CN118083910B - Magnesium-based hydrogen storage material and method for synthesizing magnesium-based hydrogen storage material with assistance of alkali metal reduced titanium dioxide catalyst - Google Patents
Magnesium-based hydrogen storage material and method for synthesizing magnesium-based hydrogen storage material with assistance of alkali metal reduced titanium dioxide catalyst Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 127
- 239000001257 hydrogen Substances 0.000 title claims abstract description 124
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 122
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000011777 magnesium Substances 0.000 title claims abstract description 102
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 88
- 239000011232 storage material Substances 0.000 title claims abstract description 70
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 41
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 36
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 41
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 21
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 12
- 238000007599 discharging Methods 0.000 claims abstract description 3
- 239000012495 reaction gas Substances 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 72
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000010439 graphite Substances 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 21
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 19
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 24
- 239000012300 argon atmosphere Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 9
- 229910012375 magnesium hydride Inorganic materials 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium peroxide Inorganic materials [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910019080 Mg-H Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention provides a magnesium-based hydrogen storage material and a method for synthesizing the magnesium-based hydrogen storage material with the assistance of an alkali metal reduced titanium dioxide catalyst, and relates to the technical field of hydrogen storage materials. The method for synthesizing the magnesium-based hydrogen storage material assisted by the alkali metal reduced titanium dioxide catalyst is a one-step synthesis method, and comprises the following steps of: under the inert atmosphere environment, adding magnesium particles, alkali metal, titanium dioxide and an auxiliary agent into a reactor, uniformly mixing in a hydrogen-rich environment or a hydrogen-poor environment, discharging redundant reaction gas, and collecting a magnesium-based hydrogen storage material, wherein the auxiliary agent is an organic solvent and/or a carbon material. The magnesium-based hydrogen storage material prepared by the one-step method has the advantages of simple operation, low energy consumption, suitability for large-scale amplification, and excellent cycle stability and low-temperature dehydrogenation absorption kinetics.
Description
Technical Field
The invention relates to the technical field of hydrogen storage materials, in particular to a magnesium-based hydrogen storage material and a method for synthesizing the magnesium-based hydrogen storage material by using an alkali metal reduced titanium dioxide catalyst.
Background
Hydrogen energy is known as the final energy source in the 21 st century because of the advantages of high energy density, rich sources, zero pollution and the like. The practical use of hydrogen energy involves three important processes: production, storage and use. The construction of hydrogen energy circulation is a key to promote the wide application of the hydrogen energy circulation. In the circulation system, the storage of hydrogen is a major bottleneck restricting the circulation of hydrogen.
Magnesium hydride has shown great potential in efficient hydrogen storage due to its high mass and volumetric hydrogen storage density. However, commercial applications have not been realized due to their thermodynamically unstable and slow hydrogen absorption kinetics and the expensive price of magnesium hydride. At present, the synthesis of magnesium hydride needs to be carried out under the conditions of high temperature and high pressure, and as the diffusion rate of hydrogen in metal hydride is low, the magnesium hydrogenation kinetics is slow, the time and energy consumption are consumed for synthesizing the magnesium hydride, the conversion rate is low, and the high hydrogen pressure causes more hidden troubles in industrial batch production.
Disclosure of Invention
The invention aims at solving the problems of the traditional preparation of the magnesium hydride serving as a hydrogen storage material, and provides a method for synthesizing the magnesium-based hydrogen storage material by using an alkali metal reduced titanium dioxide catalyst in an auxiliary way.
In order to achieve the above purpose, the invention adopts the following technical scheme: a method for synthesizing magnesium-based hydrogen storage materials with the assistance of an alkali metal reduced titanium dioxide catalyst comprises the following steps:
Under the inert atmosphere environment, adding magnesium particles, alkali metal, titanium dioxide and an auxiliary agent into a reactor, uniformly mixing in a hydrogen-rich environment or a hydrogen-poor environment, discharging redundant reaction gas, and collecting a magnesium-based hydrogen storage material;
the auxiliary agent is an organic solvent and/or a carbon material.
