CN104091937A - Lithium titanate-coated surface-treated graphite negative electrode material, preparation method and application of negative electrode material - Google Patents

Lithium titanate-coated surface-treated graphite negative electrode material, preparation method and application of negative electrode material Download PDF

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CN104091937A
CN104091937A CN201410344991.5A CN201410344991A CN104091937A CN 104091937 A CN104091937 A CN 104091937A CN 201410344991 A CN201410344991 A CN 201410344991A CN 104091937 A CN104091937 A CN 104091937A
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graphite
negative material
lithium titanate
lithium
basis
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CN104091937B (en
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赵孝连
曾国城
向黔新
梅铭
田轩周
梅建华
何玉娟
李玲
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Guizhou Zhenhua New Material Co Ltd
Guizhou Zhenhua eChem Inc
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SHENZHEN ZHENHUA NEW MATERIAL CO Ltd
SHENZHEN ZHENHUA NEW MATERIALS 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
    • 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
    • H01M4/36—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
    • 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)
  • Engineering & Computer Science (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a lithium titanate-coated surface-treated graphite negative electrode material, a preparation method and application of the negative electrode material. According to the negative electrode material, a lithium titanate coating layer is formed on the surface of the graphite-based negative electrode material particles subjected to surface treatment. The preparation method of the negative electrode material comprises (1) a surface treatment process of the graphite-based negative electrode material and (2) an in-situ generation process of the lithium titanate coating layer. The negative electrode material is applied to the lithium ion batteries, mobile storage equipment or energy storage power stations. According to the invention, based on the surfaces of appropriately-passivated graphite negative electrode particles, the graphite surface is coated with a layer of lithium titanate material, and thus the aims of optimizing the internal environment of the use of the battery and improving the battery usability are achieved in low-temperature or high-temperature use condition. By adopting the negative electrode material provided by the invention, the problems of aggregation of lithium titanate particles and non-uniform coating of the graphite particle surface caused by anisotropy can be improved.

Description

Lithium titanate coated negative material, method for making and application thereof through surface treatment graphite
Technical field
The present invention relates to field of lithium ion secondary, be specifically related to negative electrode for lithium ion battery material, this negative material is formed with lithium titanate coating layer at graphite-like basic electrode material surface.The invention still further relates to the preparation method of this negative material, i.e. the method with formation lithium titanate coating layer to graphite-like basic electrode material surface modifying.The invention still further relates to this negative material and make lithium rechargeable battery, the lithium rechargeable battery of preparation is at reversible specific capacity, and coulombic efficiency, has larger lifting in the security performances such as the multiplying power of battery, and high low temperature entirely first.
Background technology
Since the nineties in 20th century, lithium rechargeable battery entered business application, negative material has successively experienced soft/hard charcoal, graphite, the materials'use stages such as lithium titanate and silicon-carbon.Current lithium titanate anode material volume production, but its compacted density 2.0g/cm only 3, discharge platform higher (1.5V), specific capacity lower (about 160mAh/g), and self-conductive bad (conductivity: 10-9S/cm), thereby little at 3C field application value.And silicon carbon material is at present still in the popularization stage in early stage.
From combination property, because natural and Delanium is at reversible capacity, prepare processing procedure, in useful life, energy density is high, and wide material sources, the aspects such as good economy performance have larger advantage, thereby graphite-like electrode material is a kind of lithium battery negative material being most widely used, according to statistics, the use amount ratio of graphite negative electrodes in lithium battery is in 90% left and right at present.Even be in the recent period about to start electric vehicle lithium battery field, graphite negative electrodes material is still one of main candidate material.
Prior art is existing modifies or the method for modification the particle surface of graphite negative electrodes material.In the document of having consulted, common method of modifying mainly contains following several.For the bad feature of the conductivity of graphite negative electrodes material, adopt carbon nano-tube or introducing conductive agent composition to carry out modification.This kind of method can be improved the electron conduction effect of graphite material to a certain extent, but the electric conducting materials such as carbon nano-tube of introducing can reduce the specific capacity of graphite material and coulombic efficiency etc.The method of modifying that will form SEI film (Solid electrolyte interface solid electrolyte interface film) for graphite cathode particle surface has graphite surface oxidation, at graphite surface coated metal/nonmetallic ion (as amorphous carbon, polymer, alkali carbonate) group such as, lithium metal consumption while forming SEI film to reduce, and form more stable SEI film.
