Multilayer temperature control solid hydrogen storage device capable of rapidly releasing hydrogen and working method

Abstract

The invention discloses a multilayer temperature control solid hydrogen storage device capable of rapidly releasing hydrogen and a working method, and belongs to the technical field of solid hydrogen storage. The solid hydrogen storage device comprises a solid hydrogen storage module, a heat management system, a sensor system and a controller; the solid hydrogen storage module comprises a first-stage hydrogen storage module and a second-stage hydrogen storage module which are connected with the fuel cell stack through a gas circuit, the thermal management system can be respectively configured as a hydrogen desorption subsystem and a hydrogen absorption subsystem, and the controller controls the heating unit, the refrigeration unit and the multi-way valve according to the temperature of the anti-freezing solution and hydrogen absorption / desorption state information. And performing thermal management on the first-stage hydrogen storage module and the second-stage hydrogen storage module. According to the invention, thermal management can be respectively carried out in two working states of hydrogen absorption and hydrogen desorption without adding a buffer tank, and rapid hydrogen desorption and low-energy-consumption hydrogen charging in a low-temperature state can be realized.

Description

TECHNICAL FIELD

[0001] The application relates to the field of solid-state hydrogen storage technology, in particular to a multi-layer temperature control solid-state hydrogen storage device for rapid hydrogen release and a working method thereof. BACKGROUND

[0002] Solid-state hydrogen storage has the advantages of large hydrogen storage capacity, simple storage conditions and long service life. The characteristics of metal alloy are large storage capacity and safe use. However, stable hydride needs to be dehydrogenated (hydrogen released) at a high temperature. Metal hydride releases hydrogen when heated. This process is called desorption. At present, in order to meet the demand for hydrogen at low temperature, a gaseous hydrogen buffer tank is integrated in the solid-state hydrogen storage device to collect hydrogen. The system works by using the hydrogen in the buffer tank to realize the low-temperature cold start of the fuel cell system.

[0003] The main advantages of fuel cell engineering machinery include zero emission, low noise and fast hydrogenation. The solid-state hydrogen storage fuel cell engineering machinery can reduce the space of the hydrogen storage system in the overall structure arrangement, and ensure the effective volume of the material carrying of the engineering machinery. At the same time, the operating temperature of the fuel cell system is generally 50-80℃, which can effectively match the dehydrogenation temperature requirement of the solid-state hydrogen storage.

[0004] Please refer to the patent document with the publication number CN114709444A. The invention discloses a fuel cell system based on a fast self-heating solid-state hydrogen storage device. The system includes a solid-state hydrogen storage device, a gas storage tank, a fuel cell device, and a heat exchange tank. The solid-state hydrogen storage device is arranged in the heat exchange tank. The solid-state hydrogen storage device includes an outer and inner hydrogen storage tank. The outlet of the inner hydrogen storage tank extends out of the outer hydrogen storage tank and is connected to the gas storage tank. The outer and inner hydrogen storage tanks are respectively filled with low and high heat enthalpy hydrogen storage alloys. The outer hydrogen storage tank and the gas storage tank are connected to the fuel cell. The heat exchange tank is connected to the fuel cell through cold and hot water pipelines, and the hot water pipeline is provided with a circulating water pump. The invention can quickly release hydrogen at the initial start-up stage, greatly shortening the time required for the solid-state hydrogen storage device to reach normal hydrogen supply at the initial start-up stage.

[0005] Please refer to the patent document with the publication number CN114566679A. The invention discloses an all-weather fast-response solid-state hydrogen storage system for fuel cells, which includes a solid-state hydrogen storage material placement tank, a check valve, a hydrogen supply pipe, an electric heating pipe interface, a cold and hot water joint, etc. At the same time, the patent also increases the weather prediction model, which predicts the weather through historical data, and then realizes the non-lagging hydrogen supply of the system, ensuring the fast start-up of the fuel cell.

