Hydrogen storage device based on solid hydrogen storage material and hydrogen production method thereof

Abstract

The invention relates to the technical field of hydrogen preparation, and provides a hydrogen storage device based on a solid hydrogen storage material and a hydrogen production method thereof.The device comprises a fuel tank internally provided with a reaction cavity used for containing an aluminum hydride material and mixed powder; the heater is arranged on the outer side of the fuel tank; the first end of the water recycling assembly is communicated with the reaction cavity, and the second end of the water recycling assembly is communicated with the fuel cell system so as to recycle water generated by the fuel cell system to the reaction cavity; the first end of the hydrogen discharging assembly is communicated with the reaction cavity, and the second end is communicated with a fuel cell system. According to the hydrogen storage device provided by the invention, through the application of the high-specific-energy solid hydrogen storage material aluminum hydride which can be stored at normal pressure and release hydrogen at a relatively low temperature, the thermal decomposition process of the metal hydride in the fuel tank and the coupling reaction process of the metal hydride and water are optimized, and the hydrogen is produced by utilizing the hydrolysis reaction of the aluminum hydride thermal decomposition reactant simple substance aluminum and the water; meanwhile, thermal decomposition of aluminum hydride is promoted through heat released by hydrolysis reaction, hydrogen release is coupled, and effective utilization of heat is achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen production, and particularly to a hydrogen storage device based on a solid hydrogen storage material and a hydrogen production method thereof. Background Art

[0002] Solid-state hydrogen storage technology has attracted attention due to its high volumetric hydrogen storage density and good safety performance. Solid-state hydrogen storage can be carried out at normal temperature and pressure, and the fuel tank is easy to seal. In the case of hydrogen leakage, since the hydrogen release from solid-state hydrogen storage usually requires heat absorption, the hydrogen leakage speed and leakage amount can be automatically controlled, improving the safety of using the hydrogen storage device.

[0003] However, currently, the solid hydrogen storage materials have problems such as still relatively low hydrogen storage efficiency per unit volume, relatively high hydrogen release temperature for some materials (such as the hydrogen release temperature of MgH2 is 300 - 400 °C), and the need for continuous external electric heating to provide heat for hydrogen release, which are difficult to meet the requirements of some application scenarios. At the same time, the current energy utilization efficiency of fuel cells is generally between 40% and 60%. With the continuous expansion of the application working conditions of fuel cells, how to further improve the energy utilization efficiency of fuel cells is a key issue. Summary of the Invention

[0004] The present invention provides a hydrogen storage device based on a solid hydrogen storage material and a hydrogen production method thereof, so as to solve the problems that currently, the solid hydrogen storage materials have relatively low hydrogen storage efficiency per unit volume, relatively high hydrogen release temperature for some materials, and the need for continuous external electric heating to provide heat for hydrogen release.

[0005] In a first aspect, the present invention provides a hydrogen storage device based on a solid hydrogen storage material, including: A fuel tank, which forms a reaction chamber inside, and the reaction chamber is used for arranging aluminum hydride material and a mixed powder, and the mixed powder includes aluminum powder and a catalyst; A heater, which is arranged outside the fuel tank and is used for heating the fuel tank; A water recovery component, the first end of which is communicated with the reaction chamber, and the second end is used for being communicated with the fuel cell system to recover the water generated by the fuel cell system to the reaction chamber; A hydrogen discharge component, the first end of which is communicated with the reaction chamber, and the second end is used for being communicated with the fuel cell system to discharge the hydrogen generated by the thermal decomposition of aluminum hydride and the hydrolysis of aluminum into the fuel cell system.

[0006] According to the hydrogen storage device based on a solid hydrogen storage material provided by the present invention, the hydrogen discharge component includes: a hydrogen supply pipe and a regulating valve; The first end of the hydrogen supply pipe is communicated with the reaction chamber, and the second end is used for being communicated with the fuel cell system through the regulating valve.

[0007] A hydrogen storage device based on solid hydrogen storage materials provided by the present invention, wherein the fuel tank includes: a storage tank and a cover; A reaction chamber is formed inside the storage tank, and the cover is provided at the opening position of the reaction chamber; The first ends of the hydrogen discharge assembly and the water recovery assembly both pass through the cover and communicate with the reaction chamber.

