CN115744814A - Gamma-MoC/VN restricted domain catalyzed MgH2 nano composite hydrogen storage material and preparation method thereof - Google Patents
Gamma-MoC/VN restricted domain catalyzed MgH2 nano composite hydrogen storage material and preparation method thereof Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 117
- 239000001257 hydrogen Substances 0.000 title claims abstract description 116
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000011232 storage material Substances 0.000 title claims abstract description 52
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910012375 magnesium hydride Inorganic materials 0.000 title claims abstract description 5
- 238000003860 storage Methods 0.000 claims abstract description 25
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000005121 nitriding Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000010041 electrostatic spinning Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 21
- 238000003795 desorption Methods 0.000 abstract description 19
- 239000000463 material Substances 0.000 description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 238000010000 carbonizing Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000002457 bidirectional effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- RSHAOIXHUHAZPM-UHFFFAOYSA-N magnesium hydride Chemical compound [MgH2] RSHAOIXHUHAZPM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
The invention provides MgH catalyzed by gamma-MoC/VN restricted domain 2 A nano-composite hydrogen storage material and a preparation method thereof. The nano-composite hydrogen storage material takes gamma-MoC/VN as a matrix, and the MgH 2 The nano particles are loaded in the mesopores of the gamma-MoC/VN in a limited domain manner; wherein the nano-composite hydrogen storage material comprises 50-70 wt.% gamma-MoC/VN and 30-50 wt.% magnesium hydride by mass percentage. The invention discovers that the gamma-MoC/VN can be used as a novel nano limited hydrogen storage material for the first time, and the hydrogen storage material obtained by utilizing the gamma-MoC/VN not only has excellent hydrogen absorption and desorption dynamic performance, but also has good circulation stability and hydrogen storage capacity.
Description
Technical Field
The invention relates to the technical field of hydrogen storage materials, in particular to MgH catalyzed by gamma-MoC/VN restricted domain 2 A nano-composite hydrogen storage material and a preparation method thereof.
Background
The hydrogen energy source is a clean energy source using hydrogen as a carrier, but the storage of hydrogen is a technical bottleneck for realizing the application of hydrogen energy. Good safety performance, wide material source, high hydrogen storage density (7.69 wt.% and 106 kg/m) 3 ) MgH of 2 Is considered to be the most promising to meet the technical standard of the United states department of energy (DOE) vehicle-mounted hydrogen storage system (DOE), namely the technical standard of reversible release and absorption of 6.5wt.% H at-40-85 DEG C 2 ) One of the solid carriers of (1). However, higher enthalpy of formation (Δ H =76kJ/mol H2) and activation energy of reaction (Δ E =160 kJ/mol) result in MgH 2 High hydrogen absorption and desorption temperature (>300 deg.C) and slow kinetics. The hydrogen discharge and charge kinetics of the nano structure are improved by utilizing the ultrahigh activity of the nano structure, but the nano structure is gradually agglomerated and grown in the circulation process, so that the performance of the nano structure is sharply reduced.
Although MgH can be reduced by adding a catalyst 2 Energy barrier of hydrogen absorption and desorption reaction and improvement of MgH 2 Without improving its thermodynamic properties. Want to realize MgH 2 Practical application of (2) should be simultaneously to MgH 2 The thermodynamic property of the material is regulated and controlled. The particle size of the material is reduced, so that the diffusion path of hydrogen can be shortened, and MgH is promoted 2 Hydrogen absorption and desorption kinetics; but also can provide more grain boundaries and additional surface/interface free energy, and improve the thermodynamic performance of the material. Theoretical calculation shows that when MgH 2 The particle size of (2) is reduced to below 4nm and the thermodynamic properties are changed. To further reduce MgH 2 The size and the research personnel propose a 'nano confinement' strategy, the material is filled in the nano-pore channel, the interaction of the material and the nano-pore channel is utilized to promote the reaction, and a unique microenvironment is provided for the chemical reaction. At present, most of the research on the framework materials of the limited area at home and abroad focuses on the carbon substrateMaterials, metal framework compounds, and the like. The carbon matrix material mainly comprises porous activated carbon, graphene, carbon nanotubes, fullerene and the like. The carbon matrix material has large specific surface area and high porosity, but the effective hydrogen storage amount of the whole system is greatly reduced due to the limited loading efficiency and the low catalytic effect of the carbon matrix material, so the carbon matrix material is difficult to combine high MgH 2 The load rate and the good hydrogen absorption and desorption catalytic effect lose the value of practical application. The metal organic framework material has a unique pore structure and a large specific surface area, and provides a good space structure for a limited domain, but the hydrogen storage performance of the composite material can be influenced by ligands, metal ions and the like of the MOFs material, and most of the MOFs only obviously improve the hydrogen absorption/desorption unidirectional kinetics, so that the metal organic framework material temporarily does not have a good commercial prospect.
