CN116514055A - Composite hydrogen storage membrane material, preparation method thereof and hydrogen storage tank - Google Patents
Composite hydrogen storage membrane material, preparation method thereof and hydrogen storage tank Download PDFInfo
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- CN116514055A CN116514055A CN202310764357.6A CN202310764357A CN116514055A CN 116514055 A CN116514055 A CN 116514055A CN 202310764357 A CN202310764357 A CN 202310764357A CN 116514055 A CN116514055 A CN 116514055A
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- hydrogen storage
- vanadium
- layer
- substrate
- niobium
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 239000001257 hydrogen Substances 0.000 title claims abstract description 160
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 160
- 238000003860 storage Methods 0.000 title claims abstract description 127
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000012528 membrane Substances 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 327
- 239000002184 metal Substances 0.000 claims abstract description 327
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 187
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 187
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 132
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 130
- 239000010955 niobium Substances 0.000 claims abstract description 130
- 239000000758 substrate Substances 0.000 claims abstract description 97
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000004544 sputter deposition Methods 0.000 claims description 65
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 238000000151 deposition Methods 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- -1 vanadium hydride Chemical compound 0.000 abstract description 21
- 239000000843 powder Substances 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 253
- 230000007547 defect Effects 0.000 description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009832 plasma treatment Methods 0.000 description 3
- 238000005488 sandblasting Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
-
- 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
- F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
-
- 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
- F17C2203/00—Vessel construction, in particular walls or details thereof
- F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
- F17C2203/0634—Materials for walls or layers thereof
- F17C2203/0636—Metals
-
- 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
- F17C2203/00—Vessel construction, in particular walls or details thereof
- F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
- F17C2203/0634—Materials for walls or layers thereof
- F17C2203/0658—Synthetics
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The present disclosure provides a composite hydrogen storage membrane material, a method of preparing the same, and a hydrogen storage tank. The composite hydrogen storage membrane material comprises: the hydrogen storage layer is covered on the substrate and comprises a plurality of vanadium metal layers and a plurality of niobium metal layers, the vanadium metal layers and the niobium metal layers are sequentially and alternately laminated on the substrate, and the adjacent vanadium metal layers and the adjacent niobium metal layers are in contact with each other. This aspect can reduce the stability of the vanadium hydride, making the hydrogen easier to absorb and release. On the other hand, the vanadium metal layer can be supported by means of the niobium metal layer so as to maintain the overall structural stability of the vanadium metal layer, the problem of powder removal of the vanadium metal layer caused by volume change is prevented, and the reversibility of hydrogen storage of the vanadium metal layer is further improved.
Description
Technical Field
The invention relates to the technical field of hydrogen storage, in particular to a composite hydrogen storage membrane material, a preparation method thereof and a hydrogen storage tank.
Background
Hydrogen energy is an important secondary energy source, hydrogen can be obtained by electrolyzing water, the combustion product of hydrogen is water, and hydrogen also has the advantage of high combustion heat value, so that the hydrogen energy is considered to be a clean energy source which is suitable for sustainable development. In addition, the hydrogen energy has the advantages of convenient movement and wide application range, so the hydrogen energy is expected to become a supplementary energy source of an electric energy system.
How to store hydrogen efficiently and safely is an important factor limiting the further development of hydrogen energy. Current hydrogen storage modes include gaseous hydrogen storage, liquid hydrogen storage and solid hydrogen storage. Gaseous hydrogen storage refers to storing hydrogen gas in a high pressure resistant container after compression, but this has high requirements on the performance of the container itself. Liquid hydrogen storage refers to storage of hydrogen after pressurized liquefaction, which also has high requirements on the container and also presents a great safety hazard. Solid hydrogen storage refers to filling a hydrogen storage tank with a metal powder material capable of reacting with hydrogen gas, then injecting hydrogen gas into the hydrogen storage tank and combining the hydrogen gas with the metal powder material by, for example, pressurizing or cooling. The hydrogen storage material is heated to release hydrogen gas from the metal powder material when needed for use.
Compared with other metals capable of absorbing hydrogen, the metal vanadium has a higher hydrogen storage capacity, but hydrogen storage through the metal vanadium has a problem of poor reversibility of hydrogen storage.
Disclosure of Invention
In view of this, in order to improve the reversibility of hydrogen storage of metal vanadium and to increase the rate of hydrogen absorption and release of metal vanadium, it is necessary to provide a composite hydrogen storage membrane material.
