Solid hydrogen storage and fuel cell coupling system and operation method thereof

Abstract

The invention relates to the technical field of energy system design optimization, and discloses a solid hydrogen storage and fuel cell coupling system and an operation method thereof. The system comprises a solid hydrogen storage unit and a fuel cell unit, the solid hydrogen storage unit comprises a solid hydrogen storage container which is used for storing hydrogen and providing hydrogen for the fuel cell unit; the solid hydrogen storage container comprises a heat-conducting fluid substrate and a hydrogen storage material substrate filled with a solid hydrogen storage composite material which are stacked in sequence; a first flow channel is engraved on the heat-conducting fluid substrate and is used for allowing heat-conducting fluid to pass through; a second runner is engraved on the hydrogen storage material substrate and is used for hydrogen to pass through, and the first runner is not communicated with the second runner; and the fuel cell unit is used for reacting oxygen-containing gas with hydrogen from the solid hydrogen storage unit to generate power and providing heat for hydrogen desorption of the solid hydrogen storage unit. The system provided by the invention can provide stable-pressure and stable-flow hydrogen for the fuel cell unit, so that stable operation of the fuel cell unit is ensured.

Description

Technical Field

[0001] The present invention relates to the technical field of energy system design optimization, and in particular to a solid hydrogen storage and fuel cell coupling system and an operation method thereof. Background Art

[0002] Fuel cells can convert chemical energy stored in hydrogen and oxygen into electrical energy. They have the advantages of high energy conversion efficiency and environmental friendliness. During the operation of a fuel cell, about half of the energy is converted into heat energy. To ensure the stable operation of a fuel cell, efficient heat management is also crucial.

[0003] With the growing global demand for energy, as well as serious CO2 emissions and worsening environmental pollution, people are paying more and more attention to the development of clean and renewable energy. As a secondary energy source, hydrogen energy has the characteristics of wide sources, clean and carbon-free, flexible and efficient, and a wide range of application scenarios. It can be widely used in energy, transportation, industry, construction and other fields. It is an ideal interconnected medium to promote the clean and efficient use of traditional fossil energy and support the large-scale development of renewable energy. It will gradually become an important direction of the global energy technology revolution.

[0004] Hydrogen can be stored and transported. Improving the efficiency of hydrogen storage and transportation and reducing the cost of hydrogen storage and transportation are the development focuses of hydrogen storage and transportation technology. At present, hydrogen storage mainly includes three types of methods: gaseous hydrogen storage, liquid hydrogen storage, and solid hydrogen storage. High-pressure gaseous hydrogen storage is the main method of hydrogen storage at this stage, with the advantages of fast hydrogen filling and discharging speed and simple container structure. However, high-pressure gaseous hydrogen storage has disadvantages such as low volume density and low safety. At the same time, existing high-pressure equipment and high-pressure storage tank technology mostly rely on imports. Liquid hydrogen storage refers to the low-temperature liquefaction of hydrogen and storage in a low-temperature insulated liquid storage tank, which has the advantage of high hydrogen storage density. However, the high cost of liquid hydrogen equipment, high energy consumption in the liquefaction process, and evaporation loss during use are problems that need to be solved urgently. Solid hydrogen storage refers to the storage of hydrogen through chemical adsorption or physical adsorption using metal hydrides, nanomaterials, etc. as carriers. Solid hydrogen storage has the advantages of high hydrogen storage density, low hydrogen storage pressure, high hydrogen release purity, and good safety. It is an important direction for the development of hydrogen storage in the future.

[0005] Hydrogen storage alloy materials refer to a type of material that stores hydrogen in the form of metal hydrides. Hydrogen storage alloys have the advantages of good reversibility of hydrogen absorption and desorption, high hydrogen storage density per unit volume, high hydrogen desorption purity, and high safety. Metal hydrides are formed by a reversible reaction between metal alloys and hydrogen at specific temperatures and pressures. The absorption of hydrogen is an exothermic reaction, while the desorption is an endothermic process. When using a solid-state hydrogen storage system to supply hydrogen, additional heat is usually required to meet the heat requirements of the hydrogen desorption process, which will reduce the effective utilization of energy.

[0006] When working, the fuel cell stack converts the chemical energy in hydrogen and oxygen into electrical energy, but at the same time, part of the energy will also be converted into thermal energy, generating waste heat dissipation.

[0007] Therefore, it is urgent to develop a solid hydrogen storage and fuel cell coupling system to improve heat utilization. Summary of the invention

[0008] The purpose of the present invention is to overcome the problems existing in the prior art and provide a solid hydrogen storage and fuel cell coupling system and its operation method. The system of the present invention can provide hydrogen with stable pressure and flow for the fuel cell unit to ensure the stable operation of the fuel cell unit.

[0009] In order to achieve the above-mentioned object, the present invention provides a solid hydrogen storage and fuel cell coupling system on one hand, wherein the system comprises a solid hydrogen storage unit and a fuel cell unit; The solid hydrogen storage unit comprises a solid hydrogen storage container for storing hydrogen and providing hydrogen for the fuel cell unit; the solid hydrogen storage container comprises a heat transfer fluid substrate and a hydrogen storage material substrate filled with a solid hydrogen storage composite material stacked in sequence; the heat transfer fluid substrate is engraved with a first flow channel for the passage of the heat transfer fluid; the hydrogen storage material substrate is engraved with a second flow channel for the passage of hydrogen, and the first flow channel and the second flow channel are not connected; The fuel cell unit is used for reacting the oxygen-containing gas with the hydrogen from the solid hydrogen storage unit to generate electricity and provide heat for the solid hydrogen storage unit to release hydrogen.

[0010] Preferably, the first flow channel and the second flow channel are each independently a serpentine flow channel or a parallel flow channel.

[0011] Preferably, the first flow channel and the second flow channel are serpentine flow channels and are arranged in parallel.

[0012] The facets of the first flow channel and the second flow channel are independently square facets or triangular sawtooth facets, preferably triangular sawtooth facets.

[0013] Preferably, in the triangular sawtooth facet, the angle of the triangular sawtooth vertex is 50-120°, preferably 60-90°.

[0014] The second aspect of the present invention provides an operating method of the solid hydrogen storage and fuel cell coupling system of the first aspect, the method comprising: reacting an oxygen-containing gas with hydrogen from a solid hydrogen storage container in a fuel cell unit to generate electricity, while a first heat transfer fluid absorbs heat generated by the fuel cell power generation; Among them, the hydrogen release process of the solid hydrogen storage container includes: the solid hydrogen storage composite material adsorbed with hydrogen undergoes a desorption reaction, and the first heat transfer fluid that absorbs the heat generated by the fuel cell power generation is sent into the first flow channel of the heat transfer fluid substrate to provide heat for the desorption reaction of hydrogen.

[0015] Through the above technical solution, the beneficial effects of the present invention include: The system described in the present invention couples a solid hydrogen storage unit with a fuel cell unit. The solid hydrogen storage container provided by the present invention comprises a hydrogen storage material substrate and a heat transfer fluid substrate engraved with flow channels, which is beneficial for the hydrogen to fully contact and react with the solid hydrogen storage composite material during the hydrogen storage process, while keeping the hydrogen absorption reaction temperature at a favorable position, thereby increasing the hydrogen absorption rate and reducing the hydrogen absorption time; it is beneficial for the introduced heat transfer fluid to promptly remove the heat released from the hydrogen storage material substrate reaction system, thereby improving the heat exchange efficiency; it is beneficial for the heat transfer fluid to promptly provide heat for the desorption of hydrogen during the hydrogen release process, thereby providing the fuel cell with hydrogen with a stable pressure and flow, thereby ensuring the stable operation of the fuel cell stack.

[0016] At the same time, the system of the present invention can achieve efficient heat management and utilization between the solid hydrogen storage unit and the fuel cell unit, significantly improving the heat utilization rate. Preferably, the system of the present invention connects the solid hydrogen storage unit and the fuel cell unit via a thermal coupling unit, which can recycle the heat, further improve the heat utilization rate, reduce heat emissions, and have little impact on the environment.

[0017] The solid hydrogen storage container of the present invention can flexibly adjust the number of hydrogen storage material substrates and heat transfer fluid substrates, thereby changing the hydrogen storage capacity, and is convenient for coupling with fuel cell stacks of various powers. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 It is a structural schematic diagram of the solid hydrogen storage and fuel cell coupling system of the present invention; Figure 2 It is a structural schematic diagram of a cross section of a heat transfer fluid substrate or a hydrogen storage material substrate in the solid hydrogen storage container of the present invention; Figure 3 is a schematic diagram of the first and second flow channel types of the present invention ( Figure 3 In the middle, a is a serpentine flow channel. Figure 3 b in the figure indicates parallel flow channels); Figure 4 Schematic diagram of the flow channel facets in the heat transfer fluid substrate or hydrogen storage material substrate in the solid hydrogen storage container of the present invention ( Figure 4 a in the middle is a square facet. Figure 4 b in the middle is a triangular sawtooth facet. Figure 4 c in the middle is a wavy facet); Figure 5is a graph showing the relationship between hydrogen release rate / hydrogen release ratio and operation time in Example 1 of the present invention; Figure 6 is a graph showing the relationship between hydrogen release rate / hydrogen release ratio and operation time in Example 2 of the present invention; Figure 7 is a graph showing the relationship between hydrogen release rate / hydrogen release ratio and operation time in Example 3 of the present invention; Figure 8 is a graph showing the relationship between hydrogen release rate / hydrogen release ratio and operating time in Example 4 of the present invention; Fig. 9 is a schematic structural diagram of a solid hydrogen storage container of Comparative Example 1; Fig.10 is a graph showing the relationship between the hydrogen release rate / hydrogen release ratio and the operating time of Comparative Example 1 of the present invention; Fig.11 is a graph showing the relationship between the hydrogen release rate / hydrogen release ratio and the operating time of Comparative Example 2 of the present invention; Fig.12 It is a schematic structural diagram of the solid hydrogen storage container-fuel cell device of Example 5.

[0019] Marking Description DETAILED DESCRIPTION The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0020] In the present invention, unless otherwise specified, the terms "first" and "second" do not indicate a sequence or limit the materials or steps, but are only used to distinguish that they are not the same material or step. For example, the terms "first" and "second" in "first flow channel" and "second flow channel" are only used to indicate that they are not the same flow channel.