[0006] In the prior art, the focus is on how to quickly release hydrogen at low temperature in the solid-state hydrogen storage system. The main method is to add a hydrogen buffer tank to store the gaseous hydrogen released from the solid-state hydrogen storage system, thereby ensuring the quick start of the fuel cell system. However, the newly added buffer tank stores gaseous hydrogen and is limited by the release platform pressure of the solid-state hydrogen storage, and the volume hydrogen storage density is small, which will result in a large volume of the buffer tank and affect the overall arrangement of the mobile device. SUMMARY

[0007] The purpose of the present application is to overcome the shortcomings of the prior art, provide a multi-layer temperature-controlled solid-state hydrogen storage device for quickly releasing hydrogen and a working method, which aims to achieve quick hydrogen release of the solid-state hydrogen storage system at low temperature without adding a buffer tank, and at the same time realizes a low-energy hydrogen charging process through the thermal management architecture of the solid-state hydrogen storage system.

[0008] To achieve the above-mentioned purpose, the present application is realized by using the following technical solutions:

[0009] In a first aspect, the present application provides a multi-layer temperature-controlled solid-state hydrogen storage device for quickly releasing hydrogen, comprising a solid-state hydrogen storage module, a thermal management system, a sensor system and a controller; The solid-state hydrogen storage module comprises a one-stage hydrogen storage module and a two-stage hydrogen storage module connected by a gas circuit with a fuel cell stack, and the one-stage hydrogen storage module and the two-stage hydrogen storage module each contain an antifreeze for heat exchange; the one-stage hydrogen storage module is provided with a first antifreeze inlet and a first antifreeze outlet; the two-stage hydrogen storage module is provided with a second antifreeze inlet and a second antifreeze outlet; The thermal management system comprises a heating unit and a refrigeration unit connected with the one-stage hydrogen storage module and / or the two-stage hydrogen storage module through a pipeline interface; according to the connection position of the pipeline interface, the thermal management system at least has: Hydrogen release subsystem: the outlet of the heating unit is connected with the first antifreeze inlet and the second antifreeze inlet through a multi-way valve respectively; the first antifreeze outlet and the second antifreeze outlet are connected with the inlet of the heating unit; Hydrogen absorption subsystem: the outlet of the refrigeration unit is connected with the second antifreeze inlet through a multi-way valve; the outlet of the refrigeration unit is directly connected with the first antifreeze inlet; the first antifreeze outlet is connected with the second antifreeze inlet through a multi-way valve; the second antifreeze outlet is connected with the inlet of the refrigeration unit; The sensor system is used to obtain the antifreeze temperature in the one-stage hydrogen storage module and the two-stage hydrogen storage module, and the hydrogen absorption / release state information of the one-stage hydrogen storage module and the two-stage hydrogen storage module; The controller is electrically connected with the sensor system, the heating unit, the refrigeration unit and the multi-way valve, and controls the heating unit, the refrigeration unit and the multi-way valve according to the anti-freezing liquid temperature and the hydrogen absorption / desorption state information, so as to make the hydrogen desorption subsystem or the hydrogen absorption subsystem to perform thermal management on the one-stage hydrogen storage module and the two-stage hydrogen storage module.

[0010] Further, the hydrogen storage material in the one-stage hydrogen storage module is TiZr·MnCrFeV 0.2 Ni 0.8 .

[0011] Further, the hydrogen storage material in the two-stage hydrogen storage module is TiMn 1.5 B.

[0012] Further, the one-stage hydrogen storage module is provided with first hydrogen storage tanks, the capacity of the anti-freezing liquid of the one-stage hydrogen storage module is , the hydrogen desorption rate of a single first hydrogen storage tank is , and the following calculation formula is provided: ; Among them: represents the heating efficiency of the heating unit; represents the heating power of the heating unit; represents the system working time; represents the anti-freezing liquid density; represents the anti-freezing liquid volume; represents the anti-freezing liquid specific heat capacity; represents the anti-freezing liquid temperature rise; The hydrogen supply rate required when the fuel cell stack starts, is represented by the following formula: ; ; Among them: represents the fuel cell stack power; represents the hydrogen supply rate required when the fuel cell stack starts; represents the hydrogen low heat value.

