Fuel cell system and startup method based on a fast self-heating solid-state hydrogen storage device

Abstract

The present invention relates to the technical field of hydrogen fuel cells, and provides a fuel cell system and a starting method based on a rapid self-heating solid hydrogen storage device. The system includes a solid hydrogen storage device, a gas storage tank, a fuel cell device, and a heat exchange water tank; the solid hydrogen storage device is arranged in the heat exchange water tank. The solid hydrogen storage device includes an outer and an inner hydrogen storage tank. The outlet of the inner hydrogen storage tank extends out of the outer hydrogen storage tank and is communicated with the gas storage tank. The outer and inner hydrogen storage tanks are respectively filled with low- and high-enthalpy hydrogen storage alloys; the outer hydrogen storage tank and the gas storage tank are both communicated with the fuel cell; the heat exchange water tank and the fuel cell are communicated through cold and hot water pipelines, and a circulating water pump is arranged on the hot water pipeline. The present invention can rapidly self-heat and release hydrogen in the initial stage of starting, greatly shortening the time required for the solid hydrogen storage device to reach normal hydrogen supply in the initial stage of starting, enabling the fuel cell system to start quickly and stably, and the self-heating starting function can be rapidly restored. The volume of the gas storage tank and the hydrogen storage device is greatly reduced, and the safety and flexibility of the operation of the fuel cell system are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen fuel cells, and in particular to a fuel cell system and a starting method based on a rapid self-heating solid hydrogen storage device. Background Art

[0002] With the increasing demand for clean energy in all sectors of society, fuel cells using hydrogen are gradually entering the market. Among them, fuel cell systems equipped with low-pressure solid hydrogen storage devices have attracted wide attention due to their high safety, high volumetric hydrogen storage density, and fast hydrogen charging characteristics.

[0003] In the actual application of fuel cell systems, solid hydrogen storage devices need to meet the application requirements under various climatic conditions, especially pay attention to solving the hydrogen supply problem during cold start under low-temperature conditions.

[0004] The hydrogen supply problem during cold start under low-temperature conditions: When the fuel cell starts up, the hydrogen storage device should quickly supply hydrogen to the fuel cell to meet the dynamic response requirements of the system. The hydrogen absorption and desorption process of the hydrogen storage material is a chemical adsorption or desorption process, which needs to absorb heat from the environment. When the hydrogen storage device is matched with the fuel cell, under the normal working conditions of the fuel cell, the waste heat of the fuel cell can enter the hydrogen storage device through the thermal coupling heat exchange system to provide the heat source required for the hydrogen desorption of the hydrogen storage material. However, during cold start at low temperatures, the fuel cell does not operate to generate heat and cannot provide the heat source required for the hydrogen desorption of the hydrogen storage material. The hydrogen storage material can only obtain heat from the air or other heat transfer media in the surrounding environment. At this time, if the hydrogen desorption equilibrium pressure of the hydrogen storage material is low under low-temperature conditions and the hydrogen desorption driving force decreases, if the heat provided by the outside world cannot meet the hydrogen desorption requirements of the hydrogen storage material, the required hydrogen source cannot be provided for the fuel cell. At the same time, the normal working temperature of the fuel cell is generally 60°C. After it starts up itself, it also needs to go through a heating process from room temperature to the working temperature to supply full power. During this period, the waste heat is mainly used for the self-heating of the fuel cell stack and it is difficult to provide sufficient heat energy for the solid hydrogen storage device. Especially when the room temperature is too low in winter, the heat energy required for the self-heating of the circulating water used for heat exchange between the fuel cell stack and the solid hydrogen storage device also needs to be considered. Summary of the Invention

[0005] Aiming at the problems existing in the prior art, the present invention provides a fuel cell system and a starting method based on a rapid self-heating solid hydrogen storage device, which can rapidly self-heat and desorb hydrogen at the initial stage of startup without relying on the waste heat of the fuel cell and environmental heat energy, greatly shortening the time required for the solid hydrogen storage device to reach normal hydrogen supply at the initial stage of startup, enabling the fuel cell system to start quickly and stably, and the self-heating startup function can be quickly restored, greatly reducing the volume of the gas storage tank and the solid hydrogen storage device, and improving the safety and flexibility of the operation of the fuel cell system.