[0008] A hydrogen storage device based on solid hydrogen storage materials provided by the present invention, wherein the fuel tank further includes: a filter element and an elastic element; The filter element is disposed in the reaction chamber, dividing the reaction chamber into a gas storage space and a reaction space. The reaction space is provided with the aluminum hydride material, and the mixed powder is filled in the gaps of the aluminum hydride material; One side of the filter element located in the gas storage space abuts against the cover through the elastic element, and one side of the filter element located in the reaction space abuts against the aluminum hydride material.

[0009] A hydrogen storage device based on solid hydrogen storage materials provided by the present invention, wherein the water recovery assembly includes: a driving pump and a vapor-liquid separator; The vapor-liquid separator is provided with a first inlet, a second inlet, an exhaust port and a drain port. The first inlet is used to communicate with the cathode of the fuel cell system, the second inlet is used to communicate with the anode of the fuel cell system, and the drain port communicates with the reaction chamber through the driving pump.

[0010] A hydrogen storage device based on solid hydrogen storage materials provided by the present invention, wherein the water recovery assembly further includes: A radiator, the first end of which communicates with the first inlet, and the second end is used to communicate with the cathode of the fuel cell system.

[0011] A hydrogen storage device based on solid hydrogen storage materials provided by the present invention, wherein the water recovery assembly further includes: A water separator, the first end of which communicates with the vapor-liquid separator through the driving pump, and the second end is provided with a plurality of branch pipes, and each of the branch pipes is distributed among the aluminum hydride materials.

[0012] A hydrogen storage device based on solid hydrogen storage materials provided by the present invention, wherein the heater is a film heater, and the film heater surrounds the outside of the fuel tank; A temperature sensor for detecting the heating temperature is provided on the film heater.

[0013] A hydrogen storage device based on solid hydrogen storage materials provided by the present invention, wherein the hydrogen storage device further includes: A pressure relief valve, one end of which communicates with the reaction chamber and the other end communicates with the outside.

[0014] In a second aspect, the present invention further provides a hydrogen production method for a hydrogen storage device based on a solid-state hydrogen storage material, including: Controlling the heater to heat the fuel tank to generate a first hydrogen source by means of the thermal decomposition reaction of the aluminum hydride material; Controlling the water recovery component to introduce water to generate a second hydrogen source by means of the hydrolysis reaction of the generated aluminum and the mixed powder; When the heat released by the hydrolysis reaction reaches the reaction threshold, turning off the heater and using the exothermic effect of aluminum hydrolysis to maintain the thermal decomposition temperature field of aluminum hydride to achieve collaborative hydrogen production.

[0015] The hydrogen storage device based on a solid-state hydrogen storage material and its hydrogen production method provided by the present invention, through the application of the high-specific-energy solid-state hydrogen storage material aluminum hydride (AlH3) that can store hydrogen at normal pressure and release hydrogen at a relatively low temperature, optimize the thermal decomposition of the metal hydride in the fuel tank and the coupling reaction process with water, use the hydrolysis reaction of the simple substance aluminum, the thermal decomposition reactant of aluminum hydride, and water to produce hydrogen, and at the same time use the heat released by the hydrolysis reaction to promote the thermal decomposition of aluminum hydride. The two reactions are coupled to release hydrogen, realizing the effective utilization of heat. When the hydrogen storage device is applied to a fuel cell system, it can use the tail gas of the fuel cell system to recover water and react to produce hydrogen. The device that comprehensively utilizes the thermal decomposition of aluminum hydride and the hydrolysis reaction of aluminum supplies hydrogen to the fuel cell, effectively realizing the hydrogen cycle of the fuel cell system and the efficient utilization of internal heat, and improving the energy utilization efficiency of the system. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0017] Figure 1 is an overall schematic diagram of the hydrogen storage device provided by the present invention.

[0018] Figure 2 is a schematic diagram of the water recovery component provided by the present invention.

[0019] Figure 3 is one of the schematic diagrams of the disassembly of some structures in the hydrogen storage device provided by the present invention.

[0020] Figure 4 is another schematic diagram of the disassembly of some structures in the hydrogen storage device provided by the present invention.

[0021] Figure 5 is one of the schematic diagrams of the filling materials in the hydrogen storage device provided by the present invention.

[0022] Figure 6It is the second schematic diagram of the filling material in the hydrogen storage device provided by the present invention.

[0023] Figure 7 It is the schematic diagram of the water separator in the hydrogen storage device provided by the present invention.

