CN112421077B - Fuel cell low-temperature starting heating and waste heat recovery system based on heat storage of strontium chloride ammoniated - Google Patents
Fuel cell low-temperature starting heating and waste heat recovery system based on heat storage of strontium chloride ammoniated Download PDFInfo
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- CN112421077B CN112421077B CN202011320424.8A CN202011320424A CN112421077B CN 112421077 B CN112421077 B CN 112421077B CN 202011320424 A CN202011320424 A CN 202011320424A CN 112421077 B CN112421077 B CN 112421077B
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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
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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
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04052—Storage of heat in the fuel cell system
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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
- H01M8/04268—Heating of fuel cells during the start-up of the fuel cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0432—Temperature; Ambient temperature
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a fuel cell low-temperature starting heating and waste heat recovery system based on heat storage of strontium chloride ammine, and belongs to the technical field of fuel cells. The invention utilizes the principle that the heating of the strontium chloride ammine generates the chemical desorption process to obtain the ammonia gas and the strontium chloride, and stores the residual heat generated during the operation of the fuel cell in the chemical energy of the ammonia gas and the strontium chloride. When the fuel cell is started at low temperature, the heat is released in the process of obtaining the strontium chloride ammine by utilizing the chemical adsorption between the ammonia gas and the strontium chloride, and is transferred to the fuel cell stack, so that the fuel cell is helped to be quickly started at low temperature under the condition of not consuming extra electric power. The system utilizes the waste heat of the fuel cell to help the temperature rise in the low-temperature starting process, adopts a thermochemical energy storage mode, has small energy storage loss and high energy efficiency, accelerates the starting speed of the fuel cell under the condition of not consuming extra electric quantity, and eliminates the irreversible structural damage caused by low-temperature starting to the fuel cell.
Description
Technical Field
The invention relates to a fuel cell low-temperature starting and waste heat recovery system, in particular to a fuel cell low-temperature starting heating and waste heat recovery system based on heat storage of strontium chloride ammoniated.
Background
Hydrogen fuel cells, which are an important form of hydrogen energy, can convert chemical energy directly into electrical energy. The energy-saving power generation system has the advantages of high efficiency, no pollution, low noise, rapid energy supplement and the like, and is widely applied to the fields of automobiles, ships, aerospace, distributed power generation and the like. Water generated by the fuel cell during low-temperature starting may freeze, causing irreversible structural damage to the fuel cell stack.
Common methods for starting the fuel cell at low temperature include shutdown purging, external preheating, internal heating and the like. However, the shutdown purging often cannot bring away the residual moisture in the membrane electrode in a short time, and external preheating such as heating by an electric heater needs to use electricity during starting, so that the fuel cell is required to work at a low temperature or the system is provided with an additional power supply, and if the internal temperature rise does not control the mixture ratio of reactants, the safety problem may be caused.
Disclosure of Invention
Based on the problems, the invention provides a fuel cell low-temperature starting heating and waste heat recovery system based on heat storage of strontium chloride ammine. The system utilizes a thermochemistry energy storage mode, has small heat loss, can use the waste heat of the fuel cell for preheating during low-temperature starting, has high overall efficiency, does not need an additional power supply, can work for the fuel cell system for a long time, and is clean and pollution-free.
The invention discloses a fuel cell low-temperature starting heating and waste heat recovery system based on heat storage of strontium chloride ammoniated, which comprises a fuel cell stack, a hydrogen conveying device, an oxygen conveying device, a temperature sensor, a flow sensor, a load state sensor, a first water pump, a second water pump, an air pump, an electronic control unit, a load, a thermochemical heat storage device, a first three-way valve, a second three-way valve, a communicating valve, a high-pressure ammonia storage tank and a liquid storage tank, wherein the hydrogen conveying device is arranged on the fuel cell stack;
the thermochemical heat storage device comprises an insulating jacket, a liquid flow channel and a gas flow channel, wherein the liquid flow channel and the gas flow channel are arranged in the insulating jacket, the gas flow channel is filled with a strontium chloride-expanded graphite composite material, and the liquid flow channel and the gas flow channel conduct heat through the wall surface of the liquid flow channel;
the temperature sensor is connected with the fuel cell stack, the outlet of the hydrogen conveying device is connected with the cathode of the fuel cell, and the oxygen conveying device is connected with the anode of the fuel cell stack; the flow sensor is arranged in a flow channel between the liquid outlet of the fuel cell and the second water pump; the load state sensor is connected with a load; the outlet of the high-pressure ammonia storage tank is connected with the inlet of a gas flow passage of the thermochemical heat storage device through a communicating valve, and the outlet of the gas flow passage of the thermochemical heat storage device is connected with the inlet of the high-pressure ammonia storage tank through a gas pump; the second water pump is arranged in a flow channel between the liquid outlet of the fuel cell stack and the first three-way valve; the third interface of the first three-way valve is connected with the liquid storage tank, the second interface is connected with the liquid inlet of the thermochemical heat storage device, and the first interface is connected with the outlet of the second water pump; the liquid outlet of the thermochemical heat storage device is connected with a first interface of a second three-way valve; and a third interface of the second three-way valve is connected with the liquid storage tank, and a second interface is connected with a cooling liquid inlet of the fuel cell through a first water pump.
