CN113611830A - VS (virtual switch)4-graphene aerogel composite material, preparation method and application - Google Patents
VS (virtual switch)4-graphene aerogel composite material, preparation method and application Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 74
- 239000004964 aerogel Substances 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 17
- -1 Transition metal sulfides Chemical class 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000013543 active substance 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
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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 discloses a VS4-a method for preparing a graphene aerogel composite, the method comprising the steps of: step one, NaVO4And C2H5Dissolving NS in deionized water to obtain a uniform solution A; dissolving graphene oxide in deionized water to obtain a solution B; mixing the solution A and the solution B to obtain a uniform solution C; transferring the solution C to a reaction kettle to perform hydrothermal reaction to reduce graphene oxide; after the reaction is finished, standing, filtering and drying to obtain powdery VS4-a graphene aerogel composite; resulting VS4Loaded on graphene aerogel and effectively promote Li+Diffusion coefficient and electron conductivity of;the invention is applied to the lithium-sulfur battery, and the rate capability and the cycle performance of the obtained lithium-sulfur battery are obviously improved.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur battery positive electrode materials, in particular to VS4-graphene aerogel composite material, preparation method and application.
Background
Transition metal sulfides are of great interest due to their unique physical and chemical properties and have practical applications in the fields of catalysis, luminescence, energy storage, and the like. As transition metal sulfides, VS4Has a unique structure, and weak inter-chain van der waals force exists in the crystal structure of the structure, so that a loose stacking structure is provided. The large open channels between and in the chains provide potential sites for metal ion diffusion and storage, and are ideal electrode materials for lithium ion batteries.
But due to Li+Low diffusion coefficient and low electron conductivity, such that VS4The high capacity characteristic of (2) is difficult to show in a cycling process and a rate test. Therefore, there is an urgent need to develop VS with higher conductivity4And (3) a positive electrode material.
Disclosure of Invention
The first purpose of the invention is to provide a VS4Graphene aerogel composite, VS in the present invention4Loaded on graphene aerogel and effectively promote Li+Diffusion coefficient and electron conductivity.
In order to solve the technical problem, the technical scheme of the invention is as follows: VS (virtual switch)4-a method for preparing a graphene aerogel composite, comprising the steps of:
step one, NaVO4Powder and C2H5Dissolving NS in deionized water to obtain a uniform solution A;
dissolving graphene oxide in deionized water to obtain a solution B;
mixing the solution A with the solution B to obtain a uniform solution C;
transferring the solution C to a reaction kettle to perform hydrothermal reaction to reduce graphene oxide;
after the reaction is finished, standing, filtering and drying to obtain powdery VS4-a graphene aerogel composite.
Preferably NaVO4Is C2H53 to 5 times the molar amount of NS. The invention obtains high-purity VS by strictly controlling the molar ratio of the two substances4And the capacity of the lithium-sulfur battery is improved.
Preferably, the molar weight of the graphene oxide is NaVO41 to 3 times the molar amount. The method ensures the use amount of the graphene oxide and the capacity of the material on the premise of obvious modification, and is favorable for obtaining the lithium-sulfur battery with excellent performance.
Preferably, the process conditions of the hydrothermal reaction in the second step are as follows:
the reaction temperature is 140 ℃ to 200 ℃; the reaction time is 10-16 h.
In the invention, the reaction temperature is strictly controlled, the reaction temperature is too low, the reaction is not thorough or does not react, the reaction temperature is too high, byproducts are easy to appear, and VS is damaged4The purity of (2).
Further preferably, the process conditions of the hydrothermal reaction in the second step are as follows:
the reaction temperature is 160 ℃; the reaction time is 12 h.
The invention has the advantages that the time of the hydrothermal reaction is 12h, the temperature is 160 ℃, the purity of the product is high, and the time is short. Preferably NaVO4And C2H5NS is powder. The powdery material is selected and applied to the battery, is easy to mix and disperse, and is favorable for synthesizing high-purity VS4。
Preferably, the standing time of the second step is 12 to 16 hours. The invention has short standing time, non-precipitated products in the solution, low yield of the finally obtained products, long standing time and low productivity.