In the invention, magnesium particles, alkali metal, titanium dioxide and auxiliary agent are added into a reactor for ball milling or stirring at one time in an inert atmosphere environment, the reaction process is one-pot treatment, the operation flow can be simplified, the energy consumption is reduced, and compared with the magnesium-based hydrogen storage material prepared by steps, the magnesium-based hydrogen storage material has more excellent cycle stability and low-temperature dehydrogenation absorption kinetics.
Further, the molar ratio of the alkali metal to the titanium dioxide is 1:0.1-5, preferably 1:0.5-3, for example 1:0.5, 1:1, 1:2, 1:3.
Further, the mass ratio of the magnesium particles to the sum of alkali metal and titanium dioxide is 1:0.01-0.3, preferably 1:0.01-0.1, for example 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.3.
Further, the mass ratio of the magnesium particles to the auxiliary agent is 1:0.01-0.5, preferably 1:0.01-0.1, for example 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5.
Further, the alkali metal M includes, but is not limited to, one or more of Li, na, K, rb and Cs, preferably Na, K, which is reduced in the middle of the alkali metal and avoids the danger caused by too active simple substances.
Further, the organic solvent is one or more of an amine solvent, a ketone solvent and a multifunctional solvent; and/or the carbon material is one or more of ordinary graphite, graphene, expanded graphite, acetylene black and carbon nano tubes.
Further, the amine is one or more of methylamine, aniline, ethylenediamine, diisopropylamine, and triethanolamine.
Further, the ketone is one or more of methyl butanone, acetone, methyl isobutyl ketone, and methyl ethyl ketone.
Further, the multifunctional solvent is one or more of acetonitrile, pyridine and phenol.
Further, the auxiliary agent is preferably acetone, and the auxiliary agent acetone can be chemically adsorbed on the defect/surface of the sample, so as to help stabilize the synthesized magnesium nanoparticles and prevent magnesium agglomeration, thereby affecting the physical and chemical properties of the sample.
Further, the auxiliary agent is preferably an organic solvent and a carbon material, and the mass ratio of the organic solvent to the carbon material is 1-5: 1.
Further, the auxiliary agent is more preferably acetone and expanded graphite, and the mass ratio of the acetone to the expanded graphite is 1-5:1, preferably 1:1, 2: 1. 3: 1. 4: 1. 5:1.
Further, the particle diameter of the magnesium particles is 50 μm or less, and preferably the particle diameter of the magnesium particles is 0.1 μm to 50. Mu.m.
Further, the mixing method is ball milling or stirring.
Further, when the mixing is ball milling, the ball milling conditions are as follows: the atmosphere pressure is 0-100 ℃, the rotating speed is 100-600 rpm, and the ball-to-material ratio is 20-180:1, time 1 h-60 h. The preferred ball milling conditions are: the rotation speed is 200-400 rpm at room temperature, and the ball-to-material ratio is 60-140: 1, time 2 h-15 h. According to the invention, the magnesium-based hydrogen storage material with the grade of mu m can be obtained only by ball milling for 4 hours, the granularity is further reduced along with the extension of the ball milling time, and the hydrogen amount is free from any loss after the magnesium-based hydrogen storage material with the grade of mu m is recycled for 20 times.
Further, the ball milling process is stopped for 0.5 to 1min every 3 to 5min, preferably every three min, for 30s every 3 min during the ball milling process to consume accumulated heat.
Further, when the mixing is stirring, the stirring conditions are as follows: the atmosphere pressure is 1-30 MPa; the temperature is 0-100 ℃; the rotating speed is 500-10000 revolutions per minute; the time is 1-40 hours.
Further, the hydrogen partial pressure in the hydrogen-rich environment is 1 MPa-30 Mpa, for example, optionally the hydrogen partial pressure in the hydrogen-rich environment is 1.0 MPa, 2.0 MPa, 3.0 MPa, 5.0 MPa, 8 MPa, 10.0 Mpa, 15 MPa, 20 MPa, 25 MPa, 30 MPa.
Further, the hydrogen-lean environment is an inert gas environment or a vacuum.
Further, the inert gas is one or more of helium, neon, argon, krypton, and xenon.
The principle of the synthesis method of the magnesium-based hydrogen storage material is as follows: magnesium powder, alkali metal, titanium dioxide and auxiliary agent are put into a reaction vessel for one-time reaction, and the interaction of the alkali metal and the titanium dioxide reduces the titanium dioxide, and the titanium dioxide acts as a catalyst of magnesium-based materials in a hydrogen-poor environment or a hydrogen-rich environment, so that the absorption and dehydrogenation activation energy of Mg/MgH 2 is reduced.
