CN114956013A - Preparation method of VSe2 metal ultrathin nanosheet similar to graphene - Google Patents
Preparation method of VSe2 metal ultrathin nanosheet similar to graphene Download PDFInfo
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- CN114956013A CN114956013A CN202210544702.0A CN202210544702A CN114956013A CN 114956013 A CN114956013 A CN 114956013A CN 202210544702 A CN202210544702 A CN 202210544702A CN 114956013 A CN114956013 A CN 114956013A
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 11
- 239000002184 metal Substances 0.000 title claims abstract description 11
- 229910021389 graphene Inorganic materials 0.000 title claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011669 selenium Substances 0.000 claims abstract description 21
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 21
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 20
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 19
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000019253 formic acid Nutrition 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- -1 aluminum ion Chemical class 0.000 claims abstract description 14
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 3
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 44
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003517 fume Substances 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- IYKVLICPFCEZOF-UHFFFAOYSA-N selenourea Chemical compound NC(N)=[Se] IYKVLICPFCEZOF-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 238000004729 solvothermal method Methods 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 2
- 239000000843 powder Substances 0.000 abstract 1
- AWTPFHXPJRMMAX-UHFFFAOYSA-N selenium;urea Chemical compound [Se].NC(N)=O AWTPFHXPJRMMAX-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- FSJSYDFBTIVUFD-XHTSQIMGSA-N (e)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C/C(C)=O.C\C(O)=C/C(C)=O FSJSYDFBTIVUFD-XHTSQIMGSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- 229910016001 MoSe Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WCQOLGZNMNEYDX-UHFFFAOYSA-N bis(selanylidene)vanadium Chemical compound [Se]=[V]=[Se] WCQOLGZNMNEYDX-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- 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
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- 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
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- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
- Y02E60/10—Energy storage using batteries
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a graphene-like
A preparation method, a product and an application of metal ultrathin nanosheets belong to the technical field of functional material preparation. The preparation method comprises the steps of taking ammonium metavanadate and the like containing a vanadium source and tin dioxide and selenium urea containing a selenium source as precursors of preparation materials, then dispersing the precursors into a dimethylformamide organic solvent, using formic acid as a reducing agent, and carrying out a solvothermal method in a high-pressure reaction kettlePreparation of graphene-like
An ultrathin nanosheet. Finally, mixing the above obtained solution
Placing the nanosheets in a tube furnace, annealing in a protective atmosphere to remove Se powder attached to the nanosheets to obtain pure-phase graphene-like material
Description
Technical Field
The invention belongs to the field of preparation of new energy materials, and relates to a graphene-like material
A preparation method, a product and application of metal ultrathin nanosheets.
Background
Graphene, as an excellent nanomaterial with ultrathin thickness, high strength, high electrical and thermal conductivity and the like, is widely applied to the field of energy materials and is increasingly researched. Meanwhile, transition metal compound MX having a layered structure similar to graphene 2 (M = Mo, W, V, etc.; X = S, Se, Te, etc.) were successively discovered and studied, and such compound layers were connected together by van der Waals forces, and a deintercalation mechanism occurred in a battery reaction in the field of energy, and were excellent electrode materials. However, in recent years most researchers have been working on the development of chalcogenide compounds based on Mo and W, such as MoS 2 ，WS 2 ，MoSe 2 And the like, and to apply them in the energy storage field.
Vanadium diselenide, a typical two-dimensional layered transition metal selenide, has a structure similar to MoS 2 The electronic coupling effect between tetravalent vanadium in the compound can induce the metal performance of the compound. In addition to this, the present invention is,
excellent electrocatalytic properties have been demonstrated, which indicates that,
may have great potential applications in energy storage applicationsThe use value is high.