[0013] Further, in the hydrogen desorption subsystem, the heating unit, the one-stage hydrogen storage module and the multi-way valve form a first heat exchange circuit; and the heating unit, the two-stage hydrogen storage module and the multi-way valve form a second heat exchange circuit. In the hydrogen release process, the second heat exchange circuit is closed by the multi-way valve, at this time the anti-freezing fluid heated by the heating unit is input into the heating unit through the multi-way valve and the one-stage hydrogen storage module; when the temperature of the anti-freezing fluid exceeds the first threshold value, the first heat exchange circuit is closed by the multi-way valve and the second heat exchange circuit is completely opened, the anti-freezing fluid is heated by the heating unit and then input into the heating unit through the multi-way valve and the two-stage hydrogen storage module; when the temperature of the anti-freezing fluid reaches the second threshold value, the heating unit is closed.

[0014] Further, the first threshold value is 30℃; and the second threshold value is 45℃.

[0015] Further, in the hydrogen absorption subsystem: the refrigeration unit, the multi-way valve and the two-stage hydrogen storage module form a third heat exchange circuit; the refrigeration unit, the one-stage hydrogen storage module, the multi-way valve and the two-stage hydrogen storage module form a fourth heat exchange circuit. In the hydrogen absorption process, the third heat exchange circuit is closed by the multi-way valve, the anti-freezing fluid cooled by the refrigeration unit is input into the refrigeration unit through the one-stage hydrogen storage module, the multi-way valve and the two-stage hydrogen storage module, and the temperature of the refrigeration unit is set to a first set temperature; when the one-stage hydrogen storage module completes hydrogen storage, the fourth heat exchange circuit is closed by the multi-way valve and the third heat exchange circuit is opened, and the temperature of the refrigeration unit is adjusted to a second set temperature, the anti-freezing fluid cooled by the refrigeration unit is input into the refrigeration unit through the multi-way valve and the two-stage hydrogen storage module.

[0016] Further, the first set temperature is -10℃; and the second set temperature is 7℃.

[0017] In the second aspect, the application provides a working method of a multi-layer temperature-controlled solid-state hydrogen storage device for rapid release of hydrogen, which is suitable for any of the above-mentioned multi-layer temperature-controlled solid-state hydrogen storage devices for rapid release of hydrogen, and the working method comprises the following steps: Before the hydrogen absorption work is performed, the pipeline connection of the heat management system is configured as the hydrogen absorption subsystem; the temperature of the anti-freezing fluid in the one-stage hydrogen storage module and the two-stage hydrogen storage module is obtained by the sensor system; and the controller controls the heating unit and the multi-way valve according to the temperature of the anti-freezing fluid, so that the hydrogen absorption subsystem performs heat management on the one-stage hydrogen storage module and the two-stage hydrogen storage module. After the hydrogen absorption work is completed and before the hydrogen release work is performed, the pipeline connection of the heat management system is configured as the hydrogen release subsystem; and the controller controls the refrigeration unit and the multi-way valve, so that the hydrogen release subsystem performs heat management on the one-stage hydrogen storage module and the two-stage hydrogen storage module.

[0018] Compared with the prior art, the application has the following beneficial effects:

[0019] The application provides a multi-layer temperature-controlled solid-state hydrogen storage device for fast hydrogen release and a working method thereof.

[0020] The application provides a multi-layer temperature-controlled solid-state hydrogen storage device for fast hydrogen release and a working method thereof, and the low-enthalpy hydrogen storage alloy is filled in the one-stage hydrogen storage module, and the high-enthalpy hydrogen storage alloy is filled in the two-stage hydrogen storage module, so that the low-enthalpy hydrogen storage alloy and the high-enthalpy hydrogen storage alloy are matched to further guarantee the low-enthalpy hydrogen storage system to realize fast hydrogen release and low-enthalpy hydrogen absorption in the low-temperature state.

[0021] The application further sets a hydrogen release time calculation method, controls the corresponding hydrogen release time through the volume parameters of the antifreeze of different one-stage hydrogen storage modules, and can effectively guarantee the normal work of the solid-state hydrogen storage system. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 FIG. 1 is a hydrogen storage tank distribution diagram of a multi-layer temperature-controlled solid-state hydrogen storage device according to an embodiment of the application;

[0023] Figure 2 FIG. 2 is a hydrogen release subsystem schematic diagram of a multi-layer temperature-controlled solid-state hydrogen storage device according to an embodiment of the application;

[0024] Figure 3 FIG. 3 is a hydrogen absorption subsystem schematic diagram of a multi-layer temperature-controlled solid-state hydrogen storage device according to an embodiment of the application.