The invention also discloses a magnesium-based hydrogen storage material prepared by the method.
Further, the particle size of the magnesium-based hydrogen storage material is 0.01-15 microns, preferably 0.1-10 microns.
Compared with the prior art, the method for synthesizing the magnesium-based hydrogen storage material assisted by the alkali metal reduced titanium dioxide catalyst has the following advantages:
1) The invention can convert low-cost magnesium particles into high-value magnesium-based hydrogen storage materials in one step, greatly reduces energy consumption in the synthesis process, has better economic benefit compared with commercial magnesium-based materials, does not involve high temperature in the synthesis process, has higher safety and is beneficial to industrial production.
2) The auxiliary agent is an organic solvent and/or a carbon material, and can be adsorbed on the surfaces of magnesium particles by using the organic solvent, so that the stable synthesis of magnesium nano particles is facilitated, and the magnesium agglomeration is prevented; it is found that when the organic solvent adopts ketone, compared with the magnesium-based hydrogen storage material prepared from hydrocarbon, alcohol and ether, the granularity is smaller and the surface area is larger. The use of carbon materials as an auxiliary agent can suppress the cold welding effect of magnesium and alkali metals, and in addition, if ball milling is performed under a hydrogen atmosphere, the graphite-added magnesium exhibits more excellent hydrogenation ability. When the organic solvent and the carbon material are added simultaneously, the absorption and dehydrogenation kinetics are better than those of the organic solvent and the carbon material.
3) In the invention, the magnesium-based hydrogen storage material synthesized by one step has quicker absorption and dehydrogenation dynamics than the material obtained by firstly synthesizing the catalyst and then mixing the catalyst with magnesium, because alkali metal can be uniformly dispersed in magnesium, titanium dioxide and auxiliary agent during one-step synthesis, thereby avoiding the loss of alkali metal. In addition, the chemical environment of the titanium dioxide is changed, so that the generated titanium species are different, and the catalytic performance is different.
4) The invention uses alkali metal to reduce titanium dioxide to generate multivalent titanium interface, brings rich grain boundary, provides fast diffusion channel for hydrogen, and simultaneously the alkali metal can reduce work function of titanium dioxide, promote dissociation of hydrogen, and magnesium-based hydrogen storage material synthesized by compounding the catalyst has excellent hydrogenation capability and high cycle stability (such as Mg+5 wt% K-TiO 2, ball milling for 4 hours, 200 ℃ and 2 min hydrogen absorption of 5.0 wt percent, cycle for 20 times, no loss of hydrogen amount, see example 7), and the method has simple operation, low energy consumption, suitability for large-scale amplification and good application prospect in the hydrogen storage field.
5) According to the invention, a small amount of alkali metal is added into magnesium particles to reduce titanium dioxide, so that the hydrogen absorption and desorption performance of the magnesium particles can be obviously improved. The titanium dioxide has low price and adjustable Ti valence state, and can weaken Mg-H bond by compounding with magnesium hydride, and can help to dissociate H 2 and accelerate the transfer speed of hydrogen atoms in the reaction process. According to the invention, a small amount of alkali metal reduced titanium dioxide is added to enhance the mobility of Mg/MgH 2 electrons by generating and eliminating oxygen vacancies, so that the hydrogen absorption and desorption temperature experiment of Mg/MgH 2 is greatly reduced, and the magnesium particles which are not added hardly absorb hydrogen in the hydrogen atmosphere of 3Mpa at 300 ℃, and the magnesium added with a small amount of alkali metal reduced titanium dioxide can realize the room-temperature hydrogen absorption.
Drawings
FIG. 1 is a photograph of the raw magnesium powder, ball-milled magnesium powder and magnesium-based hydrogen storage material of example 1;
FIG. 2 is a temperature programmed hydrogen absorption curve of the hydrogen storage material of example 1;
FIG. 3 is an XRD pattern for the hydrogen storage material of example 2;
FIG. 4 is a temperature programmed dehydrogenation curve of the hydrogen storage material of example 2;
FIG. 5 shows the temperature programmed dehydrogenation result of example 3;
FIG. 6 is a cyclic dehydrogenation absorption curve of example 7;
FIG. 7 is a temperature programmed hydrogen absorption curve of comparative example 2.