[0024] Figure 8 It is the schematic flow diagram of the hydrogen production method provided by the present invention.

[0025] Reference numerals: 1. Fuel tank; 2. Heater; 3. Aluminum hydride material; 4. Mixed powder; 5. Water separator; 51. Water separator inlet; 52. Branch pipe; 6. Pressure relief valve; 7. Hydrogen supply pipe; 8. Regulating valve; 81. Valve outlet; 9. Filter element; 10. Elastic member; 11. Temperature sensor; 12. Vapor-liquid separator; 121. First inlet; 122. Second inlet; 123. Exhaust port; 124. Drain port; 13. Radiator; 14. Driving pump. Detailed implementation manners

[0026] To make the objectives, technical solutions and advantages of the present invention clearer, the technical solutions in the present invention will be clearly and completely described below with reference to the accompanying drawings in the present invention. Obviously, the described embodiments are some but not all of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present invention without making creative efforts shall fall within the protection scope of the present invention.

[0027] The following will be combined with Figures 1 - 8 to describe the hydrogen storage device based on solid-state hydrogen storage materials and its hydrogen production method provided by the present invention.

[0028] In some embodiments, as Figures 1 to 6 shown, the hydrogen storage device is applied to a fuel cell system and includes: a fuel tank 1, a heater 2, a water recovery component, and a hydrogen discharge component. A reaction chamber is formed in the fuel tank 1, and the reaction chamber is used to arrange an aluminum hydride material 3 and a mixed powder 4. The mixed powder 4 includes aluminum powder and a catalyst; the heater 2 is arranged outside the fuel tank 1 and is used to heat the fuel tank 1; the first end of the water recovery component is communicated with the reaction chamber, and the second end is used to be communicated with the fuel cell system to recover the water generated by the fuel cell system to the reaction chamber; the first end of the hydrogen discharge component is communicated with the reaction chamber, and the second end is used to be communicated with the fuel cell system to discharge the hydrogen generated by the thermal decomposition of aluminum hydride and the hydrolysis of aluminum into the fuel cell system.

[0029] In this embodiment, an aluminum hydride material 3 (AlH3) is disposed in the reaction chamber. The aluminum hydride material 3 can release high-purity hydrogen through thermal decomposition at a certain temperature. The thermally decomposed product, elemental aluminum, can react with water through a hydrolysis reaction to produce hydrogen under the action of a catalyst. The filled aluminum hydride material 3 is doped with a mixed powder 4 including aluminum powder and a catalyst. In the presence of an existing water source, water can be directly injected to initiate the hydrolysis reaction of aluminum to produce hydrogen. At the same time, the heat released by the hydrolysis reaction is used to promote the decomposition of the internal aluminum hydride material 3. The two reactions are coupled to release hydrogen, which can significantly save the power consumption for heating to release hydrogen through thermal decomposition.

[0030] In the fuel cell system, during the startup phase, the heater 2 can be controlled to heat the fuel tank 1 to utilize the thermal decomposition reaction of the aluminum hydride material 3 to generate a first hydrogen source, as shown in Reaction Formula (1). The first hydrogen source serves as the anode fuel of the fuel cell stack. After the fuel cell system operates stably, the water recovery component is controlled to recover the liquid water in the tail gas of the stack (in the fuel cell system) and continue to hydrolyze and produce hydrogen with the internal product, elemental aluminum, under the action of a catalyst, so as to utilize the hydrolysis reaction of the generated aluminum and the mixed powder 4 to produce a second hydrogen source, as shown in Reaction Formula (2). A large amount of heat is released during the hydrolysis reaction to promote the thermal decomposition of AlH3 to release hydrogen. When the heat released by the hydrolysis reaction reaches the reaction threshold, the heater 2 is turned off, and the exothermic effect of aluminum hydrolysis is used to maintain the thermal decomposition temperature field of aluminum hydride, so as to achieve collaborative hydrogen production. At this time, there is no need to turn on the heater 2 again, saving the power consumption of the entire fuel cell system. The above method of comprehensively utilizing the coupling of the thermal decomposition of AlH3 and the aluminum hydrolysis reaction to supply hydrogen realizes the recycling of hydrogen and saves the system power consumption, thereby improving the energy utilization efficiency of the fuel cell system.

