CN117049521A - MoS (MoS) 2 Modified nitrogen-doped carbon nano-sheet composite material and preparation and application thereof - Google Patents
MoS (MoS) 2 Modified nitrogen-doped carbon nano-sheet composite material and preparation and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 232
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 221
- 239000002135 nanosheet Substances 0.000 title claims abstract description 193
- 239000002131 composite material Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 161
- 239000002184 metal Substances 0.000 claims abstract description 161
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 103
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 86
- 239000008367 deionised water Substances 0.000 claims description 84
- 229910021641 deionized water Inorganic materials 0.000 claims description 84
- 239000000725 suspension Substances 0.000 claims description 54
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 54
- 239000004202 carbamide Substances 0.000 claims description 38
- 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 37
- 239000008103 glucose Substances 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 34
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 25
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 25
- 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 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 17
- -1 ammonium halide Chemical class 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 239000003607 modifier Substances 0.000 claims description 9
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 125000001477 organic nitrogen group Chemical group 0.000 claims description 6
- 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 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 54
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 27
- 239000007773 negative electrode material Substances 0.000 abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 11
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- 238000009830 intercalation Methods 0.000 abstract description 6
- 230000002687 intercalation Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000009831 deintercalation Methods 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 230000008595 infiltration Effects 0.000 abstract description 3
- 238000001764 infiltration Methods 0.000 abstract description 3
- 238000003760 magnetic stirring Methods 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 description 64
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 20
- 239000003273 ketjen black Substances 0.000 description 20
- 235000010413 sodium alginate Nutrition 0.000 description 20
- 229940005550 sodium alginate Drugs 0.000 description 20
- 239000000661 sodium alginate Substances 0.000 description 20
- 229910052786 argon Inorganic materials 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 14
- 239000006258 conductive agent Substances 0.000 description 14
- 239000002064 nanoplatelet Substances 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 239000011889 copper foil Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 150000001721 carbon Chemical class 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000011112 process operation Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000008240 homogeneous mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 239000004584 polyacrylic acid Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 150000002829 nitrogen Chemical class 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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
- H01M4/58—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
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/18—Nanoonions; Nanoscrolls; Nanohorns; Nanocones; Nanowalls
-
- 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
-
- 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
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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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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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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- 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
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- 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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Abstract
The invention belongs to the technical field of lithium battery material preparation, and discloses a MoS 2 The method for preparing the modified nitrogen-doped carbon nano sheet composite material and the application thereof comprises the following steps: (1) Adding an organic carbon source, a nitrogen source and a solvent into a mortar for full grinding to obtain a mixture; (2) Calcining the mixture in a tube furnace to obtain nitrogen-doped carbon nano sheets; (3) Modifying the nitrogen-doped carbon nano sheet to obtain modified nitrogen-doped carbon; (4) Will beAdding modified nitrogen-doped carbon nano-sheet into metal phase MoS 2 The precursor solution is subjected to magnetic stirring, hydrothermal treatment and vacuum drying to obtain the target composite material, the composite material is not excessively agglomerated, the tubular arrangement structure is convenient for infiltration of electrolyte, full intercalation and deintercalation of lithium ions are facilitated, the conductivity of the carbon material is improved, and the nitrogen-doped carbon serving as a negative electrode material of a lithium battery is guaranteed to have high-efficiency coulomb efficiency.
Description
Technical Field
The invention belongs to the technical field related to lithium battery materials, in particular to a lithium battery materialRelates to a MoS 2 A modified nitrogen-doped carbon nano-sheet composite material, and a preparation method and application thereof.
Background
Lithium Ion Batteries (LIBs) become the first choice of various energy storage devices because of the advantages of high energy conversion efficiency, no memory effect, good safety, green environmental protection and the like. The market development of lithium ion batteries is very rapid, and with the rapid development of electronic technology and information industry, lithium ion batteries have been widely used in portable electronic devices such as mobile phones, notebook computers, digital cameras, and the like, and in addition, the emphasis of further development of lithium ion batteries is focused on high-capacity and high-power lithium ion batteries and battery packs. Among them, the research and development of LIBs negative electrode materials is the key and technical core of lithium ion battery development. The graphite anode material is an anode material which is researched by people at the earliest and applied to the commercial production of lithium ion batteries, the theoretical specific capacity of the graphite anode material is only 372mAh/g, and the requirement of batteries with higher specific capacities cannot be met. In addition, the lithium intercalation potential of the graphite anode material is low (0-0.25V vs Li) + Li) is easy to precipitate lithium dendrite during overcharge, which causes short circuit of the battery and affects the safety performance of the lithium battery.
MoS 2 As a typical transition metal sulfide, the S-Mo-S layer spacing isAllowing lithium ions to intercalate between the layers, the intercalation potential being between 0.3 and 1.8V vs Li + And between Li and Li, the safety performance is superior to that of graphite anode materials. Furthermore, moS 2 The theoretical specific capacity (800-1000 mAh/g) of the LIBs as the negative electrode material is about 3 times of that of the carbon material, and the energy density of the LIBs can be greatly improved. MoS (MoS) 2 Has two crystal structures of a semiconductor phase and a metal phase, and the metal phase MoS 2 Not only can effectively insert and remove Li + Its excellent conductivity ensures metal phase MoS 2 Has high coulombic efficiency as LIBs cathode material. However, metallic phase MoS 2 Is a metastable phase, has higher preparation and storage difficulty, is easy to be converted from a metal phase into a 2H phase with poor conductivity, and has large sizeThe magnitude reduces its coulombic efficiency as LIBs negative electrode material. In addition, metal phase MoS 2 Li intercalation and deintercalation as LIBs negative electrode material + After which MoS is easily caused 2 Cracking and decomposition into Mo nanoparticles and less conductive LiS 2 Ultimately resulting in metal phase MoS 2 The coulombic efficiency as LIBs negative electrode material is greatly reduced.
Therefore, how to design and prepare MoS with high capacity, high stability and low price more simply, conveniently and reasonably 2 The negative electrode material is one of the technical problems to be solved in the art.
Disclosure of Invention
In response to the above-identified deficiencies or improvements in the prior art, the present invention provides a tubular arrangement of metal phases MoS 2 Modified nitrogen-doped carbon nano-sheet composite anode material and preparation method and application thereof. By the electrochemical reaction kinetics mechanism and MoS of key components thereof 2 Phase-control, nitrogen-doped carbon nano-sheet and MoS 2 Microcosmic form control, proportioning regulation and control and other means to obtain novel tubular arranged metal phase MoS 2 Modifying the nitrogen-doped carbon nano-sheet composite anode system. Compared with the existing product, the metal phase MoS 2 In a tubular arrangement without excessive agglomeration, and the metal phase MoS in the tubular arrangement 2 The electrolyte is convenient to infiltrate, and the rapid intercalation and deintercalation of lithium ions are facilitated. The nitrogen-doped carbon nano sheet improves the conductivity of the carbon material through element doping, and ensures that the nitrogen-doped carbon has high-efficiency coulomb efficiency as LIBs negative electrode material. In addition, the nitrogen-doped carbon nano-sheet takes cheap glucose and urea as a carbon source and a nitrogen source, so that the preparation cost is greatly reduced. The invention arranges metal phases MoS in a tubular manner 2 And nitrogen doped carbon nano-sheet, which not only ensures the metal phase MoS in tubular arrangement 2 The modified nitrogen-doped carbon nano-sheet composite anode material has high specific capacity and high coulomb efficiency, and simultaneously ensures metal phase MoS 2 Has excellent stability and effectively inhibits metal phase MoS 2 Li is inserted and extracted in circulation + Decomposition in the process.
