CN111525164B - Fuel cell regeneration control method and fuel cell system - Google Patents
Fuel cell regeneration control method and fuel cell system Download PDFInfo
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- CN111525164B CN111525164B CN202010378041.XA CN202010378041A CN111525164B CN 111525164 B CN111525164 B CN 111525164B CN 202010378041 A CN202010378041 A CN 202010378041A CN 111525164 B CN111525164 B CN 111525164B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04858—Electric variables
- H01M8/04925—Power, energy, capacity or load
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04858—Electric variables
- H01M8/04925—Power, energy, capacity or load
- H01M8/0494—Power, energy, capacity or load of fuel cell stacks
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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 provides a fuel cell regeneration control method and a fuel cell system. The regeneration control method of the fuel cell comprises the steps of starting short-circuit pulse control when the output power of the fuel cell is reduced to be smaller than the rated power; when the output power of the fuel cell stack is recovered to the rated power, the short-circuit pulse control is kept, and the debugging of the regeneration control program is finished; when the output power is still not recovered to the rated power, the anode oxygen distribution control and the galvanic pile regulation can be started in sequence. The invention also provides a fuel cell system which comprises a hydrogen supply unit, a fuel cell, a power supply controller, a filter and a water-gas separator. The regeneration control method of the fuel cell provided by the invention can regenerate the poisoned electrode catalyst caused by trace impurities, so that the original output capacity and power generation capacity of the fuel cell stack are recovered. The fuel cell system provided by the invention has high tolerance to impurity gas, and can solve the problem of tolerance of low-temperature proton exchange membrane fuel to impurity components contained in hydrogen.
Description
Technical Field
The invention relates to a fuel cell system and a control method thereof, in particular to a regeneration control method of a fuel cell and the fuel cell system.
Background
The fuel cell is a new high-efficiency electrochemical power supply device in recent years, has high power generation efficiency, stable operation, no noise, cleanness and environmental protection, and has wide application prospect in the fields of traffic, building, military, communication and the like. Fuel cells are of various types and have various technical routes. Among them, the pem fuel cell has advantages of high power density, low working temperature, good starting performance, mature technology, etc., and is the mainstream in industries such as small and medium-sized fixed power supplies, electric transportation, etc., especially in recent years, the rapid development of new energy industry makes it occupy about 90% of the main share of the fuel cell market. However, with the continuous progress of commercialization of fuel cell vehicles in recent years, the source, cost and filling facilities of ultra-pure hydrogen are becoming more and more prominent, and the problem of hydrogen supply is urgently needed.
The key of the hydrogen production technology lies in the aspects of ensuring the quality of hydrogen, improving the production efficiency, reducing the product cost, reducing the operation and maintenance difficulty, expanding the hydrogen supply range and the like. At present, among three common hydrogen production methods, namely chemical hydrogen production, hydrogen production by water electrolysis and biological hydrogen production, the chemical hydrogen production represented by steam reforming is dominant, and the raw materials of the chemical hydrogen production comprise natural gas, alcohol, petroleum gas, dimethyl ether, gasoline, diesel oil and the like. Wherein, the hydrogen production technology by reforming natural gas is the most mature and the industrial application is the most, and the higher reaction temperature is more suitable for being used as a fixed power supply or a combined heat and power device; the methanol reforming hydrogen production reaction temperature is low, the process is simple, the energy consumption is low, the methanol raw material is cheap and easy to obtain, the energy density is high, the hydrogen content is high, the storage and the transportation are convenient, and the method is suitable for being used as a modular or mobile hydrogen production device in the fields of standby power supplies, electric transportation and the like.
The large-scale application and popularization of hydrogen energy needs a complete hydrogen production and fuel cell system solution, and the in-situ preparation of hydrogen for fuel cells is an ideal technical route. The research and development of the in-situ hydrogen production fuel cell system relate to four main aspects of development of a high-efficiency hydrogen production catalyst, development of a miniaturized reactor, test and control of a fuel cell stack, integration of the in-situ hydrogen production fuel cell system and the like. Wherein, the miniaturization hydrogen production reactor is the key for realizing the high-efficiency integration with the fuel cell. Because the hydrogen concentration in the reformed hydrogen production product gas is not high and contains trace impurity gases including carbon monoxide, the realization of the stable and efficient combination of the fuel cell, especially the common low-temperature proton exchange membrane fuel cell stack and the hydrogen production device becomes a key point and a difficulty for developing an in-situ hydrogen production fuel cell system.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a fuel cell regeneration control method and a fuel cell system. The regeneration control method of the fuel cell can effectively regenerate the poisoned electrode catalyst of the fuel cell and recover the output power and the original power generation capacity of the fuel cell by starting short circuit pulse control, anode oxygen distribution control and electric pile regulation step by step.
In order to achieve the above object, the present invention provides a fuel cell regeneration control method including:
short circuit pulse control: when the output power of the fuel cell is reduced to be less than the rated power, continuously applying periodic short-circuit electric pulses to the cathode and the anode of the fuel cell;
when the output power of the fuel cell is recovered to the rated power, the short-circuit pulse control is kept, and the debugging of the regeneration control program is finished;
when the output power of the fuel cell is not restored to the rated power, the short-circuit pulse control further includes an operation of shortening the short-circuit pulse period while keeping the short-circuit pulse time constant.
In the specific embodiment of the present invention, during the stable power generation of the fuel cell, the output power of the fuel cell fluctuates with the change of the hydrogen purity and the operation parameters, and in this case, the output power is smaller than the rated power by: the average value of the output power gradually decays away from the nominal power over a specified time, which is related to the application scenario, typically in minutes. The case where the output power of the fuel cell is not restored to the rated power may include, but is not limited to: the average value of the output power of the fuel cell continues to decrease, the average value of the output power of the fuel cell does not increase (e.g., the output power fluctuates up and down or continues to be constant), and the power of the fuel cell recovers abnormally slowly (i.e., does not recover to the rated power within a specified time, which is related to an application scenario and is generally several minutes to several tens of minutes).
