Hydrogen electric system coupled with multiple solid-state hydrogen storage materials for ultra-high quality hydrogen storage density

Abstract

The application discloses a hydrogen and electricity system with multiple solid-state hydrogen storage materials coupling for super-high quality hydrogen storage density, and belongs to the technical field of hydrogen and electricity. The hydrogen and electricity system comprises a solid-state hydrogen storage system, a fuel cell stack and a modular solid-state hydrogen storage unit which are arranged in the solid-state hydrogen storage system, the modular solid-state hydrogen storage unit comprises a first hydrogen storage unit (a solid-state hydrogen storage material pyrolysis unit) and a second hydrogen storage unit (a solid-state hydrogen storage material hydrolysis unit) which are arranged in the first hydrogen storage unit; hydrogen outlets of the first hydrogen storage unit and the second hydrogen storage unit are connected to a hydrogen inlet of the fuel cell stack through a pipeline and a third hydrogen storage unit; and an anode tail gas outlet of the fuel cell stack is connected to a water inlet of the second hydrogen storage unit through a pipeline. The application adopts a coupling method to realize integrated design of hydrogen production by pyrolysis of solid-state hydrogen storage material, hydrogen production by hydrolysis and a fuel cell power generation system, realizes efficient utilization and release of water, heat and electricity, and realizes a hydrogen and electricity system solution with super-high energy density.

Description

Technical Field

[0001] This invention relates to the field of hydrogen power technology, and in particular to a hydrogen power system coupled with multiple solid-state hydrogen storage materials for ultra-high quality hydrogen storage density. Background Technology

[0002] To address the issue of low mass-volume hydrogen storage density in current high-pressure gaseous hydrogen storage systems, hydrogen storage systems based on solid-state hydrogen storage materials have been actively developed both domestically and internationally. Among the many hydrogen storage materials, they are mainly divided into two types: metal hydrides and composite hydrides. Many of these materials can release hydrogen through both pyrolysis and hydrolysis.

[0003] Releasing hydrogen through pyrolysis generally requires the hydrogen storage material to be able to repeatedly charge and release hydrogen, meaning it's a reversible hydrogen storage and release process. Currently, relatively mature hydrogen storage materials include Fe-Ti alloys, La-Ni alloys, and MgH2, with industrialization primarily focused on the first two, which have relatively low hydrogen storage densities, i.e., mass hydrogen storage densities below 3%. Although metal hydrides exhibit good reversibility in hydrogen release and storage reactions, their operation at high temperatures (above 100°C) requires continuous heating for hydrogen release, posing challenges in practical applications. Furthermore, the development of solid-state hydrogen storage systems operating at such high temperatures is also underway.

[0004] Hydrogen production materials via water electrolysis are irreversible hydrogen storage materials. They release hydrogen through a water electrolysis reaction and are suitable for on-site hydrogen production. Hydrogen production via water electrolysis has the following advantages: 1) High mass and volumetric hydrogen storage densities. For example, the theoretical mass hydrogen storage density of systems such as NaBH4, LiBH4, Mg(BH4)2, and MgH2 can reach up to 30%, and the volumetric hydrogen storage density of these materials is also higher than that of commercially available high-pressure hydrogen storage; 2) Hydrogen production via water electrolysis is a spontaneous exothermic reaction that occurs at room temperature and pressure, making the hydrogen production equipment relatively simple; 3) Hydrogen production materials via water electrolysis are easy to store, relatively safe, and convenient for storage and transportation; 4) The reaction byproducts are basically non-toxic and harmless, meeting the requirements of green chemistry.

[0005] While hydrogen combustion devices or heat exchangers can be installed in storage systems to improve heating and ensure proper operation of solid-state hydrogen storage materials, these solutions lead to reduced fuel efficiency due to energy losses. Although research exists both domestically and internationally to improve this by modifying the tubes within the container (such as the type, size, and location of heat exchange fins) or the loading method of the hydrogen storage material, these solutions result in a reduction in weight storage capacity due to the increased system weight. Therefore, improvements are needed to minimize the heat required to operate solid-state hydrogen systems and increase weight storage capacity. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a hydrogen-electric system coupled with multiple solid-state hydrogen storage materials for ultra-high quality hydrogen storage density, so as to reduce the heat required to operate the solid hydrogen system and improve the weight storage capacity.