To achieve the above object, according to one aspect of the present inventionThe invention firstly provides a MoS 2 The preparation method of the modified nitrogen-doped carbon nano sheet composite material comprises the following steps:
(1) Adding an organic carbon source, an organic nitrogen source and a solvent into a mortar for full grinding, so as to obtain a uniform mixture of the organic carbon source and the organic nitrogen source;
(2) Calcining the mixture in a tube furnace to obtain nitrogen-doped carbon nano sheets;
(3) Mixing a nitrogen-doped carbon nano sheet, an aqueous solution containing an organic ammonium halide modifier and deionized water to obtain a suspension, magnetically stirring the suspension, and then carrying out suction filtration, washing and drying to obtain a modified nitrogen-doped carbon nano sheet;
(4) Adding the modified nitrogen-doped carbon nano-sheet into metal phase MoS 2 Obtaining a suspension from the precursor solution, magnetically stirring, hydrothermally treating and vacuum drying the suspension to obtain tubular metal phase MoS 2 Modifying the nitrogen-doped carbon nano-sheet composite material.
Further, in the step (1), the organic carbon source is glucose, sucrose or citric acid, preferably glucose; the organic nitrogen source is urea, melamine, dicyandiamide, or polyaniline, preferably urea; the solvent is absolute ethyl alcohol or deionized water, preferably absolute ethyl alcohol.
Further, the ratio of glucose, urea and absolute ethyl alcohol in the step (1) is (4-8 g): (3-10 g): (5-8 ml).
Further, the calcining temperature in the step (2) is 650-700 ℃, and the heating rate is 5-8 ℃/min.
Further, the organic ammonium halide modifier in the step (3) is preferably polydiallyl dimethyl ammonium chloride or cetyl trimethyl ammonium bromide or dodecyl trimethyl ammonium bromide, and the mass fraction of the organic ammonium halide modifier in the aqueous solution thereof is 30-40%.
Further, the dosage ratio of the nitrogen doped carbon, the organic ammonium chloride modifier and the deionized water in the step (3) is 1-1.5 g: 2-3 ml: 100-150 ml.
Further, the suspension in the step (4) is prepared by the following steps of: 2-3 g: 60-80 ml:1 to 1.5g of ammonium molybdate tetrahydrate, thiourea, deionized water and modified nitrogen-doped carbon nano-sheets; or the dosage ratio is 4.5-5.5 g: 2-3 g: 60-80 ml:1 to 1.5g of ammonium tetrathiomolybdate, thiourea, deionized water and modified nitrogen-doped carbon nano-sheets; the suspension is stirred for 0.5-2 hours.
Further, the temperature of the hydrothermal treatment of the suspension in the step (4) is 170-220 ℃, and the hydrothermal treatment time is 10-24 hours, so that the internal structure of the tubular arrangement is obtained.
According to another aspect of the present invention, there is also provided a tubular aligned metal phase MoS prepared by the preparation method 2 Modifying the nitrogen-doped carbon nano-sheet composite anode material.
According to another aspect of the present invention, there is also provided the above-mentioned tubular aligned metal phase MoS 2 Application of the modified nitrogen-doped carbon nano-sheet composite anode material in lithium batteries.
Further, in the above application, the metal phase MoS is arranged in a tubular form 2 Uniformly mixing the modified nitrogen-doped carbon nano-sheet composite anode material, a conductive agent, a binder and deionized water, and adopting a tabletting process to align metal phases MoS in a tubular manner 2 And coating the modified nitrogen-doped carbon nano-sheet composite negative electrode material on a current collector copper foil to obtain a negative electrode plate.
Further, the conductive agent is at least one of ketjen black, super P, acetylene black, carbon fiber and carbon nano tube; the binder is at least one of sodium alginate, polyacrylic acid and polyvinylidene fluoride; wherein the metal phase MoS is arranged in a tubular manner 2 The mass ratio of the modified nitrogen-doped carbon nano-sheet composite anode material to the conductive agent to the binder is (0.6-0.8): (0.1-0.2): (0.1-0.2).
In general, compared with the prior art, the technical proposal designed by the invention provides a tubular arranged metal phase MoS 2 The modified nitrogen-doped carbon nano-sheet composite anode material and the preparation method and application thereof mainly have the following beneficial effects:
1. pipes prepared according to the inventionMetal phase MoS arranged in a like manner 2 MoS in modified nitrogen-doped carbon nano sheet composite anode material 2 The nano sheets are arranged into a tube shape, which is convenient for the infiltration of electrolyte and avoids MoS 2 Agglomeration of the nano-sheets, and due to the introduced nitrogen-doped carbon material, not only metal phase MoS can be effectively inhibited 2 Li is inserted and extracted in circulation + In-process decomposition, which also has high coulombic efficiency and high specific capacity, thus ensuring MoS 2 The stability of the nano sheet solves the problems of low specific capacity and Li embedding of carbon as LIBs negative electrode material + The potential is too low.
2. The invention adopts cheap glucose and urea as carbon source and nitrogen source of the nitrogen-doped carbon nano-sheet negative electrode material, greatly reduces the preparation cost of nitrogen-doped carbon, and can realize large-scale industrialized production.
3. The tubular metal phase MoS prepared by the invention 2 The modified nitrogen-doped carbon nano-sheet composite anode material can effectively ensure MoS by strictly controlling the temperature and time of hydrothermal treatment 2 Is a metallic phase. Metal phase MoS 2 With an octahedral structure, efficient coulombic efficiency can be achieved as an electron transport channel.
4. According to the invention, the nitrogen-doped carbon nano-sheet is subjected to surface modification by the organic ammonium halide modifier, so that the surface of the nitrogen-doped carbon nano-sheet is positively charged. The surface of the modified nitrogen-doped carbon nano sheet can effectively adsorb molybdate ions, and ensure metal phase MoS 2 The nano-sheet grows uniformly and fully on the surface of the modified nitrogen-doped carbon nano-sheet, and finally the metal phase MoS is obtained 2 Tubular arranged metal phase MoS with uniformly distributed nanosheets 2 Modifying the nitrogen-doped carbon nano-sheet.
5. The tubular metal phase MoS prepared by the invention 2 The modified nitrogen-doped carbon nano-sheet composite anode material is one of ideal anode materials of lithium batteries, and has excellent cycling stability and high specific capacity.
