CN104681804A - Carbon-coated nano lithium titanate composite material as well as preparation method and application thereof - Google Patents
Carbon-coated nano lithium titanate composite material as well as preparation method and application thereof Download PDFInfo
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- CN104681804A CN104681804A CN201510055410.0A CN201510055410A CN104681804A CN 104681804 A CN104681804 A CN 104681804A CN 201510055410 A CN201510055410 A CN 201510055410A CN 104681804 A CN104681804 A CN 104681804A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 139
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 139
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 60
- 239000010936 titanium Substances 0.000 claims abstract description 24
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- 239000003990 capacitor Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 5
- 239000004064 cosurfactant Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 18
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- 238000000593 microemulsion method Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 13
- -1 polyoxy hexenyl ether Polymers 0.000 description 13
- 238000007599 discharging Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229920002472 Starch Polymers 0.000 description 8
- 239000008107 starch Substances 0.000 description 8
- 235000019698 starch Nutrition 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 5
- 239000005642 Oleic acid Substances 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 5
- 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 4
- 206010013786 Dry skin Diseases 0.000 description 4
- 229910013063 LiBF 4 Inorganic materials 0.000 description 4
- 229910013553 LiNO Inorganic materials 0.000 description 4
- 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 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 230000005518 electrochemistry Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 150000004702 methyl esters Chemical class 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000013504 Triton X-100 Substances 0.000 description 2
- 229920004890 Triton X-100 Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000000320 mechanical mixture Substances 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 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 1
- 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 1
- 230000008901 benefit Effects 0.000 description 1
- 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 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Nanotechnology (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a carbon-coated nano lithium titanate composite material and a preparation method thereof. The preparation method comprises the following steps: 1, preparing nano lithium titanate, namely, respectively preparing micro emulsions of a lithium source and a titanium source, mixing the two types of micro emulsion, standing, centrifuging, alternatively washing with an organic solvent and water, drying, and performing high-temperature calcinations; 2, performing carbon coating on nano lithium titanate, namely, preparing a solution from an organic carbon source, adding lithium titanate granules prepared in the step 1 into the solution, performing ultrasonic dispersion, performing hydrothermal reaction, cooling after the reaction, alternatively washing with the organic solvent and water, filtering, and drying, thereby obtaining the carbon-coated nano lithium titanate composite material. Refining of lithium titanate can be achieved through a micro emulsion method, the solution can be prepared from the carbon source, and carbon coating of the nano lithium titanate can be achieved through hydrothermal reaction, so that a conductive carbon network which is uniform and dense in combination can be formed on the surface of lithium titanate, the conductivity and the large-power charge/discharge property of an electrode material are remarkably improved, and the carbon-coated nano lithium titanate composite material can be used for preparing lithium ion electric containers and lithium ion batteries.
Description
Technical field
The invention belongs to electrode material technical field, particularly, relate to a kind of carbon-coated nano lithium titanate composite material and its preparation method and application.
Background technology
Because energy and environment problem is day by day serious, the development and use of clean energy resource is extremely urgent.Along with making rapid progress of electronic technology, electronic apparatus is constantly towards direction fast development that is miniaturized and high performance.The extensive use of the portable electronic equipments such as especially mobile communication, notebook computer and video camera, has higher requirement to high-performance energy storage device, makes to have high power density lithium-ion capacitor and obtain unprecedented development.