Detailed Description
The invention is further illustrated by the following examples:
unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
Example 1:
In an argon atmosphere, the molar ratio is 1:1 to a ball milling pot, 0.05 g total of metal Na and titanium dioxide, 0.95 g total of Mg particles, 0.2 g g total of acetone (Acetone, AC) were added and mixed well. Ball milling 4 h under 200 rpm under the room temperature and argon atmosphere, and ball-to-material ratio of 120:1, stopping 1 to min after each ball milling is performed by 5 to min, and collecting magnesium-based hydrogen storage material after the ball milling is finished, wherein the particle size of the material is 1 to 15 mu m.
Characterization: the collected magnesium-based hydrogen storage material is shown in fig. 1, wherein ball-milled magnesium powder is magnesium particles without catalyst and auxiliary agent, ball milling can be performed in an inert atmosphere, and the sample is changed into silvery white particles. The color of the magnesium-based hydrogen storage material prepared by the embodiment is black, which shows that the material loses metallic luster and the particle size of the particles is obviously reduced; the temperature programming hydrogen absorption curve of the Na-TiO 2 assisted synthesized magnesium-based hydrogen storage material is shown in figure 2, and compared with commercial magnesium powder, the hydrogen absorption temperature of the magnesium-based hydrogen storage material is obviously lower, which indicates that the synthesized material has better hydrogen storage performance.
Example 2:
In an argon atmosphere, the molar ratio is 1:1 to a ball milling tank, 0.05 g of metal sodium and titanium dioxide, 0.95 g of Mg particles and 0.2 g g of acetone are added. 3Mpa hydrogen is pumped into the ball milling tank, 200 rpm ball milling is carried out on the ball milling tank under the room temperature hydrogen atmosphere for 15 h, and the ball-to-material ratio is 120:1, stopping 1 to min for every 5 to min ball milling, and collecting the magnesium-based hydrogen storage material after the ball milling is finished.
Characterization: XRD of the collected magnesium-based hydrogen storage material is shown in figure 3, diffraction peaks of magnesium hydride appear, which indicate that magnesium hydride is successfully synthesized, a temperature programming dehydrogenation curve of the magnesium-based hydrogen storage material synthesized by Na-TiO 2 is shown in figure 4, and the magnesium-based hydrogen storage material synthesized by the method can directly remove 5.8 wt% H 2, and compared with commercial magnesium hydride, the dehydrogenation temperature is remarkably reduced.
Example 3:
In an argon atmosphere, the molar ratio is 1:1 adding metal sodium and titanium dioxide into a ball milling tank to obtain 0.05 g,0.95 g of Mg particles and 0.2 g g of acetone, and uniformly mixing. Ball milling 10 h at room temperature under a hydrogen atmosphere of 3 Mpa at 200 rpm, ball to material ratio 120:1, 5: 5min min each time of ball milling is stopped at 1:1 min, and collecting magnesium-based hydrogen storage material after ball milling is finished, wherein the particle size of the material is 10 nm-0.1 mu m.
Characterization: the temperature programmed dehydrogenation results (fig. 5) indicate that the one-step synthesized hydrogen storage material has a lower dehydrogenation temperature and a faster dehydrogenation rate than comparative example 1.
Example 4:
In an argon atmosphere, the molar ratio is 1:1 adding 0.05 g of metal potassium and titanium dioxide together, 0.95 g of Mg particles and 0.1 g g of acetone into a ball milling tank, and uniformly mixing. Ball milling of 200 rpm under room temperature and 3 Mpa hydrogen atmosphere of 6h, ball-to-material ratio of 140:1, stopping 1 to min for every 5 to min ball milling, and collecting the magnesium-based hydrogen storage material after the ball milling is finished.
Example 5:
In an argon atmosphere, the molar ratio is 1:1 adding 0.05 g of metal potassium and titanium dioxide together, 0.95 g of Mg particles and 0.1g g of expanded graphite into a ball milling tank, and uniformly mixing. Ball milling of 200 rpm under room temperature and 3Mpa hydrogen atmosphere of 6 h, ball-to-material ratio of 140:1, stopping 1 to min for every 5 to min ball milling, and collecting the magnesium-based hydrogen storage material after the ball milling is finished.