Have lithium titanate is applied to reporting for work of graphite negative electrodes material at present.Document (beam is known the synthetic and performance study New Chemical Materials 2014 (2) of beautiful graphite dopping lithium titanate anode material for Yu Haiying, Wang Lei) has been studied the synthetic and chemical property of graphite dopping lithium titanate anode material.
Document (preparation and the performance study Central South University Master's thesis of a pretty silicon/carbon/graphite in lithium ion batteries thiazolinyl composite negative pole material) adopts be dried-sintering process of spraying and liquid phase reduction to prepare lithium titanate/Graphene (LTO/G) composite material, and the electro-chemical properties of material prepared by two kinds of different synthetic methods has been done to research and analyse.
Document (Guo Xuefei, preparation and the Electrochemical Properties University Of Tianjin thesis for the doctorate thereof of the coated lithium titanate composite material of lithium titanate and charcoal, tutor Wang Chengyang) has proposed preparation and the Electrochemical Properties thereof of lithium titanate and the coated lithium titanate composite material of charcoal.Based on promoting the lifting of lithium titanate high rate performance, need, in synthetic preparation on lithium titanate basis, by charcoal, be coated and improve its conductive capability, and then improve its charge/discharge high rate performance.
Chinese patent CN200610063612.0 has proposed composite lithium titanate electrode material and preparation method thereof, and the technical problem that solve is to improve the electric conductivity of lithium titanate, reduces its cost.Its method is or dopen Nano material with carbon element coated at ball-type lithium titanate particle surface, and surface forms a kind of structure with porous nano passage.
Document (Enhanced performance of spherical natural graphite coated by Li4Ti5O12as anode for lithium-ion batteries (Mi Lua, Yanyan Tian, Xiaodong Zheng, Jun Gao, Bing Huang Journal of Power Sources219188-192) adopt 4-butyl titanium organic substance is mixed with natural graphite powder and alcohol, again to the lithium acetate aqueous solution that is added dropwise to metering in mixture, form solvent/water system emulsion, while 4-butyl titanium is hydrolyzed into titanium dioxide fine particles and together with lithium salts, is adsorbed in the surface of native graphite, again above-mentioned substance is processed 12 hours under 800 ℃ of argon atmosphers, the lithium titanate content of final preparation is respectively 1wt%, 2wt%, the coated native graphite powder of lithium titanate of 5wt%.
The technology of preparing of the lithium titanate of prior art is normally prepared in oxidizing atmosphere, and basic negative material of the present invention is graphite, be a kind of reducing atmosphere generally, thereby need to come artificial augmenting response area to avoid lithium titanate not to be successfully prepared by preparing starch body.The present invention is by the surface treatment to graphite-like basis negative material particle surface, and the dispersing technology in preparation process, has obtained the coated uniform negative material in surface of the present invention.
Through SEM, detect, negative material of the present invention is compared with body graphite material, its particle surface has covered the coating of thin layer, coating is the surface that nanometer state is uniformly distributed in material, the surface transition of nano grain surface edge and bulk material is mild, show coating layer compact structure, possess good processing intensity, in the follow-up stirring/operation such as be coated with/roll, can not come off and the degradation phenomena such as reunion.
Through XRD, detect, negative material of the present invention possesses the feature spectrogram of graphite body and clad material (lithium titanate) simultaneously, shows that the structure of graphite bulk material in coated process is not changed, and has generated spinel type lithium titanate coating simultaneously.
Adopting negative material of the present invention to prepare the method for lithium rechargeable battery, is common method well known in the art.Negative material of the present invention can directly apply in power-type lithium ion secondary cell, portable storage device, energy-accumulating power station.Adopt the made button cell of negative material of the present invention to adopt the made battery of identical common negative material, have that efficiency is high first, capacity high.The lithium battery cathode plate of preparation can not analysed lithium under high compacted density, and has improved the serviceability under high low temperature condition, is applicable to portable power source, and electric automobile, in the installations and facilities such as electrical network power station.
