CN115246627A - Preparation method of nano-particle magnesium-based composite hydrogen storage material - Google Patents
Preparation method of nano-particle magnesium-based composite hydrogen storage material Download PDFInfo
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- CN115246627A CN115246627A CN202210961669.1A CN202210961669A CN115246627A CN 115246627 A CN115246627 A CN 115246627A CN 202210961669 A CN202210961669 A CN 202210961669A CN 115246627 A CN115246627 A CN 115246627A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 130
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 130
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 127
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000011232 storage material Substances 0.000 title claims abstract description 72
- 239000011777 magnesium Substances 0.000 title claims abstract description 59
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 83
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 29
- 150000003624 transition metals Chemical class 0.000 claims abstract description 28
- 229910001512 metal fluoride Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000012298 atmosphere Substances 0.000 claims abstract description 15
- 239000002905 metal composite material Substances 0.000 claims abstract description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 10
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical group [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- OEKDNFRQVZLFBZ-UHFFFAOYSA-K scandium fluoride Chemical compound F[Sc](F)F OEKDNFRQVZLFBZ-UHFFFAOYSA-K 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229940105963 yttrium fluoride Drugs 0.000 claims description 2
- RBORBHYCVONNJH-UHFFFAOYSA-K yttrium(iii) fluoride Chemical compound F[Y](F)F RBORBHYCVONNJH-UHFFFAOYSA-K 0.000 claims description 2
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 claims description 2
- 239000002064 nanoplatelet Substances 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 14
- 238000003795 desorption Methods 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 238000003466 welding Methods 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 239000000314 lubricant Substances 0.000 abstract description 2
- -1 transition metal Chemical class 0.000 abstract description 2
- 229910021561 transition metal fluoride Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 23
- 239000002135 nanosheet Substances 0.000 description 14
- 238000003860 storage Methods 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000005501 phase interface Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910012375 magnesium hydride Inorganic materials 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000000713 high-energy ball milling Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 230000006911 nucleation Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910019080 Mg-H Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
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- 238000003776 cleavage reaction Methods 0.000 description 1
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- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
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- 239000013535 sea water Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Images
Classifications
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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
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
- C01B3/0042—Intermetallic compounds; Metal alloys; Treatment thereof only containing magnesium and nickel; Treatment thereof
-
- 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
-
- 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
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/04—Hydrides of alkali metals, alkaline earth metals, beryllium or magnesium; Addition complexes thereof
-
- 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 preparation method of a nano-particle magnesium-based composite hydrogen storage material, which comprises the following steps: ball-milling nano flaky magnesium and transition metal in hydrogen atmosphere to obtain a magnesium/transition metal composite hydrogen storage material; and ball-milling the magnesium/transition metal composite hydrogen storage material and metal fluoride in a hydrogen atmosphere to obtain the nano-particle magnesium-based composite hydrogen storage material. The invention prepares the nano-particle magnesium-based composite hydrogen storage material by a multi-step in-situ hydrogenation ball milling method, and adopts the multi-step ball milling method to prepare the nano-particle magnesium-based hydrogen storage material aiming at the dilemma that the magnesium-based hydrogen storage material particles prepared by the ball milling method are easy to agglomerate and difficult to prepare nano-scale powder. Inorganic salts such as transition metal, metal fluoride and the like can be used as a hydrogen absorption and desorption catalyst and can also be used as a lubricant, and the inorganic salts are attached to the surfaces of particles in the ball milling process to inhibit the particle agglomeration caused by cold welding.
Description
Technical Field
The invention belongs to the technical field of metal hydride material preparation, and particularly relates to a preparation method of a nano-particle magnesium-based composite hydrogen storage material.
Background
The problem of hydrogen energy storage and transportation is one of key links restricting the popularization and application of hydrogen energy, a high-capacity hydrogen storage material is an effective means for solving the problem, and a magnesium-based hydrogen storage material has the advantages of high hydrogen storage capacity, rich resources, low price and the like, so that the magnesium-based hydrogen storage material becomes one of the most attractive hydrogen storage materials, but has poor hydrogen absorption/desorption dynamic performance and high hydrogen desorption temperature, thereby limiting the practical application.