Therefore, a new nano composite hydrogen storage material with excellent hydrogen storage performance and hydrogen absorption and desorption bidirectional catalytic effect is needed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides MgH catalyzed by gamma-MoC/VN restricted domain 2 A nano-composite hydrogen storage material and a preparation method thereof solve the problem that a load material in the prior art cannot have excellent hydrogen storage performance and hydrogen absorption and desorption bidirectional catalysis.
In one aspect of the invention, the MgH catalyzed by gamma-MoC/VN restricted domain is provided 2 The nano-composite hydrogen storage material takes gamma-MoC/VN as a matrix, and MgH 2 The nano particles are loaded in the mesopores of the gamma-MoC/VN in a limited domain manner;
wherein the nano-composite hydrogen storage material comprises 50-75 wt.% of gamma-MoC/VN and 25-50 wt.% of magnesium hydride.
Further, the pore volume of the gamma-MoC/VN is 0.11-0.1523cm 3 /g。
In another aspect of the invention, the MgH catalyzed by the gamma-MoC/VN restricted domain is provided 2 The preparation method of the nano-composite hydrogen storage material comprises the step of placing gamma-MoC/VN in MgBu under the hydrogen atmosphere with certain pressure 2 In the process of impregnation and hydrogenation reaction, drying to obtainGamma-MoC/VN restricted domain catalyzed MgH 2 A nanocomposite hydrogen storage material.
Has the advantages that: the hydrogen atmosphere is not only MgBu 2 The hydrogenation of (2) provides reaction conditions while avoiding MgBu 2 Contact with oxygen, due to MgBu 2 Is sensitive to oxygen, and if the oxygen is contacted in the test process, mgBu can be caused 2 Oxidation failure occurs, and MgH can not be obtained by hydrogenation 2 And thus a nanocomposite hydrogen storage material having good hydrogen storage capacity cannot be obtained.
Further, in g/ml, gamma-MoC/VN: mgBu 2 Is 0.5-1.0.
Further, the pressure is 40-50Bar, the reaction temperature is 170-200 ℃, and the reaction time is 12-24h.
Has the advantages that: within this range of conditions, the resulting nanocomposite hydrogen storage material has the best activity. Under the reaction condition, the hydrogenation of the nano-composite hydrogen storage material is incomplete, and the nano-composite hydrogen storage material is oxidized in the subsequent treatment process, so that the hydrogen storage capacity of the nano-composite hydrogen storage material is reduced. Above this reaction condition, crystal grain growth may result during the reaction, thereby reducing the stability of the nanocomposite hydrogen storage material.
Further, the drying temperature is 60-80 ℃, and the drying time is 3-6h.
Further, the preparation method of the gamma-MoC/VN comprises the following steps:
s1: h is to be 24 Mo 7 N 6 O 24 ·4H 2 O、NH 4 VO 3 Dissolving polyvinylpyrrolidone in ethanol solution, stirring, electrostatic spinning to obtain fiber film, vacuum drying, and calcining to obtain V 2 MoO 8 Solid particles;
s2: will V 2 MoO 8 Carbonizing by using CO; reuse of NH 3 And nitriding to obtain gamma-MoC/VN.
Further, in step S1, in g/g/g/ml, H 24 Mo 7 N 6 O 24 ·4H 2 O:NH 4 VO 3 The polyvinyl pyrrolidone and the ethanol solution are 0.48-0.68.
Further, in the step S1, the drying temperature is 60-80 ℃, and the time is 3 hours; the calcining temperature is 510-630 ℃; the time is 6-8h;
in the step S2, the CO gas inlet rate is 80mL/min, the carbonization temperature is 700-1000 ℃, and the time is 1-6h; NH (NH) 3 The air inlet speed is 80mL/min, the nitriding temperature is 600-900 ℃, and the time is 1-6h.
In another aspect of the invention, the invention provides MgH catalyzed by gamma-MoC/VN restricted domain 2 Application of nano composite hydrogen storage material in energy storage material.
