CN114572986A - Two-dimensional VyCr2-yCSxPreparation method of nanosheet - Google Patents
Two-dimensional VyCr2-yCSxPreparation method of nanosheet Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007873 sieving Methods 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011651 chromium Substances 0.000 claims description 48
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 18
- 239000011812 mixed powder Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000013590 bulk material Substances 0.000 claims description 7
- 239000002064 nanoplatelet Substances 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 3
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 6
- 230000007935 neutral effect Effects 0.000 abstract description 5
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 2
- 229910000570 Cupronickel Inorganic materials 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- 239000000956 alloy Substances 0.000 abstract 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000005554 pickling Methods 0.000 abstract 1
- 229910009819 Ti3C2 Inorganic materials 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000004354 sulfur functional group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010067 TiC2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
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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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/40—Electric properties
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- 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
- Y02E60/13—Energy storage using capacitors
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- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
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Abstract
The invention relates to a two-dimensional VyCr2‑yCSxA process for preparing nanosheets according to formula VyCr2‑yThe metering ratio in AlC is that vanadium powder, chromium powder, aluminum powder and carbon powder are taken to be evenly mixed and then added into a self-propagating reaction tank, a tungsten wire with the length of 5-15 cm is added, and the mixture is ignited to react under the protection of inert gas to obtain VyCr2‑yCrushing AlCMAX block material, and sieving with a 300-plus-400-mesh sieve to obtain VyCr2‑yAlCrax powder, ZnS and Na2S/K2And S, mixing the mixed salt uniformly, annealing under the protection of inert gas, and finally pickling and washing with water to be neutral to obtain the copper-nickel alloy. The method is simple, does not relate to high-risk reactants such as hydrofluoric acid and the like, has mild reaction conditions, can recycle the adopted mixed salt solvent, meets the requirements of continuous development and environmental protection, and prepares the two-dimensional VyCr2‑yCSxThe nano-sheet has good electrochemical energy storage performance.
Description
Technical Field
The invention relates to a two-dimensional VyCr2-yCSxA preparation method of a nano-sheet, belonging to the technical field of low-dimensional nano-materials.
Background
MXenes is a generic term for a new two-dimensional transition metal carbide or carbonitride. In 2011, Gogotsi and Barsum project group of Drehelle university, USA selectively etches Ti with hydrofluoric acid3AlC2A layer in MAX phase obtains a novel two-dimensional Ti3C2A nanosheet. In the process of etching the A layer, two-dimensional Ti is synchronously formed3C2The surface of the nano sheet is introduced with a large number of functional groups, therefore, the structural formula is generally written as Ti3C2Tx(T-F, OH or O). MAX is Mn+1AXnAbbreviation for phase (N ═ 1,2or3), wherein M is an early transition metal element, a is a third or fourth main group element, and X is C or N. Due to the variety of sources of MAX phase materials, some of the columns resemble Ti3C2TxMaterials of nature and construction, e.g. V2CTx、Nb2CTx、Mo2TiC2TxEtc. are collectively referred to as MXenes. MXenes materials have good mechanical, electrochemical and optical properties, e.g. Ti3C2TxThe elastic modulus of the material is up to 500GPa, the conductivity is over 10000S/cm, and the surface of the material is endowed with extremely high hydrophilicity, catalytic activity and the like by rich functional groups. Therefore, MXenes has good application potential in the fields of supercapacitors, lithium sodium ion batteries, catalysts, water treatment and the like.
In general, MXenes materials are etched with hydrofluoric acid (in situ hydrofluoric acid) and have F, OH or O functional groups on their surface. Recent research shows that functional groups on the surface of MXenes have important influence on the catalytic property and the energy storage performance of the MXenes. Therefore, the regulation of MXenes surface functionality by rational means is of great interest. For example, the prior art has employed CuCl2、CuBr2、CuI2Isoetchant for preparing MXenes with full halogen functional group such as Ti3C2Clx、Ti3C2Brx、Ti3C2Ix. The introduction of the perhalogen functional group can avoid the introduction of-OH and-O functional groups in the conventional liquid phase etching method, can endow MXenes materials with affinity with metal cations, and can improve the performance of the metal ion battery; it has also been shown that the introduction of all-sulfur functional groups into MXenes materials can impart novel properties to the materials, such as improving the performance of lithium-sulfur batteries, and the current preparation of MXenes containing sulfur functional groups is mainly focused on titanium-based MXenes such as Ti3C2Tx. With Ti-based MXenes phase, e.g. Ti3C2TxCompared with vanadium-based MXenes, the vanadium-based MXenes has better lithium affinity and electrochemical energy storage performance, the development of the vanadium-based MXenes is expected to have better performance, and no V with all-sulfur functional groups is prepared at presentyCr2-yCSxThe report of (1). In addition, the traditional method for vulcanizing MXenes mainly adopts a high-temperature annealing method to react sulfur powder, thiourea and the like with the MXenes to replace F, OH or O. The method is not only complicated, but also easily causes the damage of the two-dimensional material structure in the annealing process.