Among the currently known metal-based hydrogen storage materials, mg is one of the earliest investigated hydrogen storage materials, mgH 2 The theoretical reversible hydrogen storage capacity of 7.6wt%, the Mg content in the earth's crust is ranked eighth (2.3%), the content in seawater is third, and therefore the magnesium-based material has the advantage of low cost. However, mgH is either thermodynamic (enthalpy change-74.5 kJ/(mol H2)) or kinetic 2 There are great obstacles to the hydrogen absorption/desorption reactions. Research shows that the first reason for slow hydrogenation kinetics of Mg is that the Mg-based hydrogen storage alloy has poor oxidation resistance, easily forms an oxide layer on the surface and is not beneficial to the dissociation of hydrogen and the diffusion of hydrogen into a block; another reason is MgH 2 Diffusion of hydrogen atoms after formation of the layer on the surface is difficult because the diffusion coefficient of hydrogen gas in MgH2 (1.5X 10-16m 2/s) is much smaller than that in Mg (4X 10-13m 2/s). Reasons for the slow kinetics of dehydrogenation include the high energy required for the cleavage of the Mg-H bond, the presence of hydrogen atoms in MgH 2 Low medium diffusion coefficient and Mg in MgH 2 Surface nucleation is difficult and hydrogen atoms recombine on the Mg surface to form hydrogen molecules. In order to solve the problems, the current approaches for improving the kinetics of hydrogen absorption/dehydrogenation of Mg-based alloys mainly comprise: the kinetic barrier of the addition of catalyst, nano crystallization, nano and multi-phase compounding is basically overcome. However, the difficult problem of thermodynamic instability still remains to be overcome, and the current measures for improving the thermodynamic performance of the magnesium-based hydrogen storage alloy are alloying, nano/thin film formation, metastable and the like. But it has the disadvantages of low hydrogen storage capacity, poor cycle stability, etc.
Disclosure of Invention
The invention provides a preparation method of a nano-particle magnesium-based composite hydrogen storage material, aiming at solving the problems of low hydrogen storage capacity and poor circulation stability in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a nano-particle magnesium-based composite hydrogen storage material comprises the following steps:
1) Ball-milling nano flaky magnesium and transition metal in hydrogen atmosphere to obtain a magnesium/transition metal composite hydrogen storage material with submicron scale;
2) And performing ball milling on the submicron-scale magnesium/transition metal composite hydrogen storage material and metal fluoride in a protective atmosphere to obtain the nanoparticle magnesium-based composite hydrogen storage material.
Further, the protective atmosphere is hydrogen or argon.
Further, the weight of the transition metal is 3-20% of the total weight of the nano flaky magnesium and the transition metal.
Further, the transition metal is Ni, copper, cobalt, vanadium or Ti.
Further, in the step 1), the rotation speed of ball milling is 300-800rpm, and the ball milling time is 4-14 h.
Further, the metal fluoride is cesium fluoride, scandium fluoride, titanium fluoride, zirconium fluoride, yttrium fluoride, or lanthanum fluoride.
Furthermore, the dosage of the metal fluoride is 1-10% of the total weight of the magnesium/transition metal composite hydrogen storage material and the metal fluoride.
Further, in the step 2), the rotation speed of ball milling is 200-500rpm, and the ball milling time is 2-5h.
Further, the nano flaky magnesium powder is prepared by the following processes: mixing magnesium powder with an organic reagent, and carrying out ball milling under the protection of inert atmosphere to obtain the nano flaky magnesium powder.
Further, the inert atmosphere is argon or helium.
Further, the organic reagent is ethanol, stearic acid or alkane.