Below by specific embodiment, the preparation method of negative material of the present invention and the properties of negative material are described, and the chemical property of the lithium rechargeable battery made from this negative material.
In embodiment, institute's each reagent of using and instrument are originated as shown in table 1 and table 2 below.
Table 1: the reagent of using in embodiment and type information table
Table 2 embodiment facility information list used
Summary of the invention
Technical problem solved by the invention is: overcome in the application of graphite negative electrodes material and analyse the secure context problems such as lithium, overcome existing graphite negative electrodes material and battery system at excessive temperature or cross under low temperature and use unmatched defect, improving lithium titanate particle agglomeration that existing modification or method of modifying cause, graphite granule surface and cause the problems such as coated inhomogeneous because of anisotropy.
The present invention is evenly coated on lithium titanate predecessor the surface of treated graphite-like basis negative material, then high temperature sintering original position generates lithium titanate coating layer under protective atmosphere.Graphite-like basis negative material body is carried out to surface treatment and can effectively improve the surface energy difference that graphite granule anisotropy causes, thereby cause coated inhomogeneous defect.It is controlled that while original position generation lithium titanate on graphite body has grain size, compact structure, adhesive strength high.
With regard to application, it is low that graphite negative electrodes material has discharge platform, reversible capacity advantages of higher, but lower discharge platform also easily causes secure context risks such as analysing lithium.In addition graphite negative electrodes material is used conventionally together with carbonates electrolyte, and still, when serviceability temperature is low, the electrolytelike conductivity of ester is the decline of geometric progression, also can cause graphite negative electrodes material surface to occur the rich poly-situation of lithium metal.Thereby need to modify or modification the particle surface of graphite negative electrodes material.Existing method of modifying conventionally just carries out modification for a certain performance wherein, can not adapt with the practical application of graphite cathode material.And the process of preparation does not possess the condition that large-scale commercial applications is produced, as chemical deposition (CVD) etc.
Particularly, graphite negative electrodes material is that a class conductivity is better, and compacted density is high, and the material that specific area is moderate also needs in practical application to consider and electrolyte, and the performance of positive electrode matches mutually.For example, lithium ion is approximately 10 at the interstructural diffusive migration coefficient of graphite carbon-coating -8cm 2/ s, at cobalt acid lithium material (4.0V-4.3V Li/Li +) in diffusion coefficient be 10 -10to 10 -12cm 2/ s, the two differs nearly 100-10000 doubly, and changes with the poor state discharging and recharging.
Take specific capacity as example, the specific capacity of current commercial positive electrode be only negative pole 50% less than, accordingly when manufacturing lithium battery, the coating weight of negative plate compared with corresponding positive pole less than 50%, graphite cathode sheet some electrical and thermal conductivity performances in the situation that of compacting can be further improved, thereby in single cell body negative pole actual be a kind ofly to compare more excellent material with positive plate performance, under extreme service condition, the performance of negative pole is often excellent in positive pole, if now managed, negative pole is prepared into better and can worsens the environment for use of battery system on the contrary.
Based on above-mentioned analysis, the present invention is based on the surface of suitable passivation graphite cathode particle, in the situation that not affecting graphite cathode specific capacity, on graphite cathode surface, be coated one deck lithium titanate material, the migration velocity of lithium and the porosity of barrier film under more extreme service condition like this, electrolytical conductivity, and the ion diffusion velocity of positive electrode matches, reach optimize battery use in environment, improve the object of battery serviceability.
Specifically, the present invention proposes following technical scheme.
First aspect, the invention provides a kind of anode material for lithium-ion secondary battery, and this negative material is formed with lithium titanate coating layer on the negative material particle surface of surface treated graphite-like basis.
Preferably, wherein, described graphite-like basis negative material is selected from Delanium, native graphite, their mixture, or their modifier.Their modifier can be the coated Delanium modifier of native graphite, Graphite Coating metal oxide and its esters modifier etc.
Preferably, wherein, described surface treated graphite-like basis negative material, its average grain diameter (D50) is 5-25 μ m, specific area is 1.5-6.5m 2/ g.
