CN104659341B - Composite negative material for lithium ion battery and manufacture method of composite negative material - Google Patents

Composite negative material for lithium ion battery and manufacture method of composite negative material Download PDF

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CN104659341B
CN104659341B CN201310602828.XA CN201310602828A CN104659341B CN 104659341 B CN104659341 B CN 104659341B CN 201310602828 A CN201310602828 A CN 201310602828A CN 104659341 B CN104659341 B CN 104659341B
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negative pole
composite negative
polysiloxanes
sico
polysilazane
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CN104659341A (en
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卢世刚
阚素荣
袁敏娟
张向军
黄斌
刘莎
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China Automotive Battery Research Institute 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H01M4/1315—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. LiCoOxFy
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H01M4/13915—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. LiCoOxFy
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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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  • General Chemical & Material Sciences (AREA)
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  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a composite negative material for a lithium ion battery and a preparation method of the composite negative material. The composite material is formed by compounding at least one of SiCO, SiCNO, SiCN and SiBC, Li4Ti＜5-x＞MxO＜12-y＞Fy and C, wherein M is at least one of Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Y, Zr, Nb, Mo, Ru, Pd, Rh, Ag, In, Sn, Sb, Pb, Bi and W, x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 0 and less than or equal to 0.5. The content of at least one of SiCO, SiCNO, SiCN and SiBCN in the composite negative material accounts for 0.2 to 20 percent of the total weight, the Li4Ti＜5-x＞MxO＜12-y＞Fy accounts for 80 to 99.8 percent of the total weight, and C accounts for 0 to 20 percent of the total weight. The total weight is the sum of the weight of at least one of SiCO, SiCNO, SiCN and SiBCN and the weight of Li4Ti＜5-x＞MxO＜12-y＞Fy. Carbon or a carbon precursor and Li4Ti＜5-x＞MxO＜12-y＞Fy are added into at least one organic silicon polymer of polysiloxane, polysilazane and polyborosilazane to obtain a mixture, and after the curing and cross-linking, the mixture is pyrolyzed to obtain a composite material obtained by compounding at least one of SiCO, SiCNO, SiCN and SiBCN, Li4Ti＜5-x＞MxO＜12-y＞Fy and C. Compared with the Li4Ti＜5-x＞MxO＜12-y＞Fy, the composite material has the advantages that the compaction density and the electrochemical property of the composite material are remarkably improved.

Description

A kind of composite negative pole material and its manufacture method of lithium ion battery
Technical field
The invention mainly relates to a kind of composite negative pole material of lithium ion battery and preparation method thereof, belongs to lithium-ion electric Pond negative material preparing technical field.
Background technology
Develop from nineteen ninety Sony corporation of Japan since adopting petroleum coke for the lithium ion battery of negative pole, material with carbon element is just received To the concern of people, kind includes Delanium, native graphite, carbonaceous mesophase spherules, petroleum coke, carbon fiber etc., is commodity Change the main negative material of lithium ion battery.But material with carbon element has the disadvantage that：1 and electrolyte react, formed SEI films, Cause first charge-discharge efficiency relatively low；2nd, in the easy deposited metal lithium of negative terminal surface, along with latter stage of charging is without significantly electricity Pressure instruction, easily causes safety issue；3 and compatibility of electrolyte it is poor, such as the electrolyte containing PC is produced in graphite-like material with carbon element Raw insertion etc. altogether；4th, Volume Changes are larger in charge and discharge process, and cyclical stability is undesirable.Compared with material with carbon element, spinelle knot Structure lithium titanate charge and discharge process structure change is very little, a kind of zero strain material of being known as, thus steady with excellent circulation It is qualitative；Relative to lithium metal, in 1.55V or so, away from lithium metal sedimentation potential, in addition latter stage of charging presence is obvious for plateau potential Voltage indicate, so security is preferable；On the other hand good with compatibility of electrolyte, initial charge does not have SEI films to be formed, charge and discharge Electrical efficiency is higher.In view of above-mentioned advantage, lithium titanate with spinel structure is considered as a kind of excellent new type lithium ion battery negative pole Material, while being also a kind of promising asymmetric super-capacitor negative material.
But Li in lithium titanate+In Li4Ti5O12Middle diffusion coefficient only has 3 × 10-12cm2/ S, conductance 10-9S/cm, reduces Particle diameter, cladding, doping vario-property are the main methods for improving material property.
The preparation method of lithium titanate typically has conventional high-temperature solid phase method, sol-gal process etc., conventional high-temperature solid phase method be with TiO2With Li2CO3Or LiOH etc. synthesizes for raw material under 800 DEG C～1000 DEG C high temperature, the reaction time is general 12～24 hours, The method advantage is process is simple, and easily large-scale production, has the disadvantage that product grain is thicker, typically all micron order, uniformly Property is poor；Sol-gal process typically adopts the organic alkoxide of titanium and lithium for precursor, and Jing hydrolysis and sol gel process prepare target Product, the method is compared with conventional high-temperature solid phase method, and product chemistry purity is high, uniformity is good, particle is thinner etc., is operated in addition multiple It is miscellaneous, be not suitable for large-scale production.The present invention synthesizes first Li4Ti5-xMxO12-yFyMaterial, adds in building-up process in raw material After carbon or carbon matrix precursor, whether sinter in air atmosphere or sintering can effectively suppress particle under nonoxidizing atmosphere Grow up and reunite, effectively reduce the grain diameter of lithium titanate, improve material electrochemical performance.Stumble on raw material in experiment Synthesis reaction temperature is greatly reduced after middle addition fluoride, realizes lithium titanate synthesis at a lower temperature, reaches saving energy The purpose in source.The Li that will be obtained also is found in experiment4Ti5-xMxO12-yFyIt is added in polysiloxanes with carbon or carbon matrix precursor, The composite C/SiCO/Li obtained after high temperature pyrolysis4Ti5-xMxO12-yFyIts chemical property shakes while being greatly improved Real density there has also been and significantly improve.
SiCO be polymerized by organosiloxane monomer after in non-oxidizing atmosphere either vacuum pyrolysis obtain or by gathering Pyrolysis is obtained under non-oxidizing atmosphere or in vacuum after silicone cross-linked solidification, and organosiloxane monomer referred herein is Refer to contain and contain in molecule polymerisable group such as vinyl three (2- methoxy ethoxies) silane, aminomethyl phenyl dimethoxy silica Alkane, diphenyl dimethoxy siloxanes, aminomethyl phenyl diethoxy siloxanes, diphenyl diethoxy siloxanes etc..
Polysiloxanes be Si-O keys to repeat as main chain, on side chain silicon directly with alkyl, carboxyl, hydroxyl, amino, alcoxyl Base, alkenyl oxy, acyloxy, hydrogen, halogen and containing in hydroxyl, carboxyl, amino, hydrogen, alkenyl, the alkyl of halogen Plant or several constituted polymer that are connected, general linear polysiloxanes can be written as [R2SiO]n, cyclic polysiloxanes can remember For [RSiO1.5]n, such polymer is by the silane (RSiX of different two functions or three functional groups3) pass through hydrolytie polycondensation Reaction is generated, and wherein R is alkyl group or aromatic yl group, and X is a hydrolyzable group, such as OCH3Or Cl etc., it is many Polysiloxanes contains [R simultaneously3SiO0.5]、[R2SiO][RSiO1.5][SiO2] etc. group, wherein R can be alkyl, hydrogen-based, benzene The group such as base or vinyl.Polysiloxanes such as polymethyl siloxane, dimethyl silicone polymer, cyclomethicone, ring Five dimethyl silicone polymers, Polymethyl methacrylate, phenyl trimethicone, PSI, ammonia end Dimethyl silicone polymer, polyvinyl siloxane, polydiphenylsiloxane, dimethyl diphenyl polysiloxanes, the poly- methyl of hydroxyl Phenyl siloxane, hydroxy-end capped diphenyldimethyl polysiloxanes etc., the PSI of ethenyl blocking, hydroxyl The PSI of end-blocking, hydroxy-end capped poly- methylethoxy radical siloxane, poly- methylhydrogen silicone, containing amino Hydroxy-end capped polysiloxanes, the carboxylic polysiloxanes of side chain, hydroxy-end capped poly- p- fluorophenyl butyl siloxanes holds hydroxyl Base dimethyl silicone polymer etc..
SiCNO is that pyrolysis is obtained or consolidated by silicone cross under NH3 atmosphere by after the polymerization of organosiloxane monomer It is pyrolyzed in NH3 atmosphere after change and obtains；
SiCN is to be pyrolyzed to obtain under non-oxidizing atmosphere or in vacuum by polysilazane.Polysilazane is contained in molecule Have and replace the one of bonding strand with nitrogen-atoms with silicon atom and birds of the same feather flock together compound.Be the Si-N keys to repeat as main chain, on side chain Silicon can directly with alkyl, carboxyl, hydroxyl, amino, alkoxyl, alkenyl oxy, acyloxy, hydrogen, halogen and containing hydroxyl, Connected the constituted polymer such as carboxyl, amino, hydrogen, alkenyl, alkyl of halogen.Such as poly dimethyl silazane, vinyl gathers Silazane, [MenSi2(NH)3-(2/2)]mN=1～4, methyl ethylene polysilazane, the poly- silicon nitrogen of hydroxy-end capped aminomethyl phenyl Alkane, hydroxy-end capped methyl ethoxy polysilazane etc..