[0021] In one aspect, the present invention provides a solid hydrogen storage and fuel cell coupling system, the system comprising a solid hydrogen storage unit I and a fuel cell unit II; The solid hydrogen storage unit I comprises a solid hydrogen storage container 1, which is used to store hydrogen and provide hydrogen for the fuel cell unit II; the solid hydrogen storage container 1 comprises a heat transfer fluid substrate 5 and a hydrogen storage material substrate 6 filled with a solid hydrogen storage composite material stacked in sequence; the heat transfer fluid substrate 5 is engraved with a first flow channel for the passage of the heat transfer fluid; the hydrogen storage material substrate 6 is engraved with a second flow channel for the passage of hydrogen, and the first flow channel and the second flow channel are not connected; The fuel cell unit II is used to react the oxygen-containing gas with the hydrogen from the solid hydrogen storage unit I to generate electricity and provide heat for the solid hydrogen storage unit I to release hydrogen.

[0022] It should be noted that during the operation of the fuel cell unit, heat is provided for the solid hydrogen storage unit I to release hydrogen. Initially, the heat required for the solid hydrogen storage unit I to release hydrogen is provided by the heat transfer fluid stored in the liquid storage tank 26 in the thermal cycle unit III described below after being heated by the heating resistor 29.

[0023] Specifically, the heat transfer fluid stored in the liquid storage tank 26 in the following thermal circulation unit III is heated by the heating resistor 29, flows into the heat transfer fluid circulation inlet of the following fuel cell stack 2, and then flows into the first fluid pipeline 3 of the following solid hydrogen storage unit I, providing the solid hydrogen storage unit I with the heat required for dehydrogenation.

[0024] The heat-conducting fluid substrate 5 and the hydrogen storage material substrate 6 filled with solid hydrogen storage composite materials described in the present invention can be stacked in sequence in the order of heat-conducting fluid substrate 5 and hydrogen storage material substrate 6 as a group of two substrates, or can be stacked in the order of heat-conducting fluid substrate 5, hydrogen storage material substrate 6, and heat-conducting fluid substrate 5 as a group of three substrates.

[0025] The present invention has no particular limitation on the number of stacked heat transfer fluid substrates 5 and hydrogen storage material substrates 6, which can be appropriately selected according to the application. Preferably, the number of stacked heat transfer fluid substrates 5 and hydrogen storage material substrates 6 is independently 2-100.

[0026] Preferably, the heat transfer fluid substrate 5 has a first flow channel engraved on one side for the heat transfer fluid to pass through; the hydrogen storage material substrate 6 has a second flow channel engraved on one side for the hydrogen to pass through, and the first flow channel and the second flow channel are not connected.

[0027] The first flow channel and the second flow channel of the present invention are applicable to various flow channel types. In order to improve heat exchange efficiency, in some preferred embodiments, the first flow channel and the second flow channel are independently serpentine flow channels or parallel flow channels.

[0028] The serpentine flow channel of the present invention refers to a single curved flow channel, such as Figure 3 As shown in a.

[0029] The parallel flow channel of the present invention refers to a flow channel composed of multiple groups of parallel channels, such as Figure 3 As shown in b.

[0030] In some preferred embodiments, the ratio of the unidirectional length to the depth of the serpentine flow channel is 5-100: 1. This preferred embodiment is more conducive to improving the heat exchange efficiency.

[0031] In the present invention, the one-way length refers to the longest straight-line distance of the serpentine flow channel flowing in the same direction.

[0032] In some preferred embodiments, the ratio of the length to the depth of a single group of parallel flow channels is 5-100: 1. This preferred embodiment is more conducive to improving heat exchange efficiency.

[0033] In the present invention, the single group length refers to the longest straight-line distance of parallel flow channels flowing in the same direction.

[0034] In some preferred embodiments, the ratio of the depth of the first flow channel to the thickness of the heat transfer fluid substrate 5 is 0.4-0.9: 1, preferably 0.7-0.9: 1. With this preferred embodiment, both high heat transfer efficiency and high volume utilization can be taken into account.

[0035] In some preferred embodiments, the volume of the first flow channel accounts for 30-90%, preferably 40-70%, of the volume of the heat transfer fluid substrate 5. With this preferred embodiment, both high heat transfer efficiency and high volume utilization can be taken into account.

[0036] In some preferred embodiments, the ratio of the depth of the second flow channel to the thickness of the hydrogen storage material substrate 6 is 0.4-0.9: 1, preferably 0.7-0.9: 1. With this preferred embodiment, both high heat transfer efficiency and high volume utilization can be taken into account.

[0037] In some preferred embodiments, the volume of the second flow channel accounts for 30-90%, preferably 40-70%, of the volume of the hydrogen storage material substrate 6. With this preferred embodiment, both high heat transfer efficiency and high volume utilization can be taken into account.

[0038] In some preferred embodiments, the first flow channel and the second flow channel have the same shape and are arranged in parallel.

[0039] The parallel arrangement described in the present invention means that the flow direction of the heat transfer fluid in the first flow channel is the same as the flow direction of the hydrogen in the second flow channel.

[0040] In some preferred embodiments, the first flow channel and the second flow channel are serpentine flow channels and are arranged in parallel. With this preferred embodiment, the heat transfer efficiency can be further improved, and the hydrogen absorption and desorption speed can be increased.

[0041] In some preferred embodiments, along the stacking direction of the heat transfer fluid substrate 5 and the hydrogen storage material substrate 6 in the solid hydrogen storage container 1, the first flow channel and the second flow channel are arranged in the same direction.

[0042] In the present invention, along the stacking direction of the heat transfer fluid substrate 5 and the hydrogen storage material substrate 6 in the solid hydrogen storage container, the first flow channel and the second flow channel are arranged in the same direction, which means: When the solid hydrogen storage container is placed horizontally (the sealing end plates mentioned below are on the left and right sides, such as Figure 1 As shown), the setting position of the first flow channel on the heat transfer fluid substrate 5 and the setting position of the second flow channel on the hydrogen storage material substrate 6 can be both on the left side or on the right side.

[0043] When the solid hydrogen storage container is placed vertically (the sealing end plates mentioned below are on the upper and lower sides), the setting position of the first flow channel on the heat transfer fluid substrate 5 and the setting position of the second flow channel on the hydrogen storage material substrate 6 can be both on the upper side or on the lower side.

[0044] The present invention has no particular limitation on the facets of the flow channel, which may be square facets, such as Figure 4 As shown in a, it can also be a triangular sawtooth facet, such as Figure 4 As shown in b, it can also be a wavy facet, such as Figure 4 In some preferred embodiments, the facets of the first flow channel and the second flow channel are independently square facets or triangular sawtooth facets, preferably triangular sawtooth facets. With this preferred embodiment, the heat transfer area can be increased, thereby improving the heat transfer efficiency and making the hydrogen absorption and desorption speed faster.

[0045] In some preferred embodiments, in the triangular sawtooth facet, the triangular sawtooth is an isosceles triangle.

[0046] In some preferred embodiments, in the triangular sawtooth facets, the angle of the triangular sawtooth vertex is 50-120°, preferably 60-90°. With this preferred embodiment, the heat transfer area can be further increased, thereby improving the heat transfer efficiency and making the hydrogen absorption and desorption speed faster.

[0047] In the present invention, the facets of the first flow channel and the second flow channel refer to the cross-sections of the solid parts of the substrate.

[0048] When the facets of the first flow channel are triangular sawtooth facets, the one-way width of the first flow channel is the distance between the highest points of the triangular sawtooth.

[0049] When the facets of the second flow channel are triangular sawtooth facets, the single group width of the second flow channel is the distance between the highest points of the triangular sawtooth.

[0050] In some preferred embodiments, the solid hydrogen storage composite material is filled in the second flow channel of the hydrogen storage material substrate 6. This preferred embodiment is conducive to sufficient contact between hydrogen and the solid hydrogen storage composite material.

[0051] In some preferred embodiments, the filling volume of the solid hydrogen storage composite material accounts for 40-90% of the volume of the second flow channel, preferably 50-70%. With this preferred embodiment, the hydrogen transmission speed can be guaranteed, while increasing the contact between the solid hydrogen storage composite materials and improving the heat transfer efficiency.

[0052] The present invention has a wide range of selection for the type of the solid hydrogen storage composite material, which can be various conventional solid hydrogen storage composite materials in the art. Preferably, the solid hydrogen storage composite material includes a hydrogen storage material and a thermal conductive material. By adopting this preferred embodiment, the heat transfer coefficient of the hydrogen storage material bed can be effectively improved, while reducing the stress change caused by the expansion and contraction of the hydrogen storage material during the hydrogen absorption and desorption process.

[0053] The present invention has no particular limitation on the amount of the hydrogen storage material and the heat conductive material, which can be selected conventionally in the art. Preferably, the mass ratio of the hydrogen storage material to the heat conductive material is 1:0.01-0.2.

[0054] The present invention has a wide range of choices for the types of hydrogen storage materials, which can be conventionally selected in the art. Preferably, the hydrogen storage material is selected from at least one of titanium-based, zirconium-based, vanadium-based and rare earth-based hydrogen storage alloys.

[0055] Preferably, the rare earth series hydrogen storage alloy is a lanthanum series and / or cerium series hydrogen storage alloy. The present invention uses LaNi5 hydrogen storage material (lanthanum series hydrogen storage alloy) as an example.

[0056] The present invention has a wide range of choices for the thermally conductive material, which can be a conventional choice in the art. Preferably, the thermally conductive material is selected from at least one of expanded graphite, thermally conductive fiber, graphite sheet, carbon nanotube, aluminum powder, copper powder, titanium powder, foamed aluminum, foamed nickel and foamed copper.

[0057] The above hydrogen storage materials and thermal conductive materials are both commercially available.

[0058] The present invention has a wide range of choices for the type of the heat transfer fluid, which can be a conventional choice in the art. Preferably, the heat transfer fluid is water.

[0059] Preferably, the water is deionized water or ultrapure water.

[0060] The present invention has no particular limitation on the thickness of the heat transfer fluid substrate and the hydrogen storage material substrate, and can be appropriately selected according to the application. Preferably, the thickness of the heat transfer fluid substrate 5 and the hydrogen storage material substrate 6 are independently 5-100 mm.