[0031] The chemical reaction equations for the above two hydrogen production methods are as follows: (1)

[0032] (2)

[0033] The hydrogen storage device based on the solid hydrogen storage material provided by the present invention optimizes the thermal decomposition of the metal hydride in the fuel tank 1 and the coupling reaction process with water through the application of the high-specific-energy solid hydrogen storage material aluminum hydride (AlH3) that can store hydrogen at normal pressure and release hydrogen at a relatively low temperature. Hydrogen is produced by using the hydrolysis reaction of the thermally decomposed reactant, elemental aluminum, of aluminum hydride with water. At the same time, the heat released by the hydrolysis reaction is used to promote the thermal decomposition of aluminum hydride. The two reactions are coupled to release hydrogen, realizing the effective utilization of heat. When the hydrogen storage device is applied to a fuel cell system, hydrogen can be produced by using the water recovered from the tail gas of the fuel cell system. The device that comprehensively utilizes the thermal decomposition of aluminum hydride and the aluminum hydrolysis reaction supplies hydrogen to the fuel cell, effectively realizing the hydrogen cycle of the fuel cell system and the efficient utilization of internal heat, and improving the system energy utilization efficiency.

[0034] In some embodiments, such as Figure 3As shown in the figure, the hydrogen discharge assembly includes: a hydrogen supply pipe 7 and a regulating valve 8; the first end of the hydrogen supply pipe 7 is communicated with the reaction chamber, and the second end is used to be communicated with the fuel cell system through the regulating valve 8. The hydrogen supply pipe 7 is responsible for transporting the hydrogen generated in the reaction chamber to the fuel cell system.

[0035] In this embodiment, the hydrogen supply pipe 7 can adopt a quick connector, and the regulating valve 8 can adopt a globe valve. The globe valve is used to control the flow of hydrogen. By adjusting the opening degree of the globe valve, the flow rate of hydrogen can be accurately controlled to ensure that the fuel cell system obtains an appropriate amount of hydrogen. The globe valve is also provided with a valve outlet 81, and the valve outlet 81 transports hydrogen to the anode of the fuel cell system through an external pipeline.

[0036] In some embodiments, as Figures 1 to 6 shown, the fuel tank 1 includes: a storage tank and a cover; the storage tank is the main container part of the fuel tank 1, and a reaction chamber is formed inside. The reaction chamber is used to accommodate the aluminum hydride material 3 (AlH3) and the mixed powder 4 (including aluminum powder and catalyst). The cover is arranged at the opening position of the storage tank to seal the reaction chamber. The cover needs to have good sealing performance to prevent hydrogen leakage, and at the same time, it also needs to be able to withstand a certain pressure and temperature.

[0037] The hydrogen discharge assembly includes a hydrogen supply pipe 7 and a regulating valve 8. The first end of the hydrogen supply pipe 7 is communicated with the reaction chamber, and the second end is communicated with the fuel cell system through the regulating valve 8. The hydrogen supply pipe 7 adopts a quick connector, which is convenient for quick connection and disconnection. The regulating valve 8 adopts a globe valve, which is used to control the flow rate and pressure of hydrogen to ensure that the fuel cell system can obtain a stable hydrogen supply.

[0038] The first end of the water recovery assembly is communicated with the reaction chamber, and the second end is used to be communicated with the fuel cell system. The water recovery assembly is responsible for recovering the liquid water generated by the fuel cell system into the reaction chamber for use in the aluminum hydrolysis reaction.

[0039] In this embodiment, the fuel tank 1 further includes: a filter element 9 and an elastic element 10; the filter element 9 is arranged in the reaction chamber, separating the reaction chamber into a gas storage space and a reaction space. The aluminum hydride material 3 is arranged in the reaction space, and the mixed powder 4 is filled in the gaps of the aluminum hydride material 3; one side of the filter element 9 located in the gas storage space abuts against the cover through the elastic element 10, and one side of the filter element 9 located in the reaction space abuts against the aluminum hydride material 3. The filter element 9 allows gas to pass through but prevents solid particles from entering the gas storage space, thereby ensuring the purity of hydrogen. The elastic element 10 provides a certain elastic support. The function of the elastic element 10 is to adapt to the pressure change generated during the reaction process and ensure the sealing performance between the filter element 9 and the cover.