[0025] In the figure, 1 is a first pipeline interface, 2 is a second pipeline interface, 3 is a first hydrogen storage tank, 4 is a second hydrogen storage tank, 5 is a one-stage hydrogen storage module, 6 is a two-stage hydrogen storage module, 7 is a multi-way valve, 8 is a PTC heater, 9 is a water pump, 10 is a water outlet of a water chiller, and 11 is a water return port of the water chiller. DETAILED DESCRIPTION

[0026] The application will be further described below in combination with the drawings. The following embodiments are only used to more clearly illustrate the technical solutions of the application, and cannot be used to limit the protection scope of the application.

[0027] In the description of the present application, it needs to be understood that the terms "center", "longitudinal", "transverse", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer" and the like indicate the orientation or positional relationship shown in the drawings, which are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the present application. In addition, the terms "first", "second" and the like are only for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined with "first", "second" and the like can be explicitly or implicitly included one or more. In the description of the present application, unless otherwise specified, the meaning of "a plurality of" is two or more.

[0028] In the description of the present application, it needs to be understood that unless otherwise explicitly specified and limited, the terms "mounting", "connection", "connection" should be understood broadly, for example, it can be fixedly connected, or it can be detachably connected, or integrally connected; it can be mechanically connected, or it can be electrically connected; it can be directly connected, or it can be indirectly connected through an intermediate medium; it can be the communication inside two elements. For those skilled in the art, the specific meaning of the above terms in the present application can be understood through specific circumstances.

[0029] Embodiment 1

[0030] This embodiment introduces a multi-layer temperature-controlled solid-state hydrogen storage device for rapid release of hydrogen, which comprises a solid-state hydrogen storage module, a thermal management system, a sensor system and a controller.

[0031] Please refer to Figure 1 , Figure 2 and Figure 3 , the solid-state hydrogen storage module comprises a one-stage hydrogen storage module 5 and a two-stage hydrogen storage module 6 connected with the fuel cell stack through the gas circuit, and the one-stage hydrogen storage module 5 and the two-stage hydrogen storage module 6 both contain anti-freezing liquid for heat exchange; the one-stage hydrogen storage module 5 is provided with a first anti-freezing liquid inlet and a first anti-freezing liquid outlet; the two-stage hydrogen storage module 6 is provided with a second anti-freezing liquid inlet and a second anti-freezing liquid outlet.

[0032] Among them, the one-stage hydrogen storage module 5 is provided with a plurality of first hydrogen storage tanks 3, and the two-stage hydrogen storage module 6 is provided with a plurality of second hydrogen storage tanks 4. The first hydrogen storage tank 3 is filled with low-heat-enthalpy hydrogen storage alloy TiZr·MnCrFeV 0.2 Ni 0.8 (Baotou City Zhongke Xunda New Energy Technology Co., Ltd., CN-37); the second hydrogen storage tank 4 is filled with high-heat-enthalpy hydrogen storage alloy TiMn 1.5B (Baotou City Xianlada New Energy Technology Co., Ltd., CN-15) can ensure the rapid hydrogen release and low energy consumption hydrogen absorption of the solid-state hydrogen storage system in the low-temperature state.

[0033] The thermal management system includes a heating unit and a refrigeration unit connected with the one-stage hydrogen storage module 5 and / or the two-stage hydrogen storage module 6 through the pipeline interfaces (i.e., the first pipeline interface 1 and the second pipeline interface 2). In this embodiment, the refrigeration unit is a water chiller (the outlet of the refrigeration unit is the water chiller outlet 10, and the inlet of the refrigeration unit is the water chiller return port 11), and the heating unit is a PTC heater 8 and a water pump 9 connected by pipelines. The multi-way valve 7 is a thermostat. The connection mode of the pipeline interface adopts a detachable quick-release joint. The operator can adjust the configuration mode of the pipeline according to the specific needs of hydrogen absorption and hydrogen release. According to the connection position of the pipeline interface, the thermal management system has two configuration modes, which are the hydrogen release subsystem and the hydrogen absorption subsystem.

