CN106887616B - Fuel cell cold start system and method based on liquid organic hydrogen storage - Google Patents

Fuel cell cold start system and method based on liquid organic hydrogen storage Download PDF

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Publication number
CN106887616B
CN106887616B CN201710144330.1A CN201710144330A CN106887616B CN 106887616 B CN106887616 B CN 106887616B CN 201710144330 A CN201710144330 A CN 201710144330A CN 106887616 B CN106887616 B CN 106887616B
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heat exchanger
cooling
temperature
fuel cell
water
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CN106887616A (en
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马天才
林维康
余卓平
魏学哲
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Tongji University
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Tongji University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04007Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H01M8/04067Heat exchange or temperature measuring elements, thermal insulation, e.g. heat pipes, heat pumps, fins
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04223Auxiliary 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313Processes 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
    • H01M8/0432Temperature; Ambient temperature
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04701Temperature
    • H01M8/04708Temperature of fuel cell reactants
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Abstract

The invention relates to a fuel cell cold start system and a method based on liquid organic hydrogen storage, wherein the system comprises a galvanic pile and a reaction kettle for dehydrogenation reaction of the liquid organic hydrogen storage, the system also comprises a heat exchanger, a water cooling unit and a control unit, wherein the heat exchanger is arranged between the hydrogen output end of the reaction kettle and the galvanic pile, the water cooling unit is connected with the heat exchanger, the water cooling unit is a flow regulation type water cooling unit, and the control unit is connected with the galvanic pile and the water cooling unit; when the fuel cell is started in a cold mode, the control unit adjusts the water quantity input into the heat exchanger by the water cooling unit according to the temperature of the electric pile, and then the temperature of hydrogen input into the electric pile is improved, and the cold start of the electric pile is completed. Compared with the prior art, the invention realizes the full utilization of heat, saves energy and is efficient and economical.