Disclosure of Invention
The present invention is to solve the above-mentioned drawbacks of the background art, and to provide a two-dimensional VyCr2-yCSxThe material prepared by the preparation method of the nanosheet has good electrochemical energy storage performance.
Technical scheme
The invention adopts a self-propagating high-temperature synthesis (SHS) method to synthesize high-defect VyCr2-yMAX of AlC, and then adopting molten salt method to etch V in one stepyCr2-yTwo-dimensional V with full sulfur functional group obtained from AlCyCr2-yCSxThe specific scheme is as follows:
two-dimensional VyCr2-yCSxThe preparation method of the nanosheet comprises the following steps:
(1) according to formula VyCr2-yThe vanadium powder, the chromium powder, the aluminum powder and the carbon powder are uniformly mixed according to the metering ratio in the AlC, and then are added into a self-propagating reaction tank; the chemical formula VyCr2-yIn AlC, 0<y≤2；
(2) Adding tungsten filament into the self-propagating reaction tank, igniting under the protection of inert gas, and reacting to obtain VyCr2-yAlC MAX bulk material;
(3) will VyCr2-yCrushing and sieving AlC MAX block material to obtain VyCr2-yAlC MAX powder;
(4) will VyCr2-yAlC MAX powder, ZnS and Na2S/K2S, mixing the mixed salt uniformly to obtain mixed powder;
(5) annealing the mixed powder in the step (4) under the protection of inert gas, then acid washing and water washing to neutrality to obtain two-dimensional VyCr2-yCSxNanosheets.
Further, in the step (1), the chemical formula VyCr2-yIn AlC, y is more than or equal to 1 and less than or equal to 2.
Further, in the step (2), the length of the tungsten filament is 5-15 cm, and the inert gas is nitrogen or argon.
Further, in the step (3), the sieving is a 300-400 mesh sieving.
Further, in the step (4), VyCr2-yThe mass ratio of AlC MAX powder to ZnS is 1 (3-9).
Further, in the step (4), the ZnS is mixed with Na2S/K2The mass ratio of S mixed salt to Na is 1:62S/K2In S mixed salt, Na2S and K2The mass ratio of S is 1: 1.
Further, in the step (5), the annealing temperature is 700-950 ℃, and the annealing time is 3-10 h.
Further, in the step (5), the inert gas is nitrogen or argon, and the acid solution used for acid washing is 1mol/L hydrochloric acid solution or sulfuric acid solution.
The invention has the beneficial effects that:
the invention firstly takes vanadium powder, chromium powder, aluminum powder and carbon powder as raw materials to prepare V with high defectyCr2-yAlC MAX, and Na2S/K2S mixed salt is used as solvent, ZnS is used as etching agent to prepare two-dimensional V with all-sulfur functional groupsyCr2-yCSxNanosheets. The method is simple, does not relate to high-risk reactants such as hydrofluoric acid and the like, has mild reaction conditions, can recycle the mixed salt solvent, meets the requirements of continuous development and environmental protection, and can obtain the V of the all-sulfur functional groupyCr2-yCSxIt has excellent electrochemical energy storing performance.
Drawings
FIG. 1 is a two-dimensional V obtained in example 12CSxScanning electron microscopy of the nanoplatelets.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Two-dimensional V2CSxThe preparation method of the nanosheet comprises the following steps:
(1) uniformly mixing 51 g of vanadium powder, 32.4 g of aluminum powder and 12 g of carbon powder, and adding the mixture into a self-propagating reaction tank;
(2) adding a tungsten wire with the length of 15 cm, igniting under the protection of argon, and reacting to obtain V2AlC MAX bulk material;
(3) will V2Crushing AlC MAX block material, and sieving with 300-400 mesh sieve to obtain V2AlC MAX powder;
(4) will V2AlC MAX powder, ZnS and Na2S/K2S mixed salt is 1:9:54 (the Na)2S/K2In S mixed salt, Na2S and K2The mass ratio of S is 1:1), and the mixed powder is obtained by uniformly mixing;
(5) annealing the mixed powder in the step (4) at 950 ℃ for 10h under the protection of argon, washing with 1mol/L sulfuric acid solution, and washing with water to neutrality to obtain two-dimensional V2CSxThe nano-sheet material is coated on the surface of the substrate,the yield was 15%.
Two-dimensional V from example 12CSxThe scanning electron micrograph of the nanoplatelets is shown in figure 1.