Concrete surface treatment method is: graphite-like basis negative material joined in the aqueous solution of acid (sulfuric acid, nitric acid, acid or glacial acetic acid), stir process 2-12 hour under 50-70 ℃ of temperature conditions is then through dehydration, dry after washing.Preferably adopt nitric acid, aqueous acid concentration is 3-8mol/L, by weight, and aqueous acid: graphite=1:5-10.
Preferably, wherein, the lithium titanate grain diameter in described lithium titanate coating layer is < 1 μ m, accounts for the 0.1-2wt% of negative material total weight.Preferably, wherein, described lithium titanate coating layer is created on graphite-like basis negative material particle surface through in-situ sintering.
Preferably, wherein, described negative material specific capacity is 320-365mAh/g, and coulombic efficiency is 89-94% (test condition: button cell, corresponding metal lithium electrode (positive pole), voltage range 0.005V-2.0V) first.The negative material that employing the present invention processes is coated graphite negative material more not, high 2-5mAh/g in specific capacity, the first approximately high 2-3% of coulombic efficiency.
Another aspect of the present invention, also provides a kind of preparation method of negative material, and the method comprises the steps:
(1) surface treatment procedure of graphite-like basis negative material
Graphite-like basis negative material is carried out to surface treatment with acid solution, obtain surface treated graphite-like basis negative material;
(2) lithium titanate coating layer original position generates operation
Lithium titanate precursor powder, the surface treated graphite-like of step (1) gained basis negative material, dispersant and solvent is even; dehydration; then under protective atmosphere (preferably argon gas); 650-750 ℃ of temperature conditions sintering, obtains being formed with the negative material of lithium titanate coating layer on the negative material particle surface of surface treated graphite-like basis.Described dispersant is polyketone resin, and polyacetal resin etc. are dissolvable in water the polymer of water.In solid content, the about 0.2-3wt% of the addition of dispersant, addition is very few does not have dispersion and emulsion effect, and addition too much can cause the difficulty of production.The about 30-60wt% of the content of solid content in whole suspension.
Preferably, the method also comprises lithium titanate precursor preparation section: by the metatitanic acid of 5.0-8.0 weight portion or metatitanic acid, and the lithium salts of 1.0-5.0 weight portion is scattered in the solvent of 10-50 weight portion, then in solvent, add the glucose of 1.0-2.0 weight portion to disperse to size mixing and obtain slurry, then at 150-500 ℃, sinter the slurry of preparation into presoma powder.Presoma powder is oxide and the hydrate that contains titanium and lithium, and a small amount of undecomposed organic substance.
Preferably, described lithium salts is selected monohydrate lithium hydroxide, or one or both in lithium carbonate, and described solvent is selected from deionized water or alcohol-water mixture.Described alcohol is selected from C 10following water-soluble lower alcohol, particular methanol, ethanol or isopropyl alcohol; Deionized water/alcohol ratio range is (10～50): (90～50).
Preferably, in step (1), described surface treatment is that graphite-like basis negative material is joined in aqueous acid, and then stir process 2-12 hour under 50-70 ℃ of temperature conditions, then dry after dehydration, washing.
Preferably, in step (1), described acid is sulfuric acid, nitric acid, acid or glacial acetic acid, preferably nitric acid; The concentration of described aqueous acid is 3-8mol/L, by weight, and aqueous acid: graphite-like basis negative material=1:5-10.
Preferably, in step (2), by weight, the ratio of lithium titanate precursor powder and surface treated graphite-like basis negative material is 1-10:90-95; Described dispersant is polyketone resin or polyacetal resin, and in lithium titanate precursor powder solid content, the addition of dispersant is 0.2-3wt%; Described solvent is isopropyl alcohol or absolute ethyl alcohol; By weight, the ratio of dispersant and solvent is 2-10:80-90.
Preferably, in step (2), 650～750 ℃ of temperature conditions sintering 6-8 hour, then cooling, sieve.
Preferably, the lithium titanate grain diameter in described lithium titanate coating layer is < 1 μ m, accounts for the 0.1-2.0wt% of negative material total weight.
Another aspect of the present invention, also provides above-mentioned preparation method resulting ion secondary battery cathode material lithium.
Another aspect of the present invention, provides a kind of lithium rechargeable battery, adopts negative material recited above to prepare.
