, the third transport line may be a separate line, i.e., one end of the third transport line is in communication with the hydrogen source and the other end is in fluid communication with the gas inlet of the cathode of the pem fuel cell stack.
Alternatively, the detection means may comprise a temperature measuring means and an impedance measuring means.
Optionally, the control system opens the third delivery line after the first delivery line and the second delivery line are opened for a predetermined time or when at least one condition selected from the group consisting of a concentration of hydrogen at a location within the anode, a concentration of oxygen at a location within the cathode, and a voltage of the pem fuel cell does not change over time.
Optionally, the control system closes the third delivery line after the third delivery line is opened for a predetermined time or when at least one condition selected from a concentration of oxygen at a location within the cathode and a voltage of the pem fuel cell does not change over time.
The explosion limit of hydrogen in air is 4.0-75.6% (volume concentration), and the present application controls the oxygen concentration in the air introduced into the fuel cell by alternately performing the above steps a and b, thereby increasing the lower limit of the hydrogen concentration to be exploded, i.e., allowing more hydrogen to be doped into the cathode side, accelerating the hydrogen-oxygen reaction and releasing more heat, contributing to faster temperature rise, and thus shortening the cold start time.
The method for cold starting the proton exchange membrane fuel cell starts from the three-phase mixing safety of the mixed gas of hydrogen, oxygen and nitrogen, shortens the heating time, and simultaneously improves the safety and the hydrogen fuel economy.
The method for cold starting the proton exchange membrane fuel cell can meet the requirement of starting within tens of seconds at the temperature lower than zero DEG C.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
FIG. 1 is a schematic flow diagram of a process for cold starting a proton exchange membrane fuel cell in accordance with one embodiment of the present application;
FIG. 2 is an exemplary fuel cell power generation system according to one embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described in detail and completely with reference to the following specific embodiments of the present application and the accompanying drawings. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The method for cold starting a proton exchange membrane fuel cell of the present application comprises:
when the proton exchange membrane fuel cell can not be started normally, preparing to enter a cold start program, and comprising the following steps:
step a: providing hydrogen gas to a gas inlet of an anode of the pem fuel cell and excess air to a gas inlet of a cathode;
step b: providing hydrogen to a gas inlet of the cathode;
step c: detecting whether an exit condition occurs or not, and if so, ending the cold start program; if not, returning to execute the step a;
the exit condition is selected from at least one of the conditions that the internal temperature of the proton exchange membrane fuel cell is greater than zero and the resistance value of the proton exchange membrane fuel cell is close to the resistance value of the proton exchange membrane fuel cell in the internal ice-free state at zero.
In step a of the present application, providing excess air to the gas inlet of the cathode means providing a stoichiometric excess of air relative to the electrode reaction of the pem fuel cell.
Alternatively, although air is preferably provided, other oxygen-containing gases or pure oxygen may be used in place of air. Other oxygen-containing gases such as gas mixtures consisting of oxygen and other gases that do not participate in or affect the electrode reactions.
In the present application, the internal temperature of the fuel cell may be monitored and measured using a temperature detection device (e.g., a thermometer) provided inside the fuel cell; the resistance value of the fuel cell can be monitored and measured using an impedance measuring device provided inside the fuel cell. Other ways of measuring temperature and resistance known to those skilled in the art may also be used in the present application.
In the present application, the resistance value of the pem fuel cell in the zero-degree internal ice-free state is directly related to the total power of the fuel cell, and the size of the electrodes, and can be determined by those skilled in the art according to the fuel cell used.
Alternatively, when at least one condition selected from the group consisting of the concentration of hydrogen at a position (at an arbitrarily selected position) in the anode, the concentration of oxygen at a position (at an arbitrarily selected position) in the cathode, and the voltage of the pem fuel cell does not change with time, the implementation of step a is stopped and the implementation of step b is started.
Optionally, a time for performing the step a each time is preset, and when the time is reached, the step a is stopped and the step b is started.
Alternatively, when at least one of the oxygen concentration at a position (arbitrarily selected one position) within the cathode and the voltage of the pem fuel cell does not change with time, the implementation of step b is stopped and the implementation of step c is started.
Presetting time for implementing the step b each time, and stopping implementing the step b and starting implementing the step c when the time is up.
