CN115367801B - Near-spherical molybdenum disulfide-carbon composite material for lithium ion battery cathode and preparation method thereof - Google Patents
Near-spherical molybdenum disulfide-carbon composite material for lithium ion battery cathode and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- QXDDUAGHAWNZHJ-UHFFFAOYSA-N [C].[Mo](=S)=S Chemical compound [C].[Mo](=S)=S QXDDUAGHAWNZHJ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 29
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 16
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 9
- 239000004094 surface-active agent Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 5
- 239000011733 molybdenum Substances 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005728 strengthening Methods 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 7
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 2
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 239000008101 lactose Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OHVGNSMTLSKTGN-BTVCFUMJSA-N [C].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O Chemical compound [C].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O OHVGNSMTLSKTGN-BTVCFUMJSA-N 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 sulfide ions Chemical class 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
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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
- H01M4/5815—Sulfides
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01—INORGANIC CHEMISTRY
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A near-spherical molybdenum disulfide-carbon composite material for a lithium ion battery cathode and a preparation method thereof are provided, and the preparation method comprises the following steps: and (2) weighing ammonium heptamolybdate and thiourea according to the mol ratio of molybdenum to sulfur of 1:1-1:12, dissolving in deionized water, adding a carbon source, stirring uniformly, adding a surfactant, stirring uniformly to obtain an initial solution, performing hydrothermal reaction on the initial solution in a stirring state, and washing and drying a reaction product to obtain the near-spherical molybdenum disulfide-carbon composite material for the lithium ion battery cathode. According to the invention, the near-spherical preparation of the molybdenum disulfide-carbon composite material is realized in the process of strengthening the hydrothermal by the ammonium heptamolybdate, the carbon source and PVP, and the prepared material has high apparent density and can effectively improve the volume capacity density of the battery.
Description
Technical Field
The invention belongs to the field of lithium ion battery cathode materials, and particularly relates to a near-spherical molybdenum disulfide-carbon composite material for a lithium ion battery cathode and a preparation method thereof.
Background
Molybdenum disulfide (MoS) 2 ) The material is a cathode material for lithium ion batteries with great development potential due to the special graphene-like layered structure and the characteristic of high specific capacity (the theoretical capacity reaches 670 mAh/g). In practical application, moS 2 When a single component is used as a negative electrode material, the problems of large surface energy, easy stacking and agglomeration, poor conductivity, low ion mobility and the like of the material are limited. Typically by combining MoS 2 Material nanocrystallization and compounding to solve MoS 2 The problem of a single component as the negative electrode material. Wherein the method comprises the steps ofAnd MoS 2 The synergistic composite system comprises a plurality of material systems such as carbon materials, tin-based materials, mxenes composite materials, transition metal oxides/sulfides and the like.
The tradition is to MoS 2 When carbon compounding is carried out, the MoS is prepared by adopting a common hydrothermal or solvothermal method 2 Most of the-C composite powder is complex nano morphology, the complex morphology is difficult to maintain stability and has low bulk density, the bulk density of the nano material is low, the common hydrothermal method/solvothermal method is long in time (usually more than 20 h), and the production efficiency is low.
Disclosure of Invention
The invention aims to provide a near-spherical molybdenum disulfide-carbon composite material for a lithium ion battery cathode and a preparation method thereof, wherein the near-spherical molybdenum disulfide-carbon composite material is prepared by a specific molybdenum source and a surfactant in intensified hydrothermal reaction, and the prepared MoS 2 The C composite powder is nearly spherical, has high apparent density, greatly shortens the preparation time and improves the production efficiency.
The technical scheme adopted by the invention is as follows:
the preparation method of the near-spherical molybdenum disulfide-carbon composite material for the lithium ion battery cathode comprises the following steps:
and (2) weighing ammonium heptamolybdate and thiourea according to the mol ratio of molybdenum to sulfur of 1:1-1:12, dissolving in deionized water, adding a carbon source, stirring uniformly, adding a surfactant, stirring uniformly to obtain an initial solution, performing hydrothermal reaction on the initial solution in a stirring state, and washing and drying a reaction product to obtain the near-spherical molybdenum disulfide-carbon composite material for the lithium ion battery cathode.