Further, the alkane is cyclohexane, n-hexane or heptane; the rotation speed of ball milling under the protection of inert atmosphere is 300-500rpm, and the time is 2-6h.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts nano lamellar magnesium powder to ensure that transition metal nano particles are uniformly dispersed on the surface of the lamellar magnesium powder, and the magnesium-based composite hydrogen storage material with a high-density phase interface is obtained by in-situ ball milling. In the process of hydrogen absorption and desorption reaction, the thermodynamic and kinetic properties of the hydrogen storage material are improved by utilizing the phase interface energy difference, and the problems of over-stable thermodynamics and slow kinetic properties of the magnesium-based hydrogen storage material in the prior art are solved. The invention prepares the nano-particle magnesium-based composite hydrogen storage material by a multi-step in-situ hydrogenation ball milling method, inorganic salts such as transition group metals and metal fluorides can be used as hydrogen absorption and desorption catalysts and also can be used as lubricants, and the inorganic salts are attached to the surfaces of particles in the ball milling process to inhibit the particle agglomeration caused by cold welding, thereby overcoming the problems that the particles of the magnesium-based hydrogen storage material prepared by the ball milling method in the prior art are easy to agglomerate and difficult to prepare nano-scale powder. And the fluoride and magnesium powder can generate in-situ reaction during ball milling to generate a new phase, which is beneficial to nucleation and further promotes hydrogen absorption. The metal fluoride in the invention can obviously reduce the powder granularity, so the hydrogen storage capacity is obviously improved, and the test of the cycle performance is carried out at 300 ℃, and the result shows that the surface hydrogen storage capacity is hardly attenuated and the cycle stability is good.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a magnesium-based hydrogen storage material;
FIG. 2 is a graph of the hydrogen absorption kinetics of the Mg-5 Ni-3CsF composite hydrogen storage material;
FIG. 3 is a graph of hydrogen evolution kinetics of the Mg-5 Ni-3CsF composite hydrogen storage material;
FIG. 4 shows the results of the cycle performance test of the Mg-5 Ni-3CsF composite hydrogen storage material;
FIG. 5 is MgH 2 Hydrogen sorption kinetics curve of the hydrogen storage material;
FIG. 6 is MgH 2 Hydrogen storage material hydrogen evolution kinetics curve;
FIG. 7 shows Mg-5 Ni-3TiF 3 Hydrogen absorption kinetic curve of the composite hydrogen storage material;
FIG. 8 shows Mg-5 Ni-3TiF 3 Hydrogen evolution kinetics curve of composite hydrogen storage materials.
Detailed Description
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
The ball-to-material ratio in the invention is a mass ratio.
As shown in fig. 1, the preparation method of the nano-particle magnesium-based composite hydrogen storage material of the invention comprises the following steps:
step one, preparing nano flaky magnesium powder: mixing magnesium powder with a certain proportion of organic reagent, carrying out ball milling under the protection of argon or helium atmosphere according to a certain ball-to-material ratio, and drying in a glove box to obtain the nano flaky magnesium powder. Wherein the dosage ratio of the magnesium powder to the organic reagent is 10g:10-15mL.
Wherein the organic reagent is ethanol, stearic acid or alkane, the alkane is cyclohexane, normal hexane or heptane, the ball-material ratio range is 20-60.
And step two, putting the nano flaky magnesium, the transition metal and the steel ball into a ball milling tank according to a certain proportion in a glove box, and taking out after sealing. Connecting the ball milling tank with a hydrogen charging device, performing gas washing twice, charging specified hydrogen pressure, and checking air tightness;
wherein, the mass of the added transition metal (Ni, copper, cobalt, vanadium or Ti) is 3-20wt% of the total weight of the nano flaky magnesium and the transition metal, the ball-material ratio range is 40.
And step three, fixing the ball milling tank on a high-energy ball mill, and performing high-energy ball milling at a set ball milling rotation speed for a set ball milling time to uniformly distribute transition metal particles in the nanosheet layer magnesium powder to obtain the magnesium/transition metal composite hydrogen storage material with a submicron scale.
Wherein, the ball milling conditions are as follows: the ball milling speed is 300-800rpm, and the ball milling time is 4-14 h.
And step four, putting the magnesium/transition metal composite hydrogen storage material obtained in the step three and metal fluoride (the hydrogen absorption kinetic performance can be obviously improved by adding the fluoride) into a ball milling tank according to a certain proportion, carrying out ball milling under the conditions of certain hydrogen pressure (or helium atmosphere) and low-energy ball milling, and optimizing the particle size to obtain the nano-particle magnesium-based composite hydrogen storage material.
