CN114046443A - Multi-platform compression type hydrogen storage device and manufacturing method of hydrogen storage sheet thereof - Google Patents
Multi-platform compression type hydrogen storage device and manufacturing method of hydrogen storage sheet thereof Download PDFInfo
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- CN114046443A CN114046443A CN202110880928.3A CN202110880928A CN114046443A CN 114046443 A CN114046443 A CN 114046443A CN 202110880928 A CN202110880928 A CN 202110880928A CN 114046443 A CN114046443 A CN 114046443A
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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
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
- F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/006—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of flat products, e.g. sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0084—Solid storage mediums characterised by their shape, e.g. pellets, sintered shaped bodies, sheets, porous compacts, spongy metals, hollow particles, solids with cavities, layered solids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
- B22F2007/042—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal characterised by the layer forming method
- B22F2007/047—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal characterised by the layer forming method non-pressurised baking of the paste or slurry containing metal powder
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- 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
- Y02E60/32—Hydrogen storage
Abstract
The invention discloses a multi-platform compression type hydrogen storage device and a manufacturing method of a hydrogen storage sheet thereof, the device comprises the hydrogen storage sheet, a hydrogen storage tank body, a filter sheet, a tank opening end enclosure and a valve, the hydrogen storage sheet is divided into three different platform pressure types of low pressure, medium pressure and high pressure, the hydrogen storage sheet is a regular and firm sheet structure directly filled into the hydrogen storage tank body, the hydrogen storage sheet comprises a metal foil material, a hydrogen storage alloy, a heat conducting agent and a binder, the filter sheet is arranged in the tank opening end enclosure in advance, when the hydrogen storage sheet is filled, a plurality of hydrogen storage sheets with different platform pressures are sequentially stacked in the hydrogen storage tank body according to a certain proportion, then the tank opening end enclosure is welded, and the valve is installed. The hydrogen discharge starting temperature is low, the residual storage capacity of hydrogen can be monitored according to the change of the air pressure, the hydrogen storage alloy can be ensured to be uniformly distributed all the time in the use process, the stress concentration caused by the local enrichment of the hydrogen storage alloy is avoided, the service life is prolonged, the filling is simple, and the hydrogen discharge starting temperature has good automation potential.
Description
Technical Field
The invention relates to the technical field of hydrogen storage, in particular to a multi-platform pressure type hydrogen storage device and a manufacturing method of a hydrogen storage sheet thereof.
Background
At present, there are three main ways of storing hydrogen that have been put into practical use: gaseous hydrogen storage, liquid hydrogen storage, and solid state hydrogen storage based on hydrogen storage alloys. Compared with other hydrogen storage modes, the solid-state hydrogen storage technology has the advantages of high hydrogen storage density, low pressure, good safety, high hydrogen purity and the like, and is an important direction for the development of the hydrogen storage technology. The solid hydrogen storage tank has similar shape to that of gaseous and liquid hydrogen storage tanks, except that hydrogen storage alloy is loaded inside the hydrogen storage tank. At present, the alloy hydrogen storage and hydrogen storage device has the following defects:
(1) problem of monitoring hydrogen storage amount
The hydrogen storage alloy has a stable platform pressure when releasing hydrogen, and this characteristic has decided solid-state hydrogen storage tank is at the in-process that uses, and the atmospheric pressure of hydrogen is more stable, is difficult to monitor the remaining hydrogen storage volume in the hydrogen storage tank in real time through the change of atmospheric pressure, and what appeared thereupon is that the time of filling hydrogen can't be arranged accurately, and when hydrogen was about to run out in the hydrogen storage alloy, the phenomenon that just appears with hydrogen atmospheric pressure sudden drop leads to unable smooth hydrogen supply.
(2) The heat quantity of hydrogen discharge starting is higher
A large amount of heat needs to be absorbed during the hydrogen discharge process. For example, the LaNi5 hydrogen storage alloy material is accompanied by 30.8kJ/molH during the hydrogen discharge process2Resulting in a sharp drop in the temperature of the material itself. The rapid reduction of the hydrogen platform pressure greatly reduces the hydrogen discharge speedAnd air pressure. When an external heat source is used for heating, the overall temperature rise of the hydrogen storage tank needs a long time, and the hydrogen pressure is low in the temperature rise process, so that hydrogen can not be supplied smoothly.