[0006] The technical solution of the present invention is as follows:

[0007] A fuel cell system based on a rapid self-heating solid hydrogen storage device, characterized in that it includes a solid hydrogen storage device (1), a gas storage tank (2), a fuel cell device (3), and a heat exchange water tank (5);

[0008] The solid hydrogen storage device (1) is arranged in the heat exchange water tank (5). The solid hydrogen storage device (1) includes an outer hydrogen storage tank (1.1) and an inner hydrogen storage tank (1.2) arranged inside the outer hydrogen storage tank (1.1). The outlet (1.7) of the inner hydrogen storage tank extends out of the outer hydrogen storage tank (1.1) and is communicated with the inlet of the gas storage tank (2). The outer hydrogen storage tank (1.1) is filled with a low heat enthalpy hydrogen storage alloy (1.3), and the inner hydrogen storage tank (1.2) is filled with a high heat enthalpy hydrogen storage alloy (1.4);

[0009] The fuel cell device (3) includes a fuel cell (3.2). The outlet (1.6) of the outer hydrogen storage tank and the outlet of the gas storage tank (2) are both communicated with the inlet of the fuel cell (3.2) through a hydrogen pipeline (3.1). A solenoid valve (4) is arranged on the hydrogen pipeline (3.1) connected between the outlet (1.6) of the outer hydrogen storage tank and the fuel cell (3.2). The liquid outlet of the heat exchange water tank (5) is communicated with the liquid inlet of the fuel cell (3.2) through a cold water pipeline (3.4). The liquid outlet of the fuel cell (3.2) is communicated with the liquid inlet of the heat exchange water tank (5) through a hot water pipeline (3.5). A circulation water pump (3.3) is arranged on the hot water pipeline (3.5).

[0010] Further, filter sheets (1.8) are arranged inside the outlet (1.7) of the inner hydrogen storage tank and the outlet (1.6) of the outer hydrogen storage tank.

[0011] Further, a plurality of fins (1.5) are arranged on the outer side wall of the inner hydrogen storage tank (1.2).

[0012] Further, the plurality of fins (1.5) are radially radiated and arranged along the inner hydrogen storage tank (1.2).

[0013] Further, the heat enthalpy of the low heat enthalpy hydrogen storage alloy (1.3) is 20 - 30 KJ / mol, and the heat enthalpy of the high heat enthalpy hydrogen storage alloy (1.4) is 30 - 60 KJ / mol.

[0014] Further, the heat enthalpy of the high heat enthalpy hydrogen storage alloy (1.4) is 50 - 60 KJ / mol.

[0015] Further, the low heat enthalpy hydrogen storage alloy (1.3) is a TiMn 0.8 Fe 0.15 Co 0.05 alloy, and the high heat enthalpy hydrogen storage alloy (1.4) is a Ti 0.8Zr 0.2 Mn 1.5 Fe 0.4 Ni 0.1 alloy

[0016] A starting method for a fuel cell system of the above-mentioned solid-state hydrogen storage device based on rapid self-heating, characterized by comprising the following steps:

[0017] Step 1: Fill the external hydrogen storage tank (1.1) with hydrogen and keep the internal hydrogen storage tank (1.2) in an unfilled state;

[0018] Step 2: Start the fuel cell system, control the gas storage tank (2) to supply hydrogen to the fuel cell (3.2) and the internal hydrogen storage tank (1.2) simultaneously, start the fuel cell (3.2), and at the same time, the high heat enthalpy hydrogen storage alloy (1.4) in the internal hydrogen storage tank (1.2) absorbs hydrogen and releases heat, and the heat is conducted to the external hydrogen storage tank (1.1), and the low heat enthalpy hydrogen storage alloy (1.3) in the external hydrogen storage tank (1.1) increases in temperature and releases hydrogen;

[0019] Step 3: After the fuel cell (3.2) is started, the temperature of the stack increases, heating the water circulating inside, and the circulating water pump (3.3) pumps the hot water into the heat exchange water tank (5). The heat exchange water tank (5) provides heat for the solid-state hydrogen storage device (1). The low heat enthalpy hydrogen storage alloy (1.3) in the external hydrogen storage tank (1.1) and the high heat enthalpy hydrogen storage alloy (1.4) in the internal hydrogen storage tank (1.2) jointly increase in temperature and release hydrogen. The external hydrogen storage tank (1.1) directly supplies hydrogen to the fuel cell (3.2), and the external hydrogen storage tank (1.1) and the internal hydrogen storage tank (1.2) jointly supply hydrogen to the gas storage tank (2).