Example 6:
In an argon atmosphere, the molar ratio is 1:1 adding 0.05 g of metal potassium and titanium dioxide, 0.95 g of Mg particles, 0.05 g of expanded graphite and 0.05 g of acetone into a ball milling tank, and uniformly mixing. Ball milling of 200 rpm under room temperature and 3 Mpa hydrogen atmosphere of 6h, ball-to-material ratio of 140:1, stopping 1 to min after each ball milling is performed by 5 to min, and collecting magnesium-based hydrogen storage material after the ball milling is finished, wherein the particle size of the material is 1 to 10 mu m.
Characterization: after the end of the ball milling, the residual pressure in the milling pot was measured by means of a pressure gauge, which showed that the pressure value in the milling pot was smaller for example 6 than for examples 4 and 5, and that the material synthesized in example 6 showed the most hydrogen removal by means of an isothermal dehydrogenation test (350 ℃).
Example 7:
in an argon atmosphere, the molar ratio is 1:1 adding 0.05 g of metal K and titanium dioxide together, 0.95 g of Mg particles and 0.2 g g of acetone into a ball milling tank, and uniformly mixing. Ball milling 4h under 200 rpm under the room temperature and argon atmosphere, and ball-to-material ratio of 120:1, 30 percent s of ball milling is stopped every 3 percent min, and magnesium-based hydrogen storage material is collected after the ball milling is finished, wherein the particle size of the material is 1-15 mu m.
Characterization: the hydrogen storage material is subjected to cycle test (back pressure: hydrogen absorption 3 Mpa and dehydrogenation 0.003 Mpa) at 300 ℃, the test result is shown in fig. 6, the first dehydrogenation amount of the sample is 6.35 and wt%, and after 20 cycles, the hydrogen amount has no loss, so that the hydrogen storage material has good cycle stability.
Example 8:
In a glove box under argon atmosphere, the molar ratio is 1:2 adding metal lithium and titanium dioxide which are 0.1 g g, 0.9 g and 0.3g of pyridine into a ball milling tank, uniformly mixing, ball milling for 6 hours at 200rpm under the argon atmosphere at room temperature, and the ball-to-material ratio is 140:1, stopping 15: 15 s after each ball milling is 2 min, and collecting the magnesium-based hydrogen storage material after the ball milling is finished. The characterization proves that the hydrogen storage material has good hydrogen absorption and desorption performance and cycle stability.
Example 9:
In a glove box under argon atmosphere, the molar ratio is 1:0.1 adding metal lithium and titanium dioxide into a ball milling tank to obtain 0.3 g total, 1 g of magnesium particles and 0.01 g of carbon nano tubes, uniformly mixing, ball milling with 200: 200 rpm ball milling under room temperature and helium atmosphere for 6: 6 h, and ball-to-material ratio of 140:1, stopping 15: 15 s after each ball milling is 2 min, and collecting the magnesium-based hydrogen storage material after the ball milling is finished. The characterization proves that the hydrogen storage material has good hydrogen absorption and desorption performance and cycle stability.
Example 10:
In a glove box under argon atmosphere, the molar ratio is 1:5 adding Rb and titanium dioxide 0.1 g g, magnesium particles 0.9 g and pyridine 0.5g into a ball milling tank, uniformly mixing, ball milling with 200: 200 rpm under the atmosphere of room temperature and helium for 6: 6 h, and the ball-to-material ratio is 140:1, stopping 15: 15 s after each ball milling is 2min, and collecting the magnesium-based hydrogen storage material after the ball milling is finished. The characterization proves that the hydrogen storage material has good hydrogen absorption and desorption performance and cycle stability.
The Mg particles in examples 1 to 10 had a particle size of 50 μm or less.
