CN115092960A - Defect-rich vanadium disulfide, preparation method thereof and application of defect-rich vanadium disulfide as anode material in water-based zinc ion battery - Google Patents
Defect-rich vanadium disulfide, preparation method thereof and application of defect-rich vanadium disulfide as anode material in water-based zinc ion battery Download PDFInfo
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- NGTSQWJVGHUNSS-UHFFFAOYSA-N bis(sulfanylidene)vanadium Chemical compound S=[V]=S NGTSQWJVGHUNSS-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 230000007547 defect Effects 0.000 title claims abstract description 44
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000010405 anode material Substances 0.000 title 1
- 239000011701 zinc Substances 0.000 claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- 239000007774 positive electrode material Substances 0.000 claims abstract description 17
- 230000004913 activation Effects 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 14
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 14
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 14
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 11
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 5
- FHANEPRSLAMSJU-UHFFFAOYSA-N vanadium(4+);disulfide Chemical compound [S-2].[S-2].[V+4] FHANEPRSLAMSJU-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000001291 vacuum drying Methods 0.000 claims 2
- 210000001787 dendrite Anatomy 0.000 abstract description 7
- 239000000843 powder Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 239000010406 cathode material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 210000004027 cell Anatomy 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
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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
- H01M4/58—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
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- C01—INORGANIC CHEMISTRY
- 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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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention belongs to the technical field of water-system zinc ion batteries, and discloses defect-rich vanadium disulfide, a preparation method thereof and application thereof as a positive electrode material in a water-system zinc ion battery 2 The main preparation process of the powder material comprises a simple one-step hydrothermal method and subsequent in-situ electrochemical activation under high pressure to obtain VS 2 The material has a unique structure, and shows extremely high specific capacity and excellent rate capability when being used as a cathode material of a water system zinc ion battery; then the generation of zinc dendrite is inhibited by a simple and convenient method of applying a weak magnetic fieldLong, greatly improve VS 2 The cycle life of the/Zn battery has wide application prospect in the field of water-system zinc ion batteries.
Description
Technical Field
The invention belongs to the technical field of water-system zinc ion batteries, and particularly relates to defect-rich vanadium disulfide, a preparation method thereof and application of the defect-rich vanadium disulfide as a positive electrode material in a water-system zinc ion battery.
Background
It is well known that energy and environment are the focus of sustainable development of human society. The environmental problems caused by the use of fossil energy are increasingly prominent, and the development of large-scale energy storage technology for efficiently using renewable energy is urgently needed. Among them, the demand for electrochemical energy storage technology, especially for high-performance electrochemical energy storage devices with large capacity, fast charge, and the like, is continuously increasing. In the past decades, lithium ion batteries have been increasingly used in various fields of human life, such as 3C electronics, electric vehicles, etc., due to their high energy density. However, many key factors restrict its large-scale application, such as the use of toxic organic electrolytes, serious safety issues, and limited lithium resources, among others. In contrast, aqueous batteries are receiving increasing attention due to their low cost, high safety, and excellent ion conductivity. Wherein, the theoretical capacity of the water system zinc ion battery reaches up to 825mAh g due to the metal zinc -1 And became a hot spot of research. Unfortunately, the energy density and the cycling stability of the aqueous zinc ion battery are low due to poor conductivity of the cathode material of the aqueous zinc ion battery, large volume change during charge and discharge, corrosion of zinc metal of the cathode and growth of zinc dendrites. Therefore, the preparation of high electrochemical performance cathode materials and the inhibition of zinc dendrites are key factors in the development of aqueous zinc ion batteries.
Disclosure of Invention
In view of the deficiencies of the prior art, it is a first object of the present invention to provide defect-rich vanadium disulfide and a method for preparing the same by reacting vanadium disulfide (VS) 2 ) Introducing defects into the structure to increase VS 2 The specific capacity of (A). The preparation method is simple and has low cost。
A preparation method of defect-rich vanadium disulfide comprises the following steps:
1) dissolving ammonium metavanadate in water, adding ammonia water, stirring, adding thioacetamide after dissolving, and continuously stirring to obtain a precursor solution; preferably, the volume ratio of water to ammonia water is (10-30): 1; the mass ratio of ammonium metavanadate to thioacetamide is (1-2): (10-15). Preferably, the volume ratio of water to ammonia water may be 10: 1. 15:1, 20:1 or 30: 1; the mass ratio of ammonium metavanadate to thioacetamide can be 2:15 or 1: 10.