The object of the present invention is to provide a lithium-sulfur battery using VS4Graphene aerogel composite as positive electrode material, VS4The graphene aerogel composite material has better conductivity and stable structure, and can effectively improve the cycle performance.
In order to solve the technical problem, the technical scheme of the invention is as follows: a lithium-sulfur battery includes a positive electrode and a negative electrode,the active material used by the anode is VS prepared by the invention4-a graphene aerogel composite.
By adopting the technical scheme, the invention has the beneficial effects that:
the invention uses NaVO4Powder and C2H5NS is used as a raw material, is uniformly mixed with graphene oxide, is heated to a certain temperature by a hydrothermal reaction in deionized water, and then is subjected to C2H5Hydrolysis of NS under alkaline condition to release S2-The linkage between V and O in solution may be represented as VxOy n-Finally converted into VS4(ii) a Graphene oxide on C2H5Reducing the reduced NS into graphene, and further converting the graphene into graphene aerogel under a high-temperature environment;
C2H5NS not only functions as a reducing agent, but also functions as a sulfur donor;
VS4reacting with graphene aerogel at high temperature to form composite material VS4The surface of the graphene aerogel is more uniform, and the conductivity of the product is better;
graphene aerogels have a broader lithium ion transport network, VS4The aerogel is matched to form a composite material, and a porous structure formed by mutual crosslinking of graphene aerogel sheets can help lithium ions to be rapidly applied to VS4Medium de-intercalation, electron conductivity is improved in a microscopic mode, and multiplying power performance is improved in a macroscopic mode;
the aerogel with the three-dimensional porous structure constructed by the graphene can effectively reduce the stacking of graphene sheets, and the porous structure formed by the mutual crosslinking of the sheets is more favorable for the transmission of electrolyte and lithium ions;
VS provided by the invention4Graphene aerogel, common raw materials, simple synthesis process, easily controllable parameters, product with graphene nanostructure, endowing VS4The product has the advantages of larger specific surface area, higher conductivity, better conductivity according to the advantages of the process, stable structure and effectively improved cycle performance.
Thereby achieving the above object of the present invention.
Drawings
FIG. 1 is VS obtained in example 14-XRD spectrum of graphene aerogel composite;
FIG. 2 is VS obtained in example 14-SEM image of graphene aerogel composite;
fig. 3 is a graph showing cycle performance of lithium sulfur batteries obtained in examples 1 to 3 of the present invention and comparative example.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
This embodiment discloses a VS4-a method for preparing a graphene aerogel composite, comprising the steps of:
step one, NaVO4And C2H5Dissolving NS in deionized water of 20 times to obtain a uniform solution A; NaVO4Is C2H53 times of molar amount of NS;
dissolving graphene oxide in deionized water to obtain a uniform solution B, wherein the graphene oxide and NaVO4The molar ratio is 1: 1;
mixing the solution A with the solution B to obtain a uniform solution C;
step two, transferring the solution C into a polytetrafluoroethylene autoclave lining with the volume 5 times that of the solution C, sealing the polytetrafluoroethylene autoclave lining, and then putting the polytetrafluoroethylene autoclave lining into a stainless steel shell to perform hydrothermal reaction to reduce graphene oxide;
transferring the reaction kettle to a forced air drying oven to be heated for a certain time, wherein the reaction temperature is 140 ℃, and carrying out hydrothermal reaction for 16h to obtain the product containing three-dimensional VS4-liquid graphene aerogel, product standing for 12h, filtering, and drying precipitate to obtain powdery product VS4-graphene aerogels.
Example 2
This embodiment discloses a VS4-a method for preparing a graphene aerogel composite, comprising the steps of:
step one, rubbingThe molar ratio is 4: 1 NaVO4Powder and C2H5Dissolving NS in 25 times of deionized water, and obtaining a uniform solution A after complete dissolution; dissolving graphene oxide in deionized water to obtain a uniform solution B, wherein the graphene oxide and NaVO4The molar ratio is 2: 1; mixing the solution A with the solution B to obtain a uniform solution C. Then the solution C was transferred to a 7-fold polytetrafluoroethylene autoclave liner, sealed and placed in a stainless steel shell.
