CN116902911B - MgH supported by carbon fiber 2 Composite material and preparation method thereof - Google Patents
MgH supported by carbon fiber 2 Composite material and preparation method thereof Download PDFInfo
- Publication number
- CN116902911B CN116902911B CN202310860454.5A CN202310860454A CN116902911B CN 116902911 B CN116902911 B CN 116902911B CN 202310860454 A CN202310860454 A CN 202310860454A CN 116902911 B CN116902911 B CN 116902911B
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- mgh
- supported
- composite material
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 143
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 143
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000001257 hydrogen Substances 0.000 claims abstract description 74
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 74
- 239000002245 particle Substances 0.000 claims abstract description 16
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 48
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 29
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 claims description 29
- 239000004744 fabric Substances 0.000 claims description 26
- 239000011777 magnesium Substances 0.000 claims description 24
- 229910052749 magnesium Inorganic materials 0.000 claims description 23
- 238000005984 hydrogenation reaction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 230000007547 defect Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 125000002734 organomagnesium group Chemical group 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 11
- 230000004913 activation Effects 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 238000007327 hydrogenolysis reaction Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229910012375 magnesium hydride Inorganic materials 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 229910019080 Mg-H Inorganic materials 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- VXHZVDDBTHLZFL-UHFFFAOYSA-N [Mg].C(CCC)[Mg]CCCC Chemical compound [Mg].C(CCC)[Mg]CCCC VXHZVDDBTHLZFL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SJEYCEVXVQRZRQ-UHFFFAOYSA-N CCCCCCC.CCCC[Mg]CCCC Chemical compound CCCCCCC.CCCC[Mg]CCCC SJEYCEVXVQRZRQ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
- F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/04—Hydrides of alkali metals, alkaline earth metals, beryllium or magnesium; Addition complexes thereof
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C13/00—Details of vessels or of the filling or discharging of vessels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2221/00—Handled fluid, in particular type of fluid
- F17C2221/01—Pure fluids
- F17C2221/012—Hydrogen
Abstract
The invention relates to a MgH supported by carbon fiber 2 Composite material and preparation method thereof, wherein the composite material comprises a carbon fiber carrier and MgH formed on the surface of the carbon fiber carrier in situ 2 Particles, wherein carbon fiber support and MgH 2 The weight ratio of the particles is 60-70:30-40. The beneficial effects are that the material has better thermodynamic and kinetic properties, and the MgH is obviously improved 2 Compared with the prior art, the hydrogen storage performance of the catalyst is simple in preparation process, easy to operate, environment-friendly in raw materials, capable of being prepared and used in large scale and has certain popularization value.
Description
Technical Field
The invention relates to the technical field of solid hydrogen storage, in particular to MgH supported by carbon fibers 2 Composite materials and methods of making the same.
Background
Energy is an important source spring for improving the life and production level of modern human beings, and is also a key power for promoting the progress of human beings. Hydrogen is considered one of the most promising fossil fuel alternatives due to its relatively high energy density (142 MJ/kg), non-toxic and clean burning characteristics. With the transition of energy technology to renewable technology in recent years, the use of hydrogen as a fuel has become increasingly important. Hydrogen gas is used as a light gas to be compact,Economical, safe storage is a challenge. The most recently studied methods of hydrogen storage include chemical storage and solid state storage. MgH in various solid hydrogen storage materials 2 The characteristics of high theoretical weight density (7.6 wt.%), high Mg abundance in the crust (2.3 wt.%) and low cost have attracted considerable attention.
To prepare MgH 2 Several synthetic methods including ball milling, physical vapor deposition, liquid phase reduction, etc. have been studied for particles, but they also suffer from the disadvantages of weak metal-hydrogen affinity, nanostructure agglomeration and instability. Chinese patent No. CN110116990B discloses an in-situ preparation method of nano magnesium hydride, which utilizes ultrasonic waves to cause cavitation effect of additives in a liquid medium to promote the formation of magnesium hydride, and has the advantages of complex preparation process, long time consumption, mutual reaction during synthesis treatment and difficult control of conditions.
Aiming at the problems of the performance and the preparation method of the magnesium-based solid hydrogen storage system, the MgH with simple preparation process and remarkable performance improvement needs to be provided 2 Composite materials and methods of making the same.
Disclosure of Invention
First, the technical problem to be solved
In view of the above-mentioned shortcomings and drawbacks of the prior art, the present invention provides a carbon fiber supported MgH 2 The composite material and the preparation method thereof solve the technical problems of poor hydrogen storage and release performance and complex preparation method of the current magnesium-based solid hydrogen storage system.