[0020] Further, in the above-mentioned Step 2, when the starting ambient temperature is -20°C to 0°C and the pressure provided by the external hydrogen storage tank (1.1) is lower than 0.1 MPa, the gas storage tank (2) supplies hydrogen to the fuel cell (3.2) independently at an initial pressure of 1 MPa to 2 MPa for 5 minutes to 10 minutes, and then opens the solenoid valve (4) to supply hydrogen from the external hydrogen storage tank (1.1) to the fuel cell (3.2).

[0021] Further, the ratio of the volume value of the gas storage tank (2) to the power value of the fuel cell (3.2) is (5 - 8):1; where the unit of volume is L and the unit of power is kW.

[0022] The beneficial effects of the present invention are:

[0023] (1) The present invention can realize hydrogen supply from the gas storage tank to the fuel cell in a low-temperature environment so that the fuel cell can be quickly started by arranging an external hydrogen storage tank in the heat exchange water tank, arranging an internal hydrogen storage tank in the external hydrogen storage tank, connecting the internal hydrogen storage tank to the gas storage tank, connecting both the external hydrogen storage tank and the gas storage tank to the fuel cell, and forming a water circulation system between the fuel cell and the heat exchange water tank through a water pipe and a circulation water pump. At the same time, the gas storage tank supplies hydrogen to the internal hydrogen storage tank so that the high-enthalpy hydrogen storage alloy inside absorbs hydrogen and releases heat, and the heat is conducted to the external hydrogen storage tank so that the low-enthalpy hydrogen storage alloy inside is heated up and releases hydrogen. This enables rapid self-heating and hydrogen release at the initial stage of startup without relying on the waste heat of the fuel cell and environmental heat energy, saves time for the generation of sufficient waste heat by the fuel cell, and greatly shortens the time for the normal hydrogen supply of the solid hydrogen storage device at the initial stage of startup, enabling the fuel cell system to be quickly and stably started. It solves the technical problem that the existing fuel cell system is difficult to provide sufficient heat energy for the hydrogen release of the hydrogen storage material in the solid hydrogen storage device at startup in a low-temperature environment, thus unable to be stably started.

[0024] (2) The gas storage tank set in the present invention can independently supply hydrogen to the fuel cell when the startup ambient temperature is -20°C to 0°C and the pressure provided by the external hydrogen storage tank is small, saving time for the hydrogen release of the external hydrogen storage tank. After the fuel cell is started and the fuel cell stack can provide sufficient heat for the solid hydrogen storage device, the hydrogen storage alloys in the internal and external hydrogen storage tanks are heated up and release hydrogen together. The external hydrogen storage tank supplies hydrogen to the fuel cell stably and continuously, and the internal and external hydrogen storage tanks jointly fill hydrogen into the gas storage tank, enabling the hydrogen pressure in the gas storage tank to be restored. It realizes the ability to start again and quickly self-heat to make the external hydrogen storage tank fully release hydrogen after the system is temporarily shut down, and greatly reduces the volume of the gas storage tank for storing gaseous hydrogen and the overall volume of the solid hydrogen storage device, improving the safety and flexibility of the operation of the fuel cell system.

[0025] (3) By arranging a plurality of fins radially and radiantly on the outer side wall of the internal hydrogen storage tank, the present invention can enhance the heat conduction effect between the internal hydrogen storage tank and the external hydrogen storage tank. Description of the Drawings

[0026] Figure 1 is a schematic structural diagram of a fuel cell system based on a solid hydrogen storage device with rapid self-heating according to the present invention.

[0027] Figure 2 is a schematic structural diagram of a solid hydrogen storage device in a fuel cell system based on a solid hydrogen storage device with rapid self-heating according to the present invention.