Drawings
FIG. 1 is a metal phase MoS in tubular arrangement as provided in example 1 of the present invention 2 A preparation method of the modified nitrogen-doped carbon nano-sheet composite material and a flow diagram of performance verification;
FIG. 2 is a metal phase MoS in tubular arrangement prepared in example 1 of the present invention 2 Modifying the XRD pattern of the nitrogen-doped carbon nano-sheet composite material;
FIG. 3 is an SEM image and an energy spectrum of a nitrogen-doped carbon nano-sheet prepared in example 1 of the present invention;
FIG. 4 shows a metal phase MoS in tubular arrangement prepared in example 1 of the present invention 2 Modifying SEM (scanning electron microscope) images and energy spectrograms of the nitrogen-doped carbon nano sheet composite material;
FIG. 5 shows a metal phase MoS in tubular arrangement prepared in example 1 of the present invention 2 Room temperature charge-discharge cycle test chart of lithium battery cathode prepared by modifying nitrogen-doped carbon nano-sheet composite cathode material.
Detailed Description
The present invention will be described in further detail with reference to the drawings and 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. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The present invention will be described in further detail with reference to the drawings and 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. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention uses the key composition components of the cathode material and the electrochemical reaction kinetics mechanism and MoS of the cathode material 2 Phase control, carbon material element doping, nitrogen doped carbon nano sheet and MoS 2 Microcosmic morphology control and proportioning regulation to obtain novel tubular arranged metal phase MoS 2 Modifying the nitrogen-doped carbon nano-sheet composite anode system. Compared with the existing product, the metal phase MoS 2 In a tubular arrangement without excessive agglomeration, and the metal phase MoS in the tubular arrangement 2 Facilitating electrolyteInfiltration is beneficial to rapid intercalation and deintercalation of lithium ions. The nitrogen-doped carbon nano sheet improves the conductivity of the carbon material through element doping, and ensures that the nitrogen-doped carbon has high-efficiency coulomb efficiency as LIBs negative electrode material. In addition, the nitrogen-doped carbon nano-sheet takes cheap glucose and urea as a carbon source and a nitrogen source, so that the preparation cost is greatly reduced. The invention arranges metal phases MoS in a tubular manner 2 Combined with the nitrogen-doped carbon nano-sheet, ensures the metal phase MoS in tubular arrangement 2 The modified nitrogen-doped carbon nano-sheet composite anode material has high specific capacity and high coulomb efficiency, and simultaneously ensures metal phase MoS 2 Has excellent stability and effectively inhibits metal phase MoS 2 Li is inserted and extracted in circulation + Decomposition in the process. At the same time, metal phases MoS are arranged in a tubular manner 2 The modified nitrogen-doped carbon nano-sheet composite anode system can be coated on an anode current collector copper foil, has the advantages of simplicity in operation, strong applicability, good stability and the like, and is one of ideal anode materials for constructing a high-energy-density secondary lithium battery.
Referring to FIG. 1, the present invention provides a metal phase MoS in tubular arrangement 2 The preparation method of the modified nitrogen-doped carbon nano-sheet composite anode material comprises the following steps:
the preparation method mainly comprises the following substeps: adding glucose, urea and absolute ethyl alcohol into a mortar for full grinding to obtain a uniform mixture of the glucose and the urea; calcining the mixture in a tube furnace to obtain a nitrogen-doped carbon nano sheet; mixing nitrogen-doped carbon, polydiallyl dimethyl ammonium chloride or hexadecyl trimethyl ammonium bromide or dodecyl trimethyl ammonium bromide aqueous solution with deionized water and magnetically stirring to obtain a modified nitrogen-doped carbon nano sheet; mixing ammonium molybdate tetrahydrate, thiourea and deionized water or ammonium tetrathiomolybdate and deionized water and magnetically stirring to obtain uniform metal phase MoS 2 A precursor solution; mixing the modified nitrogen-doped carbon nano-sheet with metal phase MoS 2 Mixing the precursor solutions, magnetically stirring to obtain a suspension, performing hydrothermal treatment, suction filtration washing and vacuum drying on the suspension to obtain tubular metal phase MoS 2 Modified nitrogen doped carbon nano-sheet compositeA material. The nitrogen doped carbon nano-sheet obtained by uniformly mixing urea serving as a nitrogen source and glucose serving as a carbon source and calcining the urea serving as the nitrogen source has excellent conductivity, and the coulomb efficiency of the nitrogen doped carbon nano-sheet serving as a LIBs negative electrode material is improved. The defect concentration of the carbon nano sheet is improved through nitrogen element doping, more defects are built in the carbon nano sheet, and more Li is facilitated + To increase its specific capacity. In addition, the surfaces of the nitrogen-doped carbon nano-sheets are modified by using polydiallyl dimethyl ammonium chloride or hexadecyl trimethyl ammonium bromide or dodecyl trimethyl ammonium bromide so that the surfaces of the nitrogen-doped carbon nano-sheets have sufficient positive charges, and the nitrogen-doped carbon nano-sheets which are modified subsequently are beneficial to MoS in a metal phase 2 Adsorption of molybdate ions in precursor solution, ensuring metal phase MoS 2 Uniformly growing on the surface of the nitrogen-doped carbon nano sheet. Growing metal phase MoS on the surface of the modified nitrogen-doped carbon nano sheet by hydrothermal method 2 Nano-sheet, metal phase MoS is improved 2 Inhibit metal phase MoS during cyclic charge and discharge 2 At the same time, metal phase MoS 2 The nano sheet and the nitrogen doped carbon nano sheet have high specific capacity after being compounded, and the problem of low specific capacity of the carbon anode material is effectively solved. In addition to this, metal phase MoS 2 The nano sheets are arranged in a tubular shape on the surface of the nitrogen-doped carbon nano sheet, so that metal phase MoS is ensured 2 Full contact and infiltration of the nano-sheet and electrolyte are beneficial to Li + Is fast in and out of the (c). Metal phase MoS in tubular arrangement 2 The modified nitrogen-doped carbon nano-sheet composite anode system can be coated on an anode current collector copper foil and has the advantages of simplicity in operation, strong applicability, good stability, low cost and the like.
The preparation method mainly comprises the following steps:
and firstly, fully grinding glucose, urea and absolute ethyl alcohol in a mortar to ensure that the glucose and the urea are uniformly mixed, and further obtaining a uniform mixture of the glucose and the urea.
In some embodiments, glucose, urea and absolute ethanol are added to a mortar in a ratio of 4-8 g:3-10 g:5-8 ml and milled for 15-30 minutes to obtain a uniform mixture of glucose and urea.
Calcining the uniform mixture of glucose and urea in a tube furnace to obtain the nitrogen-doped carbon nano-sheet.
In some embodiments, the homogeneous mixture of glucose and urea is placed in a boat of alumina, and then the boat is placed in a tube furnace; introducing argon-hydrogen mixed gas with the volume ratio of 90-95:5-10 into a tubular furnace for 15-20 minutes to empty the air in the tubular furnace; heating to 650-700 ℃ at a heating rate of 5-8 ℃/min and preserving heat for 2-3 hours to obtain the nitrogen doped nano-sheet.