(II) technical scheme
In order to achieve the above purpose, the main technical scheme adopted by the invention comprises the following steps:
in a first aspect, an embodiment of the present invention provides a carbon fiber supported MgH 2 Composite material, mgH supported by carbon fiber 2 Composite material comprising carbon fiber support and MgH formed in situ on the surface of the support 2 Particles, wherein carbon fiber support and MgH 2 The weight ratio of the particles is 60-70:30-40.
According to the preferred embodiment of the invention, the MgH supported by the carbon fiber 2 The carbon fiber carrier is carbon fiber cloth or carbon fiber bundles.
According to the preferred embodiment of the invention, the MgH supported by the carbon fiber 2 The composite material is characterized in that the carbon fiber carrier is a carbon fiber carrier with defects on the surface, wherein the carbon fiber carrier is pretreated under the condition of high temperature and hydrogen atmosphere.
In a second aspect, embodiments of the present invention provide a carbon fiber supported MgH 2 The preparation method of the composite material comprises the following steps:
s1 preparation of organic magnesium supported by carbon fiber: dropwise adding the liquid alkane solution of the organic magnesium on the pretreated carbon fiber, and drying to remove the liquid alkane to prepare the organic magnesium supported by the carbon fiber;
MgH supported by S2 carbon fiber 2 Preparation of the composite material: hydrogenating the organic magnesium supported by the carbon fiber in the step S1 to obtain MgH supported by the carbon fiber 2 A composite material.
According to the preferred embodiment of the invention, the MgH supported by the carbon fiber 2 In S1, dropwise adding liquid alkane solution of organic magnesium into inert gas; the liquid alkane solution of the organomagnesium is a heptane solution of dibutylmagnesium with the concentration of 0.5-1.5 mol/L.
According to the preferred embodiment of the invention, the MgH supported by the carbon fiber 2 In S1, the concentration of the heptane solution of the dibutyl magnesium is 1mol/L, the mass volume ratio of the pretreated carbon fiber to the heptane solution of the dibutyl magnesium is 1g:40-80mL, and the heptane solution of the dibutyl magnesium is added into the pretreated carbon fiber in a plurality of times.
According to the preferred embodiment of the invention, the MgH supported by the carbon fiber 2 The preparation method of the composite material comprises the step of preparing a pretreated carbon fiber and 1 g/60 mL of 1mol/L of dibutylmagnesium heptane solution.
According to the preferred embodiment of the invention, the MgH supported by the carbon fiber 2 In the preparation method of the composite material, in S1, the pretreatment process of the carbon fiber is that the carbon fiber is dried for 2-3 hours under the hydrogen pressure of 3-5Mpa at the temperature of 280-350 ℃.
According to the preferred embodiment of the invention, the MgH supported by the carbon fiber 2 In the preparation method of the composite material, in S1, the pretreatment process of the carbon fiber is that the carbon fiber is dried for 2 hours under the hydrogen pressure of 4Mpa at 300 ℃.
According to the preferred embodiment of the invention, the MgH supported by the carbon fiber 2 In the preparation method of the composite material, in S1, the process of drying and removing the liquid alkane is vacuum drying for 10-12h.
According to the preferred embodiment of the invention, the MgH supported by the carbon fiber 2 In the preparation method of the composite material, in S2, the hydrogenation treatment process is that the composite material is heated to 200-220 ℃ under the hydrogen pressure of 5-7Mpa, and is subjected to constant temperature treatment for 2-3h.
According to the preferred embodiment of the invention, the MgH supported by the carbon fiber 2 In the preparation method of the composite material, in S2, the hydrogenation treatment process is that the composite material is heated to 200 ℃ under the hydrogen pressure of 5Mpa and is treated for 2 hours at constant temperature.
(III) beneficial effects
The beneficial effects of the invention are as follows: the MgH supported by the carbon fiber 2 In the composite material and the preparation method thereof, because the organic magnesium is subjected to in-situ hydrogenolysis on the surface of the carbon fiber cloth with high specific surface area in the protective atmosphere, the high defect of the surface of the carbon fiber cloth is used as MgH 2 Nucleation sites, further limiting MgH 2 The grain size is large, and MgH with uniform dispersion is formed 2 Particles; in the hydrogenolysis process, hydrogen atoms are continuously diffused on the surface of the carbon fiber to form C-H bonds, and under the action of the C-H bonds, the interaction between the hydrogen atoms and magnesium atoms is further promoted, so that the hydrogen atoms and the magnesium atoms are adsorbed or reacted, and strong ionic bonds between Mg-H are continuously weakened in the process, so that the hydrogen storage performance of the composite material is improved.