[0034] Please refer to Figure 2 In the hydrogen release subsystem, the outlet of the heating unit is connected with the first antifreeze inlet and the second antifreeze inlet through the multi-way valve 7; the first antifreeze outlet and the second antifreeze outlet are connected with the inlet of the heating unit; please refer to Figure 3 In the hydrogen absorption subsystem, the outlet of the refrigeration unit is connected with the second antifreeze inlet through the multi-way valve 7; the outlet of the refrigeration unit is directly connected with the first antifreeze inlet; the first antifreeze outlet is connected with the second antifreeze inlet through the multi-way valve 7; and the second antifreeze outlet is connected with the inlet of the refrigeration unit.

[0035] The sensor system is used to obtain the antifreeze temperature in the one-stage hydrogen storage module 5 and the two-stage hydrogen storage module 6, and the hydrogen absorption / release state information of the one-stage hydrogen storage module 5 and the two-stage hydrogen storage module 6; the controller is electrically connected with the sensor system, the heating unit, the refrigeration unit, and the multi-way valve 7, and controls the heating unit, the refrigeration unit, and the multi-way valve 7 according to the antifreeze temperature and the hydrogen absorption / release state information, so that the hydrogen release subsystem or the hydrogen absorption subsystem performs thermal management on the one-stage hydrogen storage module 5 and the two-stage hydrogen storage module 6.

[0036] Specifically, in the hydrogen release subsystem, the heating unit, the one-stage hydrogen storage module 5, and the multi-way valve 7 form a first heat exchange circuit; the heating unit, the two-stage hydrogen storage module 6, and the multi-way valve 7 form a second heat exchange circuit. In the hydrogen release process, the second heat exchange circuit is closed through the multi-way valve 7, at this time the antifreeze heated by the heating unit is input into the heating unit through the multi-way valve 7 and the one-stage hydrogen storage module 5; when the temperature of the antifreeze exceeds the first threshold value, the first heat exchange circuit is closed through the multi-way valve 7, and the second heat exchange circuit is completely opened, the antifreeze heated by the heating unit is input into the heating unit through the multi-way valve 7 and the two-stage hydrogen storage module 6; when the temperature of the antifreeze reaches the second threshold value, the heating unit is closed.

[0037] In addition, in the hydrogen absorption subsystem: the refrigeration unit, the multi-way valve 7 and the two-stage hydrogen storage module 6 form a third heat exchange loop; the refrigeration unit, the one-stage hydrogen storage module 5, the multi-way valve 7 and the two-stage hydrogen storage module 6 form a fourth heat exchange loop. In the hydrogen absorption process, the third heat exchange loop is closed by the multi-way valve 7, the antifreeze cooled by the refrigeration unit passes through the one-stage hydrogen storage module 5, the multi-way valve 7 and the two-stage hydrogen storage module 6, enters the refrigeration unit, and the temperature of the refrigeration unit is set to a first set temperature; when the one-stage hydrogen storage module 5 completes hydrogen storage, the fourth heat exchange loop is closed by the multi-way valve 7, the third heat exchange loop is opened, and the temperature of the refrigeration unit is adjusted to a second set temperature, the antifreeze cooled by the refrigeration unit passes through the multi-way valve 7 and the two-stage hydrogen storage module 6, and enters the refrigeration unit.

[0038] In this embodiment, the one-stage hydrogen storage module is provided with one first hydrogen storage tank, and the capacity of the antifreeze of the one-stage hydrogen storage module is , and the hydrogen release rate of a single first hydrogen storage tank is In order to ensure that the hydrogen release rate of the one-stage hydrogen storage module can meet the hydrogen demand of the fuel cell stack start-up, the following calculation formula is provided: ; Wherein: represents the heating efficiency of the PTC heater; represents the heating power (kW) of the PTC heater; represents the system working time (s); represents the density of the antifreeze (kg / m 3 ); represents the volume of the antifreeze (m 3 ); represents the specific heat capacity of the antifreeze (kJ / kg·℃); represents the temperature rise of the antifreeze (℃); The hydrogen supply rate required when the fuel cell stack starts up is represented by the following formula: ; ; Wherein: represents the power of the fuel cell stack (kW); represents the hydrogen supply rate required for the start-up of the fuel cell stack (kg / s); represents the low heat value of hydrogen, which is a fixed constant 1.2×10 5 kJ / kg.