[0061] The present invention has no particular limitation on the volume of the heat transfer fluid substrate and the hydrogen storage material substrate, and they can be appropriately selected according to the application.

[0062] The present invention has no particular limitation on the longitudinal cross-sectional shapes of the heat transfer fluid substrate and the hydrogen storage material substrate, which can be regular or irregular. Preferably, the longitudinal cross-sectional shapes of the heat transfer fluid substrate 5 and the hydrogen storage material substrate 6 are independently square or circular.

[0063] Preferably, the heat transfer fluid substrate 5 and the hydrogen storage material substrate 6 have the same longitudinal cross-sectional shape.

[0064] The present invention has no particular limitation on the materials of the heat transfer fluid substrate and the hydrogen storage material substrate, which can be conventionally selected in the art. Preferably, the heat transfer fluid substrate 5 and the hydrogen storage material substrate 6 are independently made of aluminum, aluminum alloy, copper, copper alloy, carbon steel or stainless steel.

[0065] In some preferred embodiments, the solid hydrogen storage container 1 is further provided with a first fluid pipeline 3 and a second fluid pipeline 4, wherein the first fluid pipeline 3 is connected to the fluid inlet of the heat-conducting fluid substrate 5, and the second fluid pipeline 4 is connected to the fluid outlet of the heat-conducting fluid substrate 5 for the circulation of the heat-conducting fluid.

[0066] In some preferred embodiments, the other side of the first fluid pipeline 3 and the second fluid pipeline 4 is connected to a refrigerator for absorbing the heat released by the solid hydrogen storage container 1 during hydrogen storage.

[0067] In some preferred embodiments, the solid hydrogen storage container 1 is also provided with a hydrogenation pipeline 9 and a hydrogen supply pipeline 10. The hydrogenation pipeline 9 is connected to the gas inlet of the hydrogen storage material substrate 6 to provide hydrogen to the solid hydrogen storage composite material; the hydrogen supply pipeline 10 is connected to the gas outlet of the hydrogen storage material substrate 6 and the fuel cell unit II to provide hydrogen to the fuel cell unit II.

[0068] In some preferred embodiments, the other side of the hydrogenation pipeline 9 is connected to the hydrogenation equipment via the hydrogenation solenoid valve 13 to provide hydrogen to the solid hydrogen storage container 1 .

[0069] In the present invention, when the solid hydrogen storage container 1 stores hydrogen, the hydrogenation solenoid valve 13 is opened; when the solid hydrogen storage container 1 releases hydrogen, the hydrogenation solenoid valve 13 is closed.

[0070] In some preferred embodiments, the solid hydrogen storage container 1 further comprises filters 11 disposed at the gas inlet and the gas outlet of the hydrogen storage material substrate 6 to prevent the outflow of the solid hydrogen storage composite material powder.

[0071] The present invention has no particular limitation on the type of the filter 11 , which can be a conventional choice in the art, and the present invention does not make any requirement therefor.

[0072] The present invention has no particular limitation on the accuracy of the filter 11, and the filter 11 can be designed according to the particle size of the solid hydrogen storage composite material.

[0073] In some preferred embodiments, the solid hydrogen storage container 1 further includes a sealing end plate 7 for sealing the solid hydrogen storage container 1 .

[0074] In the present invention, the thickness, volume, material and longitudinal cross-sectional shape of the sealing end plate 7 are selected to be the same as those of the heat transfer fluid substrate 5 and the hydrogen storage material substrate 6 .

[0075] In some preferred embodiments, the sealing end plates 7 are placed at both ends of the solid hydrogen storage container to seal the solid hydrogen storage container 1 .

[0076] In some preferred embodiments, the sealing end plates 7 are placed at both ends of the solid hydrogen storage reactor, and the solid hydrogen storage reactor is sealed by bolts 12 .

[0077] In some preferred embodiments, bolt openings 8 are provided on the heat transfer fluid substrate 5 , the hydrogen storage material substrate 6 , and the end sealing plate 7 .

[0078] In some preferred embodiments, the bolt 12 passes through the bolt opening 8 .

[0079] In some preferred embodiments, the system further includes a hydrogen storage tank 16 disposed between the solid hydrogen storage container 1 and the fuel cell unit II, for buffering the hydrogen from the solid hydrogen storage container 1 .

[0080] In some preferred embodiments, the inlet of the hydrogen storage tank 16 is connected to the hydrogen supply pipeline 10 of the solid hydrogen storage container 1, and the outlet is connected to the fuel cell unit II.

[0081] In the present invention, the hydrogen storage tank 16 may be provided with one inlet and one outlet, or may be provided with multiple inlets and outlets, which may be appropriately selected according to actual conditions.

[0082] In some preferred embodiments, the system further comprises a back pressure valve 15 disposed between the hydrogen supply pipeline 10 and the inlet of the hydrogen storage tank 16, for regulating the pressure of the solid hydrogen storage container 1. With this preferred embodiment, the solid hydrogen storage container 1 can be maintained at a stable pressure to discharge hydrogen.

[0083] In some preferred embodiments, the system further includes a pressure sensor 14 disposed between the hydrogen supply pipeline 10 and the back pressure valve 15 for monitoring the pressure of the solid hydrogen storage container 1 .

[0084] In some preferred embodiments, the system further comprises a flow meter 18 disposed between the outlet of the hydrogen storage tank 16 and the fuel cell unit II, for continuously providing hydrogen to the fuel cell unit II.

[0085] In some preferred embodiments, the system further comprises a hydrogen pressure reducing valve 17 disposed between the outlet of the hydrogen storage tank 16 and the flow meter 18, for providing the required hydrogen pressure for the fuel cell unit II.

[0086] In some preferred embodiments, the fuel cell unit II includes a fuel cell stack 2, the anode gas inlet of the fuel cell stack 2 is connected to the outlet of the hydrogen storage tank 16 for receiving hydrogen; the anode gas outlet of the fuel cell stack 2 is connected to the bottom inlet of the hydrogen storage tank 16 via a hydrogen compression pump 19 for recovering unreacted hydrogen. In this preferred embodiment, the unreacted hydrogen can be recovered to save energy.

[0087] In some preferred embodiments, the cathode gas inlet of the fuel cell stack 2 is used to receive the oxygen-containing gas; and the cathode gas outlet of the fuel cell stack 2 is used to discharge the oxygen-containing gas out of the system.

[0088] In some preferred embodiments, the cathode gas inlet of the fuel cell stack 2 is provided with an oxygen-containing gas filter 23 for filtering particulate matter in the oxygen-containing gas.

[0089] In some preferred embodiments, an oxygen-containing gas compression pump 22 is provided between the cathode gas inlet of the fuel cell stack 2 and the oxygen-containing gas filter 23 for pumping oxygen-containing gas to provide oxygen required by the cathode of the fuel cell.

[0090] In some preferred embodiments, an oxygen-containing gas humidifier 21 is provided between the cathode gas inlet of the fuel cell stack 2 and the oxygen-containing gas compression pump 22 for humidifying the oxygen-containing gas.

[0091] In some preferred embodiments, an oxygen-containing gas pressure reducing valve 20 is provided between the cathode gas inlet of the fuel cell stack 2 and the oxygen-containing gas humidifier 21 to provide the required oxygen-containing gas pressure for the fuel cell unit II.

[0092] In some preferred embodiments, the oxygen-containing gas is air or oxygen.

[0093] In some preferred embodiments, the cathode gas outlet of the fuel cell stack 2 is provided with a one-way valve 24 for controlling the discharge of the oxygen-containing gas out of the system.

[0094] When the fuel cell unit II is in operation, the one-way valve 24 is closed; when the fuel cell unit II stops operating, the one-way valve 24 is opened to discharge the unreacted oxygen-containing gas out of the system.

[0095] In some preferred embodiments, the system further comprises a heat circulation unit III, which is connected to the fuel cell unit II and the solid hydrogen storage unit I for heat circulation.

[0096] In some preferred embodiments, the thermal circulation unit III includes a liquid storage tank 26, the inlet of the liquid storage tank 26 is connected to the second fluid pipeline 4 of the solid hydrogen storage container 1, and is used to recover the heat transfer fluid from the solid hydrogen storage container 1; the outlet of the liquid storage tank 26 is connected to the heat transfer fluid circulation inlet of the fuel cell stack 2, and is used to absorb the heat generated by the fuel cell unit II.

[0097] In some preferred embodiments, the heat transfer fluid circulation outlet of the fuel cell stack 2 is connected to the first fluid conduit 3 of the solid hydrogen storage container 1 to provide heat for the solid hydrogen storage container 1 to release hydrogen.

[0098] In some preferred embodiments, the thermal cycle unit III further includes a heating resistor 29, which is placed below the liquid storage tank 26 and is used for preheating when the system is cold started.

[0099] In some preferred embodiments, the thermal cycle unit III further includes a temperature sensor 25, which is placed above the liquid storage tank 26 for temperature detection.

[0100] In some preferred embodiments, the outlet of the liquid storage tank 26 is connected to the circulation inlet of the heat transfer fluid of the fuel cell stack 2 via the solenoid valve 27 and the circulation pump 28 in sequence, so as to absorb the heat generated by the fuel cell unit II.

[0101] According to a particularly preferred embodiment of the present invention, Figure 1As shown, the system is cold started, and the heating resistor 29 is used to heat the heat transfer fluid in the liquid storage tank 26 when the system is started, so as to reach the temperature required for the solid hydrogen storage container 1 to release hydrogen and the fuel cell stack 2 to work. The temperature sensor 25 is used to monitor the water temperature in the liquid storage tank 26. When the fuel cell unit II is running, the back pressure valve 15 is adjusted and the pressure is monitored by the pressure sensor 14, so that the solid hydrogen storage container 1 of the solid hydrogen storage unit I releases hydrogen; the hydrogen from the solid hydrogen storage container 1 enters the anode gas inlet of the fuel cell stack 2 through the hydrogen storage tank 16, the first pressure reducing valve 17, and the flow meter 18. At the same time, the oxygen-containing gas enters the cathode gas inlet of the fuel cell stack 2 through the oxygen-containing gas filter 23, the oxygen-containing gas compression pump 22, the oxygen-containing gas humidifier 21, and the oxygen-containing gas pressure reducing valve 20. The oxygen at the cathode and the hydrogen at the anode react at the cathode and anode of the fuel cell stack 2 respectively to generate electricity and supply to the external circuit, and at the same time generate some heat. The heat transfer fluid from the liquid storage tank 26 in the thermal circulation unit III enters the fuel cell stack 2 from the heat transfer fluid circulation inlet of the fuel cell stack 2 through the solenoid valve 27 and the circulation pump 28 to absorb the heat generated by the fuel cell power generation.