The invention provides a new idea and a new choice for a magnesium-based hydrogen storage system from the perspective of hydrogenolysis of a format reagent, and the MgH supported by the carbon fiber 2 The composite material has greatly raised hydrogen absorbing capacity and rate and high hydrogen absorbing activation energyObviously reduces the peak temperature of hydrogen release by 94 ℃, has better thermodynamic and kinetic properties, and obviously improves MgH 2 Is a hydrogen storage property of the fuel cell.
The pretreated carbon fiber is used as a carrier, the mass volume ratio of the carrier to the heptane solution with the concentration of about 1mol/L of dibutylmagnesium is 1g:60mL, in the preparation process, the heptane solution is dropwise added into a reaction vessel for one time, and the pretreated carbon fiber cloth is dropwise added again after being fully impregnated, so that the dibutylmagnesium heptane solution and the pretreated carbon fiber cloth are fully and uniformly impregnated, the uniform distribution of dibutylmagnesium is facilitated, the subsequent hydrogenation treatment is complete, and the particle distribution is uniform.
In hydrogenation treatment, carbon fiber cloth adsorbed with dibutyl magnesium is placed in a closed sample chamber, 5Mpa hydrogen is filled into the sample chamber, the reaction temperature is controlled at 200 ℃, and the constant temperature is kept for 2 hours, so as to promote hydrogenation of organic magnesium (dibutyl magnesium) and facilitate formation of C-H bond, thereby preparing MgH with high purity 2 MgH supported by carbon fiber 2 A composite material.
The maximum hydrogen absorption amount of the MgH2 composite material supported by the carbon fiber prepared by the invention at 275 ℃,300 ℃ and 325 ℃ is 1.84wt%, 1.98wt% and 2.19wt%, respectively, and the corresponding hydrogen absorption activation energy is 61.7kJ/mol; the peak hydrogen release temperature is 369 ℃, and is reduced by 94 ℃ compared with the peak hydrogen release temperature of a pure MgH2 material; therefore, it has better thermodynamic and kinetic properties.
Drawings
FIG. 1 shows a carbon fiber supported MgH according to embodiment 1 of the present invention 2 A flow chart of a method for preparing the composite material;
FIG. 2 shows MgH supported by carbon fiber in example 1 of the present invention 2 XRD pattern of the composite material;
FIGS. 3a and 3d show MgH supported by carbon fiber in example 1 of the present invention 2 SEM images of different regions of the composite material at a 10 μm scale;
FIGS. 3b and 3e show MgH supported by carbon fiber in example 1 of the present invention 2 SEM images of different regions of the composite material at a 5 μm scale;
FIG. 3c and FIG. 3f are the present inventionCarbon fiber supported MgH in example 1 2 SEM images of different regions of the composite material at a 2 μm scale;
FIG. 4 shows MgH supported by carbon fiber in example 1 of the present invention 2 FTIR profile of the composite;
FIG. 5 shows MgH supported by carbon fiber in example 1 of the present invention 2 Composite material and pure MgH 2 Is a DSC curve of hydrogen release at the same temperature rising rate;
FIG. 6 shows MgH supported by carbon fiber in example 1 of the present invention 2 Hydrogen absorption performance curves of the composite materials at different temperatures;
FIG. 7 shows MgH supported by carbon fiber in example 1 of the invention 2 The hydrogen absorption activation energy curves of the composite materials at different temperatures;
FIG. 8 shows the pure MgH of comparative example 1 of the present invention 2 Hydrogen absorption performance curves at different temperatures;
FIG. 9 shows the pure MgH of comparative example 1 of the present invention 2 Hydrogen absorption activation energy curves at different temperatures;
FIG. 10 shows MgH supported by carbon fiber in example 5 of the present invention 2 XRD pattern of the composite material.
Detailed Description
The invention will be better explained by the following detailed description of the embodiments with reference to the drawings.