2) Transferring the precursor solution to a high-pressure reaction kettle with a polytetrafluoroethylene inner container for hydrothermal reaction; the temperature of the hydrothermal reaction is 180-200 ℃, and the reaction time is 8-12 h. Preferably, the temperature of the hydrothermal reaction is 180 ℃, 190 ℃ or 200 ℃, and the reaction time is 8h, 10h or 12 h.
3) After the reaction is finished and the temperature is cooled to room temperature, washing the obtained product with deionized water and absolute ethyl alcohol for 2-5 times respectively, and then carrying out centrifugal separation; preferably, the centrifugal rotating speed is 5000-10000 r/min;
4) placing the product obtained by centrifuging in a vacuum oven, and drying at 50-70 ℃ for 12-24 h to obtain vanadium disulfide;
5) preparing a positive electrode by taking vanadium disulfide as a positive electrode active material, assembling a button zinc ion battery by taking zinc trifluoromethanesulfonate with the concentration of 3-4M as an electrolyte and taking metal zinc as a negative electrode; wherein: the zinc trifluoromethanesulfonate is electrolyte with a large anion structure, has good zinc ion deposition and precipitation dynamics, and has a concentration range of 3-4M, so that the electrolyte state reaches water-in-salt, and the electrolyte in the water-in-salt can bear a high voltage window to avoid water decomposition and excessive side reactions.
6) Performing in-situ electrochemical activation on the button zinc ion battery under a voltage window to obtain VS rich in defects 2 . Preferably, the voltage window is 0.2-1.5V, 0.2-1.7V, 0.2-1.9V, 0.2-2.1V or 0.2-2.3V.
Another object of the present invention is to provide the use of the defect-rich vanadium disulfide as a positive electrode material in aqueous zinc ion batteries. Furthermore, the battery introduces a proper induction field, such as a magnetic field, in the electrochemical cycle process to inhibit the growth of zinc dendrites, and can obviously enhance the cycle stability of the zinc dendrites, so that the aqueous zinc ion battery with a wide voltage window and a long cycle life is obtained. The magnetic field is 500-5000 Gs, such as 500Gs, 1000Gs, 3000G or 5000 Gs.
The beneficial effects of the invention are as follows:
the invention adopts a one-step hydrothermal method to prepare VS 2 Followed by in situ electrochemical activation under a wide voltage window to form defects in an atomic layer of the material to obtain a defect-rich VS 2 Material of the defect-rich VS 2 More zinc storage sites and larger specific surface area are provided, so that higher capacity and excellent rate capability can be obtained. The mechanism for obtaining defects through in-situ electrochemical activation in the invention is as follows: in the charging process, when zinc ions are completely removed, charging is still continued, and the subsequent high-voltage charging process can cause escape of partial atoms, so that defects are formed in the atomic layer. According to the invention, the working voltage window of the battery is widened by improving the concentration of the electrolyte, and the growth of zinc dendrite is inhibited by a weak magnetic field provided by the permanent magnet when the water-based zinc ion battery works, so that the water-based zinc ion battery with excellent electrochemical performance is obtained.
Drawings
FIG. 1 is a scanning electron microscope photograph of vanadium disulfide prepared in step 4) of example 6;
fig. 2 is a rate performance diagram of the battery 2;
fig. 3 is a graph of the cycle performance of the battery 3;
FIG. 4 is a graph of the ultra-long cycle performance of battery 6;
fig. 5 is a cycle performance diagram of the battery 7.
Detailed Description
The invention is further described with reference to the following figures and examples.
A preparation method of defect-rich vanadium disulfide comprises the following steps:
1) dissolving ammonium metavanadate in water, then adding ammonia water, stirring, adding thioacetamide after dissolving, and continuously stirring to obtain a precursor solution; preferably, the volume ratio of water to ammonia water is (10-30): 1; the mass ratio of ammonium metavanadate to thioacetamide is (1-2): (10-15). Preferably, the volume ratio of water to ammonia water may be 10: 1. 15:1, 20:1 or 30: 1; the mass ratio of ammonium metavanadate to thioacetamide can be 2:15 or 1: 10.