According to a specific embodiment of the present invention, the short pulse control achieves an impurity removal effect on the surface of the anode catalyst by increasing the anode potential. When the output power of the fuel cell is not recovered to the rated power, the short-circuit pulse control keeps the short-circuit pulse time unchanged, and the operation of shortening the short-circuit pulse period can change the idle time by keeping the pulse short-circuit time, so that the effect of changing the duty ratio is achieved.
According to a specific embodiment of the present invention, after the short-circuit pulse control is performed, when the output power of the fuel cell is not restored to the rated power, the fuel cell regeneration control method includes starting the anode oxygen distribution control while maintaining the short-circuit pulse control (i.e., maintaining the short-circuit electric pulse time and the short-circuit electric pulse period): introducing an oxidant to the anode of the fuel cell;
when the output power of the fuel cell is recovered to the rated power, the short-circuit pulse control and the anode oxygen distribution control are kept, and the debugging of the regeneration control program is finished;
when the output power of the fuel cell is not restored to the rated power, the anode oxygen distribution control may further include an operation of increasing the distribution amount of the oxidant (i.e., the proportion of the oxidant in the fuel gas) to be fed to the anode of the fuel cell.
According to the specific embodiment of the invention, the anode oxygen distribution control can achieve the purpose of removing impurities through the reaction of the oxidant and the impurities on the surface of the anode catalyst. In particular embodiments, the maximum dosing amount of oxidant may be determined by the concentration of impurities in the fuel gas.
According to a specific embodiment of the present invention, when the output power of the fuel cell is not recovered to the rated power after the anode oxygen distribution control is performed, the fuel cell regeneration control method includes starting stack regulation while maintaining the short-circuit pulse control and the anode oxygen distribution control: the working temperature, the working humidity and the working pressure of the fuel cell are improved;
when the output power of the fuel cell is recovered to the rated power, maintaining short circuit pulse control, anode oxygen distribution control and galvanic pile regulation to maintain the normal work of the fuel cell under the condition of low-quality hydrogen, and completing the debugging of a regeneration control program;
when the working temperature, the working humidity and the working pressure of the fuel cell reach the maximum values and the output power of the fuel cell is not recovered to the rated power, the short-circuit pulse control, the anode oxygen distribution control and the galvanic pile control are stopped, and the fuel gas is stopped to be introduced into the anode of the fuel cell.
In the regeneration control method of the fuel cell, the electric pile regulation and control can improve the tolerance of the electrode catalyst to impurities by improving the working temperature, the working humidity and the working pressure of the fuel cell.
According to a specific embodiment of the present invention, in the short-circuit pulse control, the period of the short-circuit electric pulse may be controlled to be 2 to 20s, preferably 3 to 10 s.
According to a particular embodiment of the invention, in the short-circuit pulse control, the time of the short-circuit electric pulse may be controlled to be 0.1 to 0.5s, preferably 0.1 to 0.2 s.
According to an embodiment of the present invention, in the short pulse control, for a given fuel cell structure and operation condition, the specific power of the short circuit potential of the cell is determined by the resistance of the external short circuit, and an external circuit structure with low resistance value is generally adopted. In a specific embodiment, the cell short-circuit potential may be controlled to 0.4V or less, preferably 0.2V or less.
According to a particular embodiment of the invention, in the anodic oxygen distribution control, the oxidant is preferably air and/or oxygen.
Anode oxygen distribution control, according to embodiments of the present invention, may include the operation of mixing an oxidant with the fuel gas used at the anode and then passing the oxidant to the anode.
According to an embodiment of the present invention, when the oxidant is air and the concentration of impurities in the fuel gas is 100ppm or less, the amount of the oxidant mixed into the fuel gas is controlled to be less than 4 vol%, preferably less than 2 vol%.
According to an embodiment of the present invention, the oxidant and the fuel gas may be mixed and then may be dehydrated to be introduced into the anode of the fuel cell.
According to an embodiment of the present invention, the operating temperature of the fuel cell in stack regulation may be controlled to 70 to 90 ℃, preferably 70 to 80 ℃.
According to an embodiment of the present invention, the operating pressure of the fuel cell in stack regulation may be controlled to be 0.1 to 0.5MPa, preferably 0.2 to 0.3 MPa.
According to an embodiment of the present invention, in the stack regulation, the operating humidity of the fuel cell may be controlled to satisfy a humidity condition that the dew-point temperature of the fuel gas of the anode of the fuel cell is equal to or lower than the operating temperature of the fuel cell.
In a specific embodiment of the present invention, the above-described fuel cell regeneration control method may include the steps of:
1. short circuit pulse: when the output power of the fuel cell is reduced to be less than the rated power, applying periodic short-circuit electric pulses to the anode and the cathode of the fuel cell, and realizing the impurity removal effect on the surface of the anode catalyst by improving the anode potential;
when the output power of the fuel cell is recovered to the rated power, the short-circuit pulse control is kept, and the debugging of the regeneration control program is finished;
when the output power of the fuel cell is not recovered to the rated power, keeping the time of the short-circuit electric pulse unchanged, gradually shortening the period of the short-circuit electric pulse until the output power of the fuel cell is recovered to the rated power, keeping the specific pulse control program, and completing the debugging of the regeneration control program.
2. Anode oxygen distribution: when the short-circuit electric pulse period is shortened to the preset shortest pulse period and the output power of the fuel cell is still not recovered to the target value, the specific pulse control program is maintained (namely the period and the time of the short-circuit pulse are maintained), and the anode oxygen distribution control is started at the same time, and the specific process comprises the following steps:
introducing an oxidant into the anode of the fuel cell according to a preset addition amount, so that the oxidant removes impurities adsorbed on the surface of the electrode catalyst, and the reaction activity of the catalyst is recovered;
when the output power of the fuel cell is recovered to the rated power, the short-circuit pulse control and the anode oxygen distribution control are kept, and the debugging of the regeneration control program is finished;
when the output power of the fuel cell is not recovered to the rated power, the short-circuit pulse control is kept, the oxidant addition amount is increased until the output power of the fuel cell is recovered to the rated power, the short-circuit pulse control and the anode oxygen distribution control are kept, and the debugging of the regeneration control program is completed.