Step two, transferring the reaction kettle to a forced air drying oven to be heated for a certain time, wherein the reaction temperature is 170 ℃, and carrying out hydrothermal reaction for 13 hours to obtain the product containing three-dimensional VS4-liquid graphene aerogel, product standing for 14h, filtering, and drying precipitate to obtain powdery product VS4-a graphene aerogel;
example 3
This embodiment discloses a VS4-a method for preparing a graphene aerogel composite, comprising the steps of:
step one, mixing a mixture of a molar ratio of 5: 1 NaVO4Powder and C2H5Dissolving NS in 30 times of deionized water, and obtaining a uniform solution A after complete dissolution; dissolving graphene oxide in deionized water to obtain a uniform solution B, wherein the graphene oxide and NaVO4The molar ratio is 3: 1; mixing the solution A and the solution B to obtain a uniform solution C;
and step two, transferring the solution C into a 10-time polytetrafluoroethylene autoclave liner, sealing and then placing into a stainless steel shell. Transferring the reaction kettle to a forced air drying oven to be heated for a certain time, wherein the reaction temperature is 200 ℃, and carrying out hydrothermal reaction for 10 hours to obtain the product containing three-dimensional VS4-liquid graphene aerogel, product standing for 16h, filtering, and drying precipitate to obtain powdery product VS4-graphene aerogels.
Comparative example
This example is unmodified VS4。
VS of the above comparative example4VS prepared from examples 1 to 34The performance of a half-cell assembled by graphene aerogel serving as a positive electrode material and a negative electrode matched with a lithium sheetTesting, the assembly process is as follows:
and (3) placing the anode electrode active substance in the anode shell upwards, dripping electrolyte, covering the diaphragm on the surface of the working electrode, and dripping electrolyte again. And then sequentially placing the lithium sheet and the foamed nickel on the surface of the diaphragm, and finally fastening the negative electrode shell.
The lithium sulfur batteries obtained in examples 1 to 3 and comparative example were subjected to rate test and cycle performance test, wherein the results of the rate performance test are shown in table 1, and the cycle performance is shown in fig. 3.
Testing multiplying power, namely testing the discharge capacity of each group of batteries under different multiplying powers;
and (4) a cycle test, namely testing the capacity retention rate of each group of batteries after being charged at 0.5C and discharged at 1C and being cycled for 30 weeks.
FIG. 1 Rate Performance data for lithium sulfur batteries from examples 1 to 3 and comparative example
| Group of | 0.2C | 0.5C | 1C | 2C |
| Comparative example | 486mAh g-1 | 399mAh g-1 | 367mAh g-1 | 278mAh g-1 |
| Example 1 | 486mAh g-1 | 442mAh g-1 | 379mAh g-1 | 325mAh g-1 |
| Example 2 | 489mAh g-1 | 451mAh g-1 | 387mAh g-1 | 334mAh g-1 |
| Example 3 | 487mAh g-1 | 448mAh g-1 | 384mAh g-1 | 329mAh g-1 |
From the magnification data in Table 1, unmodified VS is shown4At 2C discharge, the capacity is only 278mAh g-1By combining the data of examples 1 to 3, it can be known that the conductivity of the product is improved and the rate capability is obviously improved after the graphene aerogel is modified, wherein the VS prepared by the process parameters of example 2 is used4The capacity of the graphene aerogel 2C under discharge is 334mAh g-1And capacity remaining percentage 68%.
From the cycle curves of FIG. 3, the unmodified VS is shown4After 50 weeks of cycling, the capacity remained only 84%, and after modification with the graphene aerogel, the cycle life of the product increased significantly, with capacity remaining greater than 90% after 50 weeks of cycling.