SiBCN is to be pyrolyzed to obtain under non-oxidizing atmosphere or in vacuum by PVDF hollow fiber membrane, PVDF hollow fiber membrane be with Repeat containing-C-Si-N-B-either-B-C-Si-N-or-C-B-Si-N-as main chain, on side chain Silicon can directly with alkyl, carboxyl, hydroxyl, amino, alkoxyl, alkenyl oxy, acyloxy, hydrogen, halogen and containing hydroxyl, Carboxyl, amino, hydrogen, alkenyl, connected the constituted polymer of alkyl of halogen.
SiCO, SiCNO, SiCN, SiBCN are a kind of porous skeleton structures, also containing the trip being dispersed in skeleton in structure From carbon.SiCO is the porous skeleton structure being made up of C-Si-O keys and C-C keys, while comprising the free carbon being dispersed in skeleton. SiCO also shows higher electric conductivity and heat endurance in addition to higher tap density.
The method of traditional carbon coating can improve the electric conductivity of lithium titanate, but be shaken with the lithium titanate of coated modified carbon merely Real density is relatively low, generally below 1g/cm3, the method for the present invention using at least one of SiCO, SiCNO, SiCN, SiBCN with Li4Ti5-xMxO12-yFyComposite is compounded to form with C, material conductivity is not only increased, tap density also has larger carrying It is high.
The content of the invention
The purpose of the present invention is to realize the composite negative pole material and its manufacture method of a kind of lithium ion battery.The present invention's The composite negative pole material of lithium ion battery has significant improvement in chemical property and the aspect of tap density two.
To achieve these goals, the present invention takes technical scheme below.
The present invention is a kind of composite cathode material for lithium ion cell, be it is characterized in that by SiCO, SiCNO, SiCN, SiBCN At least one and Li4Ti5-xMxO12-yFyThe composite being compounded to form with C, wherein M be Mg, V, Cr, Mn, Fe, Co, Ni, Cu, At least one of Zn, Ga, Y, Zr, Nb, Mo, Ru, Pd, Rh, Ag, In, Sn, Sb, Pb, Bi, W, 0≤x≤0.5,0≤y≤0.5, The content of at least one of SiCO, SiCNO, SiCN, SiBCN accounts for the 0.2wt%-20wt% of gross weight in the composite； Li4Ti5-xMxO12-yFyThe 80wt%-99.8wt% of gross weight is accounted for, C accounts for the 0wt%-20wt% of gross weight.It is mentioned here total Weight is at least one weight of SiCO, SiCNO, SiCN, SiBCN and Li to form composite4Ti5-xMxO12-yFyWeight Sum.
Described Li4Ti5-xMxO12-yFy, wherein 0.01≤x≤0.2.
Described Li4Ti5-xMxO12-yFy, wherein 0.01≤y≤0.2.
Described C refers to the carbon remained after carbon or carbon matrix precursor high temperature cabonization；
Described SiCO be by organosiloxane monomer be polymerized after under nonoxidizing atmosphere or in vacuum pyrolysis obtain or It is pyrolyzed under nonoxidizing atmosphere or in vacuum by polysiloxanes and is obtained；SiCNO be by organosiloxane monomer be polymerized after in NH3Under Pyrolysis is obtained or by polysiloxanes in NH3Lower pyrolysis is obtained；SiCN is by polysilazane under nonoxidizing atmosphere or in vacuum Pyrolysis is obtained；SiBCN is to be pyrolyzed to obtain under nonoxidizing atmosphere or in vacuum by PVDF hollow fiber membrane.
Described organosiloxane monomer is containing one in hydrogen bond, alkyl branches, thiazolinyl side chain and aromatic radical side chain Or one or more in multiple organosiloxane monomeric compounds.
Described polysiloxanes be Si-O keys to repeat as main chain, on side chain silicon directly with alkyl, carboxyl, hydroxyl, ammonia Base, alkoxyl, alkenyl oxy, acyloxy, hydrogen, halogen and containing hydroxyl, carboxyl, amino, hydrogen, alkenyl, halogen hydrocarbon One or more connected constituted polymer in base, the degree of polymerization is 2～2000.
The degree of polymerization of described polysiloxanes is 5～500.
Described alkyl is one or more in alkyl, alkenyl, alkynyl, aryl, aralkyl.
Described polysiloxanes is the polysiloxanes containing Si -- H bond in molecule.
Described polysiloxanes is containing the polysiloxanes of Si-OH keys in molecule.
Described polysiloxanes is the polysiloxanes containing unsaturated hydrocarbons or the derivative of unsaturated hydrocarbons in molecule.
Described polysiloxanes is the polysiloxanes containing phenyl in molecule.
Described polysiloxanes is the silicones of heat cure.
Described polysiloxanes is the polysiloxanes or can melt that the polysiloxanes of liquid either can be dissolved with solvent The polysiloxanes for melting.
Described polysilazane be Si-N keys to repeat as main chain, on side chain silicon directly with alkyl, carboxyl, hydroxyl, ammonia Base, alkoxyl, alkenyl oxy, acyloxy, hydrogen, halogen and containing hydroxyl, carboxyl, amino, hydrogen, alkenyl, halogen hydrocarbon One or more connected constituted polymer in base, the degree of polymerization is 2～2000.
The degree of polymerization of described polysilazane is 5～500.
Described alkyl is one or more in alkyl, alkenyl, alkynyl, aryl, aralkyl.
Described polysilazane is the polysilazane containing Si -- H bond in molecule.
Described polysilazane is containing the polysilazane of Si-OH keys in molecule.
Described polysilazane is the polysilazane containing unsaturated hydrocarbons or the derivative of unsaturated hydrocarbons in molecule.
Described polysilazane is the polysilazane containing phenyl in molecule.
Described polysilazane is the polysilazane or can melt that the polysilazane of liquid either can be dissolved with solvent The polysilazane for melting.
Described PVDF hollow fiber membrane be with repeat containing-C-Si-N-B-either-B-C-Si-N-or- C-B-Si-N-as main chain, on side chain silicon directly with alkyl, carboxyl, hydroxyl, amino, alkoxyl, alkenyl oxy, acyl Epoxide, hydrogen, halogen and containing one or more the connected institute's groups in hydroxyl, carboxyl, amino, hydrogen, alkenyl, the alkyl of halogen Into polymer, the degree of polymerization be 2～2000.
The degree of polymerization of described PVDF hollow fiber membrane is 5～500.
Described alkyl is one or more in alkyl, alkenyl, alkynyl, aryl, aralkyl.
Described PVDF hollow fiber membrane be liquid PVDF hollow fiber membrane either can with solvent dissolve PVDF hollow fiber membrane or The PVDF hollow fiber membrane that can be melted.
The method for preparing the composite, the method at least comprises the steps：
(1) compound of the compound of titanium, the compound of M, lithium is carried out according to atomic ratio Li/Ti+M=0.8～0.88 Dispensing, add fluoride, add raw material gross weight 0-20wt% carbon or carbon matrix precursor, raw material mentioned here it is total Weight is the weight sum of the compound of titanium, the compound of M, the compound of lithium, fluoride, above-mentioned raw material is put into and accounts for former material In the medium of 1-5 times of cumulative volume of material, uniformly mix 5～72 hours in media as well, drying forms presoma, first 200 DEG C～500 DEG C K cryogenic treatment 0～20 hour, then at 600 DEG C～900 DEG C, synthesizes 2～72 hours, obtains Li4Ti5-xMxO12-yFy.M is At least one in Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Y, Zr, Nb, Mo, Ru, Pd, Rh, Ag, In, Sn, Sb, Pb, Bi, W Kind.