[0040] To increase the density of the aluminum hydride material 3, it is necessary to press the powder material, and the size can be adjusted according to needs. When using the aluminum hydride material 3 with a diameter of 10 mm and a height of 5 mm for filling, the weight of each pressed tablet is 1 g. The inner diameter of the fuel tank 1 is 49 mm. In the case of neat arrangement, 18 pressed tablets can be placed in each layer, and the number of filling layers is 14 layers. The total filling amount of the pressed tablets is 252 g. Through the arrangement and filling of the pressed tablets, the density is significantly increased compared to the condition of loose powder filling, showing the high-density characteristics of the pressed tablets. At the same time, a mixed powder 4 (doped with aluminum powder and catalyst) can be filled in the gaps between the columnar pressed tablets of the AlH3 material. In the presence of existing water sources, the hydrolysis reaction can be quickly realized, achieving the operating state of coupling hydrogen production by thermal decomposition and hydrolysis. The hydrogen release temperature and hydrogen release amount of the aluminum hydride material 3 can be optimized according to needs.

[0041] Specifically, pressed tablets made of the aluminum hydride material 3 are stacked and filled inside the fuel tank 1. The pressed tablets can increase the material filling amount and are beneficial to heat transfer. A filter sheet (filter element 9) is arranged above the pressed tablets, and the filter sheet can block dust, splashes, and foam, etc. Above the filter sheet, a compression spring (elastic element 10) is provided. The compression spring cooperates with the cover, leaving a gas storage space to keep the air outlet unobstructed, and at the same time eliminating the expansion effect during the hydrogen production process of the aluminum hydride material 3. A mixed powder 4 (doped with aluminum powder and catalyst) can be filled in the gaps between the pressed tablets. In the presence of existing water sources, the hydrolysis reaction can be quickly realized, achieving the operating state of coupling hydrogen production by thermal decomposition and hydrolysis. A heater 2 is provided outside the storage tank to adjust the temperature of the tank body to control the hydrogen release rate of the thermal decomposition of AlH3. In the working condition without an external water source, such as in a fuel cell system, the heater 2 can be used to heat the storage tank for thermal decomposition hydrogen production first. After the fuel cell system operates, the liquid water recovered from the cathode exhaust gas of the fuel cell stack can be recycled by the water recovery component to achieve the above-mentioned operating state of coupling hydrogen production by thermal decomposition and hydrolysis.

[0042] In some embodiments, as Figures 1 to 3 shown, the water recovery component includes: a driving pump 14 and a vapor-liquid separator 12; the vapor-liquid separator 12 is provided with a first inlet 121, a second inlet 122, an exhaust port 123, and a drain port 124. The first inlet 121 is used to communicate with the cathode of the fuel cell system, the second inlet 122 is used to communicate with the anode of the fuel cell system, and the drain port 124 is connected to the reaction chamber through the driving pump 14.

[0043] In this embodiment, the vapor-liquid separator 12 is used to separate the water vapor and gas in the exhaust gas of the fuel cell system. The first inlet 121 of the vapor-liquid separator 12 is communicated with the cathode of the fuel cell system to receive the exhaust gas from the cathode. The second inlet 122 is communicated with the anode of the fuel cell system to receive the exhaust gas from the anode. The exhaust port 123 is used to discharge the separated gas. The drain port 124 is connected to the reaction chamber through the driving pump 14 to transport the separated liquid water to the reaction chamber.

[0044] During the operation of the fuel cell system, the tail gases generated at the cathode and the anode enter the vapor-liquid separator 12 through the first inlet 121 and the second inlet 122 respectively. The vapor-liquid separator 12 separates the water vapor and gas in the tail gas. The separated gas is discharged through the exhaust port 123, and the liquid water is discharged through the drain port 124. The separated liquid water is transported to the reaction chamber by the driving pump 14 for use in the aluminum hydrolysis reaction. The liquid water reacts with the aluminum powder and catalyst in the reaction chamber to generate hydrogen (H2) and aluminum hydroxide. The heat released by the hydrolysis reaction can promote the thermal decomposition of aluminum hydride, thus realizing the synergistic effect of the two hydrogen production methods.

[0045] To ensure that the reaction temperature is within a suitable range, as Figures 1 to 3 shown, the water recovery component further includes: a radiator 13. The first end of the radiator 13 is communicated with the first inlet 121, and the second end is used to communicate with the cathode of the fuel cell system.