Wherein the metal fluoride is cesium fluoride (CsF), scandium fluoride, titanium fluoride (TiF) 3 ) Or lanthanum fluoride and the like, the dosage of the metal fluoride is 1-10wt% of the total weight of the magnesium/transition metal composite hydrogen storage material and the metal fluoride, and the material ratio of the low-energy ball-milling balls is 30: 1-60, the ball milling speed is 200-500rpm, the ball milling time is 2-5h, and the hydrogen pressure is 2-4MPa.
One of the advantages of the invention is that the nano-lamellar magnesium powder is prepared by wet grinding, then the nano-transition metal powder and the nano-lamellar magnesium powder are mixed and ball-milled, in the process of high-energy ball milling, the multi-layer nano-lamellar magnesium-based hydrogen storage material is prepared by utilizing the cold welding effect, and simultaneously, new phases are formed in situ between lamellae to form a high-density phase interface, the thermodynamics and the kinetics improvement of magnesium hydride are realized by utilizing the interface energy and the synergistic hydrogen release effect, and meanwhile, higher hydrogen storage capacity is kept. In addition, csF and TiF are simultaneously used 3 The metal fluoride can obviously reduce the powder granularity, obviously improve the hydrogen storage capacity and obtain good cycle performance.
Example 1
The embodiment comprises the following steps:
step one, preparing nano lamellar magnesium powder: weighing 10g of magnesium powder and 10mL of n-hexane, loading the magnesium powder and the n-hexane into a ball milling tank, ball milling for 4h under the conditions of a ball-material ratio of 30 and 400rpm in an argon atmosphere, and taking out the magnesium powder in a glove box to obtain the nanosheet layer magnesium powder.
Step two, adding 2.76g of nanosheet layer magnesium powder and 0.15g of nickel powder into a ball milling tank in a glove box, wherein the ball-material ratio is 80;
and step three, fixing the ball milling tank in a planetary ball mill, setting the rotation speed to be 600rpm, pausing for 15min after ball milling for 2h, continuing ball milling for 2h, pausing for 15min, and milling for 8h in total to obtain the completely hydrogenated Mg-5Ni composite hydrogen storage material.
And step four, adding 0.09g of cesium fluoride and the Mg-5Ni composite hydrogen storage material obtained in the step three into a ball milling tank, and performing ball milling for 3 hours under the conditions of a ball material ratio of 1, a hydrogen pressure of 3MPa and a rotating speed of 400rpm to obtain the nano-particle Mg-5 Ni-3CsF composite hydrogen storage material.
Referring to fig. 2 and 3, in fig. 2, the ordinate is Hydrogen adsorption capacity, the abscissa is time, in fig. 3, the ordinate is Hydrogen desorption capacity, and the abscissa is time, it can be seen that the Mg-5 Ni-3CsF composite Hydrogen storage material can reach a Hydrogen adsorption capacity of 7wt% in 60min and a Hydrogen desorption capacity of 7.0wt% in 35 min.
FIG. 4 is a result of a Cycle performance test at 300 deg.C, and in FIG. 4, hydrogen adsorption capacity is shown on the ordinate, and Cycle number is shown on the abscissa, and it can be seen that there is almost no decay in Hydrogen storage capacity.
Comparative example 1
This comparative example comprises the following steps:
and (3) ball-milling 3g of magnesium powder and the steel ball for 8h according to a ball-material ratio of 80, a rotating speed of 600rpm and a hydrogen pressure of 4MPa to obtain magnesium hydride.
Referring to fig. 5 and fig. 6, it can be seen that the Mg-5 Ni-3CsF composite hydrogen storage material has a hydrogen absorption and desorption capacity of more than 7wt% at 300 ℃ and can be completely dehydrogenated within 60 min. While pure MgH 2 The hydrogen release capacity in 100min is 6.4wt%, and the hydrogen absorption capacity in 30min is only 6.3wt%. Compared with the prior art, the hydrogen absorption and desorption kinetic curve of the catalyst is obviously improved by adding the catalyst.
