CN115744814B - Gamma-MoC/VN (gamma-MoC/VN) domain-limited catalysis MgH2 nano composite hydrogen storage material and preparation method thereof - Google Patents
Gamma-MoC/VN (gamma-MoC/VN) domain-limited catalysis 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 118
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000001257 hydrogen Substances 0.000 title claims abstract description 117
- 239000011232 storage material Substances 0.000 title claims abstract description 54
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910012375 magnesium hydride Inorganic materials 0.000 title claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 title description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 238000005121 nitriding Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 238000010041 electrostatic spinning Methods 0.000 claims description 5
- 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
- 238000003763 carbonization Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 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
- 238000003860 storage Methods 0.000 abstract description 24
- 238000003795 desorption Methods 0.000 abstract description 20
- 238000010521 absorption reaction Methods 0.000 abstract description 19
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 238000001514 detection method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 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
- 230000008569 process Effects 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 238000010000 carbonizing Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000002457 bidirectional effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 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
- 239000003054 catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research 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
- 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
- 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 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
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 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
- RSHAOIXHUHAZPM-UHFFFAOYSA-N magnesium hydride Chemical compound [MgH2] RSHAOIXHUHAZPM-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 230000002035 prolonged effect Effects 0.000 description 1
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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
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Abstract
The invention provides a gamma-MoC/VN confinement catalytic MgH 2 nano composite hydrogen storage material and a preparation method thereof. The nano composite hydrogen storage material takes gamma-MoC/VN as a matrix, and MgH 2 nano particles are loaded in mesopores of the gamma-MoC/VN in a limited domain; wherein, the nano composite hydrogen storage material comprises 50 to 70wt.% of gamma-MoC/VN and 30 to 50wt.% of magnesium hydride according to mass percent. The invention discovers that the gamma-MoC/VN can be used as a novel nano-finite field hydrogen storage material for the first time, and the hydrogen storage material obtained by utilizing the gamma-MoC/VN has excellent hydrogen absorption and desorption dynamics performance, and also has good cycle stability and hydrogen storage capacity.
Description
Technical Field
The invention relates to the technical field of hydrogen storage materials, in particular to a gamma-MoC/VN confinement catalytic MgH 2 nano composite hydrogen storage material and a preparation method thereof.
Background
The hydrogen energy is a clean energy taking hydrogen as a carrier, but the storage of hydrogen is a technical bottleneck for realizing the application of hydrogen energy. MgH 2, which has good safety performance, wide material source and high hydrogen storage density (7.69 wt.% and 106kg/m 3), is considered to be one of the solid carriers most promising to meet the technical standards of the on-board hydrogen storage system of the department of energy (DOE) of the United states (-reversible release and absorption of 6.5wt.% H 2 at 40-85 ℃). However, the higher enthalpy of formation (Δh=76 kJ/mol H2) and reaction activation energy (Δe=160 kJ/mol) lead to a high hydrogen absorption and desorption temperature (> 300 ℃) of MgH 2, with slow kinetics. The ultra-high activity of the nano structure is utilized to improve the hydrogen release and charge dynamics of the nano structure, but the nano structure gradually aggregates and grows up in the circulation process, so that the performance of the nano structure is drastically reduced.
Although the catalyst can reduce the energy barrier of the MgH 2 hydrogen absorption and desorption reaction and improve the dynamic performance of MgH 2, the thermodynamic performance of the MgH 2 is not improved. To realize practical use of MgH 2, the thermodynamic properties of MgH 2 must be controlled at the same time. The particle size of the material is reduced, so that the diffusion path of hydrogen can be shortened, and the hydrogen absorption and desorption kinetics of MgH 2 can be improved; but also provides more grain boundaries and additional surface/interface free energy, improving its thermodynamic properties. Theoretical calculations show that when the particle size of MgH 2 is reduced below 4nm, the thermodynamic properties change. In order to further reduce the size of MgH 2, researchers have proposed a strategy of "nano-confinement", filling materials into the nano-pore, and using the interaction of the materials and the nano-pore to promote the reaction, providing a unique microenvironment for the chemical reaction. At present, most of research on frame materials of limited fields at home and abroad is focused on carbon matrix materials, 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 can be greatly reduced due to the limited loading efficiency and lower catalytic effect of the carbon matrix material, so that the carbon matrix material is difficult to have high MgH 2 loading rate and good hydrogen absorption and desorption catalytic effect, and the practical application value is lost. The metal organic frame material has a unique pore structure and a large specific surface area, provides a good space structure for a limited domain, but most MOFs only have obvious improvement on unidirectional kinetics of hydrogen absorption/desorption because ligands, metal ions and the like of the MOFs can influence the hydrogen storage performance of the composite material, so that the metal organic frame material has no good commercial prospect temporarily.