And thirdly, mixing the nitrogen-doped carbon nano-sheet, polydiallyl dimethyl ammonium chloride water or hexadecyl trimethyl ammonium bromide or dodecyl trimethyl ammonium bromide solution with deionized water to obtain a suspension, magnetically stirring the current suspension, and then carrying out suction filtration and washing to obtain the modified nitrogen-doped carbon.
In some embodiments, the mass fraction of the polydiallyl dimethyl ammonium chloride or cetyl trimethyl ammonium bromide or dodecyl trimethyl ammonium bromide aqueous solution is 35%; the dosage ratio of the nitrogen doped carbon, the polydiallyl dimethyl ammonium chloride or the hexadecyl trimethyl ammonium bromide or the dodecyl trimethyl ammonium bromide aqueous solution and the deionized water is 1 to 1.5g: 2-3 ml: 100-150 ml; the magnetic stirring time of the suspension is 2-3 hours; the dispersant used in the washing process is deionized water, and the washing times are 3-5 times.
Step four, adding the modified nitrogen-doped carbon nano-sheet into a metal phase MoS 2 Obtaining a suspension from the precursor solution, and sequentially performing magnetic stirring, hydrothermal treatment and vacuum drying on the current suspension to obtain tubular-arrangement metal phase MoS 2 Modifying the nitrogen-doped carbon nano-sheet composite material.
Mixing ammonium molybdate tetrahydrate, thiourea and deionized water or mixing ammonium tetrathiomolybdate and deionized water, and magnetically stirring to obtain uniform metal phase MoS 2 Precursor solution.
In some embodiments, ammonium molybdate tetrahydrate, thiourea and deionized water or ammonium tetrathiomolybdate and deionized water are mixed and magnetically stirred for 0.5 to 2 hoursObtaining uniform metal phase MoS 2 A precursor solution; next, modified nitrogen-doped carbon is added to the metallic phase MoS 2 The precursor solution is prepared into suspension, and the dosage ratio of ammonium molybdate tetrahydrate, thiourea, deionized water and modified nitrogen doped carbon is 2.5-3.5 g: 2-3 g: 60-80 ml:1 to 1.5g; or the dosage ratio of the ammonium tetrathiomolybdate, deionized water and modified nitrogen-doped carbon is 4.5 to 5.5g: 60-80 ml:1 to 1.5g, and continuously magnetically stirring the suspension for 0.5 to 2 hours; then, carrying out hydrothermal treatment on the suspension for 12-24 hours at 170-220 ℃; then vacuum drying at 60-80 ℃ to obtain tubular arranged metal phase MoS 2 Modifying the nitrogen-doped carbon nano-sheet composite material.
The obtained metal phase MoS with tubular arrangement 2 The modified nitrogen-doped carbon nano sheet composite material is applied to a lithium battery anode material, and specifically: metal phase MoS of tubular arrangement to be prepared 2 Uniformly mixing the modified nitrogen-doped carbon nano-sheet composite anode material, a conductive agent, a binder and deionized water, and adopting tabletting to arrange metal phase MoS in a tubular manner 2 And coating the modified nitrogen-doped carbon nano-sheet composite negative electrode material on a current collector copper foil to obtain a negative electrode plate. Wherein the conductive agent is at least one of ketjen black, super P, acetylene black, carbon fiber and carbon nano tube; the binder is at least one of sodium alginate, polyacrylic acid and polyvinylidene fluoride; metal phase MoS in tubular arrangement 2 The dosage ratio of the modified nitrogen-doped carbon nano-sheet composite anode material, the conductive agent, the binder and the deionized water is 0.6-0.8 g:0.1 to 0.2g:0.1 to 0.2g: 5-12 ml.
The invention is described in further detail below with reference to a few specific examples.
Example 1
Referring to fig. 2, 3 and 4, the metal phase MoS in the tubular arrangement in the present embodiment 2 The modified nitrogen-doped carbon nano-sheet composite anode material comprises metal phase MoS which is arranged in a tubular manner 2 Nanoplatelets and nitrogen doped carbon nanoplatelets. Wherein the metallic phase molybdenum sulfide precursor solution consists of ammonium molybdate tetrahydrate, thiourea and deionized water; the metal phase MoS in tubular arrangement 2 Modified nitrogen-doped carbon nano-sheet composite negative electrodeMetal phase MoS in pole material 2 The mass ratio of the carbon doped with nitrogen is 2:1, a step of; the conductive agent and the binder are ketjen black and sodium alginate; metal phase MoS in tubular arrangement 2 The modified nitrogen-doped carbon nano-sheet composite material cathode is prepared by adopting a tabletting process.
The process operation steps of this example are as follows:
(1) 5g glucose, 5g urea and 6mL absolute ethanol were added to a mortar and ground for 30 minutes to completely volatilize the absolute ethanol and obtain a homogeneous mixture of glucose and urea.
(2) Placing the uniform mixture of glucose and urea into a burning boat, and then placing the burning boat into a tube furnace; argon is firstly introduced into the tube furnace, and the volume ratio of the argon to the hydrogen is 90:10, then raising the temperature to 670 ℃ at a heating rate of 5 ℃/min, and then preserving the temperature for 1 hour to obtain the nitrogen-doped carbon nano-sheet.
(3) Nitrogen-doped carbon nano-sheets, polydiallyl dimethyl ammonium chloride aqueous solution and deionized water are mixed according to the weight ratio of 1.5g:2ml: mixing according to the proportion of 100ml, magnetically stirring for 2 hours, and then carrying out suction filtration and washing for 3 times by using deionized water to obtain the modified nitrogen-doped carbon nano-sheet. Wherein the mass fraction of the polydiallyl dimethyl ammonium chloride aqueous solution is 35%.
(4) Mixing ammonium molybdate tetrahydrate, thiourea and deionized water and magnetically stirring for 2 hours to obtain uniform metal phase MoS 2 A precursor solution; next, modified nitrogen-doped carbon is added to the metallic phase MoS 2 The precursor solution gave a suspension with an amount ratio of ammonium molybdate tetrahydrate, thiourea, deionized water and modified nitrogen-doped carbon of 3.5g:1.5g:80ml:1.5g, and the suspension is magnetically stirred for 1.5 hours; then, the suspension was hydrothermally treated at 200 ℃ for 12 hours; the suspension is then filtered and washed 3 times with deionized water and then vacuum dried at 60 ℃ to obtain metal phase MoS in tubular arrangement 2 Modifying the nitrogen-doped carbon nano-sheet composite material.
(5) Metal phase MoS of tubular arrangement to be prepared 2 Uniformly mixing the modified nitrogen-doped carbon nano-sheet composite anode material, ketjen black, sodium alginate and deionized water, and tabletting to obtain tubular metal phase MoS 2 And coating the modified nitrogen-doped carbon nano-sheet composite negative electrode material on a current collector copper foil to obtain a negative electrode plate. Wherein the metal phase MoS is arranged in a tubular manner 2 The dosage ratio of the modified nitrogen-doped carbon nano-sheet composite anode material to ketjen black to sodium alginate to deionized water is 0.6g:0.2g:0.2g:10ml.