Example 2
The embodiment comprises the following steps:
step one, preparing nano lamellar magnesium powder: weighing 10g of magnesium powder and 10mL of n-hexane, loading the magnesium powder and the n-hexane into a ball milling tank, ball milling for 4h under the conditions of a ball-material ratio of 30 and 400rpm in an argon atmosphere, and taking out the magnesium powder in a glove box to obtain the nanosheet layer magnesium powder.
Step two, adding 2.76 parts of nanosheet layer magnesium powder and 0.15 part of nickel powder into a ball milling tank in a glove box, wherein the ball-material ratio is 80;
and step three, fixing the ball milling tank in a planetary ball mill, setting the rotation speed to be 600rpm, suspending ball milling for 2h for 15min, and totally milling for 8h to obtain the fully hydrogenated Mg-5Ni composite hydrogen storage material.
Step four, adding 0.09 titanium fluoride and the Mg-5Ni composite hydrogen storage material obtained in the step three into a ball milling tank, and performing ball milling for 3 hours under the conditions of a ball-to-material ratio of 1, a hydrogen pressure of 3MPa and a rotating speed of 400rpm to obtain nano particles Mg-5 Ni-3TiF 3 A composite hydrogen storage material.
Referring to FIGS. 7 and 8, it can be seen that Mg-5 Ni-3TiF 3 The hydrogen absorption capacity of the composite hydrogen storage material reaches 6.7wt% at 300 ℃ for 30min, and the hydrogen discharge capacity within 40min reaches 7wt%.
Example 3
Step one, preparing nano lamellar magnesium powder: weighing 10g of magnesium powder and 15mL of heptane, loading the magnesium powder and the heptane into a ball milling tank, ball milling for 6h under the conditions of ball-to-material ratio of 20 and 300rpm in an argon atmosphere, and taking out the magnesium powder in a glove box to obtain the nanosheet layer magnesium powder.
Step two, adding the nanosheet layer magnesium powder and the copper powder into a ball milling tank in a glove box, wherein the ball-material ratio is 40; wherein the copper powder accounts for 3 percent of the total weight of the nanosheet layer magnesium powder and the copper powder;
and step three, fixing the ball milling tank in a planetary ball mill, setting the rotating speed to be 800rpm, pausing for 15min after ball milling for 2h, continuing ball milling for 2h, and obtaining the completely hydrogenated composite hydrogen storage material after ball milling for 4h in total.
Step four, adding scandium fluoride and the composite hydrogen storage material obtained in the step three into a ball milling tank, and carrying out ball milling for 5h under the conditions that the ball-to-material ratio is 40, the hydrogen pressure is 4MPa and the rotating speed is 200rpm, so as to obtain the nanoparticle composite hydrogen storage material. The dosage of scandium fluoride is 5 percent of the total weight of the composite hydrogen storage material and the metal fluoride,
example 4
Step one, preparing nano lamellar magnesium powder: weighing 10g of magnesium powder and 12mL of ethanol, filling the magnesium powder and the ethanol into a ball milling tank, ball milling for 2h under the atmosphere of helium and at the ball-to-material ratio of 50 and 500rpm, and taking out the magnesium powder in a glove box to obtain the nanosheet layer magnesium powder.
Step two, adding the nanosheet layer magnesium powder and the titanium powder into a ball milling tank in a glove box, wherein the ball-material ratio is 100; wherein the titanium powder accounts for 20 percent of the total weight of the nanosheet layer magnesium powder and the titanium powder;
and step three, fixing the ball milling tank in a planetary ball mill, setting the rotation speed to be 300rpm, pausing for 15min every ball milling time of 2h, and obtaining the completely hydrogenated composite hydrogen storage material after ball milling time of 14h.