Further, the addition amount of the surfactant accounts for 10-50% of the mass of the ammonium heptamolybdate.
Further, the surfactant is PVP.
Further, the addition amount of the carbon source accounts for 3-15% of the mass of the ammonium heptamolybdate.
Further, the carbon source is one or more of glucose, sucrose, fructose, maltose, lactose, starch, xylose and lignocellulose.
Further, the hydrothermal reaction under stirring is carried out by the following steps: transferring the initial solution into a high-pressure reaction kettle with magnetic stirring, wherein the reaction temperature is 180-260 ℃ and the reaction time is 6-10 h.
Further, the rotation speed of the magnetic stirring is 350-400 r/min.
Further, the washing process is as follows: firstly, the reaction products are respectively and alternately centrifuged for 5 to 10 minutes by deionized water and absolute ethyl alcohol at the rotating speed of 10000 to 12000 r/min.
Further, the drying process is as follows: the reaction product is kept at the temperature of 65-75 ℃ for 7-12 h.
The near-spherical molybdenum disulfide-carbon composite material for the lithium ion battery, which is obtained by the preparation method, is prepared from the near-spherical molybdenum disulfide-carbon composite material.
The invention has the beneficial effects that:
1. according to the invention, the near-spherical preparation of the molybdenum disulfide-carbon composite material is realized in the process of strengthening the hydrothermal by the ammonium heptamolybdate, the carbon source and PVP, the bulk density of the material is high, and the volume capacity density of the battery can be effectively improved.
2. The preparation process adopts a one-step hydrothermal preparation process, has no raw material pretreatment and no subsequent heat treatment of powder, can reduce the time of the whole preparation process to about 6 hours at the lowest, and compared with the preparation time of a common hydrothermal method/solvothermal method which is generally longer than 20 hours, the preparation process time is greatly shortened, and the preparation efficiency of the molybdenum disulfide-carbon composite material is improved.
Drawings
FIG. 1 is a flow chart of a process for preparing a near spherical molybdenum disulfide/carbon negative electrode material;
FIG. 2 is an SEM image of a near spherical molybdenum disulfide-carbon composite material prepared in example 1;
FIG. 3 is a HRTEM image of the nearly spherical molybdenum disulfide-carbon composite material prepared in example 1;
fig. 4 is a graph of charge-discharge cycles of an electrode prepared using the near spherical molybdenum disulfide-carbon composite material of example 1 and a sheet-shaped molybdenum disulfide-carbon composite material.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The preparation method of the near-spherical molybdenum disulfide-carbon composite material for the lithium ion battery cathode comprises the following steps:
and (2) weighing ammonium heptamolybdate and thiourea according to the mol ratio of molybdenum to sulfur of 1:1-1:12, dissolving in deionized water, adding a carbon source, stirring uniformly, adding a surfactant, stirring uniformly to obtain an initial solution, performing hydrothermal reaction on the initial solution in a stirring state, and washing and drying a reaction product to obtain the near-spherical molybdenum disulfide-carbon composite material for the lithium ion battery cathode.
The addition amount of the surfactant accounts for 10-50% of the mass of the ammonium heptamolybdate.
The surfactant is PVP.
The addition amount of the carbon source accounts for 3-15% of the mass of the ammonium heptamolybdate.
The carbon source is one or more of glucose, sucrose, fructose, maltose, lactose, starch, xylose and lignocellulose.
The hydrothermal reaction process under stirring state is as follows: transferring the initial solution into a high-pressure reaction kettle with magnetic stirring, wherein the reaction temperature is 180-260 ℃ and the reaction time is 6-10 h.
The rotation speed of the magnetic stirring is 350-400 r/min.
The washing process is as follows: firstly, the reaction products are respectively and alternately centrifuged for 5 to 10 minutes by deionized water and absolute ethyl alcohol at the rotating speed of 10000 to 12000 r/min.
The drying process is as follows: the reaction product is kept at the temperature of 65-75 ℃ for 7-12 h.
The near-spherical molybdenum disulfide-carbon composite material for the lithium ion battery, which is obtained by the preparation method provided by the invention.