(2) at least one of organosiloxane monomer, polysiloxanes, polysilazane, PVDF hollow fiber membrane are dissolved in organic In solvent, the addition of organic solvent is 1 according to the polymer and organic solvent volume ratio that add:1 to 1:5 add, wherein, have The addition of organic siloxane monomer is the above-mentioned ratio according to the volume after the polymerization of organosiloxane monomer and organic solvent volume Add, also, the addition of organosiloxane monomer according to organosiloxane monomer polymerization under same experimental conditions after have The pyrolysis rate of organosilicon polymer is calculating so that at least one of SiCO, SiCNO content is accounted in the anode material after being pyrolyzed The 0.2wt%-20wt% of gross weight, polysiloxanes, polysilazane, PVDF hollow fiber membrane at least one of addition according to identical Polymer-pyrolysis rate under experiment condition causes SiCO, SiCNO, SiCN, SiBCN in the anode material after pyrolysis to calculate At least one of content account for the 0.2wt%-20wt% of gross weight, then by Li4Ti5-xMxO12-yFyIt is added thereto, Li4Ti5- xMxO12-yFyAddition calculate according to the pyrolysis rate under same experimental conditions cause pyrolysis after anode material in Li4Ti5-xMxO12-yFyContent accounts for the 80wt%-99.8wt% of gross weight, is in addition additionally added carbon or carbon matrix precursor, carbon or The addition of person's carbon matrix precursor accounts for the 0-20wt% of gross weight according to carbon remaining after carbon or carbon matrix precursor pyrolysis, referred to herein Gross weight be at least one weight of SiCO, SiCNO, SiCN, SiBCN and Li to form composite4Ti5-xMxO12-yFy's Weight sum.Stir, adding curing agent or water when adding siloxanyl monomers makes it be polymerized；
(3) cross-linking products are solidify to form；
(4) under nonoxidizing atmosphere or in vacuum, by the cured product sintering, SiCO, SiCNO, SiCN, SiBCN are obtained At least one of and Li4Ti5-xMxO12-yFyThe composite being combined with C.
The compound of described titanium is at least one in titanium dioxide, metatitanic acid；
The compound of described M is oxide, carbonate, oxalates, nitrate, hydroxide, sulfate, chloride；
The compound of described lithium be lithium hydroxide, lithium carbonate, lithium chloride, lithium iodide, lithium nitrate, lithium phosphate, lithium acetate, One or more mixtures in lithium oxalate；
Described fluoride is at least one in lithium fluoride, ammonium fluoride, magnesium fluoride；
Described medium is in water, ethanol, acetone, n-butanol, normal propyl alcohol, isopropanol, fine second, ether, monoethanolamine Plant or several mixtures；
Described drying is spray drying, forced air drying, vacuum drying one of which；
Described organic solvent be acetone, toluene, dimethylbenzene, ethanol, ether, normal propyl alcohol, isopropanol, n-butanol, acetonitrile, At least one of monoethanolamine, tetrahydrofuran, DMF, chloroform, pyridine, 1-METHYLPYRROLIDONE.
Described is cured as being heating and curing, adds at least one of reheating solidification, ultraviolet light polymerization after curing agent, its In, in being heating and curing or adding curing agent to be heating and curing, solidification temperature is 20 DEG C～400 DEG C.
In described step sintering process 4., described sintering condition is 200-500 DEG C and is incubated 0-5 hours, Ran Houjia Heat is incubated 1-15 hours to 500～850 DEG C.
Described sintering condition is 300-500 DEG C of insulation 0-5 hour, is then heated to 600～750 DEG C, and 1-10 is little for insulation When.
Described non-oxidizing atmosphere is argon gas, nitrogen, NH3、H2At least one of.
The 1. described carbon of step or carbon matrix precursor are graphite, acetylene black, sucrose, glucose, fructose, starch, phenolic aldehyde tree At least one in ester.
The 2. described carbon of step or carbon matrix precursor are graphite, acetylene black, sucrose, glucose, fructose, starch, phenolic aldehyde tree At least one in ester.
A kind of negative pole of lithium rechargeable battery, has used above-mentioned compound lithium titanate anode material as negative electrode active material Matter.
A kind of lithium rechargeable battery, comprising positive pole, barrier film and has used the negative of above-mentioned compound lithium titanate at electrolyte Pole.
Advantages of the present invention：
In order to detect the physically and electrically chemical property of the lithium titanate anode material for lithium ion batteries of the present invention, with Dutch X ' Pert PRO MPD types XRD diffractometers carry out structured testing；Using Japanese HITACHI S-4800 field emission scanning electron microscope instrument (5.0kv, 8.7mm × 1.00k) carries out SEM morphology analysis to lithium titanate；Known with those of ordinary skill belonging to this area Method, assembling them into button test cell carries out electrochemical property test, with the lithium ion battery lithium titanate material of the present invention 80% (percetage by weight) of material, binding agent PVDF (Kynoar) 10%, SP10% mixing is tuned into pulpous state, is coated on Copper Foil, It is dried in atmosphere, makes electrode.It is that lithium metal piece constitutes button test cell to electrode.Electrolyte is 1M (mol/L) LiPF6/ EC+DMC etc., EC are ethylene carbonate, and DMC is dimethyl carbonate.Discharge and recharge upper and lower limit voltage be 2.5～1V, specific volume Amount computational methods C=mA × h/g, wherein C：Specific capacity, mA is current density, and h is the time, g active material weight, and temperature is 25 ± 2 DEG C, the constant current tester that computerizeds control carries out electrochemistry capacitance and loop test.
Advantages of the present invention：
The tap density and electrification of the lithium titanate anode material for lithium ion batteries can be absolutely proved by above-mentioned experiment Learn performance to be significantly increased.
Description of the drawings
The granule-morphology of Fig. 1 embodiments 1
Fig. 2 embodiment 1XRD spectrograms
The first charge-discharge curve of Fig. 3 embodiments 1
The high rate performance of Fig. 4 embodiments 5
The cyclic curve of Fig. 5 embodiments 1
Specific embodiment
Comparative example 1
11.98 grams of 33.4 grams of titanium dioxide and lithium carbonate are weighed, 10 grams of acetylene blacks are added, 2 times of volumes of raw material are added Absolute ethyl alcohol, ball milling 24 hours in absolute ethyl alcohol, spray drying obtains presoma, presoma is put in Muffle furnace, air Heated up 200 DEG C with 3 DEG C/minute of programming rate under atmosphere and be incubated 1 hour, then 750 DEG C of guarantors are warmed up to 3 DEG C/minute of programming rate Temperature 10 hours, to less than 100 DEG C, taking-up grinding obtains Li to along with the furnace cooling4Ti5O12, XRD test be pure Spinel structure, phase Chemical property, 0.1C specific capacities 168mAh/g, 5C specific capacities 120mAh/g, jolt ramming are tested to Li+/Li current potentials 1.0V to 2.5V Density 0.9g/cm3.Comparative example 2
11.94 grams of 33.4 grams of titanium dioxide and lithium carbonate are weighed, 10 grams of graphite powders are added, 0.74 gram of lithium fluoride is added, is put In entering the deionized water of 2 times of volumes of raw material, 3 grams of surfactant, ball milling 24 hours, spray drying is added to obtain presoma, Presoma is put in Muffle furnace, 200 DEG C is warmed up to 3 DEG C/minute of programming rate and is incubated 3 hours, then with 3 DEG C/minute of intensification Speed is warmed up to 630 DEG C and is incubated 10 hours, and to less than 100 DEG C, taking-up grinding obtains Li to along with the furnace cooling4Ti5O11.66F0.34, XRD surveys Try as pure Spinel structure, with respect to Li+/ Li current potentials 1.0V to 2.5V tests chemical property, and 0.1C inserts first lithium specific capacity 166mAh/g, 5C specific capacity 125mAh/g, tap density 0.8g/cm3。
Comparative example 3
11.94 grams of 32.06 grams of titanium dioxide and lithium carbonate are weighed, 1.45 grams of manganese dioxide is added, 10 grams of graphite powders are added, 0.74 gram of lithium fluoride is added, in being put into the deionized water of 2 times of volumes of raw material, 3 grams of surfactant of addition, ball milling 24 hours, Spray drying obtains presoma, and presoma is put in Muffle furnace, is warmed up to 200 DEG C of insulations 3 with 3 DEG C/minute of programming rate little When, then with 3 DEG C/minute of programming rate be warmed up to 700 DEG C be incubated 10 hours, along with the furnace cooling to be less than 100 DEG C, taking-up grinding obtain Li4Ti4.8Mn0.2O11.66F0.34, XRD tests are pure Spinel structure, with respect to Li+/Li current potentials 1.0V to 2.5V test electrifications Performance is learned, 0.1C inserts first lithium specific capacity 165mAh/g, 5C specific capacities 123mAh/g, tap density 0.9g/cm3。
Embodiment 1
Take the PSI (C of ethenyl blocking2H3)3SiO{CH3(C6H5)SiO}nSi(C2H3)3N is 150, In being put into alumina crucible, acetone dilution is added, add the volume of acetone for the PSI of ethenyl blocking 3 times of volume, then by sucrose and comparative example 1Li4Ti5O12It is added thereto, according to C/SiCO/Li4Ti5O11.66F0.34Middle C and SiCO accounts for respectively SiCO and Li4Ti5O12The 2wt% and 5wt% of gross weight adds the polymethyl-benzene base of sucrose and ethenyl blocking The addition of the PSI of siloxanes, wherein sucrose and ethenyl blocking according to sucrose under same experimental conditions and The pyrolysis rate of the PSI of ethenyl blocking is calculating.It is heated to 400 DEG C after addition while stirring, holding 5 is little When, after polysiloxanes solidification, form presoma.Crucible containing presoma is put in high temperature furnace, inertia is led to after vacuumizing Gas N2, 700 DEG C are warmed up to, after being incubated 2 hours, after naturally cooling to less than 100 DEG C, product is taken out, obtain C/ through grinding SiCO/Li4Ti5O12Composite, C account for gross weight to 2wt%, SiCO accounts for the 5wt% of gross weight, gross weight mentioned here For the PSI pyrolysis gained SiCO and Li of ethenyl blocking4Ti5O12Weight sum.With respect to Li+/ Li current potentials 1.0V to 2.5V tests chemical property, and 0.1C inserts first lithium specific capacity 168.2mAh/g, 5C specific capacities 151mAh/g, vibration density Degree 1.2g/cm3.Fig. 1, Fig. 2, Fig. 3, Fig. 5 are respectively shape appearance figure, XRD, the first charge-discharges of the lithium titanate of the embodiment synthesis Curve and cyclic curve figure.