At present, relate to
The synthesis method of the selenium dioxide block has many methods, and in 2013, the Xieti subject group synthesizes the block by using water as a solvent and ammonium metavanadate and selenium dioxide respectively
The compound is then stripped out by ultrasonic stripping
And (4) a lamellar structure. The ultrasonic stripping method has high requirements on ultrasonic power, can damage a stripped lamellar structure if being selected improperly, can strip only 30mg each time, is long in time consumption, and is not suitable for large-scale preparation; in addition, the synthesis of high crystalline quality by gas phase method (CVD) has also been investigated
However, the preparation process involves various organic solvents such as oleylamine, trioctylamine and the like in addition to the vanadium source and the selenium source, and the preparation process is extremely complicated. Therefore, the existing
The preparation method of the ultrathin nanosheet has the defects of long synthesis period, high cost, complex process and the like which are difficult to realize. Therefore, it is necessary to innovate and improve the preparation method, and to simply and rapidly prepare the ultrathin nano-sheet similar to the graphene
And the application prospect of the electrochemical energy storage material in the field of electrochemical energy storage is improved.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the background technology and provide a method with simpler process
Of ultrathin nanosheet structureThe preparation method has the advantages of simplifying the preparation process, shortening the period and reducing the cost.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
graphene-like
The preparation method of the metal ultrathin nanosheet, the product and the application thereof comprise the following specific steps:
1) and (4) crushing and pretreating the selenium source of the bulk crystal.
2) Weighing the components in a molar ratio of 2-4: 1 selenium source and vanadium source, then dissolving the selenium source in 30ml of dimethylformamide, sealing and ultrasonically dispersing, then adding the vanadium source, magnetically stirring, and then slowly dropping a certain amount of formic acid under the condition of stirring in a fume hood to obtain a mixed solution of the selenium source, the vanadium source, a reducing agent and a reaction solvent.
3) Transferring the mixed solution obtained in the step 2) to a high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, and placing the reaction kettle in an oven for high-temperature high-pressure reaction.
4) After the reaction is finished and the reaction product is naturally cooled to room temperature, the product is repeatedly centrifugally washed for 3-6 times by deionized water and absolute ethyl alcohol respectively, and then the obtained solid is placed in a vacuum drying oven to be dried for 6-10h at 50 ℃.
5) Finally, putting the finally obtained solid sample into a tube furnace, and annealing under the protection of inert gas to obtain the graphene-like material
Ultrathin nanosheet compounds.
Further, the molar ratio of the selenium source to the vanadium source in the step 2) is 2-4: 1, the ultrasonic dispersion power is 120W, the ultrasonic dispersion time is 1-4h, the volume of formic acid is 8-15ml, and the dropping speed is 40-100 drops/min.
Further, the vanadium source in the step 2) is ammonium metavanadate, vanadium pentoxide or vanadyl acetylacetonate (VO (acac) 2 ) One or more of; the selenium source is selected from selenium dioxide and selenoureaOne or more of; the solvent is one or more of Dimethylformamide (DMF) and N-methyl pyrrolidone (NMP) organic solvent.
Further, the volume of the inner lining of the high-pressure reaction kettle used in the step 3) is 100ml, the reaction temperature is 180-.
Further, in the step 5), the high-temperature annealing temperature of the sample is 400-600 ℃, the annealing time is 2-5h, and the inert protective gas is Ar or N 2 。
Further, prepared by the step 5)
The ultrathin nanosheet can be used as a positive electrode material of an aluminum ion battery.
Compared with the prior art, the invention has the following beneficial technical effects:
1) compared with the preparation method, the solvothermal method adopted by the invention has the characteristics of simple process, short preparation period and mild reaction conditions, and can be prepared at a lower temperature of 180-220 ℃ to obtain pure phase
And (4) a nano-sheet layer structure.
2) The crushing pretreatment of selenium sources such as selenium dioxide and the like shortens the dissolving time of the selenium dioxide and the like in an organic solvent; the ultrasonic dispersion of the selenium dioxide and the methyl formamide solvent ensures that the dispersion is more uniform, and the prepared selenium dioxide and methyl formamide solvent
The nano-sheets have uniform appearance.
3) The selection of the preparation materials is diversified, and VO (acac) can be adopted 2 The 5-valent vanadium can also adopt 4-valent vanadium such as ammonium metavanadate and the like as a precursor for material synthesis.
4) Adopts a solvothermal synthesis method, the solvents are dimethylformamide and N-methyl pyrrolidone organic solvents, the reaction rate is high, the reaction is full and thorough, and the prepared
Is an ultrathin nano-sheet structure.
5) The method is similar to graphene
The ultrathin nanosheet structure has a large specific surface area, provides more active sites for chemical reaction, and can be used as an anode material of an aluminum ion battery to be applied to an energy storage device.
Drawings
FIG. 1 is a photograph of a film prepared in example 1 of the present invention
X-ray diffraction spectrum of the metal ultrathin nanosheet.
FIG. 2 is a graph prepared according to example 2 of the present invention
Scanning electron microscopy of the metal ultrathin nanosheets.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1:
1) and (4) crushing the selenium dioxide blocky crystal for pretreatment.