Example 1
Respectively weighing 0.66g of ammonium heptamolybdate and 1.42g of thiourea, stirring and dissolving in 80 mL deionized water at room temperature, adding 0.06g of glucose, stirring uniformly, adding 0.24g of PVP, stirring at room temperature for 1 h, transferring the solution to a miniature magnetic stirring autoclave with the temperature and pressure of 150 mL displayed in real time, adjusting the magnetic stirring speed to 400r/min, heating to 200 ℃, and preserving heat for 7h.
After the reaction is finished, respectively using deionized water and absolute ethyl alcohol to alternatively centrifuge for 10 min at the rotation speed of 12000 r/min, washing for 3 times, and finally placing the precipitate into a blast drying oven at 70 ℃ for heat preservation for 8 h, thus obtaining the near-spherical molybdenum disulfide-carbon composite material.
As shown in fig. 2 and 3, SEM images and HRTEM images of the near-spherical molybdenum disulfide-carbon composite material show that the near-spherical molybdenum disulfide-carbon composite material is distributed in a near-spherical shape as a whole, and forms MoS 2 Is a core and amorphous carbon is a shell coating structure. The addition of carbon not only causes MoS 2 The average granularity of (2) is reduced to 50 nm, and the coating is uniform, the coating thickness is about 30 nm, which is beneficial to improving MoS 2 Is of the structure stability of (a) to alleviate MoS 2 The problem of volume expansion in the lithium intercalation-deintercalation process lays a foundation for improving the cycle stability of the battery.
By (NH) 4 ) 6 Mo 7 O 24 NH as molybdenum source 4 + /NH 3 In the hydrothermal synthesis process, an alkaline buffer system is provided in the reaction process, the pH value of the solution after the hydrothermal reaction is always kept between 8 and 9, a molybdenum oxide intermediate phase is generated in the hydrothermal reaction process of an ammonium heptamolybdate system, molybdenum disulfide is generated by the reaction of the molybdenum oxide intermediate phase and sulfide ions in the system, PVP can form nano micelles in the hydrothermal system, and the nano micelles are used as a micro-reactor of the system, moS 2 Homogeneous nucleation and growth in a microreactor, and PVP as a nonionic surfactant has hydrophilic groups and hydrophobic groups, so that MoS can be effectively inhibited 2 Stacking agglomeration during growth, such that MoS is produced 2 The shape is regular, the size is uniform, the particles are smaller, and simultaneously, the addition of the glucose carbon source can generate amorphous carbon in the hydrothermal process and coat MoS 2 Grain surface layer, thinning MoS 2 The grains further weaken the agglomeration among the grains, reduce the grain size and strengthen the magnetic stirring to make the systemThe concentration distribution is uniform, the generation of large particles caused by overhigh local concentration is improved, and finally the nano spherical molybdenum disulfide-carbon composite material with uniform size and good dispersibility is formed.
The chemical reaction equation is as follows:
(NH 4 ) 6 Mo 7 O 24 +3H 2 O→7MoO 3 (s)+6NH 3 ·3H 2 O(l) （1）
NH 2 CSNH 2 (aq) +2H 2 O→2NH 3 (g)+H 2 S(g)+CO 2 (g) （2）
H 2 S→2H + +S 2- （3）
MoO 3 (s)+3S 2- +6H + →MoS 2 (s)+SO 2 (g)+3H 2 O （4）
as shown in fig. 4, an electrode was prepared using the near-spherical molybdenum disulfide-carbon composite material, and a charge-discharge experiment (test current density 500 mA/g) was performed on the electrode to obtain a charge-discharge cycle curve. MoS (MoS) 2 The specific discharge capacities of the C electrode material after the first circle and the cycle of 100 circles are 705.2 mAh/g and 625.7 mAh/g respectively, and the capacity retention rate is 88.7%. Using sheet MoS 2 The initial specific capacity of the C nano sheet is 646.2 mAh/g, the charge and discharge cycle performance is extremely poor, the initial capacity of the cycle is rapidly reduced, the reversible capacity is reduced to be lower than 100 mAh/g after 40 cycles, and the C nano sheet is matched with the sheet MoS 2 Compared with the cycle performance of the-C, the cycle stability of the near-spherical composite material is greatly improved, which proves that the structural stability of the spherical powder is stronger and the particle-free composite material has high stability to MoS 2 The electrochemical stability of the cathode material plays a role in strengthening.