As a result as can be seen that the PSI of the present embodiment sucrose and ethenyl blocking is to Li4Ti5O12Enter The composite C/SiCO/Li formed after row is compound4Ti5O12, wherein C accounts for the 5wt% that 2%, SiCO of gross weight accounts for gross weight, There is significant improvement in chemical property and the aspect of tap density two.Electrochemistry 5C specific capacity is by the 120mAh/g before not being combined The 151mAh/g after being combined is brought up to, tap density is by the 0.9g/cm before being combined3Bring up to the 1.2g/cm after being combined3.Vibration density Degree and chemical property are significantly better than not compound Li4Ti5O12。
Embodiment 2
Take hydroxy-end capped PSI (OH)3SiO{CH3(C6H5)SiO}nSi(OH)3N is 50, is put into oxygen In changing aluminium crucible, acetone dilution is added, the volume for adding acetone is the 4 of hydroxy-end capped PSI volume Times, then by glucose and the Li of comparative example 24Ti5O11.66F0.34It is added thereto, according to C/SiCO/Li4Ti5O11.66F0.34Middle C Account for SiCO and Li4Ti5O11.66F0.34The 5wt% of gross weight adds glucose, SiCO to account for SiCO and Li4Ti5O12Gross weight 7.5wt% adds hydroxy-end capped PSI, wherein glucose and hydroxy-end capped PSI Addition calculate according to the pyrolysis rate of glucose under same experimental conditions and hydroxy-end capped PSI. 300 DEG C are heated to while stirring, are kept for 1 hour, after polysiloxanes solidification, form presoma.By the crucible containing presoma In being put into high temperature furnace, inert nitrogen gas are led to after vacuumizing, be warmed up to 725 DEG C, after being incubated 8 hours, naturally cooled to less than 100 Take out after DEG C, grinding obtains C/SiCO/Li4Ti5O11.66F0.34Composite, C accounts for the 5wt% of gross weight, and SiCO accounts for gross weight 7.5wt%, gross weight mentioned here be hydroxy-end capped PSI pyrolysis gained SiCO and Li4Ti5O11.66F0.34Weight sum.With respect to Li+/ Li current potentials 1.0V to 2.5V tests chemical property, and 0.1C discharges first ratio Capacity 167mAh/g, 5C specific capacity 148mAh/g, tap density 1.4g/cm3。
Embodiment 3
Take hydroxy-end capped poly- methylethoxy radical siloxane (OH)3SiO{CH3(OC2H5)SiO}nSi(OH)3N is 150, is put In entering alumina crucible, toluene dissolving is added, the volume for adding toluene is hydroxy-end capped poly- methylethoxy radical siloxane body Long-pending 1.5 times, then by starch and the Li of comparative example 34Ti4.8Mn0.2O11.66F0.34It is added thereto, according to C/SiCO/ Li4Ti4.8Mn0.2O11.66F0.34Middle C accounts for the 5wt% of gross weight and adds starch, and the 3wt% additions that SiCO accounts for gross weight are hydroxy-end capped Poly- methylethoxy radical siloxane, wherein starch with the addition of hydroxy-end capped poly- methylethoxy radical siloxane according to identical reality The pyrolysis rate of starch and hydroxy-end capped poly- methylethoxy radical siloxane is calculating under the conditions of testing.300 DEG C are heated to while stirring, Kept for 2 hours, after polysiloxanes solidification, form presoma.Crucible containing presoma is put in high temperature furnace, after vacuumizing Logical inert gas N2, 650 DEG C are warmed up to, after being incubated 5 hours, to take out after naturally cooling to less than 100 DEG C, grinding obtains C/ SiCO/Li4Ti4.8Mn0.2O11.66F0.34Composite, wherein C account for gross weight 5wt%, and SiCO accounts for the 3wt% of gross weight, here Described gross weight is hydroxy-end capped poly- methylethoxy radical siloxane pyrolysis gained SiCO and Li4Ti4.8Mn0.2O11.66F0.34's Weight sum.With respect to Li+/ Li current potentials 1.0V to 2.5V tests chemical property, 0.1C first discharge specific capacities 165mAh/g, 5C Specific capacity 145mAh/g, tap density 1.1g/cm3。
Embodiment 4
By poly- methylhydrogen silicone (CH3)3SiO{CH3(H)SiO}mSi(CH3)3(m=20), xylene soluble is added, The volume for adding dimethylbenzene is 2 times of poly- methylhydrogen silicone volume, according to poly- methylhydrogen silicone and curing agent weight Than for 2:1 adds curing agent divinylbenzene, adds several drops catalyst chloroplatinic acid ethanol solution (1mg/100ml ethanol), stirring Simultaneously by sucrose and the Li of embodiment 14Ti5O12It is added thereto, according to C/SiCNO/Li4Ti5O12Middle C accounts for SiCNO and Li4Ti5O12 Gross weight 2wt% adds sucrose, SiCNO to account for SiCNO and Li4Ti5O12The 7.5wt% of gross weight adds poly- methyl hydrogen silica Alkane, the wherein addition of sucrose and poly- methylhydrogen silicone are according to sucrose under same experimental conditions and poly- methylhydrogen silicone Pyrolysis rate calculating.Gross weight mentioned here is that poly- methylhydrogen silicone is pyrolyzed gained SiCNO and Li4Ti5O12Weight Amount sum.120 DEG C are heated to while stirring so that poly- methylhydrogen silicone and divinyl benzene crosslinked solidify, and form forerunner Body.Then resulting presoma is put in high temperature furnace, NH is passed through after vacuumizing3, 350 DEG C are warmed up to, 3 hours are incubated, then 800 DEG C are warmed up to, 3 hours are incubated, Temperature fall takes out to after less than 100 DEG C, and grinding obtains composite C/SiCNO/ Li4Ti5O12, wherein C accounts for the 2wt% of gross weight, and SiCNO accounts for the 7.5wt% of gross weight, and gross weight mentioned here is poly- methyl Hydrogen-containing siloxane pyrolysis gained SiCNO and Li4Ti5O12Weight sum.Spinel structure is shown through XRD tests, with respect to Li+/ Li current potentials 1.0V to 2.5V tests chemical property, and 0.1C first discharge specific capacities 166mAh/g, 5C specific capacities 149mAh/g are shaken Real density 1.5g/cm3。
Embodiment 5
Polymethyl methacrylate (CH3)3SiO{CH3(CH=CH2)SiO}nSi(CH3)3(n=400) it is, molten with acetone Solution, the volume for adding acetone is 2 times of Polymethyl methacrylate volume, is subsequently adding sucrose and comparative example 1 Li4Ti5O12, according to C/SiCO/Li4Ti5O12Middle C accounts for SiCO and Li4Ti5O12The 1wt% of gross weight, SiCO account for SiCO and Li4Ti5O12The 10wt% of gross weight adds sucrose and Polymethyl methacrylate, wherein sucrose and poly- methyl ethylene silica The addition of alkane is calculated according to the pyrolysis rate of sucrose under same experimental conditions and Polymethyl methacrylate.While stirring plus Heat is kept for 1 hour to 400 DEG C, after Polymethyl methacrylate solidification, obtains presoma.Then presoma is put into into height In warm stove, inert gas N is led to after vacuumizing2, 750 DEG C are warmed up to, after being incubated 2 hours, after naturally cooling to temperature less than 100 DEG C Take out, grinding obtains composite C/SiCO/Li4Ti5O12, wherein C accounts for the 1wt% of gross weight, and SiCO accounts for gross weight 10wt%, gross weight mentioned here is that Polymethyl methacrylate is pyrolyzed gained SiCO and Li4Ti5O12Weight sum. With respect to Li+/ Li current potentials 1.0V to 2.5V tests chemical property, 0.1C its first discharge specific capacity 165mAh/g, 5C specific capacities 147mAh/g, tap density 1.6g/cm3.Fig. 4 is the high rate performance that the embodiment synthesizes lithium titanate.