3. Regulating and controlling the galvanic pile: when the addition of the oxidant is increased to the preset maximum value and the output power of the fuel cell is still not recovered to the rated power, the short-circuit pulse control and the anode oxygen addition control are kept, and the control of the galvanic pile is started at the same time, and the specific process comprises the following steps:
the working temperature, the working humidity and the working pressure of the fuel cell are improved, so that the tolerance of the electrode catalyst to impurities is improved;
when the output power of the fuel cell is recovered to the rated power, the short-circuit pulse control, the anode oxygen distribution control and the electric pile regulation are kept, and the debugging of the regeneration control program is finished;
when the output power of the fuel cell is not recovered to the rated power, the temperature, the humidity and the pressure are continuously increased until the output power of the fuel cell is recovered to the rated power, short-circuit pulse control, anode oxygen distribution control and galvanic pile regulation are kept, and the debugging of a regeneration control program is finished;
when the working temperature, the working humidity and the working pressure of the fuel cell reach the preset maximum values and the output power of the fuel cell still cannot be recovered to the rated power, all regeneration control programs (namely short-circuit pulse control, anode oxygen distribution control and electric pile regulation and control) are stopped, and meanwhile, fuel gas is stopped from being introduced into the anode of the fuel cell.
The invention also provides a fuel cell system, which comprises a hydrogen supply unit, a fuel cell, a power supply controller, a filter and a water-gas separator,
wherein, the hydrogen supply unit, the water-gas separator and the anode of the fuel cell are connected in sequence; the filter is provided with a first outlet connected with the inlet of the cathode of the fuel cell and a second outlet connected with the inlet of the water-gas separator; a first heat exchanger is arranged between the outlet of the hydrogen supply unit and the inlet of the water-gas separator; the power supply controller is used for detecting the output power of the fuel cell and applying short-circuit electric pulse between the anode and the cathode of the fuel cell when the output power is smaller than the rated power, and the fuel cell is provided with a second heat exchanger and a pressure regulating valve.
In the above fuel cell system, the power controller may be connected to a cathode and an anode of the fuel cell, respectively, for detecting an output power of the fuel cell. When the output power of the fuel cell is reduced to be less than the rated power, the power supply controller can also apply a short-circuit electric pulse between the anode and the cathode of the fuel cell, and the short-circuit electric pulse is used for desorbing impurities on the surface of the anode catalyst to increase the output power of the fuel cell. In some embodiments, the power controller may also be coupled to an electrical load, where the fuel cell system supplies power to the load, and the power controller is configured to control the voltage and current output by the fuel cell system to the load.
In the above fuel cell system, the second heat exchanger is used for directly adjusting the temperature of the fuel cell, and specifically, the temperature of the fuel cell can be reduced by circulating cooling water between the bipolar plates of the fuel cell. When the fuel cell generates power stably, the second heat exchanger is mainly used for cooling the fuel cell, so that the over-high temperature of the fuel cell is avoided, and the stable work of the fuel cell is ensured; at the moment, the first heat exchanger is used for cooling the fuel gas output by the hydrogen supply unit, so that the phenomenon that the temperature in the fuel cell is too high after the fuel gas enters the fuel cell is avoided. The pressure regulating valve of the fuel cell is used for regulating the working pressure of the fuel cell, and the pressure regulating valve can be arranged at the outlet of the anode and the outlet of the cathode of the fuel cell.
In a specific embodiment of the invention, an impurity sensor may be provided between the outlet of the moisture separator and the inlet of the anode of the fuel cell, the impurity sensor being for monitoring the concentration of impurities in the fuel gas. The outlet of the water-gas separator can also be connected with the inlet of the hydrogen supply unit, and the impurity sensor is positioned between the water-gas separator and the hydrogen supply unit. Specifically, a control valve (e.g., a three-way valve) may be provided between the outlet of the moisture separator and the inlet of the anode of the fuel cell and the inlet of the hydrogen supply unit, in which case the impurity sensor is located between the moisture separator and the control valve.
In the fuel cell system, when the impurity sensor monitors that the concentration of impurities in the fuel gas output by the hydrogen supply unit is lower than or equal to a set threshold value, the outlet of the water-gas separator is controlled to be communicated with the inlet of the anode of the fuel cell, and the fuel gas enters the anode to participate in electrochemical reaction; when the impurity concentration in the fuel gas monitored by the impurity sensor is higher than a set threshold value, the outlet of the water-gas separator is controlled to be communicated with the inlet of the hydrogen supply unit, and the fuel gas enters the hydrogen supply unit for cyclic utilization.
In a particular embodiment of the invention, the threshold value for the impurity concentration in the fuel gas set by the impurity sensor may be set according to the type of catalyst used and the operating conditions of the fuel cell, for example the threshold value for the impurity concentration may be lower than 300ppm (preferably lower than 100 ppm).
In a specific embodiment of the present invention, a first heater may be provided between the first outlet of the filter and the inlet of the cathode of the fuel cell, and is mainly used for preheating the oxidant supplied to the cathode when the fuel cell does not start generating electricity, thereby accelerating the preheating of the fuel cell. When the fuel cell generates power stably, the heat supply amount of the first heater to the oxidant is generally reduced, and the internal temperature of the fuel cell is prevented from being too high. Accordingly, a pump may be provided between the filter and the first heater.