[0039] In summary, in combination with the volume of a single first hydrogen storage tank , the cavity volume of the one-stage hydrogen storage module is : ; More specifically, assuming that the initial power of the fuel cell stack is 3.4 kW, the power of the PTC heater is 3 kW, the efficiency is 95%, the dehydrogenation rate of the filled low-enthalpy hydrogen storage alloy material is 5 mg / s at 10℃, the heating time is 3 min, and the temperature rises from -20℃ to the target temperature of 10℃, the volume of the antifreeze is: ； The cavity volume of the one-stage hydrogen storage module is: ； ; In this embodiment, the total hydrogen storage module is 78L, i.e., the volume of the two-stage hydrogen storage module can be limited to 57.5L without changing the overall structure, so as to adapt to the case where the overall structure layout does not change.

[0040] The solid-state hydrogen storage system thermal management architecture is shown in Figure 2 and Figure 3 . The specific operation process is as follows, please refer to Figure 2 . In the system dehydrogenation process, the thermostat completely closes the cooling water circuit of the two-stage hydrogen storage module 6, i.e., the second heat exchange circuit is closed, at this time the antifreeze is heated by the PTC heater 8 and only circulates in the first heat exchange circuit, i.e., the antifreeze only passes through the one-stage hydrogen storage module 5, so as to ensure that the antifreeze can quickly rise to the target temperature, thereby realizing hydrogen release and supplying the fuel cell system for low-temperature start-up. When the target temperature of the antifreeze exceeds 30℃, the antifreeze circulation of the one-stage hydrogen storage module 5 is closed, i.e., the first heat exchange circuit is closed, and the second heat exchange circuit is completely opened, which is to protect the activity of the hydrogen storage material in the one-stage hydrogen storage module 5 and avoid thermal deactivation. When the temperature of the antifreeze reaches 45℃, the PTC heater 8 is closed, and the antifreeze of the fuel cell system provides temperature rise to reduce energy consumption.

[0041] Please refer to Figure 3, during the system hydrogen absorption process, due to the different filling materials in the hydrogen storage tanks of the first-stage hydrogen storage module 5 and the second-stage hydrogen storage module 6, different cooling strategies are set: the temperature of the refrigeration unit is set to -10℃, and the anti-freezing liquid cooled at this temperature is input into the first-stage hydrogen storage module 5; the temperature of the refrigeration unit is set to 7℃, and the anti-freezing liquid cooled at this temperature is delivered to the second-stage hydrogen storage module 6. First, the third heat exchange circuit is completely closed through the thermostat, the anti-freezing liquid cooled to -10℃ by the refrigeration unit is input into the first-stage hydrogen storage module 5 through the fourth heat exchange circuit, and due to the heat released by the hydrogen absorption reaction, the anti-freezing liquid outlet temperature of the first-stage hydrogen storage module 5 can reach above 0℃ and below 10℃, then the anti-freezing liquid is directly input into the second-stage hydrogen storage module 6, and the cooling work of the second-stage hydrogen storage module 6 is completed. The hydrogen storage amount of the first-stage hydrogen storage module 5 in this embodiment is less than that of the second-stage hydrogen storage module 6, when the first-stage hydrogen storage module 5 completes hydrogen storage, the fourth heat exchange circuit is completely closed through the thermostat, the third heat exchange circuit is opened, and the anti-freezing liquid is cooled to 7℃ by the refrigeration unit, thereby reducing energy consumption, and waiting for the second-stage hydrogen storage module 6 to complete hydrogen storage.

