Slurry hydrogen storage fuel cell system

Abstract

The invention discloses a slurry hydrogen storage fuel cell system, which comprises: a hydrogen storage slurry circulation module for storing and circulating a slurry hydrogen storage material; the slurry hydrogen storage material comprises organic liquid and metal hydride; the fuel cell adopts a liquid metal anode; the fuel cell comprises an anode inlet and an anode outlet; a separator for separating the anode discharge; the metal hydride powder feeder is used for supplementing metal hydride powder to the hydrogen storage slurry circulating module; wherein the slurry hydrogen storage material reacts on a liquid metal anode interface to generate electric energy and form organic liquid vapor; and the organic liquid vapor is discharged into the separator from the anode outlet, is separated, is conveyed into the hydrogen storage slurry circulating module, and is mixed with the metal hydride powder from the metal hydride powder feeder to form a slurry hydrogen storage material. According to the invention, direct power generation of the slurry hydrogen storage material on the fuel cell anode interface is realized, and the power density of the system is greatly improved.

Description

Technical Field

[0001] The present invention relates to the technical field of fuel cells, and in particular to a slurry hydrogen storage fuel cell system. Background Art

[0002] Fuel cells are considered a new type of energy conversion technology that can convert chemical energy stored in fuel into electrical energy and thermal energy through electrochemical reactions. They have high energy conversion efficiency. However, the lack of efficient hydrogen storage materials limits the application of fuel cells. In recent years, slurry hydrogen storage materials have attracted attention due to their unique solid-liquid composite hydrogen storage properties. This type of material disperses high-capacity solid-state hydrogen storage media (such as metal hydrides and coordination hydrides) in liquid organic carriers (such as aromatic hydrocarbons and heterocyclic compounds). It has high volumetric hydrogen storage density (>80kg H2 / m3), safe storage and transportation at normal pressure, and good heat transfer performance. It is regarded as an ideal carrier to break through the bottleneck of hydrogen supply for fuel cells.

[0003] However, existing fuel cell systems based on slurry hydrogen storage materials still have the following key defects:

[0004] (1) Complex system structure: Existing technologies generally adopt a "two-step" architecture, which first releases hydrogen from the slurry hydrogen storage material through an independent hydrogen production device (such as a catalytic reactor and a heating module), and then purifies the hydrogen and transports it to the fuel cell for power generation. This model requires the configuration of an independent hydrogen production device, resulting in a large system size and low power density, which is difficult to meet the lightweight requirements of vehicle-mounted or portable scenarios.

[0005] (2) Low fuel utilization: Existing systems usually directly discharge or burn the unreacted hydrogen discharged from the fuel cell anode, and the organic liquid carrier and solid hydride residue in the slurry hydrogen storage material are not recycled, resulting in waste of hydrogen source and carrier loss, which increases operating costs.

[0006] The statements herein merely provide background information related to the present invention and do not necessarily constitute prior art. Summary of the Invention

[0007] The purpose of the present invention is to provide a slurry hydrogen storage fuel cell system with fuel recycling to simplify the system structure of the fuel cell and improve the fuel utilization rate of the fuel cell.

[0008] In order to achieve the above objectives, the present invention provides a slurry hydrogen storage fuel cell system, comprising:

[0009] A hydrogen storage slurry circulation module is used to store and circulate slurry hydrogen storage materials; the slurry hydrogen storage materials include organic liquids and metal hydrides;

[0010] A fuel cell using a liquid metal anode; the fuel cell comprises an anode inlet and an anode outlet; the anode inlet is connected to the outlet of the hydrogen storage slurry circulation module;

[0011] A separator, wherein the inlet of the separator is connected to the anode outlet and is used to separate the anode discharge; the separator comprises a first outlet, wherein the first outlet is connected to the inlet of the hydrogen storage slurry circulation module and is used to transport the organic liquid to the hydrogen storage slurry circulation module;

[0012] a metal hydride powder feeder, wherein the outlet of the metal hydride powder feeder is connected to another inlet of the hydrogen storage slurry circulation module, and is used to replenish the metal hydride powder to the hydrogen storage slurry circulation module;

[0013] In which, the slurry hydrogen storage material reacts at the liquid metal anode interface to generate electrical energy; the organic liquid is discharged from the anode outlet into the separator, and after separation, is transported to the hydrogen storage slurry circulation module and mixed with the metal hydride powder from the metal hydride powder feeder to form a slurry hydrogen storage material.