According to some embodiments of the present disclosure, there is provided a composite hydrogen storage membrane comprising: the hydrogen storage device comprises a substrate and a hydrogen storage layer arranged on the substrate, wherein the substrate is a flexible substrate, the substrate and the hydrogen storage layer are integrally provided with a multi-layer curled structure, the hydrogen storage layer is covered on the substrate and comprises a plurality of vanadium metal layers and a plurality of niobium metal layers, the vanadium metal layers and the niobium metal layers are sequentially and alternately laminated on the substrate, and the adjacent vanadium metal layers and the niobium metal layers are mutually contacted.
In some embodiments of the present disclosure, the thickness of the vanadium metal layer is 5nm to 20nm.
In some embodiments of the present disclosure, the thickness of the niobium metal layer is 1nm to 10nm.
In some embodiments of the present disclosure, the hydrogen storage layer has a porosity of 10% -50%.
In some embodiments of the disclosure, the layer furthest from the substrate in the hydrogen storage layer is the niobium metal layer.
Further, the present disclosure also provides a method for preparing the composite hydrogen storage membrane material according to any one of the above embodiments, which includes the following steps:
providing the substrate;
sputtering vanadium metal and niobium metal on the substrate a plurality of times to form a plurality of layers of the niobium metal and a plurality of layers of the vanadium metal, respectively, the vanadium metal and the niobium metal being alternately sputtered during the sputtering.
In some embodiments of the present disclosure, when sputtering niobium metal on the vanadium metal layer that has been prepared, the sputtering power is controlled such that niobium atoms are embedded in the vanadium metal layer.
In some embodiments of the present disclosure, in the step of sputtering vanadium metal, the power density of the sputtering is controlled to be 10W/cm 2 ~20W/cm 2 。
In some embodiments of the present disclosure, in the step of sputtering niobium metal, the power density of sputtering is controlled to be 15W/cm 2 ~30W/cm 2 。
In some embodiments of the present disclosure, during the sputtering of vanadium metal multiple times and the sputtering of niobium metal multiple times, further comprising the steps of:
introducing a gasifying agent into the deposition chamber to enable the gasifying agent to be attached to the vanadium metal layer or the niobium metal layer which is prepared in advance;
and continuing to alternately sputter vanadium metal and niobium metal on the vanadium metal layer or the niobium metal layer attached with the gasifying agent, and then carrying out heating treatment on the substrate to volatilize the gasifying agent.
In some embodiments of the present disclosure, the step of introducing a gasifying agent into the deposition chamber is performed after sputtering the vanadium metal such that the gasifying agent adheres to the previously prepared vanadium metal layer.
In some embodiments of the present disclosure, the gasifying agent is water.
According to still further embodiments of the present disclosure, there is also provided a hydrogen storage tank including a tank body and the composite hydrogen storage membrane material according to any one of the above embodiments, the composite hydrogen storage membrane material being disposed in the tank body.
The composite hydrogen storage membrane material comprises a substrate and a hydrogen storage layer arranged on the substrate, wherein the substrate and the hydrogen storage layer are integrally provided with a multi-layer coiled structure, and the hydrogen storage layer is covered on the substrate in a copying manner. The hydrogen storage layer comprises vanadium metal layers and niobium metal layers which are sequentially and alternately laminated, and the adjacent vanadium metal layers and the adjacent niobium metal layers are in contact with each other.
Compared with single vanadium metal, by arranging the niobium metal layers alternating with the vanadium metal layers, an alloy-like structure can be formed at the interface between the niobium metal layers and the vanadium metal layers, and lattice defects can be generated in the vanadium metal layers. Further, the vanadium metal layers and the niobium metal layers which are alternately laminated are arranged on the substrate and integrally form a multi-layer curled structure, so that the overall effective hydrogen absorption area of the hydrogen storage layer can be effectively improved, the vanadium metal layers close to the substrate can be structurally deformed through the curled structure, and overall lattice defects are increased. This aspect can reduce the stability of the vanadium hydride, making the hydrogen easier to absorb and release. On the other hand, the vanadium metal layer can be supported by means of the niobium metal layer so as to maintain the overall structural stability of the vanadium metal layer, the problem of powder removal of the vanadium metal layer caused by volume change is prevented, and the reversibility of hydrogen storage of the vanadium metal layer is further improved.
Drawings
FIG. 1 is a schematic structural diagram of a composite hydrogen storage membrane;
FIG. 2 is a schematic cross-sectional view of a multi-layered coiled structure formed from the composite hydrogen storage membrane of FIG. 1;
FIG. 3 is a schematic illustration of steps of a method of making a composite hydrogen storage membrane;
wherein, each reference sign and meaning are as follows:
100. a substrate; 110. a hydrogen storage layer; 111. a vanadium metal layer; 112. a niobium metal layer.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items, and "multiple" as used herein includes two or more of the items.