In the present application, the time for performing step a or step b may be preset according to the total power of the battery, the flow rate of the gas introduced, the stoichiometric ratio of the electrode reaction, and other conditions.
In the present application, a concentration sensor may be employed to measure the gas concentration; a voltage measuring device may be employed to measure the battery voltage. Other ways of measuring concentration and cell voltage known to those skilled in the art may also be used in the present application.
Optionally, in step b, the method further comprises stopping supplying air to the gas inlet of the cathode; or continue to provide air to the gas inlet of the cathode.
Optionally, in step b, the method further comprises stopping the supply of air to the gas inlet of the cathode.
Optionally, in step b, the method further comprises stopping the supply of hydrogen to the gas inlet of the anode, or continuing the supply of hydrogen to the gas inlet of the anode.
Optionally, in step b, the method further comprises stopping the supply of hydrogen to the gas inlet of the anode.
In the present application, the stop of the supply of air to the gas inlet of the cathode or the continuation of the supply of air to the gas inlet of the cathode and the stop of the supply of hydrogen to the gas inlet of the anode or the continuation of the supply of hydrogen to the gas inlet of the anode may be appropriately selected depending on the total power of the fuel cell, the magnitude of the introduced gas flow rate, the real-time monitored value of the gas concentration, and the like.
In addition to supplying hydrogen to the gas inlet of the anode and air to the gas inlet of the cathode for the electrode reaction, the present application introduces important additional steps: namely, by supplying hydrogen to the gas inlet of the cathode in the step b, more hydrogen is doped into the cathode side, so that the lower limit value of the hydrogen concentration to be exploded is increased, and the safety of the operation of the fuel cell is ensured; on the other hand, in addition to the electrode reaction of the fuel cell, the simultaneous supply of oxygen and hydrogen at the cathode side causes the two gases to react at the same side electrode, thereby releasing more heat, contributing to a faster temperature rise to the temperature required for normal start-up of the fuel cell, and thus shortening the time for cold start-up.
In addition, optionally, an auxiliary heating step is added before the step a is carried out, between the step a and the step b is carried out or after the step b is carried out. Battery-assisted heating methods commonly used in the art may be suitably employed in the present application, such as by heating a coolant flowing through the battery, disposing a heating resistor element within the battery, and the like.
Optionally, when step a and/or step b are/is performed, the gas outlet of the anode and the gas outlet of the cathode may be closed or not.
Optionally, the time for each implementation of step a is less than 3 seconds.
Optionally, the time for each implementation of step b is less than 3 seconds.
The present application provides a fuel cell power generation system including:
a proton exchange membrane fuel cell stack comprised of a plurality of proton exchange membrane fuel cells, the proton exchange membrane fuel cell stack comprising an anode, a cathode, a proton exchange membrane, and a bipolar plate;
the detection device is used for detecting the internal temperature of the proton exchange membrane fuel cell stack and/or the resistance value of the proton exchange membrane fuel cell stack;
a first delivery line having one end in communication with a hydrogen source and another end in fluid communication with a gas inlet of an anode of the pem fuel cell stack;
a second delivery line having one end in communication with an air source and the other end in fluid communication with a gas inlet of a cathode of the pem fuel cell stack;
a third delivery line in fluid communication with the first delivery line and the second delivery line; and
a control system electrically connected to the PEMFC stack, the first transfer line, the second transfer line and the third transfer line;
when the control system judges that the proton exchange membrane fuel cell stack cannot be normally started and prepares to enter a cold start program according to the detection value of the detection device, the control system executes the opening and/or closing of the first conveying pipeline, the second conveying pipeline and the third conveying pipeline;
when the control system judges that an exit condition occurs according to the detection value of the detection device, the control system stops executing the opening and/or closing of the first conveying pipeline, the second conveying pipeline and the third conveying pipeline, and the cold start program is ended;
the exit condition is selected from at least one of the conditions that the internal temperature of the proton exchange membrane fuel cell is greater than zero and the resistance value of the proton exchange membrane fuel cell is close to the resistance value of the proton exchange membrane fuel cell in an internal ice-free state at zero.
Optionally, the pem fuel cell stack may also include other components as are common in the art.