2) Weighing a selenium source and a vanadium source with a molar ratio of 2:1, dissolving 0.444g of selenium dioxide in 30ml of dimethylformamide, sealing and ultrasonically dispersing for 1h in a 120w ultrasonic instrument, then adding 0.234g of ammonium metavanadate, magnetically stirring for 45min, and finally dropping 8ml of formic acid at a speed of 40 drops/min under the stirring condition in a fume hood to obtain a mixed solution of the selenium dioxide, the ammonium metavanadate, the formic acid and the dimethylformamide.
3) Transferring the mixed solution obtained in the step 2) to a 100ml high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, and placing the reaction kettle in an oven to react for 24 hours at the temperature of 200 ℃.
4) After the reaction is finished and the reaction product is naturally cooled to room temperature, the product is repeatedly centrifugally washed for 3-6 times by deionized water and absolute ethyl alcohol respectively, and then the obtained solid is placed in a vacuum drying oven to be dried for 10 hours at 50 ℃.
5) Finally, the solid sample obtained finally is placed in a tube furnace under N 2 Annealing at 500 ℃ for 2h under protection to obtain the graphene-like material
An ultra-thin nanosheet compound.
It can be seen from FIG. 1 that the sample prepared in this example is phase pure
The XRD pattern of (A) is shown,
has a distinct diffraction peak and
the standard peak (JCPDS Card No. 89-1641) is identical.
Example 2:
1) and (4) crushing and pretreating the selenium dioxide blocky crystals.
2) Weighing a mixture with a molar ratio of 3: 1 selenium source and vanadium source, then dissolving 0.666g of selenium dioxide in 30ml of dimethylformamide, sealing and ultrasonically dispersing for 3 hours in a 120w ultrasonic instrument, then adding 0.530g of vanadyl acetylacetonate, magnetically stirring for 30 minutes, and finally, dripping 10ml of formic acid at a speed of 50 drops/min under the condition of stirring in a fume hood to obtain a mixed solution of selenium dioxide, vanadyl acetylacetonate, formic acid and dimethylformamide;
3) transferring the mixed solution obtained in the step 2) to a 100ml high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, and placing the reaction kettle in an oven to react for 20 hours at the temperature of 210 ℃.
4) After the reaction is finished and the reaction product is naturally cooled to room temperature, the product is repeatedly centrifugally washed for 3-6 times by deionized water and absolute ethyl alcohol respectively, and then the obtained solid is placed in a vacuum drying oven to be dried for 8 hours at 50 ℃.
5) Finally, willThe solid sample finally obtained is placed in a tube furnace under N 2 Annealing at 450 ℃ for 3h under protection to obtain the graphene-like material
Ultrathin nanosheet compounds.
From FIG. 2, it can be seen that the graphene-like material prepared in this example
The metal nano sheets are stacked layer by layer, are connected with each other and form a plurality of gaps. Moreover, the nano-sheet layers have uniform structures and very thin thicknesses of about 10-15 nm.
Example 3:
1) and (4) crushing and pretreating the selenium dioxide blocky crystals.
2) Weighing a mixture with a molar ratio of 2:1 selenium source and a vanadium source, then 0.444g of selenium dioxide is dissolved in 30ml of dimethylformamide, the mixture is sealed and ultrasonically dispersed for 4 hours in a 120w ultrasonic instrument, then 0.364g of vanadium pentoxide is added, magnetic stirring is carried out for 60 minutes, and finally 12ml of formic acid is dripped in at the speed of 60 drops/min under the condition of stirring in a fume hood to obtain the mixed solution of the selenium dioxide, the vanadium pentoxide, the formic acid and the dimethylformamide.
3) Transferring the mixed solution obtained in the step 2) to a 100ml high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, and placing the reaction kettle in an oven to react for 26 hours at 180 ℃.
4) After the reaction is finished and the reaction product is naturally cooled to room temperature, the product is repeatedly centrifugally washed for 3-6 times by deionized water and absolute ethyl alcohol respectively, and then the obtained solid is placed in a vacuum drying oven to be dried for 6 hours at 50 ℃.
5) Finally, putting the finally obtained solid sample into a tube furnace, and annealing for 5 hours at 400 ℃ under the protection of Ar to obtain the graphene-like material
Ultrathin nanosheet compounds.
Example 4:
1) and crushing and pretreating the selenourea blocky crystal.
