CN114744152A - Vanadium tetrasulfide/vanadium carbide composite material and preparation method and application thereof - Google Patents
Vanadium tetrasulfide/vanadium carbide composite material and preparation method and application thereof Download PDFInfo
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- tetrasulfide
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- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 title claims abstract description 91
- UDKXBPLHYDCWIG-UHFFFAOYSA-M [S-2].[S-2].[SH-].S.[V+5] Chemical compound [S-2].[S-2].[SH-].S.[V+5] UDKXBPLHYDCWIG-UHFFFAOYSA-M 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000004108 freeze drying Methods 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000000725 suspension Substances 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 24
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 23
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000009830 intercalation Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 19
- PTXMVOUNAHFTFC-UHFFFAOYSA-N alumane;vanadium Chemical compound [AlH3].[V] PTXMVOUNAHFTFC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005530 etching Methods 0.000 claims abstract description 14
- 238000004729 solvothermal method Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000007773 negative electrode material Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000002135 nanosheet Substances 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 32
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 21
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 12
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011889 copper foil Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 230000002687 intercalation Effects 0.000 claims description 7
- 230000014759 maintenance of location Effects 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 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
- 239000004201 L-cysteine Substances 0.000 claims description 5
- 235000013878 L-cysteine Nutrition 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 241000764238 Isis Species 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 2
- KSECJOPEZIAKMU-UHFFFAOYSA-N [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] Chemical compound [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] KSECJOPEZIAKMU-UHFFFAOYSA-N 0.000 abstract 1
- 238000007710 freezing Methods 0.000 abstract 1
- 230000008014 freezing Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- -1 Transition Metal Sulfides Chemical class 0.000 description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 101150096839 Fcmr gene Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
Abstract
The invention provides a vanadium tetrasulfide/vanadium carbide composite material and a preparation method and application thereof. The preparation method of the vanadium tetrasulfide/vanadium carbide composite material comprises the following steps: etching, intercalating and freeze-drying the vanadium aluminum carbide to obtain few-layer V2CTxPowder; mixing a vanadium source and an organic solvent to obtain a precursor solution, and adding a few layers of V into the precursor solution2CTxPerforming low-temperature ultrasonic treatment on the powder to obtain a first suspension; adding a sulfur source into the first suspension, and stirring to obtain a second suspension; and carrying out solvothermal reaction on the second suspension, washing, freezing and drying to obtain the vanadium tetrasulfide/vanadium carbide composite material. The application comprises the step of mixing vanadium tetrasulfide/vanadium carbide composite materialThe method is applied to battery negative electrode materials. The vanadium sulfide/vanadium carbide composite material synthesized by the invention has a vanadium tetrasulfide nanosheet structure growing on the surface of vanadium carbide, so that the contact specific surface area of the electrolyte and the vanadium tetrasulfide is effectively increased, and the diffusion path of sodium ions in the material is shortened.
Description
Technical Field
The invention belongs to the technical field of sodium-ion battery electrode materials, and particularly relates to a vanadium tetrasulfide/vanadium carbide composite material as well as a preparation method and application thereof.
Background
The lithium ion battery is the most advantageous electrochemical energy storage device at present, although it has the advantages of high energy density, long cycle life, high working voltage, no memory effect and the like. However, with the development of new energy technology, the cost is increased due to excessive use of lithium resources, and safety problems caused by lithium ion batteries and the like become restrictions for further development. Sodium, which is a common group element of lithium, has a high standard potential, and sodium-ion batteries have a charge-discharge mechanism similar to that of lithium-ion batteries. Meanwhile, the sodium storage capacity is rich, the cost is low, and the fire and explosion can be avoided in safety item tests such as overcharge, overdischarge, needling, extrusion and the like. Therefore, sodium ion batteries are the most promising batteries, and can replace lithium ion batteries to become the next generation secondary batteries. Although the sodium ion battery has the advantages, sodium ions have larger radius than lithium ions, so that the electrochemical reaction power of the sodium ions is insufficient, and the rate performance is influenced. In addition, negative electrode graphite is suitable for lithium ion batteries, but does not have the ability to intercalate and deintercalate within a layer in sodium ion batteries. Therefore, the development of novel sodium-ion battery negative electrode materials is crucial to commercial application. The negative electrode of the sodium ion battery mainly comprises a carbon material, an alloy material, a titanium-based material metal oxide material and a metal sulfide material. Carbon materials have very limited sodium storage performance due to deficiencies in energy storage properties. The alloy material has higher specific capacity, but the alloying reaction in the charging and discharging process causes huge volume change, so that the cycle performance of the alloy material in the charging and discharging process of the battery is poorer. The metal oxide material and the metal sulfide material have high energy storage capacity and good application prospect, but always generate conversion reaction during charging and discharging. In the reaction process, sodium ions react to generate a metal simple substance and corresponding sodium oxide or sodium sulfide, and simultaneously, the electrode structure is damaged along with huge volume change, so that the electrode falls off from a current collector.