(3) The hydrogen absorption and expansion of the hydrogen storage alloy generate stress on the hydrogen storage tank
After the hydrogen storage alloy material is not uniformly filled initially or displacement is generated in the using process, local areas in the hydrogen storage device made of the hydrogen storage alloy material powder are enriched, and stress concentration of the local areas of the hydrogen storage tank body is caused, so that the hydrogen storage tank body is easier to generate plastic deformation in the areas until the hydrogen storage tank body is broken and fails. Therefore, the optimal design for ensuring the uniform distribution of the hydrogen storage alloy material powder is the key for ensuring the safe use and prolonging the service life of the solid-state hydrogen storage tank.
To sum up, how to develop a hydrogen storage tank which can monitor the hydrogen storage capacity and has low starting heat demand, and when realizing easy assembly, avoiding the deformation and failure of the hydrogen storage tank body caused by the local enrichment of the hydrogen tank becomes a problem to be solved urgently.
Disclosure of Invention
In order to overcome a series of defects in the prior art, the invention aims to provide a multi-platform compression type hydrogen storage device, which comprises a hydrogen storage sheet 1, a hydrogen storage tank body 2, a filter sheet 3, a tank opening end enclosure 4 and a valve 5, and is characterized in that the hydrogen storage sheet 1 is divided into three different platform pressure types of low pressure, medium pressure and high pressure, the hydrogen storage sheet 1 is a regular and firm sheet structure directly filled into the hydrogen storage tank body 2, the hydrogen storage sheet 1 comprises a metal foil, a hydrogen storage alloy, a heat conducting agent and a binder, the filter sheet 3 is arranged in the tank opening end enclosure 4 in advance, and when the hydrogen storage sheet 1 is filled, a plurality of hydrogen storage sheets 1 with different platform pressures are sequentially stacked in the hydrogen storage tank body 2 according to a certain proportion, then the tank opening end enclosure 4 is welded, and the valve 5 is installed.
Preferably, the difference of plateau pressures of the hydrogen storage sheets 1 of different plateau pressure types is not less than 0.2MPa at the same temperature.
Preferably, in the hydrogen storage sheet 1, the mass ratio of the hydrogen storage alloy material is between 80% and 95%, the mass ratio of the heat conducting agent is between 1% and 10%, the mass ratio of the binder is between 2% and 10%, and the thickness of the metal foil is between 6 μm and 25 μm.
Preferably, the hydrogen storage sheet 1 is a regular circular sheet, a regular hexagonal sheet, an octagonal sheet or a square sheet, the weight of the hydrogen storage sheet 1 is 5-150g, and the thickness of the hydrogen storage sheet 1 is 0.5-20 mm.
Preferably, the hydrogen storage sheet 1 is a circular sheet; the weight of the hydrogen storage sheet 1 is an integral multiple of 5 g.
Preferably, in the hydrogen storage sheet 1, the hydrogen storage alloy material is titanium-based AB2Type, titanium AB type, rare earth AB type3Rare earth system AB5Any one or more of type, titanium-vanadium solid solution, magnesium-based hydrogen storage alloy, coordination hydride, metal nitrogen hydride or ammonia borane; the heat conducting agent is one or a mixture of more of graphene, crystalline flake graphite, carbon nano tubes, mesocarbon microbeads, aluminum oxide, magnesium oxide, zinc oxide, aluminum nitride, boron nitride or silicon carbide; the binder is one or a mixture of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber and carboxymethyl cellulose.
Preferably, the material of the hydrogen storage tank body 2 is stainless steel or aluminum alloy; the length of the hydrogen storage tank body 2 is 50-200cm, the inner diameter is 5-20cm, and the filling quantity of the hydrogen storage sheets 1 in the hydrogen storage tank body 2 is 10-500; the material of the filter plate 3 is a powder metallurgy sintering porous material or a metal wire screen structure.
Preferably, the material of the hydrogen storage tank body 2 is 316L stainless steel or 6061 aluminum alloy; the filtering precision of the filter plate 3 is between 0.1 and 5 microns.