Embodiment 6
Polymethyl methacrylate (CH3)3SiO{CH3(CH=CH2)SiO}nSi(CH3)3(n=400) it is, molten with acetone Solution, the volume for adding acetone is 2 times of Polymethyl methacrylate volume, is subsequently adding the Li of comparative example 14Ti5O12, according to SiCO/Li4Ti5O12Middle SiCO accounts for the 10wt% of gross weight and adds Polymethyl methacrylate, Polymethyl methacrylate Addition calculate according to the pyrolysis rate of Polymethyl methacrylate under same experimental conditions.400 are heated to while stirring DEG C, kept for 1 hour, after Polymethyl methacrylate solidification, obtain presoma.Then presoma is put in high temperature furnace, Lead to inert gas N after vacuumizing2, 750 DEG C are warmed up to, after being incubated 15 hours, take out after naturally cooling to temperature less than 100 DEG C, Grinding obtains composite SiCO/Li4Ti5O12, wherein SiCO accounts for the 10wt% of gross weight, and gross weight mentioned here is poly- first Base vinylsiloxane pyrolysis gained SiCO and Li4Ti5O12Weight sum.With respect to Li+/ Li current potentials 1.0V to 2.5V test electricity Chemical property, 0.1C its first discharge specific capacity 168mAh/g, 5C specific capacities 135mAh/g, tap density 1.8g/cm3.Fig. 4 is The embodiment synthesizes the high rate performance of lithium titanate.
Embodiment 7
The liquid monomer of diphenyl dimethoxy siloxanes is dissolved in absolute ethyl alcohol, the volume of absolute ethyl alcohol is hexichol 3 times of base dimethoxysiloxane volume, add the Li of sucrose and comparative example 14Ti5O12, according to C/SiCO/Li4Ti5O12Middle C Account for SiCO and Li4Ti5O12The 4wt% of gross weight adds sucrose, SiCO to account for SiCO and Li4Ti5O12The 6wt% of gross weight adds two Phenyl dimethoxysiloxane, the wherein addition of sucrose and diphenyl dimethoxy siloxanes are by sugarcane under same experimental conditions The pyrolysis rate of the polymer after sugar and diphenyl dimethoxy siloxane polymerization is calculating.Stir process 5h, in the situation of stirring Under, a little deionized water is added in above-mentioned dispersion liquid, and 2h is kept stirring for, in the case of stirring, it is incubated between 80 DEG C of heating Process 6h makes mixed solution polymerizing curable to remove solvent, obtains presoma.Then presoma is put in high temperature furnace, is vacuumized Lead to inert gas N afterwards2, 730 DEG C are warmed up to, after being incubated 3 hours, to take out after naturally cooling to temperature less than 100 DEG C, grinding is obtained Composite C/SiCO/Li4Ti5O12, wherein C accounts for the 4wt% of gross weight, and SiCO accounts for the 6wt% of gross weight, mentioned here total Weight is pyrolysis gained SiCO and Li after diphenyl dimethoxy siloxane polymerization4Ti5O12Weight sum.With respect to Li+/ Li is electric Position 1.0V to 2.5V tests chemical property, and 0.1C its first discharge specific capacity 164mAh/g, 5C specific capacities 143.5mAh/g are shaken Real density 1.62g/cm3。
Embodiment 8
By poly- methylhydrogen silicone (CH3)3SiO{CH3(H)SiO}mSi(CH3)3(m=40) diluted with acetone, add third The volume of ketone is 1.5 times of poly- methylhydrogen silicone volume, and according to poly- methylhydrogen silicone and curing agent weight 2 are compared:1 adds Enter curing agent divinylbenzene, stirring is simultaneously by phenolic resin and the Li of embodiment 24Ti5O11.66F0.34It is added thereto, according to C/ SiCO/Li4Ti5O11.66F0.34Middle C accounts for SiCO and Li4Ti5O11.66F0.34The 4wt% of gross weight adds phenolic resin, SiCO to account for SiCO and Li4Ti5O11.66F0.34The 7.5wt% of gross weight adds poly- methylhydrogen silicone, wherein phenolic resin and poly- methyl to contain The addition of hydrogen siloxane is calculated by the pyrolysis rate of phenolic resin under same experimental conditions and poly- methylhydrogen silicone.Side Stirring side is heated to 150 DEG C so that poly- methylhydrogen silicone and divinyl benzene crosslinked solidify, and obtain presoma.Then will Resulting presoma is put in high temperature furnace, is vacuumized, and is warmed up to 450 DEG C, is incubated 3 hours, then is warmed up to 650 DEG C, and insulation 5 is little When, Temperature fall takes out to after less than 100 DEG C, and grinding obtains C/SiCO/Li4Ti5O11.66F0.34Composite, wherein C accounts for always The 4wt% of weight, SiCO account for the 7.5wt% of gross weight, and gross weight mentioned here is after poly- methylhydrogen silicone pyrolysis SiCO and Li4Ti5O11.66F0.34Weight sum.Spinel structure is shown through XRD tests.With respect to Li+/ Li current potential 1.0V are arrived 2.5V tests chemical property, 0.1C first discharge specific capacities 164mAh/g, 5C specific capacities 146mAh/g, tap density 1.55g/ cm3。
Embodiment 9
By methyl ethylene polysilazane (CH3)3Si NH[CH3(C2H3)SiNH]n Si(CH3)3, n=30 is dissolved in first In benzene, the volume for adding toluene is 2 times of methyl ethylene polysilazane volume, adds the Li of sucrose and comparative example 14Ti5O12, According to C/SiCN/Li4Ti5O12Middle C accounts for SiCN and Li4Ti5O12The 1wt% of gross weight, SiCN account for SiCN and Li4Ti5O12Gross weight 3wt% add sucrose and above-mentioned methyl ethylene polysilazane, wherein sucrose and above-mentioned methyl ethylene polysilazane plus Enter amount by the pyrolysis rate of sucrose under same experimental conditions and above-mentioned methyl ethylene polysilazane to calculate.Heating while stirring makes Toluene volatilization is obtained, 350 DEG C of solidifications are heated to, presoma is obtained.Presoma is put in high temperature furnace, is first vacuumized, be re-filled with Inert gas N2, it is warmed up to 400 DEG C, 2 hours are incubated, then it is warmed up to 800 DEG C, and 2 hours are incubated, naturally cool to less than 100 DEG C After take out, C/SiCN/Li is obtained after grinding4Ti5O12Composite, wherein C account for the 1wt% of gross weight, and SiCN accounts for gross weight 3wt%, gross weight mentioned here is the SiCN and Li after the pyrolysis of methyl ethylene polysilazane4Ti5O12Weight sum.Jing Cross XRD tests and show spinel structure.Chemical property is tested with respect to Li+/Li current potentials 1.0V to 2.5V, 0.1C discharges first ratio Capacity 163mAh/g, 5C specific capacity 147mAh/g, tap density 1.6g/cm3。
Embodiment 10
Hydroxy-end capped aminomethyl phenyl polysilazane (OH)3Si NH[CH3(C6H5)SiNH]n Si(OH)3, n=150 is molten In toluene, the amount for adding toluene is 3 times of hydroxy-end capped aminomethyl phenyl polysilazane amount to solution, adds sucrose and embodiment 1 Li4Ti5O12, according to C/SiCN/Li4Ti5O12Middle C accounts for SiCN and Li4Ti5O12The 3wt% of gross weight, SiCN account for SiCN and Li4Ti5O12The 5wt% of gross weight adds sucrose and above-mentioned hydroxy-end capped aminomethyl phenyl polysilazane, wherein sucrose and above-mentioned The addition of hydroxy-end capped aminomethyl phenyl polysilazane is by by sucrose and above-mentioned hydroxy-end capped first under same experimental conditions The pyrolysis rate of base phenyl polysilazane is calculating.Agitating heating causes toluene to volatilize, and is heated to 350 DEG C of solidifications, obtains forerunner Body.Presoma is put in high temperature furnace, is first vacuumized, be re-filled with inert gas N2, 300 DEG C are warmed up to, 2 hours are incubated, then rise Temperature is incubated 4 hours to 750 DEG C, takes out after naturally cooling to less than 100 DEG C, and C/SiCN/Li is obtained after grinding4Ti5O12Composite wood Material, wherein C accounts for the 3wt% of gross weight, and SiCN accounts for the 5wt% of gross weight, and gross weight mentioned here is hydroxy-end capped methyl SiCN and Li after the pyrolysis of phenyl polysilazane4Ti5O12Weight sum.Spinel structure is shown through XRD tests.With respect to Li+/ Li current potentials 1.0V to 2.5V tests chemical property, first discharge specific capacity 167mAh/g, 5C specific capacities 150mAh/g, jolt ramming Density 1.65g/cm3。
Embodiment 11