[0046] During operation, the tail gas generated at the cathode of the fuel cell system first enters the radiator 13. The radiator 13 reduces the temperature of the tail gas through heat exchange, preventing the overheated tail gas from entering the vapor-liquid separator 12, thereby avoiding too high a temperature in the reaction chamber. The tail gas whose temperature has been adjusted by the radiator 13 enters the vapor-liquid separator 12 for subsequent steam-water separation treatment.

[0047] The radiator 13 can effectively adjust the temperature of the tail gas, ensuring that the temperature of the tail gas entering the vapor-liquid separator 12 is within a suitable range and preventing too high a temperature in the reaction chamber. Through temperature adjustment, the radiator 13 helps to maintain the stability of the reaction temperature in the reaction chamber, ensuring the efficient progress of the thermal decomposition of aluminum hydride and the aluminum hydrolysis reaction.

[0048] To cooperate with the bulk-filled aluminum hydride material 3, in some embodiments, as Figures 5 to 7 shown, the water recovery component further includes: a water divider 5. The first end of the water divider 5 is communicated with the vapor-liquid separator 12 through the driving pump 14, and the second end is provided with a plurality of branch pipes 52, and each branch pipe 52 is distributed among the aluminum hydride materials 3.

[0049] Specifically, the first end of the water divider 5 is provided with a water divider inlet 51, and the branch pipe 52 is provided with a water divider 5 outlet. External water enters through the water divider inlet 51 and is discharged from the water divider 5 outlets of the respective branch pipes 52 below. Each branch pipe 52 is evenly distributed among the filled aluminum hydride materials 3, which is beneficial to the uniformity of reaction and heat transfer. At the same time, the gaps can be filled with the mixed powder 4, which can be doped with aluminum powder to quickly realize the hydrolysis reaction. At the same time, the heat released by the hydrolysis reaction is used to promote the thermal decomposition of aluminum hydride, and the two reactions are coupled to release hydrogen.

[0050] In some embodiments, as Figure 3As shown, the heater 2 is a film heater, which is arranged around the outside of the fuel tank 1; the film heater is usually made of a conductive material and can distribute heat evenly. The heating film is embedded with heating wires, which generate heat after being energized to heat the fuel tank 1. An insulating layer is provided on the outside of the heating film to prevent the heating wires from conducting electricity with the outside world and ensure safety. A temperature sensor 11 for detecting its heating temperature is provided on the film heater to monitor the heating temperature in real time and feed back the temperature data to the user or the corresponding control system.

[0051] In some embodiments, such as Figure 3 As shown, the hydrogen storage device further includes: a pressure relief valve 6, one end of the pressure relief valve 6 is communicated with the reaction chamber, and the other end of the pressure relief valve 6 is communicated with the outside.

[0052] During operation, the pressure relief valve 6 monitors the pressure in the reaction chamber in real time. When the pressure in the reaction chamber exceeds the set safety value, the valve core is pushed open by the gas pressure. After the valve core is opened, the gas in the reaction chamber quickly discharges through the pressure relief outlet of the pressure relief valve 6 to reduce the pressure in the reaction chamber. When the pressure in the reaction chamber drops to the safe range, the spring resets the valve core, the pressure relief valve 6 closes, and returns to the normal state. Thereby, it can prevent the pressure from overpressuring when hydrogen is released inside the reaction chamber and can ensure that the internal pressure is reduced to an appropriate range.

[0053] In a specific embodiment, such as Figure 1 As shown, when this set of hydrogen storage device is applied in a fuel cell system, under the condition of a rated output power of 100W of the fuel cell system, the hydrogen storage device carrying 720g of AlH3 material uses the heater to provide heat for the decomposition of aluminum hydride material in the fuel tank during the start-up stage of the fuel cell system. The heating temperature is 100-200°C. When the pressure in the tank is monitored to reach 0.05MPa, it meets the hydrogen release condition and can supply gas to the anode of the fuel cell stack. The pressure in the tank is controlled between 0.05 and 0.5MPa through heating adjustment; after the fuel cell system runs, the cathode exhaust gas of the stack is cooled to 20-30°C after passing through the radiator. The liquid water in the exhaust gas of the fuel cell stack of the fuel cell system is recovered through the water recovery device and pumped into the fuel tank of the hydrogen storage device by a liquid pump, and continues to undergo a hydrolysis reaction to produce hydrogen under the action of an additive with the elemental aluminum produced by the thermal decomposition of the AlH3 material inside the tank. The two reactions jointly supply materials to the anode of the stack. The water recovery amount of the fuel cell system during rated power operation for 30 minutes is 30-40 ml. The hydrogen release amount is controlled by intermittent water inlet of the liquid pump, and the pressure is monitored at 0.05-0.5MPa to control the hydrogen storage state of the fuel tank. If the fuel cell system only relies on the thermal decomposition of AlH3 material to produce hydrogen, it can supply the system to run continuously for 8 hours; when using the application of the high specific energy solid hydrogen storage device in this embodiment and realizing the recycling of hydrogen through multiple water recoveries, it can supply the system to run continuously for more than 12 hours.