Another aspect of the present invention, provides a kind of removable storage device, adopts negative material recited above to prepare.
Another aspect of the present invention, provides a kind of energy-accumulating power station, has adopted negative material recited above.
Another aspect of the present invention, provides the application of negative material recited above in manufacturing lithium ion battery, removable storage device or energy-accumulating power station.
The present invention carries out surface treatment to the surface of graphite-like basis negative material particle, then lithium titanate predecessor is evenly coated on to the surface of treated graphite-like basis negative material, then high temperature sintering original position generates lithium titanate coating layer under protective atmosphere.Graphite-like basis negative material body is carried out to surface treatment and can effectively improve the surface energy difference that graphite granule anisotropy causes, thereby cause coated inhomogeneous defect.It is controlled that while original position generation lithium titanate on graphite body has grain size, compact structure, adhesive strength high.
The negative material technique that adopts the method to prepare is simple, and the lithium rechargeable battery of preparation is at reversible specific capacity, and coulombic efficiency, and the multiplying power of full battery first, has larger lifting in the security performances such as high low temperature.This negative material can be applied to movable storage device, electric tool, and in electric automobile and energy-accumulating power station, the energy density of battery, fail safe and homogeneity of product are further promoted.
The present invention simultaneously also provides a kind of lithium rechargeable battery, and this lithium rechargeable battery for example comprises following part: electrode, electrolyte, barrier film, container.Wherein electrode comprises positive pole and negative pole, and positive pole comprises plus plate current-collecting body and is coated in the positive electrode active material layer on plus plate current-collecting body; Negative pole comprises negative current collector and is coated in the negative material of the present invention on negative current collector; Barrier film can be that simple solid insulating layer can be also the decorating film with electric conductivity; Container is positive pole, negative pole, barrier film, the electrolytical insulation inclusion body that possesses certain form.
Below in conjunction with accompanying drawing and each embodiment, the present invention and useful technique effect thereof are elaborated.
Accompanying drawing explanation
Fig. 1-a is the coated stereoscan photograph that is 15000 through the negative material enlargement ratio of surface treatment graphite of lithium titanate prepared by embodiment 4-1.
Fig. 1-b is the stereoscan photograph that the untreated graphite enlargement ratio of comparative example 1-1 is 15000.
Fig. 1-c is that lithium titanate prepared by embodiment 4-1 is coated the EDS collection of illustrative plates (* 1000) through the negative material of surface treatment graphite.
Fig. 1-d is the EDS collection of illustrative plates (* 1000) of the untreated graphite of comparative example 1-1.
Fig. 2 is that lithium titanate prepared by embodiment 4-2 is coated through the negative material of surface treatment graphite and the XRD collection of illustrative plates of the untreated graphite of comparative example 1-2.
Fig. 3-a is the button cell charging and discharging curve figure of the untreated graphite of employing comparative example 1-2 prepared of embodiment 6-2.
Fig. 3-b is the button cell charging and discharging curve figure of the employing embodiment 4-3 negative material prepared of embodiment 6-1.
Discharge curve under-20 ℃ of conditions of the full battery of employing embodiment 4-4 negative material prepared by Fig. 4 embodiment 7-1 and the full battery of the untreated graphite of employing comparative example 1-3 prepared by embodiment 7-2.
Fig. 5 is employing embodiment 4-1 prepared by embodiment 7-1,4-3, employing comparative example 1-1 prepared by the full battery of 4-4 negative material and embodiment 7-2, the high rate performance test curve of the full battery of the untreated graphite of 1-2.
Fig. 6 is the full battery of employing embodiment 4-4 negative material prepared of embodiment 7-1 and 60 ℃ of 1C/1C loop test curves of the full battery of the untreated graphite of employing comparative example 1-3 prepared by embodiment 7-2.
Embodiment
Conventionally graphite granule has obvious anisotropy, along the conductivity of hexahedron plane (x-y direction) direction, is 0.4-2.5 * 10 4s/cm, and be 1-5S/cm along the conductivity of hexahedron vertical direction (z direction).Graphite-like basis negative material body is carried out to surface treatment and can effectively improve the surface energy difference that graphite granule anisotropy causes, thereby cause coated inhomogeneous defect.In addition, graphite-like basis negative material body being carried out to surface treatment has improved existing graphite negative electrodes material and under excessive temperature or mistake low temperature, has used unmatched defect with battery system.