And step four, adding titanium fluoride and the composite hydrogen storage material obtained in the step three into a ball milling tank, and carrying out ball milling for 2h under the conditions that the ball-to-material ratio is 60, the hydrogen pressure is 3MPa and the rotating speed is 500rpm, so as to obtain the nano-particle composite hydrogen storage material. The dosage of the titanium fluoride is 10 percent of the total weight of the composite hydrogen storage material and the metal fluoride,
example 5
Step one, preparing nano lamellar magnesium powder: weighing 10g of magnesium powder and 10mL of stearic acid, filling the magnesium powder and the stearic acid into a ball milling tank, ball milling for 3h under the conditions of a ball-to-material ratio of 60 to 450rpm in an argon atmosphere, and taking out the magnesium powder in a glove box to obtain the nanosheet layer magnesium powder.
Step two, adding the nanosheet layer magnesium powder and vanadium powder into a ball milling tank in a glove box, wherein the ball-to-material ratio is 120, and the charging pressure is 3MPa; wherein the vanadium powder accounts for 20 percent of the total weight of the nanosheet layer magnesium powder and the vanadium powder;
and step three, fixing the ball milling tank in a planetary ball mill, setting the rotation speed to be 500rpm, pausing for 15min every ball milling time of 2h, continuing ball milling for 2h, pausing for 15min, and milling for 12h in total to obtain the completely hydrogenated composite hydrogen storage material.
And step four, adding the lanthanum fluoride and the composite hydrogen storage material obtained in the step three into a ball milling tank, and carrying out ball milling for 4 hours under the conditions that the ball-material ratio is 30, the helium pressure is 2MPa, and the rotating speed is 300rpm, so as to obtain the nano-particle composite hydrogen storage material. Wherein, the dosage of the lanthanum fluoride is 1 percent of the total weight of the composite hydrogen storage material and the metal fluoride,
the magnesium-based composite hydrogen storage material with high-density phase interface obtained in the invention has the density relative to pure magnesium and magnesium-based composite materials, and when transition metal is added, the transition metal is embedded in a magnesium matrix, and then the interface of magnesium and the transition metal or a new phase is formed.
The invention adopts nano-composite to improve the thermodynamic property and the kinetic property of the magnesium-based hydrogen storage material, and simultaneously keeps higher hydrogen storage capacity and good cycle performance.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (10)
1. A preparation method of a nano-particle magnesium-based composite hydrogen storage material is characterized by comprising the following steps:
1) Ball-milling nano flaky magnesium and transition metal in hydrogen atmosphere to obtain a magnesium/transition metal composite hydrogen storage material with submicron scale;
2) And performing ball milling on the submicron-scale magnesium/transition metal composite hydrogen storage material and metal fluoride in a protective atmosphere to obtain the nanoparticle magnesium-based composite hydrogen storage material.
2. The method of claim 1, wherein the transition metal is present in an amount of 3-20% by weight based on the total weight of the nano-platelet magnesium and the transition metal.
3. The method of claim 1 or 2, wherein the transition metal is Ni, cu, co, v or Ti.
4. The method for preparing nano-particle magnesium-based composite hydrogen storage material as claimed in claim 1, wherein in step 1), the rotation speed of ball milling is 300-800rpm, and the ball milling time is 4-14 h.
5. The method of claim 1, wherein the metal fluoride is cesium fluoride, scandium fluoride, titanium fluoride, zirconium fluoride, yttrium fluoride, or lanthanum fluoride.
6. The method of claim 1, wherein the metal fluoride is present in an amount of 1-10% of the total weight of the magnesium/transition metal composite hydrogen storage material and the metal fluoride.
7. The method for preparing nano-particle magnesium-based composite hydrogen storage material as claimed in claim 1, wherein in step 2), the rotation speed of ball milling is 200-500rpm, and the ball milling time is 2-5h.
8. The method of claim 1, wherein the nano-sized magnesium-based composite hydrogen storage material is prepared by the following steps: mixing magnesium powder with an organic reagent, and carrying out ball milling under the protection of inert atmosphere to obtain the nano flaky magnesium powder.
9. The method of claim 8, wherein the organic reagent is ethanol, stearic acid or alkane.
10. The method of claim 9, wherein the alkane is cyclohexane, n-hexane, or heptane; the rotation speed of ball milling under the protection of inert atmosphere is 300-500rpm, and the time is 2-6h.
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