[0102] The unreacted hydrogen is returned from the anode gas outlet to the hydrogen storage tank 16 via the hydrogen compression pump 19 for recycling.

[0103] The unreacted oxygen is discharged from the cathode gas outlet through the one-way valve 24 to the outside of the system.

[0104] The heat transfer fluid that absorbs the heat generated by the fuel cell power generation is sent from the heat transfer fluid circulation outlet of the fuel cell stack 2 into the first fluid pipeline 3 of the solid hydrogen storage container 1 to provide heat for the solid hydrogen storage container 1 to release hydrogen. The heat transfer fluid that has absorbed heat enters the liquid storage tank 26 of the thermal circulation unit III through the second fluid pipeline 4.

[0105] When the solid hydrogen storage container 1 stores hydrogen, the hydrogenation solenoid valve 13 is opened, and the hydrogen from the hydrogenation equipment is passed from the hydrogenation pipeline 9 into the second flow channel of the hydrogen storage material substrate 6 to react with the solid hydrogen storage composite material to absorb hydrogen. The pressure is adjusted by the back pressure valve 15 and the pressure sensor 14 monitors the pressure to the pressure required for the hydrogen absorption reaction; at the same time, the heat transfer fluid provided from the outside enters the first flow channel of the heat transfer fluid substrate 5 from the first fluid pipeline 3 to absorb the heat generated by the hydrogen absorption reaction. The heat transfer fluid after absorbing the heat generated by the hydrogen absorption reaction enters the liquid storage tank 26 of the thermal cycle unit III through the second fluid pipeline 4.

[0106] The second aspect of the present invention provides an operating method of the solid hydrogen storage and fuel cell coupling system of the first aspect, the method comprising: reacting an oxygen-containing gas with hydrogen from a solid hydrogen storage container in a fuel cell unit to generate electricity, while a first heat transfer fluid absorbs heat generated by the fuel cell; Among them, the hydrogen release process of the solid hydrogen storage container includes: the solid hydrogen storage composite material adsorbed with hydrogen undergoes a desorption reaction, and the first heat transfer fluid that absorbs the heat generated by the fuel cell is sent into the first flow channel of the heat transfer fluid substrate to provide heat for the desorption reaction of hydrogen.

[0107] In some preferred embodiments, the conditions for the fuel cell to generate electricity include: a temperature of 50-120° C. and a pressure of 0.1-3 MPa.

[0108] In some preferred embodiments, the present invention has no particular limitation on the power of the fuel cell unit, and the fuel cell unit may be any conventional fuel cell unit of various powers in the art.

[0109] In some preferred embodiments, the first heat transfer fluid comes from a thermal circulation unit.

[0110] In some preferred embodiments, the first heat transfer fluid that absorbs heat during the hydrogen release process is returned to the heat circulation unit for recycling. This preferred embodiment can effectively improve the heat utilization rate.

[0111] In some preferred embodiments, during the hydrogen release process, the conditions of the desorption reaction include: a temperature of 50-120° C. and a pressure of 0.1-4 MPa.

[0112] In some preferred embodiments, during the hydrogen release process, the flow rate of hydrogen is 1-1000 L / min.

[0113] In some preferred embodiments, the hydrogen storage process of the solid hydrogen storage container includes: sending hydrogen into the second flow channel of the hydrogen storage material substrate to undergo a hydrogen absorption reaction with the solid hydrogen storage composite material, and sending the second heat transfer fluid into the first flow channel of the heat transfer fluid substrate to absorb the heat generated by the hydrogen absorption reaction.

[0114] In some preferred embodiments, during the hydrogen storage process, the conditions of the hydrogen absorption reaction include: temperature of 0-50° C.; pressure of 0.1-10 MPa.

[0115] In some preferred embodiments, during the hydrogen storage process, the flow rate of the second heat transfer fluid is 0.1-1000 L / min.

[0116] The present invention has no particular limitation on the types of the first heat-conducting fluid and the second heat-conducting fluid, which can be conventionally selected in the art. In some preferred embodiments, the first heat-conducting fluid and the second heat-conducting fluid are water.

[0117] Preferably, the water is deionized water or ultrapure water.

[0118] The second heat transfer fluid in the hydrogen storage process can be provided externally, or can be provided by the heat transfer fluid stored in the solid hydrogen storage container, or can be provided by the heat transfer fluid stored in the liquid storage tank of the thermal cycle unit. In some preferred embodiments, the second heat transfer fluid in the hydrogen storage process is provided externally.

[0119] In some preferred embodiments, the second heat transfer fluid that absorbs the heat of the hydrogen absorption reaction during the hydrogen storage process is returned to the heat circulation unit for recycling. By adopting this preferred embodiment, the heat utilization rate can be further improved.

[0120] The present invention will be described in detail below through examples.

[0121] The reactor was numerically simulated using COMSO software. The mass, energy and momentum balance equations were constructed. The specific equations are as follows: Mass conservation equation for hydrogen storage materials: The mass conservation equation for gases is: in, m is the mass change, ε is the porosity of the hydrogen storage material in the inner tank 1, ρ s is the density of hydrogen storage material, t is the reaction time, u g is the velocity field of hydrogen, ρ g is the gas density.

[0122] The velocity field for hydrogen is calculated using Darcy's law: in, K is the permeability, μ g is the viscosity coefficient of hydrogen, P g is the hydrogen pressure.

[0123] For the hydrogen absorption reaction process, the reaction rate equation is as follows: For the hydrogen release reaction process, the reaction rate equation is as follows: in, C a and C d are the pre-exponential factors of hydrogen absorption and desorption reactions, E a and E d are the activation energies of hydrogen absorption and desorption reactions, respectively.R g is the gas constant, T is the reaction temperature, P eq is the equilibrium pressure of the chemical reaction, ρ ss is the density of the hydrogen storage material after hydrogen absorption is complete, ρ 0 is the initial density of the hydrogen storage material.

[0124] The equilibrium pressure of a chemical reaction can be given by the Van't Hoff equation: The energy balance equation for the hydrogen absorption and desorption reaction in the inner tank 1 is as follows: in, M g is the molar mass of hydrogen; The effective heat capacity of the hydrogen storage bed is: The effective thermal conductivity of the hydrogen storage bed is: in, C p,g and C p,s are the heat capacities of hydrogen and hydrogen storage materials, respectively, e and λ g are the effective thermal conductivities of hydrogen and hydrogen storage materials, respectively.

[0125] For the heat transfer fluid, the mass balance equation is: in, ρ f is the density of the heat transfer fluid, u f is the velocity field of the heat transfer fluid.

[0126] For a heat transfer fluid, the momentum balance equation is as follows: The heat transfer equation inside the fluid is as follows: in: in, C p,f is the heat capacity of the heat transfer fluid, λ f is the effective thermal conductivity of the heat transfer fluid, P f is the heat transfer fluid pressure.

[0127] For solid materials such as tank walls and partitions, the heat transfer equation is as follows: in, is the heat capacity of the solid (tank wall or partition), is the effective thermal conductivity of the solid (tank wall or partition).

[0128] The heat transfer equation between the inner tank, outer tank and partition is: in, q is the heat flux, h is the heat transfer coefficient between the two, T 1 and T 2 refers to the respective temperatures of the contact surfaces of the two adjacent phases where heat transfer occurs (for example, when calculating the heat transfer between the inner tank and the partition, T 1 and T 2 refers to the contact surface temperature of the inner tank body and the partition respectively).

[0129] Example 1 like Figure 1 As shown, the solid hydrogen storage container 1 includes a heat-conducting fluid substrate 5, a hydrogen storage material substrate 6, a sealing end plate 7, a first fluid pipeline 3, a second fluid pipeline 4, a hydrogenation pipeline 9 and a hydrogen supply pipeline 10. The heat-conducting fluid substrate 5, the hydrogen storage material substrate 6 and the sealing end plate 7 are all rectangular structures made of 304 stainless steel with a length of 220 mm, a width of 44 mm and a thickness of 12 mm. The heat-conducting fluid substrate 5 and the hydrogen storage material substrate 6 are stacked as a group, and the number of stacking groups is 4. The two sealing end plates 7 are stacked at both ends of the container and sealed by bolts 12. Bolt ports 8 are distributed on the heat-conducting fluid substrate 5, the hydrogen storage material substrate 6 and the sealing end plate 7, and the bolts 12 pass through the bolt ports 8.

[0130] like Figure 2 and Figure 3 As shown, the heat transfer fluid substrate 5 and the hydrogen storage material substrate 6 are respectively engraved with a serpentine liquid flow channel (first flow channel) and a serpentine gas flow channel (second flow channel) on one side (along the direction of hydrogen and heat transfer fluid introduction, both are arranged on the right side), and the first flow channel and the second flow channel are not connected. The flow channel inlet and outlet are located at both ends of the substrate, and the flow channels are arranged in parallel. Figure 4 As shown in a, the flow channel facet is a square facet.

[0131] The ratio of the unidirectional length to the depth of the first flow channel of the heat transfer fluid substrate 5 is 21:1, the ratio of the first flow channel depth to the substrate thickness is 0.88:1, and the ratio of the first flow channel volume to the substrate volume is 0.58:1. The first flow channel is filled with heat transfer fluid deionized water.

[0132] The ratio of the unidirectional length to the depth of the second flow channel of the hydrogen storage material substrate 6 is 21:1, the ratio of the second flow channel depth to the substrate thickness is 0.88:1, and the ratio of the second flow channel volume to the substrate volume is 0.58:1. The solid hydrogen storage composite material is placed in the second flow channel of the hydrogen storage material substrate 6, and the solid hydrogen storage composite material is a mixture of LaNi5 hydrogen storage material and expanded graphite, and the mass ratio of the two is 1:0.03. The filling volume of the solid hydrogen storage composite material accounts for 50% of the volume of the second flow channel.