[0028] Figure 3 is Figure 2 a sectional view taken along the A-A direction of

[0029] Figure 4 is a comparison chart of the low-temperature pressure reduction test results of the solid hydrogen storage device and the gas storage tank at 20°C / 10°C / 0°C / -10°C / -20°C.

[0030] Figure 5 It is a comparison chart of the self-heating test results after the start-up of a solid-state hydrogen storage device without a self-heating internal hydrogen storage tank and the solid-state hydrogen storage device with a self-heating internal hydrogen storage tank of the present invention in a low-temperature environment of -20°C.

[0031] In the figure, 1 - solid-state hydrogen storage device, 1.1 - external hydrogen storage tank, 1.2 - internal hydrogen storage tank, 1.3 - low heat-enthalpy hydrogen storage alloy, 1.4 - high heat-enthalpy hydrogen storage alloy, 1.5 - fin, 1.6 - external hydrogen storage tank outlet, 1.7 - internal hydrogen storage tank outlet, 1.8 - filter, 2 - gas storage tank, 3 - fuel cell device, 3.1 - hydrogen pipeline, 3.2 - fuel cell, 3.3 - circulation water pump, 3.4 - cold water pipeline, 3.5 - hot water pipeline, 4 - solenoid valve, 5 - hot water exchange tank. Specific embodiments

[0032] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

[0033] As Figure 1 shown, the fuel cell system based on the rapid self-heating solid-state hydrogen storage device of the present invention includes a solid-state hydrogen storage device 1, a gas storage tank 2, a fuel cell device 3, and a hot water exchange tank 5.

[0034] The solid-state hydrogen storage device 1 is arranged in the hot water exchange tank 5. The solid-state hydrogen storage device 1 includes an external hydrogen storage tank 1.1 and an internal hydrogen storage tank 1.2 arranged inside the external hydrogen storage tank 1.1. The internal hydrogen storage tank outlet 1.7 extends out of the external hydrogen storage tank 1.1 and is communicated with the air inlet of the gas storage tank 2. The external hydrogen storage tank 1.1 is filled with a low heat-enthalpy hydrogen storage alloy 1.3, and the internal hydrogen storage tank 1.2 is filled with a high heat-enthalpy hydrogen storage alloy 1.4. In this embodiment, the end face of the internal hydrogen storage tank outlet 1.7 extending out of the external hydrogen storage tank 1.1 is opposite to the external hydrogen storage tank outlet 1.6.

[0035] The fuel cell device 3 includes a fuel cell 3.2. The outlet of the external hydrogen storage tank 1.6 and the outlet of the gas storage tank 2 are both connected to the inlet of the fuel cell 3.2 through a hydrogen pipeline 3.1. An electromagnetic valve 4 is provided on the hydrogen pipeline 3.1 connected between the outlet of the external hydrogen storage tank 1.6 and the fuel cell 3.2. The liquid outlet of the heat exchange water tank 5 is connected to the liquid inlet of the fuel cell 3.2 through a cold water pipeline 3.4. The liquid outlet of the fuel cell 3.2 is connected to the liquid inlet of the heat exchange water tank 5 through a hot water pipeline 3.5. A circulation water pump 3.3 is provided on the hot water pipeline 3.5. A water circulation system is formed between the fuel cell 3.2 and the heat exchange water tank 5. When the fuel cell stack works, power is supplied to the circulation water pump 3.3 at the same time. The circulating water flows into the fuel cell 3.2 from the cold water pipeline 3.4, absorbs waste heat, and then flows into the heat exchange water tank 5 along the hot water pipeline 3.5, where the heat is absorbed by the hydrogen release endothermic process of the solid hydrogen storage device 1, and the cold water then flows back to the fuel cell 3.2 from the cold water pipeline 3.4.

[0036] In this embodiment, as Figure 2 shown, filter sheets 1.8 are provided inside both the outlet of the internal hydrogen storage tank 1.7 and the outlet of the external hydrogen storage tank 1.6, respectively for filtering powders of the hydrogen entering and leaving the internal hydrogen storage tank 1.2 and the external hydrogen storage tank 1.1.

[0037] A plurality of fins 1.5 are provided on the outer side wall of the internal hydrogen storage tank 1.2. In this embodiment, as Figure 3 shown, the plurality of fins 1.5 are radially radiated and arranged along the internal hydrogen storage tank 1.2, which can enhance the heat conduction effect between the internal hydrogen storage tank 1.2 and the external hydrogen storage tank 1.1.