[0054] The embodiment of the present application further provides a hydrogen production method for a hydrogen storage device based on a solid-state hydrogen storage material. The hydrogen storage device is as described above Figures 1 to 7 The relevant written description will not be elaborated here.

[0055] The hydrogen production method is as Figure 8 shown and includes the following steps: Step S810: Control the heater to start heating the fuel tank to generate a first hydrogen source by means of the thermal decomposition reaction of the aluminum hydride material.

[0056] Step S820: Control the water recovery component to introduce water to generate a second hydrogen source by means of the hydrolysis reaction of the generated aluminum and the mixed powder.

[0057] Step S830: When the heat released by the hydrolysis reaction reaches the reaction threshold, turn off the heater and use the heat release effect of aluminum hydrolysis to maintain the thermal decomposition temperature field of aluminum hydride to achieve collaborative hydrogen production.

[0058] In this embodiment, an aluminum hydride material (AlH3) is arranged in the reaction chamber. The aluminum hydride material can release high-purity hydrogen by thermal decomposition at a certain temperature. The elemental aluminum produced by the thermal decomposition can react with water to produce hydrogen under the action of a catalyst; the filled aluminum hydride material is doped with a mixed powder including aluminum powder and a catalyst. In the presence of an existing water source, water can be directly injected to carry out the hydrolysis hydrogen production reaction of aluminum, and at the same time, the heat released by the hydrolysis reaction is used to promote the decomposition of the internal aluminum hydride material. The two reactions are coupled to release hydrogen, which can greatly save the power consumption of thermal decomposition for hydrogen release by heating.

[0059] In the fuel cell system, during the startup stage, the heater can be controlled to start heating the fuel tank to generate a first hydrogen source by means of the thermal decomposition reaction of the aluminum hydride material. See Reaction Formula (1). The first hydrogen source is used as the anode fuel of the fuel cell stack.

[0060] After the fuel cell system operates stably, control the water recovery component to recover the liquid water in the tail gas of the stack (in the fuel cell system), and continue to produce hydrogen by hydrolysis with the elemental aluminum in the internal product under the action of a catalyst to generate a second hydrogen source by means of the hydrolysis reaction of the generated aluminum and the mixed powder. See Reaction Formula (2). A large amount of heat can be released in the hydrolysis reaction to promote the hydrogen release by thermal decomposition of AlH3.

[0061] When the heat released by the hydrolysis reaction reaches the reaction threshold, turn off the heater and use the heat release effect of aluminum hydrolysis to maintain the thermal decomposition temperature field of aluminum hydride to achieve collaborative hydrogen production. At this time, there is no need to turn on the heater again, saving the power consumption of the entire fuel cell system. The above method of comprehensively using the coupling of the thermal decomposition of AlH3 and the aluminum hydrolysis reaction for hydrogen supply realizes the recycling of hydrogen and saves the system power consumption, thereby improving the energy utilization efficiency of the fuel cell system.

[0062] The hydrogen production method of the hydrogen storage device based on solid-state hydrogen storage materials provided by the present invention optimizes the thermal decomposition of metal hydrides and the coupling reaction process with water in the fuel tank through the application of high specific energy solid-state hydrogen storage material aluminum hydride (AlH3) that can store hydrogen at normal pressure and release hydrogen at a relatively low temperature. Hydrogen is produced by the hydrolysis reaction of the simple substance aluminum, the thermal decomposition reactant of aluminum hydride, with water. At the same time, the heat released by the hydrolysis reaction is used to promote the thermal decomposition of aluminum hydride, and hydrogen is released by the coupling of the two reactions, realizing the effective utilization of heat. When the hydrogen storage device is applied to a fuel cell system, water can be recovered from the tail gas of the fuel cell system for hydrogen production. The device that comprehensively utilizes the thermal decomposition of aluminum hydride and the aluminum hydrolysis reaction supplies hydrogen to the fuel cell, effectively realizing the hydrogen cycle and the efficient utilization of internal heat in the fuel cell system, and improving the energy utilization efficiency of the system.