Lithium-ion capacitor is a kind of energy storage device based on ultracapacitor and the dual energy storage mechanism of lithium ion battery, positive pole adopts the material with super capacitor performance, as active carbon, negative pole adopts Lithium-ion embeding to deviate from formed material, there is energy density and power density is high, life-span length and fail safe high, be expected to be applied to pure EHV electric and hybrid vehicle field.The negative material that lithium-ion capacitor uses is generally graphite, but its energy storage potential plateau is lower, at 0 ~ 0.25V vs Li/Li
+between, often cause the generation of Li dendrite, which greatly limits the application of graphite in lithium-ion capacitor.With graphite-phase ratio, lithium titanate has very large advantage, is mainly manifested in, the deintercalation of lithium ion in lithium titanate is reversible, and lithium ion is embedding and deviating from the process of lithium titanate, and its crystal formation does not change, and change in volume is less than 1%, be therefore otherwise known as " zero strain material ".Due to " zero strain " property of lithium titanate, can avoid causing structural damage due to the flexible back and forth of electrode material in charge and discharge cycles, thus improve cycle performance and the useful life of electrode.But because the conductivity of lithium titanate is low, cause the high-power performance of material on the low side, when working under high power environment, lithium titanate special capacity fade is rapid.
At present, for improving electric conductivity, the main method adopted is the refinement of lithium titanate particle, or the material such as lithium titanate and high conductive metal, carbon and polymer carries out compound.The refinement main method of lithium titanate particle has mechanical lapping, hydro-thermal, collosol and gel and micro emulsion method etc., wherein micro emulsion method is by controlling the proportioning of each material in microemulsion, thus the effective size controlling lithium titanate particle, enable the lithium titanate particle of preparation reach nanoscale.But time prepared by lithium titanate, in solid-phase sintering process, particle easily grows, reunites seriously, is unfavorable for the preparation of nanoscale lithium titanate.The method of compound mainly contains mechanical mixture, high-temperature calcination and coated; wherein to there is the operating time long for mechanical mixing; mix uneven; be difficult to control the shortcomings such as the surface configuration of product and particle size; there is the reunion of particle under calcining heat high (500 ~ 800 DEG C), hot conditions and need the shortcomings such as inert gas shielding in high-temperature calcination; compare with high-temperature calcination with mechanical mixture, it is the most general way that the carbon of lithium titanate and good conductivity carries out coated.But, existing carbon method for coating exist the operating time long, coated uneven, combine closely, calcining heat is high, need the problems such as inert gas shielding, is unfavorable for the exploitation of the coated lithium titanate particle of carbon.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of carbon-coated nano lithium titanate composite material.The present invention utilizes micro emulsion method to realize the refinement of lithium titanate, and carbon source is made solution, utilize hydro-thermal reaction to realize the carbon of nanoscale lithium titanate coated, form even, compact conductive carbon network on lithium titanate surface, significantly improve the conductivity of electrode material and high-power charge-discharge performance.
Another object of the present invention is to the carbon-coated nano lithium titanate composite material providing said method to prepare.
Another object of the present invention is to provide above-mentioned composite material preparing the application in lithium-ion capacitor and lithium ion battery.
Above-mentioned purpose of the present invention is achieved by the following technical programs.
A preparation method for carbon-coated nano lithium titanate composite material, comprises the steps:
S1. the preparation of nano lithium titanate: oil phase, surfactant and cosurfactant are mixed to get microemulsion, lithium source, titanium source are added microemulsion respectively, prepare lithium source microemulsion and titanium source microemulsion, by two kinds of microemulsion mixing, stir, leave standstill, centrifugal, get precipitation organic solvent and water and carry out alternately washing, dry, obtain lithium titanate particle after high-temperature calcination;
S2. the carbon of nano lithium titanate is coated: organic carbon source is made solution, then adds the nano lithium titanate particle that S1 prepares, ultrasonic disperse; The mixture obtained is carried out hydro-thermal reaction under elevated pressure conditions, after reaction cooling, takes out product, carry out alternately washing with organic solvent and water, filter, after drying, obtain carbon-coated nano lithium titanate composite material.
The present invention adopts micro emulsion legal system for lithium titanate, prepares nanoscale lithium titanate particle, has larger specific area, improves the high rate charge-discharge performance of lithium titanate; And in the coated process of carbon, carbon source is made solution, be beneficial to the surface covering lithium titanate equably, after hydro thermal method carbonization, even, compact conductive carbon network is formed on lithium titanate surface, be conducive to the conductivity improving electrode material, after lithium titanate coated with carbon, high-power charge-discharge performance is significantly improved; Utilize hydro-thermal reaction to carry out in the coated process of carbon, reaction temperature is lower, the agglomeration that can effectively avoid nano lithium titanate to occur in high-temperature burning process, keeps high-ratio surface, improves the conductance of material, thus improves the high-power performance of composite material.