The invention also aims to provide a method for manufacturing the hydrogen storage sheet 1, which comprises the following steps:
s1, mixing
Adding hydrogen storage alloy powder, a heat conducting agent and a binder into mixing equipment at the same time, and obtaining uniformly distributed premixed powder in a batch mixing mode;
s2 pulping
Adding the uniformly premixed powder batch-mixed in the step S1 into a solvent, and stirring and mixing to obtain uniform and stable slurry;
s3, coating and drying
Coating the slurry prepared in the step S2 on a metal foil, and drying to finally obtain a coiled hydrogen storage sheet 1;
s4, roll pressing
Rolling the hydrogen storage sheet 1 rolled in step S3 to obtain a flat hydrogen storage sheet 1 having a uniform thickness;
s5, slicing
And cutting the hydrogen storage sheets 1 leveled in the step S4 into hydrogen storage sheets 1 with the same size by adopting a die cutter or a sheet cutter.
Preferably, in step S1, in the batch mixing process, the hydrogen storage alloy powder, the heat conducting agent, and the binder need to be added simultaneously;
in step S2, the premixed powder is added into a solvent with a certain mass in batches, and a double-planet stirrer is adopted for stirring and mixing;
in step S2, the selected solvent is one or a mixture of several of nitrogen methyl pyrrolidone, isopropanol, ethanol or deionized water;
in step S3, a transfer type or extrusion type coating machine is adopted to coat the slurry on the metal foil, and the slurry directly enters an oven to be dried during drying;
in step S6, filling the hydrogen storage sheets 1 from bottom to top in sequence, welding the tank mouth end enclosure for sealing after the expected filling quantity is reached, and welding a filter sheet on the tank mouth end enclosure for filtering fine particles in the hydrogen storage tank;
according to the steps S1-S5, hydrogen storage sheets 1 with low pressure, medium pressure and high pressure of three different plateau pressures are respectively prepared in sequence.
Compared with the prior art, the invention has the following beneficial effects:
the invention has provided a multi-platform die mould hydrogen storage device and its hydrogen storage slice preparation method, mix the hydrogen storage alloy material, heat-conducting agent, agglomerant of different platform pressures to stir and disperse evenly respectively, stir and obtain the hydrogen storage slurry, and then coat, dry, roll and get the hydrogen storage slice with different platform pressures, and then pack the hydrogen storage slice with different platform pressures into the hydrogen storage tank according to certain proportion, through the hydrogen storage slice prepared in the invention, guarantee the homogeneity of filling of the hydrogen storage alloy, can avoid the hydrogen storage alloy in absorbing and releasing the pulverization of the hydrogen course to drop effectively at the same time, guarantee the hydrogen storage alloy keeps distributing evenly all the time in the course of using, avoid the stress concentration caused by partial enrichment of the hydrogen storage alloy, improve service life; the hydrogen release starting temperature of the high-platform-pressure hydrogen storage alloy material in the hydrogen storage tank is low, the high-platform-pressure hydrogen storage alloy material can enter a rapid hydrogen release stage in a short time, and before the optimal hydrogen release temperature is reached, the hydrogen is preferentially released by the hydrogen storage sheet with relatively high platform pressure, so that the use requirement is met. With the gradual rise of the temperature, the hydrogen storage sheet with relatively low platform pressure also starts to release hydrogen, and the starting process of the hydrogen storage tank does not need to be subjected to a temperature rise process in advance; the hydrogen storage sheets with different platform pressures are sequentially discharged, and occupy different platform pressures from high to low respectively, and the hydrogen storage sheets in the hydrogen storage tank are designed in advance, so that the residual hydrogen amount in the hydrogen storage tank can be approximately obtained according to the change of the hydrogen pressure.
Drawings
Fig. 1 is a schematic structural view of a multi-platform pressure-type hydrogen storage tank according to the present invention.
The reference numbers in the figures are:
1-hydrogen storage sheet, 2-hydrogen storage tank body, 3-filter sheet, 4-tank mouth end socket and 5-valve.
Detailed Description
In order to make the implementation objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be described in more detail below with reference to the accompanying drawings in the embodiments of the present invention. In the drawings, the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The described embodiments are only some, but not all embodiments of the invention.
All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiments and the directional terms described below with reference to the drawings are exemplary and intended to be used in the explanation of the invention, and should not be construed as limiting the invention.