In the present invention, the sum of the parts of the components in the composition may be 100 parts by weight, if not stated to the contrary. Unless otherwise indicated, the percentages (including weight percent) of the present invention are based on the total weight of the composition, and, in addition, "wt%" herein means mass percent and "at%" means atomic percent.
In this context, unless otherwise indicated, the individual reaction steps may or may not be performed in the order herein. For example, other steps may be included between the respective reaction steps, and the order of the reaction steps may be appropriately changed. This can be determined by the skilled person based on routine knowledge and experience. Preferably, the reaction processes herein are performed sequentially.
The vanadium metal, after absorbing hydrogen, is capable of forming three hydrides in succession, respectively vanadium hydride (V 2 H) Vanadium Hydride (VH) and vanadium dihydride (VH) 2 ). At the beginning of the absorption of hydrogenWhen the hydrogen molecules are adsorbed on the surface of vanadium metal, the hydrogen molecules break bonds to form hydrogen atoms, and the hydrogen atoms diffuse into the lattice of the vanadium metal and form an interstitial solid solution. When the metal vanadium absorbs hydrogen, firstly forming less hydrogen vanadium hydride, then forming vanadium hydride, and finally forming hydrogen-rich vanadium dioxide. On release of hydrogen, vanadium dioxide loses hydrogen atoms and forms vanadium or vanadium hydride, which is more stable, and vanadium metal can release only about half of the hydrogen in general, which limits its practical hydrogen storage capacity. In addition, there is also a mismatch problem between the lattices of the vanadium metal and the hydride of the vanadium metal, which leads to pulverization of the vanadium metal and eventually to loss of the hydrogen storage amount.
In order to improve hydrogen storage reversibility of vanadium, the present disclosure provides a composite hydrogen storage membrane material, comprising: the hydrogen storage layer is formed by laminating a plurality of vanadium metal layers and a plurality of niobium metal layers alternately in sequence, and the adjacent vanadium metal layers and the adjacent niobium metal layers are in contact with each other.
Compared with single vanadium metal, by arranging the niobium metal layers alternating with the vanadium metal layers, an alloy-like structure can be formed at the interface between the niobium metal layers and the vanadium metal layers, and lattice defects can be generated in the vanadium metal layers. Further, the vanadium metal layers and the niobium metal layers which are alternately laminated are arranged on the substrate and integrally form a multi-layer curled structure, so that the overall effective hydrogen absorption area of the hydrogen storage layer can be effectively improved, the vanadium metal layers close to the substrate can be structurally deformed through the curled structure, and overall lattice defects are increased. This aspect can reduce the stability of the vanadium hydride, making the hydrogen easier to absorb and release. On the other hand, the vanadium metal layer can be supported by means of the niobium metal layer so as to maintain the overall structural stability of the vanadium metal layer, the problem of powder removal of the vanadium metal layer caused by volume change is prevented, and the reversibility of hydrogen storage of the vanadium metal layer is further improved.
Fig. 1 of the present disclosure provides a schematic structural diagram of a composite hydrogen storage membrane. Referring to fig. 1, the composite hydrogen storage membrane material comprises a substrate 100 and a hydrogen storage layer 110 arranged on the substrate 100, wherein the hydrogen storage layer 110 is profiled and covered on the substrate 100, the hydrogen storage layer 110 comprises a plurality of vanadium metal layers 111 and a plurality of niobium metal layers 112, the vanadium metal layers 111 and the niobium metal layers 112 are sequentially and alternately laminated and arranged on the substrate 100, and adjacent vanadium metal layers 111 and niobium metal layers 112 are mutually contacted. The ellipses therein represent a plurality of vanadium metal layers 111 and a plurality of niobium metal layers 112 alternately stacked.
It will be appreciated that the contact between the adjacent vanadium metal layers 111 and the niobium metal layer 112 corresponds to the introduction of niobium metal between the multiple vanadium metal layers 111, which can cause defects in the crystal lattice of the vanadium metal layers 111, and further reduce the stability of vanadium hydride or vanadium hydride, so that hydrogen in the vanadium hydride or vanadium hydride is more easily released. In addition, the niobium metal layer 112 and the vanadium metal layer 111 may be prepared by deposition, for example, physical vapor deposition, which makes it easier to prepare both the vanadium metal layer 111 and the niobium metal layer 112 compared to the casting method in the conventional art.
In some examples of this embodiment, each vanadium metal layer 111 may be a continuous film, meaning that the vanadium metal layer 111 is entirely overlaid on the substrate 100 or entirely overlaid on other metal layers located below. Further, each niobium metal layer 112 may be a continuous or discontinuous film. When the niobium metal layer 112 is a discontinuous film layer, the niobium metal layer 112 may include a plurality of spaced apart islands of niobium metal.