[0007] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0008] A hydrogen-electric system coupled with multiple solid-state hydrogen storage materials for ultra-high hydrogen storage density includes a solid-state hydrogen storage system, wherein the solid-state hydrogen storage system comprises a fuel cell stack and at least one modular solid-state hydrogen storage unit, wherein:

[0009] The modular solid-state hydrogen storage unit includes a first hydrogen storage unit and a second hydrogen storage unit inserted in the first hydrogen storage unit. The first hydrogen storage unit is a solid-state hydrogen storage material pyrolysis unit, and the second hydrogen storage unit is a solid-state hydrogen storage material hydrolysis unit.

[0010] The hydrogen outlets of the first and second hydrogen storage units are connected to the hydrogen inlet of the fuel cell stack via a pipeline and then to the third hydrogen storage unit.

[0011] The anode exhaust port of the fuel cell stack is connected to the water inlet of the second hydrogen storage unit via a pipeline and an anode exhaust gas circulation pump.

[0012] The solid-state hydrogen storage system includes a fuel cell cathode cooling fan located between the fuel cell stack and the modular solid-state hydrogen storage unit.

[0013] Furthermore, one-way valves are provided on the pipelines corresponding to the hydrogen outlets of the first and second hydrogen storage units.

[0014] And / or, the hydrogen inlet pipeline of the third hydrogen storage unit is equipped with a first solenoid valve.

[0015] Furthermore, a second solenoid valve is provided on the hydrogen outlet pipeline of the third hydrogen storage unit;

[0016] And / or, the hydrogen outlet pipeline of the third hydrogen storage unit is equipped with a filter and a pressure regulating valve.

[0017] Furthermore, a tail gas solenoid valve is provided on the pipeline between the anode tail gas port of the fuel cell stack and the anode tail gas circulation pump.

[0018] Furthermore, the solid hydrogen storage system has an adjustable air inlet on the side of the fuel cell stack away from the fuel cell cathode cooling fan.

[0019] Furthermore, the solid-state hydrogen storage system has an adjustable air outlet on the side of the modular solid-state hydrogen storage unit away from the heat dissipation fan of the fuel cell cathode.

[0020] Furthermore, the solid-state hydrogen storage system is equipped with a hydrogen charging port, which is connected to the hydrogen charging port of the first hydrogen storage unit via a pipeline.

[0021] Furthermore, the hydrogen storage material in the first hydrogen storage unit is Fe-Ti alloy, La-Ni alloy, NH3BH3, AlH3 or MgH2;

[0022] And / or, the hydrogen storage material in the second hydrogen storage unit is NaAlH4, NaBH4, Mg(BH4)2 or LiH.

[0023] Furthermore, the edge of the first hydrogen storage unit is provided with several heat dissipation ribs extending in the axial direction.

[0024] And / or, the second hydrogen storage unit is columnar.

[0025] The present invention has the following beneficial effects:

[0026] This invention proposes a hydrogen-electric system solution that couples multiple solid-state hydrogen storage materials for ultra-high energy density. By leveraging the advantages of current solid-state hydrogen storage material systems, a coupling method is used to achieve an integrated design of hydrogen production through pyrolysis of solid-state hydrogen storage materials, hydrogen production through water electrolysis, and a fuel cell power generation system. This enables the efficient utilization and release of water, heat, and electricity, resulting in a hydrogen-electric system solution with ultra-high energy density. Attached Figure Description

[0027] Figure 1 This is a schematic diagram of the product structure of the hydrogen-electric system coupled with multiple solid-state hydrogen storage materials for ultra-high quality hydrogen storage density according to the present invention.