Aiming at the technical problems of poor hydrogen storage and release performance, complex preparation method and the like of the current magnesium-based solid hydrogen storage system, the embodiment of the invention provides a carbon fiber supported MgH 2 In-situ hydrogenolysis of organic magnesium on the surface of carbon fiber cloth with high specific surface area under protective atmosphere, and the high defect of the surface of the carbon fiber cloth can be used as MgH after pretreatment 2 Nucleation sites, further limiting MgH 2 The grain size is large, and MgH with uniform dispersion is formed 2 And (3) particles. In the hydrogenolysis process, hydrogen atoms continuously diffuse on the surface of the carbon fiber to form C-H bonds, and under the action of the C-H bonds, the interaction between the hydrogen atoms and magnesium atoms is further promoted to enable the hydrogen atoms and the magnesium atoms to be adsorbedOr reacting; compared with the prior art, the preparation process is simple, the operation is easy, the raw materials are environment-friendly, and the preparation and use of the carbon fiber cloth can be realized on a large scale, so that the hydrogen storage performance of the composite material is improved.
The invention provides a new idea and a new choice for a magnesium-based hydrogen storage system from the perspective of hydrogenolysis of a format reagent, and the MgH supported by the carbon fiber 2 The composite material has greatly raised hydrogen absorbing capacity and rate, obviously lowered hydrogen absorbing activation energy, peak hydrogen releasing temperature lowered by 94 deg.c, better thermodynamic and dynamic performance and obviously improved MgH 2 Is a hydrogen storage property of the fuel cell.
As shown in fig. 1, the specific preparation process is that firstly, a carbon fiber carrier is pretreated at high temperature under the hydrogen atmosphere to remove the groups on the surface of the carbon fiber carrier and simultaneously remove the water; then, dropwise adding the liquid alkane solution of the organic magnesium on the pretreated carbon fiber carrier, and vacuum drying to remove the liquid alkane to prepare the organic magnesium supported by the carbon fiber; finally, carrying out hydrogenation treatment on the organic magnesium supported by the carbon fiber to obtain MgH supported by the carbon fiber 2 A composite material.
In order that the above-described aspects may be better understood, exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present invention are shown in the drawings, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1
The present embodiment provides a carbon fiber supported MgH 2 The preparation method of the composite material is shown in fig. 1, and the preparation process comprises the following specific steps:
(1) Pretreatment of carbon fiber cloth: arranging the carbon fiber at 300 ℃ and drying for 2 hours under the hydrogen pressure of 4 Mpa;
(2) Dipping treatment: weighing 0.05g of the carbon fiber cloth pretreated in the step (1), placing the carbon fiber cloth into a beaker, sucking 3mL of dibutylmagnesium heptane solution with the final concentration of 1mol/L by using a syringe with the volume of 5mL in a sealed glove box filled with argon, dripping the dibutylmagnesium heptane solution into the beaker, stopping adding 0.5mL of the dibutylmagnesium heptane solution every time, and gradually dripping 3mL of dibutylmagnesium heptane solution after the pretreated carbon fiber cloth is fully immersed;
(3) Drying to remove the organic solvent: placing the carbon fiber cloth subjected to the impregnation treatment in the step (2) into a vacuum chamber, and vacuum drying for 12 hours, and removing the heptane solvent to obtain the carbon fiber supported organic magnesium composite material;
(4) And (3) hydrotreating: placing the organic magnesium composite material supported by the carbon fiber in the step (3) into a sample chamber, evacuating air in the sample chamber, filling 5Mpa hydrogen into the sample chamber, placing the sample chamber into a resistance furnace for heating, heating to 200 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 3 hours at a constant temperature to obtain the MgH supported by the carbon fiber 2 Composite MgH 2 @CC。
For the composite material MgH prepared by the method 2 The @ CC was tested as follows:
(1) XRD test: in a sealed and argon filled glove box, samples of 2cm x 2cm size were mounted flat on slides with double sided tape and the slides were sealed around with tape. Scanning in a range of 10-90 degrees with a step size of 0.02 degrees, and the scanning speed is 5 degrees/min.
The results are shown in FIG. 2, wherein MgBu2@CC refers to a pretreated carbon fiber cloth-supported organomagnesium composite, with pretreated carbon fiber cloth (cc) as a control; as seen from FIG. 2, the characteristic peak of dibutylmagnesium disappeared after the hydrogenation treatment of MgBu2@CC, and MgH was found by the comparison of pdf cards 2 Indicating that the dibutylmagnesium after hydrogenation treatment has been completely converted into MgH 2 And successfully load on the surface of the carbon cloth, at the moment, mgH 2 Is present at about 33wt%.
(2) SEM test: in a sealed and argon-filled glove box, 2cm×2 cm-sized carbon fiber-supported MgH was taken 2 The composite material is uniformly adhered on the conductive adhesive and stuck on the surface of the copper plate, and is placed into a sample chamber for observing the morphology after metal spraying treatment.
