CN117613304A - Multi-solid-state hydrogen storage material coupling hydrogen-electricity system oriented to ultrahigh-quality hydrogen storage density - Google Patents
Multi-solid-state hydrogen storage material coupling hydrogen-electricity system oriented to ultrahigh-quality hydrogen storage density Download PDFInfo
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- CN117613304A CN117613304A CN202311574123.1A CN202311574123A CN117613304A CN 117613304 A CN117613304 A CN 117613304A CN 202311574123 A CN202311574123 A CN 202311574123A CN 117613304 A CN117613304 A CN 117613304A
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 318
- 239000001257 hydrogen Substances 0.000 title claims abstract description 318
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 318
- 238000003860 storage Methods 0.000 title claims abstract description 183
- 239000011232 storage material Substances 0.000 title claims abstract description 49
- 238000010168 coupling process Methods 0.000 title claims abstract description 16
- 230000008878 coupling Effects 0.000 title claims abstract description 13
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 61
- 239000000446 fuel Substances 0.000 claims abstract description 55
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000007062 hydrolysis Effects 0.000 claims abstract description 19
- 238000000197 pyrolysis Methods 0.000 claims abstract description 14
- 230000005611 electricity Effects 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- 229910002593 Fe-Ti Inorganic materials 0.000 claims description 2
- 229910020828 NaAlH4 Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000013461 design Methods 0.000 abstract description 4
- 238000010248 power generation Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052987 metal hydride Inorganic materials 0.000 description 6
- 150000004681 metal hydrides Chemical class 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001502 supplementing effect Effects 0.000 description 4
- 239000002918 waste heat Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- -1 complex hydrides Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005429 filling process Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 229910012375 magnesium hydride Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910019582 Cr V Inorganic materials 0.000 description 1
- 229910008015 Li-M Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000191 radiation effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
- H01M8/04216—Reactant storage and supply, e.g. means for feeding, pipes characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
- F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C13/00—Details of vessels or of the filling or discharging of vessels
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C13/00—Details of vessels or of the filling or discharging of vessels
- F17C13/04—Arrangement or mounting of valves
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04014—Heat exchange using gaseous fluids; Heat exchange by combustion of reactants
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04067—Heat exchange or temperature measuring elements, thermal insulation, e.g. heat pipes, heat pumps, fins
- H01M8/04074—Heat exchange unit structures specially adapted for fuel cell
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2205/00—Vessel construction, in particular mounting arrangements, attachments or identifications means
- F17C2205/03—Fluid connections, filters, valves, closure means or other attachments
- F17C2205/0302—Fittings, valves, filters, or components in connection with the gas storage device
- F17C2205/0352—Pipes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2221/00—Handled fluid, in particular type of fluid
- F17C2221/01—Pure fluids
- F17C2221/012—Hydrogen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
- F17C2223/01—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
- F17C2223/0146—Two-phase
- F17C2223/0176—Solids and gas
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses a hydrogen-electricity system for coupling multiple solid hydrogen storage materials facing ultra-high quality hydrogen storage density, belonging to the technical field of hydrogen electricity, wherein the hydrogen-electricity system comprises a solid hydrogen storage system, a fuel cell stack and a modularized solid hydrogen storage unit are arranged in the solid hydrogen storage system, and the modularized solid hydrogen storage unit comprises a first hydrogen storage unit (a solid hydrogen storage material pyrolysis unit) and a second hydrogen storage unit (a solid hydrogen storage material hydrolysis unit) inserted in the first hydrogen storage unit; the hydrogen outlets of the first hydrogen storage unit and the second hydrogen storage unit are connected to the hydrogen inlet of the fuel cell stack through the third hydrogen storage unit by pipelines; the anode tail gas port of the fuel cell stack is connected to the water inlet of the second hydrogen storage unit through a pipeline. The invention adopts a coupling method to realize the integrated design of the three of the pyrolysis hydrogen production, the hydrolysis hydrogen production and the fuel cell power generation system of the solid hydrogen storage material, realize the high-efficiency utilization and release of water, heat and electricity and realize the solution of the hydrogen-electricity system with ultra-high energy density.
Description
Technical Field
The invention relates to the technical field of hydrogen electricity, in particular to a hydrogen electricity system coupled by multiple solid hydrogen storage materials for ultrahigh-quality hydrogen storage density.