[0133] The first fluid conduit 3 is communicated with the fluid inlet of the heat-conducting fluid substrate 5 , and the second fluid conduit 4 is communicated with the fluid outlet of the heat-conducting fluid substrate 5 , for circulation of the heat-conducting fluid.

[0134] The hydrogenation pipeline 9 is communicated with the gas inlet of the hydrogen storage material substrate 6 , and the hydrogen supply pipeline 10 is communicated with the gas outlet of the hydrogen storage material substrate 6 and the fuel cell unit II.

[0135] There are filters 11 at the gas inlet and outlet of the hydrogen storage material substrate 6. The filter 11 is a 316 stainless steel sintered porous material with a filtering accuracy of 0.5 μm.

[0136] When the solid hydrogen storage container stores hydrogen, the hydrogenation solenoid valve 13 is opened and connected to the hydrogen cylinder, and the back pressure valve 15 is automatically adjusted to 0.8 MPa. Monitor the pressure of the pressure sensor 14 until the pressure reaches the set hydrogenation pressure. The hydrogen inlet pressure is maintained at 0.8 MPa and passed into the second flow channel of the hydrogen storage material substrate 6, and the solid hydrogen storage composite material undergoes a hydrogen absorption reaction at an initial temperature of 20°C. In each heat transfer fluid substrate 5, the second heat transfer fluid (deionized water) at 20°C introduced from the outside is sent into its first flow channel at a flow rate of 3 L / min to absorb the heat generated by the hydrogen absorption reaction. The second heat transfer fluid that absorbs the heat of the hydrogen absorption reaction during the hydrogen storage process returns to the thermal circulation unit for recycling. Compared with the comparative example, the heat transfer fluid flows more evenly in the first fluid flow channel and has a higher heat exchange efficiency, so that the hydrogen storage bed and the heat transfer fluid have a faster heat exchange efficiency, and the heat generated by the hydrogen storage material absorbing hydrogen can be transferred to the heat transfer fluid faster, avoiding excessive temperature of the hydrogen storage material, thereby facilitating an increase in the hydrogen absorption rate and a reduction in the hydrogen absorption time.

[0137] When the fuel cell is running, the hydrogen pressure in the solid hydrogen storage container 1 is reduced to 0.2MPa by adjusting the back pressure valve 15, so that the solid hydrogen storage container 1 releases hydrogen at a rate of 40 L / min. The heating resistor 29 is used to preheat the heat transfer fluid (deionized water) to reach the required operating temperature of the fuel cell of 75°C. The hydrogen pressure reducing valve 17 is adjusted to 0.18 MPa to maintain a stable pressure to provide the hydrogen required by the fuel cell. In the fuel cell unit, the hydrogen at the anode and the oxygen at the cathode react at the two poles to generate electricity, and the power of the fuel cell unit is 4 kW. At the same time, the first heat transfer fluid from the thermal cycle unit absorbs the heat generated by the fuel cell; the first heat transfer fluid of about 70°C that absorbs the heat generated by the fuel cell is sent to the first flow channel of the heat transfer fluid substrate 5 of the solid hydrogen storage container 1 to provide heat for hydrogen release, and the first heat transfer fluid that absorbs heat during hydrogen release returns to the thermal cycle unit for recycling. In the above process, the residual heat of the fuel cell can be used to release heat in solid hydrogen storage, maintain the steady pressure and steady flow of hydrogen release of the solid hydrogen storage device, and improve the energy utilization efficiency.

[0138] Using the above equation, the change values ​​of various parameters in the reactor over time are calculated.

[0139] like Figure 5 As shown, the solid-state hydrogen storage device can maintain a hydrogen release rate of 40 L / min for 370 s and maintain the power operation of the fuel cell at 4 kW. At this time, the solid-state hydrogen storage device releases 91wt% of the total amount of stored hydrogen. This shows that the solid-state hydrogen storage container of the present invention has a good heat exchange effect, a high hydrogen release rate, and most of the stored hydrogen can be quickly released to meet the full power and stable operation requirements of the fuel cell.

[0140] Compared with the traditional solid-state hydrogen storage-fuel cell coupling device (Comparative Example 1), the continuous working time is increased to 2.5 times, and compared with the solid-state hydrogen storage-fuel cell coupling device without flow channel (Comparative Example 2), the continuous working time is increased to 1.5 times.

[0141] Compared with the solid-state hydrogen storage container-fuel cell device without thermal cycle unit coupling (Example 5), the hydrogen release process is reduced to provide heat for the solid-state hydrogen storage container by a total of 425 kJ.

[0142] Example 2 like Figure 1As shown, the solid hydrogen storage container 1 includes a heat-conducting fluid substrate 5, a hydrogen storage material substrate 6, a sealing end plate 7, a first fluid pipeline 3, a second fluid pipeline 4, a hydrogenation pipeline 9 and a hydrogen supply pipeline 10. The heat-conducting fluid substrate 5, the hydrogen storage material substrate 6 and the sealing end plate 7 are all rectangular structures made of 304 stainless steel with a length of 70 mm, a width of 44 mm and a thickness of 15 mm. The heat-conducting fluid substrate 5 and the hydrogen storage material substrate 6 are stacked as a group, and the number of stacking groups is 14. Two sealing end plates 7 are stacked at both ends of the container and sealed by bolts 12. Bolt ports 8 are distributed on the heat-conducting fluid substrate 5, the hydrogen storage material substrate 6 and the sealing end plate 7, and the bolts 12 pass through the bolt ports 8.

[0143] like Figure 2 and Figure 3 As shown, the heat transfer fluid substrate 5 and the hydrogen storage material substrate 6 are respectively engraved with a serpentine liquid flow channel (first flow channel) and a serpentine gas flow channel (second flow channel) on one side (along the direction of hydrogen and heat transfer fluid introduction, both are arranged on the right side), and the first flow channel and the second flow channel are not connected. The flow channel inlet and outlet are located on both sides of the substrate, and the flow channels are arranged in parallel. Figure 4 As shown in a, the flow channel facet is a square facet.

[0144] The ratio of the unidirectional length to the depth of the first flow channel on the heat transfer fluid substrate 5 is 6:1, the ratio of the first flow channel depth to the substrate thickness is 0.67:1, and the ratio of the flow channel volume to the substrate volume is 0.42:1. The first flow channel is filled with heat transfer fluid deionized water.

[0145] The ratio of the unidirectional length to the depth of the second flow channel of the hydrogen storage material substrate 6 is 6:1, the ratio of the second flow channel depth to the substrate thickness is 0.67:1, and the ratio of the flow channel volume to the substrate volume is 0.42:1. The solid hydrogen storage composite material is placed in the second flow channel of the hydrogen storage material substrate 6, and the solid hydrogen storage composite material is a mixture of LaNi5 hydrogen storage material and expanded graphite, and the mass ratio of the two is 1:0.03. The filling volume of the solid hydrogen storage composite material accounts for 50% of the volume of the second flow channel.

[0146] The first fluid conduit 3 is communicated with the fluid inlet of the heat-conducting fluid substrate 5 , and the second fluid conduit 4 is communicated with the fluid outlet of the heat-conducting fluid substrate 5 , for circulation of the heat-conducting fluid.

[0147] The hydrogenation pipeline 9 is communicated with the gas inlet of the hydrogen storage material substrate 6 , and the hydrogen supply pipeline 10 is communicated with the gas outlet of the hydrogen storage material substrate 6 and the fuel cell unit II.

[0148] There are filters 11 at the gas inlet and outlet of the hydrogen storage material substrate 6. The filter 11 is a 316 stainless steel sintered porous material with a filtering accuracy of 0.5 μm.

[0149] When the solid hydrogen storage container stores hydrogen, the hydrogenation solenoid valve 13 is opened and connected to the hydrogen cylinder, and the back pressure valve 15 is automatically adjusted to 4 MPa. Monitor the pressure of the pressure sensor 14 until the pressure reaches the set hydrogenation pressure. The hydrogen inlet pressure is maintained at 4 MPa and passed into the second flow channel of the hydrogen storage material substrate 6, and the solid hydrogen storage composite material undergoes a hydrogen absorption reaction at an initial temperature of 20°C. In each heat transfer fluid substrate 5, the second heat transfer fluid (deionized water) at 20°C introduced from the outside is sent into its first flow channel at a flow rate of 1.4 L / min to absorb the heat generated by the hydrogen absorption reaction. The second heat transfer fluid that absorbs the heat of the hydrogen absorption reaction during the hydrogen storage process returns to the thermal circulation unit for recycling. Compared with the comparative example, the heat transfer fluid flows more evenly in the first fluid flow channel and has a higher heat exchange efficiency, so that the hydrogen storage bed and the heat transfer fluid have a faster heat exchange efficiency, and the heat generated by the hydrogen storage material absorbing hydrogen can be transferred to the heat transfer fluid faster, avoiding excessive temperature of the hydrogen storage material, thereby facilitating an increase in the hydrogen absorption rate and a reduction in the hydrogen absorption time.

[0150] When the fuel cell is running, the hydrogen pressure in the solid hydrogen storage container 1 is reduced to 0.2MPa by adjusting the back pressure valve 15, so that the solid hydrogen storage container 1 releases hydrogen at a rate of 40 L / min. The heating resistor 29 is used to preheat the heat transfer fluid (deionized water) to reach the required operating temperature of the fuel cell of 75°C. The hydrogen pressure reducing valve 17 is adjusted to 0.18 MPa to maintain a stable pressure to provide the hydrogen required by the fuel cell. In the fuel cell unit, the hydrogen at the anode and the oxygen at the cathode react at the two poles to generate electricity, and the power of the fuel cell unit is 4 kW. At the same time, the first heat transfer fluid from the thermal cycle unit absorbs the heat generated by the fuel cell; the first heat transfer fluid of about 70°C that absorbs the heat generated by the fuel cell is sent to the first flow channel of the heat transfer fluid substrate 5 of the solid hydrogen storage container 1 to provide heat for hydrogen release, and the first heat transfer fluid that absorbs heat during the hydrogen release process returns to the thermal cycle unit for recycling. In the above process, the residual heat of the fuel cell can be used to release heat in solid hydrogen storage, and the heat utilization rate is significantly improved.