[0028] Figure 2 for Figure 1 Physical images of the modular solid-state hydrogen storage unit, where (a) is a perspective view and (b) is a top view. Detailed Implementation

[0029] To make the technical problems, technical solutions and advantages of the present invention clearer, a detailed description will be given below in conjunction with the accompanying drawings and specific embodiments.

[0030] In the description of this invention, it should be understood that the terms "upper", "lower", "front", "rear", "left", "right", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0031] This invention provides a hydrogen-electric system coupled with multiple solid-state hydrogen storage materials for ultra-high hydrogen storage density, such as... Figure 1-2 As shown, the system includes a solid-state hydrogen storage system 1, which contains a fuel cell stack 16 and at least one modular solid-state hydrogen storage unit 10, wherein:

[0032] The modular solid-state hydrogen storage unit 10 includes a first hydrogen storage unit 11 and a second hydrogen storage unit 12 inserted in the first hydrogen storage unit 11. The first hydrogen storage unit 11 is a solid-state hydrogen storage material pyrolysis unit, and the second hydrogen storage unit 12 is a solid-state hydrogen storage material hydrolysis unit.

[0033] The hydrogen outlet 111 of the first hydrogen storage unit 11 and the hydrogen outlet 121 of the second hydrogen storage unit 12 are connected to the hydrogen inlet 161 of the fuel cell stack 16 via a pipeline after being merged.

[0034] The anode exhaust port 162 of the fuel cell stack 16 is connected to the water inlet 122 of the second hydrogen storage unit 12 via a pipeline and an anode exhaust gas circulation pump 3.

[0035] The solid hydrogen storage system 1 has a fuel cell cathode cooling fan 13 between the fuel cell stack 16 and the modular solid hydrogen storage unit 10.

[0036] This invention proposes a hydrogen-electric system solution that couples multiple solid-state hydrogen storage materials for ultra-high energy density. By leveraging the advantages of current solid-state hydrogen storage material systems, a coupling method is used to achieve an integrated design of hydrogen production through pyrolysis of solid-state hydrogen storage materials, hydrogen production through water electrolysis, and a fuel cell power generation system. This enables the efficient utilization and release of water, heat, and electricity, resulting in a hydrogen-electric system solution with ultra-high energy density.

[0037] In this invention, the solid hydrogen storage materials contained in the solid hydrogen storage system 1 mainly include composite hydrogen storage materials, metal hydrides, and hydrogen storage alloys.

[0038] Among them, composite hydrogen storage materials can be selected from M 1 AlH4, M 2 (AlH4)2, M 3 BH4, M 4 (BH4)2, M 5 (BH4)3, M 6 NH2, M 7 (NH2)2, Li2NH, MgNH, lithium magnesium imide, NaBP2H8, NH3BH3, NH4B3H8, NH2B2H5, and combinations thereof, wherein M 1 Is it Li, Na, or Al, M? 2 Is it Mg or Ca, M 3 Is it Li, Na, or K, M4 Is it Mg or Ca, M 5 Is it Al or Ti, M? 6 It is either Li or Na, and M 7 It is Mg or Ca.

[0039] Metal hydrides and metal hydrides in hydrogen storage alloys can be M 8 H, M 9 H2, AlH3, or combinations thereof, wherein M 8 It is Li, Na, K, Rb, or Cs, and M 9 It is Mg, Ca, Sc, Ti, or V. The storage alloys in metal hydrides and hydrogen storage alloys are Ti-Cr-V alloys, TiFe, and Pd-M. 10 Li-M 11 Mg-Co alloys, La-Ni alloys, or combinations thereof, wherein M 10 Refers to Ba, Y, or La, and M 11 This refers to Ti, V, Zr, Nb, or Hf.

[0040] Typical hydrogen storage materials in the first hydrogen storage unit (solid hydrogen storage material pyrolysis unit) 11 include: Fe-Ti alloy, La-Ni alloy, NH3BH3, AlH3, MgH2, etc.

[0041] Typical hydrogen storage materials in the second hydrogen storage unit (solid hydrogen storage material hydrolysis unit) 12 include NaAlH4, NaBH4, Mg(BH4)2, and LiH.