In a particular embodiment of the invention, the second outlet of the filter may be connected to a passage between the outlet of the hydrogen supply unit and the inlet of the moisture separator. For example, the second outlet of the filter may be connected to a passage between the outlet of the hydrogen supply unit and the first heat exchanger. When the output power of the fuel cell is reduced below the rated power and the electric pulse control is applied to the anode and the cathode of the fuel cell by using the power controller, the output power can not be recovered to the rated power, the oxidant in the filter is added into the fuel gas produced by the hydrogen supply unit, the mixed gas of the oxidant and the fuel gas enters the anode of the fuel cell after cooling and dehydration, and the output power of the fuel cell is improved by the removing effect of the oxidant on the surface of the anode catalyst.
In a particular embodiment of the invention, the filter may further be provided with a third outlet connected to the inlet of the hydrogen supply unit. Correspondingly, a second heater can be arranged between the third outlet of the filter and the inlet of the hydrogen supply unit to preheat the oxidant flowing to the hydrogen supply unit, and a pump (such as an air pump) can be arranged between the second heater and the outlet of the filter to facilitate the oxidant to flow from the filter to the hydrogen supply unit according to a specific flow.
According to a specific embodiment of the present invention, the hydrogen supply unit may be a hydrogen production unit, or may be a low quality hydrogen source. Preferably, the hydrogen supply unit comprises a combustor and a reformer, the inlet of the hydrogen supply unit is the inlet of the combustor, the outlet of the hydrogen supply unit is the outlet of the reformer, and the outlet of the combustor is connected with the inlet of the reformer. At the moment, the outlet of the reformer is sequentially connected with the first heat exchanger and the water-gas separator; and a channel between the outlet of the reformer and the inlet of the first heat exchanger is connected with the first outlet of the filter, and the fuel gas output by the reformer and the oxidant output by the filter are mixed and then are conveyed to the anode of the fuel cell through the water-gas separator. The inlet of the burner may be connected to the third outlet of the filter so that the filter delivers the oxidant required for the combustion reaction to the burner. When a second heat supplier is arranged between the burner and the filter, the second heat supplier can preheat the oxidant and improve the combustion efficiency.
In a specific embodiment of the present invention, the first heat exchanger and the second heat exchanger may be connected to other low-temperature heat loads, and the first heat supply device and the second heat supply device may be connected to other high-temperature heat sources. Preferably, the first heat exchanger and/or the second heat exchanger are/is connected with the first heat supply device and/or the second heat supply device, so that the heat utilization rate in the system is improved.
According to a specific embodiment of the invention, the outlet of the moisture separator may be connected with a water tank for collecting water separated in the moisture separator. In some embodiments, the water tank may be provided with a plurality of water inlets respectively connected to other water sources, and the inside of the water tank is generally provided with a drain port for draining the excessive stored water and a filtering and purifying device.
According to a specific embodiment of the present invention, an evaporator may be connected to an outlet of the water tank. Accordingly, a pump (e.g., a water pump) may be disposed between the evaporator and the water tank. The evaporator may be connected to other high temperature heat sources to increase the temperature of the evaporator to vaporize water entering the evaporator.
According to the embodiment of the present invention, the outlet of the evaporator may be connected to the inlet of the cathode of the fuel cell for increasing the humidity of the cathode of the fuel cell, and at this time, the heat supply strength of the first heat supply unit 11 may be increased to cooperate with the evaporator to prevent the water vapor in the oxidant from condensing before entering the fuel cell. In some embodiments, the outlet of the evaporator may be connected to a connection channel between the first outlet of the filter and the inlet of the cathode of the fuel cell, and the water in the water tank may be pumped into the evaporator according to a set flow rate, converted into water vapor, uniformly mixed with the oxidant, and then co-introduced into the cathode of the fuel cell.
In the above fuel cell system, preferably, the fuel cell is provided with a temperature sensor for monitoring an operating temperature of the fuel cell to avoid the operating temperature of the fuel cell from being higher than a set temperature range. In some embodiments, the temperature range of the fuel cell may be controlled to be 50 to 90 ℃, preferably 60 to 80 ℃.
In the specific embodiment of the invention, the fuel gas can be a gas produced by using one or a combination of more than two of methanol, ethanol, ethylene glycol, propanol, formic acid, acetic acid, natural gas, methane, liquefied petroleum gas, dimethyl ether, gasoline and diesel oil as a raw material and through processes of hydrocarbon hydrogen production, alcohol hydrogen production, coal hydrogen production, water electrolysis hydrogen production, biological hydrogen production and the like. The impurities in the fuel gas may include one or a combination of two or more of carbon monoxide, carbon dioxide, nitrogen, argon, helium, methane, methanol, formic acid, and oxygen.
In the above fuel cell system, the fuel cell may be a low temperature proton exchange membrane fuel cell, an intermediate temperature phosphoric acid proton exchange membrane fuel cell, a phosphoric acid fuel cell, a molten carbonate fuel cell, a high temperature oxide fuel cell.
The invention has the beneficial effects that:
1. the regeneration control method of the fuel cell can effectively remove impurity molecules adsorbed on the surface of the anode catalyst of the fuel cell, effectively regenerate the poisoned electrode catalyst caused by trace impurities, and recover the original output capacity and power generation capacity of the fuel cell. When the control method can not effectively recover the performance of the fuel cell, the anode gas supply can be cut off, and the failure of the fuel cell can be prevented.
2. The regeneration control method of the fuel cell provided by the invention can improve the tolerance of the fuel cell to various impurity gases, greatly reduce the requirement of the hydrogen fuel cell on the quality of the hydrogen-containing fuel gas, effectively reduce the hydrogen cost, reduce the difficulty of hydrogen production and expand the hydrogen supply mode. The regeneration control method of the fuel cell can also realize the direct combination with a small-sized in-situ hydrogen production device, and accelerate the application and popularization of the hydrogen fuel cell technology in the fields of electric vehicles, distributed energy sources and the like.