[0038] The heat enthalpy of the low heat enthalpy hydrogen storage alloy 1.3 is 20 - 30 KJ / mol, and the heat enthalpy of the high heat enthalpy hydrogen storage alloy 1.4 is 30 - 60 KJ / mol. Preferably, the heat enthalpy of the high heat enthalpy hydrogen storage alloy 1.4 is 50 - 60 KJ / mol.

[0039] The starting method of the fuel cell system based on the rapid self-heating solid hydrogen storage device of the present invention includes the following steps:

[0040] Step 1: Fill the external hydrogen storage tank 1.1 with hydrogen and keep the internal hydrogen storage tank 1.2 in an unfilled state;

[0041] Step 2: Turn on the fuel cell system, control the gas storage tank 2 to supply hydrogen to both the fuel cell 3.2 and the internal hydrogen storage tank 1.2 at the same time, start the fuel cell 3.2, and at the same time, the high heat enthalpy hydrogen storage alloy 1.4 in the internal hydrogen storage tank 1.2 absorbs hydrogen and releases heat, and the heat is conducted to the external hydrogen storage tank 1.1, and the low heat enthalpy hydrogen storage alloy 1.3 in the external hydrogen storage tank 1.1 is heated and releases hydrogen;

[0042] Step 3: After the fuel cell 3.2 is started, the temperature of the stack rises, heating the water in the internal circulation. The circulation water pump 3.3 pumps the hot water into the heat exchange water tank 5. The heat exchange water tank 5 provides heat for the solid hydrogen storage device 1. The low heat enthalpy hydrogen storage alloy 1.3 in the external hydrogen storage tank 1.1 and the high heat enthalpy hydrogen storage alloy 1.4 in the internal hydrogen storage tank 1.2 are heated up together to release hydrogen. The external hydrogen storage tank 1.1 directly supplies hydrogen to the fuel cell 3.2, and the external hydrogen storage tank 1.1 and the internal hydrogen storage tank 1.2 jointly supply hydrogen to the gas storage tank 2.

[0043] Among them, the gas storage tank 2 has the following functions during the operation of the fuel cell system of the present invention: 1) When the temperature is low and the remaining hydrogen storage amount in the external hydrogen storage tank 1.1 is low, it is a hydrogen pressure maintaining tank that ensures the cold start hydrogen supply of the fuel cell 3.2; 2) During the normal operation process, it is a buffer tank that keeps the hydrogen pressure and flow rate stable.

[0044] When the starting ambient temperature is -20°C to 0°C and the pressure provided by the external hydrogen storage tank 1.1 is lower than 0.1 MPa, the gas storage tank 2 supplies hydrogen to the fuel cell 3.2 independently at an initial pressure of 1 MPa to 2 MPa for 5 minutes to 10 minutes, and then the solenoid valve 4 is opened to supply hydrogen to the fuel cell 3.2 from the external hydrogen storage tank 1.1. While the gas storage tank 2 supplies hydrogen to the fuel cell 3.2, it also supplies hydrogen to the internal hydrogen storage tank 1.2, so that the temperature of the internal hydrogen storage tank 1.2 reaches 40 - 45°C, the temperature of the external hydrogen storage tank 1.1 reaches above 10°C, and the hydrogen release pressure of the external hydrogen storage tank 1.1 reaches 0.2 - 0.3 MPa. The volume of the gas storage tank 2 is determined according to the power of the fuel cell 3.2, and the ratio of the volume value of the gas storage tank 2 to the power value of the fuel cell 3.2 is 5 - 8:1; among them, the unit of volume is L and the unit of power is kW.

[0045] When the fuel cell system of the present invention operates normally, the solid hydrogen storage device 1 releases hydrogen. Due to the limitation of heat and mass transfer of the metal hydride bed in its tank, the hydrogen release flow rate of the solid hydrogen storage device 1 will have certain fluctuations. The gas storage tank 2 can be used as a buffer tank for the hydrogen released by the solid hydrogen storage device 1, improving the stability of the hydrogen source, making the hydrogen supply pressure and flow rate to the fuel cell 3.2 more stable, and meeting the dynamic response requirements of the fuel cell 3.2 for operation.