Therefore, a novel 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 existing in the prior art, the invention provides a gamma-MoC/VN finite field catalyzed MgH 2 nano composite hydrogen storage material and a preparation method thereof, which 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, a gamma-MoC/VN confinement catalyzed MgH 2 nano composite hydrogen storage material is provided, wherein the nano composite hydrogen storage material takes gamma-MoC/VN as a matrix, and MgH 2 nano particles are supported in mesopores of the gamma-MoC/VN in a confinement manner;
Wherein, the nano composite hydrogen storage material comprises 50 to 75wt.% of gamma-MoC/VN and 25 to 50wt.% of magnesium hydride according to mass percent.
Further, the gamma-MoC/VN has a pore volume of 0.11-0.1523cm 3/g.
In another aspect, the invention provides a preparation method of the MgH 2 nano composite hydrogen storage material by gamma-MoC/VN finite field catalysis, which comprises the steps of carrying out impregnation and hydrogenation reaction on gamma-MoC/VN in MgBu 2 under a hydrogen atmosphere with certain pressure, and drying to obtain the MgH 2 nano composite hydrogen storage material by gamma-MoC/VN finite field catalysis.
The beneficial effects are that: the hydrogen atmosphere not only provides reaction conditions for the hydrogenation of MgBu 2, but also avoids the contact of MgBu 2 with oxygen, because MgBu 2 is very sensitive to oxygen, if the MgBu 2 is contacted with oxygen in the test process, oxidation failure can occur, mgH 2 can not be obtained by hydrogenation, and thus the nano-composite hydrogen storage material with good hydrogen storage capacity can not be obtained.
Further, the gamma-MoC/VN: mgBu 2 is 0.5-1.0:10-20 in g/ml.
Further, the pressure is 40-50Bar, the reaction temperature is 170-200 ℃, and the reaction time is 12-24h.
The beneficial effects are that: within this range of conditions, the resulting nanocomposite hydrogen storage material has the best activity. Under the reaction conditions, incomplete hydrogenation of the nanocomposite hydrogen storage material can be caused, and oxidation of the nanocomposite hydrogen storage material can be caused during subsequent processing, thereby reducing the hydrogen storage capacity of the nanocomposite hydrogen storage material. Above the reaction conditions, grains grow 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: dissolving H 24Mo7N6O24·4H2O、NH4VO3 and polyvinylpyrrolidone in an ethanol solution, stirring, preparing a fiber film through electrostatic spinning, drying in vacuum, and calcining to obtain V 2MoO8 solid particles;
S2: carbonizing V 2MoO8 with CO; and nitriding by using NH 3 to obtain gamma-MoC/VN.
Further, in the step S1, the concentration of H 24Mo7N6O24·4H2O:NH4VO3, polyvinylpyrrolidone and ethanol solution is 0.48-0.68:0.11-0.31:0.5-1.0:8.41-11.41 in terms of g/g/ml.
Further, in the step S1, the drying temperature is 60-80 ℃ and the drying time is 3 hours; the calcination temperature is 510-630 ℃; the time is 6-8h;
In the step S2, the CO air inlet rate is 80mL/min, the carbonization temperature is 700-1000 ℃ and the time is 1-6h; NH 3 gas inlet rate 80mL/min, nitriding temperature 600-900 ℃ and nitriding time 1-6h.
In still another aspect, the invention provides an application of the gamma-MoC/VN confinement catalyzed MgH 2 nano-composite hydrogen storage material in an energy storage material.
MgBu 2 is a dibutylmagnesium solution including 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 taken as an example for specific explanation.