[0151] like Figure 6 As shown, the solid-state hydrogen storage device can maintain a hydrogen release rate of 40 L / min for 361 s and maintain a power operation of 4 kW for the fuel cell. At this time, the solid-state hydrogen storage device releases 90 wt% of the total amount of stored hydrogen.

[0152] Compared with the traditional solid-state hydrogen storage-fuel cell coupling device (Comparative Example 1), the continuous working time is increased to 2.4 times, and compared with the solid hydrogen storage-fuel cell coupling device without flow channel (Comparative Example 2), the continuous working time is increased to 1.5 times.

[0153] Example 3 like Figure 1As shown, the solid hydrogen storage container 1 includes a heat-conducting fluid substrate 5, a hydrogen storage material substrate 6, a sealed end plate 7, a first fluid pipeline 3, a second fluid pipeline 4, a hydrogenation pipeline 9 and a hydrogen supply pipeline 10. The heat-conducting fluid substrate 5, the hydrogen storage material substrate 6 and the sealed end plate 7 are all made of 304 stainless steel with a length of 110 mm, a width of 40 mm and a thickness of 7 mm. The heat-conducting fluid substrate 5 and the hydrogen storage material substrate 6 are stacked as a group, and the number of stacking groups is 16 groups. Two sealed end plates 7 are stacked at both ends of the container respectively and sealed by bolts 12. Bolt ports 8 are distributed on the heat-conducting fluid substrate 5, the hydrogen storage material substrate 6 and the sealed end plate 7, and the bolts 12 pass through the bolt ports 8.

[0154] like Figure 2 and Figure 3 As shown, the heat transfer fluid substrate 5 and the hydrogen storage material substrate 6 are respectively engraved with a serpentine liquid flow channel (first flow channel) and a serpentine gas flow channel (second flow channel) on one side (along the direction of hydrogen and heat transfer fluid introduction, both are arranged on the right side), and the first flow channel and the second flow channel are not connected. The flow channel inlet and outlet are located on both sides of the substrate, and the flow channels are arranged in parallel. Figure 4 As shown in b, the flow channel facet is a triangular sawtooth facet, the triangular sawtooth is an isosceles triangle, and the vertex angle is 90°.

[0155] The ratio of the unidirectional length to the depth of the first flow channel on the heat transfer fluid substrate 5 is 17:1, the ratio of the first flow channel depth to the substrate thickness is 0.83:1, and the ratio of the flow channel volume to the substrate volume is 0.54:1. The first flow channel is filled with heat transfer fluid deionized water.

[0156] The ratio of the unidirectional length to the depth of the second flow channel of the hydrogen storage material substrate 6 is 17:1, the ratio of the second flow channel depth to the substrate thickness is 0.83:1, and the ratio of the flow channel volume to the substrate volume is 0.54:1. The solid hydrogen storage composite material is placed in the second flow channel of the hydrogen storage material substrate 6, and the solid hydrogen storage composite material is a mixture of LaNi5 hydrogen storage material and expanded graphite, and the mass ratio of the two is 1:0.05. The solid hydrogen storage composite material accounts for 50% of the volume of the second flow channel.

[0157] The first fluid conduit 3 is communicated with the fluid inlet of the heat-conducting fluid substrate 5 , and the second fluid conduit 4 is communicated with the fluid outlet of the heat-conducting fluid substrate 5 , for circulation of the heat-conducting fluid.

[0158] The hydrogenation pipeline 9 is communicated with the gas inlet of the hydrogen storage material substrate 6 , and the hydrogen supply pipeline 10 is communicated with the gas outlet of the hydrogen storage material substrate 6 and the fuel cell unit II.

[0159] A filter 11 is provided at the gas inlet and outlet of each hydrogen storage material substrate 6. The filter 11 is made of 316 stainless steel sintered porous material with a filtering accuracy of 0.5 μm.

[0160] When the solid hydrogen storage container stores hydrogen, the hydrogenation solenoid valve 13 is opened and connected to the hydrogen cylinder, and the back pressure valve 15 is automatically adjusted to 4 MPa. Monitor the pressure of the pressure sensor 14 until the pressure reaches the set hydrogenation pressure. The hydrogen inlet pressure is maintained at 4 MPa and passed into the second flow channel of the hydrogen storage material substrate, and the solid hydrogen storage composite material undergoes a hydrogen absorption reaction at an initial temperature of 20°C. In each heat transfer fluid substrate 5, the second heat transfer fluid (deionized water) at 20°C introduced from the outside is sent into its first flow channel at a flow rate of 0.72 L / min to absorb the heat generated by the hydrogen absorption reaction. The second heat transfer fluid that absorbs the heat of the hydrogen absorption reaction during the hydrogen storage process returns to the thermal circulation unit for recycling. Compared with the comparative example, the heat transfer fluid flows more evenly in the first fluid flow channel and has a higher heat exchange efficiency, so that the hydrogen storage bed and the heat transfer fluid have a faster heat exchange efficiency, and the heat generated by the hydrogen storage material absorbing hydrogen can be transferred to the heat transfer fluid faster, avoiding excessive temperature of the hydrogen storage material, thereby facilitating an increase in the hydrogen absorption rate and a reduction in the hydrogen absorption time.

[0161] When the fuel cell is running, the back pressure valve 15 is adjusted to reduce the hydrogen pressure in the solid hydrogen storage container 1 to 0.2 MPa, so that the solid hydrogen storage container 1 releases hydrogen at a rate of 40 L / min. The heating resistor 29 is used to preheat the heat transfer fluid (deionized water) to the required operating temperature of the fuel cell of 75°C. The hydrogen pressure reducing valve 17 is adjusted to 0.18 MPa to maintain a stable pressure to provide the hydrogen required by the fuel cell. In the fuel cell unit, the hydrogen at the anode and the oxygen at the cathode undergo electrochemical reactions at the two poles to generate electricity, and the power of the fuel cell unit is 4 kW. At the same time, the first heat transfer fluid from the thermal cycle unit absorbs the heat generated by the fuel cell; the first heat transfer fluid of about 70°C that absorbs the heat generated by the fuel cell is sent to the first flow channel of the heat transfer fluid substrate 5 of the solid hydrogen storage container 1 to provide heat for hydrogen release, and the first heat transfer fluid that absorbs heat during the hydrogen release process returns to the thermal cycle unit for recycling.

[0162] like Figure 7 As shown, the solid-state hydrogen storage device can maintain a hydrogen release rate of 40 L / min for 397 s and maintain a power operation of 4 kW for the fuel cell. At this time, the solid-state hydrogen storage device releases 97 wt% of the total amount of stored hydrogen.

[0163] Compared with the traditional solid-state hydrogen storage-fuel cell coupling device (Comparative Example 1), the continuous working time is increased to 2.6 times, and compared with the solid hydrogen storage-fuel cell coupling device without flow channel (Comparative Example 2), the continuous working time is increased to 1.6 times.

[0164] Example 4 like Figure 1As shown, the solid hydrogen storage container 1 includes a heat-conducting fluid substrate 5, a hydrogen storage material substrate 6, a sealing end plate 7, a first fluid pipeline 3, a second fluid pipeline 4, a hydrogenation pipeline 9 and a hydrogen supply pipeline 10. The heat-conducting fluid substrate 5, the hydrogen storage material substrate 6 and the sealing end plate 7 are all rectangular structures made of 304 stainless steel with a length of 110 mm, a width of 40 mm and a thickness of 7 mm. The heat-conducting fluid substrate 5 and the hydrogen storage material substrate 6 are stacked as a group, and the number of stacking groups is 22 groups. Two sealing end plates 7 are stacked at both ends of the container and sealed by bolts 12. Bolt ports 8 are distributed on the heat-conducting fluid substrate 5, the hydrogen storage material substrate 6 and the sealing end plate 7, and the bolts 12 pass through the bolt ports 8.

[0165] like Figure 2 and Figure 3 As shown, the heat transfer fluid substrate 5 and the hydrogen storage material substrate 6 are respectively engraved with parallel liquid flow channels (first flow channels) and parallel gas flow channels (second flow channels) on one side (along the direction of hydrogen and heat transfer fluid introduction, both are arranged on the right side), and the first flow channel and the second flow channel are not connected. The flow channel inlet and outlet are located on both sides of the substrate, and the flow channels are arranged in parallel. Figure 4 As shown in a, the flow channel facet is a square facet.

[0166] The ratio of the length to the depth of the first flow channel on the heat transfer fluid substrate 5 is 22:1, the ratio of the first flow channel depth to the substrate thickness is 0.71:1, and the ratio of the flow channel volume to the substrate volume is 0.39:1. The first flow channel is filled with heat transfer fluid deionized water.

[0167] The ratio of the length to the depth of the second flow channel of the hydrogen storage material substrate 6 is 22:1, the ratio of the depth of the second flow channel to the thickness of the substrate is 0.71:1, and the ratio of the flow channel volume to the substrate volume is 0.39:1. The solid hydrogen storage composite material is placed in the second flow channel of the hydrogen storage material substrate 6, and the solid hydrogen storage composite material is a mixture of LaNi5 hydrogen storage material and expanded graphite, and the mass ratio of the two is 1:0.03. The filling volume of the solid hydrogen storage composite material accounts for 50% of the volume of the second flow channel.

[0168] The first fluid conduit 3 is communicated with the fluid inlet of the heat-conducting fluid substrate 5 , and the second fluid conduit 4 is communicated with the fluid outlet of the heat-conducting fluid substrate 5 , for circulation of the heat-conducting fluid.

[0169] The hydrogenation pipeline 9 is communicated with the gas inlet of the hydrogen storage material substrate 6 , and the hydrogen supply pipeline 10 is communicated with the gas outlet of the hydrogen storage material substrate 6 and the fuel cell unit II.

[0170] There are filters 11 at the gas inlet and outlet of the hydrogen storage material substrate 6. The filter 11 is a 316 stainless steel sintered porous material with a filtering accuracy of 0.5 μm.