2) Transferring the precursor solution to a high-pressure reaction kettle with a polytetrafluoroethylene inner container for hydrothermal reaction; the temperature of the hydrothermal reaction is 180-200 ℃, and the reaction time is 8-12 h. Preferably, the temperature of the hydrothermal reaction is 180 ℃, 190 ℃ or 200 ℃, and the reaction time is 8h, 10h or 12 h.
3) After the reaction is finished and the temperature is cooled to room temperature, washing the obtained product with deionized water and absolute ethyl alcohol for 2-5 times respectively, and then carrying out centrifugal separation; preferably, the centrifugal rotating speed is 5000-10000 r/min;
4) placing the product obtained by centrifugation in a vacuum oven, and drying at the temperature of 50-70 ℃ for 12-24 h to obtain vanadium disulfide;
5) preparing a positive electrode by taking vanadium disulfide as a positive electrode active material, assembling a button zinc ion battery by taking zinc trifluoromethanesulfonate with the concentration of 3-4M as an electrolyte and taking metal zinc as a negative electrode;
6) performing in-situ electrochemical activation on the button zinc ion battery under a voltage window to obtain VS rich in defects 2 . Preferably, the voltage window is 0.2-1.5V, 0.2-1.7V, 0.2-1.9V, 0.2-2.1V or 0.2-2.3V.
Example 1
VS rich in defects 2 The preparation method comprises the following steps:
1) dissolving 2mmol of ammonium metavanadate in 30ml of deionized water, adding 2ml of ammonia water, stirring, adding 15mmol of thioacetamide after dissolution, and continuously stirring to obtain a precursor solution;
2) transferring the precursor solution into a high-pressure reaction kettle with a 50ml polytetrafluoroethylene inner container, and reacting for 10 hours at 180 ℃;
3) after the reaction is finished and the temperature is cooled to room temperature, washing the reaction product by using deionized water and absolute ethyl alcohol for three times respectively, and centrifugally collecting powder at the rotating speed of 8000 r/min;
4) placing the product obtained by centrifugation in a vacuum oven, and drying at 60 ℃ for 24h to obtain vanadium disulfide;
5) assembling a button zinc ion battery by using vanadium disulfide as a positive electrode material, 4M zinc trifluoromethanesulfonate as an electrolyte and metal zinc as a negative electrode;
6) performing in-situ electrochemical activation on the button cell under a voltage window of 0.2-1.5V to obtain VS rich in defects 2 。
Example 2
Defect-rich VS 2 The preparation method comprises the following steps:
1) dissolving 2mmol of ammonium metavanadate in 30ml of deionized water, adding 2ml of ammonia water, stirring, adding 15mmol of thioacetamide after dissolution, and continuously stirring to obtain a precursor solution;
2) transferring the precursor solution into a high-pressure reaction kettle with a 50ml polytetrafluoroethylene inner container, and reacting for 10 hours at 180 ℃;
3) after the reaction is finished and the temperature is cooled to room temperature, washing the reaction product by using deionized water and absolute ethyl alcohol for three times respectively, and centrifugally collecting powder at the rotating speed of 8000 r/min;
4) placing the product obtained by centrifugation in a vacuum oven, and drying at 60 ℃ for 24h to obtain vanadium disulfide;
5) assembling a button zinc ion battery by using vanadium disulfide as a positive electrode material, 4M zinc trifluoromethanesulfonate as an electrolyte and metal zinc as a negative electrode;
6) performing in-situ electrochemical activation on the button cell under a voltage window of 0.2-1.7V to obtain defect-rich VS 2 。
Example 3
VS rich in defects 2 The preparation method comprises the following steps:
1) dissolving 2mmol of ammonium metavanadate in 30ml of deionized water, adding 2ml of ammonia water, stirring, adding 15mmol of thioacetamide after dissolution, and continuously stirring to obtain a precursor solution;
2) transferring the precursor solution into a high-pressure reaction kettle with a 50ml polytetrafluoroethylene inner container, and reacting for 10 hours at 180 ℃;
3) after the reaction is finished and the temperature is cooled to room temperature, washing the reaction product by using deionized water and absolute ethyl alcohol for three times respectively, and centrifugally collecting powder at the rotating speed of 8000 r/min;