Preferably, the concentration in described titanium source is 20mmol/L ~ 1mol/L, and the concentration in described lithium source is 17mmol/L ~ 1mol/L.
Preferably, temperature dry described in S1 is 50 ~ 100 DEG C, and the time is 2 ~ 20h, and vacuum degree is 0.1 ~ 101kPa.
Preferably, the temperature of high-temperature calcination described in S1 is 500 ~ 800 DEG C, and the time is 6 ~ 15h.
Preferably, the concentration of organic carbon source described in S2 is 10 ~ 300g/L.
Preferably, the temperature of hydro-thermal reaction described in S2 is 100 ~ 280 DEG C, and the reaction time is 3 ~ 20h, and reaction pH is 8 ~ 13.More preferably, the temperature of hydro-thermal reaction described in S2 is 110 ~ 230 DEG C.
Preferably, temperature dry described in S2 is 20 ~ 100 DEG C, and the time is 0.5 ~ 8h, and vacuum degree is 0.1 ~ 101kPa.
Preferably, in the carbon-coated nano lithium titanate composite material for preparing of S2, the content of carbon is 2% ~ 20%.
Preferably, the ultrasonic disperse time described in S2 is 0.5 ~ 40h.
More preferably, described preparation method comprises the steps:
S1. the preparation of nano lithium titanate: oil phase, surfactant and cosurfactant are mixed and obtains microemulsion; Getting 50mmol/L ~ 0.55mol/L titanium source adds in microemulsion, stir 2h and prepare titanium source microemulsion, 42 mmol/L ~ 0.46mol/L lithium sources of getting add in microemulsion, stir 1h and prepare lithium source microemulsion, by titanium source microemulsion and the mixing of lithium source microemulsion, stir 3h, leave standstill 24h, centrifugal, get precipitation organic solvent and water alternately washs several times, at 65 ~ 80 DEG C, vacuum degree is under the condition of 0.1 ~ 1kPa, dry 10 ~ 20h, then 6 ~ 15h is calcined at 500 ~ 800 DEG C, naturally obtain nano lithium titanate particle after cooling;
S2. the carbon of nano lithium titanate is coated: organic carbon source is made the solution that concentration is 100 ~ 150g/L, adds the nano lithium titanate particle that S1 prepares, ultrasonic disperse 1h; The mixture obtained is moved into hydrothermal reaction kettle, and control pH 9 ~ 11,150 ~ 180 DEG C reacts 5 ~ 12h, product alternately washs several times with organic solvent and water after taking out, and filters, 65 ~ 80 DEG C of vacuumize 5 ~ 8h, vacuum degree is 0.5 ~ 1kPa, obtains carbon-coated nano lithium titanate composite material.
Preferably, oil phase described in S1 is one or more in cyclohexane, toluene, oleic acid or carrene.
Preferably, surfactant described in S1 is one or more in Triton X-100 (Triton X-100), softex kw (CTAB), OPEO (OP), cetyl polyoxy hexenyl ether or neopelex.
Preferably, cosurfactant described in S1 is n-butanol.
Preferably, titanium source described in S1 is one or more in Titanium Nitrate, tetraethyl titanate, metatitanic acid methyl esters, isopropyl titanate or iso-butyl titanate.
Preferably, lithium source described in S1 is one or more in lithium chloride, lithium acetate, lithium nitrate, lithium sulfate or lithium hydroxide.
Preferably, organic solvent described in S1 is one or more in acetone, methyl alcohol, ethanol or carbon tetrachloride, and organic solvent described in S2 is one or more in acetone, methyl alcohol, DMSO or butanols.