[0063] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A hydrogen storage device based on solid-state hydrogen storage materials, characterized in that, Applied to a fuel cell system, including: A fuel tank, within which a reaction chamber is formed, and the reaction chamber is used for arranging an aluminum hydride material and a mixed powder, and the mixed powder includes aluminum powder and a catalyst; A heater, arranged outside the fuel tank, for heating the fuel tank; A water recovery assembly, with a first end communicating with the reaction chamber and a second end for communicating with the fuel cell system, for recovering the water generated by the fuel cell system to the reaction chamber; A hydrogen discharge assembly, with a first end communicating with the reaction chamber and a second end for communicating with the fuel cell system, for discharging the hydrogen generated by the thermal decomposition of aluminum hydride and the hydrolysis of aluminum into the fuel cell system.

2. The hydrogen storage device based on solid-state hydrogen storage material according to claim 1, wherein The hydrogen discharge assembly includes: a hydrogen supply pipe and a regulating valve; The first end of the hydrogen supply pipe communicates with the reaction chamber, and the second end communicates with the fuel cell system through the regulating valve.

3. The hydrogen storage device based on solid-state hydrogen storage materials according to claim 1, characterized in that, The fuel tank includes: a storage tank and a cover; The reaction chamber is formed within the storage tank, and the cover is provided at the opening position of the reaction chamber; The first ends of the hydrogen discharge assembly and the water recovery assembly both pass through the cover and communicate with the reaction chamber.

4. The hydrogen storage device based on solid-state hydrogen storage material according to claim 3, characterized in that, The fuel tank further includes: a filter element and an elastic element; The filter element is arranged in the reaction chamber, separating the reaction chamber into a gas storage space and a reaction space. The aluminum hydride material is arranged in the reaction space, and the mixed powder is filled in the gaps of the aluminum hydride material; One side of the filter element located in the gas storage space abuts against the cover through the elastic element, and one side of the filter element located in the reaction space abuts against the aluminum hydride material.

5. The hydrogen storage device based on solid-state hydrogen storage materials according to claim 1, characterized in that, The water recovery assembly includes: a driving pump and a vapor-liquid separator; The vapor-liquid separator is provided with a first inlet, a second inlet, an exhaust port, and a drain port. The first inlet is used for communicating with the cathode of the fuel cell system, the second inlet is used for communicating with the anode of the fuel cell system, and the drain port communicates with the reaction chamber through the driving pump.

6. The hydrogen storage device based on solid-state hydrogen storage materials according to claim 5, wherein, The water recovery assembly further includes: A radiator, with a first end communicating with the first inlet and a second end for communicating with the cathode of the fuel cell system.

7. The hydrogen storage device based on solid-state hydrogen storage materials according to claim 5, characterized in that, The water recovery assembly further includes: A water distributor, with a first end communicating with the vapor-liquid separator through the driving pump, and a second end provided with a plurality of branch pipes, and each of the branch pipes is distributed among the aluminum hydride materials.

8. The hydrogen storage device based on solid-state hydrogen storage materials according to any one of claims 1-7, characterized in that, The heater is a film heater, and the film heater surrounds the outside of the fuel tank; A temperature sensor for detecting its heating temperature is provided on the film heater.

9. The hydrogen storage device based on solid-state hydrogen storage material according to any one of claims 1-7, characterized in that, The hydrogen storage device further includes: A pressure relief valve, with one end communicating with the reaction chamber and the other end communicating with the outside.

10. A hydrogen production method using a hydrogen storage device based on a solid-state hydrogen storage material as described in any one of claims 1-9, characterized in that, Including: Controlling the heater to heat the fuel tank to utilize the thermal decomposition reaction of the aluminum hydride material to generate a first hydrogen source; Controlling the water recovery assembly to introduce water to utilize the hydrolysis reaction of the generated aluminum and the mixed powder to generate a second hydrogen source; When the heat released by the hydrolysis reaction reaches the reaction threshold, turning off the heater and utilizing the heat release effect of aluminum hydrolysis to maintain the thermal decomposition temperature field of aluminum hydride to achieve synergistic hydrogen production.

Images