3. The fuel cell system provided by the invention has the characteristics of simple process flow, convenience and quickness in operation, high reliability, strong self-adaptive capacity and the like, and can realize functions of miniaturization, modularization, intellectualization and the like.
4. The fuel cell system provided by the invention has high tolerance to impurity gas, can stably run under low-quality hydrogen, effectively solves the problem of tolerance of low-temperature proton exchange membrane fuel to impurity components contained in the hydrogen, and can realize stable running of the hydrogen fuel cell, especially the low-temperature proton exchange membrane fuel cell, under the condition of low-quality hydrogen or direct combination with a hydrogen production device.
Drawings
Fig. 1 is a schematic configuration diagram of a fuel cell system of example 1.
Fig. 2 is a flowchart of a fuel cell regeneration control method of embodiment 2.
Description of the symbols
The system comprises a hydrogen supply unit 1, a reformer 1a, a combustor 1b, a filter 2, a fuel cell stack 3, an anode 3a, a cathode 3b, a power controller 4, a load 5, a water-gas separator 6, a water tank 7, an evaporator 8, a second heat supplier 9, a first heat exchanger 10, a first heat supplier 11, a second heat exchanger 12, an air pump 13, an air pump 14, an air pump 15, a water pump 16, an impurity sensor 17, a temperature sensor 18, a three-way valve 19 and pressure regulating valves 20 and 21.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The present embodiment provides a fuel cell system, and fig. 1 is a schematic structural diagram of the fuel cell system. As shown in fig. 1, the fuel cell system includes a hydrogen supply unit 1, a fuel cell stack 3, a power supply controller 4, a filter 2, and a moisture separator 6. The hydrogen supply unit 1 is provided with a burner 1b and a reformer 1a inside, and an outlet of the burner 1b communicates with an inlet of the reformer 1 a. The power supply controller 4 may be connected to a load 5 to supply power to the fuel cell system.
The filter 2 is used for filtering and purifying the oxidant, and a filtering and purifying device is arranged in the filter. The oxidant filtered by the filter 2 may be air or pure oxygen, in this embodiment air is used. The first outlet of the filter 2 is connected with the inlet of the cathode 3b of the fuel cell stack 3, and an air pump 15 and a first heater 11 are sequentially arranged between the filter 2 and the cathode 3b and used for delivering the preheated oxidant to the cathode 3b of the fuel cell stack 3. A third outlet of the filter 2 is connected to an inlet of the burner 1b for feeding an oxidant to the burner 1b of the hydrogen supply unit 1. An air pump 14 and a second heater 9 are sequentially arranged between the third outlet of the filter 2 and the inlet of the burner 1b for preheating the oxidant. The second outlet of the filter 2 is also communicated with a channel between the outlet of the reformer 1a and the inlet of the water separator 6, and is used for realizing anode oxygen distribution control of the fuel cell stack 3. The second outlet of the filter 2 is provided with an air pump 13, and the outlet of the air pump 13 is communicated with a passage between the outlet of the reformer 1a and the inlet of the moisture separator 6.
The burner 1b is used to supply heat to the reformer 1 a. The combustion raw material and the oxidant are fed into the combustor 1b to undergo a combustion reaction or a combustion catalytic reaction, the exhaust gas generated by the combustion is discharged through the exhaust port, and the heat generated by the combustion is transferred to the reformer 1a, so that the reformer 1a is heated to a temperature required for the reforming reaction. The combustion raw material for the combustor 1b may be fuel outside the system, or fuel gas that does not participate in the electrochemical reaction in the anode 3a of the fuel cell stack 3 or fuel gas containing excessive impurities that flows out from the moisture separator 6.
The reformer 1a is used to reform hydrogen to produce a fuel gas (typically a hydrogen-rich fuel gas) required for the anode 3a of the fuel cell stack 3. The hydrogen production raw material is introduced into the reformer 1a according to a preset flow rate to participate in the hydrogen production reaction, and when the hydrogen production adopts the steam reforming reaction, the reactant also comprises water besides the hydrogen production raw material. In this case, water may be supplied from an external water source or system internal circulation water, preferably from the water tank 7 (in this case, the inlet of the reformer 1a is connected to the outlet of the water tank 7), thereby achieving the recycling of system internal water and achieving the purpose of eliminating the need for external water supply. The outlet of the reformer 1a is connected to the inlet of the moisture separator 6, with a first heat exchanger 10 disposed therebetween for cooling the fuel gas. The outlet of the water-gas separator 6 is connected with the anode 3a of the fuel cell stack 3, so that the fuel gas generated by the reforming reaction is dehydrated in the water-gas separator 6 before entering the anode 3a, and the excessive water is prevented from entering the fuel cell stack 3 to cause flooding and the power generation performance attenuation. The moisture separator 6 is also connected with a water tank 7 for collecting water separated from the fuel gas by the moisture separator 6 into the water tank 7 and supplying water to the inside of the system (e.g., to the reformer 1 a).
An impurity sensor 17 is arranged at the outlet of the moisture separator 6 and used for monitoring the impurity concentration in the fuel gas. The outlet of the moisture separator 6 is connected to the inlet of the anode 3a of the fuel cell stack 3 and the inlet of the combustor 1b via a three-way valve 19. When the impurity sensor 17 monitors that the impurity concentration in the fuel gas is lower than or equal to a set threshold value, the three-way valve 19 is controlled to enable the outlet of the water-gas separator 6 to be communicated with the anode 3a of the fuel cell stack 3, and the fuel gas enters the anode 3 a; when the impurity sensor 17 monitors that the impurity concentration in the fuel gas is higher than a set value, the three-way valve 19 is controlled to communicate the outlet of the moisture separator 6 with the inlet of the burner 1b, and the fuel gas enters the burner 1 b.