It is understood that the vanadium metal layer 111 refers to the vanadium metal layer 111 containing vanadium metal, and the vanadium metal layer 111 may also contain other metal atoms. The niobium metal layer 112 refers to that the niobium metal layer 112 contains niobium metal, and the niobium metal layer 112 may contain other metal atoms. In some examples of this embodiment, the vanadium metal layer 111 may contain niobium metal atoms, and by further doping the niobium metal atoms in the vanadium metal layer 111, the lattice defects in the vanadium metal layer 111 can be further improved, and the stability of vanadium hydride or vanadium hydride can be further reduced.
In some examples of this embodiment, the thickness of each vanadium metal layer 111 may be 5 nm-100 nm. By setting the thickness of each vanadium metal layer 111 to 100nm or less, it is possible to make the inside of the vanadium metal layer 111 closer to the adjacent niobium metal layer 112 and to make the vanadium metal layer 111 have relatively more defects therein. By setting the thickness of the vanadium metal layer 111 to be more than 5nm, the preparation of the vanadium metal layer 111 is facilitated to form a continuous film layer, so that the vanadium metal layer 111 has higher hydrogen storage capacity.
Further, the thickness of each vanadium metal layer 111 may be 5nm, 10nm, 20nm, 30nm, 50nm, 80nm, or 100nm. Further, the thickness of each vanadium metal layer 111 may be in a range between any two of the above thicknesses.
In some examples of this embodiment, each niobium metal layer 112 may be 1nm to 10nm thick. The main function of the niobium metal layer 112 is to embed into the vanadium metal layer 111 to introduce lattice defects, and the thickness of the niobium metal layer 112 is set to be 1 nm-10 nm, so that the introduced amount of the niobium metal layer 112 can be reduced as much as possible, the diffusion of hydrogen atoms between adjacent vanadium metal layers 111 is facilitated, and the overall hydrogen storage capacity of the composite hydrogen storage membrane material is improved.
Further, the thickness of each niobium metal layer 112 may be 1nm, 2nm, 3nm, 5nm, 7nm, or 10nm. Further, the thickness of each niobium metal layer 112 may be in a range between any two of the above thicknesses.
In some examples of this embodiment, the total thickness of the hydrogen storage layer 110 in the composite hydrogen storage membrane may be 100nm to 5000nm. By controlling the total thickness of the hydrogen storage layer 110 to be 100 nm-5000 nm, the composite hydrogen storage membrane material can ensure higher hydrogen storage amount and facilitate diffusion of hydrogen atoms in the hydrogen storage layer 110 so as to ensure the absorption and release rate of hydrogen.
Further, the total thickness of the hydrogen storage layer 110 may be 100nm, 500nm, 1000nm, 2000nm, 3000nm, or 5000nm. Further, the total thickness of the hydrogen storage layer 110 may be in a range between any two of the above thicknesses.
Referring to fig. 1, in some examples of this embodiment, the total number of layers of the vanadium metal layer 111 in the hydrogen storage layer 110 may be 20 to 500. For example, the total number of vanadium metal layers 111 may be 20, 50, 100, 200, 300, or 500. Further, the total number of the vanadium metal layers 111 may be in a range between any two of the above layers. The total number of layers of the vanadium metal layer 111 is controlled, so that a specific process can be saved while the vanadium metal layer 111 has a higher diffusion rate of hydrogen atoms.
Referring to fig. 1, in some examples of this embodiment, the total number of niobium metal layers 112 in hydrogen storage layer 110 may be 20 to 500. For example, the total number of niobium metal layers 112 may be 20, 50, 100, 200, 300, or 500. The total number of niobium metal layers 112 may also be in the range between any two of the above.
In some examples of this embodiment, the hydrogen storage layer 110 may have micropores therein. Micropores in the hydrogen storage layer 110 can increase the specific surface area of the hydrogen storage layer 110, which can allow the hydrogen storage layer 110 to have more hydrogen adsorption sites. Further, at least a portion of the micropores may be disposed in the vanadium metal layer 111, which can further increase lattice defects of the vanadium metal layer 111, help to further reduce bonding stability between hydrogen atoms and vanadium metal, and increase diffusion rate of hydrogen atoms in the vanadium metal layer 111.
In some examples of this embodiment, the porosity of the hydrogen storage layer 110 may be 10% -50%. To ensure a high hydrogen storage capacity and absorption and release rates of hydrogen while maintaining the structural integrity of the hydrogen storage layer 110.