Testing tubular arranged metal phases MoS 2 The modified nitrogen-doped carbon nano-sheet composite anode material is assembled into Li// tubular arranged metal phase MoS 2 Modifying the cycle performance of the negative electrode of the lithium battery of the nitrogen-doped carbon nano sheet, and 1000mAh g at room temperature -1 Metal phase MoS arranged in tubular form at current density 2 Specific capacity of modified nitrogen-doped carbon nano-sheet composite anode material system is 792mAh g -1 The specific capacity is 814mAh g after 100 charge and discharge cycles -1 。
Example 2
The tubular aligned metal phase MoS in this embodiment 2 The modified nitrogen-doped carbon nano-sheet composite anode material comprises metal phase MoS which is arranged in a tubular manner 2 Nanoplatelets and nitrogen doped carbon nanoplatelets. Wherein the metallic phase molybdenum sulfide precursor solution consists of ammonium molybdate tetrahydrate, thiourea and deionized water; the metal phase MoS in tubular arrangement 2 Metal phase MoS in modified nitrogen-doped carbon nano-sheet composite anode material 2 The mass ratio of the carbon doped with nitrogen is 1.5:1, a step of; the conductive agent and the binder are ketjen black and sodium alginate; metal phase MoS in tubular arrangement 2 The modified nitrogen-doped carbon nano-sheet composite material cathode is prepared by adopting a tabletting process.
The process operation steps of this example are as follows:
(1) 5g glucose, 6g urea and 6mL absolute ethanol were added to a mortar and ground for 30 minutes to completely volatilize the absolute ethanol and obtain a homogeneous mixture of glucose and urea.
(2) Placing the uniform mixture of glucose and urea into a burning boat, and then placing the burning boat into a tube furnace; argon is firstly introduced into the tube furnace, and the volume ratio of the argon to the hydrogen is 90:10, and then raising the temperature to 670 ℃ at a heating rate of 5 ℃/min, and then preserving the temperature for 1 hour, thereby obtaining the nitrogen-doped carbon nano-sheet.
(3) Nitrogen-doped carbon nano-sheets, polydiallyl dimethyl ammonium chloride aqueous solution and deionized water are mixed according to the weight ratio of 1.5g:2ml: mixing according to the proportion of 100ml, magnetically stirring for 2 hours, and then carrying out suction filtration and washing for 3 times by using deionized water to obtain the modified nitrogen-doped carbon nano-sheet. Wherein the mass fraction of the polydiallyl dimethyl ammonium chloride aqueous solution is 35%.
(4) Mixing ammonium molybdate tetrahydrate, thiourea and deionized water and magnetically stirring for 2 hours to obtain uniform metal phase MoS 2 A precursor solution; next, modified nitrogen-doped carbon is added to the metallic phase MoS 2 The precursor solution gave a suspension with an amount ratio of ammonium molybdate tetrahydrate, thiourea, deionized water and modified nitrogen-doped carbon of 3.5g:1.5g:80ml:2.25g, and the suspension is magnetically stirred for a further 1.5 hours; then, the suspension was hydrothermally treated at 200 ℃ for 12 hours; the suspension is then filtered and washed 3 times with deionized water and then vacuum dried at 60 ℃ to obtain metal phase MoS in tubular arrangement 2 Modifying the nitrogen-doped carbon nano-sheet composite material.
(5) Metal phase MoS of tubular arrangement to be prepared 2 Uniformly mixing the modified nitrogen-doped carbon nano-sheet composite anode material, ketjen black, sodium alginate and deionized water, and tabletting to obtain tubular metal phase MoS 2 And coating the modified nitrogen-doped carbon nano-sheet composite negative electrode material on a current collector copper foil to obtain a negative electrode plate. Wherein the metal phase MoS is arranged in a tubular manner 2 The dosage ratio of the modified nitrogen-doped carbon nano-sheet composite anode material to ketjen black to sodium alginate to deionized water is 0.8g:0.1g:0.1g:10ml.
Testing tubular arranged metal phases MoS 2 The modified nitrogen-doped carbon nano-sheet composite anode material is assembled into Li// tubular arranged metal phase MoS 2 Modifying the cycle performance of the negative electrode of the lithium battery of the nitrogen-doped carbon nano sheet, and 1000mAh g at room temperature -1 Metal phase MoS arranged in tubular form at current density 2 The specific capacity of the modified nitrogen-doped carbon nano-sheet composite anode material system is 723mAh g -1 The specific capacity is 715mAh g after 100 charge and discharge cycles -1 。
Example 3
The tubular aligned metal phase MoS in this embodiment 2 The modified nitrogen-doped carbon nano-sheet composite anode material comprises metal phase MoS which is arranged in a tubular manner 2 Nanoplatelets and nitrogen doped carbon nanoplatelets. Wherein the metallic phase molybdenum sulfide precursor solution consists of ammonium tetrathiomolybdate and deionized water; the metal phase MoS in tubular arrangement 2 Metal phase MoS in modified nitrogen-doped carbon nano-sheet composite anode material 2 The mass ratio of the carbon doped with nitrogen is 2:1, a step of; the conductive agent and the binder are ketjen black and sodium alginate; metal phase MoS in tubular arrangement 2 The modified nitrogen-doped carbon nano-sheet composite material cathode is prepared by adopting a tabletting process.
The process operation steps of this example are as follows:
(1) 5g glucose, 5g urea and 6mL absolute ethanol were added to a mortar and ground for 30 minutes to completely volatilize the absolute ethanol and obtain a homogeneous mixture of glucose and urea.
(2) Placing the uniform mixture of glucose and urea into a burning boat, and then placing the burning boat into a tube furnace; argon is firstly introduced into the tube furnace, and the volume ratio of the argon to the hydrogen is 90:10, and then raising the temperature to 670 ℃ at a heating rate of 5 ℃/min, and then preserving the temperature for 1 hour, thereby obtaining the nitrogen-doped carbon nano-sheet.
(3) Nitrogen-doped carbon nano-sheets, polydiallyl dimethyl ammonium chloride aqueous solution and deionized water are mixed according to the weight ratio of 1.5g:2ml: mixing according to the proportion of 100ml, magnetically stirring for 2 hours, and then carrying out suction filtration and washing for 3 times by using deionized water to obtain the modified nitrogen-doped carbon nano-sheet. Wherein the mass fraction of the polydiallyl dimethyl ammonium chloride aqueous solution is 35%.
(4) Mixing ammonium tetrathiomolybdate and deionized water and magnetically stirring for 1.5 hours to obtain uniform metal phase MoS 2 A precursor solution; next, modified nitrogen-doped carbon is added to the metallic phase MoS 2 The precursor solution gave a suspension with an amount ratio of ammonium tetrathiomolybdate, deionized water and modified nitrogen-doped carbon of 4.5g:80ml:2.25g, and the suspension is magnetically stirred for a further 1.5 hours; then, the suspension was hydrothermally treated at 200 ℃ for 24 hours; the suspension is then filtered and washed 3 times with deionized water and then vacuum dried at 60 ℃ to obtain metal phase MoS in tubular arrangement 2 Modifying the nitrogen-doped carbon nano-sheet composite material.