In a wide embodiment of the invention, the multi-platform compression type hydrogen storage device comprises a hydrogen storage sheet 1, a hydrogen storage tank body 2, a filter sheet 3, a tank opening end enclosure 4 and a valve 5, and is characterized in that the hydrogen storage sheet 1 is divided into three different platform pressure types of low pressure, medium pressure and high pressure, the hydrogen storage sheet 1 is a regular and firm sheet structure directly filled into the hydrogen storage tank body 2, the hydrogen storage sheet 1 comprises a metal foil, a hydrogen storage alloy, a heat conducting agent and a binder, the filter sheet 3 is arranged in the tank opening end enclosure 4 in advance, and when the hydrogen storage sheet 1 is filled, the hydrogen storage sheets 1 with different platform pressures are firstly stacked in sequence in the hydrogen storage tank body 2 according to a certain proportion, then the tank opening end enclosure 4 is welded, and the valve 5 is installed.
Preferably, the difference of plateau pressures of the hydrogen storage sheets 1 of different plateau pressure types is not less than 0.2MPa at the same temperature.
Preferably, in the hydrogen storage sheet 1, the mass ratio of the hydrogen storage alloy material is between 80% and 95%, the mass ratio of the heat conducting agent is between 1% and 10%, the mass ratio of the binder is between 2% and 10%, and the thickness of the metal foil is between 6 μm and 25 μm.
Preferably, the hydrogen storage sheet 1 is a regular circular sheet, a regular hexagonal sheet, an octagonal sheet or a square sheet, the weight of the hydrogen storage sheet 1 is 5-150g, and the thickness of the hydrogen storage sheet 1 is 0.5-20 mm.
Preferably, the hydrogen storage sheet 1 is a circular sheet; the weight of the hydrogen storage sheet 1 is an integral multiple of 5 g.
Preferably, in the hydrogen storage sheet 1, the hydrogen storage alloy material is titanium-based AB2Type, titanium AB type, rare earth AB type3Rare earth system AB5Any one or more of type, titanium-vanadium solid solution, magnesium-based hydrogen storage alloy, coordination hydride, metal nitrogen hydride or ammonia borane; the heat conducting agent is one or a mixture of more of graphene, crystalline flake graphite, carbon nano tubes, mesocarbon microbeads, aluminum oxide, magnesium oxide, zinc oxide, aluminum nitride, boron nitride or silicon carbide; the binder is one or a mixture of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber and carboxymethyl cellulose.
Preferably, the material of the hydrogen storage tank body 2 is stainless steel or aluminum alloy; the length of the hydrogen storage tank body 2 is 50-200cm, the inner diameter is 5-20cm, and the filling quantity of the hydrogen storage sheets 1 in the hydrogen storage tank body 2 is 10-500; the material of the filter plate 3 is a powder metallurgy sintering porous material or a metal wire screen structure.
Preferably, the material of the hydrogen storage tank body 2 is 316L stainless steel or 6061 aluminum alloy; the filtering precision of the filter plate 3 is between 0.1 and 5 microns.
The invention also aims to provide a method for manufacturing the hydrogen storage sheet 1, which comprises the following steps:
s1, mixing
Adding hydrogen storage alloy powder, a heat conducting agent and a binder into mixing equipment at the same time, and obtaining uniformly distributed premixed powder in a batch mixing mode;
s2 pulping
Adding the uniformly premixed powder batch-mixed in the step S1 into a solvent, and stirring and mixing to obtain uniform and stable slurry;
s3, coating and drying
Coating the slurry prepared in the step S2 on a metal foil, and drying to finally obtain a coiled hydrogen storage sheet 1;
s4, roll pressing
Rolling the hydrogen storage sheet 1 rolled in step S3 to obtain a flat hydrogen storage sheet 1 having a uniform thickness;
s5, slicing
And cutting the hydrogen storage sheets 1 leveled in the step S4 into hydrogen storage sheets 1 with the same size by adopting a die cutter or a sheet cutter.
Preferably, in step S1, in the batch mixing process, the hydrogen storage alloy powder, the heat conducting agent, and the binder need to be added simultaneously;
in step S2, the premixed powder is added into a solvent with a certain mass in batches, and a double-planet stirrer is adopted for stirring and mixing;
in step S2, the selected solvent is one or a mixture of several of nitrogen methyl pyrrolidone, isopropanol, ethanol or deionized water;
in step S3, a transfer type or extrusion type coating machine is adopted to coat the slurry on the metal foil, and the slurry directly enters an oven to be dried during drying;
in step S6, filling the hydrogen storage sheets 1 from bottom to top in sequence, welding the tank mouth end enclosure for sealing after the expected filling quantity is reached, and welding a filter sheet on the tank mouth end enclosure for filtering fine particles in the hydrogen storage tank;
according to the steps S1-S5, hydrogen storage sheets 1 with low pressure, medium pressure and high pressure of three different plateau pressures are respectively prepared in sequence.