Background
In order to solve the problem of low mass hydrogen storage density of the existing high-pressure gas hydrogen storage system, hydrogen storage systems based on solid hydrogen storage materials are actively developed at home and abroad. Among the numerous hydrogen storage materials, there are mainly two kinds of metal hydrides and complex hydrides, wherein relatively many hydrogen storage materials can release hydrogen either by pyrolysis or by hydrolysis.
The release of hydrogen by pyrolysis generally requires that the hydrogen storage material be repeatedly charged and discharged, a reversible hydrogen storage process. The more mature hydrogen storage materials currently include: fe-Ti alloy, la-Ni alloy and MgH 2 And the like, industrialization has been focused mainly on the former two of which the hydrogen storage density is relatively low, that is, the mass hydrogen storage density is 3% or less. Although metal hydrides are very reversible in terms of hydrogen evolution and storage reactions, hydrogen evolution requires continuous heat supply and presents difficulties in practical applications due to operation at high temperatures (above 100 ℃). In addition, the development of such solid-state hydrogen storage systems operating at high temperaturesAlso in progress.
The material for producing hydrogen by hydrolysis belongs to irreversible hydrogen storage materials, releases hydrogen by hydrolysis reaction, and is suitable for producing hydrogen on site by hydrogen. The hydrolysis hydrogen production has the following advantages: 1) The mass hydrogen storage density and the volume hydrogen storage density are higher, such as NaBH 4 、LiBH 4 、Mg(BH 4 ) 2 、MgH 2 The theoretical mass hydrogen storage density of the equal system can reach about 30 percent, and the volume hydrogen storage density of the material is higher than that of commercial high-pressure hydrogen storage; 2) The hydrolysis hydrogen production is spontaneous exothermic reaction and is carried out at normal temperature and normal pressure, and the hydrogen production device is relatively simple; 3) The hydrolysis hydrogen production material is easy to store, relatively safe and convenient to store and transport; 4) The reaction byproducts are basically nontoxic and harmless, and meet the requirements of green chemistry.
Although in order to achieve proper operation of the solid hydrogen storage material, a hydrogen combustion device may be installed in the storage system, or a heat exchanger may be installed to improve its heat supply. In this case, the heat exchanger may heat the storage container by using a battery power source. However, these solutions result in a reduction of fuel efficiency due to energy loss. Although there are studies at home and abroad to improve problems by changing the heat exchange fins, type, size, location, etc. of tubes in the container, or the loading method of the hydrogen storage material, these solutions result in a reduction in weight storage capacity due to an increase in the weight of the system. Accordingly, improvements are needed to minimize the amount of heat required to operate a solid state hydrogen system and to increase the weight storage capacity.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a hydrogen-electricity system which is oriented to the coupling of multiple solid-state hydrogen storage materials with ultra-high quality hydrogen storage density, so as to reduce the heat required by running the solid-state hydrogen system and improve the weight storage capacity.
In order to solve the technical problems, the invention provides the following technical scheme:
a hydrogen electric system facing to multi-solid-state hydrogen storage material coupling of ultra-high quality hydrogen storage density comprises a solid-state hydrogen storage system, wherein a fuel cell stack and at least one modularized solid-state hydrogen storage unit are arranged in the solid-state hydrogen storage system, and the hydrogen electric system comprises:
the modularized solid hydrogen storage unit comprises a first hydrogen storage unit and a second hydrogen storage unit inserted in the first hydrogen storage unit, wherein the first hydrogen storage unit is a solid hydrogen storage material pyrolysis unit, and the second hydrogen storage unit is a solid hydrogen storage material hydrolysis unit;
the hydrogen outlet of the first hydrogen storage unit and the hydrogen outlet of the second hydrogen storage unit are connected to the hydrogen inlet of the fuel cell stack through the third hydrogen storage unit after being converged through a pipeline;
the anode tail gas port of the fuel cell stack is connected to the water inlet of the second hydrogen storage unit through a pipeline by an anode tail gas circulating pump;
and a fuel cell cathode radiator fan is arranged between the fuel cell stack and the modularized solid hydrogen storage unit in the solid hydrogen storage system.
Furthermore, the pipelines corresponding to the hydrogen outlet of the first hydrogen storage unit and the hydrogen outlet of the second hydrogen storage unit are respectively provided with a one-way valve;
and/or a first electromagnetic valve is arranged on the hydrogen inlet pipeline of the third hydrogen storage unit.
Further, a second electromagnetic valve is arranged on a hydrogen outlet pipeline of the third hydrogen storage unit;
and/or a filter and a pressure stabilizing valve are arranged on the hydrogen outlet pipeline of the third hydrogen storage unit.