MgBu 2 Is a dibutylmagnesium solution, and includes dibutylmagnesium 1.0M hexane, dibutylmagnesium 1.0M heptane, dibutylmagnesium 0.5M heptane, etc. In the examples of the present invention, dibutylmagnesium 1.0M heptane is used as an example for specific explanation.
The technical principle of the invention is as follows: the gamma-MoC/VN is a molybdenum nitride and vanadium carbide heterostructure, and was originally found to be a water electrolysis catalyst and electrocatalytic for water decomposition to hydrogen. Through further research and exploration, the inventor unexpectedly finds that the gamma-MoC/VN is used as a nano confinement framework material for preparing the hydrogen storage material, and the obtained hydrogen storage material not only has excellent hydrogen absorption and desorption dynamic performance, but also has stable cycle performance. The principle of the method is probably that the gamma-MoC/VN heterojunction has bidirectional catalytic performance and can catalyze MgH 2 The hydrogen releasing reaction of the catalyst can catalyze the hydrogen absorption reaction of Mg, and the hydrogen absorption and release performance is improved; at the same time MgH 2 The particles are confined in the mesopores of the gamma-MoC/VN heterojunction, the hydrogen absorption and desorption temperature can be reduced, the sintering agglomeration caused by hydrogen absorption and desorption cyclic reaction can be effectively inhibited, and MgH is enabled to be 2 The nano structure is better maintained in the recycling process, and the cycling stability of the hydrogen storage material is prolonged.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention discovers that the gamma-MoC/VN can be used as a novel nano-confinement hydrogen storage material for the first time, and the hydrogen storage material obtained by utilizing the gamma-MoC/VN not only has excellent hydrogen absorption and desorption dynamic performance, but also has good cycle stability and hydrogen storage capacity. The hydrogen storage capacity can reach 3.84wt.%, and 3.84wt.% hydrogen can be reversibly absorbed within 20min under the conditions of 250 ℃ and 3 MPa; 3.84wt.% hydrogen can be released within 20min at 250 ℃ under 0.02 MPa; the hydrogen storage capacity after 20 cycles is 3.73wt.%, the maximum hydrogen storage capacity attenuation is lower than 3%, and the synergistic effect of nano catalysis and nano confinement is realized.
(2) The preparation method is simple, has controllable conditions, and has high practical application value and good commercial prospect.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1 Gamma-MoC/VN Domain catalyzed MgH 2 Preparation of nano composite hydrogen storage material
(1) 0.48g H 24 Mo 7 N 6 O 24 ·4H 2 O、0.31g NH 4 VO 3 Mixing with 0.5g polyvinylpyrrolidone (PVP) powder in 8.41mL ethanol solution, stirring, electrostatic spinning to obtain fiber film, vacuum drying at 60 deg.C for 8 hr, calcining at 510 deg.C for 8 hr to obtain V 2 MoO 8 Solid particles;
(2) Will V 2 MoO 8 Carbonizing with CO at 700 deg.C at an air inlet rate of 80mL/min for 1h; then NH is used at 600 ℃ at an inlet rate of 80mL/min 3 Nitriding for 1h to obtain porous gamma-MoC/VN, and detecting the pore volume of the nano-composite hydrogen storage material to be 0.11cm by a nitrogen adsorption-desorption method 3 /g；
(3) With 10mL of MgBu 2 (1.0M heptane solution) 1.0g of porous gamma-MoC/VN and mechanical stirring at 200 ℃ and 40bar high pressure hydrogen atmosphere for 12h, natural cooling and vacuum drying at 60 ℃ for 6h to obtain 25wt.% MgH catalyzed by 75wt.% gamma-MoC/VN domains 2 Nanocomposite hydrogen storage material with a hydrogen storage capacity of 1.92wt.%.