The present invention will be described in further detail below with reference to the accompanying drawings, which illustrate embodiments of the present invention.
Example 1
A multi-platform compression type hydrogen storage device comprises the following specific manufacturing processes and structures:
(1) preparation of Hydrogen storage sheets 1 of different plateau pressures
Preparing a low-pressure hydrogen storage sheet:
hydrogen storage alloy powder (rare earth hydrogen storage alloy material with room temperature hydrogen discharge platform pressure of 0.2 MPa), heat conducting agent and binder are mixed according to the proportion of 88: 7: 5, mixing in batches; the hydrogen storage alloy powder of the embodiment is rare earth AB5 type, the heat conducting agent is graphene, the binder is polyvinylidene fluoride (PVDF), and the solvent is nitrogen methyl pyrrolidone (NMP for short). Preparing a low-pressure hydrogen storage sheet with the diameter of 80mm and the thickness of 2mm by the working procedures of homogenizing, coating, drying, rolling and cutting;
preparation of medium pressure hydrogen storage sheet
Mixing hydrogen storage alloy powder (titanium hydrogen storage alloy material with room temperature hydrogen release platform pressure of 0.8 MPa), heat conducting agent and binder in a proportion of 88: 7: 5, mixing in batches; the hydrogen storage alloy powder of the embodiment is titanium AB2 type, the heat conducting agent is graphene, the binder is polyvinylidene fluoride (PVDF), and the solvent is nitrogen methyl pyrrolidone (NMP for short). Preparing a medium-pressure hydrogen storage sheet with the diameter of 80mm and the thickness of 2mm by the working procedures of homogenizing, coating, drying, rolling and cutting;
preparation of high pressure hydrogen storage sheet
Hydrogen storage alloy powder (rare earth-calcium-titanium-nickel hydrogen storage alloy material with room temperature hydrogen discharge platform pressure of 1.4 MPa), heat conducting agent and binder are mixed according to the weight ratio of 88: 7: 5, mixing in batches; the hydrogen storage alloy powder of the embodiment is titanium AB2 type, the heat conducting agent is graphene, the binder is polyvinylidene fluoride (PVDF), and the solvent is nitrogen methyl pyrrolidone (NMP for short). Preparing a high-pressure hydrogen storage sheet with the diameter of 80mm and the thickness of 2mm by the working procedures of homogenizing, coating, drying, rolling and cutting;
(2) structure of hydrogen storage tank 2
Referring to the structure of the attached figure 1, the hydrogen storage tank body 2 has the diameter of 10cm, the wall thickness of 3mm and the length of 70cm, hydrogen storage sheets 1 with different platform pressures are sequentially arranged, finally, a tank opening end enclosure 4 is welded, a valve 5 is installed, and a filter sheet 3 is welded on the tank opening end enclosure 4 in advance.
(3) Arrangement of hydrogen storage sheets 1
The hydrogen storage sheets 1 are stacked in this order from the bottom to the top, and are first loaded with 10 low-pressure hydrogen storage sheets having a height of 20cm in total, then with 10 medium-pressure hydrogen storage sheets having a height of 20cm in total, and finally with 10 high-pressure hydrogen storage sheets having a height of 20cm in total. Finally, 30 hydrogen storage sheets 1 were loaded to a height of about 60 cm.
The hydrogen storage device is easy to fill and has no dust flying phenomenon. After repeated hydrogen charging and discharging cycles, the hydrogen storage tank body 2 has no abnormal deformation and has stable integral structure.