The results are shown below, wherein FIG. 3a and FIG. 3d show that the scale of 10 μm is not selectedObserving the same region, selecting different regions for observation under the scale of 5 μm in FIG. 3b and FIG. 3e, and selecting different regions for observation under the scale of 2 μm in FIG. 3c and FIG. 3 f; FIGS. 3a, 3b, and 3c show MgH at 10 μm, 5 μm, and 2 μm scales in order 2 The state in which the particles are supported on the surface of the carbon fiber; it can be seen that MgH 2 The particles are successfully loaded on the surface of the carbon fiber, mgH on the surface 2 The particles are in a dispersion distribution state, and simultaneously show MgH obtained by hydrogenation of dibutyl magnesium 2 The particle size is fine and uniform.
(3) FTIR test to analyze the type and strength of its chemical bonds:
the method comprises collecting MgH supported by 1cm×1cm carbon fiber 2 The mass ratio of the composite material to potassium bromide (KBr) is 1:10, and placing the mixture into an infrared spectrometer, and characterizing MgH supported by carbon fibers by Fourier transform infrared spectroscopy 2 Characteristic absorption peak of covalent bond vibration in composite material, wavelength range is 500-3000 cm -1 。
The result is shown in FIG. 4, at 1150-1500cm -1 The peak of the region corresponds to the Mg-H stretch band, at 759-1000cm -1 The peaks of the regions correspond to Mg-H bending bands at 2850-2960cm -1 The peaks of the regions correspond to C-H bonds, which are found during hydrogen diffusion to form C-H bonds in MgH 2 Further promotes the interaction between hydrogen atoms and magnesium in the hydrogen absorption and desorption process, thereby improving MgH 2 Is a hydrogen storage property of the fuel cell.
Example 2
The present example differs from example 1 only in the pretreatment conditions of the carbon fiber cloth in step (1). In this embodiment: the carbon fibers were dried at 350℃under 3MPa of hydrogen for 2 hours.
Example 3
The present example differs from example 1 only in the pretreatment conditions of the carbon fiber cloth in step (1). In this embodiment: the carbon fibers were dried at 280℃under 5MPa of hydrogen for 3 hours.
Example 4
This example differs from example 1 only in the hydrotreating conditions in step (4), in which: direction sampleFilling 7Mpa hydrogen into the sample chamber, heating the sample chamber in a resistance furnace, keeping the temperature at 220 ℃ for 2 hours, and obtaining the MgH supported by the carbon fiber 2 Composite MgH 2 @CC。
The composite MgH prepared in examples 1-4 was tested 2 MgH in @ CC 2 There was no significant difference in the loading of (c). Therefore, under the condition that the soaking treatment and the hydrogenation treatment are the same, when the pretreatment condition of the carbon fiber cloth is 280-350 ℃ and the drying is carried out under the hydrogen pressure of 3-5Mpa for 2-3 hours, the composite material MgH with stable loading capacity can be prepared if the treatment time is prolonged properly at the lower pretreatment temperature 2 @ CC product.
In addition, under the condition that the pretreatment and the impregnation treatment conditions of the carbon fiber cloth are the same, when the hydrogenation treatment conditions are 5-7Mpa hydrogen pressure and 200-220 ℃ constant temperature treatment is carried out for 2-3 hours, if the treatment time is properly shortened at a higher hydrogenation treatment temperature, the composite material MgH with stable load can be prepared 2 @ CC product.
Example 5
The difference between this example and example 1 is only that the dipping treatment conditions in step (2) are different, in this example: a syringe having a volume of 5mL was used to aspirate 2mL of dibutylmagnesium heptane solution having a final concentration of 1mol/L, followed by a dropwise addition operation.
MgH supported by carbon fiber prepared in this example 2 XRD test results of composite material, as shown in FIG. 10, mgH 2 Is characterized by reduced peak intensity, reduced peak width and MgH 2 Is about 24.2wt%. In this example, since a smaller dibutylmagnesium heptane solution was used, mgH was used in this example compared with the previous examples 2 The load of (c) decreases.
Comparative example 1
This comparative example provides pure MgH 2 A material.
Comparative example 2
The difference from example 1 is that (2) the dipping treatment: 5mL of dibutylmagnesium heptane solution with the final concentration of 1mol/L is sucked by a syringe with the volume of 5mL, and the dibutylmagnesium heptane solution is added into the pretreated carbon fiber cloth at one time.