The present invention adopts gel method preparation to be coated and uses lithium titanate predecessor, then lithium titanate predecessor is evenly coated on to the surface of treated graphite-like basis negative material, then high temperature sintering original position generates lithium titanate coating layer under protective atmosphere.On graphite body, original position generates lithium titanate to have grain size controlled, compact structure, adhesive strength high.
Anode material for lithium-ion secondary battery of the present invention is formed with lithium titanate coating layer on the negative material particle surface of surface treated graphite-like basis.Concrete, lithium titanate coating layer is created on graphite-like basis negative material particle surface through in-situ sintering.Lithium titanate grain diameter in described lithium titanate coating layer is < 1 μ m, accounts for the 0.1-2wt% of negative material total weight.Lithium titanate coating layer of the present invention generates by gel method with lithium titanate precursor, below can be described in further detail method.
Corresponding metal lithium electrode, voltage range 0.005V-2.0V, described negative material specific capacity is 320-365mAh/g, coulombic efficiency is 89-94% first.The negative material that employing the present invention processes is coated graphite negative material more not, high 2-5mAh/g in specific capacity, the first approximately high 2-3% of coulombic efficiency.
Described graphite-like basis negative material is selected from Delanium material, natural graphite material, their mixture, or their modifier.The Delanium here refers to the conventional artificial graphite material of negative electrode that can commercially obtain.Their modifier can be the coated Delanium modifier of native graphite, Graphite Coating metal oxide and its esters modifier etc.Preferably, the average grain diameter (D of graphite-like basis negative material particle 50) be 5-25 μ m.
Described surface treated graphite-like basis negative material, its average grain diameter (D50) is 5-25 μ m, specific area is 1.5-6.5m 2/ g.Concrete surface treatment method is: graphite-like basis negative material joined in the aqueous solution of acid (sulfuric acid, nitric acid, acid or glacial acetic acid), stir process 2-12 hour under 50-70 ℃ of temperature conditions is then through dehydration, dry after washing.Preferably adopt nitric acid, aqueous acid concentration is 3-8mol/L, by weight, and aqueous acid: graphite=1:5-10.
On the whole, the preparation method about negative material of the present invention comprises following operation:
(1) surface treatment procedure of graphite-like basis negative material
Graphite-like basis negative material is carried out to surface treatment with acid solution, obtain surface treated graphite-like basis negative material.
Concrete, will under the negative material stirring condition of graphite-like basis, join in aqueous acid, then stir process 2-12 hour under 50-70 ℃ of temperature conditions, then standby after dehydration, washing, preferably regulates pH value to neutral (5.5-7.0).Described acid is sulfuric acid, nitric acid, acid or glacial acetic acid, preferably nitric acid.The concentration of described aqueous acid is 3-8mol/L, by weight, and aqueous acid: graphite-like basis negative material=1:5-10.
(2) lithium titanate precursor preparation section
By the metatitanic acid of 5.0-8.0 weight portion or metatitanic acid, and the lithium salts of 1.0-5.0 weight portion is scattered in the solvent of 10-50 weight portion, then in solvent, adds the glucose of 1.0-2.0 weight portion to disperse to size mixing and obtains slurry.The charging sequence of above-mentioned material can be adjusted as the case may be, can optionally heat up or stirring at normal temperature, disperses to size mixing.At 150-500 ℃, sinter the slurry of preparation into presoma powder again.Described lithium salts is selected from hydrogenation lithium and hydrate thereof, or one or more in lithium carbonate, and described solvent is selected from deionized water or alcohol-water mixture.Described alcohol is selected from C 10following water-soluble lower alcohol, for example methyl alcohol, ethanol or isopropyl alcohol.Deionized water/alcohol ratio range is (10～50): (90～50).Presoma powder is oxide and the hydrate that contains titanium and lithium, and a small amount of undecomposed organic substance.
(3) preparation of dispersion liquid
The dispersant of 2-10 part is joined in the solvent of 80-90 part, dispersed with stirring is evenly standby.Described dispersant is polyketone resin or polyacetal resin; Described solvent is isopropyl alcohol or absolute ethyl alcohol.