Description

Fuel cell cold start system and method based on liquid organic hydrogen storage
Technical Field
The present invention relates to a fuel cell cold start system and method, and more particularly, to a fuel cell cold start system and method based on liquid organic hydrogen storage.
Background
A fuel cell is an electrochemical reaction device that directly converts chemical energy into electrical energy. Depending on the electrolyte, it can be classified into proton exchange membrane fuel cells, alkaline fuel cells, phosphoric acid fuel cells, molten carbonate fuel cells and solid oxide fuel cells. The proton exchange membrane fuel cell has low working temperature, high current density, high response speed and stable performance. Moreover, the reaction product is only water, and is not corrosive. Therefore, the proton exchange membrane fuel cell has wide market prospect in the fields of vehicle transportation, standby power supply and the like.
However, when the fuel cell stack is in an environment below zero, water generated by the fuel cell reaction cannot be normally discharged out of the stack, even is frozen, so that the catalytic layer in the stack is partially or completely covered, and the chemical reaction is terminated, so that the stack cannot be normally started. In addition, the proton exchange membrane is damaged when the proton exchange membrane is more serious, and the galvanic pile is damaged. Therefore, a reasonable cold start method is needed to realize cold start of the galvanic pile under the low-temperature condition.
A fuel cell cold start heating apparatus applied by CN 304011605U heats a cathode end, an anode end, and a stack body of a stack by an electric heater. In the system and the method for rapidly heating the cold start of the fuel cell, which are disclosed in CN 103825037A, the cold start is realized by heating the hydrogen of the anode. In the proton exchange membrane fuel cell cold starting device disclosed in CN 203218389U, a heating element is embedded in the middle of a carbon plate of a galvanic pile, and the temperature of the galvanic pile is increased by a method of heating the carbon plate, so that the galvanic pile is cold started. In a low-temperature cold start fuel cell system and a utilization method thereof, which are applied by CN105390715A, cold start of a galvanic pile is realized by a method of heating cathode inlet air and anode inlet air. The above related patents are all based on a fuel cell system of a high-pressure hydrogen storage mode, so that the temperature of a galvanic pile is quickly raised, and the galvanic pile is started at a low temperature. However, there is no cold start system and method for a fuel cell system based on normal temperature and pressure organic hydrogen storage.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a fuel cell cold start system and a method based on liquid organic hydrogen storage.
The aim of the invention can be achieved by the following technical scheme:
the cold starting system of the fuel cell based on the liquid organic hydrogen storage comprises a galvanic pile and a reaction kettle for carrying out dehydrogenation reaction on the liquid organic hydrogen storage, and also comprises a heat exchanger, a water cooling unit and a control unit, wherein the heat exchanger is arranged between a hydrogen output end of the reaction kettle and the galvanic pile, the water cooling unit is connected with the heat exchanger, the water cooling unit is a flow-adjustable water cooling unit, and the control unit is connected with the galvanic pile and the water cooling unit;
when the fuel cell is started in a cold mode, the control unit adjusts the water quantity input into the heat exchanger by the water cooling unit according to the temperature of the electric pile, and then the temperature of hydrogen input into the electric pile is improved, and the cold start of the electric pile is completed.
The control unit comprises a temperature sensor and a controller, wherein the temperature sensor is arranged at the outlet of the anode of the electric pile, and the controller is connected with the temperature sensor and the water cooling unit.
The water cooling unit comprises a cooling water supply tank, a cooling water recovery tank and an electromagnetic valve, wherein the cooling water supply tank is communicated with the input end of the heat exchanger through a main cooling pipeline, the output end of the heat exchanger is connected with the cooling water recovery tank, the main cooling pipeline is further connected with a cooling water bypass pipeline, the tail end of the cooling water bypass pipeline is communicated with the cooling water recovery tank, the electromagnetic valve is arranged in the cooling water bypass pipeline, and the electromagnetic valve is connected with the control unit.
The water cooling unit comprises a cooling water supply tank, a cooling water recovery tank and an electric proportional valve, wherein the cooling water supply tank is communicated with the input end of the heat exchanger through a main cooling pipeline, the output end of the heat exchanger is connected with the cooling water recovery tank, the electric proportional valve is arranged in the main cooling pipeline, and the electric proportional valve is connected with the controller.
And a filtering cooler for filtering and cooling the hydrogen is arranged between the reaction kettle and the heat exchanger.
A filter for secondary filtering of the hydrogen is arranged between the heat exchanger and the electric pile.
A fuel cell cold start method based on liquid organic hydrogen storage specifically comprises the following steps:
and starting the electric pile, wherein the control unit acquires the temperature of the electric pile in real time, and when the temperature is smaller than a set value, the control unit controls the water quantity input into the heat exchanger by the water cooling unit to carry out circulation control, so that the electric pile temperature runs at the normal temperature at the set value.
Compared with the prior art, the invention has the following advantages:
(1) The invention is provided with the heat exchanger and the water cooling unit capable of adjusting the flow of water entering the heat exchanger, and when the electric pile is cold started, the temperature of hydrogen entering the electric pile is increased by reducing the water quantity entering the heat exchanger, thereby realizing cold start, belonging to waste heat utilization, needing no additional energy consumption and saving energy consumption;
(2) The invention has simple structure and convenient use;
(3) According to the invention, the control unit is arranged to measure the temperature of the spot pile in real time so as to control the water cooling unit to work, so that closed-loop control is realized, the precision is high, the stability is good, and the galvanic pile can be effectively and rapidly started in a low-temperature environment;
drawings
Fig. 1 is a schematic diagram showing the structure of a cold start system for a fuel cell based on liquid organic hydrogen storage according to embodiment 1;
fig. 2 is a schematic diagram showing the structure of a cold start system for a fuel cell based on liquid organic hydrogen storage according to embodiment 2.
In the figure, 1 is a reaction kettle, 2 is a pretreatment device, 3 is a heat exchanger, 4 is a hydrogen pipeline, 5 is a post-treatment device, 6 is a galvanic pile, 7 is a temperature sensor, 8 is a controller, 9 is a main cooling pipeline, 10 is a cooling water bypass pipeline, 11 is an electromagnetic valve, and 12 is an electric proportional valve.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