The fuel cell stack 3 is used to generate electrochemical reactions and generate electrical energy. Which is provided with a temperature sensor 18, a pressure regulating valve 20, a pressure regulating valve 21, and a second heat exchanger 12. The temperature sensor 18 is used for monitoring the operating temperature of the fuel cell stack 3, and when the operating temperature is higher than a set temperature interval, the temperature control of the fuel cell stack 3 can be realized by adjusting the heat exchange amount of the first heat exchanger 10, the first heat supplier 11 and the second heat exchanger 12. The temperature range of the fuel cell stack 3 is generally 50 to 90 c, preferably 60 to 80 c. In the fuel cell stack 3, the fuel gas in the anode 3a and the oxidant in the cathode 3b generate electric energy and heat energy by electrochemical reaction. The unreacted fuel gas after the reaction is discharged through the pressure regulating valve 20 (if the burner 1b uses the fuel gas as fuel, the pressure regulating valve 20 may be connected to the burner 1b, and the connection relationship is not shown in fig. 1), and the unreacted oxidant is discharged through the pressure regulating valve 21. When the cathode 3b of the fuel cell stack 3 needs humidification, an evaporator 8 is also connected to a passage between the first heater 11 and the cathode 3 b. The inlet of the evaporator 8 is connected to the outlet of the water tank 7, and a water pump 16 is provided therebetween. At this time, the water in the water tank 7 flows into the evaporator 8 by the water pump 16 according to a set flow rate to be evaporated, the generated water vapor is mixed with the preheated oxidant output from the first outlet of the filter 2, the humidity of the oxidant can be improved, and the oxidant containing the water vapor then enters the cathode 3b of the fuel cell stack 3 to participate in the electrochemical reaction.
In the fuel cell system provided in the present embodiment, the first heat exchanger 10, the first heat supplier 11 and the second heat exchanger 12 can adjust the amount of heat exchange by changing their operating parameters, so as to cool or raise the fuel gas or the fuel cell stack 3 to a desired temperature, thereby ensuring that the fuel cell stack 3 operates in a suitable temperature range. The first and second heat supply devices 11 and 9 can preheat gas or liquid flowing through and raise the temperature of oxidant or steam to a desired temperature. The first heater 11 and the second heater 9 can be connected with an external high-temperature heat source; and the heat exchanger can also be connected with the first heat exchanger 10 and/or the second heat exchanger 12, so that the heat utilization rate of the system is improved, and energy is saved. The air pump 13, the air pump 14 and the air pump 15 are used for controlling the oxidant to be output from the filter 2 at a certain flow rate.
Example 2
The present embodiment provides a fuel cell regeneration control method performed in the fuel cell system of embodiment 1, and fig. 2 is a flowchart of the fuel cell regeneration control method.
When the power controller 4 monitors that the output power of the fuel cell stack 3 is reduced to be less than the rated power (the rated power is generally related to factors such as the volume of the fuel cell stack, the performance of a membrane electrode, the working condition of the stack, the quality of hydrogen and the like), a regeneration control regulation program is started, and the method specifically comprises the following steps:
1. short circuit pulse: when the output power of the fuel cell stack 3 is less than the rated power, the power controller 4 applies periodic short-circuit electric pulses to the anode 3a and the cathode 3b of the fuel cell stack 3,
(1) when the output power of the fuel cell stack 3 is restored to the rated power, the short-circuit pulse control (i.e. the pulse period and time are maintained unchanged) at the moment is maintained, and the debugging of the regeneration control program is completed;
(2) when the output power of the fuel cell stack 3 fails to return to the rated power, the short-circuit pulse time (for example, 0.5s) is kept unchanged, the pulse cycle is gradually shortened until the output power of the fuel cell stack 3 returns to the rated power, the short-circuit pulse control at that time is kept, and the debugging of the regeneration control program is completed.
2. Anode oxygen distribution: when the short-circuit pulse period has been shortened to a preset minimum pulse period (for example, 5s) and the output power of the fuel cell stack 3 has not been recovered to the rated power, the short-circuit pulse control is maintained while the anode oxygen distribution control is started: the filter 2 filters and purifies air as an oxidant, and outputs the air (i.e., the oxidant) at a predetermined flow rate by an air pump 13, and the air is mixed with the fuel gas output from the reformer 1a, dehydrated by the moisture separator 6, and introduced into the anode 3a of the fuel cell stack 3. After the oxidant enters the anode 3a, the oxidant reacts with impurities adsorbed on the surface of the electrode catalyst to desorb the impurities, so that the reaction activity of the anode catalyst is recovered, and the output power is improved;
(1) when the output power of the fuel cell stack 3 is restored to the rated power, the short-circuit pulse control (namely, the electric pulse period and time) and the anode oxygen distribution control (namely, the oxidant introduction amount) are kept, and the debugging of the regeneration control program is finished;
(2) when the output power of the fuel cell stack 3 is not recovered to the rated power, adjusting the air pump 13 to increase the oxidant dosage until the output power of the fuel cell stack 3 is recovered to the rated power, keeping the short-circuit pulse and anode oxygen distribution control, and completing the debugging of the regeneration control program;
3. regulating and controlling the galvanic pile: when the dosage of the oxidant has increased to a preset maximum value (for example, 3 vol% of the fuel gas) and the output power of the fuel cell stack 3 still fails to return to the rated power, the short-circuit pulse control and the anode oxygen distribution control are maintained, and the stack regulation is started: the heat exchange intensity of the first heat exchanger 10 and the second heat exchanger 12 is reduced so as to improve the working temperature of the fuel cell stack 3; the dehydration rate of the water-gas separator 6 is reduced to improve the working humidity of the fuel cell stack 3; the pressure regulating valve 20 and the pressure regulating valve 21 are adjusted simultaneously to increase the operating pressure of the fuel cell stack 3;
(1) when the output power of the fuel cell stack 3 is recovered to the rated power, the short-circuit pulse control, the anode oxygen distribution control and the electric stack regulation are kept, and the debugging of the regeneration control program is finished;
(2) when the output power of the fuel cell stack 3 is not recovered to the rated power, continuously improving the working temperature, the working humidity and the working pressure of the fuel cell stack 3 until the output power of the fuel cell stack 3 is recovered to a target value, keeping short-circuit pulse control, anode oxygen distribution control and galvanic pile regulation, and completing the debugging of a regeneration control program;
(3) when the operating temperature, the operating humidity and the operating pressure of the fuel cell stack 3 reach the preset maximum values (for example, the operating temperature reaches 80 ℃, the operating humidity reaches the level of 70 ℃ of the dew-point temperature of the cell fuel of the anode 3a, and the operating pressure reaches 0.3MPa), and the output power of the fuel cell stack 3 still fails to recover to the rated power, the regeneration control fails, all regeneration control programs are stopped, meanwhile, the fuel gas is stopped from being introduced into the anode 3a, the three-way valve 19 is switched to the outlet of the water-gas separator 6 to be connected with the inlet of the combustor 1b, so that the fuel gas enters the combustor 1b to be combusted, and the operation of the fuel cell stack 3 is stopped.