The technical principle of the invention is as follows: the gamma-MoC/VN is a hetero-structure of molybdenum nitride and vanadium carbide, and the gamma-MoC/VN can be used as an electrolytic water catalyst for preparing hydrogen through electrocatalytic water decomposition. Through further research and exploration, the inventor unexpectedly discovers that the gamma-MoC/VN is used as a nano-finite field framework material for preparing the hydrogen storage material, and the obtained hydrogen storage material not only has excellent hydrogen absorption and desorption kinetic performance, but also has stable cycle performance. The principle is probably that the gamma-MoC/VN heterojunction has bidirectional catalytic performance, so that the MgH 2 hydrogen desorption reaction can be catalyzed, the Mg hydrogen absorption reaction can be catalyzed, and the hydrogen absorption and desorption performance is improved; meanwhile, mgH 2 particles are limited in mesopores of the gamma-MoC/VN heterojunction, so that the hydrogen absorption and desorption temperature can be reduced, sintering agglomeration caused by hydrogen absorption and desorption cyclic reaction can be effectively inhibited, the nano structure of MgH 2 can be better maintained in the cyclic use process, and the cyclic stability of the hydrogen storage material can be 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-finite field hydrogen storage material for the first time, and the hydrogen storage material obtained by utilizing the gamma-MoC/VN has excellent hydrogen absorption and desorption dynamics performance, and also has good cycle stability and hydrogen storage capacity. The hydrogen storage capacity can reach 3.84wt.% and can reversibly absorb 3.84wt.% of hydrogen within 20min under the conditions of 250 ℃ and 3 MPa; 3.84wt.% hydrogen can be released within 20min at 250 ℃,0.02 MPa; after 20 cycles, the hydrogen storage capacity is 3.73wt.%, the maximum hydrogen storage capacity attenuation is less 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 scheme of the invention is further described below by referring to examples.
Example 1 preparation of Gamma-MoC/VN Limited catalytic MgH 2 Nano composite Hydrogen storage Material
(1) Uniformly stirring 0.48g H 24Mo7N6O24·4H2O、0.31g NH4VO3 g polyvinylpyrrolidone (PVP) powder and 8.41mL ethanol solution, preparing a fiber film through electrostatic spinning, drying in vacuum at 60 ℃ for 8 hours, and calcining at 510 ℃ for 8 hours to obtain V 2MoO8 solid particles;
(2) Carbonizing V 2MoO8 with CO at 700 ℃ at an air intake rate of 80mL/min for 1h; nitriding with NH 3 at 600 ℃ at an air inlet rate of 80mL/min for 1h to obtain porous gamma-MoC/VN, wherein the pore volume of the nano composite hydrogen storage material detected by a nitrogen adsorption and desorption method is 0.11cm 3/g;
(3) 1.0g of porous gamma-MoC/VN was impregnated with 10mL of MgBu 2 (1.0M heptane solution) and mechanically stirred at 200℃under a high pressure hydrogen atmosphere of 40bar for 12h, and after natural cooling, dried under vacuum at 60℃for 6h to obtain 75wt.% gamma-MoC/VN domain-catalyzed 25wt.% MgH 2 nanocomposite hydrogen storage material with a hydrogen storage capacity of 1.92wt.%.
Example 2 preparation of Gamma-MoC/VN Limited catalytic MgH 2 Nano composite Hydrogen storage Material
(1) Uniformly stirring 0.78g H 24Mo7N6O24·4H2O、0.21g NH4VO3 and 0.75g polyvinylpyrrolidone (PVP) powder in 9.91mL ethanol solution, preparing a fiber film through electrostatic spinning, drying in vacuum at 70 ℃ for 7h, and calcining at 570 ℃ for 7h to obtain V 2MoO8 solid particles;
(2) Carbonizing V 2MoO8 with CO at 800 ℃ at an air intake rate of 80mL/min for 3.5h; nitriding with NH 3 at 750 ℃ at an air inlet rate of 80mL/min for 3.5h to obtain porous gamma-MoC/VN, wherein the pore volume of the nano composite hydrogen storage material detected by a nitrogen adsorption and desorption method is 0.13cm 3/g;
(3) 0.75g of porous gamma-MoC/VN is immersed in 15mLMgBu 2 (1.0M heptane solution) and mechanically stirred for 18h under high pressure hydrogen atmosphere at 185 ℃ and 45bar, and after natural cooling, the mixture is dried in vacuum at 70 ℃ for 4h, thus obtaining 66wt.% gamma-MoC/VN limit-catalyzed 34wt.% MgH 2 nano composite hydrogen storage material with a hydrogen storage capacity of 2.26wt.%.