[0014] Optionally, the organic liquid in the slurry hydrogen storage material is a hydrogenated organic liquid; the hydrogenated organic liquid includes any one of methylcyclohexane, perhydro N-ethylcarbazole, perhydrodibenzyltoluene, and a hydrogenated blended polymer.

[0015] Optionally, the hydrogen storage slurry circulation module includes: a hydrogenation reactor, a slurry storage tank; the hydrogenation reactor includes a first inlet, a second inlet, and a third inlet; the separator further includes a second outlet;

[0016] The first inlet and the second inlet of the hydrogenation reactor are connected to the first outlet and the second outlet of the separator respectively, and the third inlet of the hydrogenation reactor is connected to the outlet of the metal hydride powder feeder; the outlet of the hydrogenation reactor is connected to the inlet of the slurry storage tank; the outlet of the slurry storage tank is connected to the anode inlet;

[0017] Part of the hydrogenated organic liquid reacts at the liquid metal anode interface to generate electricity and produce dehydrogenated organic liquid; part of the hydrogenated organic liquid undergoes a side reaction at the anode of the fuel cell to generate hydrogen; the dehydrogenated organic liquid and hydrogen are discharged from the anode outlet into the separator, and after separation, are transported to the hydrogenation reactor; the metal catalyst powder is transported to the hydrogenation reactor through the metal hydride powder feeder; the dehydrogenated organic liquid and hydrogen react under the catalytic action of the metal hydride powder to regenerate into hydrogenated organic liquid, and the hydrogenated organic liquid and the metal hydride powder are mixed to form a slurry hydrogen storage material.

[0018] Optionally, the pressure in the hydrogenation reactor is 10 bar to 50 bar, and the temperature is 100° C. to 300° C.

[0019] Optionally, the hydrogen storage slurry circulation module further includes: an organic liquid storage tank and a hydrogen buffer tank; the inlet of the organic liquid storage tank is connected to the first outlet of the separator, and the outlet of the organic liquid storage tank is connected to the first inlet of the hydrogenation reactor; the inlet of the hydrogen buffer tank is connected to the second outlet of the separator, and the outlet of the hydrogen buffer tank is connected to the second inlet of the hydrogenation reactor.

[0020] Optionally, in the slurry hydrogen storage material, the mass ratio of the organic liquid to the metal hydride is 1:1 to 4:1.

[0021] Optionally, the material of the liquid metal anode includes any one of antimony, bismuth, and antimony-bismuth alloy.

[0022] Optionally, the metal hydride includes any one of lithium-based hydride, barium-based hydride, and rare earth hydride.

[0023] Optionally, the operating temperature of the fuel cell is 600°C to 800°C.

[0024] Optionally, the anode exhaust further comprises metal oxides; the separator further comprises a third outlet, and the slurry hydrogen storage fuel cell system further comprises a solid recovery tank; the third outlet of the separator is connected to the inlet of the solid recovery tank.

[0025] Compared with the prior art, the beneficial effects of the technical solution of the present invention include at least:

[0026] (1) The present invention uses liquid metal as the anode of the fuel cell, so that the slurry hydrogen storage material (including organic liquid and metal hydride) can directly enter the fuel cell to generate electricity. The liquid metal (such as Sb) and the O 2- The reaction forms a liquid metal oxide (such as Sb2O2) and releases electrons; the slurry hydrogen storage material acts as a reducing agent fuel for the liquid metal oxide, and continuously regenerates the liquid metal oxide into liquid metal during operation, thereby enabling the fuel cell to generate electricity sustainably. During operation, due to the density difference between the formed liquid metal oxide and the liquid metal, it can leave the liquid metal reaction zone of the anode through buoyancy, float to the anode interface, contact with the metal hydride introduced into the anode interface, undergo a reduction reaction, and dynamically regenerate into liquid metal (such as Sb2O3→Sb). Under this anode reaction mechanism, the present invention does not need to use hydrogen as fuel, so there is no need to set up an additional hydrogen production device, which simplifies the system structure of the fuel cell and helps to improve the power density of the fuel cell system.