[0171] When the solid hydrogen storage container stores hydrogen, the hydrogenation solenoid valve 13 is opened and connected to the hydrogen cylinder, and the back pressure valve 15 is automatically adjusted to 0.8 MPa. Monitor the pressure of the pressure sensor 14 until the pressure reaches the set hydrogenation pressure. The hydrogen inlet pressure is maintained at 0.8 MPa and passed into the second flow channel of the hydrogen storage material substrate, and the solid hydrogen storage composite material undergoes a hydrogen absorption reaction at an initial temperature of 20°C. In each heat transfer fluid substrate 5, the second heat transfer fluid (deionized water) at 20°C introduced from the outside is sent into its first flow channel at a flow rate of 3 L / min to absorb the heat generated by the hydrogen absorption reaction. The second heat transfer fluid that absorbs the heat of the hydrogen absorption reaction during the hydrogen storage process returns to the thermal circulation unit for recycling. Compared with the comparative example, the heat transfer fluid flows more evenly in the first fluid flow channel and has a higher heat exchange efficiency, so that the hydrogen storage bed and the heat transfer fluid have a faster heat exchange efficiency, and the heat generated by the hydrogen storage material absorbing hydrogen can be transferred to the heat transfer fluid faster, avoiding excessive temperature of the hydrogen storage material, thereby facilitating an increase in the hydrogen absorption rate and a reduction in the hydrogen absorption time.

[0172] When the fuel cell is running, the hydrogen pressure in the solid hydrogen storage container 1 is reduced to 0.2MPa by adjusting the back pressure valve 15, so that the solid hydrogen storage container 1 releases hydrogen at a rate of 40 L / min. The heating resistor 29 is used to preheat the heat transfer fluid (deionized water) to reach the required operating temperature of the fuel cell of 75°C. The hydrogen pressure reducing valve 17 is adjusted to 0.4 MPa to maintain a stable pressure to provide the hydrogen required by the fuel cell. In the fuel cell unit, the hydrogen at the anode and the oxygen at the cathode react at the two poles to generate electricity, and the power of the fuel cell unit is 1.8 kW. At the same time, the first heat transfer fluid from the thermal cycle unit absorbs the heat generated by the fuel cell; the first heat transfer fluid of about 70°C that absorbs the heat generated by the fuel cell is sent to the first flow channel of the heat transfer fluid substrate of the solid hydrogen storage container 1 to provide heat for hydrogen release, and the first heat transfer fluid that absorbs heat during the hydrogen release process returns to the thermal cycle unit for recycling. In the above process, the residual heat of the fuel cell can be used to release heat in solid hydrogen storage, and the heat utilization rate is significantly improved.

[0173] like Figure 8 As shown, the solid-state hydrogen storage device can maintain a hydrogen release rate of 40 L / min for 276 s and maintain a power operation of 4 kW for the fuel cell. At this time, the solid-state hydrogen storage device releases 69 wt% of the total amount of stored hydrogen.

[0174] Compared with the traditional solid-state hydrogen storage-fuel cell coupling device (Comparative Example 1), the continuous working time is increased to 1.8 times, and compared with the solid-state hydrogen storage-fuel cell coupling device without flow channel (Comparative Example 2), the continuous working time is increased to 1.1 times.

[0175] Example 5 The method of Example 1 was followed, except that Fig.12As shown, there is no thermal cycle unit III in the system. The first fluid pipeline 3 of the solid hydrogen storage container is no longer connected to the fuel cell unit II, and the second fluid pipeline 4 of the solid hydrogen storage container is no longer connected to the thermal cycle unit III, but are directly connected to an external heating and cooling constant temperature circulating water bath; the heat transfer fluid circulation inlet of the fuel cell stack is no longer connected to the thermal cycle unit III, and the heat transfer fluid circulation outlet of the fuel cell stack is no longer connected to the solid hydrogen storage unit I, but are directly connected to an external constant temperature water bath.

[0176] When the solid hydrogen storage container stores hydrogen, the hydrogenation solenoid valve 13 is opened to connect with the hydrogen cylinder, and the back pressure valve 15 is automatically adjusted to 0.8 MPa. The pressure of the pressure sensor 14 is monitored until the pressure reaches the set hydrogenation pressure. The hydrogen inlet pressure is maintained at 0.8 MPa and passed into the second flow channel of the hydrogen storage material substrate, and the solid hydrogen storage composite material undergoes a hydrogen absorption reaction at an initial temperature of 20°C. In each heat transfer fluid substrate 5, the second heat transfer fluid (deionized water) at 20°C introduced from the outside is sent into its first flow channel at a flow rate of 3 L / min to absorb the heat generated by the hydrogen absorption reaction.

[0177] When the fuel cell is running, the back pressure valve 15 is adjusted to reduce the hydrogen pressure in the solid hydrogen storage container 1 to 0.2 MPa, so that the solid hydrogen storage container 1 releases hydrogen at a rate of 40 L / min. An external constant temperature water bath is used to heat the fuel cell to reach the required operating temperature of 75°C for the fuel cell. The hydrogen pressure reducing valve 17 is adjusted to 0.18 MPa to maintain a stable pressure to provide the hydrogen required by the fuel cell. In the fuel cell unit, the hydrogen at the anode and the oxygen at the cathode react at the two poles to generate electricity, and the power of the fuel cell unit is 4 kW.

[0178] The solid-state hydrogen storage device can maintain a hydrogen release rate of 40 L / min for 370 seconds and maintain the fuel cell's power operation of 4 kW. At this time, an additional 340 KJ of heat must be provided from the outside to meet the heat absorption requirements of the hydrogen release process.

[0179] Comparative Example 1 Prior art solid hydrogen storage and fuel cell coupling system like Fig. 9In the comparative example shown, the solid hydrogen storage container (hydrogen storage alloy reactor) consists of a cylindrical inner tank body, a cylindrical outer tank body, a fluid pipeline and an air pipe. The outer tank body is sleeved outside the inner tank body, and both the inner tank body and the outer tank body are made of 304 stainless steel. The height of the inner tank body is 137 mm, the inner diameter of the inner tank body is 50 mm, the height of the outer tank body is 137 mm, the inner diameter of the outer tank body is 70 mm, and the volume of the inner tank body is the same as the total volume of the second flow channel in Example 1. The air pipe is arranged at the top of the inner tank body and is connected to the inner tank body. The diameter of the air pipe is 6 mm. A filter is arranged inside the air pipe. The filter is made of sintered 316L stainless steel with an accuracy of 2μm. Hydrogen enters or is discharged from the inner tank body through the air pipe after being filtered by the filter. The solid hydrogen storage composite material is placed in the inner tank body. The solid hydrogen storage composite material is a mixture of LaNi5 hydrogen storage material and expanded graphite, and the mass ratio of the two is 1:0.03. The volume ratio of the solid hydrogen storage composite material to the second flow channel is 50%. The heat transfer fluid is introduced into the fluid pipeline of the outer tank body, and the heat transfer fluid is deionized water.

[0180] During the hydrogen storage process, the hydrogen inlet pressure is maintained at 0.8 MPa and passed into the inner tank body, and the solid hydrogen storage composite material in the inner tank body 1 undergoes hydrogen absorption reaction under the pressure of the initial temperature of 20°C; external deionized water at a temperature of 20°C is passed through the fluid inlet at a flow rate of 0.8 L / min from the fluid pipeline inlet of the outer tank body, absorbing the heat generated by the hydrogen absorption reaction and then flowing out through the fluid pipeline outlet. Due to the uneven distribution of deionized water in the outer tank body, the deionized water and the hydrogen storage material in some areas cannot fully exchange heat, and the heat generated by the hydrogen absorption process cannot be moved, and the hydrogen absorption rate is low.

[0181] When the fuel cell is running, the hydrogen pressure in the inner tank is controlled to 0.2 MPa, so that the solid hydrogen storage container releases hydrogen at a rate of 40 L / min. External deionized water at a temperature of 75°C is introduced from the fluid pipe inlet of the outer tank at a flow rate of 3 L / min through the fluid inlet to provide the heat required for the hydrogen release reaction and then flows out through the fluid pipe outlet. In the fuel cell unit, the hydrogen at the anode and the oxygen at the cathode react at the two poles to generate electricity, and the power of the fuel cell unit is 4 kW. Deionized water at about 70°C that absorbs the heat generated by the fuel cell is sent to the inner tank of the hydrogen storage alloy reactor to provide heat for hydrogen release. The deionized water that absorbs heat during the hydrogen release process returns to the thermal cycle unit for recycling.

[0182] like Fig.10 As shown, the solid-state hydrogen storage device can maintain a hydrogen release rate of 40 L / min for 151 s and maintain a power operation of 4 kW for the fuel cell. At this time, the solid-state hydrogen storage device releases 42 wt% of the total amount of stored hydrogen.

[0183] Comparative Example 2 The method of Example 1 is followed, except that the heat transfer fluid substrate 5 and the hydrogen storage material substrate 6 of the solid hydrogen storage container are not provided with flow channels, but are provided with square grooves.

[0184] The heat transfer fluid substrate 5 is engraved with a square groove, and a liquid inlet and outlet are respectively provided at both ends of the groove. The ratio of the groove length to the depth is 21:1, the ratio of the groove depth to the substrate thickness is 0.8:1, and the ratio of the groove volume to the substrate volume is 0.58:1. Deionized water flows through the groove.

[0185] The hydrogen storage material substrate 6 is engraved with a square groove, and a gas inlet and outlet are provided at both ends of the groove. The ratio of the groove length to the depth is 21:1, the ratio of the groove depth to the substrate thickness is 0.8:1, the ratio of the groove volume to the substrate volume is 0.58:1, and the total volume of the groove is the same as the total volume of the second flow channel of the hydrogen storage material substrate 6 in Example 1. A solid hydrogen storage composite material is placed in the groove, and the solid hydrogen storage composite material is a mixture of LaNi5 hydrogen storage material and expanded graphite, and the mass ratio of the two is 1:0.03. The solid hydrogen storage composite material accounts for 50% of the volume of the groove.