As can be seen from the combination of FIGS. 1 and 2 and tables 1 and 3, VS was obtained according to the present invention4All strong diffraction peaks of graphene aerogel compositesMonoclinic phase VS capable of accurately corresponding to body centered cubic4. VS removal4No other phase peak was detected, indicating VS4VS in graphene aerogels4High phase purity of (2). A diffraction peak of an obvious graphite-like substance does not appear in a spectrogram in fig. 1, which indicates that the graphene aerogel maintains a good graphene laminated structure and is not stacked; with further reference to fig. 2, it can be seen from (a) and (b) that the graphene aerogel presents a porous network structure, which is favorable for Li+To be transmitted. Upon further magnification, as shown in FIGS. 2 (c) and (d), show a number of VS widths of about 20nm and lengths of about 100nm4The nano materials are uniformly distributed on the surface of the graphene aerogel, as indicated by arrows; it can be seen that VS provided by the present invention4Graphene aerogel composites incorporating nanostructures of graphene, imparting VS4Larger specific surface area, higher conductivity, compared with VS alone4The lithium-sulfur battery cathode material has the advantages that the rate capability and the cycle performance of the lithium-sulfur battery are greatly improved, and the lithium-sulfur battery cathode material is stable in structure and good in conductivity.
Claims (8)
1. VS (virtual switch)4-a method for preparing a graphene aerogel composite, characterized in that: the method comprises the following steps:
step one, NaVO4And C2H5Dissolving NS in deionized water to obtain a uniform solution A;
dissolving graphene oxide in deionized water to obtain a solution B;
mixing the solution A and the solution B to obtain a uniform solution C;
transferring the solution C to a reaction kettle to perform hydrothermal reaction to reduce graphene oxide;
and after the reaction is finished, standing, filtering and drying to obtain the powdery VS 4-graphene aerogel composite material.
2. The method of claim 1, wherein the VS 4-graphene aerogel composite is prepared by: NaVO4Is C2H5NS molar weight3 to 5 times of.
3. A VS as claimed in claim 14-a method for preparing a graphene aerogel composite, characterized in that: the molar weight of the graphene oxide is NaVO41 to 3 times the molar amount.
4. A VS as claimed in claim 14-a method for preparing a graphene aerogel composite, characterized in that: the process conditions of the hydrothermal reaction in the second step are as follows:
the reaction temperature is 140 ℃ to 200 ℃; the reaction time is 10-16 h.
5. A VS as defined in claim 44-a method for preparing a graphene aerogel composite, characterized in that: the process conditions of the hydrothermal reaction in the second step are as follows:
the reaction temperature is 160 ℃; the reaction time is 12 h.
6. A VS as claimed in claim 14-a method for preparing a graphene aerogel composite, characterized in that: NaVO4And C2H5NS is powder.
7. A VS as claimed in claim 14-a method for preparing a graphene aerogel composite, characterized in that: and the standing time of the second step is 12 to 16 hours.
8. A lithium sulfur battery comprising a positive electrode and a lithium sheet negative electrode, characterized in that: the active material used for the positive electrode is VS prepared according to any one of claims 1 to 74-a graphene aerogel composite.
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Citations (3)
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|---|---|---|---|---|
| CN109776851A (en) * | 2019-01-04 | 2019-05-21 | 浙江工业大学 | A kind of bacteria cellulose/metal sulfide plural gel and preparation method thereof and conductive processing method |
| CN110299527A (en) * | 2019-07-02 | 2019-10-01 | 张蓓 | A kind of lithium ion battery negative material and preparation method thereof |
| CN113130863A (en) * | 2021-03-22 | 2021-07-16 | 郑州大学 | VS (virtual switch)4/rGO composite material, preparation method thereof and application in zinc ion battery |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776851A (en) * | 2019-01-04 | 2019-05-21 | 浙江工业大学 | A kind of bacteria cellulose/metal sulfide plural gel and preparation method thereof and conductive processing method |
| CN110299527A (en) * | 2019-07-02 | 2019-10-01 | 张蓓 | A kind of lithium ion battery negative material and preparation method thereof |
| CN113130863A (en) * | 2021-03-22 | 2021-07-16 | 郑州大学 | VS (virtual switch)4/rGO composite material, preparation method thereof and application in zinc ion battery |
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| Title |
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| 吴丽军: "钒氧(硫)化物锂离子电池正极材料制备及其电化学性能研究", 《中国博士学位论文全文数据库(电子期刊)》 * |
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