[0042] The edge of the first hydrogen storage unit 11 may be provided with several heat dissipation ribs 113 extending in the axial direction to improve the heat dissipation effect. The second hydrogen storage unit 12 may be columnar and inserted into the first hydrogen storage unit 11 to improve the heat conduction effect between the two.

[0043] To facilitate the guidance of hydrogen flow, one-way valves 14 can be provided on the pipelines corresponding to the hydrogen outlet 111 of the first hydrogen storage unit 11 and the hydrogen outlet 121 of the second hydrogen storage unit 12.

[0044] A first solenoid valve 4 can be installed on the hydrogen inlet pipeline of the third hydrogen storage unit 2 (i.e., the pipeline between the third hydrogen storage unit 2 and the solid hydrogen storage system 1 / modular solid hydrogen storage unit 10), and a second solenoid valve 5 can be installed on the hydrogen outlet pipeline of the third hydrogen storage unit 2 (i.e., the pipeline between the third hydrogen storage unit 2 and the fuel cell stack 16) for convenient control. A filter 6 and a pressure regulating valve 7 can also be installed on the hydrogen outlet pipeline of the third hydrogen storage unit 2 to filter and regulate the gas pressure.

[0045] A tail exhaust solenoid valve 8 can be installed on the pipeline between the anode exhaust port 162 and the anode exhaust circulation pump 3 of the fuel cell stack 16 for convenient control.

[0046] An adjustable air inlet 17 may be provided on the side of the fuel cell stack 16 away from the fuel cell cathode cooling fan 13. An adjustable air outlet 18 may be provided on the side of the modular solid hydrogen storage unit 10 away from the fuel cell cathode cooling fan 13. The number of adjustable air outlets 18 can be flexibly set as needed, for example, the two shown in the figure.

[0047] The hydrogen-electric system products of this invention are mainly aimed at scenarios requiring low to medium power, long endurance, and high safety, including portable power supplies, small to medium-sized power supplies, emergency power supplies, drone power supply systems, and power supply systems for small to medium-sized unmanned vessels, etc., and have significant advantages, especially in high and low temperature or other harsh operating conditions. Its working process can be referred to as follows:

[0048] First, the second solenoid valve 5 is opened, and hydrogen required for the anode reaction is supplied to the fuel cell stack 16 through the third hydrogen storage unit 2 after gas filtration and pressure stabilization. Simultaneously, oxygen required for the cathode reaction is supplied to the fuel cell stack 16 through the fuel cell cathode cooling fan 13, while simultaneously controlling the operating temperature of the fuel cell stack 16 within a safe range. The anode exhaust gas generated after the reaction in the fuel cell stack 16, including some unreacted hydrogen and reaction product water, is directly input into the second hydrogen storage unit 12 through the exhaust solenoid valve 8 and the anode exhaust gas circulation pump 3. The solid hydrogen storage material in the second hydrogen storage unit 12 undergoes a hydrolysis reaction upon contact with water, generating hydrogen and heat. This heat is transferred to the first hydrogen storage unit 11 via heat transfer. Meanwhile, the waste heat generated by the fuel cell system enters the modular solid hydrogen storage unit 10 through the fuel cell cathode cooling fan 13 to heat the solid hydrogen storage material in the first hydrogen storage unit 11, achieving thermal dehydrogenation of hydrogen in the first hydrogen storage unit 11. The hydrogen produced by the first hydrogen storage unit 11 and the second hydrogen storage unit 12 is combined after passing through the one-way valve 14. At this time, the first solenoid valve 4 is opened to replenish the hydrogen to the third hydrogen storage unit 2. The operating temperature of the modular solid-state hydrogen storage unit 10 can be adjusted through the adjustable air outlet 18.