Example 2
A multi-platform compression type hydrogen storage device comprises the following specific manufacturing processes and structures:
(1) preparation of Hydrogen storage sheets 1 of different plateau pressures
Preparing a low-pressure hydrogen storage sheet:
mixing hydrogen storage alloy powder (rare earth hydrogen storage alloy material with room temperature hydrogen discharge platform pressure of 0.6 MPa), heat conducting agent and binder in a proportion of 88: 7: 5, mixing in batches; the hydrogen storage alloy powder of the embodiment is rare earth AB5 type, the heat conducting agent is flake graphite, the binder is styrene butadiene rubber and sodium carboxymethyl cellulose (SBR and CMC-Na), and the solvent is deionized water. Preparing a low-pressure hydrogen storage sheet with the diameter of 60mm and the thickness of 5mm by the working procedures of homogenizing, coating, drying, rolling and cutting;
preparation of medium pressure hydrogen storage sheet
Hydrogen storage alloy powder (titanium hydrogen storage alloy material with room temperature hydrogen release platform pressure of 1.2 MPa), heat conducting agent and binder are mixed in a proportion of 88: 7: 5, mixing in batches; the hydrogen storage alloy powder of the embodiment is titanium AB2 type, the heat conducting agent is flake graphite, the binder is styrene butadiene rubber and sodium carboxymethyl cellulose (SBR and CMC-Na), and the solvent is deionized water. Preparing a medium-pressure hydrogen storage sheet with the diameter of 60mm and the thickness of 5mm by the procedures of homogenizing, coating, drying, rolling and cutting;
preparation of high pressure hydrogen storage sheet
Hydrogen storage alloy powder (rare earth-calcium-nickel hydrogen storage alloy material with room temperature hydrogen discharge platform pressure of 2.4 MPa), heat conducting agent and binder are mixed according to the proportion of 88: 7: 5, mixing in batches; the hydrogen storage alloy powder of the embodiment is rare earth-calcium-nickel Mm1-xCaxNi5 type, the heat conducting agent is crystalline flake graphite, the binder is styrene butadiene rubber and sodium carboxymethylcellulose (SBR and CMC-Na), and the solvent is deionized water. Preparing hydrogen storage sheets with the diameter of 60mm and the thickness of 5mm by the procedures of homogenizing, coating, drying, rolling and cutting;
(2) structure of hydrogen storage tank 2
Referring to the structure of the attached figure 1, the hydrogen storage tank body 2 with the diameter of 8cm, the wall thickness of 3mm and the length of 200cm is sequentially filled with hydrogen storage sheets 1 with different platform pressures, finally, a tank opening end enclosure 4 is welded, a valve 5 is installed, and a filter sheet 3 is welded on the tank opening end enclosure 4 in advance.
(3) Arrangement of hydrogen storage sheets 1
The hydrogen storage sheets 1 are sequentially stacked from bottom to top, one low-pressure hydrogen storage sheet, one medium-pressure hydrogen storage sheet and one high-pressure hydrogen storage sheet are sequentially stacked, every three hydrogen storage sheets are 1 group, and the hydrogen storage sheets are sequentially filled in the hydrogen storage tank body 2. 120 low-pressure hydrogen storage sheets, 120 medium-pressure hydrogen storage sheets and 120 high-pressure hydrogen storage sheets are loaded, and the total number is 120. Finally, 360 hydrogen storage sheets 1 were charged, and the total height was about 180 cm.
The hydrogen storage device is easy to fill and has no dust flying phenomenon. After repeated hydrogen charging and discharging cycles, the hydrogen storage tank body 2 has no abnormal deformation and has stable integral structure.
Finally, it should be pointed out that: the above examples are only for illustrating the technical solutions of the present invention, and are not limited thereto. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The utility model provides a many platforms die mould hydrogen storage device, includes hydrogen storage sheet (1), the hydrogen storage tank body (2), cassette (3), jar mouth head (4) and valve (5), its characterized in that, hydrogen storage sheet (1) divide into low pressure, middling pressure and the three different platform pressure type of high pressure, hydrogen storage sheet (1) is for directly filling regular firm lamellar structure in the hydrogen storage tank body (2), hydrogen storage sheet (1) includes metal foil, hydrogen storage alloy, heat-conducting agent and binder, and cassette (3) set up in advance in jar mouth head (4), when filling hydrogen storage sheet (1), stack hydrogen storage sheet (1) that a plurality of different platforms pressed with certain proportion in proper order after the inside of the hydrogen storage tank body (2), weld jar mouth head (4) again and install valve (5).
2. The hydrogen storage device of multiple plateau pressures of claim 1, wherein the difference of plateau pressures of hydrogen storage sheets (1) of different plateau pressure types is not less than 0.2MPa at the same temperature.