4) placing the product obtained by centrifugation in a vacuum oven, and drying at 60 ℃ for 24h to obtain vanadium disulfide;
5) assembling a button zinc ion battery by using vanadium disulfide as a positive electrode material, 4M zinc trifluoromethanesulfonate as an electrolyte and metal zinc as a negative electrode;
6) performing in-situ electrochemical activation on the button cell under a voltage window of 0.2-1.9V to obtain VS rich in defects 2 。
Example 4
Defect-rich VS 2 The preparation method comprises the following steps:
1) dissolving 2mmol of ammonium metavanadate in 30ml of deionized water, adding 2ml of ammonia water, stirring, adding 15mmol of thioacetamide after dissolution, and continuously stirring to obtain a precursor solution;
2) transferring the precursor solution into a high-pressure reaction kettle with a 50ml polytetrafluoroethylene inner container, and reacting for 10 hours at 180 ℃;
3) after the reaction is finished and the temperature is cooled to room temperature, washing the reaction product by using deionized water and absolute ethyl alcohol for three times respectively, and centrifugally collecting powder at the rotating speed of 8000 r/min;
4) placing the product obtained by centrifugation in a vacuum oven, and drying at 60 ℃ for 24h to obtain vanadium disulfide;
5) assembling the button cell by using vanadium disulfide as a positive electrode material, 4M zinc trifluoromethanesulfonate as an electrolyte and metal zinc as a negative electrode;
6) performing in-situ electrochemical activation on the button cell under a voltage window of 0.2-2.1V to obtain VS rich in defects 2 。
Example 5
Defect-rich VS 2 The preparation method comprises the following steps:
1) dissolving 2mmol of ammonium metavanadate in 30ml of deionized water, then adding 2ml of ammonia water, stirring, adding 15mmol of thioacetamide after dissolution, and continuously stirring to obtain a precursor solution;
2) transferring the precursor solution into a high-pressure reaction kettle with a 50ml polytetrafluoroethylene inner container, and reacting for 10 hours at 180 ℃;
3) after the reaction is finished and the temperature is cooled to room temperature, washing the reaction product by using deionized water and absolute ethyl alcohol for three times respectively, and centrifugally collecting powder at the rotating speed of 8000 r/min;
4) placing the product obtained by centrifugation in a vacuum oven, and drying at 60 ℃ for 24h to obtain vanadium disulfide;
5) assembling the button cell by using vanadium disulfide as a positive electrode material, 4M zinc trifluoromethanesulfonate as an electrolyte and metal zinc as a negative electrode;
6) performing in-situ electrochemical activation on the button cell under a voltage window of 0.2-2.3V to obtain VS rich in defects 2 。
Example 6
Defect-rich VS 2 The preparation method comprises the following steps:
1) dissolving 2mmol of ammonium metavanadate in 30ml of deionized water, then adding 2ml of ammonia water, stirring, adding 15mmol of thioacetamide after dissolution, and continuously stirring to obtain a precursor solution;
2) transferring the precursor solution into a high-pressure reaction kettle with a 50ml polytetrafluoroethylene inner container, and reacting for 10 hours at 180 ℃;
3) after the reaction is finished and the temperature is cooled to room temperature, washing the reaction product by using deionized water and absolute ethyl alcohol for three times respectively, and centrifugally collecting powder at the rotating speed of 8000 r/min;
4) drying the product obtained by centrifugation in a vacuum oven at 60 ℃ for 24h to obtain vanadium disulfide;
5) assembling the button cell by using vanadium disulfide as a positive electrode material, 4M zinc trifluoromethanesulfonate as an electrolyte and metal zinc as a negative electrode;
6) performing in-situ electrochemical activation on the button cell at a voltage window of 0.2-1.9V to obtain defect-rich VS 2 。
FIG. 1 is a scanning electron microscope image of vanadium disulphide obtained in step 4) of example 6, VS being obtained in FIG. 1 by a simple one-step hydrothermal synthesis 2 The material is made of nano-sheetsThe assembled accordion-shaped structure can provide larger specific surface area and more active sites, and is favorable for the infiltration of electrolyte and the embedding and extraction of zinc ions.