(5) Metal phase MoS of tubular arrangement to be prepared 2 Uniformly mixing the modified nitrogen-doped carbon nano-sheet composite anode material, ketjen black, sodium alginate and deionized water, and tabletting to obtain tubular metal phase MoS 2 And coating the modified nitrogen-doped carbon nano-sheet composite negative electrode material on a current collector copper foil to obtain a negative electrode plate. Wherein the metal phase MoS is arranged in a tubular manner 2 The dosage ratio of the modified nitrogen-doped carbon nano-sheet composite anode material to ketjen black to sodium alginate to deionized water is 0.6g:0.2g:0.2g:10ml.
Testing tubular arranged metal phases MoS 2 The modified nitrogen-doped carbon nano-sheet composite anode material is assembled into Li// tubular arranged metal phase MoS 2 Modifying the cycle performance of the negative electrode of the lithium battery of the nitrogen-doped carbon nano sheet, and 1000mAh g at room temperature -1 Metal phase MoS arranged in tubular form at current density 2 Specific capacity of modified nitrogen-doped carbon nano-sheet composite anode material system is 783mAh g -1 The specific capacity is 775mAh g after 100 charge and discharge cycles -1 。
Example 4
The tubular aligned metal phase MoS in this embodiment 2 The modified nitrogen-doped carbon nano-sheet composite anode material comprises metal phase MoS which is arranged in a tubular manner 2 Nanoplatelets and nitrogen doped carbon nanoplatelets. Wherein the metallic phase molybdenum sulfide precursor solution consists of ammonium molybdate tetrahydrate, thiourea and deionized water; the metal phase MoS in tubular arrangement 2 Metal phase MoS in modified nitrogen-doped carbon nano-sheet composite anode material 2 The mass ratio of the carbon doped with nitrogen is 2:1, a step of; the conductive agent and the binder are Super P and polyacrylic acid; metal phase MoS in tubular arrangement 2 The modified nitrogen-doped carbon nano-sheet composite material cathode is prepared by adopting a tabletting process.
The process operation steps of this example are as follows:
(1) 5g glucose, 5g urea and 6mL absolute ethanol were added to a mortar and ground for 30 minutes to completely volatilize the absolute ethanol and obtain a homogeneous mixture of glucose and urea.
(2) Placing the uniform mixture of glucose and urea into a burning boat, and then placing the burning boat into a tube furnace; argon is firstly introduced into the tube furnace, and the volume ratio of the argon to the hydrogen is 90:10, and then raising the temperature to 670 ℃ at a heating rate of 5 ℃/min, and then preserving the temperature for 1 hour, thereby obtaining the nitrogen-doped carbon nano-sheet.
(3) Nitrogen-doped carbon nano-sheets, polydiallyl dimethyl ammonium chloride aqueous solution and deionized water are mixed according to the weight ratio of 1.5g:2ml: mixing according to the proportion of 100ml, magnetically stirring for 2 hours, and then carrying out suction filtration and washing for 3 times by using deionized water to obtain the modified nitrogen-doped carbon nano-sheet. Wherein the mass fraction of the polydiallyl dimethyl ammonium chloride aqueous solution is 35%.
(4) Mixing ammonium tetrathiomolybdate and deionized water and magnetically stirring for 1.5 hours to obtain uniform metal phase MoS 2 A precursor solution; next, modified nitrogen-doped carbon is added to the metallic phase MoS 2 The precursor solution gave a suspension with an amount ratio of ammonium molybdate tetrahydrate, thiourea, deionized water and modified nitrogen-doped carbon of 3.5g:1.5g:80ml:1.5g, and the suspension is magnetically stirred for 1.5 hours; then, the suspension was hydrothermally treated at 200 ℃ for 24 hours; the suspension is then filtered and washed 3 times with deionized water and then vacuum dried at 60 ℃ to obtain metal phase MoS in tubular arrangement 2 Modifying the nitrogen-doped carbon nano-sheet composite material.
(5) Metal phase MoS of tubular arrangement to be prepared 2 Uniformly mixing the modified nitrogen-doped carbon nano-sheet composite anode material, super P, polyacrylic acid and deionized water, and tabletting to align metal phase MoS in a tubular shape 2 And coating the modified nitrogen-doped carbon nano-sheet composite negative electrode material on a current collector copper foil to obtain a negative electrode plate. Wherein the metal phase MoS is arranged in a tubular manner 2 The dosage ratio of the modified nitrogen-doped carbon nano-sheet composite anode material to Super P to polyacrylic acid to deionized water is 0.6g:0.2g:0.2g:10ml.
Testing tubular arranged metal phases MoS 2 The modified nitrogen-doped carbon nano-sheet composite anode material is assembled into Li// tubular arranged metal phase MoS 2 Modifying the cycle performance of the negative electrode of the lithium battery of the nitrogen-doped carbon nano sheet, and 1000mAh g at room temperature -1 Metal phase MoS arranged in tubular form at current density 2 Modifying nitrogenSpecific capacity of the carbon nano sheet doped composite anode material system is 792mAh g -1 After 100 charge and discharge cycles, the specific capacity is 786mAh g -1 。
Example 5
The tubular aligned metal phase MoS in this embodiment 2 The modified nitrogen-doped carbon nano-sheet composite anode material comprises metal phase MoS which is arranged in a tubular manner 2 Nanoplatelets and nitrogen doped carbon nanoplatelets. Wherein the metallic phase molybdenum sulfide precursor solution consists of ammonium molybdate tetrahydrate, thiourea and deionized water; the metal phase MoS in tubular arrangement 2 Metal phase MoS in modified nitrogen-doped carbon nano-sheet composite anode material 2 The mass ratio of the carbon doped with nitrogen is 2:1, a step of; the conductive agent and the binder are acetylene black and polyvinylidene fluoride; metal phase MoS in tubular arrangement 2 The modified nitrogen-doped carbon nano-sheet composite material cathode is prepared by adopting a tabletting process.
The process operation steps of this example are as follows:
(1) 5g glucose, 5g urea and 6mL absolute ethanol were added to a mortar and ground for 30 minutes to completely volatilize the absolute ethanol and obtain a homogeneous mixture of glucose and urea.
(2) Placing the uniform mixture of glucose and urea into a burning boat, and then placing the burning boat into a tube furnace; argon is firstly introduced into the tube furnace, and the volume ratio of the argon to the hydrogen is 90:10, and then raising the temperature to 670 ℃ at a heating rate of 5 ℃/min, and then preserving the temperature for 1 hour, thereby obtaining the nitrogen-doped carbon nano-sheet.
(3) Nitrogen-doped carbon nano-sheets, polydiallyl dimethyl ammonium chloride aqueous solution and deionized water are mixed according to the weight ratio of 1.5g:2ml: mixing according to the proportion of 100ml, magnetically stirring for 2 hours, and then carrying out suction filtration and washing for 3 times by using deionized water to obtain the modified nitrogen-doped carbon nano-sheet. Wherein the mass fraction of the polydiallyl dimethyl ammonium chloride aqueous solution is 35%.