Comparative example 1:
In a glove box under argon atmosphere, the molar ratio is 1:1 adding metal Na and titanium dioxide 1 g and acetone 0.2 g into a ball milling tank, uniformly mixing, ball milling by 200 rpm under the atmosphere of argon at room temperature for 3 h, stopping 1 min for each ball milling by 5 min, and collecting the catalyst after ball milling. The mass ratio is 0.95:0.05: the magnesium particles, the catalyst and the acetone are respectively weighed according to the proportion of 0.2, 1.2 g of the mixture is put into a ball milling tank, ball milling is carried out for 10h at room temperature under 200 rpm of 3 Mpa hydrogen atmosphere, and the ball-to-material ratio is 120:1, stopping 1 to min for every 5 to min ball milling, and collecting the magnesium-based hydrogen storage material after the ball milling is finished.
Characterized, fig. 5 is a temperature programmed dehydrogenation curve for the hydrogen storage materials of example 3 and comparative example 1, showing that example 3 has a lower dehydrogenation temperature and a faster dehydrogenation rate than comparative example 1.
Comparative example 2:
In argon atmosphere, adding 0.95 g of magnesium particles into a ball milling tank according to a mole ratio of 1:1 adding metal sodium and titanium dioxide into a ball milling tank to form 0.05 g, carrying out ball milling on the ball milling tank at 200 rpm to form 4 and h at room temperature after the ball milling tank is vacuumized, wherein the ball material ratio is 120:1, stopping 1 to min for every 5 to min ball milling, and collecting the magnesium-based hydrogen storage material after the ball milling is finished.
Characterization: the temperature programmed hydrogen absorption curve of the collected hydrogen storage material without the addition of the auxiliary agent is shown in fig. 7, the hydrogen absorption kinetics of the hydrogen storage material is obviously inferior to that of example 1, the temperature increasing rate and the hydrogen pressure are the same, the Mg+5 wt% Na-TiO 2 -AC can absorb 6.8 wt% H 2 at 300 ℃, and the Mg+5 wt% Na-TiO 2 without the addition of the auxiliary agent only absorbs 5.5 wt% H 2.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (8)
1. The method for synthesizing the magnesium-based hydrogen storage material assisted by the alkali metal reduced titanium dioxide catalyst is characterized by comprising the following steps of:
Under the inert atmosphere environment, adding magnesium particles, alkali metal, titanium dioxide and an auxiliary agent into a reactor, uniformly mixing in a hydrogen-rich environment or a hydrogen-poor environment, discharging redundant reaction gas, and collecting a magnesium-based hydrogen storage material;
the mass ratio of the magnesium particles to the auxiliary agent is 1:0.01-0.5;
the auxiliary agent is an organic solvent and a carbon material, and the mass ratio of the organic solvent to the carbon material is 1:1;
The carbon material is one or more of ordinary graphite, graphene, expanded graphite, acetylene black and carbon nano tubes;
The organic solvent is one or more of methyl butanone, acetone, methyl isobutyl ketone and methyl ethyl ketone.
2. The method for synthesizing a magnesium-based hydrogen storage material assisted by an alkali metal reduced titania catalyst according to claim 1, wherein the molar ratio of the alkali metal to the titania is 1:0.1-5, and the mass ratio of the magnesium particles to the sum of the alkali metal and the titania is 1:0.01-0.3.
3. The method for synthesizing a magnesium-based hydrogen storage material assisted by an alkali metal reduced titania catalyst according to claim 1, wherein the alkali metal is one or more of Li, na, K, rb and Cs.
4. The method for synthesizing magnesium-based hydrogen storage material assisted by an alkali metal reduced titanium dioxide catalyst according to claim 1, wherein the auxiliary agent is acetone and expanded graphite, and the mass ratio of the acetone to the expanded graphite is 1:1.
5. The method for synthesizing a magnesium-based hydrogen storage material assisted by an alkali metal reduced titania catalyst according to claim 1, wherein the magnesium particles have a particle size of 50 μm or less.
6. The method for synthesizing magnesium-based hydrogen storage material assisted by an alkali metal reduced titania catalyst according to claim 1, wherein the mixing method is ball milling or stirring.
7. The method for synthesizing the magnesium-based hydrogen storage material assisted by the alkali metal reduced titanium dioxide catalyst according to claim 1, wherein the partial pressure of hydrogen in the hydrogen-rich environment is 1 MPa-30 Mpa; the hydrogen-lean environment is an inert gas environment or a vacuum.
8. A magnesium-based hydrogen storage material, characterized in that it is prepared by the method according to any one of claims 1-7.
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