[0049] In the hydrogen-electric system product of this invention, the solid-state hydrogen storage system 1 can be composed of one or more modular solid-state hydrogen storage units 10, which can be flexibly combined and provide convenient hydrogen replenishment. The second hydrogen storage unit 12 releases hydrogen through hydrolysis to achieve high-quality hydrogen storage density. The second hydrogen storage unit 12 can be replaced using a quick-change mode, and the reaction products in the second hydrogen storage unit 12 can be recovered and regenerated. The first hydrogen storage unit 11 uses the heat from the hydrolysis of hydrogen produced by the second hydrogen storage unit 12 and the waste heat from the fuel cell stack 16 to achieve thermal hydrogen release without external heating, thereby improving the overall energy utilization and operating performance of the system.

[0050] Meanwhile, for different application scenarios, the first hydrogen storage unit 11 in the modular solid-state hydrogen storage unit 10 can simultaneously meet both online and offline hydrogen replenishment needs. During online hydrogen replenishment, the solid-state hydrogen storage system 1 can be equipped with a hydrogen filling port 9, which is connected to the first hydrogen storage unit's hydrogen filling port 112 via a pipeline. In this case, the first hydrogen storage unit 11 is a reversible solid-state hydrogen storage system. Thus, a hydrogen source of approximately 1-5 MPa is provided through the hydrogen filling port 9 to replenish the first hydrogen storage unit 11 online. Because the reversible solid-state hydrogen storage filling process is exothermic, it is necessary to adjust the fuel cell cathode cooling fan 13 and the adjustable air outlet 18 to promptly dissipate the heat during the filling process in order to improve filling efficiency. For offline hydrogen replenishment, hydrogen filling equipment can be specifically designed for the modular solid-state hydrogen storage unit 10 to improve the efficiency and convenience of hydrogen replenishment.

[0051] Chinese invention patent application CN116510640A describes the need for solvents with low freezing point aqueous solutions, such as calcium chloride, sodium chloride, or aluminum chloride, for low-temperature operation during startup. This invention pertains to a solid-state hydrogen storage system that does not require water replenishment and recycles the water produced by the fuel cell stack 16, improving the system's energy efficiency. Furthermore, the product water produced by the fuel cell stack 16 is above 50°C, which effectively ensures operation under low-temperature conditions and facilitates the hydrolysis reaction in the second hydrogen storage unit 12.

[0052] Chinese invention patent application CN103579652A utilizes a water circulation system during fuel cell operation to heat the reactor and initiate the hydrolysis reaction. The hydrolysis reactor is connected to the proton exchange membrane fuel cell via pipelines. The water generated by the proton exchange membrane fuel cell can balance the water consumed by MgH2 hydrolysis, achieving water recycling and theoretically eliminating the need for external water injection. However, because heat transfer is achieved through a water circulation system, the overall system weight and volume increase significantly, severely impacting the overall energy density. Furthermore, the considerable heat generated by MgH2 hydrolysis can affect the normal operation of the fuel cell system when the water circulation temperature rises. This invention employs a coupled operating mode of multiple solid-state hydrogen storage materials, enabling effective heat distribution and utilization within the system. It utilizes an air-cooled fuel cell, allowing the overall thermal management of the modular solid-state hydrogen storage unit 10 to be well coupled with the waste heat of the fuel cell stack 16, while maintaining a degree of independence and minimizing impact on the fuel cell stack 16.

[0053] In summary, this invention provides a hydrogen-electric system solution that couples multiple solid-state hydrogen storage materials to achieve ultra-high hydrogen storage density, mainly as follows:

[0054] 1) Currently, the mass hydrogen storage density of major hydrogen storage systems is below 5%, which restricts the development of the hydrogen energy industry. This invention can achieve ultra-high mass hydrogen storage density. Through different material combinations, the system hydrogen storage density can reach more than 10 wt%.

[0055] 2) Currently, mainstream high-pressure hydrogen storage and liquid hydrogen storage rely on hydrogen refueling infrastructure. However, for solid hydrogen storage, the practical solid hydrogen storage technology has low hydrogen storage performance. This invention can realize the coupling of reversible solid pyrolysis hydrogen storage and irreversible solid water electrolysis hydrogen storage systems, and realize reliable structural design and rapid replacement technology.