In some examples of this embodiment, in the hydrogen storage layer 110, the porosity of the hydrogen storage layer 110 may be 10%, 20%, 30%, 40%, or 50%, and the porosity of the hydrogen storage layer 110 may also be in a range between any two of the above.
Referring to fig. 1, in some examples of this embodiment, among the hydrogen storage layers 110, the layer farthest from the substrate 100 is the niobium metal layer 112. The layer farthest from the substrate 100 is the niobium metal layer 112, so that the niobium metal layer 112 can protect the vanadium metal layer 111 located inside from the outermost side and ensure the structural stability of the vanadium metal layer 111 when absorbing hydrogen and releasing hydrogen.
Referring to fig. 1, in some examples of this embodiment, the substrate 100 is provided with hydrogen storage layers 110 on both opposite side surfaces, which can further increase the hydrogen storage amount of the composite hydrogen storage membrane material.
It is understood that the composite hydrogen storage membrane material shown in fig. 1 has a long straight planar structure, but the composite hydrogen storage membrane material may not be limited to the long straight planar structure. For example, the composite hydrogen storage membrane material may be curved, bent, or wound.
Fig. 2 shows a schematic cross-sectional view of a multilayer coiled structure formed based on the composite hydrogen storage membrane of fig. 1. Referring to fig. 2, in the composite hydrogen storage membrane material, the substrate 100 is a flexible substrate, and the substrate 100 and the hydrogen storage layer 110 have a multilayer rolled structure as a whole. Wherein, the multi-layered rolled structure refers to a multi-layered cylindrical structure in which the substrate 100 and the hydrogen storage layer 110 are integrally rotated about a rotation axis to form a continuous, inside-out distribution. It is understood that the hydrogen storage layer 110 may be integrally attached to the substrate 100, whereby the hydrogen storage layer 110 and the substrate 100 can maintain the stability of the overall structure when curled.
In some examples of this embodiment, the flexible substrate may be selected from a polymer film or a metal foil. Wherein the polymer film may include, but is not limited to, one or more of polyimide, polyethylene, polypropylene, and polymethyl methacrylate. The metal foil may include, but is not limited to, one or more of copper, aluminum, iron, nickel, and titanium.
Further, the present disclosure also provides a method for preparing the composite hydrogen storage membrane material according to the above embodiment, and fig. 3 is a schematic step diagram of a method for preparing the composite hydrogen storage membrane material, and referring to fig. 3, the preparation method includes steps S1 to S4, specifically as follows.
In step S1, a substrate 100 is provided.
In some examples of this embodiment, the substrate 100 may be a flexible substrate. The flexible substrate may be selected from a polymer film or a metal foil. The polymer film may include, but is not limited to, one or more of polyimide, polyethylene, polypropylene, and polymethyl methacrylate. The metal foil may include, but is not limited to, one or more of copper, aluminum, iron, nickel, and titanium.
In some examples of this embodiment, the substrate 100 is selected to have a thickness of 1 μm to 100 μm. For example, in this embodiment, a copper foil having a thickness of 5 μm may be selected as the substrate 100.
In some examples of this embodiment, a step of roughening the substrate 100 may also be included. The roughening treatment of the substrate 100 has the effect of forming a relief structure on the surface of the substrate 100, which can increase the surface area of the substrate 100 and increase the surface area of the entire hydrogen storage layer 110 to be subsequently produced.
In some examples of this embodiment, the substrate 100 may be roughened by one or more selected from the group consisting of plasma bombardment, laser irradiation, sand blasting, sanding, and embossing. Wherein, the plasma bombardment refers to the surface of the substrate 100 is bombarded by plasma, the plasma treatment can be performed in a film plating device, and the plasma treatment can clean impurities on the surface of the substrate 100 on one hand and can form a loose and porous structure on the surface of the substrate 100 on the other hand. Sand blasting refers to ejecting abrasive to the surface of the substrate 100 to form irregularly distributed pits in the surface of the substrate 100. Sanding refers to the grinding of the surface of the substrate 100 with a sanding medium to provide a degree of non-planarity to the surface of the substrate 100. It will be appreciated that by plasma treatment, laser irradiation, sand blasting or sanding, irregular relief structures can be formed on the surface of the substrate 100. Imprinting refers to the use of a mold or other medium to form a specific pattern on the surface of the substrate 100. The embossing may form a regular or irregular relief structure.
Wherein the substrate 100 may be placed in a sputtering chamber to facilitate a subsequent process of preparing a metal layer.
In step S2, a vanadium metal layer 111 is formed by sputtering a vanadium metal on the substrate 100.