[0042] Embodiment 2

[0043] The embodiment provides a working method of a multi-layer temperature-controlled solid-state hydrogen storage device for rapid release of hydrogen, which is suitable for the multi-layer temperature-controlled solid-state hydrogen storage device for rapid release of hydrogen in Embodiment 1, and the working method comprises the following steps: Before hydrogen absorption work is performed, the pipeline connection of the heat management system is configured as a hydrogen absorption subsystem; the anti-freezing liquid temperature in the first-stage hydrogen storage module and the second-stage hydrogen storage module is acquired through the sensor system; and the controller controls the heating unit and the multi-way valve according to the anti-freezing liquid temperature, so that the hydrogen absorption subsystem performs heat management on the first-stage hydrogen storage module and the second-stage hydrogen storage module. After hydrogen absorption work is completed and before hydrogen release work is performed, the pipeline connection of the heat management system is configured as a hydrogen release subsystem; and the controller controls the refrigeration unit and the multi-way valve, so that the hydrogen release subsystem performs heat management on the first-stage hydrogen storage module and the second-stage hydrogen storage module.

[0044] The above merely describes the preferred embodiments of the present application, and it should be noted that, for ordinary skilled persons in the technical field, several improvements and modifications can be made without departing from the technical principles of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.

[0045] It should be pointed out finally that the above embodiments are only used for illustrating the technical solutions of the present disclosure but not for limiting the protection scope thereof, and although the present disclosure is described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the specific embodiments of the present disclosure can be changed, modified or replaced equivalently by those skilled in the art after reading the present disclosure, but these changes, modifications or equivalent replacements are all within the protection scope of the disclosed claims.

Claims

1. A solid-state hydrogen storage device for rapid hydrogen release with multi-layer temperature control, characterized in that, This includes solid-state hydrogen storage modules, thermal management systems, sensor systems, and controllers; The solid-state hydrogen storage module includes a first-stage hydrogen storage module and a second-stage hydrogen storage module connected to the fuel cell stack via a gas path. Both the first-stage and second-stage hydrogen storage modules contain antifreeze for heat exchange. The first-stage hydrogen storage module is provided with a first antifreeze inlet and a first antifreeze outlet. The second-stage hydrogen storage module is provided with a second antifreeze inlet and a second antifreeze outlet. The thermal management system includes a heating unit and a cooling unit connected to a first-stage hydrogen storage module and / or a second-stage hydrogen storage module via pipe interfaces; depending on the connection location of the pipe interfaces, the thermal management system has at least: Hydrogen release subsystem: The outlet of the heating unit is connected to the first antifreeze inlet and the second antifreeze inlet via a multi-port valve; the first antifreeze outlet and the second antifreeze outlet are connected to the inlet of the heating unit; Hydrogen absorption subsystem: The outlet of the refrigeration unit is connected to the second antifreeze inlet via a multi-way valve; the outlet of the refrigeration unit is directly connected to the first antifreeze inlet; the first antifreeze outlet is connected to the second antifreeze inlet via a multi-way valve; the second antifreeze outlet is connected to the inlet of the refrigeration unit; The sensor system is used to acquire the antifreeze temperature in the first-stage hydrogen storage module and the second-stage hydrogen storage module, as well as the hydrogen absorption / desorption status information of the first-stage hydrogen storage module and the second-stage hydrogen storage module. The controller is electrically connected to the sensor system, heating unit, cooling unit, and multi-way valve, and controls the heating unit, cooling unit, and multi-way valve according to the antifreeze temperature and hydrogen absorption / desorption status information, so that the hydrogen release subsystem or hydrogen absorption subsystem performs thermal management on the first-stage hydrogen storage module and the second-stage hydrogen storage module.

2. The solid-state hydrogen storage device for rapid hydrogen release with multi-layer temperature control according to claim 1, characterized in that, The hydrogen storage material in the first-stage hydrogen storage module is TiZr·MnCrFeV. 0.2 Ni 0.8 .

3. The solid-state hydrogen storage device for rapid hydrogen release with multi-layer temperature control according to claim 2, characterized in that, The hydrogen storage material in the second-stage hydrogen storage module is TiMn. 1.5 B.