[0027] (2) Furthermore, in the slurry hydrogen storage material of the present application, the organic liquid used may be a hydrogenated organic liquid, which can improve the hydrogen storage density of the slurry hydrogen storage material, and the hydrogenated organic liquid can also be used as a reducing agent fuel for the liquid metal oxide, reducing the liquid metal oxide to regenerate it into liquid metal, thereby facilitating the anode reaction and generating more electricity.

[0028] (3) Furthermore, the fuel cell system of the present invention recovers the organic liquid at the anode outlet of the fuel cell and the hydrogen generated by the side reaction (thermal catalytic dehydrogenation reaction) of the hydrogenated organic liquid. In the hydrogenation reactor, a hydrogenation reaction occurs under the catalytic action of the metal hydride powder, and the hydrogenated organic liquid is regenerated into a hydrogenated organic liquid. The new slurry hydrogen storage material is made together with the metal hydride powder and then re-enters the fuel cell to generate electricity, which is beneficial to improving the fuel utilization rate of the fuel cell system. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a schematic diagram of a slurry hydrogen storage fuel cell system of the present invention.

[0030] Figure 2 This is a schematic diagram of the operating principle of a fuel cell in a slurry hydrogen storage fuel cell system of the present invention.

[0031] Description of the accompanying drawings:

[0032] Slurry storage tank 10

[0033] Fuel Cell 20

[0034] Anode inlet 21

[0035] Anode outlet 22

[0036] Anode 23

[0037] Liquid metal reaction zone 232

[0038] Anode interface 231

[0039] cathode 24

[0040] Electrolyte 25

[0041] Separator 30

[0042] First Exit 31

[0043] Second Exit 32

[0044] Third Exit 33

[0045] Metal hydride powder feeder 40

[0046] Hydrogenation reactor 50

[0047] First entrance 51

[0048] Second entrance 52

[0049] Third entrance 53

[0050] Slurry pump 60

[0051] Solids recovery tank 70

[0052] Hydrogen buffer tank 80

[0053] Hydrogen pressure pump 90

[0054] Organic liquid storage tank 100

[0055] Organic liquid pump 110

[0056] Gas flow route R1

[0057] Liquid flow route R2

[0058] Solid flow route R3. DETAILED DESCRIPTION

[0059] The following is a further detailed description of a slurry hydrogen storage fuel cell system proposed by the present invention in conjunction with the accompanying drawings and specific embodiments. According to the following description, the advantages and features of the present invention will be clearer. It should be noted that the drawings are in a very simplified form and are not in precise proportions, which are only used to conveniently and clearly assist in explaining the purpose of the embodiments of the present invention. In order to make the purposes, features and advantages of the present invention more obvious and easy to understand, please refer to the drawings. It should be noted that the structures, proportions, sizes, etc. illustrated in the drawings of this specification are only used to match the contents disclosed in the specification for people familiar with this technology to understand and read, and are not used to limit the conditions for the implementation of the present invention, so they have no technical significance. Any modification of the structure, change in the proportional relationship or adjustment of the size should still fall within the scope of the technical content disclosed by the present invention without affecting the efficacy and purpose that can be achieved by the present invention.

[0060] As described in the background art, existing fuel cell systems that use slurry hydrogen storage materials as hydrogen sources have problems such as complex system structure and low fuel utilization. In the prior art, slurry hydrogen storage materials are composed of micron or nanometer-scale solid hydrogen storage materials (such as metal hydrides, etc.) uniformly suspended in an organic liquid (Liquid Organic Hydrogen Carrier, LOHC) to form a paste-like mixed system. The organic liquid is used as a dispersion medium to enhance mass transfer and thermal management. The organic liquid is usually an aromatic hydrocarbon, a heterocyclic compound, etc., for example, toluene, dibenzyltoluene, etc.