Carbon fiber prepared in this comparative exampleSupported MgH 2 The composite material adopts a one-time adding mode to lead to MgH because of more dibutyl magnesium heptane solution 2 The deposition growth is carried out on the surface of the carbon fiber, the particle agglomeration phenomenon is obvious, and partial dibutylmagnesium is incompletely hydrogenated in the subsequent hydrogenation reaction process.
Comparative example 3
The difference from example 1 is that (1) the step of pretreatment of the carbon fiber cloth was omitted.
MgH supported by carbon fiber prepared in this comparative example 2 Since the composite material is not pretreated with carbon fiber cloth, mgH in this comparative example is compared with the previous examples 1 to 5 2 The loading of MgH is greatly reduced, and the product after hydrogenation is MgH 2 The purity is low, and the hydrogen storage requirement cannot be met.
Application example 1
Composite MgH prepared in example 1 2 The @ CC is subjected to a hydrogen desorption test, and the hydrogen desorption peak temperature is tested by the following steps: taking 5mg of MgH supported by carbon fiber 2 The composite material is placed in an alumina crucible, and is placed on a sample table for heating, the temperature rising rate is 10 ℃/min under the nitrogen blowing, and the target temperature is 500 ℃.
The test results are shown in FIG. 5, which shows the MgH supported by carbon fiber 2 The peak temperature of the hydrogen release of the composite material is 369 ℃. Whereas in comparative example 1 pure MgH 2 The material had a hydrogen desorption peak temperature of 463 ℃ (see fig. 9), in contrast to MgH 2 The peak temperature of hydrogen release of the @ CC composite material is reduced by 94 ℃.
Application example 2
Composite MgH prepared in example 1 2 The hydrogen absorption test is carried out on the @ CC, the hydrogen absorption peak temperature is tested, and the test method is as follows: in a sealed and argon-filled glove box, 0.15g of carbon fiber-supported MgH was taken 2 The composite material is sheared and put into a manual rod sample chamber and connected to a P-C-T device, the heating rate is 5 ℃/min, and the hydrogen absorption amount is calculated according to the pressure changes at different temperatures.
As can be seen from the analysis of FIGS. 6 and 7, the maximum hydrogen absorption amounts at 275℃and 300℃and 325℃were 1.84wt%, 1.98wt% and 2.19wt%, respectively; the corresponding hydrogen absorption activation energy was 61.7kJ/mol.
Whereas in comparative example 1 pure MgH 2 The maximum hydrogen absorption of the material at 275 ℃,300 ℃ and 325 ℃ is only 0.85wt%, 1.11wt% and 1.27wt% (see fig. 8); correspondingly, pure MgH 2 The material had a hydrogen absorption activation energy of 96.9kJ/mol (see FIG. 9). As can be seen by comparison, the MgH supported by the carbon fiber prepared by the invention 2 The hydrogen absorption capacity and the hydrogen absorption rate of the composite material are greatly improved, and the hydrogen absorption activation energy is far lower than that of pure MgH 2 The hydrogen absorption activation energy of the material is 96.9kJ/mol, thus the MgH supported by the carbon fiber can be seen 2 The hydrogen absorption and activation energy of the composite material is obviously reduced, thereby improving MgH 2 Hydrogen absorption kinetics of (c).
In the invention, as the best embodiment, the embodiment 1 adopts the mass volume ratio of the pretreated carbon fiber to the 1mol/L of the heptane solution of the dibutyl magnesium to be 1 g/60 mL, and the pretreated carbon fiber cloth is dripped into a beaker for each time, and is dripped again after being fully immersed once, so that the heptane solution of the dibutyl magnesium and the pretreated carbon fiber cloth are fully and uniformly immersed, the dibutyl magnesium is uniformly distributed, the reaction is thorough during the subsequent hydrogenation treatment, and the particle distribution is uniform; in the hydrogenation treatment, 5Mpa hydrogen gas is filled into the sample chamber, the temperature is kept at 200 ℃ for 2 hours, which is favorable for the hydrogenation of organic magnesium (dibutyl magnesium) and the formation of C-H bond, so as to prepare high-purity MgH 2 MgH supported by carbon fiber 2 Composite MgH 2 @CC。
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 (9)
1. MgH supported by carbon fiber 2 A composite material characterized in that: the carbon fiber is supportedMgH 2 Composite material comprising carbon fiber carrier and MgH formed on the surface of the carbon fiber carrier in situ 2 Particles, wherein carbon fiber support and MgH 2 The weight ratio of the particles is 60-70:30-40;
the carbon fiber carrier is a carbon fiber carrier with defects on the surface, which is pretreated under the condition of high temperature and hydrogen atmosphere; the carbon fiber carrier is carbon fiber cloth or carbon fiber bundles.