Further, a tail electromagnetic valve is arranged on a pipeline between the anode tail gas port of the fuel cell stack and the anode tail gas circulating pump.
Furthermore, an adjustable air inlet is arranged on one side of the fuel cell stack, which is far away from the cathode cooling fan of the fuel cell, of the solid hydrogen storage system.
Furthermore, an adjustable air outlet is arranged on one side of the modularized solid hydrogen storage unit, which is far away from the cathode cooling fan of the fuel cell, of the solid hydrogen storage system.
Further, a hydrogen charging port is arranged on the solid hydrogen storage system and is connected with the hydrogen charging port of the first hydrogen storage unit through a pipe.
Further, the hydrogen storage material in the first hydrogen storage unit is Fe-Ti alloy, la-Ni alloy or NH 3 BH 3 、AlH 3 Or MgH 2 ；
And/or the hydrogen storage materials in the second hydrogen storage unit are NaAlH4 and NaBH 4 、Mg(BH 4 ) 2 Or LiH.
Further, the edge of the first hydrogen storage unit is provided with a plurality of heat dissipation convex ribs extending along the axial direction;
and/or, the second hydrogen storage unit is columnar.
The invention has the following beneficial effects:
the invention provides a multi-solid-state hydrogen storage material coupling hydrogen-electricity system solution for ultrahigh-quality hydrogen storage density, which utilizes the advantages of the existing solid-state hydrogen storage material system and adopts a coupling method to realize the integrated design of the three of the pyrolysis hydrogen production, the hydrolysis hydrogen production and the fuel cell power generation system of the solid-state hydrogen storage material, realize the high-efficiency utilization and release of water, heat and electricity and realize the hydrogen-electricity system solution of ultrahigh-energy density.
Drawings
FIG. 1 is a schematic diagram of the product architecture of a multi-solid hydrogen storage material coupled hydrogen electric system for ultra-high quality hydrogen storage density of the present invention;
fig. 2 is a physical view of the modular solid hydrogen storage unit of fig. 1, wherein (a) is a perspective view and (b) is a top view.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
In the description of the present invention, it should be understood that the directions or positional relationships indicated by the terms "upper", "lower", "front", "rear", "left", "right", etc., are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention.
The invention provides a hydrogen electric system for coupling multi-solid-state hydrogen storage materials facing ultra-high-quality hydrogen storage density, which is shown in fig. 1-2, and comprises a solid-state hydrogen storage system 1, wherein a fuel cell stack 16 and at least one modularized solid-state hydrogen storage unit 10 are arranged in the solid-state hydrogen storage system 1, and the hydrogen electric system comprises the following components:
the modularized solid hydrogen storage unit 10 comprises a first hydrogen storage unit 11 and a second hydrogen storage unit 12 inserted in the first hydrogen storage unit 11, wherein the first hydrogen storage unit 11 is a solid hydrogen storage material pyrolysis unit, and the second hydrogen storage unit 12 is a solid hydrogen storage material hydrolysis unit;
the hydrogen outlet 111 of the first hydrogen storage unit 11 and the hydrogen outlet 121 of the second hydrogen storage unit 12 are connected to the hydrogen inlet 161 of the fuel cell stack 16 through the third hydrogen storage unit 2 (specifically, may be a hydrogen storage tank) after being converged through a pipeline;
the anode tail gas port 162 of the fuel cell stack 16 is connected to the water inlet 122 of the second hydrogen storage unit 12 through the anode tail gas circulation pump 3 by a pipe;
a fuel cell cathode cooling fan 13 is provided within the solid state hydrogen storage system 1 between the fuel cell stack 16 and the modular solid state hydrogen storage unit 10.
The invention provides a multi-solid-state hydrogen storage material coupling hydrogen-electricity system solution for ultrahigh-quality hydrogen storage density, which utilizes the advantages of the existing solid-state hydrogen storage material system and adopts a coupling method to realize the integrated design of the three of the pyrolysis hydrogen production, the hydrolysis hydrogen production and the fuel cell power generation system of the solid-state hydrogen storage material, realize the high-efficiency utilization and release of water, heat and electricity and realize the hydrogen-electricity system solution of ultrahigh-energy density.
In the present invention, the solid hydrogen storage materials contained in the solid hydrogen storage system 1 mainly include a composite hydrogen storage material and a metal hydride and a hydrogen storage alloy.