Example 1
As shown in fig. 1, the fuel cell cold start system based on liquid organic hydrogen storage comprises a pile 6 and a reaction kettle 1 for dehydrogenation reaction of the liquid organic hydrogen storage, and further comprises a heat exchanger 3, a water cooling unit and a control unit, wherein the heat exchanger 3 is arranged between the hydrogen output end of the reaction kettle 1 and the pile 6, the water cooling unit is connected with the heat exchanger 3, the water cooling unit is a flow regulation type water cooling unit, and the control unit is connected with the pile 6 and the water cooling unit; during cold start of the fuel cell, the control unit adjusts the water quantity input into the heat exchanger 3 by the water cooling unit according to the temperature of the electric pile 6, so that the temperature of hydrogen input into the electric pile 6 is increased, and the cold start of the electric pile 6 is completed.
The control unit comprises a temperature sensor 7 and a controller 8, wherein the temperature sensor 7 is arranged at the anode outlet of the electric pile 6, and the controller 8 is connected with the temperature sensor 7 and the water cooling unit. The controller 8 is a digital controller 8 commonly used in the market, such as a singlechip, an ARM controller 8, etc.
The water cooling unit comprises a cooling water supply tank, a cooling water recovery tank and an electromagnetic valve 11, wherein the cooling water supply tank is communicated with the input end of the heat exchanger 3 through a main cooling pipeline 9, the output end of the heat exchanger 3 is connected with the cooling water recovery tank, the main cooling pipeline 9 is also connected with a cooling water bypass pipeline 10, the tail end of the cooling water bypass pipeline 10 is communicated with the cooling water recovery tank, the electromagnetic valve 11 is arranged in the cooling water bypass pipeline 10, and the electromagnetic valve 11 is connected with the control unit.
A pretreatment device 2 is arranged between the reaction kettle 1 and the heat exchanger 3, and the pretreatment device 2 is a filtering cooler for filtering and cooling hydrogen. A post-treatment device 5 is arranged between the heat exchanger 3 and the electric pile 6, and the post-treatment device 5 is used for carrying out a filter for carrying out secondary filtration on the hydrogen, so that the purity of the hydrogen entering the fuel cell electric pile is ensured. The heat exchanger 3 is connected to the aftertreatment device 5 via a hydrogen line 4.
A fuel cell cold start method based on liquid organic hydrogen storage specifically comprises the following steps:
the electric pile 6 is started, the control unit collects the temperature of the electric pile 6 in real time, and when the temperature is smaller than a set value, the control unit controls the water quantity input into the heat exchanger 3 by the water cooling unit to carry out circulation control, so that the temperature of the electric pile 6 runs at the normal temperature at the set value.
The working principle of the embodiment is as follows: one end of the heat exchanger 3 is filled with high-temperature hydrogen, and the other end is filled with cooling water. The cooling water line of the heat exchanger 3 comprises a main cooling line 9 and a cooling water bypass line 10. A solenoid valve 11 is installed on the cold water bypass line to control the opening and closing of the cold water bypass line 10. When the galvanic pile 6 needs to be started in a low-temperature environment, the temperature sensor 7 collects temperature data at the anode outlet where the galvanic pile 6 is installed, and when the temperature is less than or equal to 0 ℃, the controller 8 sends out a command to control the electromagnetic valve 11 to be opened. At this time, since a part of the cooling water flows through the radiator via the bypass line, the flow rate of the cooling water actually flowing through the radiator is reduced, and the heat quantity of the high-temperature hydrogen is reduced. The high-temperature hydrogen passes through the heat exchanger 3 and the post-treatment device at a higher temperature, and finally enters the electric pile 6 at a set cold start temperature T1. When the temperature sensor 7 detects that the temperature at the anode outlet of the electric pile 6 is higher than the set switching temperature T0, the control unit sends an instruction to control the electromagnetic valve 11 to be closed. At this time, the cooling water passes through the heat exchanger 3 entirely, and a large amount of heat is carried away from the high-temperature hydrogen, and the high-temperature hydrogen is post-treated and finally runs at a set normal temperature T2. The magnitude relation of T0, T1 and T2 is T0> T1> T2.
Example 2
In this embodiment, as shown in fig. 2, the water cooling unit includes a cooling water supply tank, a cooling water recovery tank and an electric proportional valve 12, the cooling water supply tank is communicated with the input end of the heat exchanger 3 through the main cooling pipeline 9, the output end of the heat exchanger 3 is connected with the cooling water recovery tank, the electric proportional valve 12 is arranged in the main cooling pipeline 9, and the electric proportional valve 12 is connected with the controller 8. The remainder was the same as in example 1.
The working principle of the implementation is as follows: an electric proportional valve 12 is installed on the main cooling line 9 to regulate the flow rate of cooling water in the main cooling line 9. When the galvanic pile 6 needs to be started in a low-temperature environment, the temperature sensor 7 collects temperature data at the anode outlet where the galvanic pile 6 is installed, and when the temperature is less than or equal to 0 ℃, the controller 8 sends out a command to adjust the opening of the electric proportional valve 12. At the time of cold start, the opening degree of the electric proportional valve 12 is kept at a minimum state, at this time, the flow rate of cold water flowing through the radiator is minimized, and the heat quantity of taking away high-temperature hydrogen gas is reduced. The high-temperature hydrogen passes through the heat exchanger 3 and the post-treatment device at a higher temperature, and finally at a higher set cold start temperature T cold Into the stack 6. During the cold start process, the temperature sensor 7 detects that the anode temperature of the electric pile 6 is continuously increased, the opening of the electric proportional valve 12 is correspondingly increased under the control of the controller 8, the inlet air temperature of the hydrogen is continuously reduced, and the temperature of the temperature sensor 7 is kept to be slowly increased. When the temperature sensor 7 detects that the anode temperature of the electric pile 6 is greater than the set switching temperature T change When the system enters a temperature operation mode, the electric proportional valve 12 is finely adjusted to maintain the temperature of the hydrogen gas inlet at a set temperature T H2 Is unchanged.
The foregoing detailed description is given by way of example only and is not intended to limit the scope of the claims to those skilled in the art in order to better understand the present patent; any equivalent alterations or modifications made according to the spirit of the disclosure are within the scope of the present invention.