[0061] To address these issues, the present invention proposes a slurry hydrogen storage fuel cell system for the first time. This system utilizes a liquid metal anode in conjunction with a slurry hydrogen storage material, enabling direct use of the slurry hydrogen storage material for power generation. The liquid metal oxidizes to form a liquid metal oxide, releasing electrons. The slurry hydrogen storage material then reduces the liquid metal oxide back to liquid metal, thereby continuously regenerating the fuel cell's anode material. This anode reaction mechanism eliminates the need for hydrogen as fuel, eliminating the need for a hydrogen production device. This simplifies the system structure and improves the fuel cell system's power density. Furthermore, the organic liquid used in the present invention can be a hydrogenated organic liquid, and can also participate in the reduction of liquid metal oxides, thereby realizing rapid regeneration of liquid metal, which is beneficial for the fuel cell to generate more electricity; further, the present invention designs the fuel cell system structure, and recovers the by-product hydrogen gas (produced by the thermal catalytic dehydrogenation reaction of the hydrogenated organic liquid) and the organic liquid at the anode outlet of the fuel cell, so that the hydrogen gas and the organic liquid are prepared into hydrogenated organic liquid through hydrogenation reaction in the hydrogenation reactor, and then together with the metal hydride powder to form a slurry hydrogen storage material, re-enter the fuel cell to generate electricity, realizing the recycling of the hydrogen source, thereby improving the fuel utilization rate of the system.

[0062] The technical solution of the present invention is described in detail below with reference to the accompanying drawings and embodiments.

[0063] Example

[0064] like Figure 1 As shown, this embodiment provides a slurry hydrogen storage fuel cell system, comprising: a slurry storage tank 10, a fuel cell 20, a separator 30, a metal hydride powder feeder 40, and a hydrogenation reactor 50. The fuel cell 20 includes an anode inlet 21 and an anode outlet 22. The anode inlet 21 is connected to the outlet of the slurry storage tank 10, and the slurry storage tank 10 is used to provide slurry hydrogen storage material to the fuel cell 20. The anode outlet 12 is connected to the inlet of the separator 30, and the separator 30 is used to separate the discharge discharged from the anode outlet 12. The separator 30 includes a first outlet 31, a second outlet 32, and a third outlet 33. The hydrogenation reactor 50 includes a first inlet 51, a second inlet 52, and a third inlet 53. The first inlet 51 and the second inlet 52 of the hydrogenation reactor 50 are connected to the first outlet 31 and the second outlet 32 ​​of the separator 30, respectively. The third inlet 53 of the hydrogenation reactor 50 is connected to the outlet of the metal hydride powder feeder 40. The outlet of the hydrogenation reactor 50 is connected to the inlet of the slurry storage tank 10 . Figure 1 The cathode inlet and cathode outlet of the fuel cell 20 of this embodiment are not shown. The cathode inlet is used to introduce air or O2, and the cathode outlet is used to discharge unreacted air or O2.

[0065] This embodiment provides a slurry hydrogen storage fuel cell system. The flow paths of the entire slurry hydrogen storage fuel cell system include a gas flow path R1, a liquid flow path R2, and a solid flow path R3. The gas flow path R1 shows the flow of gases such as hydrogen, the liquid flow path R2 shows the flow of liquids or liquid vapors such as slurry hydrogen storage fuel, dehydrogenated organic liquid, and hydrogenated organic liquid, and the solid flow path R3 shows the flow of solids such as metal hydrides and metal oxides. The specific flow patterns are described below.

[0066] In this embodiment, the slurry storage tank 10 is used to store slurry hydrogen storage material. When the slurry hydrogen storage fuel cell system is running, the slurry hydrogen storage material is transported to the anode inlet 21 of the fuel cell 20 as fuel for the fuel cell.

[0067] In this embodiment, the slurry hydrogen storage fuel cell system further includes a slurry pump 60 , which is used to pump the slurry hydrogen storage material in the slurry storage tank 10 to the anode inlet 21 of the fuel cell 20 .