Application example
Defect-rich VS prepared in examples 1 to 6 respectively 2 The conductive material is used as a positive electrode active material, and the conductive material, acetylene black and PVDF as a binder are mixed according to the mass ratio of 7: 2:1 mixing and coating on a stainless steel mesh to prepare a positive electrode; then 4M zinc trifluoromethanesulfonate is used as electrolyte, and metal zinc is used as a negative electrode to assemble the button type water system zinc ion battery; labeled as battery 1, battery 2, battery 3, battery 4, battery 5, and battery 6, respectively.
Comparative application example
The vanadium disulfide prepared in step 4) of example 1 is used as a positive electrode active material, and the button water-based zinc ion battery is assembled by referring to the process in the application example and is marked as a battery 7.
Electrochemical performance test
The batteries 1 to 5 and the battery 7 are placed in a magnetic field-free environment for electrochemical performance test, and the battery 6 is placed in a 4000Gs weak magnetic field provided by a permanent magnet for electrochemical performance test.
FIG. 2 is a graph of rate performance of cell 2 in electrochemical tests conducted over a voltage window of 0.2-1.9V, as seen at 1A g -1 Has a current density of 332mAh g -1 High specific capacity even at 20A g -1 The specific capacity of the alloy still keeps 227mAh g under the high current density -1 And when the current density returns to 1A g again -1 Then, the water still returns to 307mAh g -1 High specific capacity value of (2). It can be seen that battery 2 has excellent rate performance.
FIG. 3 shows the results of the cycling performance test of cell 3 over a voltage window of 0.2-1.9V, as seen at 5A g -1 After 1000 cycles of the current density of the current, 193mAh g still remains -1 But at around 1200 cycles due to severe zinc dendrites resulting in rapid capacity fade.
FIG. 4 is an ultra-long cycle performance of the battery 6FIG. 4 shows that the reference numeral 5A g -1 After 7000 cycles of circulation at the current density of (1), 126mAh g still remains -1 The specific capacity of (A). It is known that the cycle performance of the battery can be remarkably improved under the induction of a magnetic field of 4000 Gs.
FIG. 5 shows the results of the cycling performance test of the battery 7 at a voltage window of 0.2-1.5V, as seen in FIG. 5 at 5A g -1 At a current density of (1), the original VS is clearly seen 2 Can only show limited specific capacity when no defect is introduced.
It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. 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 (10)
1. A preparation method of defect-rich vanadium disulfide is characterized by comprising the following steps: the method comprises the following steps: preparing vanadium disulfide; and then assembling a zinc ion battery by using vanadium disulfide as a positive electrode material, zinc trifluoromethanesulfonate as an electrolyte and zinc as a negative electrode, and performing in-situ electrochemical activation under a voltage window of 0.2-2.3V to obtain the defect-rich vanadium disulfide.
2. The method of claim 1, wherein the defect-rich vanadium disulfide is prepared by: the method for preparing the vanadium disulfide comprises the following steps: dissolving ammonium metavanadate in water, then adding ammonia water, stirring, adding thioacetamide after dissolving, and continuously stirring to obtain a precursor solution; and carrying out hydrothermal reaction on the precursor solution, and washing and drying a product after the hydrothermal reaction is finished to obtain the vanadium disulfide.
3. The method of claim 2, wherein the defect-rich vanadium disulfide is prepared by: the volume ratio of the water to the ammonia water is (10-30): 1.
4. the method of claim 2, wherein the defect-rich vanadium disulfide is prepared by: the mass ratio of the ammonium metavanadate to the thioacetamide is (1-2): (10-15).
5. The method of claim 2, wherein the defect-rich vanadium disulfide is prepared by: the temperature of the hydrothermal reaction is 180-200 ℃, and the reaction time is 8-12 h.
6. The method of manufacturing defect-rich vanadium disulfide according to claim 2, wherein: the drying is vacuum drying; the temperature of vacuum drying is 50-70 ℃, and the time is 12-24 h.
7. The method of manufacturing defect-rich vanadium disulfide according to claim 1, wherein: the concentration of the electrolyte is 3-4M.
8. Defect-rich vanadium disulphide produced according to the production process of any one of claims 1 to 7.
9. Use of the defect-rich vanadium disulfide of claim 8 as a positive electrode material in an aqueous zinc ion battery.
10. The use of the defect-rich vanadium disulfide as a positive electrode material in an aqueous zinc-ion battery according to claim 9, wherein the aqueous zinc-ion battery is placed in a magnetic field environment when in use, and the magnetic field is 500-5000 Gs.
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