Transition Metal Sulfides (TMS) have large specific surface areas and atomic exposures, and their electrochemical reactions always occur at the surface or interface. Moreover, TMS can exploit all oxidation states of transition metals, which gives them a higher theoretical capacity. Therefore, TMS has a wide range of applications in energy storage and conversion, and in particular they show great potential as negative electrode materials for SIBs. Metal sulfides of V, e.g. V3S4、V5S8、VS2And VS4Due to the unique crystal structure and the multiple valence states of V, there is a great deal of interest in the field of energy storage. VS4By S connecting two adjacent V atoms2-The dimer forms a one-dimensional parallel chain structure. VS4The weaker inter-chain van der waals forces in (b) weaken the interaction between adjacent chains, resulting in a loose structure. VS4Distance between chains
Specific diameter of sodium ion
Is much larger, and facilitates the insertion/extraction of sodium ions into/from the channel. These characteristics give VS4High theoretical specific capacity (1196mAh g)-1). However, VS4Have lower conductivity and greater volume expansion during the electrochemical process, resulting in poor cycling and rate performance.
Disclosure of Invention
The present invention aims to address at least one of the above-mentioned deficiencies of the prior art. For example, one of the objects of the present invention is to provide a method for preparing a vanadium tetrasulfide/vanadium carbide composite material. Another object of the present invention is to provide a vanadium tetrasulfide/vanadium carbide composite material. The invention also aims to provide application of the vanadium tetrasulfide/vanadium carbide composite material.
In order to achieve the above objects, an aspect of the present invention is to provide a method for preparing a vanadium tetrasulfide/vanadium carbide composite material, the method for preparing the sameThe method comprises the following steps: etching, intercalating and freeze-drying the vanadium aluminum carbide to obtain few-layer V2CTxPowder; mixing a vanadium source and an organic solvent to obtain a precursor solution, and adding a few layers of V into the precursor solution2CTxPerforming low-temperature ultrasonic treatment on the powder to obtain a first suspension; adding a sulfur source into the first suspension, and stirring to obtain a second suspension; carrying out solvothermal reaction on the second suspension, washing, and freeze-drying to obtain a vanadium tetrasulfide/vanadium carbide composite material; wherein the vanadium source comprises ammonium metavanadate and/or vanadyl acetylacetonate, the organic solvent comprises one or more of ethylene glycol, N-methylpyrrolidone, N-dimethylformamide and methanol, and the sulfur source comprises one of thioacetamide, L-cysteine and thiourea.
In an exemplary embodiment of an aspect of the invention, the vanadium aluminum carbide is etched, intercalated, and freeze-dried to obtain few layers V2CTxThe powder may include: adopting hydrofluoric acid to etch vanadium aluminum carbide, and centrifugally washing to obtain multilayer V2CTx(ii) a To multiple layers V2CTxAdding tetrabutylammonium hydroxide into the mixture, and subjecting the multilayer V to inert atmosphere2CTxIntercalation, centrifugal washing to obtain suspension; ultrasonically stripping and centrifuging the turbid liquid, and taking supernatant liquid to obtain few-layer V2CTxA dispersion liquid; the few layers V2CTxFreeze drying the dispersion to obtain V2CTxAnd (3) powder.
In an exemplary embodiment of an aspect of the present invention, the solvent thermal reaction, washing, and freeze-drying of the second suspension to obtain the vanadium tetrasulfide/vanadium carbide composite material may include: and reacting the second suspension at 160-200 ℃ for 8-36 hours to obtain a reaction product, washing the reaction product, and freeze-drying under a vacuum condition to obtain the vanadium tetrasulfide/vanadium carbide composite material.
In an exemplary embodiment of an aspect of the present invention, the molar ratio of the vanadium source to the sulfur source may be 1:4 to 6; the mixing ratio of the vanadium source to the organic solvent can be 1 mmol: 15-35 mL; the vanadium source and the few layers V2CTxOf powdersMass ratio 1 mmol: 30-160 mg.
In one exemplary embodiment of an aspect of the present invention, the plurality of layers V2CTxThe number of layers (V) can be 20-50, and the number of layers (V) is less2CTxThe number of powder layers may be 1 to 10.
In an exemplary embodiment of an aspect of the present invention, the concentration of the hydrofluoric acid may be 35 to 45%, the etching temperature may be 30 to 40 ℃, and the etching time may be 20 to 26 hours; the concentration of the tetrabutyl ammonium hydroxide can be 2-7%, and the intercalation time can be 20-26 h; the few layers V2CTxThe freeze-drying temperature of the dispersion liquid can be-55-65 ℃, and the time can be 20-26 h; the freeze drying temperature of the second suspension liquid can be-55-65 ℃ and the time can be 20-26 h.
Another aspect of the present invention provides a vanadium tetrasulfide/vanadium carbide composite material prepared by the method for preparing a vanadium tetrasulfide/vanadium carbide composite material as described in any one of the above aspects, wherein the vanadium tetrasulfide/vanadium carbide composite material has a structure of: vanadium tetrasulfide nanosheets are uniformly distributed on the surface of the vanadium carbide, wherein the vanadium carbide is of an amorphous structure, and the specific surface area of the vanadium tetrasulfide/vanadium carbide composite material is 30-50 m2 g-1。
In another aspect, the invention provides an application of the vanadium tetrasulfide/vanadium carbide composite material, and the application comprises the application of the vanadium tetrasulfide/vanadium carbide composite material to a battery negative electrode material.