Will be two-dimensional V2CSxFiltering the nano-sheet into a film by suction, and directly using V2CSxThe film is used as a working electrode, YP50 active carbon is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode, and the concentration is 1mol/L H2SO4For the electrolyte, two-dimensional V was measured at a current density of 1A/g2CSxThe specific capacity of the nano-sheet electrode material is up to 392F/g.
Example 2
Two-dimensional V1Cr1CSxThe preparation method of the nanosheet comprises the following steps:
(1) uniformly mixing 25.5 g of vanadium powder, 26 g of chromium powder, 21.6 g of aluminum powder and 12 g of carbon powder, and adding the mixture into a self-propagating reaction tank;
(2) adding a tungsten wire with the length of 5 cm, igniting under the protection of nitrogen, and reacting to obtain V1Cr1AlC MAX bulk material;
(3) will V1Cr1Crushing AlC MAX block material, and sieving with 300-400 mesh sieve to obtain V1Cr1AlC MAX powder;
(4) will VyCr2-yAlC MAX powder, ZnS and Na2S/K2The S mixed salt is 1:3:3 (the Na)2S/K2In S mixed salt, Na2S and K2The mass ratio of S is 1:1), and the mixed powder is obtained by uniformly mixing;
(5) annealing the mixed powder in the step (4) at 700 ℃ for 3h under the protection of nitrogen, washing with 1mol/L hydrochloric acid solution, and washing with water to be neutral to obtain two-dimensional V1Cr1CSxNanoplatelets in 25% yield.
Will be two-dimensional V1Cr1CSxFiltering the nano-sheet into a film by suction, and directly using V1Cr1CSxThe film is used as a working electrode, YP50 active carbon is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode, and the concentration is 1mol/L H2SO4As an electrolyte, two-dimensional V was measured at a current density of 1A/g1Cr1CSxThe specific capacity of the nano-sheet electrode material is up to 351F/g.
Example 3
Two-dimensional V1.5Cr0.5CSxThe preparation method of the nanosheet comprises the following steps:
(1) uniformly mixing 38.25 g of vanadium powder, 13 g of chromium powder, 27 g of aluminum powder and 12 g of carbon powder, and adding the mixture into a self-propagating reaction tank;
(2) adding 10 cm long tungsten filament, igniting under nitrogen protection, and reacting to obtain V1.5Cr0.5AlC MAX bulk material;
(3) will V1.5Cr0.5Crushing AlC MAX block material, and sieving with 300-400 mesh sieve to obtain V1.5Cr0.5AlC MAX powder;
(4) will V1.5Cr0.5AlC MAX powder, ZnS and Na2S/K2S mixed salt is 1:6:18 (the Na)2S/K2In S mixed salt, Na2S and K2The mass ratio of S is 1:1), and the mixed powder is obtained by uniformly mixing;
(5) annealing the mixed powder in the step (4) at 800 ℃ for 6h under the protection of argon, washing with 1mol/L hydrochloric acid solution, and washing with water to be neutral to obtain two-dimensional V1.5Cr0.5CSxNanoplatelets in 72% yield.
Will be two-dimensional V1.5Cr0.5CSxFiltering the nano-sheet into a film by suction, and directly using V1.5Cr0.5CSxThe film is used as a working electrode, YP50 active carbon is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode, and the concentration is 1mol/L H2SO4For the electrolyte, two-dimensional V was measured at a current density of 1A/g1.5Cr0.5CSxThe specific capacity of the nano-sheet electrode material is as high as 435F/g.
Example 4
Two-dimensional V1.8Cr0.2CSxThe preparation method of the nano sheet comprises the following steps:
(1) uniformly mixing 45.9 g of vanadium powder, 5.2 g of chromium powder, 32.4 g of aluminum powder and 12 g of carbon powder, and adding the mixture into a self-propagating reaction tank;
(2) adding 10 cm long tungsten filament, igniting under nitrogen protection, and reacting to obtain V1.8Cr0.2AlC MAX bulk material;
(3) will V1.8Cr0.2Crushing AlC MAX block material, and sieving with a 300-400 mesh sieve to obtain V1.8Cr0.2AlC MAX powder;
(4) will V1.8Cr0.2AlC MAX powder, ZnS and Na2S/K2S mixed salt is 1:6:36 (the Na)2S/K2In S mixed salt, Na2S and K2The mass ratio of S is 1:1), and the mixed powder is obtained by uniformly mixing;
(5) annealing the mixed powder in the step (4) at 800 ℃ for 10h under the protection of argon, washing with 1mol/L hydrochloric acid solution, and washing with water to be neutral to obtain two-dimensional V1.8Cr0.2CSxNanoplatelets in a yield of 57%.