Wherein the composite hydrogen storage material may be selected from M 1 AlH 4 、M 2 (AlH 4 ) 2 、M 3 BH 4 、M 4 (BH 4 ) 2 、M 5 (BH 4 ) 3 、M 6 NH 2 、M 7 (NH 2 ) 2 、Li 2 NH, mgNH, lithium magnesium imide, naBP 2 H 8 、NH 3 BH 3 、NH 4 B 3 H 8 、NH 2 B 2 H 5 And combinations thereof, wherein M 1 Is Li, na, or Al, M 2 Is Mg or Ca, M 3 Is Li, na, or K, M 4 Is Mg or Ca, M 5 Is Al or Ti, M 6 Is Li or Na, and M 7 Is Mg or Ca.
The metal hydride in the metal hydride and the hydrogen storage alloy can be M 8 H、M 9 H 2 、AlH 3 Or a combination thereof, wherein M 8 Li, na, K, rb, or Cs, and M 9 Mg, ca, sc, ti, or V. The storage alloy in the metal hydride and the hydrogen storage alloy is Ti-Cr-V alloy, tiFe, pd-M 10 、Li-M 11 Mg-Co alloy, la-Ni alloy, or combinations thereof, where M 10 Refers to Ba, Y, or La, and M 11 Ti, V, zr, nb, or Hf.
The hydrogen storage material in the first hydrogen storage unit (solid hydrogen storage material pyrolysis unit) 11 is typically: fe-Ti alloy, la-Ni alloy, NH 3 BH 3 、AlH 3 、MgH 2 Etc.
The hydrogen storage material in the second hydrogen storage unit (solid hydrogen storage material hydrolysis unit) 12 is typically: naAlH4, naBH 4 、Mg(BH 4 ) 2 LiH, etc.
The edge of the first hydrogen storage unit 11 may be provided with a plurality of heat radiation ribs 113 extending in the axial direction to enhance the heat radiation effect. The second hydrogen storage unit 12 may be columnar, and is inserted and connected in the first hydrogen storage unit 11, so as to improve the heat conduction effect between the two.
To facilitate the guiding of the hydrogen gas flow, the pipelines corresponding to the hydrogen outlet 111 of the first hydrogen storage unit 11 and the hydrogen outlet 121 of the second hydrogen storage unit 12 may be provided with check valves 14.
The hydrogen inlet pipeline of the third hydrogen storage unit 2 (i.e. the pipeline between the third hydrogen storage unit 2 and the solid hydrogen storage system 1/the modularized solid hydrogen storage unit 10) can be provided with a first electromagnetic valve 4, and the hydrogen outlet pipeline of the third hydrogen storage unit 2 (i.e. the pipeline between the third hydrogen storage unit 2 and the fuel cell stack 16) can be provided with a second electromagnetic valve 5, so as to facilitate control. A filter 6 and a pressure stabilizing valve 7 can be further arranged on the hydrogen outlet pipeline of the third hydrogen storage unit 2 so as to filter and stabilize the gas.
A tail gas discharge solenoid valve 8 may be provided on a line between the anode tail gas port 162 of the fuel cell stack 16 and the anode tail gas circulation pump 3 to facilitate control.
The solid state hydrogen storage system 1 may be provided with an adjustable air inlet 17 on the side of the fuel cell stack 16 remote from the fuel cell cathode radiator fan 13. The solid-state hydrogen storage system 1 may be provided with adjustable air outlets 18 on the side of the modularized solid-state hydrogen storage unit 10 away from the fuel cell cathode radiator fan 13, and the number of the adjustable air outlets 18 may be flexibly set according to the needs, for example, two as shown in the figure.
The hydrogen-electricity system product provided by the invention is mainly oriented to the scene requirements under the conditions of low and medium power, long endurance and high safety, and comprises a portable power supply, a small and medium power supply, an emergency power supply, an unmanned aerial vehicle power supply system, an unmanned small and medium ship power supply system and the like, and has great advantages particularly under high and low temperature or other severe working conditions. The working process can be referred to as follows:
first, the second electromagnetic valve 5 is opened, and hydrogen required by the anode reaction is provided for the fuel cell stack 16 after gas filtration and pressure stabilization through the third hydrogen storage unit 2; meanwhile, oxygen required for the cathode reaction is supplied to the fuel cell stack 16 by the fuel cell cathode heat radiation fan 13, and at the same time, the operating temperature of the fuel cell stack 16 is controlled to be within a safe range. The anode tail gas generated after the reaction of the fuel cell stack 16, comprising partially incompletely reacted hydrogen and reaction product water, is directly input into the second hydrogen storage unit 12 through the tail gas electromagnetic valve 8 and the anode tail gas circulating pump 3, and the solid hydrogen storage materials in the second hydrogen storage unit 12 undergo hydrolysis reaction when meeting water, and hydrogen and heat are generated. The heat is supplied to the first hydrogen storage unit 11 in a heat transfer mode, and meanwhile, the waste heat generated by the fuel cell system enters the modularized solid hydrogen storage unit 10 through the fuel cell cathode cooling fan 13 to heat the solid hydrogen storage material of the first hydrogen storage unit 11, so that the pyrolysis hydrogen release of the first hydrogen storage unit 11 is realized. The hydrogen generated in the first hydrogen storage unit 11 and the second hydrogen storage unit 12 is converged after passing through the check valve 14, and at this time, the first electromagnetic valve 4 is opened to supplement the hydrogen to the third hydrogen storage unit 2. The operating temperature in the modular solid state hydrogen storage unit 10 may be regulated by the adjustable air outlet 18.