In an exemplary embodiment of yet another aspect of the present invention, the applying may include: mixing the vanadium tetrasulfide/vanadium carbide composite material with a conductive agent and a binder according to the mass ratio of 5-8: 1-2: 0.5-1, coating the mixture on a copper foil, and drying the copper foil to obtain the working electrode.
In an exemplary embodiment of still another aspect of the present invention, the working electrode is between 0.1 to 10Ag-1After 50-100 times of cyclic charge and discharge under current density, the capacity retention rate is 42-52% of the first time, and the cyclic performance is stable.
Compared with the prior art, the beneficial effects of the invention can comprise at least one of the following:
(1) according to the vanadium tetrasulfide/vanadium carbide composite material synthesized by the method, vanadium tetrasulfide uniformly grows on the surface of vanadium carbide, and the vanadium tetrasulfide nanosheet structure vertically grows on the surface of vanadium carbide, so that the contact specific surface area of electrolyte and vanadium tetrasulfide is effectively increased, and the diffusion path of sodium ions in the material is shortened.
(2) Because few layers of vanadium carbide exist in the vanadium tetrasulfide/vanadium carbide composite material, the vanadium tetrasulfide provides nucleation sites during growth so that the vanadium tetrasulfide grows on the surface of the vanadium carbide; meanwhile, the existence of few layers of vanadium carbide improves the conductivity of vanadium tetrasulfide, so that the composite material has excellent rate performance.
Drawings
Fig. 1 shows an SEM image of example 1 of the present invention.
Figure 2 shows the XRD pattern of example 1 of the present invention.
FIG. 3 shows that the current density of application example 1 of the present invention is 1A g-1Cyclic stability curve of time.
Fig. 4 shows the rate performance curves for different current densities for application example 1 of the present invention.
FIG. 5 shows that the current density of application example 2 of the present invention is 1A g-1Cyclic stability curve of time.
FIG. 6 shows that the current density of application example 3 of the present invention is 1A g-1Cyclic stability curve of time.
Detailed Description
Hereinafter, a vanadium tetrasulfide/vanadium carbide composite material of the present invention, a method for preparing the same, and applications thereof will be described in detail with reference to the accompanying drawings and exemplary embodiments.
Because of VS4Have lower conductivity and greater volume expansion during electrochemical processes, resulting in poor cycling and rate performance. In order to solve the above problems, the current common using method is: (1) construction of micron-sized VS4The volume expansion can be suppressed by increasing the specific surface area. (2) The introduction of carbon materials (such as graphene, carbon nanotubes and the like) to construct the composite material can improve the conductivity of the materialMeanwhile, the electron transmission efficiency in the electrochemical process is improved. In addition, VS can be effectively inhibited by introducing the carbon material matrix4The stack grows in the growth process, thereby improving the reaction power of sodium ions.
First exemplary embodiment
In a first exemplary embodiment of the present invention, a method of preparing a vanadium tetrasulfide/vanadium carbide composite material includes the steps of:
s1, mixing vanadium and aluminum carbide (V)2AlC) etching, intercalation, freeze drying to obtain few-layer V2CTxAnd (3) powder.
Specifically, in a polytetrafluoroethylene reaction kettle, vanadium aluminum carbide is etched by hydrofluoric acid (HF), and is centrifugally washed to obtain a multilayer V2CTx. Wherein, the rotating speed of the centrifugal equipment can be 3000-4000 rpm/min, and the washing can be carried out to be neutral by adopting deionized water. The concentration of the hydrofluoric acid can be 35-45%, the etching temperature (water bath temperature for short) can be 30-40 ℃, and the etching time (water bath time for short) can be 20-26 h. For example, the centrifuge device speed may be 3500, 3600, 3800 rpm/min; the concentration of hydrofluoric acid can be 38, 40 and 42%; the etching temperature can be 33, 35 and 38 ℃; the etching time can be 22 and 24 hours.
Wherein a temperature higher than 40 ℃ causes the prepared few layers of vanadium carbide to be oxidized. When the etching time is less than 20 hours, the vanadium aluminum carbide is not successfully etched, and enough vanadium carbide cannot be obtained; too long an etching time of more than 26 hours can result in oxidation of the vanadium carbide.
Subsequently, to the multilayer V2CTxAdding tetrabutylammonium hydroxide into the mixture, and subjecting the multilayer V to inert atmosphere2CTxIntercalation is carried out, and suspension is obtained by centrifugal washing. The inert atmosphere includes, but is not limited to, argon, nitrogen, and mixtures thereof. The concentration of tetrabutylammonium hydroxide can be 2-7%, the intercalation time can be 20-26 h, and the tetrabutylammonium hydroxide is centrifugally washed to be neutral to obtain a suspension. For example, tetrabutylammonium hydroxide concentration may be 3, 5% and intercalation time may be 22, 24 h.
Wherein, the concentration of tetrabutylammonium hydroxide is lower than 2 percent, so that the multilayer vanadium carbide can not be intercalated, thereby leading toSo that the subsequent ultrasonic stripping can not strip a few layers of vanadium carbide. An intercalation time of less than 20h can result in the failure of subsequent ultrasonic exfoliation to successfully exfoliate few layers of vanadium carbide. Then, V after intercalation2CTxAnd centrifuging and washing the mixture to be neutral through 3000-5000 rpm/min.