[0186] When the solid hydrogen storage container stores hydrogen, open the hydrogenation solenoid valve 13 and connect it to the hydrogen cylinder, and automatically adjust the back pressure valve 15 to 0.8 MPa. Monitor the pressure of the pressure sensor 14 until the pressure reaches the set hydrogenation pressure. The hydrogen inlet pressure is maintained at 0.8 MPa and passed into the groove of the hydrogen storage material substrate, and the solid hydrogen storage composite material undergoes a hydrogen absorption reaction at an initial temperature of 20°C. The second heat transfer fluid (deionized water) at 20°C introduced from the outside is sent into the groove of the heat transfer fluid substrate 5 at a flow rate of 3 L / min to absorb the heat generated by the hydrogen absorption reaction. The second heat transfer fluid that absorbs the heat of the hydrogen absorption reaction during the hydrogen storage process is returned to the thermal circulation unit for recycling. Due to the uneven distribution of deionized water in the groove structure, the deionized water and the hydrogen storage material in some areas cannot fully exchange heat, and the heat generated by the hydrogen absorption of the hydrogen storage material cannot be fully removed, and the hydrogen absorption rate is low.

[0187] When the fuel cell is running, the hydrogen pressure in the solid hydrogen storage container 1 is reduced to 0.2MPa by adjusting the back pressure valve 15, so that the solid hydrogen storage container 1 releases hydrogen at a rate of 40 L / min. The heating resistor 29 is used to preheat the heat transfer fluid (deionized water) to reach the required operating temperature of the fuel cell of 75°C. The hydrogen pressure reducing valve 17 is adjusted to 0.18MPa to maintain a stable pressure to provide the hydrogen required by the fuel cell. In the fuel cell unit, the hydrogen at the anode and the oxygen at the cathode react at the two poles to generate electricity, and the power of the fuel cell unit is 4 kW. At the same time, the first heat transfer fluid from the thermal cycle unit absorbs the heat generated by the fuel cell; the first heat transfer fluid of about 70°C that absorbs the heat generated by the fuel cell is sent into the groove of the heat transfer fluid substrate of the solid hydrogen storage container to provide heat for hydrogen release, and the first heat transfer fluid that absorbs heat during the hydrogen release process returns to the thermal cycle unit for recycling. In the above process, the residual heat of the fuel cell can be used to release heat in solid hydrogen storage, and the heat utilization rate is significantly improved.

[0188] like Fig.11 As shown, the solid-state hydrogen storage device can maintain a hydrogen release rate of 40 L / min for 248 s and maintain a power operation of 4 kW for the fuel cell. At this time, the solid-state hydrogen storage device releases 53 wt% of the total amount of stored hydrogen.

[0189] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A solid hydrogen storage and fuel cell coupling system, characterized in that: The system comprises a solid hydrogen storage unit (I) and a fuel cell unit (II); The solid hydrogen storage unit (I) comprises a solid hydrogen storage container (1) for storing hydrogen and providing hydrogen for a fuel cell unit (II); the solid hydrogen storage container (1) comprises a heat transfer fluid substrate (5) and a hydrogen storage material substrate (6) filled with a solid hydrogen storage composite material, which are stacked in sequence; the heat transfer fluid substrate (5) is engraved with a first flow channel for the passage of a heat transfer fluid; the hydrogen storage material substrate (6) is engraved with a second flow channel for the passage of hydrogen, and the first flow channel and the second flow channel are not connected; The fuel cell unit (II) is used to react the oxygen-containing gas with the hydrogen from the solid hydrogen storage unit (I) to generate electricity and to provide heat for the solid hydrogen storage unit (I) to release hydrogen.

2. The system according to claim 1, wherein: The first flow channel and the second flow channel are independently serpentine flow channels or parallel flow channels; Preferably, the ratio of the unidirectional length to the depth of the serpentine flow channel is 5-100:1; Preferably, the ratio of the length to the depth of a single group of parallel flow channels is 5-100:1; Preferably, the ratio of the depth of the first flow channel to the thickness of the heat transfer fluid substrate (5) is 0.4-0.9:1, preferably 0.7-0.9:1; Preferably, the volume of the first flow channel accounts for 30-90% of the volume of the heat transfer fluid substrate (5), preferably 40-70%; Preferably, the ratio of the depth of the second flow channel to the thickness of the hydrogen storage material substrate (6) is 0.4-0.9:1, preferably 0.7-0.9:1; Preferably, the volume of the second flow channel accounts for 30-90% of the volume of the hydrogen storage material substrate (6), preferably 40-70%.

3. The system according to claim 2, wherein: The first flow channel and the second flow channel have the same shape and are arranged in parallel; Preferably, the first flow channel and the second flow channel are serpentine flow channels and are arranged in parallel; Preferably, along the stacking direction of the heat transfer fluid substrate (5) and the hydrogen storage material substrate (6) in the solid hydrogen storage container (1), the first flow channel and the second flow channel are arranged in the same direction.

4. The system according to any one of claims 1 to 3, wherein: The facets of the first flow channel and the second flow channel are independently square facets or triangular sawtooth facets, preferably triangular sawtooth facets; Preferably, in the triangular sawtooth facet, the angle of the triangular sawtooth vertex is 50-120°, preferably 60-90°.

5. The system according to any one of claims 1 to 4, wherein: The solid hydrogen storage composite material is filled in the second flow channel of the hydrogen storage material substrate (6); Preferably, the solid hydrogen storage container (1) is further provided with a first fluid pipeline (3) and a second fluid pipeline (4), wherein the first fluid pipeline (3) is connected to a fluid inlet of the heat-conducting fluid substrate (5), and the second fluid pipeline (4) is connected to a fluid outlet of the heat-conducting fluid substrate (5), for circulation of the heat-conducting fluid; Preferably, the solid hydrogen storage container (1) is further provided with a hydrogenation pipeline (9) and a hydrogen supply pipeline (10); the hydrogenation pipeline (9) is in communication with the gas inlet of the hydrogen storage material substrate (6) and is used to provide hydrogen to the solid hydrogen storage composite material; the hydrogen supply pipeline (10) is in communication with the gas outlet of the hydrogen storage material substrate (6) and the fuel cell unit (II) and is used to provide hydrogen to the fuel cell unit (II); Preferably, the solid hydrogen storage container (1) further comprises filters (11) arranged at the gas inlet and the gas outlet of the hydrogen storage material substrate (6) to prevent the outflow of the solid hydrogen storage composite material powder; Preferably, the solid hydrogen storage container (1) further comprises a sealing end plate (7) for sealing the solid hydrogen storage container (1).

6. The system according to claim 5, wherein: The system further comprises a hydrogen storage tank (16) disposed between the solid hydrogen storage container (1) and the fuel cell unit (II) and used for buffering hydrogen from the solid hydrogen storage container (1); Preferably, the inlet of the hydrogen storage tank (16) is connected to the hydrogen supply pipeline (10) of the solid hydrogen storage container (1), and the outlet is connected to the fuel cell unit (II).

7. The system according to claim 6, wherein: The fuel cell unit (II) comprises a fuel cell stack (2), wherein the anode gas inlet of the fuel cell stack (2) is connected to the outlet of the hydrogen storage tank (16) for receiving hydrogen; the anode gas outlet of the fuel cell stack (2) is connected to the inlet of the hydrogen storage tank (16) via a hydrogen compression pump (19) for recovering unreacted hydrogen; Preferably, the cathode gas inlet of the fuel cell stack (2) is used to receive the oxygen-containing gas; and the cathode gas outlet of the fuel cell stack (2) is used to discharge the oxygen-containing gas out of the system.

8. The system according to claim 7, wherein: The system further comprises a heat circulation unit (III), wherein the heat circulation unit (III) is connected to the fuel cell unit (II) and the solid hydrogen storage unit (I) for heat circulation; Preferably, the thermal circulation unit (III) comprises a liquid storage tank (26), the inlet of the liquid storage tank (26) being connected to the second fluid pipeline (4) of the solid hydrogen storage container (1) for recovering the heat transfer fluid from the solid hydrogen storage container (1); the outlet of the liquid storage tank (26) being connected to the heat transfer fluid circulation inlet of the fuel cell stack (2) for absorbing the heat generated by the fuel cell unit (II); Preferably, the heat transfer fluid circulation outlet of the fuel cell stack (2) is connected to the first fluid pipeline (3) of the solid hydrogen storage container (1) to provide heat for the solid hydrogen storage container (1) to release hydrogen; Preferably, the thermal cycle unit (III) further comprises a heating resistor (29), wherein the heating resistor (29) is placed below the liquid storage tank (26) and is used for preheating when the system is cold started; Preferably, the thermal cycle unit (III) further comprises a temperature sensor (25), wherein the temperature sensor (25) is placed above the liquid storage tank (26) and is used for temperature detection.

9. A method for operating a solid hydrogen storage and fuel cell coupling system according to any one of claims 1 to 8, characterized in that: The method comprises: reacting an oxygen-containing gas with hydrogen from a solid hydrogen storage container in a fuel cell unit to generate electricity, while a first heat transfer fluid absorbs heat generated by the fuel cell power generation; Among them, the hydrogen release process of the solid hydrogen storage container includes: the solid hydrogen storage composite material adsorbed with hydrogen undergoes a desorption reaction, and the first heat transfer fluid that absorbs the heat generated by the fuel cell power generation is sent into the first flow channel of the heat transfer fluid substrate to provide heat for the desorption reaction of hydrogen.

10. The method according to claim 9, wherein: The conditions for the fuel cell to generate electricity include: a temperature of 50-120°C and a pressure of 0.1-3MPa; Preferably, the first heat transfer fluid comes from a thermal circulation unit.

11. The method according to claim 9 or 10, wherein: During the hydrogen release process, the conditions of the desorption reaction include: a temperature of 50-120° C. and a pressure of 0.1-4 MPa; Preferably, during the hydrogen release process, the flow rate of the hydrogen is 1-1000 L / min.

12. The method according to claim 9, wherein: The hydrogen storage process of the solid hydrogen storage container includes: sending hydrogen into the second flow channel of the hydrogen storage material substrate to react with the solid hydrogen storage composite material to absorb hydrogen, and sending the second heat transfer fluid into the first flow channel of the heat transfer fluid substrate to absorb heat generated by the hydrogen absorption reaction; Preferably, during the hydrogen storage process, the conditions of the hydrogen absorption reaction include: temperature of 0-50°C; pressure of 0.1-10MPa; Preferably, the second heat transfer fluid in the hydrogen storage process is provided externally.

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