4. The solid-state hydrogen storage device for rapid hydrogen release with multi-layer temperature control according to claim 3, characterized in that, The first-stage hydrogen storage module is equipped with The first hydrogen storage tank, wherein the antifreeze capacity of the first-stage hydrogen storage module is [missing information]. The hydrogen release rate of a single first hydrogen storage tank is It has the following calculation formula: ； in: This indicates the heating efficiency of the heating unit; This indicates the heating power of the heating unit; Indicates system operating time; Indicates the density of the antifreeze; Indicates the volume of antifreeze; This indicates the specific heat capacity of the antifreeze; This indicates the temperature rise of the antifreeze; The hydrogen supply rate required for the startup of a fuel cell stack is expressed by the following formula: ； ； in: Indicates the power of the fuel cell stack; This indicates the hydrogen supply rate required for the fuel cell stack to start up; This indicates the low calorific value of hydrogen.

5. The solid-state hydrogen storage device for rapid hydrogen release with multi-layer temperature control according to claim 4, characterized in that, In the hydrogen release subsystem, the heating unit, the first-stage hydrogen storage module, and the multi-way valve form a first heat exchange circuit; the heating unit, the second-stage hydrogen storage module, and the multi-way valve form a second heat exchange circuit. During hydrogen release, the second heat exchange circuit is closed via a multi-way valve. At this time, the antifreeze heated by the heating unit passes through the multi-way valve and the first-stage hydrogen storage module and is input into the heating unit. When the temperature of the antifreeze exceeds a first threshold, the first heat exchange circuit is closed via the multi-way valve, and the second heat exchange circuit is fully opened. The antifreeze, after being heated by the heating unit, passes through the multi-way valve and the second-stage hydrogen storage module and is input into the heating unit. When the temperature of the antifreeze reaches a second threshold, the heating unit is closed.

6. The solid-state hydrogen storage device for rapid hydrogen release with multi-layer temperature control according to claim 5, characterized in that, The first threshold is 30°C; the second threshold is 45°C.

7. The solid-state hydrogen storage device for rapid hydrogen release with multi-layer temperature control according to claim 3, characterized in that, In the hydrogen absorption subsystem: the refrigeration unit, the multi-way valve, and the two-stage hydrogen storage module form a third heat exchange circuit; the refrigeration unit, the first-stage hydrogen storage module, the multi-way valve, and the second-stage hydrogen storage module form a fourth heat exchange circuit. During hydrogen absorption, the third heat exchange circuit is closed via a multi-way valve. The antifreeze cooled by the refrigeration unit passes through the first-stage hydrogen storage module, the multi-way valve, and the second-stage hydrogen storage module before being input into the refrigeration unit, and the temperature of the refrigeration unit is set to the first set temperature. After the first-stage hydrogen storage module completes hydrogen storage, the fourth heat exchange circuit is closed via the multi-way valve, the third heat exchange circuit is opened, and the temperature of the refrigeration unit is adjusted to the second set temperature. The antifreeze cooled by the refrigeration unit passes through the multi-way valve and the second-stage hydrogen storage module before being input into the refrigeration unit.

8. The solid-state hydrogen storage device for rapid hydrogen release with multi-layer temperature control according to claim 7, characterized in that, The first set temperature is -10℃; the second set temperature is 7℃.

9. A method for operating a multi-layer temperature-controlled solid-state hydrogen storage device for rapid hydrogen release, characterized in that, The solid-state hydrogen storage device for rapid hydrogen release with multi-layer temperature control as described in any one of claims 1 to 8, the operating method comprising the following steps: Before hydrogen absorption, the pipeline connection of the thermal management system is configured as the hydrogen absorption subsystem; the temperature of the antifreeze in the first-stage hydrogen storage module and the second-stage hydrogen storage module is obtained through the sensor system; the controller controls the heating unit and the multi-way valve according to the antifreeze temperature, so that the hydrogen absorption subsystem performs thermal management on the first-stage hydrogen storage module and the second-stage hydrogen storage module. After the hydrogen absorption operation is completed and before the hydrogen release operation is completed, the pipeline connection of the thermal management system is configured as the hydrogen release subsystem; the controller controls the refrigeration unit and the multi-way valve so that the hydrogen release subsystem performs thermal management on the first-stage hydrogen storage module and the second-stage hydrogen storage module.

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