Preferably, titanium source microemulsion described in S1 and lithium source microemulsion hybrid mode are rapid mixing.
Preferably, organic carbon source described in S2 is one or more in maltose, fructose, lactose or starch, and more preferably, organic carbon source described in S2 is that maltose is or/and starch.
Preferably, for disperseing the dispersant of organic carbon source described in S2 to be water or ethanol.
The carbon-coated nano lithium titanate composite material that a kind of said method prepares.
The application in lithium-ion capacitor and lithium ion battery prepared by a kind of above-mentioned composite material.
Compared with prior art, beneficial effect of the present invention is:
(1) the present invention adopts micro emulsion legal system for lithium titanate, and the lithium titanate particle prepared, at nanoscale, has larger specific area, improves the high rate charge-discharge performance of lithium titanate; Carbon source is made solution by the present invention, be beneficial to the surface covering lithium titanate equably, after hydro thermal method carbonization, even, compact conductive carbon network is formed on lithium titanate surface, be conducive to the conductivity improving composite material, after lithium titanate coated with carbon, high-power charge-discharge performance is significantly improved.
(2) the present invention is in the coated process of carbon, the reaction temperature of hydro-thermal reaction is lower, the agglomeration that can effectively avoid nano lithium titanate to occur in high-temperature burning process, keeps high-ratio surface, improve the conductance of material, thus improve the high-power performance of composite material.
(3) particle diameter of lithium titanate particulate is nanoscale, ensure that lithium titanate composite material is in charge and discharge process, the distance of lithium ion diffusion is shorter, greatly increases the diffusion rate of lithium ion, thus achieves the raising greatly of lithium titanate composite material fast charging and discharging performance of the present invention.
(4) preparation technology of composite material of the present invention is simple, and cost is low, easily realizes suitability for industrialized production; In electrode material preparation process of the present invention, do not have poisonous and hazardous material to produce, meet the requirement of environmental protection.
Accompanying drawing explanation
Fig. 1 is the XRD analysis of nano lithium titanate particle prepared by the embodiment of the present invention 1.
Fig. 2 is the pore-size distribution of nano lithium titanate particle prepared by the embodiment of the present invention 1.
Embodiment
Below in conjunction with Figure of description and specific embodiment, the present invention is described in further details, but embodiment does not limit in any form the present invention.Unless stated otherwise, the present invention adopts reagent, method and apparatus are the art conventional reagent, method and apparatus.
embodiment 1
Get 0.67L Triton-100,0.4L n-butanol and 1.1L cyclohexane, stir, mix and obtain microemulsion, add 0.5L, 0.2mol/L metatitanic acid methyl esters, stir 2h and prepare titanium source microemulsion; Get 0.67L Triton-100,0.4L n-butanol and 1.1L cyclohexane, stir, mix and obtain microemulsion, add 0.5L, 0.17mol/L LiNO
3stir 1h, form lithium source microemulsion, by titanium source microemulsion and lithium source microemulsion rapid mixing, stir 3h, leave standstill 24h, centrifugal, carry out alternately washing 4 times to precipitation second alcohol and water, at 65 DEG C, vacuum degree is under the condition of 0.1kPa, dry 16h, obtain the presoma of lithium titanate, presoma calcines 15h at 500 DEG C, naturally after cooling, obtain the nanoparticle of lithium titanate, XRD analysis and the pore-size distribution result of nano lithium titanate particle are shown in Fig. 1, Fig. 2 respectively; The starch solution of preparation 0.1L, 130g/L, then in this solution, add the nanoscale lithium titanate particle of the above-mentioned preparation of 88g, ultrasonic disperse 1h, this mixture is moved into hydrothermal reaction kettle, and control pH is 11,150 DEG C of reaction 12h, product takes out rear butanols and deionized water replaces washed product 3 times, 68 DEG C of vacuumize 7h, vacuum degree is 0.5kPa, obtains carbon-coated nano lithium titanate composite material.