[0056] 3) Currently used solid hydrogen storage materials for hydrogen production through hydrolysis all require a water tank of a corresponding proportion, which seriously affects the energy density of the overall system. This invention utilizes solid hydrogen storage materials with high hydrogen storage density for hydrogen production through hydrolysis and achieves a hydrogen production solution without the need for water replenishment by recovering the water after the fuel cell reaction.

[0057] 4) At present, the coupling of waste heat between solid hydrogen storage and fuel cell systems has not achieved the ideal effect. This invention can couple the heat required for the pyrolysis of solid hydrogen storage materials with the heat generated by the operation of fuel cells, thereby improving the overall heat utilization.

[0058] 5) The current technical route for solid hydrogen storage is constrained by the source of heat required for pyrolysis and the utilization of heat from hydrogen production by hydrolysis, and a comprehensive solution has not yet been found. This invention can couple the heat required for pyrolysis of solid hydrogen storage materials with the heat released from hydrogen production by hydrolysis of solid hydrogen storage materials to achieve overall energy efficiency.

[0059] The above description represents the preferred embodiments of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A hydrogen-electric system coupled with multiple solid-state hydrogen storage materials for ultra-high hydrogen storage density, characterized in that, This includes a solid-state hydrogen storage system, which contains a fuel cell stack and at least one modular solid-state hydrogen storage unit, wherein: The modular solid-state hydrogen storage unit includes a first hydrogen storage unit and a second hydrogen storage unit inserted in the first hydrogen storage unit. The first hydrogen storage unit is a solid-state hydrogen storage material pyrolysis unit, and the second hydrogen storage unit is a solid-state hydrogen storage material hydrolysis unit. The hydrogen outlets of the first and second hydrogen storage units are connected to the hydrogen inlet of the fuel cell stack via a pipeline and then to the third hydrogen storage unit. The anode exhaust port of the fuel cell stack is connected to the water inlet of the second hydrogen storage unit via a pipeline and an anode exhaust gas circulation pump. The solid hydrogen storage system includes a fuel cell cathode cooling fan located between the fuel cell stack and the modular solid hydrogen storage unit. The hydrogen storage material in the first hydrogen storage unit is Fe-Ti alloy, La-Ni alloy, NH3BH3, AlH3 or MgH2; The hydrogen storage material in the second hydrogen storage unit is NaAlH4, NaBH4, Mg(BH4)2 or LiH; The edge of the first hydrogen storage unit is provided with several heat dissipation ribs extending in the axial direction. The second hydrogen storage unit is columnar.

2. The hydrogen-electric system according to claim 1, characterized in that, One-way valves are provided on the pipelines corresponding to the hydrogen outlet of the first hydrogen storage unit and the hydrogen outlet of the second hydrogen storage unit. And / or, the hydrogen inlet pipeline of the third hydrogen storage unit is equipped with a first solenoid valve.

3. The hydrogen-electric system according to claim 2, characterized in that, A second solenoid valve is installed on the hydrogen outlet pipeline of the third hydrogen storage unit; And / or, the hydrogen outlet pipeline of the third hydrogen storage unit is equipped with a filter and a pressure regulating valve.

4. The hydrogen-electric system according to claim 1, characterized in that, A tail exhaust solenoid valve is installed on the pipeline between the anode tail gas port of the fuel cell stack and the anode tail gas circulation pump.

5. The hydrogen-electric system according to claim 1, characterized in that, The solid hydrogen storage system has an adjustable air inlet on the side of the fuel cell stack away from the fuel cell cathode cooling fan.

6. The hydrogen-electric system according to claim 5, characterized in that, The solid-state hydrogen storage system has an adjustable air outlet on the side of the modular solid-state hydrogen storage unit away from the heat dissipation fan of the fuel cell cathode.

7. The hydrogen-electric system according to claim 1, characterized in that, The solid hydrogen storage system is equipped with a hydrogen charging port, which is connected to the hydrogen charging port of the first hydrogen storage unit via a pipeline.

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