[0046] In this embodiment, a low-temperature simulation environment test is carried out on the system of the present invention. Fill TiMn 0.8 Fe 0.15 Co 0.05 alloy powder in the external hydrogen storage tank 1.1, and fill Ti 0.8 Zr 0.2 Mn 1.5 Fe 0.4 Ni 0.1Alloy powder. The external hydrogen storage tank 1.1 is filled with hydrogen at room temperature (20 °C) to 3 MPa, and the internal hydrogen storage tank 1.2 remains unfilled. Subsequently, 70% of the hydrogen in the external hydrogen storage tank 1.1 is released, leaving 30% of the residual hydrogen storage capacity. After the pressure stabilizes, the pressure at room temperature (20 °C) is measured to be 2.621 MPa. After the air pressure stabilizes, it is cooled with low-temperature circulating antifreeze to 10 °C, and the internal pressure change of the external hydrogen storage tank 1.1 is measured through a pressure gauge. After the pressure stabilizes, it is further cooled to 0 °C, and after the pressure stabilizes, it is continuously cooled to -10 °C, and after the pressure stabilizes, it is continuously cooled to -20 °C. The same cooling operation is applied to the gas storage tank 2. The curves of the internal pressures of the external hydrogen storage tank 1.1 and the gas storage tank 2 changing with temperature are as Figure 4 shown. It can be seen from Figure 4 that the pressure in the external hydrogen storage tank 1.1 drops to 1.592 MPa at 10 °C, drops to 0.436 MPa at 0 °C, and has dropped below 0.001 MPa at -10 °C; while the pressure in the gas storage tank 2 drops to 2.689 MPa at 10 °C, drops to 2.391 MPa at 0 °C, drops to 2.098 MPa at -10 °C, and drops to 1.814 MPa at -20 °C.

[0047] Subsequently, a low-temperature self-heating test is carried out on the system. At an ambient temperature of -20 °C, the hydrogen in the gas storage tank 2 is used to start the fuel cell 3.2, and the circulating water is turned on to introduce the waste heat of the fuel cell 3.2 stack into the heat exchange water tank 5 of the solid hydrogen storage device without a self-heating internal hydrogen storage tank 1.2. After 10 minutes, the temperature of the solid hydrogen storage device rises from -20.1 °C to -12.4 °C, and the outlet hydrogen pressure is still less than 0.001 MPa. After 17 minutes, the outlet temperature of the solid hydrogen storage device rises from -19.9 °C to 10.4 °C, and the outlet hydrogen pressure reaches 0.168 MPa. Under the same conditions, the hydrogen in the gas storage tank 2 is introduced into the internal hydrogen storage tank 1.2 of the solid hydrogen storage device 1. After 5 minutes, the temperature of the internal hydrogen storage tank 1.2 rises from -19.8 °C to 41.3 °C, the outlet temperature of the external gas storage tank 1.1 rises from -20.2 °C to 11.2 °C, and the outlet hydrogen pressure of the external hydrogen storage tank 1.1 reaches 0.171 MPa. The temperature and pressure changes of the solid hydrogen storage device without a self-heating internal hydrogen storage tank and the solid hydrogen storage device with a self-heating internal hydrogen storage tank of the present invention after starting in a -20 °C low-temperature environment are as Figure 5 shown.

[0048] The results show that for an ordinary solid-state hydrogen storage device, when the hydrogen storage capacity of the external hydrogen storage tank 1.1 is 30%, the internal pressure will drop to nearly 0 MPa at -10°C and cannot supply hydrogen to the fuel cell. However, the hydrogen gas pressure in the gas storage tank 2 can remain at 1.814 MPa at -20°C and can supply sufficient starting hydrogen to the fuel cell. At the same time, for a solid-state hydrogen storage device without using the rapid self-heating internal hydrogen storage tank 1.2, it takes 16 minutes to start normal hydrogen supply, while for a solid-state hydrogen storage device using the rapid self-heating internal hydrogen storage tank, it only takes 5 minutes to achieve the effect of normal hydrogen supply, which can significantly reduce the volume of the gas storage tank for storing gaseous hydrogen in the hydrogen storage device, reduce the overall volume of the hydrogen storage device, and improve the safety and flexibility of the power system operation.