Example 3 preparation of Gamma-MoC/VN Limited catalytic MgH 2 Nano composite Hydrogen storage Material
(1) Uniformly stirring 0.68g H 24Mo7N6O24·4H2O、0.11g NH4VO3 and 1.0g polyvinylpyrrolidone (PVP) powder in 11.41mL ethanol solution, preparing a fiber film through electrostatic spinning, vacuum drying at 80 ℃ for 3 hours, and calcining at 630 ℃ for 6 hours to obtain V 2MoO8 solid particles;
(2) Carbonizing V 2MoO8 at 1000 ℃ with CO for 6 hours at an air intake rate of 80 mL/min; nitriding with NH 3 at 900 ℃ at an air inlet rate of 80mL/min for 6h to obtain porous gamma-MoC/VN, wherein the pore volume of the nano composite hydrogen storage material detected by a nitrogen adsorption and desorption method is 0.1523cm 3/g;
(3) 0.5g of porous gamma-MoC/VN is immersed with 20mLMgBu 2 (1.0M heptane solution), mechanically stirred for 24 hours under high-pressure hydrogen atmosphere at 170 ℃ and 50bar, naturally cooled and dried in vacuum at 80 ℃ for 3 hours to obtain 50wt.% gamma-MoC/VN limit-catalyzed 50wt.% MgH 2 nano composite hydrogen storage material with a hydrogen storage capacity of 3.84wt.%.
The following performance tests were performed on the gamma-MoC/VN confinement catalyzed MgH 2 nanocomposite hydrogen storage material prepared in example 3.
Test example 1 hydrogen storage Capacity detection
The detection method comprises the following steps: different temperature gradients (100-300 ℃) are set through a PCT hydrogen storage performance tester, H 2 (2-5 MPa) with different pressures are filled, the change of the hydrogen adsorption quantity along with time is recorded, when the adsorption quantity curve gradually becomes gentle, the adsorption quantity curve is considered to be the maximum adsorption quantity which can be realized by the material in the test, and the maximum hydrogen storage capacity of the material is finally determined through comparing the adsorption quantity under different test conditions.
Detection result: the hydrogen storage capacity can reach 3.84wt.%.
Test example 2 hydrogen absorption and desorption kinetics test
The detection method comprises the following steps: DSC tests are carried out by setting different heating rate gradients (2-10 ℃/min), a DSC curve is drawn to find out the peak temperature, and the formula is utilized:
Wherein T p and beta are peak temperature and heating rate respectively, the fraction of Mg converted into MgH 2, E a is activation energy, F KAS () represents a function of the conversion fraction, R is a gas constant, and apparent activation energy E a is calculated to express the hydrogen release kinetic performance of the composite material;
By setting different temperature gradients (100-300 ℃), filling H 2 (2-5 MPa) with different pressures, respectively recording the time-varying amount of hydrogen adsorption, and finally drawing curves of the time-varying amount of hydrogen adsorption/desorption under different conditions, and utilizing the formula:
ln[-ln(1-a)]＝n ln k+n ln t
Wherein the fraction of Mg to MgH 2 at t time, k is an effective kinetic parameter, n is Avrami index, and the activation energy E a is calculated to determine the hydrogen absorption kinetic performance of the composite material
Detection result: reversibly absorbing 3.84wt.% hydrogen at 250 ℃ under 3MPa conditions for 20 min; 3.84wt.% hydrogen can be released within 20min at 250℃and 0.02 MPa.
Test example 3 cycle stability performance test
The detection method comprises the following steps: and obtaining the optimal hydrogen absorption/desorption conditions through hydrogen storage dynamic performance detection, repeating the hydrogen absorption/desorption process on the composite material under the conditions, recording the total amount of the absorbed/desorbed hydrogen of the composite material in each process, drawing a total amount data graph of the absorbed/desorbed hydrogen successively, and observing and calculating the change trend of the data graph to determine the cycle stability of the composite material.
Detection result: after 20 cycles the hydrogen storage capacity was 3.73wt.%, the maximum hydrogen storage capacity decay was less than 3%.
The gamma-MoC/VN confinement catalyzed MgH 2 nanocomposite hydrogen storage materials prepared in examples 1-2 had similar properties to example 3.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and 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 and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (9)
1. A preparation method of a gamma-MoC/VN confinement catalytic MgH 2 nano composite hydrogen storage material is characterized by comprising the following steps: under the hydrogen atmosphere of a certain pressure, carrying out impregnation and hydrogenation reaction on gamma-MoC/VN in MgBu 2, and drying to obtain the gamma-MoC/VN finite field catalyzed MgH 2 nano composite hydrogen storage material;
the nano composite hydrogen storage material takes gamma-MoC/VN as a matrix, and MgH 2 nano particles are loaded in mesopores of the gamma-MoC/VN in a limited domain;
The nano composite hydrogen storage material comprises, by mass, 50-75wt% of gamma-MoC/VN and 25-50wt% of magnesium hydride.