[0068] The slurry hydrogen storage material has fluidity and comprises an organic liquid and a metal hydride. The mass ratio of the organic liquid to the metal hydride is generally 1:1 to 4:1, depending on the material combination and hydrogen storage requirements. In this embodiment, in order to increase the hydrogen storage content of the slurry hydrogen storage material, the slurry hydrogen storage material comprises a hydrogenated organic liquid and a metal hydride. The mass ratio of the hydrogenated organic liquid to the metal hydride is 3:1. The hydrogenated organic liquid is denoted as H n -LOHC (where n represents the atomic ratio of H), the metal hydride is recorded as MH m (wherein M represents a metal atom and m represents the atomic ratio of H). In some embodiments, the hydrogenated organic liquid comprises any one of methylcyclohexane, perhydro N-ethylcarbazole, perhydrodibenzyltoluene, and a hydrogenated polymer blend; wherein the hydrogenated polymer blend includes but is not limited to a blend of hydrogenated polyethylene and hydrogenated polypropylene, a hydrogenated styrene-butadiene-styrene block copolymer, a blend of hydrogenated polyphenylene ether and hydrogenated polyphenylene sulfide, a blend of hydrogenated polyphenylene ether and hydrogenated polyphenylene sulfide, etc. The metal hydride comprises any one of lithium-based hydride, barium-based hydride, and rare earth hydride. The decomposition temperature of the metal hydride is relatively high and decomposition does not occur at the operating temperature of the fuel cell. In this embodiment, the hydrogenated organic liquid is perhydrodibenzyltoluene, and the metal hydride is lithium hydride (LiH).

[0069] The operating principle diagram of the fuel cell 20 is as follows: Figure 2As shown. The fuel cell 20 contains an anode 23, a cathode 24, and an electrolyte 25. The anode 23 used in the fuel cell 20 is a liquid metal anode. In some embodiments, the material of the liquid metal anode includes at least one of antimony (Sb), bismuth (Bi), and antimony-bismuth (Sb-Bi) alloy. In this embodiment, the anode material of the fuel cell 20 is liquid Sb, and the mutual conversion of liquid metal (Sb) and liquid metal oxide (Sb2O3) occurs continuously during the fuel cell reaction process; the cathode material of the fuel cell 20 is perovskite oxide; the electrolyte 25 of the fuel cell 20 is a solid oxide electrolyte, and the electrolyte material is gadolinium-doped cerium oxide. The electrolyte 25 has high oxygen ion conductivity at high temperature. When the slurry hydrogen storage fuel cell system is running, the reaction occurring at the cathode 24 of the fuel cell 20 is: O2+4e - →2O 2- The electrolyte 25 converts the O generated on the cathode side into 2 - transferred to the anode 23 to participate in the oxidation reaction of the liquid Sb anode. In this embodiment, in the liquid Sb anode, the hydrogenated organic liquid and the metal hydride both participate in the anode reaction, and the reactions that occur include:

[0070] (1) The hydrogenated organic liquid reacts at the liquid Sb anode to generate the dehydrogenated organic liquid (denoted as LOHC). The reaction equation includes:

[0071] 2Sb+3O 2- →Sb2O3+6e - ,

[0072]

[0073] (2) Metal hydride reacts at the liquid Sb anode to form metal oxide. The reaction equation includes:

[0074] 2Sb+3O 2- →Sb2O3+6e - ,

[0075]

[0076] (3) Some hydrogenated organic liquids will undergo thermal catalytic dehydrogenation reaction (side reaction) at the fuel cell operating temperature (600℃~800℃):

[0077]

[0078] Among them, H n -LOHC and LOHC are vaporized into H at the fuel cell operating temperature (600℃~800℃) respectively. n-LOHC vapor, LOHC vapor, floating above liquid Sb and liquid Sb2O3 (anode interface 231). MH m 、M2O m Although solid, its density is lower than that of liquid Sb and liquid Sb2O3, and it will float on the anode interface 231 in the form of solid particles. During the reaction, since the density of Sb2O3 is lower than that of Sb, Sb obtains O near the electrolyte 25. 2- After Sb2O3 is generated, it can leave the liquid metal reaction zone 232 under the action of buoyancy and float to the anode interface 231 to react with the hydrogenated organic liquid and metal hydride. After the reaction, Sb2O3 is reduced, and the generated Sb can sink to the bottom of the anode 23 under the action of gravity. During this process, oxygen is rapidly transported in the form of Sb2O3 within the liquid Sb anode through natural convection.