Example 2 Gamma-MoC/VN Domain catalyzed MgH 2 Preparation of nano composite hydrogen storage material
(1) 0.78g H 24 Mo 7 N 6 O 24 ·4H 2 O、0.21g NH 4 VO 3 Mixing with 0.75g polyvinylpyrrolidone (PVP) powder in 9.91mL ethanol solution, stirring, electrospinning to obtain fiber film, vacuum drying at 70 deg.C for 7 hr, and calcining at 570 deg.C for 7 hr to obtain the final productGet V 2 MoO 8 Solid particles;
(2) Will V 2 MoO 8 Carbonizing at 800 deg.C with CO at an air inlet rate of 80mL/min for 3.5h; then using NH at 750 ℃ at an inlet rate of 80mL/min 3 Nitriding for 3.5h to obtain porous gamma-MoC/VN, and detecting the pore volume of the nano-composite hydrogen storage material to be 0.13cm by a nitrogen adsorption and desorption method 3 /g；
(3) With 15 mM MgBu 2 (1.0M heptane solution) 0.75g of porous gamma-MoC/VN was immersed and mechanically stirred at 185 ℃ and 45bar high pressure hydrogen atmosphere for 18h, naturally cooled and dried at 70 ℃ for 4h under vacuum to obtain 66wt.% gamma-MoC/VN domain-catalyzed 34wt.% MgH 2 Nanocomposite hydrogen storage material with a hydrogen storage capacity of 2.26wt.%.
Example 3 Gamma-MoC/VN Domain catalyzed MgH 2 Preparation of nano composite hydrogen storage material
(1) 0.68g H 24 Mo 7 N 6 O 24 ·4H 2 O、0.11g NH 4 VO 3 Mixing with 1.0g polyvinylpyrrolidone (PVP) powder in 11.41mL ethanol solution, stirring, electrostatic spinning to obtain fiber film, vacuum drying at 80 deg.C for 3 hr, calcining at 630 deg.C for 6 hr to obtain V 2 MoO 8 Solid particles;
(2) Will V 2 MoO 8 Carbonizing with CO at 1000 deg.C at an air inlet rate of 80mL/min for 6h; then using NH at an inlet rate of 80mL/min at 900 DEG C 3 Nitriding for 6h to obtain porous gamma-MoC/VN, and detecting the pore volume of the nano-composite hydrogen storage material to be 0.1523cm by a nitrogen adsorption and desorption method 3 /g；
(3) Using 20 mM MgBu 2 (1.0M heptane solution) 0.5g of porous gamma-MoC/VN was immersed and mechanically stirred at 170 ℃ under 50bar high pressure hydrogen atmosphere for 24h, naturally cooled and dried at 80 ℃ under vacuum for 3h to obtain 50wt.% MgH catalyzed by 50wt.% gamma-MoC/VN confinement 2 Nanocomposite hydrogen storage material with a hydrogen storage capacity of 3.84wt.%.
MgH catalyzed by gamma-MoC/VN confinement prepared in example 3 2 The nanocomposite hydrogen storage material was subjected to the following performance tests.
Test example 1 detection of Hydrogen storage Capacity
The detection method comprises the following steps: setting different temperature gradients (100-300 ℃) by a PCT hydrogen storage performance tester, and filling H with different pressures 2 (2-5 MPa), recording the change of hydrogen adsorption quantity along with time, determining the maximum adsorption quantity which can be realized by the material in the test after the adsorption quantity curve gradually becomes gentle, and finally determining the maximum hydrogen storage capacity of the material by comparing the adsorption quantities under different test conditions.
And (3) detection results: the hydrogen storage capacity can be up to 3.84wt.%.
Test example 2 kinetic detection of Hydrogen absorption and desorption
The detection method comprises the following steps: performing DSC test by setting different temperature rise rate gradients (2-10 ℃/min), drawing a DSC curve to find out the peak temperature, and using a formula:
wherein T is p And beta is the peak temperature and the heating rate respectively for converting Mg into MgH 2 Fraction of, E a For activation energy, F KAS () A function representing the conversion fraction, R being a gas constant, and calculating an apparent activation energy E a The hydrogen evolution dynamic performance of the composite material is expressed;
by setting different temperature gradients (100-300 ℃), filling H with different pressures 2 (2-5 MPa) and respectively recording the change of the hydrogen adsorption capacity along with the time, finally drawing a curve of the change of the hydrogen adsorption/desorption capacity along with the time under different conditions, and utilizing a formula:
ln[-ln(1-a)]＝n ln k+n ln t
in which Mg is converted into MgH at time t 2 K is an effective kinetic parameter, n is an Avrami index, and the activation energy E is calculated a Determination of hydrogen absorption kinetics of composite materials
And (3) detection results: reversibly absorbing 3.84wt.% hydrogen within 20min at 250 ℃ under 3 MPa; 3.84wt.% hydrogen can be released within 20min at 250 ℃ under 0.02 MPa.