2. The method for preparing the gamma-MoC/VN domain-limited catalyzed MgH 2 nano-composite hydrogen storage material as claimed in claim 1, wherein the pore volume of the gamma-MoC/VN is 0.11-0.1523cm 3/g.
3. The method for preparing the gamma-MoC/VN confinement catalyzed MgH 2 nano-composite hydrogen storage material according to claim 1, which is characterized in that: gamma-MoC/VN: mgBu 2 in g/ml is 0.5-1.0:10-20.
4. The method for preparing the gamma-MoC/VN confinement catalyzed MgH 2 nano-composite hydrogen storage material according to claim 1, which is characterized in that: the pressure is 40-50 Bar, the reaction temperature is 170-200 ℃, and the reaction time is 12-24h.
5. The method for preparing the gamma-MoC/VN confinement catalyzed MgH 2 nano-composite hydrogen storage material according to claim 1, which is characterized in that: the drying temperature is 60-80 ℃ and the drying time is 3-6h.
6. The method for preparing the gamma-MoC/VN confinement catalyzed MgH 2 nano-composite hydrogen storage material according to claim 1, which is characterized in that: the preparation method of the gamma-MoC/VN comprises the following steps:
S1: dissolving H 24Mo7N6O24·4H2O、NH4VO3 and polyvinylpyrrolidone in an ethanol solution, stirring, preparing a fiber film through electrostatic spinning, drying in vacuum, and calcining to obtain V 2MoO8 solid particles;
S2: carbonization of V 2MoO8 with CO and nitridation with NH 3 gives γ -MoC/VN.
7. The method for preparing the gamma-MoC/VN confinement catalyzed MgH 2 nano-composite hydrogen storage material according to claim 6, which is characterized in that: in the step S1, the ratio of H 24Mo7N6O24·4H2O:NH4VO3 to polyvinylpyrrolidone to ethanol solution is 0.48-0.78:0.11-0.31:0.5-1.0:8.41-11.41 in terms of g/g/ml.
8. The method for preparing the gamma-MoC/VN confinement catalyzed MgH 2 nano-composite hydrogen storage material according to claim 6, which is characterized in that: in the step S1, the drying temperature is 60-80 ℃ and the drying time is 3-8h; the calcination temperature is 510-630 ℃; the time is 6-8h;
In the step S2, the CO air inlet rate is 80mL/min, the carbonization temperature is 700-1000 ℃ and the time is 1-6h; NH 3 gas inlet rate 80mL/min, nitriding temperature 600-900 ℃ and nitriding time 1-6h.
9. The application of the gamma-MoC/VN domain-catalyzed MgH 2 nano-composite hydrogen storage material prepared by the preparation method of the gamma-MoC/VN domain-catalyzed MgH 2 nano-composite hydrogen storage material in energy storage materials.
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| US20100310941A1 (en) * | 2009-06-05 | 2010-12-09 | Prashant Nagesh Kumta | Compositions Including Nano-Particles and a Nano-Structured Support Matrix and Methods of preparation as reversible high capacity anodes in energy storage systems |
| CN104649229A (en) * | 2015-01-23 | 2015-05-27 | 上海大学 | Method for preparing nanometer limited range magnesium-based hydrogen storage material |
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| CN110182759A (en) * | 2019-06-05 | 2019-08-30 | 浙江大学 | Bamboo-like carbon nano tubes load MgH2Nano-particles reinforcement hydrogen storage material and preparation method thereof |
| CA3019718A1 (en) * | 2018-10-03 | 2020-04-03 | Reza Alipour Moghadam Esfahani | Fuel cell catalyst support based on doped titanium suboxides |
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| CN104649229A (en) * | 2015-01-23 | 2015-05-27 | 上海大学 | Method for preparing nanometer limited range magnesium-based hydrogen storage material |
| CN107170974A (en) * | 2017-05-26 | 2017-09-15 | 中南大学 | A kind of carbon coating MoSe2/ graphene electro spinning nano fiber and preparation method thereof |
| CA3019718A1 (en) * | 2018-10-03 | 2020-04-03 | Reza Alipour Moghadam Esfahani | Fuel cell catalyst support based on doped titanium suboxides |
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