Example 2
Respectively weighing 0.66g of ammonium heptamolybdate and 2.56g of thiourea, stirring at room temperature, dissolving in 80 mL deionized water, adding 0.06g of glucose, stirring uniformly, adding 0.066g of PVP, stirring at room temperature for 1 h, transferring the solution to a miniature magnetic stirring autoclave with the temperature and pressure of 150 mL displayed in real time, stirring at the magnetic stirring speed of 350r/min, heating to 260 ℃, and preserving heat for 7h.
After the reaction is finished, respectively using deionized water and absolute ethyl alcohol to alternatively centrifuge for 5 min at the rotating speed of 10000 r/min, washing for 3 times, and finally placing the precipitate into a blast drying oven at 65 ℃ to keep the temperature for 10h, thus obtaining the approximately spherical molybdenum disulfide-carbon powder material.
Example 3
Respectively weighing 0.66g of ammonium heptamolybdate and 1.42g of thiourea, stirring at room temperature, dissolving in 80 mL deionized water, adding 0.09g of glucose, stirring uniformly, adding 0.12g of PVP, stirring at room temperature for 1 h, transferring the solution to a miniature magnetic stirring autoclave with the temperature and pressure of 150 mL displayed in real time, stirring at the magnetic stirring speed of 380r/min, heating to the temperature of 180 ℃, and preserving heat for 10h.
After the reaction is finished, respectively using deionized water and absolute ethyl alcohol to alternatively centrifuge for 10 min at the rotation speed of 12000 r/min, washing for 3 times, and finally placing the precipitate into a blast drying oven at 70 ℃ for heat preservation for 7h, thus obtaining the approximately spherical molybdenum disulfide-carbon powder material.
Example 4
Respectively weighing 0.66g of ammonium heptamolybdate and 3.4g of thiourea, stirring at room temperature, dissolving in 80 mL deionized water, adding 0.04g of glucose, stirring uniformly, adding 0.33g of PVP, stirring at room temperature for 1 h, transferring the solution to a miniature magnetic stirring autoclave with the temperature and pressure of 150 mL displayed in real time, stirring at the magnetic stirring speed of 400r/min, heating to 260 ℃, and preserving heat for 6h.
After the reaction is finished, respectively using deionized water and absolute ethyl alcohol to alternatively centrifuge for 10 min at the rotation speed of 12000 r/min, washing for 3 times, and finally placing the precipitate into a blast drying oven at 70 ℃ for heat preservation for 7h, thus obtaining the approximately spherical molybdenum disulfide-carbon powder material.
It should be noted that the above embodiments are only for illustrating the present invention, but the present invention is not limited to the above embodiments, and any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention falls within the protection scope of the present invention.
Claims (3)
1. The preparation method of the near-spherical molybdenum disulfide-carbon composite material for the lithium ion battery cathode is characterized by comprising the following steps of:
respectively weighing 0.66g of ammonium heptamolybdate and 1.42g of thiourea, stirring at room temperature to dissolve in 80 mL deionized water, adding 0.06g of glucose, stirring uniformly, adding 0.24g of PVP, stirring at room temperature to 1 h, transferring the solution to a miniature magnetic stirring autoclave with the temperature and pressure of 150 mL displayed in real time, adjusting the magnetic stirring speed to 400r/min, heating to 200 ℃, preserving heat for 7h, washing and drying the reaction product, and thus obtaining the near-spherical molybdenum disulfide-carbon composite material for the lithium ion battery cathode.
2. The method for preparing the near-spherical molybdenum disulfide-carbon composite material for the negative electrode of the lithium ion battery as claimed in claim 1, wherein the washing process is as follows: firstly, the reaction products are respectively and alternately centrifuged for 5 to 10 minutes by deionized water and absolute ethyl alcohol at the rotating speed of 10000 to 12000 r/min.
3. The method for preparing the near-spherical molybdenum disulfide-carbon composite material for the negative electrode of the lithium ion battery as claimed in claim 1, wherein the drying process is as follows: the reaction product is kept at the temperature of 65-75 ℃ for 7-12 h.
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