Hydroxy-end capped methyl ethoxy polysilazane (OH)3SiNH{CH3(OC2H5)SiNH}nSi(OH)3N=130, it is molten In toluene, the amount for adding toluene is 2 times of hydroxy-end capped methyl ethoxy polysilazane amount to solution, adds sucrose and comparative example 2 Li4Ti5O11.66F0.34, according to C/SiCN/Li4Ti5O11.66F0.34Middle C accounts for SiCN and Li4Ti5O11.66F0.34Gross weight 1wt% adds sucrose, SiCN to account for SiCN and Li4Ti5O11.66F0.34The 7.5wt% of gross weight adds above-mentioned hydroxy-end capped methyl Ethyoxyl polysilazane, wherein the addition of sucrose and above-mentioned hydroxy-end capped methyl ethoxy polysilazane is according to identical experiment Under the conditions of sucrose and above-mentioned hydroxy-end capped methyl ethoxy polysilazane pyrolysis rate calculating.Agitating heating causes toluene to wave Send out, be heated to 350 DEG C of solidifications, obtain presoma.Presoma is put in high temperature furnace, is first vacuumized, be re-filled with inert gas N2, it is warmed up to 400 DEG C, 2 hours are incubated, then it is warmed up to 800 DEG C, and 2 hours are incubated, take out after naturally cooling to less than 100 DEG C, grind C/SiCN/Li is obtained after mill4Ti5O11.66F0.34Composite, wherein C account for the 1wt% of gross weight, and SiCN accounts for gross weight 7.5wt%, gross weight mentioned here be the SiCN after hydroxy-end capped methyl ethoxy polysilazane pyrolysis and Li4Ti5O11.66F0.34Weight sum.Spinel structure is shown through XRD tests.With respect to Li+/ Li current potentials 1.0V to 2.5V is surveyed Examination chemical property, 0.1C first discharge specific capacities 166mAh/g, 5C specific capacities 148mAh/g, tap density 1.67g/cm3。
Embodiment 12
Take the hydroxy-end capped polysiloxanes (OH) containing amino3SiO{CH3[(C3H6)NH2)]SiO}nSi(OH)3N is 100 In being put into alumina crucible, acetone solution is added, the volume for adding acetone is the hydroxy-end capped polysiloxanes volume containing amino 4.5 times, be subsequently adding the Li of sucrose and comparative example 24Ti5O11.66F0.34, according to C/SiCO/Li4Ti5O11.66F0.34Middle C and SiCO accounts for respectively SiCO/Li4Ti5O11.66F0.34The 1wt% and 15wt% of gross weight adds sucrose and containing the hydroxy-end capped of amino Polysiloxanes, the wherein addition of sucrose and the hydroxy-end capped polysiloxanes containing amino according to sucrose under same experimental conditions and This contains the pyrolysis rate of the hydroxy-end capped polysiloxanes of amino to calculate.200 DEG C are heated to while stirring, are kept for 3 hours, wait to gather After cured silicone, presoma is obtained.Crucible containing presoma is put in high temperature furnace, inert gas N is led to after vacuumizing2, 675 DEG C are warmed up to, after being incubated 4 hours, are taken out after naturally cooling to 100 DEG C, grinding obtains composite C/SiCO/ Li4Ti5O11.66F0.34, remaining C accounts for the 1wt% of gross weight after sucrose carbonization decomposition, and SiCO accounts for the 15wt% of gross weight, described Gross weight be SiCO and Li after the hydroxy-end capped polysiloxanes pyrolysis containing amino4Ti5O11.66F0.34Weight sum.Jing Cross XRD tests and show spinel structure.With respect to Li+/ Li current potentials 1.0V to 2.5V tests chemical property, first discharge specific capacity 168mAh/g, 5C specific capacity be 149mAh/g, tap density 1.7g/cm3。
Embodiment 13
Take heat cured silicones-PSI (CH3)3SiO{CH3(C6H5)SiO}nSi(CH3)3N is 200 In being put into alumina crucible, xylene soluble is added, the volume for adding dimethylbenzene is heat-curable silicone-polymethyl-benzene base silica 3.5 times of alkane volume, are subsequently adding the Li of sucrose and comparative example 24Ti5O11.66F0.34, according to C/SiCO/Li4Ti5O11.66F0.34 Middle C accounts for SiCO and Li4Ti5O11.66F0.34The 2wt% of gross weight adds sucrose, SiCO to account for SiCO and Li4Ti5O11.66F0.34Gross weight The 20wt% of amount adds heat cured silicones-PSI, wherein sucrose and heat cured silicones-poly- methyl The addition of phenyl siloxane is according to sucrose under same experimental conditions and the heat cured silicones-PSI heat Solution rate is calculating.210 DEG C are heated to while stirring, are kept for 3 hours, after the silicones solidification, obtain presoma.Will be containing front The crucible for driving body is put in high temperature furnace, and inert gas N is led to after vacuumizing2, 825 DEG C are warmed up to, after being incubated 4 hours, natural cooling Take out after being less than 100 DEG C to temperature, grinding obtains composite C/SiCO/Li4Ti5O11.66F0.34, wherein C accounts for gross weight 2wt%, SiCO account for the 20wt% of gross weight, and gross weight mentioned here is heat-curable silicone-PSI heat SiCO and Li after solution4Ti5O11.66F0.34Weight sum.Spinel structure is shown through XRD tests.With respect to Li+/Li current potentials 1.0V to 2.5V tests chemical property, 0.1C first discharge specific capacities 165.3mAh/g, 5C specific capacities 147mAh/g, vibration density Degree 1.75g/cm3。
Embodiment 14
Take the carboxylic polysiloxanes (CH of side chain3)3SiO{[(CH2)m(COOH)](C6H5)SiO}nSi(CH3)3N is 150 In being put into alumina crucible, acetone dilution is added, the volume for adding acetone is the 1.5 of the carboxylic polysiloxanes volume of side chain Times, it is subsequently adding the Li of sucrose and comparative example 24Ti5O11.66F0.34, according to C/SiCO/Li4Ti5O11.66F0.34Middle C account for SiCO and Li4Ti5O11.66F0.34The 5wt% of gross weight adds sucrose, SiCO to account for SiCO and Li4Ti5O11.66F0.34The 2wt% of gross weight The carboxylic polysiloxanes of side chain is added, wherein the addition of sucrose and the carboxylic polysiloxanes of side chain is according to identical experiment bar Sucrose is calculated with the pyrolysis rate of the carboxylic polysiloxanes of the side chain under part.360 DEG C are heated to while stirring, are kept for 6 hours, After polysiloxanes solidification, presoma is obtained.Crucible containing presoma is put in high temperature furnace, inert gas is led to after vacuumizing Argon gas, is warmed up to 600 DEG C, after being incubated 10 hours, takes out after naturally cooling to 100 DEG C, and grinding obtains composite C/SiCO/ Li4Ti5O11.66F0.34, wherein C accounts for the 2wt% that 5%, SiCO of gross weight accounts for gross weight, and gross weight mentioned here contains for side chain SiCO and Li after the polysiloxanes pyrolysis of carboxyl4Ti5O11.66F0.34Weight sum.Spinelle knot is shown through XRD tests Structure.With respect to Li+/ Li current potentials 1.0V to 2.5V tests chemical property, 0.1C first discharge specific capacities 164.2mAh/g, 5C specific volumes Amount 155mAh/g, tap density 1.3g/cm3。
Embodiment 15
Take hydroxy-end capped poly- p- fluorophenyl butyl siloxanes (OH)3SiO{C4H9(C6H4F)SiO}nSi(OH)3N is 80 In being put into alumina crucible, acetone solution is added, the volume for adding acetone is hydroxy-end capped poly- p- fluorophenyl methyl siloxanes 2.5 times of volume, are subsequently adding the Li of sucrose and comparative example 24Ti5O11.66F0.34, according to C/SiCO/Li4Ti5O11.66F0.34Middle C Account for SiCO and Li4Ti5O11.66F0.34The 5wt% of gross weight adds sucrose, SiCO to account for SiCO and Li4Ti5O11.66F0.34Gross weight 3wt% adds hydroxy-end capped poly- p- fluorophenyl butyl siloxanes, wherein sucrose and hydroxy-end capped poly- p- fluorophenyl butyl The addition of siloxanes is according to sucrose under same experimental conditions and the pyrolysis rate of hydroxy-end capped poly- p- fluorophenyl butyl siloxanes To calculate.300 DEG C are heated to while stirring, are kept for 3 hours, after hydroxy-end capped poly- p- fluorophenyl butyl cured silicone, Obtain presoma.Crucible containing presoma is put in high temperature furnace, inert gas N is led to after vacuumizing2, 675 DEG C are warmed up to, protect Temperature is taken out after 4 hours after naturally cooling to 100 DEG C, and grinding obtains composite C/SiCO/Li4Ti5O11.66F0.34, wherein C accounts for The 5wt% of gross weight, SiCO account for the 3wt% of gross weight, and gross weight mentioned here is hydroxy-end capped poly- p- fluorophenyl butyl SiCO and Li after siloxanes pyrolysis4Ti5O11.66F0.34Weight sum.Spinel structure is shown through XRD tests.With respect to Li+/ Li current potentials 1.0V to 2.5V tests chemical property, 0.1C first discharge specific capacities 169.2mAh/g, 5C specific capacities 157mAh/ G, tap density 1.45g/cm3。