It will be appreciated that a vanadium metal target may be employed as a target in a sputtering apparatus, which is bombarded to deposit the vanadium metal on the substrate 100, thereby obtaining vanadium metal and forming the vanadium metal layer 111.
In some examples of this embodiment, the temperature of the substrate 100 may be controlled to 25-380 ℃ prior to sputtering the vanadium metal. Further, the temperature of the substrate 100 may be controlled to 25 ℃ to 300 ℃. Further, the temperature of the substrate 100 may be controlled to be 25 ℃ to 100 ℃. It will be appreciated that the material of the substrate 100 should ensure that it does not melt or otherwise react chemically at elevated temperatures.
In some examples of this embodiment, a longer substrate 100 may be employed, for example, the substrate 100 may be 1 to 10000m in length. In an actual sputtering process, the substrate 100 may be gradually moved while sputtering the vanadium metal so that the substrate 100 gradually passes through the deposition area to achieve a continuous vanadium metal layer 111 on the substrate 100.
In some examples of this embodiment, the length of the substrate 100 may be 1m, 100m, 1000m, 3000m, 5000m, or 10000m. The length of the substrate 100 may also range between any two of the lengths described above.
During sputtering, the vanadium metal is accelerated and has a certain initial kinetic energy, which results in the natural existence of nano-scale to micro-scale micropores in the vanadium metal layer 111 formed by sputtering, so that the vanadium metal layer 111 has a larger specific surface area, which helps to increase the diffusion rate of hydrogen atoms during hydrogen storage.
In some examples of this embodiment, in the step of sputtering the vanadium metal layer 111, the sputtering power density may be controlled to be 10W/cm 2 ~20W/cm 2 . For example, in the step of preparing the vanadium metal layer 111 by sputtering, the sputtering power density may be controlled to be 10W/cm 2 、12W/cm 2 、14W/cm 2 、16W/cm 2 、18W/cm 2 Or 20W/cm 2 . The sputtering power density can also be controlled within a range between any two of the power densities described above. By controlling the power density of the vanadium metal layer 111 to be 10W/cm 2 ~20W/cm 2 The uniformity of the vanadium metal layer 111 can be ensured while the vanadium metal layer 111 has a proper amount of micropores.
In some examples of this embodiment, the thickness of sputtered vanadium metal layer 111 may be controlled to be 5 nm-100 nm. It is understood that the thickness of the vanadium metal layer 111 may be controlled by controlling the sputtering time.
In step S3, a niobium metal layer 112 is formed by sputtering a niobium metal layer 111.
It will be appreciated that a niobium metal target may be employed as a target in a sputtering apparatus that is bombarded to deposit on the substrate 100 to obtain niobium metal and form the niobium metal layer 112.
In some examples of this embodiment, steps S2 and S3 may be performed in two different deposition chambers, which may have a transport rail therebetween, and during actual fabrication, the substrate 100 is placed on the transport rail and transported from the deposition chamber where the vanadium metal is sputtered to the deposition chamber where the niobium metal is sputtered.
In some examples of this embodiment, the temperature of the substrate 100 may be controlled to 25-380 ℃ prior to sputtering the niobium metal. Further, the temperature of the substrate 100 may be controlled to 25 ℃ to 300 ℃. Further, the temperature of the substrate 100 may be controlled to be 25 ℃ to 100 ℃. It will be appreciated that the material of the substrate 100 should ensure that it does not melt or otherwise react chemically at elevated temperatures.
During the sputtering process, the niobium metal particles are accelerated and have a certain initial kinetic energy, which can cause the niobium metal particles to bombard and embed into the surface layer of the vanadium metal layer 111, further causing lattice defects in the vanadium metal layer 111.
In some examples of this embodiment, in the step of sputtering to prepare the niobium metal, the sputtering power density may be controlled to be 15W/cm 2 ~30W/cm 2 . Further, the sputtering power density during sputtering of niobium metal is higher than during sputtering of vanadium metal. Controlling the sputtering power density during sputtering of the niobium metal to be higher helps to embed the niobium metal further into the already prepared vanadium metal layer 111 and to form more micropores on the surface of the already prepared vanadium metal layer 111 and the surface of the niobium metal layer 112.
In some examples of this embodiment, in the step of sputter preparing the niobium metal layer 112, the sputter power density may be controlled to be 15W/cm 2 、18W/cm 2 、21W/cm 2 、25W/cm 2 、28W/cm 2 Or 30W-cm 2 . The sputtering power density can also be controlled within a range between any two of the power densities described above.
In some examples of this embodiment, the thickness of sputtered niobium metal layer 112 may be controlled to be 5 nm-100 nm. It will be appreciated that the thickness of the niobium metal layer 112 may be controlled by controlling the sputtering time.