Test example 3 measurement of circulation stability
The detection method comprises the following steps: the optimal hydrogen absorption/desorption condition is obtained through hydrogen storage dynamic performance detection, the hydrogen absorption/desorption process is repeated on the composite material under the condition, the total hydrogen absorption/desorption amount of the composite material in each process is recorded, a data graph of the total hydrogen absorption/desorption amount is drawn gradually, and the change trend of the data graph is observed and calculated to determine the cycle stability of the composite material.
And (3) detection results: the hydrogen storage capacity after 20 cycles was 3.73wt.%, with a maximum hydrogen storage capacity decay of less than 3%.
Gamma-MoC/VN Domain catalyzed MgH prepared in examples 1-2 2 The nanocomposite hydrogen storage material had similar properties to example 3.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. MgH catalyzed by gamma-MoC/VN restricted domain 2 The nano-composite hydrogen storage material is characterized in that: the nano-composite hydrogen storage material takes gamma-MoC/VN as a matrix, and the MgH 2 The nano particles are loaded in the mesopores of the gamma-MoC/VN in a limited domain manner;
wherein the nano-composite hydrogen storage material comprises 50-75 wt.% gamma-MoC/VN and 25-50 wt.% magnesium hydride by mass percentage.
2. A γ -MoC/VN gamut catalyzed MgH of claim 1 2 A nanocomposite hydrogen storage material, characterized in that the pore volume of the gamma-MoC/VN is from 0.11 to 0.1523cm 3 /g。
3. MgH catalyzed by gamma-MoC/VN restricted domain 2 Nano composite hydrogen storage materialThe preparation method is characterized in that: under the hydrogen atmosphere with certain pressure, the gamma-MoC/VN is placed in MgBu 2 The MgH catalyzed by gamma-MoC/VN limited domain is obtained after the impregnation and hydrogenation reaction and the drying 2 A nanocomposite hydrogen storage material.
4. A gamma-MoC/VN-zoned catalyzed MgH of claim 3 2 The preparation method of the nano-composite hydrogen storage material is characterized by comprising the following steps: calculated by g/ml, gamma-MoC/VN: mgBu 2 Is 0.5-1.0.
5. A gamma-MoC/VN-zoned catalyzed MgH of claim 3 2 The preparation method of the nano-composite hydrogen storage material is characterized by comprising the following steps: the pressure is 40-50Bar, the reaction temperature is 170-200 ℃, and the reaction time is 12-24h.
6. A gamma-MoC/VN-domain catalyzed MgH of claim 3 2 The preparation method of the nano-composite hydrogen storage material is characterized by comprising the following steps: the drying temperature is 60-80 deg.C, and the drying time is 3-6h.
7. A gamma-MoC/VN-zoned catalyzed MgH of claim 3 2 The preparation method of the nano-composite hydrogen storage material is characterized by comprising the following steps: the preparation method of the gamma-MoC/VN comprises the following steps of:
s1: will H 24 Mo 7 N 6 O 24 ·4H 2 O、NH 4 VO 3 Dissolving polyvinylpyrrolidone in ethanol solution, stirring, electrostatic spinning to obtain fiber film, vacuum drying, and calcining to obtain V 2 MoO 8 Solid particles;
s2: will V 2 MoO 8 Carbonising with CO and then with NH 3 And nitriding to obtain gamma-MoC/VN.
8. A gamma-MoC/VN-domain catalyzed MgH of claim 7 2 The preparation method of the nano-composite hydrogen storage material is characterized by comprising the following steps: in step S1, in g/g/g/ml, H 24 Mo 7 N 6 O 24 ·4H 2 O:NH 4 VO 3 The polyvinyl pyrrolidone and ethanol solution is 0.48-0.78, 0.11-0.31, and the weight ratio is 8.41-11.41.
9. A gamma-MoC/VN-zoned catalyzed MgH of claim 7 2 The preparation method of the nano-composite hydrogen storage material is characterized by comprising the following steps: in the step S1, the drying temperature is 60-80 ℃ and the time is 3-8h; the calcining temperature is 510-630 ℃; the time is 6-8h;
in the step S2, the CO gas inlet rate is 80mL/min, the carbonization temperature is 700-1000 ℃, and the time is 1-6h; NH 3 The air inlet rate is 80mL/min, the nitriding temperature is 600-900 ℃, and the time is 1-6h.
10. A gamma-MoC/VN-restricted catalyzed MgH of claim 1 or 2 2 The application of the nano composite hydrogen storage material in energy storage materials.
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