Embodiment 16
Take hydroxyl-terminated injecting two methyl siloxane OH (CH3)2SiO{(CH3)2SiO}nSi(CH)2OH, n are put into aluminum oxide for 200 In crucible, curing agent (CH is added3)3Si{OSiH(CH3)}36OSi(CH3)3, the body of curing agent and terminal hydroxy group polymethyl siloxane Product ratio is 1:5, add catalyst dibutyltin dilaurylate, the addition of catalyst to account for the 0.8% of gross weight, add solvent Dimethylbenzene, the volume for adding dimethylbenzene is 1.5 times of hydroxyl-terminated injecting two methyl siloxane and curing agent volume sum, is subsequently adding The Li of sucrose and comparative example 24Ti5O11.66F0.34, according to C/SiCO/Li4Ti5O11.66F0.34Middle C account for SiCO and Li4Ti5O11.66F0.34The 3wt% of gross weight adds sucrose, SiCO to account for SiCO and Li4Ti5O11.66F0.34The 6wt% of gross weight adds Enter hydroxyl-terminated injecting two methyl siloxane and curing agent, the wherein addition of sucrose and hydroxyl-terminated injecting two methyl siloxane and curing agent Calculate according to the pyrolysis rate of sucrose under same experimental conditions and hydroxyl-terminated injecting two methyl siloxane.70 are heated to while stirring DEG C, kept for 3 hours, after hydroxyl-terminated injecting two methyl siloxane solidification, obtain presoma.Crucible containing presoma is put into into height In warm stove, N is led to after vacuumizing2And H2Mixed gas, are warmed up to 650 DEG C, after being incubated 8 hours, after naturally cooling to less than 100 DEG C Take out, grinding obtains composite C/SiCO/Li4Ti5O11.66F0.34, wherein C accounts for the 3wt% of gross weight, and SiCO accounts for gross weight 6wt%, gross weight mentioned here is the SiCO and Li after hydroxyl-terminated injecting two methyl siloxane pyrolysis4Ti5O11.66F0.34Weight Sum.Spinel structure is shown through XRD tests.With respect to Li+/ Li current potentials 1.0V to 2.5V tests chemical property, and 0.1C is first Secondary specific discharge capacity 170.2mAh/g, 5C specific capacities 160mAh/g, tap density 1.61g/cm3。
Embodiment 17
PVDF hollow fiber membrane molecular structural formula is as follows, wherein m for 40, n be 120, p be 40, dissolve poly- borosilicate with toluene Azane, then by sucrose and the Li of comparative example 24Ti5O11.66F0.34It is added thereto, according to C/SiBCN/Li4Ti5O11.66F0.34Middle C Account for SiBCN and Li4Ti5O11.66F0.34The 4wt% of gross weight adds sucrose, SiBCN to account for SiBCN and Li4Ti5O11.66F0.34Gross weight The 5wt% of amount adds above-mentioned PVDF hollow fiber membrane, the wherein addition of sucrose and above-mentioned PVDF hollow fiber membrane to pass through same experimental conditions The pyrolysis rate of lower sucrose and above-mentioned PVDF hollow fiber membrane is calculating.It is heated to 250 DEG C and is incubated 2 hours, after stirring solidification, is put into high temperature In stove, N is led to after vacuumizing2Gas, is warmed up to 850 DEG C, is incubated 1 hour, and Temperature fall takes out to after less than 100 DEG C, and grinding is obtained C/SiBCN/Li4Ti5O11.66F0.34Composite, wherein C account for the 4wt% of gross weight, and SiBCN accounts for the 5wt% of gross weight, here Described gross weight is the SiBCN and Li after PVDF hollow fiber membrane pyrolysis4Ti5O11.66F0.34Weight sum.Material is examined through XRD Survey and show spinel structure.Electrochemical property test, with respect to Li+/ Li current potential 1.0V to 2.5V, 0.1C first discharge specific capacities are 165mAh/g, 5C specific capacity 141mAh/g, tap density 1.57g/cm3。
As a result as can be seen that the above-mentioned PVDF hollow fiber membrane of the present embodiment is to Li4Ti5O11.66F0.34Formed after carrying out being combined Composite C/SiBCO/Li4Ti5O11.66F0.34, wherein C accounts for the 4wt% of gross weight, and SiBCO accounts for the 5wt% of gross weight, in electricity Chemical property and the aspect of tap density two have significant improvement.Electrochemistry 5C specific capacity is brought up to by the 125mAh/g before being combined 141mAh/g after compound, tap density is by the 0.8g/cm before being combined3Bring up to the 1.57g/cm after being combined3。
The embodiment material electrochemical performance of table 1 and tap density

Claims (43)

1. a kind of composite cathode material for lithium ion cell, it is characterized in that by least one of SiCO, SiCNO, SiCN, SiBCN with Li4Ti5-xMxO12-yFyBe compounded to form composite with C, wherein M be Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Y, Zr, At least one of Nb, Mo, Ru, Pd, Rh, Ag, In, Sn, Sb, Pb, Bi, W, 0≤x≤0.5,0≤y≤0.5, the composite The content of at least one of middle SiCO, SiCNO, SiCN, SiBCN accounts for the 0.2wt%-20wt% of gross weight, Li4Ti5-xMxO12- yFyThe 80wt%-99.8wt% of gross weight is accounted for, C accounts for the 0wt%-20wt% of gross weight；Gross weight mentioned here is to form multiple SiCO, SiCNO, SiCN, SiBCN of condensation material at least one weight and Li4Ti5-xMxO12-yFyWeight sum.
2. composite negative pole material according to claim 1, is characterized in that described Li4Ti5-xMxO12-yFy, wherein 0.01≤x ≤0.2。
3. composite negative pole material according to claim 1, is characterized in that described Li4Ti5-xMxO12-yFy, wherein 0.01≤y ≤0.2。
4. composite negative pole material according to claim 1, is characterized in that described C refers to carbon or carbon matrix precursor pyrocarbon The carbon remained after change.
5. composite negative pole material according to claim 1, is characterized in that described SiCO is gathered by organosiloxane monomer Pyrolysis is obtained or is pyrolyzed to obtain under nonoxidizing atmosphere or in vacuum by polysiloxanes under nonoxidizing atmosphere or in vacuum after conjunction Arrive；Described SiCNO be by organosiloxane monomer be polymerized after in NH3Lower pyrolysis is obtained or by polysiloxanes in NH3Lower pyrolysis Obtain；Described SiCN is to be pyrolyzed to obtain under nonoxidizing atmosphere or in vacuum by polysilazane；Described SiBCN is by poly- boron Silazane is pyrolyzed under nonoxidizing atmosphere or in vacuum and obtains.
6. composite negative pole material according to claim 5, it is characterized in that described organosiloxane monomer be containing hydrogen bond, One kind or several in alkyl branches, thiazolinyl side chain and aromatic radical side chain in the organosiloxane monomeric compound of one or more Kind.
7. composite negative pole material according to claim 5, is characterized in that described polysiloxanes is the Si-O keys to repeat For main chain, on side chain silicon directly with alkyl, carboxyl, hydroxyl, amino, alkoxyl, alkenyl oxy, acyloxy, hydrogen, halogen and Containing one or more connected the constituted polymer in hydroxyl, carboxyl, amino, hydrogen, alkenyl, the alkyl of halogen, polymerization Spend for 2～2000.
8. composite negative pole material according to claim 7, the degree of polymerization that it is characterized in that described polysiloxanes is 5～500.
9. the composite negative pole material according to claim 7 or 8, is characterized in that described alkyl is alkyl, alkenyl, alkynes One or more in base, aryl, aralkyl.
10. the composite negative pole material according to claim 7 or 8, is characterized in that described polysiloxanes is contained in molecule The polysiloxanes of Si -- H bond.
11. composite negative pole materials according to claim 7 or 8, is characterized in that described polysiloxanes is contained in molecule The polysiloxanes of Si-OH keys.
12. composite negative pole materials according to claim 7 or 8, is characterized in that described polysiloxanes is contained in molecule The polysiloxanes of the derivative of unsaturated hydrocarbons or unsaturated hydrocarbons.
13. composite negative pole materials according to claim 7 or 8, is characterized in that described polysiloxanes is contained in molecule The polysiloxanes of phenyl.