Then, the suspension is ultrasonically stripped and centrifuged, and the upper suspension is taken out to obtain a few-layer V2CTxAnd (3) dispersing the mixture. Wherein the centrifugal speed can be 4500-5500 rpm/min. For example, the rotational speed of the apparatus during centrifugation may be 4600, 4800, 5000, 5200, 5400 rpm/min. In addition, the ultrasonic stripping time can be 60-120 min, and the ultrasonic stripping is carried out in a nitrogen or argon atmosphere.
Finally, few layers V are formed2CTxFreeze drying the dispersion to obtain V2CTxAnd (3) powder. Wherein, few layers V2CTxThe freeze-drying temperature of the dispersion liquid can be between-55 and-65 ℃, and the time can be between 20 and 26 hours. For example, the freeze-drying temperature can be-58, -60, -63 ℃; the time can be 22 and 24 hours.
Wherein, a plurality of layers V2CTxThe number of layers (V) can be 20-50, and less layers2CTxThe number of powder layers may be 1 to 10.
Here, the mixing ratio of vanadium aluminum carbide, hydrofluoric acid, tetrabutylammonium hydroxide may be 1 g: 20-40 mL: 10-30 mL.
Here, V2CTxT in the powder represents V2C surface attached functional group, x represents a number. For example, the functional group can be-F, -OH, -O.
S2, mixing a vanadium source and an organic solvent to obtain a precursor solution, and adding a few layers of V into the precursor solution2CTxAnd (5) performing low-temperature ultrasonic treatment on the powder to obtain a first suspension.
Here, the vanadium source includes ammonium metavanadate (NH)4VO3) And/or vanadyl acetylacetonate (VO (acac)2) The organic solvent includes Ethylene Glycol (EG), N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), and methanol (CH)3OH) is used.
Here, a vanadium source, a sulfur source, and a few layers of V are used2CTxMixing a vanadium source and an organic solvent as a template, and stirring at 55-65 ℃ for 25-35 min to obtain a precursor solution. For example, the mixing temperature of the vanadium source and the organic solvent can be 58, 60, 62 ℃; the stirring time can be 28, 30 and 33 min.
Here, when the heating temperature is less than 55 ℃, the vanadium source is caused to be hardly soluble or insoluble in the organic solvent; when the heating temperature is higher than 65 ℃, the vanadium source may be decomposed.
Subsequently, a few layers V are added to the precursor solution2CTxAnd (5) performing low-temperature ultrasonic treatment on the powder to obtain a black suspension. Wherein, the low temperature includes but is not limited to ice bath, the temperature can be 3-10 ℃, and the time can be 1.5-2.5 h.
Wherein, few layers V2CTxCompared with multilayer V2CTxHas larger specific surface area, can be in V2CTxGrowing more VS on the surface4。
Wherein, the vanadium source: the molar ratio of the sulfur source can be 1: 4-6; a vanadium source: the mixing ratio of the organic solvent may be 1 mmol: 15-35 mL; a vanadium source: few layers V2CTxThe mixing ratio of the powders may be 1 mmol: 30-160 mg. For example, ammonium metavanadate: the mol ratio of thioacetamide can be 1: 4-6; ammonium metavanadate: the mixing ratio of ethylene glycol may be 1 mol: 13-16 mL; ammonium metavanadate: few layers V2CTxThe mixing ratio of the powders may be 1 mmol: 30-160 mg.
And S3, adding a sulfur source into the first suspension, and stirring to obtain a second suspension.
Here, the sulfur source includes thioacetamide (CH)3CSNH2) L-cysteine (C)3H7NO2S), thiourea (CH)4N2S).
Here, the stirring time may be 20 to 40min, and the stirring temperature may be 40 to 60 ℃.
And S4, carrying out solvothermal reaction on the second suspension, washing, and freeze-drying to obtain the vanadium tetrasulfide/vanadium carbide composite material.
Theoretically, vanadium tetrasulfide and V2CTxThe mass ratio of the powders may be 1: 0.168 to 0.64. And performing solvothermal reaction on the second suspension for 8-36 hours at 160-200 ℃ in a polytetrafluoroethylene stainless steel autoclave to obtain a reaction product, washing the reaction product, and freeze-drying to obtain the vanadium tetrasulfide/vanadium carbide composite material. Wherein, the washing can be carried out by ethanol and water for more than three times, and the freeze drying is carried out under the vacuum condition. For example, the temperature may be 170, 180, 190 ℃ and the time may be 10, 15, 20, 25, 30, 35 hours. In addition, the freeze drying temperature of the second suspension can be-55 to-65 ℃ and the time can be 20 to 26 hours. For example, the freeze-drying temperature can be-58, -60, -63 ℃; the time can be 22 and 24 hours.
Second exemplary embodiment
In a second exemplary embodiment of the present invention, there is provided a vanadium tetrasulfide/vanadium carbide composite material prepared by the above-mentioned method, the vanadium tetrasulfide/vanadium carbide composite material having the structure: vanadium tetrasulfide nano sheets are uniformly distributed on the surface of vanadium carbide, wherein the vanadium carbide is of an amorphous structure, and the specific surface area of the vanadium tetrasulfide/vanadium carbide composite material is 30-50 m2 g-1。
The vanadium tetrasulfide/vanadium carbide composite material has a structure that micron-sized flaky vanadium tetrasulfide nano sheets are evenly anchored on the surface of vanadium carbide.