(4) lithium titanate coating layer original position generates operation
Step (2) gained lithium titanate precursor powder joined in step (3) gained dispersion liquid and is uniformly dispersed, for example, adopt conventional dispersion machine to disperse, obtaining mixed dispersion liquid.The use amount of dispersant, the powder amount of easily disperseing as required regulates, and preferred, in lithium titanate precursor powder solid content, the addition of dispersant is 0.2-3wt%.Then, above-mentioned mixed dispersion liquid is joined in the negative material of the surface treated graphite-like of step (1) gained basis, and mix, by weight, the ratio of lithium titanate precursor powder and surface treated graphite-like basis negative material is 1-10:90-95.Then under protective atmosphere (preferred nitrogen or argon gas), 650～750 ℃ of temperature conditions sintering 6-8 hour, then cooling, sieve, obtain being formed with the negative material of lithium titanate coating layer on the negative material particle surface of surface treated graphite-like basis.The average grain diameter 5-25 μ m of negative material finished product, lithium titanate microscopic particles diameter < 1 μ m in coating layer.Preferably, before sintering, low-temperature material vacuumize is dewatered.
Lithium titanate particle is coated on negative material surface, graphite-like basis by Van der Waals force and forms coating layer.Concrete, by He Tai source, lithium source, in graphite surface original position, generate lithium titanate, because lithium is for falling low melting point, at high temperature there is fluxing action, therefore can strengthen the intensity of lithium titanate coating layer.
The surface treatment of embodiment 1 graphite basis negative material
Embodiment 1-1
Get the 3mol/L sulfuric acid solution 20kg preparing and pour in enamel jacket reactor, open stirring and dissolving, then to take 100kg average grain diameter (D50) be the graphous graphite powder of 5 μ m, then join in reactor while stirring.After reinforced, be warming up to 50 ℃ and stir 5 hours, with centrifuge, leach material, water washing is standby to pH value 6.0-7.0.Below corresponding undressed graphite is called to comparative example 1-1.
Embodiment 1-2
Getting the 8mol/L salpeter solution 20kg preparing pours in enamel jacket reactor, open stirring and dissolving, the graphous graphite powder that takes 80kg average grain diameter (D50) again and be 10 μ m joins in reactor while stirring, after reinforced, being warming up to 70 ℃ stirs 2 hours, with centrifuge filter, water washing is to pH value 5.5-7, leach material standby, material solid content by weight approximately 90%.Below corresponding undressed graphite is called to comparative example 1-2.
Embodiment 1-3
Getting the 4mol/L acetum 20kg preparing pours in enamel jacket reactor, open stirring and dissolving, the graphous graphite powder that takes 60kg average grain diameter (D50) again and be 25 μ m joins in reactor while stirring, after reinforced, being warming up to 70 ℃ stirs 12 hours, with centrifuge filter, water washing is to pH value 5.5-7, leach material standby, material solid content by weight approximately 90%.Below corresponding undressed graphite is called to comparative example 1-3.
Embodiment 2 lithium titanate precursor material preparations
Embodiment 2-1
In rustless steel container, pour 10kg deionized water into, then add 2kg monohydrate lithium hydroxide to dissolve, add glucose 0.5kg to stir, then weigh metatitanic acid 7.5kg and join in container and stir, optionally heat up or stirring at normal temperature.By mole lithium: titanium=1.23, stir discharging after 2 hours, pack in container that in 300 ℃, to dry discharging in 2 hours standby into.
Embodiment 2-2
In rustless steel container, pour 10kg absolute ethyl alcohol into, then add 2kg lithium carbonate to dissolve, add glucose 0.5kg to stir, then weigh metatitanic acid 6.95kg and join in container and stir, optionally heat up or stirring at normal temperature.By mole lithium: titanium=1.23, stir discharging after 1 hour, pack in container that in 500 ℃, to dry discharging in 2 hours standby into.
Embodiment 3 dispersion liquid preparations
Embodiment 3-1
In rustless steel container, pour 100kg isopropyl alcohol into, then add 5kg polyketone resin KY-120L, dispersed with stirring evenly obtains dispersion liquid, standby.