Using the carbon-coated nano lithium titanate composite material for preparing as electrode active material, according to electrode active material: carbon black: PVDF=85:10:5, add NMP and size mixing, on aluminium foil, be coated with upper electrode material with coating machine, thickness is at 125 μm, 100 DEG C of dryings, NMP is volatilized, make its thickness at 70 ~ 90 μm with roll squeezer jewelling paper tinsel, under argon atmosphere, be assembled into asymmetric capacitor in glove box, active carbon is as positive pole and use excessive positive electrode, 1.5mol/L LiBF
4as electrolyte, carry out constant current charge-discharge test, when charging and discharging currents density be 0.5A/g(negative pole be benchmark) time, the specific capacity of lithium titanate composite material reaches 100F/g, show prepare composite materials there is good capacitive property; When charging and discharging currents density is 2.5A/g, circulate 5000 times time, capability retention 92%, show prepare compound there is excellent electrochemistry cycle performance.
embodiment 2
Get 200g CTAB, 8L n-butanol and 22L toluene, stir, mix and obtain microemulsion, add 1L, 0.5mol/L metatitanic acid methyl esters, stir 2h and prepare titanium source microemulsion; Get 200g CTAB, 8L n-butanol and 22L toluene, stir, mix and obtain microemulsion, add 1L, 0.42mol/L LiNO
3stir 1h, form lithium source microemulsion, by titanium source microemulsion and lithium source microemulsion rapid mixing, stir 3h, leave standstill 24h, centrifugal, alternately washing 3 times is carried out to precipitation second alcohol and water, at 73 DEG C, vacuum degree is under the condition of 0.5kPa, dry 20h, obtain the presoma of lithium titanate, presoma calcines 8h at 650 DEG C, naturally after cooling, obtains the nanoparticle of lithium titanate.The starch solution of preparation 0.1L, 140g/L, then in this solution, add the nano lithium titanate particle of the above-mentioned preparation of 71g, ultrasonic disperse 1h, this mixture is moved into hydrothermal reaction kettle, and pH is 9,180 DEG C of reaction 8h, product takes out rear butanols and deionized water replaces washed product 4 times, 78 DEG C of vacuumize 5h, vacuum degree is 1kPa, obtains carbon-coated nano lithium titanate composite material.
Using the carbon-coated nano lithium titanate composite material for preparing as electrode active material, according to electrode active material: carbon black: PVDF=85:10:5, add NMP and size mixing, on aluminium foil, be coated with upper electrode material with coating machine, thickness is at 125 μm, 90 DEG C of dryings, NMP is volatilized, make its thickness at 70 ~ 90 μm with roll squeezer jewelling paper tinsel, under argon atmosphere, be assembled into asymmetric capacitor in glove box, active carbon is as positive pole and use excessive positive electrode, 1.5 mol/L LiBF
4as electrolyte, carrying out constant current charge-discharge test, is benchmark when charging and discharging currents density is 0.7A/g(with negative pole) time, the specific capacity of composite material reaches 88F/g, shows that the composite materials prepared has good capacitive property; When charging and discharging currents density is 3A/g, circulate 4000 times time, capability retention 89%, show prepare compound there is excellent electrochemistry cycle performance.
embodiment 3
Get 18g cetyl polyoxy hexenyl ether, 0.8L n-butanol and 2.2L toluene, stir, mix and obtain microemulsion, add 1.2L, 50mmol/L isopropyl titanate, stir 2h and prepare titanium source microemulsion; Get 18g cetyl polyoxy hexenyl ether, 0.8L n-butanol and 2.2L toluene, stir, mix and obtain microemulsion, add 1.2L, 42mmol/L LiCl and stir 1h, form lithium source microemulsion, by titanium source microemulsion and lithium source microemulsion rapid mixing, stir 3h, leave standstill 24h, centrifugal, alternately washing 3 times is carried out, at 81 DEG C to precipitation fourth alcohol and water, vacuum degree is under the condition of 1kPa, dry 10h, obtain the presoma of lithium titanate, presoma calcines 6h at 800 DEG C, naturally, after cooling, the nanoparticle of lithium titanate is obtained.The maltose solution of preparation 0.1L, 100g/L, then in this solution, add the nano lithium titanate particle of the above-mentioned preparation of 48g, ultrasonic disperse 1h, this mixture is moved into hydrothermal reaction kettle, and pH is 11,160 DEG C of reaction 5h, product takes out rear acetone and deionized water replaces washed product 4 times, 76 DEG C of vacuumize 6h, vacuum degree is 0.8kPa, obtains carbon-coated nano lithium titanate composite material.