[0079] In this embodiment, H2, H n -LOHC vapor, LOHC vapor is a gas and can be directly discharged from the anode outlet 22 of the fuel cell 20, MH m 、M2O m Due to their low density, they float above the liquid Sb and liquid Sb2O3 and can be discharged from the anode outlet 22 of the fuel cell 20 by regular filtration. The discharge from the anode outlet 22 includes H2, water vapor, and incompletely reacted H n -LOHC vapor, LOHC vapor, unreacted MH m 、M2O m .

[0080] The exhaust from the anode outlet 22 of the fuel cell 20 enters the separator 30 through the inlet of the separator 30 and is cooled and physically separated by the separator 30. n -LOHC steam, LOHC steam enters the separator 30 and is cooled to liquid, thus separating from H2. n -There is a density difference between LOHC and LOHC, which can further realize the n - Separation between LOHC and LOHC. In some embodiments, the separator 30 includes but is not limited to a vertical separator and a horizontal separator. In this embodiment, the separator 30 is a vertical separator.

[0081] After separation, LOHC, unreacted H n-LOHC is transported to the interior of the hydrogenation reactor 50 through the first outlet 31 of the separator 30; H2 is transported to the interior of the hydrogenation reactor 50 through the second outlet 32 ​​of the separator 30; and metal hydride powder is transported to the interior of the hydrogenation reactor 50 through the metal hydride powder feeder 40. Under the catalytic action of the metal hydride powder, H2 and LOHC undergo a hydrogenation reaction of the organic liquid in the hydrogenation reactor 50: LOHC+H2→H n -LOHC, the reaction pressure is 10 bar ~ 50 bar, the reaction temperature is 100 ℃ ~ 300 ℃. The hydrogenation reaction re-prepares the dehydrogenated organic liquid LOHC into hydrogenated organic liquid H n -LOHC, hydrogenated organic liquid H n After the LOHC is mixed with the metal hydride powder to form a new slurry hydrogen storage material, it re-enters the slurry storage tank 10 and serves as fuel for the fuel cell 20, thereby achieving effective recycling of the reaction products of the fuel cell 20.

[0082] In this embodiment, the separator 30 further comprises a third outlet 33, and the slurry hydrogen storage fuel cell system further comprises a solid recovery tank 70; the third outlet 33 of the separator 30 is connected to the solid recovery tank 70. Metal oxide M2O m , unreacted metal hydride MH m The solid is discharged from the third outlet 33 and enters the solid recovery tank 70 .

[0083] In this embodiment, the slurry hydrogen storage fuel cell system further includes a hydrogen buffer tank 80. The second outlet 32 ​​of the separator 30 is sequentially connected to the hydrogen buffer tank 80 and the hydrogenation reactor 50. The hydrogen buffer tank 80 is used to store hydrogen from the second outlet 32 ​​of the separator 30. In some embodiments, the pipeline connecting the hydrogen buffer tank 80 and the hydrogenation reactor 50 further includes a hydrogen pressure pump 90 for pumping the hydrogen in the hydrogen buffer tank 80 into the hydrogenation reactor 50 and adjusting the pressure of the pumped hydrogen to provide the required reaction pressure for the hydrogenation reactor 50.