Third exemplary embodiment
In a third exemplary embodiment of the present invention, there is provided a use of a vanadium tetrasulfide/vanadium carbide composite material, the use comprising applying the vanadium tetrasulfide/vanadium carbide composite material described above to a battery anode material.
In this embodiment, the application may include: mixing the vanadium tetrasulfide/vanadium carbide composite material, a conductive agent and a binder according to the mass ratio of 5-8: 1-2: 0.5-1, coating the mixture on a copper foil, and drying the copper foil to be used as a working electrode.
In the embodiment, after the working electrode is charged and discharged for 50-100 times in a circulating manner, the capacity retention rate can be 42-52% of the first time, and the rate performance is stable. For example, the capacity retention rate may be first 42.3%, 45.4%, 51%.
In order to better understand the above exemplary embodiments of the present invention, the preparation and application of a vanadium tetrasulfide/vanadium carbide composite material are described below in connection with specific examples.
Example 1
The preparation method of the vanadium tetrasulfide/vanadium carbide composite material comprises the following steps:
(1) 2g of vanadium aluminum carbide (V)2AlC) is added into a polytetrafluoroethylene reaction kettle, 40mL of hydrofluoric acid (HF) with the concentration of 40% is added into the reaction kettle, and the reaction is carried out for 24 hours in a water bath at 35 ℃. After the reaction, the mixture is centrifuged at 3500rpm/min, washed to be neutral by deionized water, transferred to a gas washing bottle, added with 20mL of 5% tetrabutylammonium hydroxide, and intercalated for 24 hours by introducing gas in an argon or nitrogen atmosphere. The V after intercalation2CTxWashed again to neutrality by centrifugation at 3500 rpm/min. Introducing argon or nitrogen again into the washed product, ultrasonically stripping for 1h, centrifuging at high speed of 5000rpm/min to separate supernatant, and freeze-drying at-60 deg.C for 24h to obtain few-layer V2CTxAnd (3) powder.
(2) 2mmol of ammonium metavanadate (NH) was taken4VO3) 30mL of Ethylene Glycol (EG) was added thereto, and stirred at 60 ℃ for half an hour to obtain a yellow solution, and 40mg of a small layer V was added thereto2CTxPowder, ice-bath ultrasonic for 2 h.
(3) 10mmol of thioacetamide (CH) was further added thereto3CSNH2) And transferring the solution to a 80mL polytetrafluoroethylene stainless steel high-pressure reaction kettle, carrying out solvothermal reaction at 160 ℃, preserving heat for 24 hours, and cooling to room temperature after the solvothermal reaction is finished. The product was washed several times with deionized water and ethanol, respectively. And freeze-drying the mixture for 24 hours at the temperature of minus 60 ℃ to obtain the vanadium tetrasulfide/vanadium carbide composite material.
Fig. 1 shows an SEM image of example 1 of the present invention. Figure 2 shows the XRD pattern of example 1 of the present invention. As shown in fig. 1, the composite material is formed by uniformly distributing vanadium tetrasulfide nano sheets on the surface of vanadium carbide, which indicates that the vanadium tetrasulfide is anchored on the surface of the vanadium carbide. As shown in FIG. 2, the XRD patterns of the vanadium tetrasulfide/vanadium carbide composite material respectively show characteristic peaks, wherein 9.2 degrees corresponds to the (002) crystal face of the vanadium carbide. Wherein the peak of 15.8 degrees and 17.0 degrees corresponds to the (110) (020) crystal face of the vanadium tetrasulfide, and is consistent with the standard card (JCPDF Cards 87-0603). The XRD chart illustrates the successful synthesis of vanadium tetrasulfide/vanadium carbide composites.
Example 2
The preparation method of the vanadium tetrasulfide/vanadium carbide composite material comprises the following steps:
(1) 2g of vanadium aluminum carbide (V)2AlC) is added into a polytetrafluoroethylene reaction kettle, 80mL of hydrofluoric acid (HF) with the concentration of 40 percent is added into the polytetrafluoroethylene reaction kettle, water bath is carried out at 40 ℃, and the reaction is carried out for 24 hours. After the reaction, the mixture is centrifuged at 3500rpm/min, washed to be neutral by deionized water, transferred to a gas washing bottle, added with 20mL of 5% tetrabutylammonium hydroxide, and intercalated for 24 hours by introducing gas in an argon or nitrogen atmosphere. The V after intercalation2CTxWashed again to neutrality by centrifugation at 5000 rpm/min. Introducing argon or nitrogen again into the washed product, ultrasonically stripping for 2h, centrifuging at high speed of 5000rpm/min to separate supernatant, and freeze drying at-60 deg.C for 24h to obtain few-layer V2CTxAnd (3) powder.
(2) 2mmol of ammonium metavanadate (NH) was taken4VO3) 30mL of Ethylene Glycol (EG) was added thereto, and stirred at 55 ℃ for half an hour to obtain a yellow solution, to which 90mg of a small layer V was added2CTxPowder, ice-bath ultrasonic for 2 h.