Using the carbon-coated nano lithium titanate composite material for preparing as electrode active material, according to electrode active material: carbon black: PVDF=85:10:5, add NMP and size mixing, on aluminium foil, be coated with upper electrode material with coating machine, thickness is at 125 μm, 100 DEG C of dryings, NMP is volatilized, make its thickness at 70 ~ 90 μm with roll squeezer jewelling paper tinsel, under argon atmosphere, be assembled into asymmetric capacitor in glove box, active carbon is as positive pole and use excessive positive electrode, 1.5 mol/L LiBF
4as electrolyte, carrying out constant current charge-discharge test, is benchmark when charging and discharging currents density is 1A/g(with negative pole) time, the specific capacity of composite material reaches 75F/g, shows that the composite materials prepared has good capacitive property; When charging and discharging currents density is 3A/g, circulate 5000 times time, capability retention 88%, show prepare compound there is excellent electrochemistry cycle performance.
embodiment 4
Get 0.8L Triton-100,0.8L n-butanol and 2.2L oleic acid, stir, mix and obtain microemulsion, add 1.2L, 0.45mol/L isopropyl titanate, stir 2h and prepare titanium source microemulsion; 0.8L Triton-100,0.8L n-butanol and 2.2L oleic acid, stir, mix and obtain microemulsion, add 1.2L, 0.38mol/L LiCl and stir 1h, form lithium source microemulsion, titanium source microemulsion and lithium source microemulsion rapid mixing, stir 3h, leave standstill 24h, centrifugal, alternately washing 4 times is carried out, at 78 DEG C to precipitation carbon tetrachloride and water, vacuum degree is under the condition of 0.8kPa, dry 14h, obtain the presoma of lithium titanate, presoma calcines 10h at 650 DEG C, naturally, after cooling, the nanoparticle of lithium titanate is obtained.The starch solution of preparation 0.1L, 150g/L, then in this solution, add the nano lithium titanate particle of the above-mentioned preparation of 80g, ultrasonic disperse 1h, this mixture is moved into hydrothermal reaction kettle, and pH is 10,180 DEG C of reaction 12h, product takes out rear DMSO and deionized water replaces washed product 3 times, 72 DEG C of vacuumize 8h, vacuum degree is 1kPa, obtains carbon-coated nano lithium titanate composite material.
Using the carbon-coated nano lithium titanate composite material for preparing as electrode active material, according to electrode active material: carbon black: PVDF=85:10:5, add NMP and size mixing, on aluminium foil, be coated with upper electrode material with coating machine, thickness is at 125 μm, 100 DEG C of dryings, NMP is volatilized, make its thickness at 70 ~ 90 μm with roll squeezer jewelling paper tinsel, under argon atmosphere, be assembled into asymmetric capacitor in glove box, active carbon is as positive pole and use excessive positive electrode, 1.5 mol/L LiBF
4as electrolyte, carrying out constant current charge-discharge test, is benchmark when charging and discharging currents density is 0.8A/g(with negative pole) time, the specific capacity of composite material reaches 83F/g, shows that the composite materials prepared has good capacitive property; When charging and discharging currents density is 2A/g, circulate 5000 times time, capability retention 90%, show prepare compound there is excellent electrochemistry cycle performance.