(4) Mixing ammonium tetrathiomolybdate and deionized water and magnetically stirring for 0.5-2 hours to obtain uniform metal phase MoS 2 A precursor solution; next, modified nitrogen-doped carbon is added to the metallic phase MoS 2 Obtaining suspension in precursor solution, ammonium molybdate tetrahydrate, thiourea and deionized waterThe water to modified nitrogen doped carbon usage ratio was 3.5g:1.5g:80ml:1.5g, and the suspension is magnetically stirred for 1.5 hours; then, the suspension was hydrothermally treated at 200 ℃ for 24 hours; the suspension is then filtered and washed 3 times with deionized water and then vacuum dried at 60 ℃ to obtain metal phase MoS in tubular arrangement 2 Modifying the nitrogen-doped carbon nano-sheet composite material.
(5) Metal phase MoS of tubular arrangement to be prepared 2 Uniformly mixing the modified nitrogen-doped carbon nano-sheet composite anode material, acetylene black, polyvinylidene fluoride and deionized water, and tabletting to align metal phases MoS in a tubular manner 2 And coating the modified nitrogen-doped carbon nano-sheet composite negative electrode material on a current collector copper foil to obtain a negative electrode plate. Wherein the metal phase MoS is arranged in a tubular manner 2 The dosage ratio of the modified nitrogen-doped carbon nano-sheet composite anode material to the acetylene black to the polyvinylidene fluoride to the deionized water is 0.8g:0.1g:0.1g:10ml.
Testing tubular arranged metal phases MoS 2 The modified nitrogen-doped carbon nano-sheet composite anode material is assembled into Li// tubular arranged metal phase MoS 2 Modifying the cycle performance of the negative electrode of the lithium battery of the nitrogen-doped carbon nano sheet, and 1000mAh g at room temperature -1 Metal phase MoS arranged in tubular form at current density 2 Specific capacity of modified nitrogen-doped carbon nano-sheet composite anode material system is 783mAh g -1 The specific capacity is 766mAh g after 100 charge and discharge cycles -1 。
Example 6
The tubular aligned metal phase MoS in this embodiment 2 The modified nitrogen-doped carbon nano-sheet composite anode material comprises metal phase MoS which is arranged in a tubular manner 2 Nanoplatelets and nitrogen doped carbon nanoplatelets. Wherein the metallic phase molybdenum sulfide precursor solution consists of ammonium molybdate tetrahydrate, thiourea and deionized water; the metal phase MoS in tubular arrangement 2 Metal phase MoS in modified nitrogen-doped carbon nano-sheet composite anode material 2 The mass ratio of the carbon doped with nitrogen is 2:1, a step of; the conductive agent and the binder are ketjen black and sodium alginate; metal phase MoS in tubular arrangement 2 The modified nitrogen-doped carbon nano-sheet composite material cathode is prepared by adopting a tabletting process.
The process operation steps of this example are as follows:
(1) 5g glucose, 5g urea and 6mL absolute ethanol were added to a mortar and ground for 30 minutes to completely volatilize the absolute ethanol and obtain a homogeneous mixture of glucose and urea.
(2) Placing the uniform mixture of glucose and urea into a burning boat, and then placing the burning boat into a tube furnace; argon is firstly introduced into the tube furnace, and the volume ratio of the argon to the hydrogen is 95:5, then raising the temperature to 670 ℃ at a heating rate of 5 ℃/min, and then preserving the temperature for 1 hour to obtain the nitrogen-doped carbon nano-sheet.
(3) Nitrogen-doped carbon nano-sheets, hexadecyl trimethyl ammonium bromide aqueous solution and deionized water are mixed according to the weight ratio of 1.5g:2ml: mixing according to the proportion of 100ml, magnetically stirring for 2 hours, and then carrying out suction filtration and washing for 3 times by using deionized water to obtain the modified nitrogen-doped carbon nano-sheet. Wherein the mass fraction of the hexadecyl trimethyl ammonium bromide aqueous solution is 35%.
(4) Mixing ammonium molybdate tetrahydrate, thiourea and deionized water and magnetically stirring for 2 hours to obtain uniform metal phase MoS 2 A precursor solution; next, modified nitrogen-doped carbon is added to the metallic phase MoS 2 The precursor solution gave a suspension with an amount ratio of ammonium molybdate tetrahydrate, thiourea, deionized water and modified nitrogen-doped carbon of 3.5g:1.5g:80ml:1.5g, and the suspension is magnetically stirred for 1.5 hours; then, the suspension was hydrothermally treated at 200 ℃ for 12 hours; the suspension is then filtered and washed 3 times with deionized water and then vacuum dried at 60 ℃ to obtain metal phase MoS in tubular arrangement 2 Modifying the nitrogen-doped carbon nano-sheet composite material.
(5) Metal phase MoS of tubular arrangement to be prepared 2 Uniformly mixing the modified nitrogen-doped carbon nano-sheet composite anode material, ketjen black, sodium alginate and deionized water, and tabletting to obtain tubular metal phase MoS 2 And coating the modified nitrogen-doped carbon nano-sheet composite negative electrode material on a current collector copper foil to obtain a negative electrode plate. Wherein the metal phase MoS is arranged in a tubular manner 2 The dosage ratio of the modified nitrogen-doped carbon nano-sheet composite anode material to ketjen black to sodium alginate to deionized water is 0.8g:0.1g:0.1g:10ml.
Testing tubular arranged metal phases MoS 2 The modified nitrogen-doped carbon nano-sheet composite anode material is assembled into Li// tubular arranged metal phase MoS 2 Modifying the cycle performance of the negative electrode of the lithium battery of the nitrogen-doped carbon nano sheet, and 1000mAh g at room temperature -1 Metal phase MoS arranged in tubular form at current density 2 Specific capacity of modified nitrogen-doped carbon nano-sheet composite anode material system is 788mAh g -1 After 100 charge and discharge cycles, the specific capacity is 786mAh g -1 。
Comparative example 1
In this comparative example, metal phase MoS 2 The precursor solution consists of ammonium molybdate tetrahydrate, thiourea and deionized water; the conductive agent and the binder are ketjen black and sodium alginate; metal phase MoS in tubular arrangement 2 The nano sheet material cathode is prepared by adopting a tabletting process.
The process operation steps of this comparative example are as follows:
(1) Mixing ammonium molybdate tetrahydrate, thiourea and deionized water and magnetically stirring for 2 hours to obtain uniform metal phase MoS 2 A precursor solution; the dosage ratio of ammonium molybdate tetrahydrate, thiourea and deionized water was 3.5g:1.5g:80ml, the suspension is stirred magnetically for a further 1.5 hours; then, the solution was hydrothermally treated at 200 ℃ for 12 hours; the suspension is then filtered and washed 3 times with deionized water and then vacuum dried at 60 ℃ to obtain metal phase MoS in tubular arrangement 2 A nano-sheet.