[0084] In this embodiment, the slurry hydrogen storage fuel cell further comprises: an organic liquid storage tank 100, and the first outlet 31 of the separator 30 is connected to the organic liquid tank 100 and the hydrogenation reactor 50 in sequence. The organic liquid storage tank 100 is used to store the LOHC and unreacted H n In some embodiments, the pipeline connecting the organic liquid storage tank 100 and the hydrogenation reactor 50 further comprises an organic liquid pump 110 for pumping the LOHC and unreacted Hn -LOHC is pumped into the hydrogenation reactor 50 and can be used to adjust the pressure of the pumped organic liquid, thereby providing the desired reaction pressure for the hydrogenation reactor 50.

[0085] In this embodiment, by controlling the flow rate of hydrogen gas pumped into the hydrogenation reactor 50, the flow rate of the organic liquid, and the content of the added metal hydride powder, the re-made slurry hydrogen storage material has the required hydrogen storage capacity and appropriate fluidity.

[0086] The working process of a slurry hydrogen storage fuel cell system of this embodiment includes:

[0087] Slurry hydrogen storage material in the slurry storage tank (composed of H n -LOHC、MH m The slurry is pumped by a slurry pump to the anode inlet of the fuel cell, where an electrochemical reaction and a dehydrogenation side reaction occur, and the generated products include hydrogen, organic liquid LOHC vapor, metal oxide (M2O m ), water vapor, and the resulting products are discharged from the anode outlet of the fuel cell and enter the separator for separation. After separation by the separator, the hydrogen is transported to the hydrogen buffer tank, from which the hydrogen in the hydrogen buffer tank is pumped to the hydrogenation reactor by a hydrogen pump. The LOHC vapor is liquefied and separated by the separator and transported to the organic liquid storage tank. The LOHC in the organic liquid storage tank is pumped to the hydrogenation reactor by an organic liquid pump. M2O m After separation in the separator, it is transported to the solid recovery tank. The metal hydride powder is fed to the hydrogenation reactor by the metal hydride powder feeder. In the hydrogenation reactor, hydrogen and LOHC react under the catalysis of the metal hydride powder to regenerate H n -LOHC, and fuse it with metal hydride powder to generate new slurry hydrogen storage material, which is then resupplied to the fuel cell for power generation, thus realizing the recycling of fuel.

[0088] In summary, the present invention uses liquid metal as the anode of the fuel cell, and the O 2- The reaction forms liquid metal oxide and releases electrons. The slurry hydrogen storage material (comprising an organic liquid and a metal hydride) acts as a reducing fuel for the liquid metal oxide, regenerating it into liquid metal to achieve continuous power generation. Under this mechanism, the present invention does not require an additional hydrogen production device to prepare the fuel, simplifying the system structure and improving power density. The use of hydrogenated organic liquid in the slurry hydrogen storage material can increase the hydrogen storage density and, as a reducing fuel, facilitates the anode reaction to generate more electricity. At the same time, the system recovers the organic liquid vapor at the anode outlet and the hydrogen generated by the thermal catalytic dehydrogenation reaction, regenerating it into hydrogenated organic liquid through a hydrogenation reaction in the hydrogenation reactor, thereby improving fuel utilization.

[0089] It should be noted that, in this document, the terms "comprises," "includes," or any other variations thereof are intended to encompass non-exclusive inclusion, such that a process, method, article, or apparatus comprising a series of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus. In the absence of further limitations, an element defined by the phrase "comprising a ..." does not exclude the presence of other identical elements in the process, method, article, or apparatus comprising the element.

[0090] Although the present invention has been described in detail through the above preferred embodiments, it should be understood that the above description is not intended to limit the present invention. After reading the above description, various modifications and substitutions of the present invention will become apparent to those skilled in the art. Therefore, the scope of protection of the present invention should be defined by the appended claims.