14. composite negative pole materials according to claim 7 or 8, is characterized in that described polysiloxanes is the silicon of heat cure Resin.
15. composite negative pole materials according to claim 7 or 8, is characterized in that described polysiloxanes is the poly- silicon of liquid Oxygen alkane either being capable of the polysiloxanes that dissolved with solvent or the polysiloxanes that can be melted.
16. composite negative pole materials according to claim 5, is characterized in that described polysilazane is the Si-N keys to repeat For main chain, on side chain silicon directly with alkyl, carboxyl, hydroxyl, amino, alkoxyl, alkenyl oxy, acyloxy, hydrogen, halogen and Containing one or more connected the constituted polymer in hydroxyl, carboxyl, amino, hydrogen, alkenyl, the alkyl of halogen, polymerization Spend for 2～2000.
17. composite negative pole materials according to claim 16, it is characterized in that described polysilazane the degree of polymerization be 5～ 500。
18. composite negative pole materials according to claim 16 or 17, it is characterized in that described alkyl be alkyl, alkenyl, One or more in alkynyl, aryl, aralkyl.
19. composite negative pole materials according to claim 16 or 17, is characterized in that described polysilazane is contained in molecule There is the polysilazane of Si -- H bond.
20. composite negative pole materials according to claim 16 or 17, is characterized in that described polysilazane is contained in molecule There is the polysilazane of Si-OH keys.
21. composite negative pole materials according to claim 16 or 17, is characterized in that described polysilazane is contained in molecule There is the polysilazane of the derivative of unsaturated hydrocarbons or unsaturated hydrocarbons.
22. composite negative pole materials according to claim 16 or 17, is characterized in that described polysilazane is contained in molecule There is the polysilazane of phenyl.
23. composite negative pole materials according to claim 16 or 17, is characterized in that described polysilazane is the poly- of liquid Silazane either being capable of the polysilazane that dissolved with solvent or the polysilazane that can be melted.
24. composite negative pole materials according to claim 5, it is characterized in that described PVDF hollow fiber membrane be with repeat containing- C-Si-N-B-either-B-C-Si-N-or-C-B-Si-N-as main chain, silicon is directly and hydrocarbon on side chain Base, carboxyl, hydroxyl, amino, alkoxyl, alkenyl oxy, acyloxy, hydrogen, halogen and containing hydroxyl, carboxyl, amino, hydrogen, One or more connected constituted polymer in alkenyl, the alkyl of halogen, the degree of polymerization is 2～2000.
25. composite negative pole materials according to claim 24, it is characterized in that described PVDF hollow fiber membrane the degree of polymerization be 5～ 500。
26. composite negative pole materials according to claim 24 or 25, it is characterized in that described alkyl be alkyl, alkenyl, One or more in alkynyl, aryl, aralkyl.
27. composite negative pole materials according to claim 24 or 25, is characterized in that described PVDF hollow fiber membrane is liquid PVDF hollow fiber membrane either being capable of the PVDF hollow fiber membrane that dissolved with solvent or the PVDF hollow fiber membrane that can be melted.
A kind of 28. methods for preparing composite negative pole material described in claim 1, the method at least comprises the steps：
(1) compound of the compound of titanium, the compound of M, lithium is carried out into dispensing according to atomic ratio Li/Ti+M=0.8～0.88, Fluoride is added, the carbon or carbon matrix precursor of raw material gross weight 0-20wt%, the gross weight of raw material mentioned here is added It is compound, the compound of M, the compound of lithium, the weight sum of fluoride of titanium, above-mentioned raw material is put into account for raw material total In the medium of volume 1-5 times, uniformly mix 5～72 hours in media as well, drying forms presoma, first low at 200 DEG C～500 DEG C Temperature is processed 0～20 hour, then at 600 DEG C～900 DEG C, is synthesized 2～72 hours, obtains Li4Ti5-xMxO12-yFy；M be Mg, V, At least one of Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Y, Zr, Nb, Mo, Ru, Pd, Rh, Ag, In, Sn, Sb, Pb, Bi, W；
(2) at least one of organosiloxane monomer, polysiloxanes, polysilazane, PVDF hollow fiber membrane are dissolved in into organic solvent In, the addition of organic solvent is 1 according to the polymer and organic solvent volume ratio that add:1 to 1:5 add, wherein, organosilicon The addition of oxygen alkane monomer is added according to the above-mentioned ratio of the volume after the polymerization of organosiloxane monomer and organic solvent volume, Further, the addition of organosiloxane monomer is gathered according to the organosilicon after the organosiloxane monomer polymerization under same experimental conditions The pyrolysis rate of compound is calculating so that at least one of SiCO, SiCNO content accounts for gross weight in the anode material after being pyrolyzed 0.2wt%-20wt%, polysiloxanes, polysilazane, PVDF hollow fiber membrane at least one of addition according to identical experiment bar Polymer-pyrolysis rate under part is caused in the anode material after pyrolysis in SiCO, SiCNO, SiCN, SiBCN at least to calculate A kind of content accounts for the 0.2wt%-20wt% of gross weight, then by Li4Ti5-xMxO12-yFyIt is added thereto, Li4Ti5-xMxO12-yFy's Addition calculates Li in the anode material caused after pyrolysis according to the pyrolysis rate under same experimental conditions4Ti5-xMxO12- yFyContent accounts for the 80wt%-99.8wt% of gross weight, is in addition additionally added carbon or carbon matrix precursor, carbon or carbon matrix precursor Addition accounts for the 0-20wt% of gross weight according to carbon remaining after carbon or carbon matrix precursor pyrolysis, and gross weight mentioned here is shape Into SiCO, SiCNO, SiCN, SiBCN of composite at least one weight and Li4Ti5-xMxO12-yFyWeight sum；Stir Mix uniform, adding curing agent or water when adding organosiloxane monomer makes it be polymerized；
(3) cross-linking products are solidify to form；
(4) under nonoxidizing atmosphere or in vacuum, the cured product sintering is obtained in SiCO, SiCNO, SiCN, SiBCN extremely A kind of few and Li4Ti5-xMxO12-yFyThe composite being combined with C.
29. methods according to claim 28, is characterized in that, the compound of described titanium is in titanium dioxide, metatitanic acid At least one.
30. methods according to claim 28, is characterized in that, the compound of described M is oxide, carbonate, oxalic acid Salt, nitrate, hydroxide, sulfate, chloride.
31. methods according to claim 28, is characterized in that, the compound of described lithium is lithium hydroxide, lithium carbonate, chlorine Change one or more mixtures in lithium, lithium iodide, lithium nitrate, lithium phosphate, lithium acetate, lithium oxalate.
32. methods according to claim 28, is characterized in that, described fluoride is in lithium fluoride, ammonium fluoride, magnesium fluoride At least one.
33. methods according to claim 28, is characterized in that, described medium be water, ethanol, acetone, n-butanol, positive third One or more mixtures in alcohol, isopropanol, acetonitrile, ether, monoethanolamine.
34. methods according to claim 28, is characterized in that, described drying is that sprays drying, forced air drying, vacuum are dry Dry one of which.
35. methods according to claim 28, is characterized in that, described organic solvent is acetone, toluene, dimethylbenzene, second Alcohol, ether, normal propyl alcohol, isopropanol, n-butanol, acetonitrile, monoethanolamine, tetrahydrofuran, DMF, chloroform, pyridine, N- crassitudes At least one of ketone.
36., according to the method described in claim 28, is characterized in that, it is described be cured as being heating and curing, add after curing agent again plus At least one of heat cure, ultraviolet light polymerization, wherein, in being heating and curing or adding curing agent to be heating and curing, solidification temperature is 20 DEG C～400 DEG C.
37. methods according to claim 28, is characterized in that, in the sintering process of described step (4), described sintering Condition is 200-500 DEG C of insulation 0-5 hour, is then heated to 500～850 DEG C, is incubated 1-15 hours.
38. methods according to claim 37, is characterized in that, described sintering condition is that 300-500 DEG C of insulation 0-5 is little When, 600～750 DEG C are then heated to, it is incubated 1-10 hours.
39. methods according to claim 28, is characterized in that, described non-oxidizing atmosphere is argon gas, nitrogen, NH3、H2 At least one of.
40. methods according to claim 28, is characterized in that, the carbon or carbon matrix precursor in the step (1) be graphite, At least one in acetylene black, sucrose, glucose, fructose, starch, phenolic resin.
41. methods according to claim 28, is characterized in that, the carbon or carbon matrix precursor in the step (2) be graphite, At least one in acetylene black, sucrose, glucose, fructose, starch, phenolic resin.
A kind of 42. negative poles of lithium rechargeable battery, is characterized in that, it use the compound titanium of claim 1-27 any one Sour lithium titanate cathode material is used as negative electrode active material.
A kind of 43. lithium rechargeable batteries, is characterized in that comprising positive pole, barrier film, the negative pole described in electrolyte and claim 42.
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