In the present application, the third conveying pipeline is in fluid communication with the first conveying pipeline and the second conveying pipeline, which means that the third conveying pipeline may be disposed between the first conveying pipeline and the second conveying pipeline, and both ends of the third conveying pipeline share a part of pipelines with the first conveying pipeline and the second conveying pipeline respectively; alternatively, however, the third transport line may be a separate line, i.e., one end of the third transport line is in communication with the hydrogen source and the other end is in fluid communication with the gas inlet of the cathode of the pem fuel cell stack.
Alternatively, the detection means may comprise a temperature measuring means and an impedance measuring means.
Optionally, the control system opens the third delivery line after the first delivery line and the second delivery line are opened for a predetermined time or when at least one condition selected from the group consisting of a concentration of hydrogen at a location within the anode, a concentration of oxygen at a location within the cathode, and a voltage of the pem fuel cell does not change over time.
Optionally, the control system closes the third delivery line after the third delivery line is opened for a predetermined time or when at least one condition selected from a concentration of oxygen at a location within the cathode and a voltage of the pem fuel cell does not change over time.
Understandably, the opening and closing of the first conveying pipeline and the second conveying pipeline can be controlled by the control system according to the practical application condition, so that the aim of adjusting the balance relation between the hydrogen and oxygen mixing safety and the rapid heating by controlling the introduction amount of the air and the hydrogen during the cold start is fulfilled.
The following is a schematic flow diagram of a method for cold starting a pem fuel cell of the present application as shown in fig. 1 and is explained with reference to an exemplary fuel cell power generation system of fig. 2. However, it should be understood that the method of the present application is not limited to such a specific fuel cell power generation system.
Firstly, preparation for normal starting of the proton exchange membrane fuel cell under the condition of being lower than zero degrees centigrade (such as thirty degrees centigrade below zero) is made, and whether the normal starting can be carried out is judged.
Then, if the proton exchange membrane fuel cell is judged not to be normally started according to a temperature detection device (not shown), a cold start program is entered:
step a: opening valves 7 and 1 of an anode gas inlet through a control system 9, namely opening a first conveying pipeline 10, and introducing hydrogen into a gas inlet of an anode of a proton exchange membrane fuel cell stack 8 (hereinafter referred to as a cell stack 8); opening valves 6 and 4 of the cathode gas inlet, namely opening the second conveying pipeline 11, introducing excess air into the gas inlet of the cathode of the cell stack 8, and keeping a valve 5 between the first conveying pipeline 10 and the second conveying pipeline 11 in a closed state, namely not opening the third conveying pipeline 12; during the step a, the valve 2 of the anode gas outlet and the valve 3 of the cathode gas outlet are kept closed to ensure that the heat generated by the reaction in the cell remains inside the fuel cell.
At least one of the concentration of hydrogen at a location within the anode, the concentration of oxygen at a location within the cathode, and the voltage of the stack is monitored using a concentration sensor or a voltage test device. When it is observed that the at least one condition does not change with time, or after a predetermined time, the implementation of step a is stopped and step b is ready to be started.
Step b: by means of the control system 9, keeping the valve 7 of the anode gas inlet open, but closing the valve 1 of the anode gas inlet, i.e. closing the first delivery line, the supply of hydrogen to the gas inlet of the anode is stopped; closing the valve 6 of the cathode gas inlet and stopping the supply of air to the gas inlet of the cathode; the valve 4 holding the cathode gas inlet is opened while the valve 5, i.e., the third delivery line 12, is opened, thereby supplying hydrogen gas to the gas inlet of the cathode. During the implementation of step b, the valve 2 of the anode gas outlet and the valve 3 of the cathode gas outlet may be kept closed.
At least one of a concentration of oxygen at a location within the cathode and a voltage of the stack is monitored using a concentration sensor or a voltage testing device. When it is observed that the at least one condition does not change with time, or after a predetermined time, the third delivery line 12 is closed, the execution of step b is stopped, and step c is ready to be executed.
Step c:
the internal temperature of the fuel cell is detected using a thermometer (not shown) provided inside the fuel cell.
The resistance value of the fuel cell is detected by an impedance measuring device (not shown) provided inside the fuel cell.