In the hydrogen electric system product of the invention, the solid-state hydrogen storage system 1 can be composed of one or more groups of modularized solid-state hydrogen storage units 10, can be flexibly combined and realizes the convenience of hydrogen supply. The second hydrogen storage unit 12 realizes high-quality hydrogen storage density by hydrolyzing and releasing hydrogen, the second hydrogen storage unit 12 can be replaced by a quick-change mode, and the reaction product in the second hydrogen storage unit 12 is recovered and regenerated. The first hydrogen storage unit 11 realizes the thermal decomposition and the hydrogen release without an external heating mode through the heat generated by the hydrolysis of the second hydrogen storage unit 12 and the waste heat of the fuel cell stack 16, thereby improving the whole energy utilization and the working performance of the system.
Meanwhile, according to different use scenes, the first hydrogen storage unit 11 in the modularized solid hydrogen storage unit 10 can simultaneously meet two modes of on-line hydrogen supplementing and off-line hydrogen supplementing. When hydrogen is supplemented online, the solid-state hydrogen storage system 1 can be provided with a hydrogen filling port 9, the hydrogen filling port 9 is connected with the first hydrogen storage unit hydrogen filling port 112 through a pipeline, the first hydrogen storage unit 11 is a reversible solid-state hydrogen storage system at the moment, thus, a hydrogen source of about 1-5 MPa is provided through the hydrogen filling port 9, and online hydrogen supplementation is carried out on the first hydrogen storage unit 11, because the reversible solid-state hydrogen storage hydrogen filling process is an exothermic process, and at the moment, in order to improve the hydrogen filling efficiency, the heat of the hydrogen filling process is required to be timely discharged by adjusting the cathode cooling fan 13 and the adjustable air outlet 18 of the fuel cell. When supplementing hydrogen off-line, the charging equipment can be specially designed for the modularized solid-state hydrogen storage unit 10 to improve the charging efficiency and convenience.
In chinese patent application CN116510640a, a solvent for low-freezing point aqueous solution, such as one or more of calcium chloride, sodium chloride or aluminum chloride, is required for low-temperature operation at low-temperature start-up. The invention belongs to a solid hydrogen storage system without supplementing water, and recycles the water generated by the fuel cell stack 16, thereby improving the energy efficiency of the system; and the product water generated by the fuel cell stack 16 is above 50 ℃, so that the operation at low temperature can be well ensured, and the hydrolysis reaction of the second hydrogen storage unit 12 is facilitated.
In the chinese patent application CN103579652a, a water circulation system is used in the operation of the fuel cell to heat the reactor and start the hydrolysis reaction. The hydrolysis reactor is connected with the proton exchange membrane fuel cell through a pipeline, water generated by the operation of the proton exchange membrane fuel cell can be balanced with water consumed by the hydrolysis of MgH2, the cyclic utilization of the water is realized, and the external water injection is not needed in theory. Because the water circulation system is used for transferring heat, the weight and the volume of the whole system can be greatly increased, and the energy density of the whole system is seriously affected; since MgH2 hydrolysis generates considerable heat, the normal operation of the fuel cell system is affected when the water circulation temperature increases. The invention adopts the coupling working mode of various solid hydrogen storage materials, can realize the effective distribution and utilization of the heat in the system, adopts the form of an air-cooled fuel cell, and the integral thermal management of the modularized solid hydrogen storage unit 10 and the waste heat of the fuel cell stack 16 can be well coupled, and has certain independence and little influence on the fuel cell stack 16.