It can be appreciated that, through steps S2 to S3, a vanadium metal layer 111 and a niobium metal layer 112 can be prepared, and the niobium metal layer 112 and the vanadium metal layer 111 are sequentially stacked on the substrate 100.
In step S4, vanadium metal is sputtered a plurality of times and niobium metal is sputtered a plurality of times to form a multi-layered niobium metal layer 112 and a multi-layered vanadium metal layer 111, respectively.
It will be appreciated that during the sputtering process vanadium metal and niobium metal are alternately sputtered. In sputtering vanadium metal to prepare the vanadium metal layer 111, the vanadium metal may be formed by sputtering on the surface of the niobium metal layer 112 that has been prepared. In sputtering the niobium metal to prepare the niobium metal layer 112, the niobium metal may be sputter formed on the surface of the vanadium metal layer 111 that has been prepared. And, adjacent niobium metal layers 112 and vanadium metal layers 111 are in contact with each other.
In some examples of this embodiment, the temperature of the substrate 100 may be controlled to 25-100 ℃ while sputtering vanadium metal and niobium metal.
In some examples of this embodiment, the sputtering power density of the sputtered vanadium metal may be 10W/cm when alternately sputtering vanadium metal multiple times and niobium metal multiple times 2 ~20W/cm 2 . The power density of the vanadium metal may be the same or may be different for each sputtering, which may be selected depending on the actual properties of the vanadium metal layer 111 desired.
In some examples of this embodiment, the sputtering power density of the sputtered niobium metal may be 15W/cm when alternately sputtering vanadium metal multiple times and niobium metal multiple times 2 ~30W/cm 2 . The power density of the niobium metal may be the same or may vary each time, which may be selected based on the actual properties of the niobium metal layer 112 desired.
It will be appreciated that the specific thicknesses of the prepared vanadium metal layer 111 and niobium metal layer 112 may be controlled by controlling the time when the vanadium metal and niobium metal are sputtered.
In some examples of this embodiment, during the alternating sputtering of vanadium metal and niobium metal, the following steps may also be included: and introducing a gasifying agent into the deposition chamber, attaching the gasifying agent to the vanadium metal layer 111 or the niobium metal layer 112 prepared in advance, then continuing to alternately sputter vanadium metal and niobium metal on the vanadium metal layer 111 or the niobium metal layer 112 attached with the gasifying agent, and then heating the substrate 100 to volatilize the gasifying agent.
The gasifying agent is attached to the vanadium metal layer 111 or the niobium metal layer 112 prepared in advance in the alternative sputtering process, and then the gasifying agent is gasified after the vanadium metal layer 111 and the niobium metal layer 112 are continuously prepared on the vanadium metal layer 111 or the niobium metal layer 112, so that the gasifying agent is volatilized, more micropores can be generated in the vanadium metal layer 111 and the niobium metal layer 112 in the volatilizing process, and the specific surface area of the vanadium metal layer 111 and the niobium metal layer 112 is further improved.
It will be appreciated that in some examples of this embodiment, the sputtering power and the amount of gasifying agent may be controlled such that the porosity of the composite hydrogen storage membrane material is 10% -50%.
In some examples of this embodiment, forming one or more vanadium metal layers 111 and one or more niobium metal layers 112 may be prepared between the step of introducing the gasifying agent into the deposition chamber and the step of volatilizing the gasifying agent. Further, between the step of introducing the gasifying agent into the deposition chamber and the step of volatilizing the gasifying agent, 10 vanadium metal layers 111 and 10 niobium metal layers 112 may be prepared.
Wherein the gasifying agent may be a material that can be attached to a previously prepared metal layer and can be rapidly removed by heating. This requires that the gasifying agent has a suitable evaporation temperature. In this embodiment, the gasifying agent may be steam. In other embodiments, the gasifying agent may also be other agents having suitable vaporization temperatures.
In some examples of this embodiment, in the step of heating the substrate 100 to volatilize the gasifying agent, the temperature of the substrate 100 may be controlled to 120 ℃ to 200 ℃.
In some examples of this embodiment, the step of introducing a gasifying agent into the deposition chamber is performed after sputtering the vanadium metal such that the gasifying agent adheres to the previously prepared vanadium metal layer 111. It is understood that by attaching the gasifying agent to the vanadium metal layer 111, the niobium metal layer 112 prepared later can be covered on the gasifying agent, which can avoid the influence of introducing the gasifying agent on the performance of the vanadium metal layer 111 as much as possible.