2) Weighing the components in a molar ratio of 2:1 selenium source and vanadium source, then 0.492g of selenourea is dissolved in 30ml of N-methyl pyrrolidone, sealed and ultrasonically dispersed for 2 hours in a 120w ultrasonic instrument, then 0.234g of ammonium metavanadate is added, magnetic stirring is carried out for 30min, and finally, 8ml of formic acid is dripped in under the stirring condition in a fume hood at the speed of 50 drops/min to obtain the mixed solution of the selenourea, the ammonium metavanadate, the formic acid and the N-methyl pyrrolidone.
3) Transferring the mixed solution obtained in the step 2) to a 100ml high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, and placing the reaction kettle in an oven to react for 20 hours at the temperature of 200 ℃.
4) After the reaction is finished and the reaction product is naturally cooled to room temperature, the product is repeatedly centrifugally washed for 3-6 times by deionized water and absolute ethyl alcohol respectively, and then the obtained solid is placed in a vacuum drying oven to be dried for 8 hours at 50 ℃.
5) Finally, putting the finally obtained solid sample into a tube furnace, and annealing for 5 hours at 600 ℃ under the protection of Ar to obtain the graphene-like material
Ultrathin nanosheet compounds.
Example 5:
1) and crushing and pretreating the selenourea blocky crystal.
2) Weighing the components in a molar ratio of 4: 1 selenium source and vanadium source, then 0.984g of selenourea is dissolved in 30ml of N-methyl pyrrolidone, sealed and ultrasonically dispersed for 3 hours in a 120w ultrasonic instrument, then 0.234g of ammonium metavanadate is added, magnetic stirring is carried out for 60min, and finally 15ml of formic acid is dripped in under the condition of stirring in a fume hood at the speed of 100 drops/min to obtain the mixed solution of the selenourea, the ammonium metavanadate, the formic acid and the N-methyl pyrrolidone.
3) Transferring the mixed solution obtained in the step 2) to a 100ml high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, and placing the reaction kettle in an oven to react for 22 hours at 190 ℃.
4) After the reaction is finished, naturally cooling to room temperature, respectively using deionized water and absolute ethyl alcohol to repeatedly centrifugally wash the product for 3-6 times, and then putting the obtained solid into a vacuum drying oven to dry for 16 hours at 50 ℃.
5) Finally, putting the finally obtained solid sample into a tube furnace, and annealing for 3h at 550 ℃ under the protection of Ar to obtain the graphene-like material
Ultrathin nanosheet compounds.
Example 6:
1) and (4) crushing and pretreating the selenium dioxide blocky crystals.
2) Weighing the components in a molar ratio of 2:1 selenium source and a vanadium source, then 0.444g of selenium dioxide is dissolved in a mixed solution of 15ml of N-methyl pyrrolidone and 15ml of dimethylformamide, the mixture is sealed and ultrasonically dispersed for 2 hours in a 120w ultrasonic instrument, then 0.234g of ammonium metavanadate is added, magnetic stirring is carried out for 60min, and finally 6ml of formic acid is dripped in the mixed solution of the selenium dioxide, the ammonium metavanadate, the formic acid, the dimethylformamide and the N-methyl pyrrolidone at the speed of 100 drops/min under the stirring condition in a fume hood to obtain the mixed solution of the selenium dioxide, the ammonium metavanadate, the formic acid, the dimethylformamide and the N-methyl pyrrolidone.
3) Transferring the mixed solution obtained in the step 2) to a 100ml high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, and placing the reaction kettle in an oven to react for 18 hours at the temperature of 200 ℃.
4) After the reaction is finished and the reaction product is naturally cooled to room temperature, the product is repeatedly centrifugally washed for 3-6 times by deionized water and absolute ethyl alcohol respectively, and then the obtained solid is placed in a vacuum drying oven to be dried for 10 hours at 50 ℃.