In summary, the present invention provides a solution for a hydrogen-electricity system coupled by a plurality of solid hydrogen storage materials with ultra-high quality hydrogen storage density, which is mainly implemented as follows:
1) The mass hydrogen storage density of the main hydrogen storage system at present is below 5%, the development of the hydrogen energy industry is restricted, the ultrahigh mass hydrogen storage density can be realized, and the system hydrogen storage density can reach above 10wt% through different material combinations;
2) The high-pressure hydrogen storage and the liquid hydrogen storage of the current main stream depend on hydrogenation infrastructure, and for solid hydrogen storage, the practical solid hydrogen storage technology has lower hydrogen storage performance, and the invention can realize the coupling of a reversible solid pyrolysis hydrogen storage system and an irreversible solid hydrolysis hydrogen storage system, and realize reliable structural design and quick replacement technology;
3) The prior technical products for producing hydrogen by hydrolyzing the solid hydrogen storage material need to carry a water storage tank with corresponding proportion, so that the energy density of the whole system is seriously affected;
4) At present, the coupling of the waste heat of the solid hydrogen storage and the fuel cell system cannot achieve an ideal effect, and the invention can realize the coupling of the heat required by the pyrolysis of the solid hydrogen storage material and the working heat production of the fuel cell, thereby improving the overall heat utilization;
5) The current technical route of solid hydrogen storage is limited by the source of heat required by pyrolysis and the utilization of the heat generated by hydrolysis, and a comprehensive solution is not obtained.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The utility model provides a hydrogen electricity system of many solid-state hydrogen storage material couplings towards super high quality hydrogen storage density which characterized in that includes solid-state hydrogen storage system, be equipped with fuel cell stack and at least one modularization solid-state hydrogen storage unit in the solid-state hydrogen storage system, wherein:
the modularized solid hydrogen storage unit comprises a first hydrogen storage unit and a second hydrogen storage unit inserted in the first hydrogen storage unit, wherein the first hydrogen storage unit is a solid hydrogen storage material pyrolysis unit, and the second hydrogen storage unit is a solid hydrogen storage material hydrolysis unit;
the hydrogen outlet of the first hydrogen storage unit and the hydrogen outlet of the second hydrogen storage unit are connected to the hydrogen inlet of the fuel cell stack through the third hydrogen storage unit after being converged through a pipeline;
the anode tail gas port of the fuel cell stack is connected to the water inlet of the second hydrogen storage unit through a pipeline by an anode tail gas circulating pump;
and a fuel cell cathode radiator fan is arranged between the fuel cell stack and the modularized solid hydrogen storage unit in the solid hydrogen storage system.
2. The hydrogen power system according to claim 1, wherein the pipelines corresponding to the hydrogen outlet of the first hydrogen storage unit and the hydrogen outlet of the second hydrogen storage unit are respectively provided with a one-way valve;
and/or a first electromagnetic valve is arranged on the hydrogen inlet pipeline of the third hydrogen storage unit.
3. The hydrogen power system according to claim 2, wherein a second electromagnetic valve is provided on the hydrogen outlet pipe of the third hydrogen storage unit;
and/or a filter and a pressure stabilizing valve are arranged on the hydrogen outlet pipeline of the third hydrogen storage unit.
4. The hydrogen power system of claim 1, wherein a tail gas solenoid valve is provided on a line between an anode tail gas port of the fuel cell stack and the anode tail gas circulation pump.
5. The hydrogen power system of claim 1 wherein said solid state hydrogen storage system has an adjustable air inlet on a side of said fuel cell stack remote from said fuel cell cathode heat sink fan.
6. The hydrogen power system of claim 5, wherein said solid state hydrogen storage system has an adjustable air outlet on a side of said modular solid state hydrogen storage unit remote from said fuel cell cathode heat sink fan.
7. The hydrogen power system of claim 1, wherein the solid state hydrogen storage system is provided with a hydrogen charging port, and the hydrogen charging port is connected to the hydrogen charging port of the first hydrogen storage unit through a pipe.
8. The hydrogen power system of claim 1, wherein the hydrogen storage material in said first hydrogen storage unit is Fe-Ti alloy, la-Ni alloy, NH 3 BH 3 、AlH 3 Or MgH 2 ；
And/or the hydrogen storage materials in the second hydrogen storage unit are NaAlH4 and NaBH 4 、Mg(BH 4 ) 2 Or LiH.
9. The hydrogen power system according to claim 1, wherein the edge of the first hydrogen storage unit is provided with a plurality of heat radiation ribs extending in the axial direction;
and/or, the second hydrogen storage unit is columnar.
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