2. A carbon fiber supported MgH as claimed in claim 1 2 The preparation method of the composite material is characterized by comprising the following steps:
s1 preparation of organic magnesium supported by carbon fiber: dropwise adding the liquid alkane solution of the organic magnesium on the pretreated carbon fiber, and drying to remove the liquid alkane to prepare the organic magnesium supported by the carbon fiber;
MgH supported by S2 carbon fiber 2 Preparation of the composite material: hydrogenating the organic magnesium supported by the carbon fiber in the step S1 to obtain MgH supported by the carbon fiber 2 A composite material;
s1, dropwise adding a liquid alkane solution of organic magnesium into inert gas; the liquid alkane solution of the organomagnesium is a heptane solution of dibutylmagnesium with the concentration of 0.5-1.5 mol/L.
3. The carbon fiber supported MgH of claim 2 2 The preparation method of the composite material is characterized by comprising the following steps: in the S1, the concentration of the heptane solution of the dibutyl magnesium is 1mol/L, the mass volume ratio of the pretreated carbon fiber to the heptane solution of the dibutyl magnesium is 1g:40-80mL, and the heptane solution of the dibutyl magnesium is added into the pretreated carbon fiber in multiple times.
4. A carbon fiber supported MgH as claimed in claim 3 2 The preparation method of the composite material is characterized by comprising the following steps: the mass volume ratio of the pretreated carbon fiber to 1mol/L of dibutylmagnesium in heptane solution is 1 g/60 mL.
5. A carbon fiber supported as claimed in claim 2MgH 2 The preparation method of the composite material is characterized by comprising the following steps: in S1, the pretreatment process of the carbon fiber is that the carbon fiber is dried for 2-3 hours under the hydrogen pressure of 3-5Mpa at the temperature of 280-350 ℃.
6. The carbon fiber supported MgH of claim 5 2 The preparation method of the composite material is characterized by comprising the following steps: in S1, the pretreatment process of the carbon fiber is that the carbon fiber is dried for 2 hours at 300 ℃ under 4Mpa hydrogen pressure.
7. The carbon fiber supported MgH of claim 2 2 The preparation method of the composite material is characterized by comprising the following steps: in S1, the process of drying and removing the liquid alkane is vacuum drying for 10-12h.
8. The carbon fiber supported MgH of claim 2 2 The preparation method of the composite material is characterized by comprising the following steps: in the step S2, the hydrogenation treatment is carried out by heating to 200-220 ℃ under the hydrogen pressure of 5-7Mpa and carrying out constant temperature treatment for 2-3h.
9. The carbon fiber supported MgH of claim 8 2 The preparation method of the composite material is characterized by comprising the following steps: in S2, the hydrogenation treatment is carried out by heating to 200 ℃ under 5Mpa hydrogen pressure and carrying out constant temperature treatment for 2h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310860454.5A CN116902911B (en) | 2023-07-13 | 2023-07-13 | MgH supported by carbon fiber 2 Composite material and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310860454.5A CN116902911B (en) | 2023-07-13 | 2023-07-13 | MgH supported by carbon fiber 2 Composite material and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116902911A CN116902911A (en) | 2023-10-20 |
CN116902911B true CN116902911B (en) | 2024-01-30 |
Family
ID=88352444
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310860454.5A Active CN116902911B (en) | 2023-07-13 | 2023-07-13 | MgH supported by carbon fiber 2 Composite material and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116902911B (en) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005330151A (en) * | 2004-05-20 | 2005-12-02 | Nikon Corp | Carbon material having cavity layer and its producing method |
CN1743066A (en) * | 2004-08-31 | 2006-03-08 | 中国科学院金属研究所 | A kind of nanocomposite hydrogen storage material and preparation method thereof |
CN103922276A (en) * | 2014-04-04 | 2014-07-16 | 长安大学 | Preparation method of hydrogen storage material with high reversible hydrogen storage capacity |
CN105492374A (en) * | 2013-06-14 | 2016-04-13 | 南威尔士大学商业服务有限公司 | Synthesis and hydrogen storage properties of manganese hydrides |
CN106410210A (en) * | 2016-10-31 | 2017-02-15 | 复旦大学 | Preparation method of metal hydride/nano carbon composite materials |