As a preferred scheme of the invention, the outer side of the thermochemical heat storage device is an insulating jacket, the inner side of the thermochemical heat storage device is provided with a snakelike liquid flow channel, and a strontium chloride-expanded graphite composite material is filled between the jacket and the liquid flow channel; openings are formed in two opposite sides of the heat insulation cladding and used for the inlet and outlet of ammonia gas; and the ammonia gas enters the thermochemical heat storage device from one side, and flows back to the high-pressure ammonia storage tank from the other side through the air pump.
As a preferable scheme of the invention, the high-pressure ammonia storage tank is connected with a gas inlet of the phase-change heat storage device through a connecting valve, and gas can be supplied by opening the valve without electric drive when the high-pressure ammonia storage tank starts to work.
The invention also discloses a fuel cell low-temperature starting heating and waste heat recovery method based on the heat storage of the strontium chloride ammine of the system, which comprises the following steps: when the fuel cell is started at a low temperature, the communicating valve is controlled to be opened, ammonia gas in the high-pressure ammonia storage tank enters the thermochemical heat storage device, the ammonia gas and the strontium chloride-expanded graphite composite material perform a chemical adsorption reaction to generate strontium ammine chloride and release heat, and fluid in the liquid flow channel absorbs heat and transfers the heat to the fuel cell stack to help the fuel cell stack to be started quickly;
when the fuel cell stack operates, the communicating valve is closed, the waste heat of the fuel cell is transferred to the thermochemical heat storage device through fluid, the strontium chloride ammoniate is chemically desorbed under the heating of the fluid in the liquid flow passage, and the generated ammonia gas returns to the high-pressure ammonia storage tank again.
As a preferable aspect of the present invention, the electronic control unit judges whether the fuel cell stack is normally operated or started at a low temperature, based on the temperature sensor, the flow sensor, and the load state sensor;
when the electronic control unit judges that the fuel cell is about to start at a low temperature, entering a preheating mode; the electronic control unit controls the communicating valve to be opened, so that ammonia gas enters the thermochemical heat storage device through the gas flow passage inlet of the thermochemical heat storage device; controlling the first three-way valve, the second three-way valve and the second water pump to enable liquid in the liquid storage tank to flow into the thermochemical heat storage device to complete heat exchange, and then sending the liquid into a coolant flow channel of the fuel cell stack to transfer heat released in the process of obtaining the strontium ammine chloride by carrying out chemical adsorption on ammonia and the strontium chloride-expanded graphite composite material to the fuel cell stack;
when the electronic control unit judges that the fuel cell stack normally works, the waste heat recovery mode is entered; the electronic control unit controls the communicating valve to be closed, the second water pump and the first three-way valve are opened to enable the fluid with the waste heat of the fuel cell stack to enter the thermochemical heat storage device, and under the action of the heat brought by the thermochemical heat storage device, the strontium chloride ammoniated absorbs the heat to complete the chemical desorption process, so that strontium chloride and ammonia are obtained; controlling the air pump to be started, and inputting the obtained ammonia gas into the high-pressure ammonia storage tank again to realize the process of storing the waste heat of the fuel cell in the form of chemical energy; and controlling the second three-way valve to convey the fluid after heat exchange to the liquid storage tank.
As a preferable scheme of the present invention, when the load sensor detects that the load has an energy demand and the fuel cell stack needs to supply energy, the temperature state of the fuel cell stack is judged according to the temperature sensor, and if the temperature sensor indicates that the fuel cell stack is in a low temperature state (usually below zero), the fuel cell stack enters a low temperature start (preheating mode); if the temperature sensor displays that the fuel cell stack is in a non-low temperature state and the flow sensor detects that the liquid flow of the liquid outlet of the fuel cell stack is in the flow range of normal operation of the fuel cell stack, the fuel cell is judged to be in a normal operation state and enters a waste heat recovery mode. If the temperature sensor displays that the fuel cell stack is in a non-low temperature state, and the flow sensor does not detect that the liquid flow of the liquid outlet of the fuel cell stack is in the flow range of normal operation of the fuel cell stack, it is judged that the fuel cell is about to be started in a normal temperature state, and the system does not work.
Compared with the prior art, the invention has the advantages that:
(1) in the process of preheating the fuel cell stack at the low temperature, an extra power supply is not needed, ammonia gas is provided for the thermochemical heat storage device by opening the communication valve, the stored heat can be released through the thermochemical process, and the heat is brought into the fuel cell stack through fluid so as to preheat the fuel cell stack at the low temperature.
(2) The heat source for preheating the fuel cell stack is from the waste heat in the working process of the fuel cell, and the chemical energy stored in the thermochemical heat storage device is from the waste heat in the normal working process of the fuel cell, so that the aim of preheating the fuel cell at low temperature is fulfilled, the waste heat of the fuel cell is recovered, and the total energy efficiency of the system is improved.
(3) Chemical energy storage mainly includes three major categories: concentration difference energy storage, chemical adsorption process and chemical reaction process. However, the liquid tank for storing energy by concentration difference and the heat exchange equipment have very complicated structures and are difficult to be introduced to vehicles and ships; the exothermic reaction in the chemical reaction process usually requires certain starting conditions (for example, high temperature initiation reaction is performed), the exothermic reaction process is very violent and difficult to control, the requirement on equipment is very high, and the exothermic reaction cannot be basically used in cold starting due to the generally high exothermic temperature; the loss of reaction raw materials also requires that the raw materials must be periodically replenished, and the waste heat cannot be utilized to store energy generally. The invention can realize cold start by utilizing the chemical adsorption process and store energy by utilizing waste heat.
In addition, the conventional chemical adsorption process is usually a hydrated salt system with water as adsorbate, however, the system needs gaseous water to assist heat storage and heat release, and is not suitable for the system of the present invention. The invention releases and absorbs heat by utilizing the chemical adsorption and chemical desorption processes of mutual conversion of ammonia gas, strontium chloride and strontium ammine chloride, has small energy loss, stable energy storage, high efficiency and safety, and can be used for a long time. The ammonia gas is in a gaseous state within the working temperature range, circulation is convenient to realize, the method has wide applicability to temperature change, and the requirement on pressure control is low.
Drawings
FIG. 1 is a schematic diagram of a fuel cell low-temperature start-up heating and waste heat recovery system based on heat storage of strontium chloride ammine.
FIG. 2 is a schematic view of a thermochemical heat storage apparatus.
Fig. 3 is a schematic diagram of a fuel cell low-temperature start heating and waste heat recovery system control method based on strontium ammine chloride heat storage.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, 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 invention.
It should be noted that all the directional indicators (such as up, down, left, right, front, and rear … …) in the embodiment of the present invention are only used to explain the relative position relationship between the components, the movement situation, etc. in a specific posture (as shown in the drawing), and if the specific posture is changed, the directional indicator is changed accordingly.
In addition, the descriptions related to "first", "second", etc. in the present invention are only for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present invention, unless otherwise expressly stated or limited, the terms "connected," "secured," and the like are to be construed broadly, and for example, "secured" may be a fixed connection, a removable connection, or an integral part; the connection can be mechanical connection, electrical connection, physical connection or wireless communication connection; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The present invention will be described in further detail with reference to the accompanying drawings.
As shown in fig. 1, the invention provides a fuel cell low-temperature start-up heating and waste heat recovery system based on heat storage of strontium chloride ammoniate, which comprises a temperature sensor 1, a hydrogen conveying device 2, a fuel cell stack 3, an oxygen conveying device 4, a first water pump 5, a flow sensor 6, a load state sensor 7, a second water pump 8, an electronic control unit 9, a load 10, an air pump 11, a thermochemical heat storage device 12, a liquid storage tank 13, a first three-way valve 14, a high-pressure ammonia storage tank 15, a communication valve 16 and a second three-way valve 17; the thermochemical energy storage device 12 is a combined device and comprises an insulating jacket 121, a gas flow channel 122 and a serpentine liquid flow channel 123, wherein the gas flow channel is filled with a strontium chloride-expanded graphite composite material.
The preparation method of the strontium chloride-expanded graphite composite material of the present example refers to the prior art documents (Wu S., Li T.X., Wang R.Z. Experimental identification and theromynamic analysis of ammonia oxidation equilibrium on lithium salts Energy.161(2018), 955-962.), wherein the purity of the strontium chloride material is higher than 99%, purchased from national pharmaceutical group chemical agents, Inc.; the expanded graphite may be prepared from expandable graphite powder available from Shanghai Yifan graphite Co., Ltd. the preparation of expanded graphite is described in the prior art documents (Zhang P., Wang C., Wang R.Z. composite reactive block for heat transfer system and improvement of system performance, Journal of Chemical Engineering of Japan.40(2007), 1275-1280.).
As shown in the attached figure 2, the invention utilizes the principle that ammonia and strontium chloride generate chemical adsorption to obtain ammonia strontium chloride and emit heat, and the ammonia strontium chloride is heated to generate chemical desorption to obtain ammonia and strontium chloride and absorb heat, recovers and stores waste heat generated by the normal operation of the fuel cell, releases heat when the fuel cell is started at low temperature, and preheats the fuel cell stack 3. The chemical adsorption process of ammonia and strontium chloride and the chemical desorption process of strontium chloride ammine can be expressed as follows:
wherein both reactions (1) and (2) are reversible reactions. The thermochemical heat storage process has a greater heat storage density, a longer energy storage period and extremely low heat loss compared to conventional sensible heat storage and latent heat storage. The traditional latent heat storage (such as phase change material storage) generally needs larger volume of phase change material due to low heat storage density, while the heat storage density of chemical heat storage is large (about more than 5 times of the heat storage of phase change material), so that the requirement of 1 fuel cell cold start can be met only by smaller volume, and the method is suitable for application scenes of fuel cells which have requirements on equipment volume, such as vehicles and ships. The ammonia complex system taking ammonia gas as adsorbate is characterized in that heat storage and heat release can be carried out at relatively low temperature, the ammonia gas is gaseous at low temperature, the control of the heat release process is convenient, other thermochemistry is in reverse province, higher reaction temperature is generally needed, and the stable heat storage and heat release process is difficult to realize in the working temperature interval of the fuel cell. When the fuel cell stack needs to be preheated, ammonia gas is introduced into the gas flow channel 122 of the thermochemical heat storage device 12 through the communicating valve 16, and a chemical adsorption process is carried out, namely, the reactions (1) and (2) are carried out rightwards, and heat is released; when the waste heat of the fuel cell stack needs to be recovered, the heat enters a liquid flow channel of the thermochemical heat storage device through fluid, the heat is transferred to the strontium chloride ammine, and a chemical desorption process is carried out, namely, the reactions (1) and (2) are carried out leftwards to absorb the heat. Through the circulation process of chemical reaction, the waste heat of the fuel cell is efficiently stored and released to preheat the fuel cell stack 3 under the condition of low-temperature starting.
The invention comprises two major loops, a gas loop and a liquid loop. The gas loop comprises a high-pressure ammonia storage tank 15, a communication valve 16, a thermochemical heat storage device gas flow passage 122 and a gas pump 11; an outlet of the high-pressure ammonia storage tank 15 is connected with a communicating valve 16, the communicating valve 16 is connected with an inlet of a thermochemical heat storage device gas flow passage 122, an outlet of the thermochemical heat storage device gas flow passage 122 is connected with an air pump 11, and the obtained ammonia gas is input into the inlet of the high-pressure ammonia storage tank 15 through the air pump 11; the liquid loop comprises a fuel cell stack 3, a first water pump 5, a second water pump 8, a first three-way valve 14, a second three-way valve 17 and a thermochemical heat storage device liquid channel 123; the liquid outlet of the fuel cell stack is connected with the second water pump 8, the liquid with the residual heat can be stored in the liquid storage tank 13 through the three-way valve 16, or can enter the liquid flow channel 123 of the thermochemical heat storage device to exchange heat with the thermochemical device 12, and the chemical desorption process of the strontium chloride ammine occurs, then the outlet of the liquid flow channel 123 of the thermochemical heat storage device is connected with the second three-way valve 17, and the fluid flowing through the second three-way valve 17 can be input into the fuel cell stack 3 through the first water pump 5, and can also enter the liquid storage tank 13 to be stored. The gas loop and the liquid loop are independent, only heat exchange occurs, and no matter exchange occurs; the hydrogen conveying device 2 is connected with the cathode of the fuel cell stack 3 to convey hydrogen for the fuel cell stack, the oxygen conveying device 4 is connected with the anode of the fuel cell stack 3 to convey oxygen for the fuel cell stack, and the temperature sensor 1 is connected with the fuel cell stack 3 to monitor the temperature of the fuel cell stack 3; the flow sensor 4 is arranged on a flow channel between the liquid outlet of the fuel cell stack 3 and the second water pump 8 and used for monitoring the flow of the liquid outlet of the fuel cell; the load state sensor 7 is connected to the load 10, and monitors the state of the load 10 to determine the next operating state of the fuel cell stack 3.
As shown in figure 3, the invention provides a fuel cell low-temperature starting heating and waste heat recovery system control method based on heat storage of strontium chloride ammine. The electronic control unit 9 determines whether the fuel cell stack 3 is operating normally or starting at a low temperature based on the temperature sensor 1, the flow sensor 6, and the load state sensor 7. When the fuel cell stack 3 is started at a low temperature, the system enters a preheating mode, the electronic control unit 9 controls the communicating valve 16 to be opened, ammonia gas in the high-pressure ammonia storage tank 15 enters the gas flow passage 122 of the thermochemical heat storage device 12, and chemically adsorbs strontium chloride-expanded graphite composite material therein to release heat, and controls the liquid storage tank 13 and the first three-way valve 14 to enable fluid to enter the liquid flow passage of the thermochemical heat storage device 12, and the fluid absorbs heat and is transferred to the fuel cell stack 3 through the second three-way valve 17 and the first water pump 5 to help the fuel cell stack 3 to be quickly started; when the fuel cell runs, the system enters a waste heat recovery mode, the electronic control unit 9 controls the communication valve 16 to be closed, the second water pump 8 and the first three-way valve 14 are controlled, fluid with waste heat of the fuel cell stack 3 enters a liquid flow channel of the thermochemical heat storage device 12, heat of the fluid is transferred to the thermochemical heat storage device 12, the strontium chloride amide hydrate is subjected to chemical desorption under the condition of being heated by the heat of the fluid in the liquid flow channel, and generated ammonia gas passes through an outlet of a gas flow channel of the thermochemical energy storage device 12 and returns to the high-pressure ammonia storage tank 15 through the air pump 11. The conversion and storage of the waste heat energy of the fuel cell stack 3 to the chemical energy of the chemical desorption product are completed.
The foregoing description is only for the purpose of illustrating the functional architecture and operational aspects of the present system and is not intended to be limiting. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A fuel cell low-temperature starting heating and waste heat recovery system based on heat storage of strontium chloride ammoniated is characterized by mainly comprising a fuel cell stack, a hydrogen conveying device, an oxygen conveying device, a temperature sensor, a flow sensor, a load state sensor, a first water pump, a second water pump, an air pump, an electronic control unit, a load, a thermochemical heat storage device, a first three-way valve, a second three-way valve, a communicating valve, a high-pressure ammonia storage tank and a liquid storage tank;
the thermochemical heat storage device comprises an insulating jacket, a liquid flow channel and a gas flow channel, wherein the liquid flow channel and the gas flow channel are arranged in the insulating jacket, the gas flow channel is filled with a strontium chloride-expanded graphite composite material, and the liquid flow channel and the gas flow channel conduct heat through the wall surface of the liquid flow channel;
the temperature sensor is connected with the fuel cell stack, the outlet of the hydrogen conveying device is connected with the cathode of the fuel cell, and the oxygen conveying device is connected with the anode of the fuel cell stack; the flow sensor is arranged in a flow channel between the liquid outlet of the fuel cell and the second water pump; the load state sensor is connected with a load; the outlet of the high-pressure ammonia storage tank is connected with the inlet of a gas flow passage of the thermochemical heat storage device through a communicating valve, and the outlet of the gas flow passage of the thermochemical heat storage device is connected with the inlet of the high-pressure ammonia storage tank through a gas pump; the second water pump is arranged in a flow channel between the liquid outlet of the fuel cell stack and the first three-way valve; the third interface of the first three-way valve is connected with the liquid storage tank, the second interface is connected with the liquid inlet of the thermochemical heat storage device, and the first interface is connected with the outlet of the second water pump; the liquid outlet of the thermochemical heat storage device is connected with a first interface of a second three-way valve; the third interface of the second three-way valve is connected with the liquid storage tank, and the second interface is connected with the cooling liquid inlet of the fuel cell through the first water pump;
the outer side of the thermochemical heat storage device is provided with an insulating shell, the inner side of the thermochemical heat storage device is provided with a snakelike liquid flow channel, and a strontium chloride-expanded graphite composite material is filled between the shell and the liquid flow channel; openings are formed in two opposite sides of the heat insulation cladding and used for the inlet and outlet of ammonia gas; the ammonia gas enters the thermochemical heat storage device from one side, and flows back to the high-pressure ammonia storage tank from the other side through the air pump;
the high-pressure ammonia storage tank is connected with a gas inlet of the phase-change heat storage device through a connecting valve, and gas can be supplied by opening the valve without electric drive when the high-pressure ammonia storage tank starts to work.