When the measured internal temperature of the proton exchange membrane fuel cell is higher than zero, or the resistance value of the proton exchange membrane fuel cell is close to the resistance value of the proton exchange membrane fuel cell in an internal ice-free state at zero, entering a normal starting mode; if not, returning to execute the step a until the standard is met, and starting the normal starting mode.
In another embodiment of the present application, the gas outlet valve 3 of the cathode is opened occasionally to discharge the accumulated nitrogen gas before performing step a, or between performing step a and step b, or after performing step b.
In another embodiment of the present application, an auxiliary heating step is added to accelerate cold start before step a is performed, between step a and step b is performed or after step b is performed.
Those skilled in the art will understand that the number and arrangement of the valves of the anode gas inlet, the anode gas outlet, the cathode gas inlet and the cathode gas outlet of the cell stack can be varied reasonably on the basis of fig. 1 as long as the implementation requirements of step a and step b are met.
The method of the present application and its advantages are further explained below by taking the example of a cold start 80KW automotive fuel cell stack.
According to the requirement of the U.S. department of energy, when an 80KW automobile fuel cell stack is started from minus 20 degrees, the required energy is not more than 5MJ, and when the energy consumed by starting from minus 20 degrees is less than 1MJ, the energy used for heating the fuel cell is less than 4 MJ.
Taking now an example of 3.5MJ of energy to heat the fuel cell and 45% efficiency when the fuel cell is operating at rated power, a hydrogen flow of 5.33kg/h is required for an 80KW fuel cell stack.
When the method is adopted to carry out cold start of the fuel cell for 80KW vehicles, the volume concentration of hydrogen is 9% (when the oxygen concentration is controlled to be below 4.5%) and the volume concentration of hydrogen is more than 75% (when the hydrogen is excessive, the oxygen is less than 25%, and the reactive concentration of the hydrogen is 50%), and the average value is 30%, so that the hydrogen flow is 1.6 kg/h. The high calorific value of hydrogen was 143 MJ/kg. The amount of hydrogen needed to generate 3.5MJ is 0.0245 kg. According to the flow, the required time is 55 seconds, namely, the temperature of the 80KW automobile fuel cell can be increased to be above zero in 55 seconds by the method, and cold starting is realized.
Therefore, by implementing the cold start method, the concentration of oxygen in the air introduced into the battery is controlled, so that the lower limit value of the concentration of the hydrogen to be exploded is increased, the hydrogen-oxygen reaction is accelerated, more heat is released, the temperature is increased more quickly, the cold start time is shortened, and the operation safety and the hydrogen fuel economy of the fuel cell are improved.
The above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.
Claims (7)
1. A method for cold starting a proton exchange membrane fuel cell, comprising:
when the proton exchange membrane fuel cell can not be started normally, preparing to enter a cold start program, and comprising the following steps:
step a: providing hydrogen gas to a gas inlet of an anode of the pem fuel cell and excess air to a gas inlet of a cathode;
wherein when at least one condition selected from the group consisting of the concentration of hydrogen at a position in the anode, the concentration of oxygen at a position in the cathode, and the voltage of the PEM fuel cell does not change with time, or a time preset for each execution of step a is reached, the execution of step a is stopped and step b is started,
step b: providing hydrogen to a gas inlet of the cathode;
wherein when at least one condition selected from the group consisting of the concentration of oxygen at a position within the cathode and the voltage of the PEM fuel cell does not change with time, or a time preset for each execution of step b is reached, the execution of step b is stopped and step c is started,
step c: detecting whether an exit condition occurs or not, and if so, ending the cold start program; if not, returning to execute the step a;
the exit condition is selected from at least one of the conditions that the internal temperature of the proton exchange membrane fuel cell is greater than zero and the resistance value of the proton exchange membrane fuel cell is close to the resistance value of the proton exchange membrane fuel cell in an internal ice-free state at zero,
wherein a gas outlet of the cathode is occasionally opened to discharge accumulated nitrogen gas before the step a is performed, or between the step a and the step b is performed, or after the step b is performed.
2. The method of claim 1, wherein an auxiliary heating step is added before step a is performed, between step a and step b is performed, or after step b is performed.
3. The method of claim 1, wherein the time for each performance of step a is less than 3 seconds.
4. The method of claim 1, wherein the time for each performance of step b is less than 3 seconds.
5. The method of claim 1, wherein in step b, further comprising stopping the supply of air to the gas inlet of the cathode; or continue to provide air to the gas inlet of the cathode.
6. The method of claim 1, wherein in step b, further comprising stopping or continuing to supply hydrogen to the gas inlet of the anode.
7. A fuel cell power generation system comprising:
a proton exchange membrane fuel cell stack comprised of a plurality of proton exchange membrane fuel cells, the proton exchange membrane fuel cell stack comprising an anode, a cathode, a proton exchange membrane, and a bipolar plate;
the detection device is used for detecting the internal temperature of the proton exchange membrane fuel cell stack and/or the resistance value of the proton exchange membrane fuel cell stack;
a first delivery line having one end in communication with a hydrogen source and another end in fluid communication with a gas inlet of an anode of the pem fuel cell stack;
a second delivery line having one end in communication with an air source and the other end in fluid communication with a gas inlet of a cathode of the pem fuel cell stack;
a third delivery line in fluid communication with the first delivery line and the second delivery line; and
a control system electrically connected to the PEMFC stack, the first transfer line, the second transfer line and the third transfer line;
when the control system judges that the proton exchange membrane fuel cell stack cannot be normally started and prepares to enter a cold start program according to the detection value of the detection device, the control system executes the opening and/or closing of the first conveying pipeline, the second conveying pipeline and the third conveying pipeline;
when the control system judges that an exit condition occurs according to the detection value of the detection device, the control system stops executing the opening and/or closing of the first conveying pipeline, the second conveying pipeline and the third conveying pipeline, and the cold start program is ended;
the exit condition is selected from at least one of the conditions that the internal temperature of the proton exchange membrane fuel cell stack is greater than zero and the resistance value of the proton exchange membrane fuel cell stack is close to the resistance value of the proton exchange membrane fuel cell stack in the ice-free state at zero,
wherein a gas outlet of a cathode of the PEM fuel cell stack is irregularly opened to discharge accumulated nitrogen gas after the control system performs opening and/or closing of the first, second, and third transfer lines,
wherein the control system opens the third delivery line after the first delivery line and the second delivery line are opened for a predetermined time or when at least one condition selected from the group consisting of a concentration of hydrogen at a location in the anode, a concentration of oxygen at a location in the cathode, and a voltage of the PEM fuel cell does not change with time,
wherein the control system closes the third delivery line after the third delivery line is opened for a predetermined time or when at least one condition selected from a concentration of oxygen at a location within the cathode and a voltage of the PEM fuel cell does not change over time.
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| CN111470880A (en) * | 2019-01-23 | 2020-07-31 | 元创绿能科技股份有限公司 | Ion exchange membrane with multiple pores and manufacturing method thereof |
| CN110492136A (en) * | 2019-09-11 | 2019-11-22 | 同济大学 | One proton exchanging film fuel battery blow device and method |
| CN110828864B (en) * | 2019-11-01 | 2021-02-19 | 中车工业研究院有限公司 | Non-auxiliary starting method and system for hydrogen-oxygen electrochemical reaction device |
| CN112825361A (en) * | 2019-11-21 | 2021-05-21 | 上海德威明兴新能源科技有限公司 | Water/heat balance method for fuel cell |
| CN111082103B (en) * | 2019-12-31 | 2021-08-20 | 上海神力科技有限公司 | Low-temperature self-starting method of fuel cell system |
| CN113206277B (en) * | 2021-04-12 | 2022-04-22 | 中国科学院大连化学物理研究所 | Low-temperature quick self-starting method and system for fuel cell |
| CN116666689B (en) * | 2023-08-01 | 2023-12-08 | 山东美燃氢动力有限公司 | Low-temperature cold start control method of fuel cell system and fuel cell system |
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| CN101170194A (en) * | 2006-10-27 | 2008-04-30 | 新源动力股份有限公司 | A method for proton exchange film fuel battery under zero degree |
| KR101240979B1 (en) * | 2010-11-17 | 2013-03-11 | 현대자동차주식회사 | Purge device and method for cold starting of fuel cell |
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