KR20180068716A (en) * | 2016-12-14 | 2018-06-22 | 현대자동차주식회사 | Hydrogen storage composite material and manufacturing method thereof |
WO2023071963A1 (en) * | 2021-10-25 | 2023-05-04 | 上海交通大学 | Nano magnesium hydride-loaded composite material and preparation method therefor |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3041952A1 (en) * | 2015-10-06 | 2017-04-07 | Univ Bordeaux | MAGNESIUM-BASED MATERIAL FOR THE PRODUCTION OF DIHYDROGEN OR ELECTRICITY |
-
2023
- 2023-07-13 CN CN202310860454.5A patent/CN116902911B/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005330151A (en) * | 2004-05-20 | 2005-12-02 | Nikon Corp | Carbon material having cavity layer and its producing method |
CN1743066A (en) * | 2004-08-31 | 2006-03-08 | 中国科学院金属研究所 | A kind of nanocomposite hydrogen storage material and preparation method thereof |
CN105492374A (en) * | 2013-06-14 | 2016-04-13 | 南威尔士大学商业服务有限公司 | Synthesis and hydrogen storage properties of manganese hydrides |
CN103922276A (en) * | 2014-04-04 | 2014-07-16 | 长安大学 | Preparation method of hydrogen storage material with high reversible hydrogen storage capacity |
CN106410210A (en) * | 2016-10-31 | 2017-02-15 | 复旦大学 | Preparation method of metal hydride/nano carbon composite materials |
KR20180068716A (en) * | 2016-12-14 | 2018-06-22 | 현대자동차주식회사 | Hydrogen storage composite material and manufacturing method thereof |
WO2023071963A1 (en) * | 2021-10-25 | 2023-05-04 | 上海交通大学 | Nano magnesium hydride-loaded composite material and preparation method therefor |
Also Published As
Publication number | Publication date |
---|---|
CN116902911A (en) | 2023-10-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zhang et al. | The synthesis and hydrogen storage properties of a MgH2 incorporated carbon aerogel scaffold | |
US6517800B1 (en) | Production of single-walled carbon nanotubes by a hydrogen arc discharge method | |
US20120082615A1 (en) | Method for storing hydrogen in a porous monolithic material, composite material obtained, and applications | |
CN100374367C (en) | Technical method and schedule for preparation of foam carbon material used asphalt as raw material | |
JP5835787B2 (en) | Microporous carbon material, method for producing microporous carbon material, and hydrogen storage method using microporous carbon material | |
CN108380227B (en) | Hydrogen evolution electrocatalytic material and preparation method thereof | |
JP2014055110A (en) | Method for producing microporous carbonaceous material | |
Tang et al. | Hypercrosslinked porous poly (styrene-co-divinylbenzene) resin: a promising nanostructure-incubator for hydrogen storage | |
Yuan et al. | Highly ordered mesoporous carbon synthesized via in situ template for supercapacitors | |
CN112357902A (en) | Mesoporous carbon material with high specific surface area, and preparation method and application thereof | |
CN116902911B (en) | MgH supported by carbon fiber 2 Composite material and preparation method thereof | |
KR100692699B1 (en) | Method of preparing Pt catalyst for fuel cell electrode | |
EP1061044A1 (en) | Production of single-walled carbon nanotubes | |
Zhao et al. | Three-dimensional layered porous graphene aerogel hydrogen getters | |
CN114293086B (en) | Hydrogen storage high-entropy alloy and preparation method thereof | |
CN113089014B (en) | Super-hydrophilic super-gas-dredging efficient hydrogen evolution catalyst with core-shell structure and preparation method thereof | |
CN115354346A (en) | P-induced doped CoFe-LDH/porous carbon electrolysis water hydrogen evolution electrode material and preparation and application thereof | |
CN110983495B (en) | Active carbon fiber hole expanding method | |
CN113546631A (en) | La modified Ni/Al2O3Catalyst, preparation method and application | |
CN113130873A (en) | Porous bismuth-carbon material, preparation method and application thereof | |
RU2744163C1 (en) | High-density three-dimensional electroconductive micro- and mesoporous material based on carbon nanotubes and/or low-layer graphenes and method for production thereof | |
CN111908464B (en) | Method for preparing foam carbon material by using tannic acid | |
CN111876640A (en) | Gasification slag magnesium-nickel alloy hydrogen storage composite material and preparation method thereof | |
CN109659151A (en) | A method of different Carbon-based supercapacitor electrode materials are prepared by regulating and controlling lignin molecule amount | |
CN114988378B (en) | N-doped black phosphazene photocatalyst, and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |