CN106711417A - Method for preparing nanometer titania coated graphite cathode material - Google Patents

Method for preparing nanometer titania coated graphite cathode material Download PDF

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Publication number
CN106711417A
CN106711417A CN201611250974.0A CN201611250974A CN106711417A CN 106711417 A CN106711417 A CN 106711417A CN 201611250974 A CN201611250974 A CN 201611250974A CN 106711417 A CN106711417 A CN 106711417A
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graphite
titanium dioxide
cathode material
coated
water
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刘瑶
黄光艳
林定文
张文博
舒方君
周环波
丁先红
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Hubei Uee Energy Technology Co Ltd
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Hubei Uee Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a method for preparing a nanometer titania coated graphite cathode material. The method comprises the steps that A, graphite is added into a mixed solution of glacial acetic acid, water and absolute ethyl alcohol at room temperature under the stirring condition, the materials are fully mixed, and a mixture is obtained; B, a titanate and absolute ethyl alcohol mixed solution is dropwise added into the mixture obtained in the step A within a certain time at room temperature under the stirring condition, standing is carried out for several hours, drying is carried out, and metatitanic acid gel coated powdered graphite is obtained; C, the metatitanic acid gel coated powdered graphite obtained in the step B is placed in a program temperature control furnace, the temperature is raised to 350 DEG C to 850 DEG C at a certain heating rate, the constant temperature is kept for several hours under the vacuum condition, the product is naturally cooled to room temperature, and the anatase and rutile type nanometer titania coated graphite material is obtained. The grain size of the nanometer titania coated graphite cathode material ranges from 1 micrometer to 35 micrometers, and high specific discharge capacity, good cycle performance and high high-rate charge and discharge performance are achieved.

Description

A kind of preparation method of nanometer titanium dioxide-coated graphite cathode material
Technical field
The invention belongs to lithium ion battery negative material, catalyst additive technical field, be more particularly to a kind of lithium from The preparation method of sub- battery modified graphite cathode material.Nanometer titanium dioxide-coated graphite material prepared by the present invention can be used Make lithium ion battery negative material, it is also possible to photochemical catalyst, electrochemical catalyst, the catalyst of organic synthesis for water process And the additive of fine product chemical products etc..
Background technology
At present, the negative material typically graphite material that lithium ion battery is used.The phase of lithium ion battery negative material Research is closed also to be concentrated mainly on to the modified of native graphite, new CNT, Graphene, amorphous carbon and numerous metals Oxide etc..Wherein, graphite is the carbon negative pole material for being used for lithium ion battery earliest, and its good conductivity, crystallinity is high, with complete Whole layered crystal structure, insertion and the abjection of suitable lithium ion.But, graphite as lithium ion battery negative electrode active material Material, because its is nonpolar, density is low, mechanical strength is poor, the graphite cathode pole piece and organic electrolyte (LiPF of manufacture6EC- EMC-DMC solution, EC- ethylene carbonates, EMC- methyl ethyl carbonates, DMC- dimethyl carbonates) spy such as poor compatibility, difficult wetting Point；The specific capacity of graphite cathode is relatively low, charge-discharge performance is poor；In addition, in manufacture lithium ion battery negative During pole piece, graphite also has that, decentralization poor with the compatibility of water be low, poor processability, production process graphite dust The deficiencies such as pollution production environment and equipment.
The material of " having similar to graphite laminate structure " that CNT is made up of the coaxial carbon plate layer of single or multiple lift. The sp of CNT2Hybrid structure and draw ratio high bring a series of excellent properties for it.This special microcosmic knot Structure causes that the insert depth of lithium ion is small, stroke is short and embedded location is more (pipe interior and interlayer gap, hole etc.), while because of carbon Nanotube conductive performance very well, with the conduction of preferable electronics and ion transport capacity, is suitable as lithium ion battery negative material. Therefore, CNT is used as lithium ion battery negative material, it is clear that than traditional graphite electrode advantageously.But using carbon nanometer Pipe there is also weak point directly as lithium ion battery negative material：1) irreversible capacity is larger first, first charge-discharge effect Rate is than relatively low；2) carbon nanometer tube negative pole lacks the voltage platform of stabilization；3) there is current potential hysteresis in CNT.Additionally, carbon The synthesis cost of nanotube is high.These all limit practical application of the CNT as lithium ion battery negative material.Stone Black alkene (Graphene) be one kind only by carbon atom with sp2Hybridized orbit constitutes the flat film of hexangle type lattice, that is, only One two-dimensional material of carbon atom thickness.Compared to other Carbon Materials such as CNT, Graphene has unique microstructure, this So that Graphene has larger specific surface area and cellular void structure, with storage lithium ability higher.Additionally, material is in itself With good chemical stability, high electron mobility and excellent mechanical property, it is had as electrode material and protrude Advantage.Similar with CNT, coulombic efficiency is low, charge and discharge platform is higher and circulates due to circulating first for pure grapheme material Less stable, synthesis cost are very high, commercial value shortcoming etc. defect, and the Carbon Materials of current commercialization can not be replaced directly to use Make lithium ion battery negative material.Metal oxide-carbon is (such as：SnO、VO2、TiO2、LixFe2O3、Li4Mn2O12、Li4Ti5O12Cover Carbon material etc.) material as lithium ion battery negative pole, due in organic electrolyte solution carbon surface formed can allow electronics and The freely through passivation layer of lithium ion, while this passivation layer ensure that electrode good cycle performance, can cause electrode tight The loss of the first charge-discharge irreversible capacity of weight, can even cause the structure change and poor electric contact of electrode interior sometimes. In addition, being likely to cause battery failure because of the decomposition of protective layer under high temperature or producing safety problem.
In order to improve the above-mentioned not enough or defect of lithium ion battery negative material, function admirable, high security are produced Lithium ion battery, those skilled in the relevant art mainly research and develop novel cathode material for lithium ion battery, modified graphite cathode material Material etc..Document " silicon monoxide/carbon/expanded graphite is used as lithium ion battery negative material [J] " (battery, 2016,46 (3)： 121-124.) report：With polyvinyl butyral resin as carbon source, in silicon monoxide (SiO) coated with carbon bed, then with expansion stone Ink is compound, the method for preparing used as negative electrode of Li-ion battery SiO/C/ exfoliated-graphite composites, it is said that：The SiO/C/ expanded graphites The 100th reversible specific capacity of circulation of 200mA/g rate charge-discharges of composite is 545mAh/g.Document " phosphoric acid and organic Study on the modification [J] of the amine to natural graphite negative electrode material " (Shanghai second Industry Univ's journal, 2016,33 (3)：217-221.) Report：With SPA treatment, the correlative study of organic amine pyrolytic carbon coated graphite material.Document " lithium ion battery negative material Material modified graphite CGS Study on Preparation [J] " (power technology, 2016,40 (5)：959-960,1093.) describe and use coal tar The method that the mixture covering of oil asphalt and asphalt prepares carbon-coated lithium ion battery negative material.Document " carbon nanometer The preparation of pipe/native graphite composite negative pole material and sign [J] " (artificial lens journal, 2016,45 (4)：1041-1046.) it is situated between Continued a kind of method of use carbon nano-tube modification natural graphite negative electrode material.It is said that the CNT of the document/graphite composite wood Specific capacity first, reversible specific capacity, cyclical stability and the high current charge-discharge expected all are significantly improved.Document " carbon bag Cover the synthesis [J] of spherical graphite negative material " (Heilungkiang engineering college journal, 2016,7 (1)：35-40.) describe a kind of logical Cross the method that dipping-evaporation solvent-pyrolysis charring technology prepares the carbon coating spheroidal graphite materials with carbon nucleus-shell structure. The document does not introduce the chemical property of synthetic material.Document " self-supporting WS2The electrostatic spinning system of/carbon fibre composite It is standby and its as the application [J] of lithium ion battery negative material " (Science Bulletin, 2016,61 (8)：912) describe and utilize electrostatic Spining technology is prepared for one kind " two-dimentional WS2Nanometer sheet is uniformly embedded in carbon nano-fiber composite material ", document claims, the technology system Standby composite membrane section bar material does not need conductive agent, bonding agent, can be directly used as lithium ion battery negative, can be soft directly from making Property battery device.Document " preparation of jute base carbon fibre/MnO/C lithium ion battery negative materials and its chemical property [J] " (Chinese Journal of Inorganic Chemistry, 2016,32 (5)：It is raw material 811-817) to describe with tossa, potassium permanganate and polymer pyrroles, The technology of " carbon fiber/MnO/C " lithium ion battery negative material is prepared through more numerous and diverse step.Carbon fiber/MnO/C materials exist There is effective electron channel and the polynary cooperative effect on composition in structure, shown as lithium cell cathode material higher Specific capacity, good cycle performance and high rate performance.The reality that the document does not provide secure lithium ion battery can Capable technological parameter and process conditions etc.." metatitanic acid high temperature solid-state method prepares lithium ion battery negative material spinelle to document Li4Ti5O12[J] " (electronic original part and material, 2016,35 (3)：19-21) report and synthesize " spinel-type with solid reaction process Li4Ti5O12Negative material "." the spinel-type Li of document report4Ti5O12The first charge-discharge capacity of negative material " is 158.63mAh/g, (electric current) efficiency is 98.7%.Document " ZnFe2O4The preparation of lithium ion battery negative material and electrochemistry [J] can be studied " (Journal of Inorganic Materials, 2016,31 (1)：34-38) have studied with hydro-thermal-solid phase that Zn, Fe chloride are raw material Reaction method prepares " ZnFe2O4The contents such as the technology and chemical property of negative material ".The ZnFe of document synthesis2O4Negative pole material Expect to be nanometer porous spherical particle, with reversible specific capacity and relatively stable cycle performance higher.
Additionally, document " sulfonated gilsonite coated graphite is used as lithium ion battery negative material [J] " (power technology, 2015,39 (5)：889-924) report：With water soluble sulfonated pitch as covering material, complete in aqueous to natural flaky graphite Surface coated composite technology of preparing, it was reported that：The first discharge specific capacity of the composite is 351.8mAh/g. Document " the preparation and its high performance lithium ionic cell cathode material application of uniform load nickel oxide nanoparticle porous hard carbon ball [J] " (Acta PhySico-Chimica Sinica, 2015,31 (2)：268-276) describe one kind and prepare lithium ion battery negative material using hydro-thermal method The technology of material.It is said that under the composite 100mA/g current density charge conditions of document report synthesis, initial charge specific volume It is 764mAh/g to measure, and charge specific capacity is maintained at 777mAh/g after circulation in 100 weeks；Under 800mA/g current density charge conditions, fill Capacitance 380mAh/g." zinc replaces to spinelle Li document2MnTi3O8Lithium ion battery negative material microstructure and electrochemistry The influence [J] of performance " (non-ferrous metal engineering, 2015,5 (6)：1-6) synthesize Li with sol-gel process2MnTi3O8Presoma coagulates Glue material, adds ZnAc2, zinc substitution is prepared to spinelle Li through high-temperature calcination2MnTi3O8Lithium ion battery negative material.Text Offer title：The zinc of synthesis replaces to spinelle Li2MnTi3O8Specific volume of the lithium ion battery negative material after 36 charge and discharge cycles Amount is respectively 199.4mAh/g and 260.2mAh/g.Document " lithium ion battery negative material Li4Ti5O12Synthesis and performance grind Study carefully [J] " (electrochemistry, 2015,21 (2)：181-186) describe with TiO2, lithium acetate be raw material, synthesis in solid state lithium ion battery Negative pole Li4Ti5O12The method of material.Report synthesis Li4Ti5O1210C high magnification first discharge specific capacities reach 143.0mAh/ g.Document " three-dimensional multistage hole class Graphene carries di-iron trioxide lithium ion battery negative material [J] " (electrochemistry, 2015,21 (1)：66-71), with synthetic technologys such as numerous and diverse ion exchange, liquid phase reactor, solid phase roastings, synthesize and have studied and be three-dimensional porous Graphene carries performance of the di-iron trioxide as lithium ion battery negative material.Document claims：The Fe of synthesis2O3- 3D HPG materials First discharge specific capacity is up to 1745mAh/g, and 50 times circulation specific capacity is maintained at 1095mAh/g.Document " multilevel hierarchy SnO2Receive Popped rice is used as high performance lithium ionic cell cathode material [J] " (Science Bulletin, 2015,60 (9)：892-895) describe " flower-shape Nano SnO2" negative material solvent-thermal method technology of preparing.Flower-shape nano SnO prepared by the document2The reversible capacity of negative material It is 350.7mAh/g.Document " lamellar titanosilicate compound is used as lithium ion battery negative energy storage material [J] " (inorganic chemistry Report, 2015,31 (12)：2425-2431) have studied and use lamellar titanosilicate Na4Ti2Si8O22·4H2O (Na-JDF-L1) through from Sub- exchange process prepares lithium ion battery negative material.It is main by by TiO2It is incorporated into Li (Na)-JDF-L1, effectively improves material The coulombic efficiency first and multiplying power discharging property of material.
There are numerous synthesis about titanium dioxide, modified and application patent to disclose.Chinese patent (application number 200910063398.2) " a kind of preparation method of nano silicon dioxide coated by nano titanium dioxide ", Chinese patent (Shen are disclosed Number please 200910063399.7) disclose " a kind of preparation method of nano-titanium dioxide coated nano-aluminium oxide ", China Patent (application number 200910116178.9) is disclosed " using the side of electroless nickel-copper phosphorus alloy solid support of modified nano titanium dioxide Method ", Chinese patent (application number 200910002490.8) discloses a kind of " preparation side of iron-doped nitrogen-doped nano titanium dioxide powder Method ", Chinese patent (application number 200810243732.8) discloses a kind of " system of nano titanium oxide-zinc oxide composite powder Preparation Method ", Chinese patent (application number 200810123979.2) discloses " a kind of doped nanometer titanium oxide photocatalyst Preparation method ", Chinese patent (application number 200810031600.9) discloses " preparation method of Ag-carried nanometer titanium dioxide ", in State's patent (ZL 200610085237.X) is disclosed " nanometer titanium dioxide/selenium dioxide composition and preparation method thereof ", China Patent (ZL 02147872.4) discloses " a kind of nano titanium oxide and its production and use ", Chinese patent (ZL 99116814.3) disclose " a kind of preparation method of nano titanium oxide ".United States Patent (USP) (the patent No.：9,260,316B2, 2016,2,16) a kind of " titania nanoparticles, titanate, nanoscale lithium titanate particles and preparation method thereof ", the public affairs are disclosed Opening technology has a kind of one between crystalline phase and amorphous phase middle corresponding standard of formation there is provided manufacture nano titanium oxide Crystalline phase provides possibility, and is applied to the preparation of lithium ion battery negative material." one kind is based on activated carbon system to Chinese invention patent The preparation method [p] of standby composite " (number of patent application 2,015 10720807.7) discloses " a kind of based on activated carbon system The preparation method of standby composite ".Technology disclosed in the patent of invention is mainly activated carbon, silica, polymer, nitric acid Nickel, bonding agent and too acid butyl ester etc. be raw material, purifying water process material is prepared based on activated carbon.Chinese invention patent " a kind of active carbon nanofibers and preparation method thereof [P] " (number of patent application 201610179105.7) discloses a kind of cylinder The technology of preparing of " a kind of active carbon nanofibers ".Technology concrete measure disclosed in the patent of invention is：It is with polyacrylonitrile Carbon source, DMF is solvent, is in-situ activation agent with phosphorous acid.By the warm and fine phosphorous acid of a certain amount of polypropylene (H3PO3) be dissolved in after mixing after DMF and form precursor liquid after, presoma is prepared by method of electrostatic spinning fine Dimension, then be carbonized under the protection of high temperature inert gas, obtain with high-specific surface area, the activated carbon Nanowire of high porosity Dimension.NACF prepared by the disclosure technology can be used as the catalyst of function admirable and catalyst carrier, ultracapacitor Electrode etc. (refers to its specification digest).Chinese invention patent " a kind of Graphene doping polyacrylonitrile center hole activated carbon fiber and Its preparation method [P] " (number of patent application 201610058563.5) is there is provided a kind of Graphene doping polyacrylonitrile mesopore activity Carbon fibe and preparation method thereof.Technology concrete scheme is disclosed in the patent：Prepare Graphene doping blend spinning stoste；Using Wet spinning technology carries out spinning, is impregnated 5~24 hours in reaming agent solution is catalyzed, and work is put into after being dried at 80~120 DEG C Change in stove, pre-oxidized 2~5 hours in 200~300 DEG C in air atmosphere, activation is taken out after furnace cooling, obtains Graphene Doping polyacrylonitrile center hole activated carbon fiber.It is said that Graphene doping polyacrylonitrile center hole activated carbon fiber obtained in the invention The Graphene excellent due to the addition of electric conductivity, and with suitable central hole structure, preferable electric conductivity, be especially suitable for doing The electrode of ultracapacitor.(referring to its summary part).Chinese invention patent " the electrode of super capacitor mesoporous work of polyacrylonitrile Property Carbon fibe and preparation method thereof [P] " (number of patent application 201610060357.8) disclose that a kind of " electrode of super capacitor is used The technology of preparing of the mesoporous activated Carbon fibe of polyacrylonitrile ", its step includes：Pore creating material organic compound and/or high polymer are added Enter in solvent, then stirred 3~24 hours at 50~80 DEG C, obtain the solution containing pore creating material；By polyacrylonitrile pulp with The described solution containing pore creating material mixes, obtains blend spinning stoste；Spinning is carried out using wet spinning technology, is mixed Precursor；Mixing precursor is impregnated 5~24 hours in reaming agent solution is catalyzed, in being put into activation furnace after being dried at 80~120 DEG C Pre-oxidation, activation, carbonization, obtain the mesoporous activated Carbon fibe of electrode of super capacitor polyacrylonitrile.Chinese patent (application number 201610764551.4) disclose " a kind of preparation method of LITHIUM BATTERY graphite/absorbent charcoal composite material ".The inventive technique is disclosed A kind of utilization biomass raw material are raw material, the technology of the preparation LITHIUM BATTERY activated carbon of more efficient.There is not yet relevant nanometer two Technology prepared by titanium-oxide-coated graphite material is disclosed or used.
The content of the invention
The purpose of the present invention is to there are provided a kind of preparation method of nanometer titanium dioxide-coated graphite cathode material, side The raw materials used abundance of method, technical equipment are relatively simple, easy, technological process is simple, production technology low cost, and preparation is received Rice coated by titanium dioxide graphite cathode material, with the particle size distribution range (particle diameter distribution of modified graphite used by depending on wider With the preparation technology parameter of the covering amount of nano titanium oxide and collosol and gel etc.), coated by titanium dioxide amount, crystal structure etc. are all It is easily controlled, manufacture lithium ion battery negative electrode has good processing characteristics and fillibility higher, compacting higher close The features such as spending.
In order to realize above-mentioned purpose, the present invention uses following technical scheme：
A kind of preparation method of nanometer titanium dioxide-coated graphite cathode material, its step is：
The first step, under room temperature (about 25,26,27 or 28 DEG C, same as below), stirring condition, by the graphite of 60~250g It is added in the mixed solution of 20~120mL glacial acetic acid and 20~50mL water and 100~400mL absolute ethyl alcohols, is sufficiently mixed, obtains To graphite and the mixture of glacial acetic acid, water and absolute ethyl alcohol；
Second step, under room temperature, stirring condition, in 30~120 minutes, by 50~400mL titanate esters with 100~ 400mL absolute ethyl alcohol mixed liquors are added drop-wise in graphite that the first step obtains and the mixture of glacial acetic acid, water and absolute ethyl alcohol, are stood 0.5~24 hour, dried 4~24 hours under the conditions of 120~150 DEG C, obtain canescence or grey or grey black metatitanic acid gel Coated graphite powder；
3rd step, the metatitanic acid gel coated graphite powder for obtaining second step are placed in general program temperature control, vacuum Muffle furnace In, it is warming up to 350~850 DEG C, under 0.01~0.001MPa vacuum conditions with 1~10 DEG C per minute of heating rate, constant temperature 4~ 24 hours, room temperature is naturally cooled to, that is, obtain canescence or grey or grey black nanometer titanium dioxide-coated powdered graphite；
In order to the present invention is better achieved, described titanate esters are butyl titanate (i.e. tetra-n-butyl titanate, as follows), titanium The mixtures of the isometric mixing of any one or two to four kinds in sour tetra-ethyl ester, metatitanic acid n-propyl, isopropyl titanate；
Described water is any one in distilled water, redistilled water, pure water or deionized water.
A kind of nanometer titanium dioxide-coated graphite cathode material of the present invention is exactly to be prepared from according to the method described above 's.
The present invention compared with prior art, has the following advantages that and beneficial effect：
1st, a kind of nanometer titanium dioxide-coated graphite cathode material prepared using the present invention, because clad titanium dioxide Density it is larger with respect to graphite, and mechanical performance is higher, and physical and chemical stability is preferably, relatively low with density and easy form more tiny The graphite-phase ratio of powder, is easier to dispersion in water, with more preferable cathode pole piece processing characteristics, and is electrolysed with lithium ion battery Liquid has preferable compatibility, can relatively effectively improve the quality of cathode pole piece, significantly improves lithium ion battery production efficiency；
2nd, a kind of nanometer titanium dioxide-coated graphite cathode material prepared using the present invention, manufactured lithium ion battery (referred to charging and discharging capacity and high-rate discharge ability higher higher：Figure 17, Figure 18), 0.1C multiplying powers highest electric discharge ratio Capacity (is referred to for 499mAh/g：Embodiment 4, Figure 14), 1C first discharge specific capacities are up to 382mAh/g, discharging efficiency highest (refer to for 94.9%：Embodiment 3,4, Figure 14,15,16,17) multiplying power highest specific discharge capacity (referred to up to 435mAh/g：Implement Example 4, Figure 16, Figure 17), (hereinafter referred to as " comparative sample ", refers to the graphite of uncoated titanium dioxide：Embodiment 9) highest electric discharge Specific capacity is only that 305mAh/g (is referred to：Figure 16, Figure 17)；150 charge and discharge cycles amount conservation rates of 5C multiplying powers are up to 84.4%, comparative sample (is referred to for 56.7%：Figure 17)；200 charge and discharge cycles capability retentions of 10C multiplying powers are up to 80.5%, comparative sample is only 37.5% (to refer to：Embodiment 4, embodiment 9, Figure 17)；
3rd, the particle diameter distribution using a kind of nanometer titanium dioxide-coated graphite cathode material of present invention synthesis is wider, and main To depend on the preparation technology parameter of the particle diameter, coated by titanium dioxide amount and collosol and gel of graphite material to be modified, titanium dioxide Covering amount and cladding thickness it is easily controllable, and the nanometer titanium dioxide-coated graphite cathode material of easily controllable synthesis particle diameter (refer to：Each embodiment, accompanying drawing SEM photograph, Figure 13)；
4th, a kind of nano titanium oxide prepared using the present invention covers the particle of the nano titanium oxide of graphite cathode material Particle diameter, the crystal structure of thickness, covering amount and titanium dioxide of coated by titanium dioxide layer etc. are easily controllable, can be according to difference Type lithium ion battery (rate, capacity type, Life Type lithium ion battery etc.) actual client need, prepare titanium dioxide Covering amount difference, grain diameter difference, crystal structure difference and electrical property have the nanometer titanium dioxide-coated stone of different Black negative material；
5th, using the present invention prepare a kind of nanometer titanium dioxide-coated graphite material preparation technology is flexible, equipment simple, Raw material are relatively inexpensive, prepare the comprehensive low production cost of modified graphite cathode material, it is easy to accomplish modelling industrial production.
6th, a kind of nanometer titanium dioxide-coated graphite cathode material prepared using the present invention, is used in the appropriate bonding agent that reduces In the case of amount, pole piece dry linting, shedding phenomenon weaken significantly, and in lithium ion battery negative manufacturing process, it is right to effectively reduce Workshop environment causes dust pollution, with good economic benefits and significant environmental benefit and social benefit；
Brief description of the drawings
The SEM photograph of nanometer titanium dioxide-coated graphite cathode material prepared by Fig. 1 embodiments 1；
The SEM photograph of nanometer titanium dioxide-coated graphite cathode material prepared by Fig. 2 embodiments 2；
XRD (the explanation of nanometer titanium dioxide-coated graphite cathode material prepared by Fig. 3 embodiments 2：A diffraction maximums are sharp Perovskite type crystal diffraction maximum, G diffraction maximums are the diffraction maximum of graphite)；
The SEM photograph of nanometer titanium dioxide-coated graphite cathode material prepared by Fig. 4 embodiments 3；
The SEM photograph of nanometer titanium dioxide-coated graphite cathode material prepared by Fig. 5 embodiments 4；
XRD (the explanation of nanometer titanium dioxide-coated graphite cathode material prepared by Fig. 6 embodiments 4：A diffraction maximums are sharp Perovskite type crystal diffraction maximum, G diffraction maximums are the diffraction maximum of graphite)；
The SEM photograph of nanometer titanium dioxide-coated graphite cathode material prepared by Fig. 7 embodiments 5；
The SEM photograph of nanometer titanium dioxide-coated graphite cathode material prepared by Fig. 8 embodiments 6；
XRD (the explanation of nanometer titanium dioxide-coated graphite cathode material prepared by Fig. 9 embodiments 6：A diffraction maximums are sharp Perovskite type crystal diffraction maximum, G diffraction maximums are the diffraction maximum of graphite)；
The SEM photograph of nanometer titanium dioxide-coated graphite cathode material prepared by Figure 10 embodiments 7；
The SEM photograph of nanometer titanium dioxide-coated graphite cathode material prepared by Figure 11 embodiments 8；
XRD (the explanation of nanometer titanium dioxide-coated graphite cathode material prepared by Figure 12 embodiments 8：A diffraction maximums are sharp Perovskite type crystal diffraction maximum, R diffraction maximums are rutile-type crystal diffraction peak, and G diffraction maximums are the diffraction maximum of graphite)；
The particle diameter D50 and average grain diameter of Figure 13 exemplary embodiments synthetic materials.
Figure 14 exemplary embodiments and comparative example 0.1C multiplying powers, 300 charge and discharge cycles specific discharge capacities；
The 1C multiplying power first charge-discharge Capacity Ratios of Figure 15 exemplary embodiments and comparative example's material compared with；
The highest specific capacity of each embodiments of Figure 16,1C multiplying powers 100 and 300 circulation volumes, capability retentions；
Figure 17 embodiments 4,6,9 are in 1~200 circulation specific discharge capacity of 0.1C, 1C, 5C and 10C multiplying power；
Figure 18 embodiments 4 are in 5C multiplying powers, 281~300 cycle charge-discharge curves；
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is done and is further described in detail.
Embodiment 1:
A kind of preparation method of nanometer titanium dioxide-coated graphite cathode material, its step is：
The first step, under room temperature, stirring condition, the graphite of 60g is added to 120mL glacial acetic acid and 50mL water and 100mL In the mixed solution of absolute ethyl alcohol, it is sufficiently mixed, obtains the mixture of graphite and glacial acetic acid, distilled water and absolute ethyl alcohol；
Second step, under room temperature, stirring condition, in 30 minutes, by butyl titanate 100mL, metatitanic acid n-propyl 100mL, The 400mL mixtures of isopropyl titanate 100mL, tetraethyl titanate 100mL mixing, are added drop-wise to 100mL absolute ethyl alcohol mixed liquors In graphite and the mixture of glacial acetic acid, distilled water and absolute ethyl alcohol that the first step is obtained, 0.5 hour is stood, under the conditions of 120 DEG C Dry 4 hours, obtain canescence or grey metatitanic acid gel coated graphite powder；
3rd step, the metatitanic acid gel coated graphite powder for obtaining second step are placed in temperature programmed control stove, with per minute 10 DEG C heating rate be warming up to 350 DEG C, under 0.01MPa vacuum conditions, constant temperature 24 hours naturally cools to room temperature, that is, obtain ash White or grey nanometer titanium dioxide-coated powdered graphite；
Pattern, particle diameter and the crystal for preparing nanometer titanium dioxide-coated graphite cathode material are determined with SEM, XRD technology Structure, using the nanometer titanium dioxide-coated graphite cathode material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held The lithium ion battery for 1000mAh is measured, (charging under the conditions of each multiplying power limits voltage in 0.1C and 1C charge-discharge magnifications 4.2V, final discharging voltage be 3.0V, it is same as below) under the conditions of determine lithium ion battery charge and discharge cycle electric performance, preparation receive Specific discharge capacity of rice coated by titanium dioxide graphite cathode material etc..Result shows：Prepare gained nanometer titanium dioxide-coated stone The pattern of black negative material keeps the pattern and particle diameter of original graphite substantially, is the polymorphs such as irregular spheroid, barred body, its Grain particle size range between 1~30 μm (Fig. 1), D50 (median particle diameter, or particle mean size, same as below) is about 12.5 μm of (accompanying drawings 13), coated by titanium dioxide layer is anatase titanium dioxide crystal；The highest of nanometer titanium dioxide-coated graphite cathode material is put Electric specific capacity is 455mAh/g (0.1C multiplying powers)；1C multiplying power first discharge specific capacity 351mAh/g, discharging efficiency is 91.2%, most Specific discharge capacity high is 392mAh/g, 100 charge and discharge cycles capability retentions 95.6%, 300 charge and discharge cycles capacity guarantors Holdup 90.6% (Figure 14,15,16).
Embodiment 2:
A kind of preparation method of nanometer titanium dioxide-coated graphite cathode material, its step is：
The first step, under room temperature, stirring condition, the graphite of 85g is added to 100mL glacial acetic acid and 40mL water and 200mL In the mixed solution of absolute ethyl alcohol, it is sufficiently mixed, obtains the mixture of graphite and glacial acetic acid, redistilled water and absolute ethyl alcohol；
Second step, under room temperature, stirring condition, in 60 minutes, by butyl titanate 120mL, metatitanic acid n-propyl 120mL, The 360mL mixtures of tetraethyl titanate 120mL mixing, the graphite that the first step is obtained is added drop-wise to 200mL absolute ethyl alcohol mixed liquors In the mixture of glacial acetic acid, redistilled water and absolute ethyl alcohol, 1 hour is stood, dried 6 hours under the conditions of 130 DEG C, obtained Canescence or grey metatitanic acid gel coated graphite powder；
3rd step, the metatitanic acid gel coated graphite powder for obtaining second step are placed in temperature programmed control stove, with 5 DEG C per minute Heating rate be warming up to 450 DEG C, under 0.005MPa vacuum conditions, constant temperature 20 hours naturally cools to room temperature, that is, obtain greyish white Color or grey nanometer titanium dioxide-coated powdered graphite；
Pattern, particle diameter and the crystal for preparing nanometer titanium dioxide-coated graphite cathode material are determined with SEM, XRD technology Structure, using the nanometer titanium dioxide-coated graphite cathode material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held The lithium ion battery for 1000mAh is measured, charge and discharge cycle electric performance, the system of lithium ion battery are determined under the conditions of 1C charge-discharge magnifications Specific discharge capacity of standby nanometer titanium dioxide-coated graphite cathode material etc..Result shows：Prepare gained nano titanium oxide bag The pattern for covering graphite cathode material keeps the pattern and particle diameter of original graphite substantially, is the polymorphs such as irregular spheroid, barred body, Its particle size range between 2~20 μm (Fig. 2), D50 is about 18.5 μm (Figure 13), and coated by titanium dioxide layer is Detitanium-ore-type (Fig. 3, A diffraction maximum are anatase titanium dioxide crystal diffraction peak, titanium dioxide XRD standard card JCPDS cards to titanium dioxide crystal Number：21-1272, same as below), the initial crystalline grain diameter of nano titanium oxide is in 10~47.5nm scopes (TiO2Diffraction Peak half-peak breadth is calculated, same as below, Fig. 3)；The highest specific discharge capacity of nanometer titanium dioxide-coated graphite cathode material is 408mAh/g (1C multiplying powers), 1C multiplying powers first discharge specific capacity are 336mAh/g, and discharging efficiency is 89.9% (Figure 15), 100 times Charge and discharge cycles capability retention 96.3%, 300 times circulation conservation rate 91.8% (is referred to：Figure 16).
Embodiment 3:
A kind of preparation method of nanometer titanium dioxide-coated graphite cathode material, its step is：
The first step, under room temperature, stirring condition, the graphite of 105g is added to 80mL glacial acetic acid and 30mL water and 300mL In the mixed solution of absolute ethyl alcohol, it is sufficiently mixed, obtains the mixture of graphite and glacial acetic acid, pure water and absolute ethyl alcohol；
Second step, under room temperature, stirring condition, in 90 minutes, butyl titanate 160mL, metatitanic acid n-propyl 160mL are mixed The 320mL mixtures of conjunction, graphite and glacial acetic acid, pure water and the nothing that the first step is obtained are added drop-wise to 300mL absolute ethyl alcohol mixed liquors In the mixture of water-ethanol, 2 hours are stood, dried 8 hours under the conditions of 140 DEG C, obtain grey or grey black metatitanic acid gel bag Cover powdered graphite；
3rd step, the metatitanic acid gel coated graphite powder for obtaining second step are placed in temperature programmed control stove, with 2 DEG C per minute Heating rate be warming up to 550 DEG C, under 0.002MPa vacuum conditions, constant temperature 16 hours naturally cools to room temperature, that is, obtain grey Or grey black nanometer titanium dioxide-coated powdered graphite；
Pattern, particle diameter and the crystal for preparing nanometer titanium dioxide-coated graphite cathode material are determined with SEM, XRD technology Structure, using the nanometer titanium dioxide-coated graphite cathode material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held The lithium ion battery for 1000mAh is measured, charge and discharge cycle electric performance, the system of lithium ion battery are determined under the conditions of 1C charge-discharge magnifications Specific discharge capacity of standby nanometer titanium dioxide-coated graphite cathode material etc..Result shows：Prepare gained nano titanium oxide bag The pattern for covering graphite cathode material keeps the pattern and particle diameter of original graphite substantially, is the polymorphs such as irregular spheroid, barred body, Its particle size range between 1~35 μm (Fig. 4), D50 is about 20.5 μm (Figure 13), and coated by titanium dioxide layer is Detitanium-ore-type Titanium dioxide crystal；The highest specific discharge capacity of nanometer titanium dioxide-coated graphite cathode material be 424mAh/g (1C multiplying powers), 1C multiplying powers first discharge specific capacity is 382mAh/g, and discharging efficiency is 91.3% (accompanying drawing 14), and 100 times charge and discharge cycles capacity is protected Holdup 96.3%, 300 times circulation conservation rate 91.8% (is referred to：Figure 16).
Embodiment 4:
A kind of preparation method of nanometer titanium dioxide-coated graphite cathode material, its step is：
The first step, under room temperature, stirring condition, the graphite of 125g is added to 60mL glacial acetic acid and 20mL water and 400mL In the mixed solution of absolute ethyl alcohol, it is sufficiently mixed, obtains the mixture of graphite and glacial acetic acid, deionized water and absolute ethyl alcohol；
Second step, under room temperature, stirring condition, in 120 minutes, 275mL butyl titanates are mixed with 400mL absolute ethyl alcohols Close drop to be added in graphite that the first step obtains and the mixture of glacial acetic acid, deionized water and absolute ethyl alcohol, stand 4 hours, Dried 6 hours under the conditions of 150 DEG C, obtain grey or grey black metatitanic acid gel coated graphite powder；
3rd step, the metatitanic acid gel coated graphite powder for obtaining second step are placed in temperature programmed control stove, with 1 DEG C per minute Heating rate be warming up to 550 DEG C, under 0.001MPa vacuum conditions, constant temperature 8 hours naturally cools to room temperature, that is, obtain grey Or grey black nanometer titanium dioxide-coated powdered graphite；
Pattern, particle diameter and the crystal for preparing nanometer titanium dioxide-coated graphite cathode material are determined with SEM, XRD technology Structure, using the nanometer titanium dioxide-coated graphite cathode material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held The lithium ion battery for 1000mAh is measured, the charge and discharge of lithium ion battery is determined under the conditions of 0.1C, 1C, 5C and 10C charge-discharge magnification Cycle electric performance, the specific discharge capacity for preparing nanometer titanium dioxide-coated graphite cathode material etc..Result shows：Gained is prepared to receive The pattern of rice coated by titanium dioxide graphite cathode material keeps the pattern and particle diameter of original graphite substantially, be irregular spheroid, The polymorphs such as barred body, its particle size range between 1~35 μm (Fig. 5), D50 is about 16.5 μm (Figure 13), titanium dioxide bag Coating is anatase titanium dioxide crystal, and the initial crystalline grain diameter of nano titanium oxide is in 5~35.5nm scopes (figure 6)；The highest specific discharge capacity of nanometer titanium dioxide-coated graphite cathode material is 499mAh/g (0.1C multiplying powers) (Figure 14, figure 17), 435mAh/g (1C multiplying powers) (Figure 16, Figure 17), 420mAh/g (5C multiplying powers) (Figure 17, Figure 18), 391mAh/g (10C multiplying powers) (Figure 16), 1C multiplying powers first discharge specific capacity is 379mAh/g, and discharging efficiency is 94.8% (Figure 15), 100 charge and discharge cycles Capability retention 98.1%, 300 charge and discharge cycles capability retentions 94.3% (Figure 16), 5C multiplying powers, 100 circulation volumes are protected Holdup 91.2%, 150 circulation volume conservation rates 84.2%, 10C multiplying powers, 150 circulation volume conservation rates 84.1%, 200 times Circulation volume conservation rate 78.3% (Figure 17, Figure 18).
Embodiment 5:
A kind of preparation method of nanometer titanium dioxide-coated graphite cathode material, its step is：
The first step, under room temperature, stirring condition, the graphite of 165g is added to 40mL glacial acetic acid and 50mL water and 400mL In the mixed solution of absolute ethyl alcohol, it is sufficiently mixed, obtains the mixture of graphite and glacial acetic acid, deionized water and absolute ethyl alcohol；
Second step, under room temperature, stirring condition, it is in 30~120 minutes, 225mL metatitanic acids n-propyl is anhydrous with 400mL Alcohol mixeding liquid is added drop-wise in graphite that the first step obtains and the mixture of glacial acetic acid, deionized water and absolute ethyl alcohol, stands 6 small When, dried 16 hours under the conditions of 120 DEG C, obtain canescence or grey or grey black metatitanic acid gel coated graphite powder；
3rd step, the metatitanic acid gel coated graphite powder for obtaining second step are placed in temperature programmed control stove, with 2 DEG C per minute Heating rate be warming up to 650 DEG C, under 0.001MPa vacuum conditions, constant temperature 12 hours naturally cools to room temperature, that is, obtain greyish white Color or grey or grey black nanometer titanium dioxide-coated powdered graphite；
Pattern, particle diameter and the crystal for preparing nanometer titanium dioxide-coated graphite cathode material are determined with SEM, XRD technology Structure, using the nanometer titanium dioxide-coated graphite cathode material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held The lithium ion battery for 1000mAh is measured, charge and discharge cycle electric performance, the system of lithium ion battery are determined under the conditions of 1C charge-discharge magnifications Specific discharge capacity of standby nanometer titanium dioxide-coated graphite cathode material etc..Result shows：Prepare gained nano titanium oxide bag The pattern for covering graphite cathode material keeps the pattern and particle diameter of original graphite substantially, is the polymorphs such as irregular spheroid, barred body, Its particle size range between 2~20 μm (Fig. 7), D50 is about 18.5 μm (Figure 13), and coated by titanium dioxide layer is Detitanium-ore-type Titanium dioxide crystal；The highest specific discharge capacity of nanometer titanium dioxide-coated graphite cathode material is 423mAh/g, and 1C multiplying powers are first Secondary specific discharge capacity is 368mAh/g, discharging efficiency is 91.6% (Figure 13), 100 charge and discharge cycles capability retentions 95.7%, 300 charge and discharge cycles capability retentions 93.7% (Figure 16).
Embodiment 6:
A kind of preparation method of nanometer titanium dioxide-coated graphite cathode material, its step is：
The first step, under room temperature, stirring condition, the graphite of 200g is added to 20mL glacial acetic acid and 40mL water and 400mL In the mixed solution of absolute ethyl alcohol, it is sufficiently mixed, obtains the mixture of graphite and glacial acetic acid, deionized water and absolute ethyl alcohol；
Second step, under room temperature, stirring condition, it is in 30~120 minutes, 165mL isopropyl titanates is anhydrous with 400mL Alcohol mixeding liquid is added drop-wise in graphite that the first step obtains and the mixture of glacial acetic acid, deionized water and absolute ethyl alcohol, stands 12 Hour, dried 18 hours under the conditions of 140 DEG C, obtain canescence or grey or grey black metatitanic acid gel coated graphite powder；
3rd step, the metatitanic acid gel coated graphite powder for obtaining second step are placed in temperature programmed control stove, with 5 DEG C per minute Heating rate be warming up to 650 DEG C, under 0.005MPa vacuum conditions, constant temperature 6 hours naturally cools to room temperature, that is, obtain greyish white Color or grey or grey black nanometer titanium dioxide-coated powdered graphite；
Pattern, particle diameter and the crystal for preparing nanometer titanium dioxide-coated graphite cathode material are determined with SEM, XRD technology Structure, using the nanometer titanium dioxide-coated graphite cathode material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held The lithium ion battery for 1000mAh is measured, the charge and discharge of lithium ion battery is determined under the conditions of 0.1C, 1C, 5C and 10C charge-discharge magnification Cycle electric performance, the specific discharge capacity for preparing nanometer titanium dioxide-coated graphite cathode material etc..Result shows：Gained is prepared to receive The pattern of rice coated by titanium dioxide graphite cathode material keeps the pattern and particle diameter of original graphite substantially, be irregular spheroid, The polymorphs such as barred body, its particle size range between 2~30 μm (Fig. 8), D50 is about 15.5 μm (Figure 13), titanium dioxide bag Coating is anatase titanium dioxide crystal, and the initial crystalline grain diameter of nano titanium oxide is at 20~45.8nm (Fig. 9)；Receive The highest specific discharge capacity of rice coated by titanium dioxide graphite cathode material is 476mAh/g (0.1C multiplying powers) (Figure 14, Figure 17), 410mAh/g (1C multiplying powers) (Figure 16, Figure 17), discharge capacity is 344mAh/g, discharging efficiency for 90.1% (schemes to 1C multiplying powers first 15), 100 charge and discharge cycles capability retentions 95.8%, 300 charge and discharge cycles capability retentions 92.2% (Figure 18).5C Multiplying power, 100 charge and discharge cycles capability retentions 82.1%, 150 charge and discharge cycles capability retentions 81.9%, 10C multiplying powers, 150 charge and discharge cycles capability retentions 73.5%, 200 charge and discharge cycles capability retentions 71.4% (Figure 17).
Embodiment 7:
A kind of preparation method of nanometer titanium dioxide-coated graphite cathode material, its step is：
The first step, under room temperature, stirring condition, by the graphite of 225g be added to 80mL glacial acetic acid and 40 water and 300mL without In the mixed solution of water-ethanol, it is sufficiently mixed, obtains the mixture of graphite and glacial acetic acid, deionized water and absolute ethyl alcohol；
Second step, under room temperature, stirring condition, it is in 30~120 minutes, 105mL tetraethyl titanates is anhydrous with 300mL Alcohol mixeding liquid is added drop-wise in graphite that the first step obtains and the mixture of glacial acetic acid, deionized water and absolute ethyl alcohol, stands 18 Hour, dried 20 hours under the conditions of 130 DEG C, obtain canescence or grey or grey black metatitanic acid gel coated graphite powder；
3rd step, the metatitanic acid gel coated graphite powder for obtaining second step are placed in temperature programmed control stove, with per minute 10 DEG C heating rate be warming up to 750 DEG C, under 0.002MPa vacuum conditions, constant temperature 8 hours naturally cools to room temperature, that is, obtain ash White or grey or grey black nanometer titanium dioxide-coated powdered graphite；
Pattern, particle diameter and the crystal for preparing nanometer titanium dioxide-coated graphite cathode material are determined with SEM, XRD technology Structure, using the nanometer titanium dioxide-coated graphite cathode material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.1C, 1C charge-discharge magnification is electrical Specific discharge capacity that, nanometer titanium dioxide-coated graphite cathode material can be prepared etc..Result shows：Prepare gained nanometer titanium dioxide The pattern of titanium coated graphite negative material keeps the pattern and particle diameter of original graphite substantially, is that irregular spheroid, barred body etc. are more Body, its particle size range between 5~30 μm (Figure 10), D50 is about 18.5 μm (Figure 13), and coated by titanium dioxide layer is sharp Titanium ore type titanium dioxide crystal；The highest specific discharge capacity of nanometer titanium dioxide-coated graphite cathode material is 403mAh/g (1C Multiplying power), 1C multiplying powers first discharge specific capacity is 355mAh/g, discharging efficiency is 92.5% (Figure 15), 100 charge and discharge cycles appearances Amount conservation rate 96.3%, 300 charge and discharge cycles capability retentions 94.5% (Figure 16).
Embodiment 8:
A kind of preparation method of nanometer titanium dioxide-coated graphite cathode material, its step is：
The first step, under room temperature, stirring condition, the graphite of 250g is added to 40mL glacial acetic acid and 50mL water and 400mL In the mixed solution of absolute ethyl alcohol, it is sufficiently mixed, obtains the mixture of graphite and glacial acetic acid, deionized water and absolute ethyl alcohol；
Second step, under room temperature, stirring condition, it is in 30~120 minutes, 50mL tetraethyl titanates is anhydrous with 100mL Alcohol mixeding liquid is added drop-wise in graphite that the first step obtains and the mixture of glacial acetic acid, deionized water and absolute ethyl alcohol, stands 24 Hour, dried 24 hours under the conditions of 120 DEG C, obtain canescence or grey or grey black metatitanic acid gel coated graphite powder；
3rd step, the metatitanic acid gel coated graphite powder for obtaining second step are placed in temperature programmed control stove, with 5 DEG C per minute Heating rate be warming up to 850 DEG C, under 0.001MPa vacuum conditions, constant temperature 4 hours naturally cools to room temperature, that is, obtain greyish white Color or grey or grey black nanometer titanium dioxide-coated powdered graphite；
Pattern, particle diameter and the crystal for preparing nanometer titanium dioxide-coated graphite cathode material are determined with SEM, XRD technology Structure, using the nanometer titanium dioxide-coated graphite cathode material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.1C, 1C charge-discharge magnification is electrical Specific discharge capacity that, nanometer titanium dioxide-coated graphite cathode material can be prepared etc..Result shows：Prepare gained nanometer titanium dioxide The pattern of titanium coated graphite negative material keeps the pattern and particle diameter of original graphite substantially, is that irregular spheroid, barred body etc. are more Body, its particle size range between 1~30 μm (Figure 11), D50 is about 16.5 μm (Figure 13), and coated by titanium dioxide layer is main It is anatase titanium dioxide crystal (Figure 12, A diffraction maximum, JCPDS card 21-1272), contains rutile titanium dioxide crystal (Figure 12, R diffraction maximum, JCPDS card 21-1276), the initial crystalline grain diameter of nano titanium oxide is in 1~25nm (TiO2Spread out Peak half-peak breadth is penetrated to calculate, same as below)；The highest specific discharge capacity of nanometer titanium dioxide-coated graphite cathode material is 461mAh/g (0.1C multiplying powers) (Figure 14), 422mAh/g (1C multiplying powers), 1C multiplying powers first discharge specific capacity are 378mAh/g, electric discharge Efficiency is 91.7% (Figure 15), 100 charge and discharge cycles capability retentions 95.6%, 300 charge and discharge cycles capability retentions 90.6% (Figure 16).
Comparative example 9:
Using the graphite cathode material of uncoated nano titanium oxide as negative electrode active material, manufacture cathode pole piece assembling is held The lithium ion battery for 1000mAh is measured, the electric discharge specific volume of lithium ion battery is determined under the conditions of 0.1C~10C charge-discharge magnifications Amount, charge and discharge cycle electric performance etc., as a result show：Its highest specific discharge capacity is followed successively by 305mAh/g, 214mAh/g, 176mAh/ G, 176mAh/g；1C multiplying powers first discharge specific capacity is 241mAh/g, discharging efficiency is 68.2%, 100 charge and discharge circulation volumes Conservation rate 58.8%, 300 charge and discharge circulation volume conservation rates 41.6%, 5C, 10C electric discharge 100,200 circulation volume conservation rates point Wei not 57.4%, 37.5% (Figure 14, Figure 15, Figure 16, Figure 17).
As described above, you can preferably realize the present invention.

Claims (1)

1. a kind of preparation method of nanometer titanium dioxide-coated graphite cathode material, its step is：
The first step, under room temperature, stirring condition, the graphite of 60~250g is added to 20~120mL glacial acetic acid and 20~50mL In the mixed solution of water and 100~400mL absolute ethyl alcohols, it is sufficiently mixed, obtains graphite mixed with glacial acetic acid, water and absolute ethyl alcohol Compound；
Second step, under room temperature, stirring condition, in 30~120 minutes, by 50~400mL titanate esters and 100~400mL without Water-ethanol mixed liquor is added drop-wise in graphite that the first step obtains and the mixture of glacial acetic acid, water and absolute ethyl alcohol, stands 0.5~24 Hour, dried 4~24 hours under the conditions of 120~150 DEG C, obtain canescence or grey or grey black metatitanic acid gel coated graphite Powder；
3rd step, the metatitanic acid gel coated graphite powder for obtaining second step are placed in temperature programmed control stove, with 1~10 DEG C per minute Heating rate be warming up to 350~850 DEG C, under 0.01~0.001MPa vacuum conditions, constant temperature 4~24 hours is naturally cooled to Room temperature, obtains canescence or grey or grey black nanometer titanium dioxide-coated powdered graphite；
Described titanate esters are one kind in butyl titanate, tetraethyl titanate, metatitanic acid n-propyl, isopropyl titanate or two to four kinds etc. The mixture of volume mixture；
Described water is any one in distilled water, redistilled water, pure water or deionized water.
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CN108574098A (en) * 2018-05-16 2018-09-25 华南师范大学 A kind of nanometer titanium dioxide-coated graphite lithium ion battery negative material and preparation method thereof
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CN108574098A (en) * 2018-05-16 2018-09-25 华南师范大学 A kind of nanometer titanium dioxide-coated graphite lithium ion battery negative material and preparation method thereof
CN109346692A (en) * 2018-10-10 2019-02-15 青岛泰达华润新能源科技有限公司 A kind of lithium ion battery negative material and preparation method thereof
CN109346692B (en) * 2018-10-10 2021-06-04 青岛泰达华润新能源科技有限公司 Lithium ion battery cathode material and preparation method thereof
CN111599995A (en) * 2020-04-28 2020-08-28 惠州锂威新能源科技有限公司 Cathode material, preparation method thereof and high-voltage lithium ion battery
CN111969185A (en) * 2020-07-07 2020-11-20 湖南大学 Coated TiO2Graphite double-ion battery composite positive electrode material and preparation method thereof
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Application publication date: 20170524