5) Finally, the solid sample obtained finally is placed in a tube furnace in N 2 Annealing at 450 ℃ for 5h under protection to obtain the graphene-like material
Ultrathin nanosheet compounds.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above examples, those skilled in the art should understand that: other modifications and equivalents of the technical solution of the present invention should be covered by the claims of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. Graphene-like
The preparation method of the metal ultrathin nanosheet is characterized by comprising the following steps:
1) crushing and pretreating a selenium source of the bulk crystal;
2) weighing the components in a molar ratio of 2-4: 1, dissolving a selenium source and a vanadium source in 30ml of dimethylformamide, sealing and ultrasonically dispersing, then adding the vanadium source, magnetically stirring, and then slowly dripping a certain amount of formic acid under the stirring condition in a fume hood to obtain a mixed solution of the selenium source, the vanadium source, a reducing agent and a reaction solvent;
3) transferring the mixed solution obtained in the step 2) into a high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, and placing the reaction kettle in a drying oven for high-temperature reaction;
4) after the reaction is finished and the reaction product is naturally cooled to room temperature, respectively using deionized water and absolute ethyl alcohol to repeatedly centrifugally wash the reaction product for 3-6 times, and then putting the obtained solid into a vacuum drying oven to dry for 6-16h at 50 ℃;
5) finally, putting the finally obtained solid sample into a tube furnace, and annealing under the protection of inert gas to obtain the graphene-like material
Ultrathin nanosheet compounds.
2. Graphene-like according to claim 1
The preparation method of the ultrathin nanosheet is characterized by comprising the following steps: and (2) performing comminuted pretreatment on the selenium dioxide bulk crystal sample in the step 1).
3. Graphene-like according to claim 1
The preparation method of the ultrathin nanosheet is characterized by comprising the following steps: the ultrasonic dispersion power of the step 2) is 120W, the ultrasonic dispersion time is 1-4h, the volume of formic acid is 6-15ml, and the dropping speed is 40-100 drops/min.
4. Graphene-like according to claim 1
The preparation method of the ultrathin nanosheet is characterized by comprising the following steps: the vanadium source in the step 2) is ammonium metavanadate, vanadium pentoxide and vanadyl acetylacetonate (VO)
(acac) 2 ) One or more of; the selenium source refers to one or more of selenium dioxide and selenourea.
5. Graphene-like according to claim 1
The preparation method of the ultrathin nanosheet is characterized by comprising the following steps: the solvent used in the step 2) is one or more of Dimethylformamide (DMF) and N-methylpyrrolidone (NMP) organic solvents.
6. Graphene-like according to claim 1
The preparation method of the ultrathin nanosheet is characterized by comprising the following steps: the volume of the inner lining of the high-pressure reaction kettle used in the step 3) is 100ml, the reaction temperature is 180-.
7. Graphene-like according to claim 1Is
The preparation method of the ultrathin nanosheet is characterized by comprising the following steps: in the step 5), the high-temperature annealing temperature of the sample is 400- 2 。
8. Graphene-like according to any one of claims 1-7
The ultrathin nano-sheet is prepared by the preparation method and is similar to graphene
An ultrathin nanosheet.
9. Graphene-like according to any one of claims 1-8
Graphene-like ultrathin nanosheet prepared by preparation method
The ultrathin nanosheet is applied to the anode material of the aluminum ion battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109052340A (en) * | 2018-10-10 | 2018-12-21 | 陕西科技大学 | A kind of preparation method of selenium/selenizing vanadium compound phase material |
| CN109279584A (en) * | 2018-10-10 | 2019-01-29 | 陕西科技大学 | A kind of self assembly VSe2The synthetic method of nanometer sheet |
| CN110124694A (en) * | 2019-06-04 | 2019-08-16 | 济南大学 | A kind of preparation and the reduction application of electro-catalysis nitrogen of ultrathin nanometer sheet vanadium doping nanometer nickel sulfide powder |
| CN113533451A (en) * | 2021-07-14 | 2021-10-22 | 中国人民解放军国防科技大学 | Co Co-doped with Sn and Mn3O4Nanosheet, preparation method and application of nanosheet as gas-sensitive material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109052340A (en) * | 2018-10-10 | 2018-12-21 | 陕西科技大学 | A kind of preparation method of selenium/selenizing vanadium compound phase material |
| CN109279584A (en) * | 2018-10-10 | 2019-01-29 | 陕西科技大学 | A kind of self assembly VSe2The synthetic method of nanometer sheet |
| CN110124694A (en) * | 2019-06-04 | 2019-08-16 | 济南大学 | A kind of preparation and the reduction application of electro-catalysis nitrogen of ultrathin nanometer sheet vanadium doping nanometer nickel sulfide powder |
| CN113533451A (en) * | 2021-07-14 | 2021-10-22 | 中国人民解放军国防科技大学 | Co Co-doped with Sn and Mn3O4Nanosheet, preparation method and application of nanosheet as gas-sensitive material |
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