2. A fuel cell low-temperature starting heating and waste heat recovery method based on strontium ammine chloride heat storage of the system of claim 1 is characterized in that when the fuel cell is started at a low temperature, a control communication valve is opened, ammonia gas in a high-pressure ammonia storage tank enters a thermochemical heat storage device, the ammonia gas and a strontium chloride-expanded graphite composite material perform a chemical adsorption reaction to generate strontium ammine chloride and release heat, and fluid in a liquid flow channel absorbs heat and transfers the heat to a fuel cell stack to help the fuel cell stack to be started quickly;
when the fuel cell stack operates, the communicating valve is closed, the waste heat of the fuel cell is transferred into the thermochemical heat storage device through fluid, the strontium chloride ammoniated generates chemical desorption under the heating of the fluid in the liquid flow passage, and the generated ammonia gas returns to the high-pressure ammonia storage tank again;
the electronic control unit judges whether the fuel cell stack normally operates or starts at a low temperature according to the temperature sensor, the flow sensor and the load state sensor;
when the electronic control unit judges that the fuel cell is about to start at a low temperature, entering a preheating mode; the electronic control unit controls the communicating valve to be opened, so that ammonia gas enters the thermochemical heat storage device through the gas flow passage inlet of the thermochemical heat storage device; controlling the first three-way valve, the second three-way valve and the second water pump to enable liquid in the liquid storage tank to flow into the thermochemical heat storage device to complete heat exchange, and then sending the liquid into a coolant flow channel of the fuel cell stack to transfer heat released in the process of obtaining the strontium ammine chloride by carrying out chemical adsorption on ammonia and the strontium chloride-expanded graphite composite material to the fuel cell stack;
when the electronic control unit judges that the fuel cell stack normally works, the waste heat recovery mode is entered; the electronic control unit controls the communicating valve to be closed, the second water pump and the first three-way valve are opened to enable the fluid with the waste heat of the fuel cell stack to enter the thermochemical heat storage device, and under the action of the heat brought by the thermochemical heat storage device, the strontium chloride ammoniated absorbs the heat to complete the chemical desorption process, so that strontium chloride and ammonia are obtained; controlling the air pump to be started, and inputting the obtained ammonia gas into the high-pressure ammonia storage tank again to realize the process of storing the waste heat of the fuel cell in the form of chemical energy; and controlling the second three-way valve to convey the fluid after heat exchange to the liquid storage tank.
3. The method of claim 2, wherein: when a load sensor detects that the load has an energy requirement and the fuel cell stack needs to supply energy, judging the temperature state of the fuel cell stack according to a temperature sensor, and if the temperature sensor displays that the fuel cell stack is in a low-temperature state, starting at a low temperature;
if the temperature sensor displays that the fuel cell stack is in a non-low temperature state and the flow sensor detects that the liquid flow of the liquid outlet of the fuel cell stack is in the flow range of normal operation of the fuel cell stack, judging that the fuel cell is in a normal operation state, and entering a waste heat recovery mode; if the temperature sensor displays that the fuel cell stack is in a non-low temperature state, and the flow sensor does not detect that the liquid flow of the liquid outlet of the fuel cell stack is in the flow range of normal operation of the fuel cell stack, it is judged that the fuel cell is about to be started in a normal temperature state, and the system does not work.
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