In some examples of this embodiment, in the step of alternately sputtering vanadium metal and niobium metal, the last sputtered metal is niobium metal such that the layer of hydrogen storage layer 110 furthest from substrate 100 is niobium metal layer 112.
It can be appreciated that the hydrogen storage composite coiled material shown in fig. 1 can be prepared through the steps S1 to S4. Further, after the hydrogen storage layer 110 is completed, the substrate 100 and the hydrogen storage layer 110 may be integrally wound to form a composite hydrogen storage membrane material having a multi-layered coiled structure as shown in fig. 2.
Compared with single vanadium metal, by arranging the niobium metal layers alternating with the vanadium metal layers, an alloy-like structure can be formed at the interface between the niobium metal layers and the vanadium metal layers, and lattice defects can be generated in the vanadium metal layers. Further, the vanadium metal layers and the niobium metal layers which are alternately laminated are arranged on the substrate and integrally form a multi-layer curled structure, so that the overall effective hydrogen absorption area of the hydrogen storage layer can be effectively improved, the vanadium metal layers close to the substrate can be structurally deformed through the curled structure, and overall lattice defects are increased. This aspect can reduce the stability of the vanadium hydride, making the hydrogen easier to absorb and release. On the other hand, the vanadium metal layer can be supported by means of the niobium metal layer so as to maintain the overall structural stability of the vanadium metal layer, the problem of powder removal of the vanadium metal layer caused by volume change is prevented, and the reversibility of hydrogen storage of the vanadium metal layer is further improved.
Further, the present disclosure also provides a hydrogen storage tank including a tank body and the composite hydrogen storage membrane material as in the above embodiment, the composite hydrogen storage membrane material being disposed in the tank body.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A composite hydrogen storage membrane material, comprising: the hydrogen storage device comprises a substrate and a hydrogen storage layer arranged on the substrate, wherein the substrate is a flexible substrate, the substrate and the hydrogen storage layer are integrally provided with a multi-layer curled structure, the hydrogen storage layer is covered on the substrate and comprises a plurality of vanadium metal layers and a plurality of niobium metal layers, the vanadium metal layers and the niobium metal layers are sequentially and alternately laminated on the substrate, and the adjacent vanadium metal layers and the niobium metal layers are mutually contacted.
2. The composite hydrogen storage membrane material according to claim 1, wherein the thickness of the vanadium metal layer is 5 nm-100 nm; and/or the number of the groups of groups,
the thickness of the niobium metal layer is 1 nm-10 nm.
3. The composite hydrogen storage membrane material according to any one of claims 1 to 2, wherein the hydrogen storage layer is provided with micropores, and the porosity of the hydrogen storage layer is 10% -50%.
4. The composite hydrogen storage membrane of claim 3, wherein the layer furthest from the substrate in the hydrogen storage layer is the niobium metal layer.
5. A method for preparing the composite hydrogen storage membrane material according to any one of claims 1 to 4, comprising the steps of:
providing the substrate;
sputtering vanadium metal on the substrate a plurality of times and sputtering niobium metal a plurality of times to form a plurality of layers of the niobium metal and a plurality of layers of the vanadium metal, respectively, the vanadium metal and the niobium metal being alternately sputtered during the sputtering.
6. The method according to claim 5, wherein, when sputtering niobium metal on the vanadium metal layer that has been prepared, sputtering power is controlled so that niobium atoms are embedded in the vanadium metal layer.
7. The method according to claim 6, wherein in the step of sputtering vanadium metal, the power density of sputtering is controlled to be 10W/cm 2 ~20W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or the number of the groups of groups,
in the step of sputtering the niobium metal, the power density of sputtering was controlled to 15W/cm 2 ~30W/cm 2 。
8. The method according to any one of claims 5 to 7, further comprising the steps of, in the process of sputtering vanadium metal a plurality of times and sputtering niobium metal a plurality of times:
introducing a gasifying agent into the deposition chamber to enable the gasifying agent to be attached to the vanadium metal layer or the niobium metal layer which is prepared in advance;
and continuing to alternately sputter vanadium metal and niobium metal on the vanadium metal layer or the niobium metal layer attached with the gasifying agent, and then carrying out heating treatment on the substrate to volatilize the gasifying agent.
9. The method of claim 8, wherein the step of introducing a gasifying agent into the deposition chamber is performed after sputtering the vanadium metal such that the gasifying agent adheres to the previously prepared vanadium metal layer; and/or the number of the groups of groups,
the gasifying agent is water.
10. A hydrogen storage tank, characterized by comprising a tank body and the composite hydrogen storage membrane material according to any one of claims 1 to 4, wherein the composite hydrogen storage membrane material is arranged in the tank body.
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