Claims

1. A slurry hydrogen storage fuel cell system, characterized in that: include: A hydrogen storage slurry circulation module is used to store and circulate slurry hydrogen storage materials; the slurry hydrogen storage materials include organic liquids and metal hydrides; A fuel cell using a liquid metal anode; the fuel cell comprises an anode inlet and an anode outlet; the anode inlet is connected to the outlet of the hydrogen storage slurry circulation module; A separator, wherein the inlet of the separator is connected to the anode outlet and is used to separate the anode discharge; the separator comprises a first outlet, wherein the first outlet is connected to the inlet of the hydrogen storage slurry circulation module and is used to transport the organic liquid to the hydrogen storage slurry circulation module; a metal hydride powder feeder, wherein the outlet of the metal hydride powder feeder is connected to another inlet of the hydrogen storage slurry circulation module, and is used to replenish the metal hydride powder to the hydrogen storage slurry circulation module; In which, the slurry hydrogen storage material reacts at the liquid metal anode interface to generate electrical energy; the organic liquid is discharged from the anode outlet into the separator, and after separation, is transported to the hydrogen storage slurry circulation module and mixed with the metal hydride powder from the metal hydride powder feeder to form a slurry hydrogen storage material.

2. The slurry hydrogen storage fuel cell system according to claim 1, characterized in that: The organic liquid in the slurry hydrogen storage material is a hydrogenated organic liquid; the hydrogenated organic liquid comprises any one of methylcyclohexane, perhydro N-ethylcarbazole, perhydrodibenzyltoluene, and a hydrogenated blended polymer.

3. The slurry hydrogen storage fuel cell system according to claim 2, characterized in that: The hydrogen storage slurry circulation module includes: a hydrogenation reactor and a slurry storage tank; the hydrogenation reactor includes a first inlet, a second inlet, and a third inlet; the separator also includes a second outlet; The first inlet and the second inlet of the hydrogenation reactor are connected to the first outlet and the second outlet of the separator respectively, and the third inlet of the hydrogenation reactor is connected to the outlet of the metal hydride powder feeder; the outlet of the hydrogenation reactor is connected to the inlet of the slurry storage tank; the outlet of the slurry storage tank is connected to the anode inlet; Part of the hydrogenated organic liquid reacts at the liquid metal anode interface to generate electricity and produce dehydrogenated organic liquid; part of the hydrogenated organic liquid undergoes a side reaction at the anode of the fuel cell to generate hydrogen; the dehydrogenated organic liquid and hydrogen are discharged from the anode outlet into the separator, and after separation, are transported to the hydrogenation reactor; the metal catalyst powder is transported to the hydrogenation reactor through the metal hydride powder feeder; the dehydrogenated organic liquid and hydrogen react under the catalytic action of the metal hydride powder to regenerate into hydrogenated organic liquid, and the hydrogenated organic liquid and the metal hydride powder are mixed to form a slurry hydrogen storage material.

4. The slurry hydrogen storage fuel cell system according to claim 3, characterized in that: The pressure in the hydrogenation reactor is 10 bar to 50 bar, and the temperature is 100° C. to 300° C.

5. The slurry hydrogen storage fuel cell system according to claim 3, characterized in that: The hydrogen storage slurry circulation module also includes: an organic liquid storage tank and a hydrogen buffer tank; the inlet of the organic liquid storage tank is connected to the first outlet of the separator, and the outlet of the organic liquid storage tank is connected to the first inlet of the hydrogenation reactor; the inlet of the hydrogen buffer tank is connected to the second outlet of the separator, and the outlet of the hydrogen buffer tank is connected to the second inlet of the hydrogenation reactor.

6. The slurry hydrogen storage fuel cell system according to claim 1, characterized in that: In the slurry hydrogen storage material, the mass ratio of the organic liquid to the metal hydride is 1:1 to 4:

1.

7. The slurry hydrogen storage fuel cell system according to claim 1, wherein: The material of the liquid metal anode includes any one of antimony, bismuth, and antimony-bismuth alloy.

8. The slurry hydrogen storage fuel cell system according to claim 1, wherein: The metal hydride includes any one of lithium-based hydride, barium-based hydride, and rare earth hydride.

9. The slurry hydrogen storage fuel cell system according to claim 1, wherein: The operating temperature of the fuel cell is 600°C to 800°C.

10. The slurry hydrogen storage fuel cell system according to claim 1, wherein: The anode exhaust further comprises metal oxides; the separator further comprises a third outlet, and the slurry hydrogen storage fuel cell system further comprises a solid recovery tank; the third outlet of the separator is connected to the inlet of the solid recovery tank.

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