Claims (41)
1. A fuel cell regeneration control method, the method comprising:
short circuit pulse control: when the output power of the fuel cell is reduced to be less than the rated power, continuously applying periodic short-circuit electric pulses to the cathode and the anode of the fuel cell; when the output power of the fuel cell is recovered to the rated power, the short-circuit pulse control is kept, and the debugging of the regeneration control program is finished; when the output power of the fuel cell is not recovered to the rated power, the short-circuit pulse control further comprises the operation of keeping the time of the short-circuit electric pulse unchanged and shortening the period of the short-circuit electric pulse;
after the short-circuit pulse control is performed, when the output power of the fuel cell is not recovered to the rated power, the anode oxygen distribution control is started while the short-circuit pulse control is maintained: introducing an oxidant to the anode of the fuel cell; when the output power of the fuel cell is recovered to the rated power, the short-circuit pulse control and the anode oxygen distribution control are kept, and the debugging of the regeneration control program is finished; when the output power of the fuel cell is not recovered to the rated power, the anode oxygen distribution control further comprises an operation of increasing the distribution amount of the oxidant introduced to the anode of the fuel cell;
after anode oxygen distribution control is carried out, when the output power of the fuel cell is not recovered to the rated power, the control of the short-circuit pulse and the anode oxygen distribution control are kept, and meanwhile, the regulation and control of the galvanic pile are started: the working temperature, the working humidity and the working pressure of the fuel cell are improved; when the output power of the fuel cell is recovered to the rated power, the short-circuit pulse control, the anode oxygen distribution control and the electric pile regulation are kept, and the debugging of the regeneration control program is finished; when the working temperature, the working humidity and the working pressure of the fuel cell reach the maximum values and the output power of the fuel cell is not recovered to the rated power, the short-circuit pulse control, the anode oxygen distribution control and the galvanic pile control are stopped, and the fuel gas is stopped to be introduced into the anode of the fuel cell.
2. The fuel cell regeneration control method according to claim 1, wherein in the short-circuit pulse control, the period of the short-circuit electric pulse is 2 to 20s, the time of the short-circuit electric pulse is 0.1 to 0.5s, and the cell short-circuit potential is 0.4V or less.
3. The fuel cell regeneration control method according to claim 1 or 2, wherein in the short-circuit pulse control, the period of the short-circuit electric pulse is 3 to 10 seconds, the time of the short-circuit electric pulse is 0.1 to 0.2 seconds, and the cell short-circuit potential is 0.2V or less.
4. The control method according to claim 1, wherein in the anode oxygen distribution control, the oxidizing agent is air and/or oxygen.
5. The control method according to claim 1 or 4, wherein the anode oxygen distribution control includes an operation of mixing an oxidant with a fuel gas for an anode of the fuel cell and then introducing the mixed oxidant into the anode.
6. The control method according to claim 5, wherein when the oxidizing agent is air and the concentration of the impurities in the fuel gas is 100ppm or less, the amount of the oxidizing agent blended in the fuel gas is less than 4 vol%.
7. The control method according to claim 6, wherein when the oxidizing agent is air and the concentration of the impurities in the fuel gas is 100ppm or less, the amount of the oxidizing agent blended in the fuel gas is less than 2 vol%.
8. The control method according to claim 5, wherein the oxidant is mixed with the fuel gas and then dehydrated to be introduced into an anode of the fuel cell.
9. The regeneration control method for a fuel cell according to claim 1, wherein in the stack regulation, the operating temperature of the fuel cell is 70 to 90 ℃, the operating pressure of the fuel cell is 0.1 to 0.5MPa, and the operating humidity of the fuel cell is a humidity condition that the dew-point temperature of the cell fuel at the anode of the fuel cell is equal to or lower than the operating temperature of the fuel cell.
10. The regeneration control method of a fuel cell according to claim 1 or 9, wherein in the stack control, an operating temperature of the fuel cell is 70 to 80 ℃, and an operating pressure of the fuel cell is 0.2 to 0.3 MPa.
11. A fuel cell system comprises a hydrogen supply unit, a fuel cell, a power supply controller, a filter and a water-gas separator;
wherein, the hydrogen supply unit, the water-gas separator and the anode of the fuel cell are connected in sequence;
the filter is respectively provided with a first outlet connected with the inlet of the cathode of the fuel cell and a second outlet connected with the inlet of the water-gas separator;
a first heat exchanger is arranged between the outlet of the hydrogen supply unit and the inlet of the water-gas separator;
the power supply controller is used for detecting the output power of the fuel cell and applying short-circuit electric pulse between the anode and the cathode of the fuel cell when the output power is less than the rated power;
the fuel cell is provided with a second heat exchanger and a pressure regulating valve.
12. The fuel cell system of claim 11, wherein a first heat supply is provided between the first outlet of the filter and the inlet of the cathode of the fuel cell.