embodiment 5
Get 16g neopelex, 0.8L n-butanol and 2.2L oleic acid, stir, mix and obtain microemulsion, add 1.5L, 50mmol/L isopropyl titanate, stir 2h and prepare titanium source microemulsion; 16g neopelex, 0.8L n-butanol and 2.2L oleic acid, stir, mix and obtain microemulsion, add 1.5L, 42mmol/L LiNO
3stir 1h, form lithium source microemulsion, titanium source microemulsion and lithium source microemulsion rapid mixing, stir 2h, leave standstill 10h, centrifugal, alternately washing 4 times is carried out to precipitation carbon tetrachloride and water, at 62 DEG C, vacuum degree is under the condition of 0.6kPa, dry 15h, obtain the presoma of lithium titanate, presoma calcines 10h at 700 DEG C, naturally after cooling, obtains the nanoparticle of lithium titanate.The maltose solution of preparation 0.1L, 110g/L, then in this solution, add the nano lithium titanate particle of the above-mentioned preparation of 60g, ultrasonic disperse 1h, this mixture is moved into hydrothermal reaction kettle, and pH is 10,130 DEG C of reaction 5h, product takes out rear methyl alcohol and deionized water replaces washed product 4 times, 69 DEG C of vacuumize 8h, vacuum degree is 1kPa, obtains carbon-coated nano lithium titanate composite material.
embodiment 6
Get 20gOP, 0.8L n-butanol and 2.2L toluene, stir, mix and obtain microemulsion, add 1L, 0.2mol/L metatitanic acid methyl esters, stir 2h, prepare titanium source microemulsion; 20gOP, 0.8L n-butanol and 2.2L toluene, stir, mix and obtain microemulsion; Add 1L, 0.17mol/L LiNO
3stir 1h, form lithium source microemulsion, by titanium source microemulsion and lithium source microemulsion rapid mixing, stir 3h, leave standstill 24h, centrifugal, alternately washing 3 times is carried out to precipitation second alcohol and water, at 63 DEG C, vacuum degree is under the condition of 0.5kPa, dry 16h, obtain the presoma of lithium titanate, presoma calcines 12h at 600 DEG C, naturally after cooling, obtains the nanoparticle of lithium titanate.The starch solution of preparation 0.1L, 150g/L, then in this solution, add the nano lithium titanate particle of the above-mentioned preparation of 68g, ultrasonic disperse 1h, this mixture is moved into hydrothermal reaction kettle, and pH is 8,190 DEG C of reaction 10h, product takes out rear butanols and deionized water replaces washed product 4 times, 71 DEG C of vacuumize 7h, vacuum degree is 0.8kPa, obtains carbon-coated nano lithium titanate composite material.
comparative example 1
The method that this comparative example prepares carbon-coated nano lithium titanate composite material is basic identical with embodiment 1, except in the coated process of S2 carbon, organic carbon source is different from the hybrid mode of lithium titanate particle.The hybrid mode of this comparative example organic carbon source and lithium titanate particle is: nanoscale lithium titanate particle starch solution and S1 prepared mixes, then is added in 0.1L water, ultrasonic disperse 1h.The carbon-coated nano lithium titanate composite material that this comparative example and embodiment 1 obtain is carried out constant current charge-discharge test, controls charging and discharging currents density and cycle-index respectively, compare specific capacity and the capability retention of both composite materials, the results are shown in Table 1.
comparative example 2
the method that this comparative example prepares carbon-coated nano lithium titanate composite material is basic identical with embodiment 1, except this comparative example also adopts the method for high-temperature calcination in the coated process of S2 carbon after hydro-thermal reaction.The coated method of this comparative example carbon is: by mixture at pH 8 ~ 13, carry out the hydro-thermal reaction of 5 ~ 12h under the condition that temperature is 100 ~ 280 DEG C, then 500 ~ 800 DEG C of calcining 5 ~ 15h under reducing atmosphere, obtains carbon-coated nano lithium titanate composite material.The carbon-coated nano lithium titanate composite material that this comparative example and embodiment 1 obtain is carried out constant current charge-discharge test, controls charging and discharging currents density and cycle-index respectively, compare specific capacity and the capability retention of both composite materials, the results are shown in Table 1.