3. The multi-platform profiled hydrogen storage device according to claim 1, wherein in the hydrogen storage sheet (1), the mass ratio of the hydrogen storage alloy material is between 80% and 95%, the mass ratio of the heat conducting agent is between 1% and 10%, the mass ratio of the binder is between 2% and 10%, and the thickness of the metal foil is between 6 μm and 25 μm.
4. The multi-platform pressure type hydrogen storage device according to claim 1, wherein the hydrogen storage sheet (1) is a regular circular sheet, a regular hexagonal sheet, an octagonal sheet or a square sheet, the weight of the hydrogen storage sheet (1) is 5-150g, and the thickness of the hydrogen storage sheet (1) is 0.5-20 mm.
5. The multi-platform profiled hydrogen storage device according to claim 4, wherein the hydrogen storage sheet (1) is a circular sheet; the weight of the hydrogen storage sheet (1) is an integral multiple of 5 g.
6. The multi-platform profiled hydrogen storage device as claimed in claim 1, wherein in the hydrogen storage sheet (1), the hydrogen storage alloy material is titanium AB2Type, titanium AB type, rare earth AB type3Rare earth system AB5Any one or more of type, titanium-vanadium solid solution, magnesium-based hydrogen storage alloy, coordination hydride, metal nitrogen hydride or ammonia borane; the heat conducting agent is one or a mixture of more of graphene, crystalline flake graphite, carbon nano tubes, mesocarbon microbeads, aluminum oxide, magnesium oxide, zinc oxide, aluminum nitride, boron nitride or silicon carbide; the binder is one or a mixture of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber and carboxymethyl cellulose.
7. The multi-platform profiled hydrogen storage device as claimed in claim 1, wherein the material of the hydrogen storage tank (2) is stainless steel or aluminum alloy; the length of the hydrogen storage tank body (2) is 50-200cm, the inner diameter is 5-20cm, and the filling quantity of the hydrogen storage sheets (1) in the hydrogen storage tank body (2) is 10-500; the material of the filter sheet (3) is a powder metallurgy sintering porous material or a metal wire screen structure.
8. The multi-platform pressure type hydrogen storage device according to claim 7, wherein the material of the hydrogen storage tank (2) is 316L stainless steel or 6061 aluminum alloy; the filtering precision of the filter plate (3) is between 0.1 and 5 microns.
9. The multi-platform-type hydrogen storage device as claimed in any one of claims 1 to 8, wherein the manufacturing method of the hydrogen storage sheet comprises the following steps:
s1, mixing
Adding hydrogen storage alloy powder, a heat conducting agent and a binder into mixing equipment at the same time, and obtaining uniformly distributed premixed powder in a batch mixing mode;
s2 pulping
Adding the uniformly premixed powder batch-mixed in the step S1 into a solvent, and stirring and mixing to obtain uniform and stable slurry;
s3, coating and drying
Coating the slurry prepared in the step S2 on a metal foil, and drying to finally obtain a coiled hydrogen storage sheet (1);
s4, roll pressing
Rolling the rolled hydrogen storage sheet (1) in the step S3 to obtain a flat hydrogen storage sheet (1) with uniform thickness;
s5, slicing
And cutting the hydrogen storage sheets (1) leveled in the step S4 into hydrogen storage sheets (1) with the same size by adopting a die cutter or a sheet cutter.
10. The hydrogen storage device of claim 9, wherein the hydrogen storage device is a multi-stage type hydrogen storage device,
in step S1, hydrogen storage alloy powder, a heat conducting agent, and a binder need to be added simultaneously during batch mixing;
in step S2, the premixed powder is added into a solvent with a certain mass in batches, and a double-planet stirrer is adopted for stirring and mixing;
in step S2, the selected solvent is one or a mixture of several of nitrogen methyl pyrrolidone, isopropanol, ethanol or deionized water;
in step S3, a transfer type or extrusion type coating machine is adopted to coat the slurry on the metal foil, and the slurry directly enters an oven to be dried during drying;
in the step S6, filling the hydrogen storage sheets (1) from bottom to top in sequence, welding the tank mouth end enclosure for sealing after the expected filling quantity is reached, and welding a filter sheet on the tank mouth end enclosure for filtering fine particles in the hydrogen storage tank body;
according to the steps S1-S5, hydrogen storage sheets (1) with low pressure, medium pressure and high pressure different plateau pressures are respectively prepared in sequence.
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