(2) The prepared tubular arrangement MoS 2 Uniformly mixing the nano sheet negative electrode material, ketjen black, sodium alginate and deionized water, and tabletting to obtain tubular metal phase MoS 2 And coating the nano-sheet negative electrode material on a current collector copper foil to obtain a negative electrode plate. Wherein the metal phase MoS is arranged in a tubular manner 2 The dosage ratio of the nano-sheet cathode material, ketjen black, sodium alginate and deionized water is 0.8g:0.1g:0.1g:10ml.
Testing of pure MoS in tubular arrays 2 The nano-sheet negative electrode material is arranged into Li// tubular arrangement MoS 2 The cycle performance of the negative electrode of the lithium battery of the nano sheet is 1000mAh g at room temperature -1 Metal phase MoS arranged in tubular form at current density 2 NanosheetsThe specific capacity of the negative electrode material system is 853mAh g -1 The specific capacity is only 422mAh g after 100 charge and discharge cycles -1 。
Comparative example 2
Metal phase MoS in this comparative example 2 The modified carbon nano-sheet composite anode material comprises metal phase MoS 2 Nanoplatelets and carbon nanoplatelets. Wherein the metal phase MoS 2 The precursor solution consists of ammonium molybdate tetrahydrate, thiourea and deionized water; the metal phase MoS 2 Metal phase MoS in modified carbon nano sheet composite anode material 2 The mass ratio of the carbon to the carbon is 2:1, a step of; the conductive agent and the binder are ketjen black and sodium alginate; petal-shaped metal phase MoS 2 The modified carbon nano-sheet composite material cathode is prepared by adopting a tabletting process.
The process operation steps of this comparative example are as follows:
(1) Placing sucrose into a burning boat, and then placing the burning boat into a tube furnace; argon is firstly introduced into the tube furnace, and the volume ratio of the argon to the hydrogen is 90:10, and then raising the temperature to 670 ℃ at a heating rate of 5 ℃/min, and then preserving the temperature for 1 hour, thereby obtaining the carbon nano-sheet.
(2) Mixing ammonium molybdate tetrahydrate, thiourea and deionized water and magnetically stirring for 2 hours to obtain uniform metal phase MoS 2 A precursor solution; next, adding carbon nano-sheets to the metal phase MoS 2 The precursor solution is prepared into suspension, and the dosage ratio of the ammonium molybdate tetrahydrate, thiourea, deionized water and the carbon nano-sheet is 3.1g:2.8g:80ml:1.5g, and the suspension is magnetically stirred for 1.5 hours; then, the suspension was hydrothermally treated at 180 ℃ for 12 hours; filtering and washing the suspension with deionized water for 3 times, and vacuum drying at 60deg.C to obtain petal-shaped metal phase MoS 2 Modifying the carbon nano-sheet composite material.
(3) The prepared petal-shaped arrangement MoS 2 Uniformly mixing the modified carbon nano-sheet composite anode material, ketjen black, sodium alginate and deionized water, and tabletting to obtain petal-shaped arranged metal phase MoS 2 And coating the modified carbon nano-sheet composite negative electrode material on a current collector copper foil to obtain a negative electrode plate. Wherein, the metal phase MoS is arranged in a petal shape 2 The dosage ratio of the modified carbon nano-sheet composite anode material, ketjen black, sodium alginate and deionized water is 0.8g:0.1g:0.g:10ml.
Testing petal-shaped arrangement MoS 2 The modified carbon nano-sheet composite anode material is assembled into Li// petal-shaped arrangement MoS 2 Modifying the cycle performance of the negative electrode of the lithium battery of the carbon nano sheet, and 1000mAh g at room temperature -1 Petal-shaped arrangement MoS under current density 2 The specific capacity of the modified carbon nano-sheet composite anode material system is 635mAh g -1 After 100 charge and discharge cycles, the specific capacity is only 542mAh g -1 。
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. MoS (MoS) 2 The preparation method of the modified nitrogen-doped carbon nano sheet composite material is characterized by comprising the following steps of:
(1) Adding an organic carbon source, an organic nitrogen source and a solvent into a mortar for full grinding, so as to obtain a uniform mixture of the organic carbon source and the organic nitrogen source;
(2) Calcining the mixture in a tube furnace to obtain nitrogen-doped carbon nano sheets;
(3) Mixing a nitrogen-doped carbon nano sheet, an aqueous solution containing an organic ammonium halide modifier and deionized water to obtain a suspension, stirring the suspension, and then carrying out suction filtration, washing and drying to obtain a modified nitrogen-doped carbon nano sheet;
(4) Adding the modified nitrogen-doped carbon nano-sheet into metal phase MoS 2 Obtaining a suspension from the precursor solution, stirring, performing hydrothermal treatment and vacuum drying on the suspension to obtain tubular-arrangement metal phase MoS 2 Modifying the nitrogen-doped carbon nano-sheet composite material.
2. The method of claim 1, wherein the organic carbon source in step (1) is glucose, sucrose or citric acid, preferably glucose; the organic nitrogen source is urea, melamine, dicyandiamide, or polyaniline, preferably urea; the solvent is absolute ethyl alcohol or deionized water, preferably absolute ethyl alcohol.
3. The preparation method according to claim 2, wherein the ratio of glucose, urea and absolute ethanol in the step (1) is (4-8 g): (3-10 g): (5-8 ml).
4. The method according to claim 1, wherein the calcination temperature in the step (2) is 650 to 700 ℃ and the temperature rise rate is 5 to 8 ℃/min.
5. The preparation method according to claim 1, wherein the organic ammonium halide modifier in the step (3) is polydiallyl dimethyl ammonium chloride or hexadecyl trimethyl ammonium bromide or dodecyl trimethyl ammonium bromide, and the mass fraction of the organic ammonium halide modifier in the aqueous solution thereof is 30-40%.
6. The method according to claim 1, wherein the nitrogen-doped carbon, the organic ammonium halide modifier and the deionized water are used in the following ratio (1 to 1.5 g): (2-3 ml): (100-150 ml).
7. The method according to claim 1, wherein the suspension in step (4) is used in an amount of 2.5 to 3.5g: 2-3 g: 60-80 ml:1 to 1.5g of ammonium molybdate tetrahydrate, thiourea, deionized water and modified nitrogen-doped carbon nano-sheets;
or the dosage ratio is 4.5-5.5 g: 2-3 g: 60-80 ml:1 to 1.5g of ammonium tetrathiomolybdate, thiourea, deionized water and modified nitrogen-doped carbon nano-sheets;
the suspension is stirred for 0.5-2 hours.
8. The method according to claim 1 or 7, wherein the suspension is hydrothermally treated in step (4) at a temperature of 170 to 220 ℃ for a duration of 10 to 24 hours.
9. A MoS prepared by the method of any one of claims 1-8 2 Modifying the nitrogen-doped carbon nano-sheet composite material.
10. The MoS of claim 9 2 The application of the modified nitrogen-doped carbon nano-sheet composite material in the negative electrode of the lithium battery.
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