[0049] It can be seen that the solid-state hydrogen storage device 1 in the fuel cell system of the present invention not only has a high weight hydrogen storage rate and meets the requirements for continuous power supply of the fuel cell 3.2, but also meets the requirements for cold start of the fuel cell 3.2 through system design. When the fuel cell 3.2 starts at low temperature and the hydrogen storage material cannot release hydrogen quickly, the gas storage tank 2 in the system can provide the starting hydrogen source for the fuel cell 3.2 first, and at the same time release hydrogen into the internal hydrogen storage tank 1.2. The high heat enthalpy hydrogen storage alloy in the internal hydrogen storage tank 1.2 is in an unhydrogenated state and releases a large amount of heat after absorbing hydrogen, heating the low heat enthalpy hydrogen storage alloy in the external hydrogen storage tank 1.1, so that the low heat enthalpy hydrogen storage alloy in the external hydrogen storage tank 1.1 can quickly heat up and provide a hydrogen source that meets the starting requirements in terms of pressure and flow rate, realizing the stable start of the fuel cell 3.2. After the fuel cell 3.2 operates stably, the temperature of the fuel cell stack rises, and the waste heat dissipated by it is introduced into the heat exchange water tank 5 through the hot water pipeline to heat the solid-state hydrogen storage device 1, further increasing the temperature of the hydrogen storage bed in the solid-state hydrogen storage device 1 and promoting the normal hydrogen release of the hydrogen storage alloy. Since the hydrogen release temperature of the high heat enthalpy hydrogen storage alloy in the internal hydrogen storage tank 1.2 is lower than that of the low heat enthalpy hydrogen storage alloy in the external hydrogen storage tank 1.1, during the normal operation of the fuel cell 3.2, the internal hydrogen storage tank 1.2 absorbs waste heat and first discharges the hydrogen inside, and together with the external hydrogen storage tank 1.1, replenishes hydrogen to the gas storage tank 2, so that the rapid self-heating start function returns to the standby state.

[0050] Obviously, the above embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. The above embodiments are only used to explain the present invention and do not constitute a limitation on the protection scope of the present invention. Based on the above embodiments, all other embodiments obtained by those skilled in the art without creative labor, that is, all modifications, equivalent replacements, and improvements made within the spirit and principle of this application, all fall within the protection scope required by the present invention.

Claims

1. A fuel cell system based on a rapid self-heating solid-state hydrogen storage device, characterized in that, It includes a solid-state hydrogen storage device (1), a gas storage tank (2), a fuel cell device (3), and a heat exchange water tank (5). The solid-state hydrogen storage device (1) is arranged in the heat exchange water tank (5). The solid-state hydrogen storage device (1) includes an outer hydrogen storage tank (1.1) and an inner hydrogen storage tank (1.2) arranged inside the outer hydrogen storage tank (1.1). The outlet (1.7) of the inner hydrogen storage tank extends out of the outer hydrogen storage tank (1.1) and is communicated with the inlet of the gas storage tank (2). The outer hydrogen storage tank (1.1) is filled with a low heat enthalpy hydrogen storage alloy (1.3), and the inner hydrogen storage tank (1.2) is filled with a high heat enthalpy hydrogen storage alloy (1.4). The fuel cell device (3) includes a fuel cell (3.2). The outlet (1.6) of the outer hydrogen storage tank and the outlet of the gas storage tank (2) are both communicated with the inlet of the fuel cell (3.2) through a hydrogen pipeline (3.1). An electromagnetic valve (4) is arranged on the hydrogen pipeline (3.1) connected between the outlet (1.6) of the outer hydrogen storage tank and the fuel cell (3.2). The liquid outlet of the heat exchange water tank (5) is communicated with the liquid inlet of the fuel cell (3.2) through a cold water pipeline (3.4). The liquid outlet of the fuel cell (3.2) is communicated with the liquid inlet of the heat exchange water tank (5) through a hot water pipeline (3.5). A circulation water pump (3.3) is arranged on the hot water pipeline (3.5).