Will be two-dimensional V1.8Cr0.2CSxFiltering the nano-sheet into a film by suction, and directly using V1.8Cr0.2CSxThe film is used as a working electrode, YP50 active carbon is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode, and the concentration is 1mol/L H2SO4For the electrolyte, two-dimensional V was measured at a current density of 1A/g1.8Cr0.2CSxThe specific capacity of the nano-sheet electrode material is up to 335F/g.
Example 5
Two-dimensional V1.2Cr0.6CSxThe preparation method of the nanosheet comprises the following steps:
(1) uniformly mixing 30.6 g of vanadium powder, 15.6 g of chromium powder, 30.0 g of aluminum powder and 12 g of carbon powder, and adding the mixture into a self-propagating reaction tank;
(2) adding 10 cm long tungsten filament, igniting under nitrogen protection, and reacting to obtain V1.2Cr0.6AlC MAX bulk material;
(3) will V1.2Cr0.6AlC MAXCrushing the block material, and sieving with a sieve of 300 meshes and 400 meshes to obtain V1.2Cr0.6AlC MAX powder;
(4) will V1.2Cr0.6AlC MAX powder, ZnS and Na2S/K2S mixed salt is 1:6:54 (the Na)2S/K2In S mixed salt, Na2S and K2The mass ratio of S is 1:1), and the mixed powder is obtained by uniformly mixing;
(5) annealing the mixed powder in the step (4) at 800 ℃ for 8h under the protection of argon, washing with 1mol/L sulfuric acid solution, and washing with water to be neutral to obtain two-dimensional V1.2Cr0.6CSxNanoplatelets in 63% yield.
Will be two-dimensional V1.2Cr0.6CSxFiltering the nano-sheet into a film by suction, and directly using V1.2Cr0.6CSxThe film is used as a working electrode, YP50 active carbon is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode, and the concentration is 1mol/L H2SO4For the electrolyte, two-dimensional V was measured at a current density of 1A/g1.2Cr0.6CSxThe specific capacity of the nano-sheet electrode material is up to 375F/g.
In summary, the invention provides a VyCr2-yCSxThe nano-sheet is a fluorine-free two-dimensional material prepared based on a molten salt method, has good energy storage performance and can be used as a super capacitor electrode material. The preparation can meet the requirements of continuous development and environmental protection, and has wide sources and low price.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (8)
1. Two-dimensional VyCr2-yCSxOf nanosheetsThe preparation method is characterized by comprising the following steps:
(1) according to formula VyCr2-yThe vanadium powder, the chromium powder, the aluminum powder and the carbon powder are uniformly mixed according to the metering ratio in the AlC, and then are added into a self-propagating reaction tank; the chemical formula VyCr2-yIn AlC, 0<y≤2；
(2) Adding tungsten filament into the self-propagating reaction tank, igniting under the protection of inert gas, and reacting to obtain VyCr2-yAlC MAX bulk material;
(3) will VyCr2-yCrushing and sieving AlC MAX block material to obtain VyCr2-yAlC MAX powder;
(4) will VyCr2-yAlC MAX powder, ZnS and Na2S/K2S, mixing the mixed salt uniformly to obtain mixed powder;
(5) annealing the mixed powder in the step (4) under the protection of inert gas, then acid washing and water washing to neutrality to obtain two-dimensional VyCr2-yCSxNanosheets.
2. The two-dimensional V of claim 1yCr2-yCSxA process for the preparation of nanoplatelets characterized in that in step (1), the compound of formula VyCr2-yIn AlC, y is more than or equal to 1 and less than or equal to 2.
3. The two-dimensional V of claim 1yCr2-yCSxThe preparation method of the nanosheet is characterized in that in the step (2), the tungsten filament is 5-15 cm long, and the inert gas is nitrogen or argon.
4. The two-dimensional V of claim 1yCr2-yCSxThe preparation method of the nano-sheet is characterized in that in the step (3), the sieving is performed by a 300-400-mesh sieve.
5. The two-dimensional V of claim 1yCr2-yCSxThe preparation method of the nano-sheet is characterized by comprising the following steps(4) In, VyCr2- yThe mass ratio of AlC MAX powder to ZnS is 1 (3-9).
6. The two-dimensional V of claim 1yCr2-yCSxThe preparation method of the nano sheet is characterized in that in the step (4), the ZnS and Na2S/K2The mass ratio of S mixed salt to Na is 1:62S/K2In S mixed salt, Na2S and K2The mass ratio of S is 1: 1.
7. The two-dimensional V of claim 1yCr2-yCSxThe preparation method of the nano-sheet is characterized in that in the step (5), the annealing treatment temperature is 700-950 ℃, and the annealing time is 3-10 h.
8. The two-dimensional V of any one of claims 1 to 7yCr2-yCSxThe preparation method of the nanosheet is characterized in that in the step (5), the inert gas is nitrogen or argon, and the acid solution used for acid washing is 1mol/L hydrochloric acid solution or sulfuric acid solution.
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