13. The fuel cell system according to claim 11 or 12, wherein the second outlet of the filter is connected to a passage between the outlet of the hydrogen supply unit and the inlet of the moisture separator.
14. The fuel cell system according to claim 13, wherein the second outlet of the filter is connected to a passage between the outlet of the hydrogen supply unit and the first heat exchanger.
15. The fuel cell system according to any one of claims 11, 12, and 14, wherein an impurity sensor is provided between an outlet of the moisture separator and an inlet of an anode of the fuel cell.
16. The fuel cell system of claim 13, wherein an impurity sensor is provided between an outlet of the moisture separator and an inlet of an anode of the fuel cell.
17. The fuel cell system of claim 15, wherein the outlet of the moisture separator is further connected to an inlet of the hydrogen supply unit, and the impurity sensor is positioned between the outlet of the moisture separator and the inlet of the hydrogen supply unit.
18. The fuel cell system of claim 16, wherein the outlet of the moisture separator is further connected to an inlet of the hydrogen supply unit, and the impurity sensor is positioned between the outlet of the moisture separator and the inlet of the hydrogen supply unit.
19. The fuel cell system according to claim 17 or 18, wherein a control valve is provided between an outlet of the moisture separator and an inlet of an anode of the fuel cell and an inlet of the hydrogen supply unit, and the impurity sensor is located between the moisture separator and the control valve.
20. A fuel cell system according to any one of claims 11, 12 and 14, wherein the filter is provided with a third outlet connected to an inlet of a hydrogen supply unit.
21. The fuel cell system according to claim 13, wherein the filter is provided with a third outlet connected to an inlet of the hydrogen supply unit.
22. The fuel cell system of claim 20, wherein a second heat supply is provided between the third outlet of the filter and the inlet of the hydrogen supply unit.
23. The fuel cell system of claim 21, wherein a second heat supply is provided between the third outlet of the filter and the inlet of the hydrogen supply unit.
24. The fuel cell system according to any one of claims 11-12, 14, 16-18, 21-23, wherein the hydrogen supply unit comprises a combustor and a reformer, an inlet of the hydrogen supply unit is an inlet of the combustor, an outlet of the hydrogen supply unit is an outlet of the reformer, and an outlet of the combustor is connected to an inlet of the reformer.
25. The fuel cell system according to claim 13, wherein the hydrogen supply unit includes a combustor and a reformer, an inlet of the hydrogen supply unit is an inlet of the combustor, an outlet of the hydrogen supply unit is an outlet of the reformer, and an outlet of the combustor is connected to an inlet of the reformer.
26. The fuel cell system according to claim 15, wherein the hydrogen supply unit includes a combustor and a reformer, an inlet of the hydrogen supply unit is an inlet of the combustor, an outlet of the hydrogen supply unit is an outlet of the reformer, and an outlet of the combustor is connected to an inlet of the reformer.
27. The fuel cell system according to claim 19, wherein the hydrogen supply unit includes a combustor and a reformer, an inlet of the hydrogen supply unit is an inlet of the combustor, an outlet of the hydrogen supply unit is an outlet of the reformer, and an outlet of the combustor is connected to an inlet of the reformer.
28. The fuel cell system according to claim 20, wherein the hydrogen supply unit includes a combustor and a reformer, an inlet of the hydrogen supply unit is an inlet of the combustor, an outlet of the hydrogen supply unit is an outlet of the reformer, and an outlet of the combustor is connected to an inlet of the reformer.
29. The fuel cell system of any of claims 11-12, 14, 16-18, 21-23, 25-28, wherein a water tank is connected to an outlet of the moisture separator.
30. The fuel cell system according to claim 13, wherein a water tank is connected to an outlet of the moisture separator.
31. The fuel cell system according to claim 15, wherein a water tank is connected to an outlet of the moisture separator.
32. The fuel cell system of claim 19, wherein a water tank is connected to an outlet of the moisture separator.
33. The fuel cell system of claim 20, wherein a water tank is connected to an outlet of the moisture separator.
34. The fuel cell system of claim 24, wherein a water tank is connected to an outlet of the moisture separator.
35. The fuel cell system of claim 29, wherein an evaporator is connected to an outlet of the water tank.
36. The fuel cell system of any of claims 30-34, wherein an evaporator is connected to an outlet of the water tank.
37. The fuel cell system of claim 35, wherein the outlet of the evaporator is connected to the inlet of the fuel cell cathode.
38. The fuel cell system of claim 36, wherein the outlet of the evaporator is connected to the inlet of the fuel cell cathode.
39. The fuel cell system according to claim 37 or 38, wherein the evaporator is connected to a connection passage between the first outlet of the filter and the cathode of the fuel cell.
40. The fuel cell system according to any one of claims 11, 12, and 14, wherein the fuel cell is provided with a temperature sensor, and the pressure regulating valves are provided at an outlet of an anode and an outlet of a cathode of the fuel cell, respectively.
41. The fuel cell system according to claim 13, wherein the fuel cell is provided with a temperature sensor, and the pressure regulating valves are provided at an outlet of an anode and an outlet of a cathode of the fuel cell, respectively.
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| CN114024010A (en) * | 2021-11-05 | 2022-02-08 | 北京化工大学 | Method for relieving anode poisoning of proton exchange membrane fuel cell by using transient temperature rise |
| CN114388839A (en) * | 2021-12-28 | 2022-04-22 | 新源动力股份有限公司 | Recovery method of coolant polluted membrane electrode |
| CN115000456A (en) * | 2022-05-12 | 2022-09-02 | 亿创氢能源科技(张家港)有限公司 | Short-circuit test method for electric pile in fuel cell system |
| CN115548393A (en) * | 2022-10-21 | 2022-12-30 | 上海氢晨新能源科技有限公司 | Fuel cell performance recovery method, device and system |
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