(3) 10mmol of L-cysteine (C) was added thereto3H7NO2S), transferring the solution to a 100mL polytetrafluoroethylene stainless steel high-pressure reaction kettle, carrying out solvothermal reaction at 180 ℃, preserving heat for 20h, and cooling to room temperature after completion. The product was washed several times with deionized water and ethanol, respectively. And freeze-drying the mixture for 24 hours at the temperature of minus 60 ℃ to obtain the vanadium tetrasulfide/vanadium carbide composite material.
Example 3
The preparation method of the vanadium tetrasulfide/vanadium carbide composite material comprises the following steps:
(1) 2g of vanadium aluminum carbide (V)2AlC) is added into a polytetrafluoroethylene reaction kettle, 40mL of hydrofluoric acid (HF) with the concentration of 40 percent is added into the polytetrafluoroethylene reaction kettle, and the mixture is reacted for 24 hours in a water bath at 40 ℃. After the reaction, the mixture is centrifuged at 3500rpm/min, washed to be neutral by deionized water, transferred to a gas washing bottle, added with 20mL of tetrabutylammonium hydroxide with the concentration of 7 percent, and intercalated for 24 hours by introducing gas in the atmosphere of argon or nitrogen. The V after intercalation2CTxWashed again to neutrality by centrifugation at 5000 rpm/min. Introducing argon or nitrogen into the washed product again for ultrasonic stripping for 2h, centrifuging at a high speed of 5000rpm/min to separate supernatant, and freeze-drying at-60 deg.C for 24h to obtain few-layer V2CTxAnd (3) powder.
(2) Taking 2mmol of vanadyl acetylacetonate (VO (acac)2) 40mL of N, N-Dimethylformamide (DMF) was added thereto, and the mixture was stirred at 25 ℃ for half an hour to obtain a blue-green solution, and 150mg of sublayer V was further added thereto2CTxPowder, ice-bath ultrasonic for 2 h.
(3) 10mmol of thioacetamide (CH) was further added thereto3CSNH2) And transferring the solution to a 100mL polytetrafluoroethylene stainless steel high-pressure reaction kettle, carrying out solvothermal reaction at 160 ℃, preserving heat for 24 hours, and cooling to room temperature after the solvothermal reaction is finished. The product was washed several times with deionized water and ethanol, respectively. And freeze-drying the mixture for 24 hours at the temperature of minus 60 ℃ to obtain the vanadium tetrasulfide/vanadium carbide composite material.
Example 4
(1) 2g of vanadium aluminum carbide (V)2AlC) is added into a polytetrafluoroethylene reaction kettle, 40mL of hydrofluoric acid (HF) with the concentration of 40% is added into the reaction kettle, and the reaction is carried out for 24 hours in a water bath at 35 ℃. After the reaction, 3500rpm/min is centrifuged, deionized water is used for washing the reaction product until the reaction product is neutral, the reaction product is transferred to a gas washing bottle, 20mL of 5% tetrabutylammonium hydroxide is added into the gas washing bottle, and the reaction product is subjected to intercalation for 24 hours under the atmosphere of argon or nitrogen. The V after intercalation2CTxWashed again to neutrality by centrifugation at 3500 rpm/min. Introducing argon or nitrogen again into the washed product, ultrasonically stripping for 1h, centrifuging at high speed of 5000rpm/min to separate supernatant, and freeze-drying at-60 deg.C for 24h to obtain few-layer V2CTxAnd (3) powder.
(2) 2mmol of ammonium metavanadate (NH) was taken4VO3) To this was added 50mL of methanol (CH)3OH) was stirred at 60 ℃ for half an hour to give a yellow solution, to which 40mg of sublayer V was added2CTxPowder, ice-bath ultrasonic for 2 h.
(3) 10mmol of thioacetamide (CH) was further added thereto3CSNH2) And transferring the solution to a 100mL polytetrafluoroethylene stainless steel high-pressure reaction kettle, carrying out solvothermal reaction at 180 ℃, preserving heat for 24h, and cooling to room temperature after the solvothermal reaction is finished. The product was washed several times with deionized water and ethanol, respectively. And freeze-drying the mixture for 24 hours at the temperature of minus 60 ℃ to obtain the vanadium tetrasulfide/vanadium carbide composite material.
Example 5
(1) 2g of vanadium aluminum carbide (V)2AlC) is added into a polytetrafluoroethylene reaction kettle, 40mL of hydrofluoric acid (HF) with the concentration of 40 percent is added into the reaction kettle, the mixture is subjected to 35 ℃ water bath, and the reaction is carried out for 24 hours. After the reaction, the mixture is centrifuged at 3500rpm/min, washed to be neutral by deionized water, transferred to a gas washing bottle, added with 20mL of 5% tetrabutylammonium hydroxide, and intercalated for 24 hours by introducing gas in an argon or nitrogen atmosphere. The V after intercalation2CTxWashed again to neutrality by centrifugation at 3500 rpm/min. Introducing argon or nitrogen again into the washed product, ultrasonically stripping for 1h, centrifuging at 5000rpm/min to separate supernatant, and freeze-drying at-60 deg.C for 24h to obtain small layer V2CTxAnd (3) powder.
(2) Taking 2mmol of vanadyl acetylacetonate (VO (acac)2) 40mL of N-methylpyrrolidone (NMP) was added thereto, and stirred at 25 ℃ for half an hour to obtain a blue-green solution, and 40mg of a small layer V was added thereto2CTxPowder, ice-bath ultrasonic for 2 h.