Claims (7)

1. The cold starting system of the fuel cell based on the liquid organic hydrogen storage comprises a galvanic pile (6) and a reaction kettle (1) for carrying out dehydrogenation reaction on the liquid organic hydrogen storage, and is characterized by further comprising a heat exchanger (3), a water cooling unit and a control unit, wherein the heat exchanger (3) is arranged between the hydrogen output end of the reaction kettle (1) and the galvanic pile (6), the water cooling unit is connected with the heat exchanger (3), the water cooling unit is a flow-adjustable water cooling unit, and the control unit is connected with the galvanic pile (6) and the water cooling unit;
during cold start of the fuel cell, the control unit adjusts the water quantity input into the heat exchanger (3) by the water cooling unit according to the temperature of the electric pile (6), so that the temperature of hydrogen input into the electric pile (6) is increased, and the cold start of the electric pile (6) is completed.
2. The cold start system of fuel cell based on liquid organic hydrogen storage according to claim 1, wherein the control unit comprises a temperature sensor (7) and a controller (8), the temperature sensor (7) is arranged at the anode outlet of the electric pile (6), and the controller (8) is connected with the temperature sensor (7) and the water cooling unit.
3. The fuel cell cold start system based on liquid organic hydrogen storage according to claim 1, wherein the water cooling unit comprises a cooling water supply tank, a cooling water recovery tank and an electromagnetic valve (11), the cooling water supply tank is communicated with the input end of the heat exchanger (3) through a main cooling pipeline (9), the output end of the heat exchanger (3) is connected with the cooling water recovery tank, the main cooling pipeline (9) is further connected with a cooling water bypass pipeline (10), the tail end of the cooling water bypass pipeline (10) is communicated with the cooling water recovery tank, the electromagnetic valve (11) is arranged in the cooling water bypass pipeline (10), and the electromagnetic valve (11) is connected with the control unit.
4. The cold start system of a fuel cell based on liquid organic hydrogen storage according to claim 1, wherein the water cooling unit comprises a cooling water supply tank, a cooling water recovery tank and an electric proportional valve (12), the cooling water supply tank is communicated with the input end of the heat exchanger (3) through a main cooling pipeline (9), the output end of the heat exchanger (3) is connected with the cooling water recovery tank, the electric proportional valve (12) is arranged in the main cooling pipeline (9), and the electric proportional valve (12) is connected with the controller (8).
5. The cold start system of fuel cell based on liquid organic hydrogen storage according to claim 1, wherein a filter cooler for filtering and cooling hydrogen is arranged between the reaction kettle (1) and the heat exchanger (3).
6. A cold start-up system for fuel cells based on liquid organic hydrogen storage according to claim 1, characterized in that a filter for secondary filtering of hydrogen is arranged between the heat exchanger (3) and the stack (6).
7. A method for cold starting with a fuel cell cold start system based on liquid organic hydrogen storage according to claim 1, characterized in that it comprises in particular:
the electric pile (6) is started, the control unit collects the temperature of the electric pile (6) in real time, and when the temperature is larger than or smaller than a set value, the control unit controls the water quantity input into the heat exchanger (3) by the water cooling unit to carry out circulation control, so that the temperature of the electric pile (6) runs at the normal temperature at the set value.
CN201710144330.1A 2017-03-10 2017-03-10 Fuel cell cold start system and method based on liquid organic hydrogen storage Active CN106887616B (en)

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Publication number Priority date Publication date Assignee Title
CN109326806A (en) * 2018-11-23 2019-02-12 武汉氢阳能源有限公司 A kind of fuel cell system for realizing cold start-up
CN110120535B (en) * 2019-06-10 2024-04-02 新源动力股份有限公司 Low-temperature quick starting system and starting method for fuel cell stack
CN112242539A (en) * 2019-10-30 2021-01-19 北京新能源汽车技术创新中心有限公司 Thermal management system for fuel cell stack and vehicle provided with same

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CN105390715A (en) * 2015-11-04 2016-03-09 北京氢璞创能科技有限公司 Low-temperature cold-start fuel cell system and use method therefor
CN105633435A (en) * 2015-12-31 2016-06-01 北京建筑大学 Vehicular fuel battery system and working method thereof
CN206574800U (en) * 2017-03-10 2017-10-20 同济大学 A kind of cold boot of fuel cell system based on liquid organic hydrogen storage

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CN103825037A (en) * 2014-03-14 2014-05-28 江苏绿遥燃料电池系统制造有限公司 Fuel cell fast heating system and method adopting cold starting
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