comparative example 3
The preparation method of this comparative example S1 nano lithium titanate is identical with embodiment 1, and the carbon method for coating of S2 nano lithium titanate is different from embodiment 1.The coated method of this comparative example carbon is: nanoscale lithium titanate particle starch solution and S1 prepared mixes, then is added in 0.1L water, ultrasonic disperse 1h; This mixture is moved into hydrothermal reaction kettle, at pH 8 ~ 13, under the condition that temperature is 100 ~ 280 DEG C, reacts 5 ~ 12h, reaction butanols and deionized water replace washed product 4 times, drying, 500 ~ 800 DEG C of calcining 5 ~ 15h, obtain carbon-coated nano lithium titanate composite material under reducing atmosphere.The carbon-coated nano lithium titanate composite material that this comparative example and embodiment 1 obtain is carried out constant current charge-discharge test, controls charging and discharging currents density and cycle-index respectively, compare specific capacity and the capability retention of both composite materials, the results are shown in Table 1.
The different preparation method of table 1 is on the impact of composite property
Claims (10)
1. a preparation method for carbon-coated nano lithium titanate composite material, is characterized in that, comprises the steps:
S1. the preparation of nano lithium titanate: oil phase, surfactant and cosurfactant are mixed to get microemulsion, lithium source, titanium source are added microemulsion respectively, prepare lithium source microemulsion and titanium source microemulsion, by two kinds of microemulsion mixing, stir, leave standstill, centrifugal, get precipitation organic solvent and water and carry out alternately washing, dry, obtain lithium titanate particle after high-temperature calcination;
S2. the carbon of nano lithium titanate is coated: organic carbon source is made solution, then adds the nano lithium titanate particle that S1 prepares, ultrasonic disperse; The mixture obtained is carried out hydro-thermal reaction under elevated pressure conditions, after reaction cooling, takes out product, carry out alternately washing with organic solvent and water, filter, after drying, obtain carbon-coated nano lithium titanate composite material.
2. preparation method according to claim 1, is characterized in that, described in S1, the concentration in titanium source is 20mmol/L ~ 1mol/L, and the concentration in described lithium source is 17mmol/L ~ 1mol/L.
3. preparation method according to claim 1, is characterized in that, temperature dry described in S1 is 50 ~ 100 DEG C, and the time is 2 ~ 20h, and vacuum degree is 0.1 ~ 101kPa.
4. preparation method according to claim 1, is characterized in that, the temperature of high-temperature calcination described in S1 is 500 ~ 800 DEG C, and the time is 6 ~ 15h.
5. preparation method according to claim 1, is characterized in that, the concentration of organic carbon source described in S2 is 10 ~ 300g/L.
6. preparation method according to claim 1, is characterized in that, the temperature of hydro-thermal reaction described in S2 is 100 ~ 280 DEG C, and the reaction time is 3 ~ 20h, and reaction pH is 8 ~ 13.
7. preparation method according to claim 1, is characterized in that, temperature dry described in S2 is 20 ~ 100 DEG C, and the time is 0.5 ~ 8h, and vacuum degree is 0.1 ~ 101kPa.
8. preparation method according to claim 1, is characterized in that, in the carbon-coated nano lithium titanate composite material that S2 prepares, the content of carbon is 2% ~ 20%.
9. the carbon-coated nano lithium titanate composite material for preparing of method described in any one of claim 1 ~ 8.
10. the application in lithium-ion capacitor and lithium ion battery prepared by composite material described in claim 9.
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| CN112885992A (en) * | 2021-01-12 | 2021-06-01 | 厦门厦钨新能源材料股份有限公司 | Preparation method and application of lithium ion battery negative electrode material |
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