(3) 10mmol of L-cysteine (C) was added thereto3H7NO2S), transferring the solution to a 100mL polytetrafluoroethylene stainless steel high-pressure reaction kettle, carrying out solvothermal reaction at 180 ℃, preserving heat for 24h, and cooling to room temperature after completion. VS with smaller size can be obtained by replacing the vanadium source sulfur source and the reaction solvent4Nanoplatelet productWashing with deionized water and ethanol several times. And freeze-drying the mixture for 24 hours at the temperature of minus 60 ℃ to obtain the vanadium tetrasulfide/vanadium carbide composite material.
Application example 1
The application of the vanadium tetrasulfide/vanadium carbide composite material is applied to a battery negative electrode material, and comprises the following steps:
the vanadium tetrasulfide/vanadium carbide composite material prepared in example 1, a conductive agent (carbon black) and a binder (PVDF) are fully ground in a mortar according to the mass ratio of 7: 2: 1, coated on a copper foil, and dried in an oven at 60 ℃ for 12 hours to serve as a working electrode after being coated.
Subsequently, 1M NaPF was applied to the sodium metal as counter electrode and glass fiber (Whatman, GF/D) as membrane6And dissolving DME as an electrolyte to assemble the CR2032 button cell.
And (3) carrying out constant-current charge and discharge tests at room temperature, wherein the voltage range is 0.01-2.50V, and two circulation and multiplying power modes are adopted. The circulation is 50 times at 1A/g current; the multiplying power is respectively tested by 100mA/g, 200mA/g, 500mA/g, 1000mA/g, 2000mA/g, 5000mA/g, 10000mA/g and 100mA/g current in sequence, and each current density is tested for 10 times. FIG. 3 shows that the current density of application example 1 of the present invention is 1Ag-1Cyclic stability curve of time. Fig. 4 shows the rate performance curves for different current densities for application example 1 of the present invention. As shown in FIG. 3, the first discharge specific capacity of the working electrode was 800mAhg-1The first charging specific capacity is 624mAhg-1The first coulombic efficiency was 78.1%. After 50 times of circulation, the discharge specific capacity of the material is 388mAhg-1The capacity retention was 48.5% of the first time. As shown in FIG. 4, when the current density is 5Ag-1And 10Ag-1Still has 319mAhg-1And 284mAhg-1The specific capacity and the rate capability are stable.
Application example 2
The application of the vanadium tetrasulfide/vanadium carbide composite material is applied to a battery negative electrode material, and comprises the following steps:
the vanadium tetrasulfide/vanadium carbide composite material prepared in example 2, a conductive agent (carbon black) and a binder (PVDF) are fully ground in a mortar according to the mass ratio of 7: 2: 1, coated on a copper foil, and dried in an oven at 60 ℃ for 12 hours to serve as a working electrode after being coated.
Subsequently, 1M NaPF was applied to the sodium metal as counter electrode and glass fiber (Whatman, GF/D) as membrane6And dissolving DME as an electrolyte to assemble the CR2032 button cell.
And carrying out constant current charge and discharge test at room temperature, wherein the voltage range is 0.01-2.50V, and constant current charge and discharge circulation is adopted. The circulation is 50 times at 1A/g current; FIG. 5 shows that the current density of application example 2 of the present invention is 1Ag-1Cyclic stability curve of time. As shown in FIG. 5, the specific first discharge capacity of the working electrode was 768mAhg-1The first charging specific capacity is 591mAhg-1The first coulombic efficiency was 77%. After 50 times of circulation, the discharge specific capacity of the material is 349mAhg-1The capacity retention was 45.4% of the first time.
Application example 3
The application of the vanadium tetrasulfide/vanadium carbide composite material is applied to a battery negative electrode material, and comprises the following steps:
the vanadium tetrasulfide/vanadium carbide composite material prepared in example 3, a conductive agent (carbon black) and a binder (PVDF) are fully ground in a mortar according to the mass ratio of 7: 2: 1, coated on a copper foil, and dried in an oven at 60 ℃ for 12 hours to serve as a working electrode after being coated.
Subsequently, 1M NaPF was applied to the sodium metal as counter electrode and glass fiber (Whatman, GF/D) as membrane6And dissolving DME as an electrolyte to assemble the CR2032 button cell.
And carrying out constant current charge and discharge test at room temperature, wherein the voltage range is 0.01-2.50V, and constant current charge and discharge circulation is adopted. The circulation is 50 times at 1A/g current; FIG. 6 shows that the current density of application example 3 of the present invention is 1Ag-1Cyclic stability curve of time. As shown in FIG. 6, the specific first discharge capacity of the working electrode was 674mAhg-1The first charging specific capacity is 502mAhg-1The first coulombic efficiency was 74.5%. After circulating for 50 times, the discharge specific capacity of the material is 285mAhg-1Capacity retention ratio of42.3% of.