2. The fuel cell system based on a rapid self-heating solid-state hydrogen storage device according to claim 1, characterized in that, Filter sheets (1.8) are arranged in both the outlet (1.7) of the inner hydrogen storage tank and the outlet (1.6) of the outer hydrogen storage tank.

3. The fuel cell system based on a rapid self-heating solid-state hydrogen storage device according to claim 1, characterized in that, A plurality of fins (1.5) are arranged on the outer side wall of the inner hydrogen storage tank (1.2).

4. The fuel cell system based on a rapid self-heating solid-state hydrogen storage device according to claim 3, characterized in that, The plurality of fins (1.5) are radially radiated and arranged along the inner hydrogen storage tank (1.2).

5. The fuel cell system based on a rapid self-heating solid-state hydrogen storage device according to claim 1, characterized in that, The heat enthalpy of the low heat enthalpy hydrogen storage alloy (1.3) is 20 - 30 KJ / mol, and the heat enthalpy of the high heat enthalpy hydrogen storage alloy (1.4) is 30 - 60 KJ / mol.

6. The fuel cell system based on a rapid self-heating solid-state hydrogen storage device according to claim 5, characterized in that, The heat enthalpy of the high heat enthalpy hydrogen storage alloy (1.4) is 50 - 60 KJ / mol.

7. The fuel cell system based on a rapid self-heating solid-state hydrogen storage device according to claim 1, characterized in that, The low heat enthalpy hydrogen storage alloy (1.3) is TiMn 0.8 Fe 0.15 Co 0.05 alloy, and the high heat enthalpy hydrogen storage alloy (1.4) is Ti 0.8 Zr 0.2 Mn 1.5 Fe 0.4 Ni 0.1 alloy.

8. A starting method for the fuel cell system based on a rapid self-heating solid-state hydrogen storage device according to any one of claims 1 to 7, characterized in that, It includes the following steps: Step 1: Fill hydrogen into the outer hydrogen storage tank (1.1) and keep the inner hydrogen storage tank (1.2) in an unfilled state. Step 2: Start the fuel cell system, control the gas storage tank (2) to supply hydrogen to both the fuel cell (3.2) and the inner hydrogen storage tank (1.2) simultaneously, start the fuel cell (3.2), and at the same time, the high heat enthalpy hydrogen storage alloy (1.4) in the inner hydrogen storage tank (1.2) absorbs hydrogen and releases heat, and the heat is conducted to the outer hydrogen storage tank (1.1), and the low heat enthalpy hydrogen storage alloy (1.3) in the outer hydrogen storage tank (1.1) heats up and releases hydrogen. Step 3: After the fuel cell (3.2) is started, the temperature of the stack rises, heating the water circulating inside. The circulation water pump (3.3) pumps the hot water into the heat exchange water tank (5). The heat exchange water tank (5) provides heat for the solid-state hydrogen storage device (1). The low heat enthalpy hydrogen storage alloy (1.3) in the outer hydrogen storage tank (1.1) and the high heat enthalpy hydrogen storage alloy (1.4) in the inner hydrogen storage tank (1.2) jointly heat up and release hydrogen. The outer hydrogen storage tank (1.1) directly supplies hydrogen to the fuel cell (3.2). The outer hydrogen storage tank (1.1) and the inner hydrogen storage tank (1.2) jointly fill hydrogen into the gas storage tank (2).

9. The starting method for the fuel cell system based on a rapid self-heating solid-state hydrogen storage device according to claim 8, characterized in that, In step 2, when the starting ambient temperature is -20°C to 0°C and the pressure provided by the external hydrogen storage tank (1.1) is lower than 0.1 MPa, the gas storage tank (2) supplies hydrogen to the fuel cell (3.2) independently at an initial pressure of 1 MPa to 2 MPa for 5 minutes to 10 minutes, and then the solenoid valve (4) is opened to supply hydrogen from the external hydrogen storage tank (1.1) to the fuel cell (3.2).

10. The starting method for the fuel cell system based on a rapid self-heating solid-state hydrogen storage device according to claim 8, characterized in that, The ratio of the volume value of the gas storage tank (2) to the power value of the fuel cell (3.2) is (5 - 8):1; where the unit of volume is L and the unit of power is kW.

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