Although the present invention has been described above in connection with exemplary embodiments, it will be apparent to those skilled in the art that various modifications and changes may be made to the exemplary embodiments of the present invention without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of vanadium tetrasulfide/vanadium carbide composite material is characterized by comprising the following steps:
etching, intercalating and freeze-drying vanadium aluminum carbide to obtain few-layer V2CTxPowder;
mixing a vanadium source and an organic solvent to obtain a precursor solution, and adding a few layers of V into the precursor solution2CTxPerforming low-temperature ultrasonic treatment on the powder to obtain a first suspension;
adding a sulfur source into the first suspension, and stirring to obtain a second suspension;
carrying out solvothermal reaction on the second suspension, washing, and freeze-drying to obtain a vanadium tetrasulfide/vanadium carbide composite material;
wherein the vanadium source comprises ammonium metavanadate and/or vanadyl acetylacetonate, the organic solvent comprises one or more of ethylene glycol, N-methylpyrrolidone, N-dimethylformamide and methanol, and the sulfur source comprises one of thioacetamide, L-cysteine and thiourea.
2. The method for preparing vanadium tetrasulfide/vanadium carbide composite material according to claim 1, characterized in that the vanadium aluminum carbide is etched, intercalated, freeze-dried to obtain few layers of V2CTxThe powder comprises:
adopting hydrofluoric acid to etch vanadium aluminum carbide, and centrifugally washing to obtain multilayer V2CTx；
To multiple layers V2CTxAdding tetrabutylammonium hydroxide into the mixture, and subjecting the multilayer V to inert atmosphere2CTxIntercalation, centrifugal washing to obtain suspension;
will be described inTaking supernatant after ultrasonic stripping and centrifugation of turbid liquid to obtain few-layer V2CTxA dispersion liquid;
the few layers V2CTxFreeze drying the dispersion to obtain V2CTxAnd (3) powder.
3. The method for preparing the vanadium tetrasulfide/vanadium carbide composite material as claimed in claim 1, wherein the step of subjecting the second suspension to solvothermal reaction, washing and freeze-drying to obtain the vanadium tetrasulfide/vanadium carbide composite material comprises:
and reacting the second suspension at 160-200 ℃ for 8-36 hours to obtain a reaction product, washing the reaction product, and freeze-drying under a vacuum condition to obtain the vanadium tetrasulfide/vanadium carbide composite material.
4. The method for preparing the vanadium tetrasulfide/vanadium carbide composite material according to claim 1, wherein the molar ratio of the vanadium source to the sulfur source is 1: 4-6;
the mixing ratio of the vanadium source to the organic solvent is 1 mmol: 15-35 mL;
the vanadium source and the few layers V2CTxThe mixing ratio of the powders was 1 mmol: 30-160 mg.
5. The method of preparing a vanadium tetrasulfide/vanadium carbide composite material according to claim 2, characterized in that said multilayer V is2CTxThe number of layers of (A) is 20-50, and the number of layers of (B) is less than V2CTxThe number of powder layers is 1-10.
6. The preparation method of the vanadium tetrasulfide/vanadium carbide composite material according to claim 2, wherein the concentration of the hydrofluoric acid is 35-45%, the etching temperature is 30-40 ℃, and the etching time is 20-26 h;
the concentration of the tetrabutyl ammonium hydroxide is 2-7%, and the intercalation time is 20-26 h;
the few layers V2CTxThe freeze-drying temperature of the dispersion liquid is-55 to-65 ℃, and the time isIs 20-26 h;
the freeze drying temperature of the second suspension is-55 to-65 ℃, and the time is 20 to 26 hours.
7. A vanadium tetrasulfide/vanadium carbide composite material, characterized in that it is prepared by the method for preparing a vanadium tetrasulfide/vanadium carbide composite material according to any one of claims 1 to 6, and the structure of said vanadium tetrasulfide/vanadium carbide composite material is:
vanadium tetrasulfide nano sheets are uniformly distributed on the surface of vanadium carbide, wherein the vanadium carbide is of an amorphous structure, and the specific surface area of the vanadium tetrasulfide/vanadium carbide composite material is 30-50 m2 g-1。
8. Use of a vanadium tetrasulfide/vanadium carbide composite material, characterized in that it comprises the application of a vanadium tetrasulfide/vanadium carbide composite material according to claim 7 to a battery negative electrode material.
9. Use of vanadium tetrasulfide/carbide composite material according to claim 8, characterized in that it comprises:
mixing the vanadium tetrasulfide/vanadium carbide composite material, a conductive agent and a binder according to the mass ratio of 5-8: 1-2: 0.5-1, coating the mixture on a copper foil, and drying the copper foil to be used as a working electrode.
10. Use of a vanadium tetrasulfide/vanadium carbide composite material according to claim 9, characterized in that said working electrode is comprised between 0.1A and 10A g-1After 50-100 times of cyclic charge and discharge under current density, the capacity retention rate is 42-52% of the first time, and the cyclic performance is stable.
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| CN115440961A (en) * | 2022-09-30 | 2022-12-06 | 济南大学 | Two-dimensional layered vanadium carbide and vanadium sulfide composite electrode material and preparation method thereof |
| CN117153578A (en) * | 2023-09-11 | 2023-12-01 | 哈尔滨师范大学 | Cobalt ion intercalated vanadium carbide nano-sheet and preparation method and application thereof |
| CN117153578B (en) * | 2023-09-11 | 2024-03-12 | 哈尔滨师范大学 | Cobalt ion intercalated vanadium carbide nano-sheet and preparation method and application thereof |
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