Embodiment 3-2
In rustless steel container, pour 100kg absolute ethyl alcohol into, then add 5kg polyacetal resin CF-A101, dispersed with stirring evenly obtains dispersion liquid, standby.
Embodiment 4
Embodiment 4-1
Get embodiment 2-1 material 5.5kg and embodiment 3-1 dispersion soln 13.0kg, join in container and with dispersion machine and disperse, then joined in the three-dimensional mixer that 70kg embodiment 1-1 material is housed mix and blend 50min.After mixing, take out material; first material is adopted under 60 ℃ of vacuum conditions of vacuum drier dry; again under argon atmospher protection gas condition in vacuum atmosphere oven 650 ℃ dry 6 hours; then after below being naturally cooled to 200 ℃, stop passing into protection gas discharging; material takes out the packing discharging of pulverizing and be up to the standards of cooling rear employing pulverizing mill, and material average grain diameter (D50) is 5.3 μ m after testing.The coated negative material through surface treatment graphite of lithium titanate below this embodiment being obtained is called embodiment 4-1.
Embodiment 4-2
Get embodiment 2-2 material 5.5kg and embodiment 3-2 dispersion soln 13.0kg, join in container and with dispersion machine and disperse, then joined in the three-dimensional mixer that 100kg embodiment 1-2 material is housed mix and blend.After mixing, take out material, first that material is complete with vacuumize at 60 ℃ of vacuum driers.Again under argon atmospher protection gas condition in vacuum atmosphere oven 650 ℃ dry 8 hours; then after below being naturally cooled to 200 ℃, stop passing into protection gas discharging; material takes out the packing discharging of pulverizing and be up to the standards of cooling rear employing pulverizing mill, and material average grain diameter (D50) is 11.5 μ m after testing.The coated negative material through surface treatment graphite of lithium titanate below this embodiment being obtained is called embodiment 4-2.
Embodiment 4-3
Get embodiment 2-2 material 5.5kg and embodiment 3-1 dispersion soln 13.0kg, join in container and with dispersion machine and disperse, then joined in the three-dimensional mixer that 70kg embodiment 1-2 material is housed and mix 50min.After mixing, take out material, first that material is complete with vacuumize at 60 ℃ of vacuum driers.Again under argon atmospher protection gas condition in vacuum atmosphere oven 300 ℃ dry 8 hours; then after below being naturally cooled to 200 ℃, stop passing into protection gas discharging; material takes out the packing discharging of pulverizing and be up to the standards of cooling rear employing pulverizing mill; material average grain diameter (D50) is 11.3 μ m after testing, and the coated negative material through surface treatment graphite of the lithium titanate below this embodiment being obtained is called embodiment 4-3.
Embodiment 4-4
Get embodiment 2-1 material 5.5kg and embodiment 3-1 dispersion liquid 15.0kg, join in container and disperse with dispersion machine, then joined and 100kg is housed gets in the three-dimensional mixer of executing routine 1-3 material and mix.After mixing, take out material, first that material is complete with vacuumize at 60 ℃ of vacuum driers.Again under argon atmospher protection gas condition in vacuum atmosphere oven 700 ℃ dry 8 hours; then after below being naturally cooled to 200 ℃, stop passing into protection gas discharging; material takes out the packing discharging of pulverizing and be up to the standards of cooling rear employing pulverizing mill; material average grain diameter (D50) is 25.3 μ m after testing, and the coated negative material through surface treatment graphite of the lithium titanate below this embodiment being obtained is called embodiment 4-4.
Embodiment 5 sample powder Electronic Speculum (SEM) and X-ray diffraction (XRD) test
The untreated graphite of the negative material that embodiment of the present invention 4-1 is made and comparative example 1-1 is made test specimens product go forward side by side line scanning Electronic Speculum (SEM) and EDS face and some elementary analysis.Electronic Speculum multiplication factor is 15000 times, and EDS multiplication factor is 1000 times, and the result of embodiment 4-1 negative material is as shown in Fig. 1-a and 1-c.The result of the untreated graphite of comparative example 1-1 is as shown in Fig. 1-b and 1-d.Shown in table 3, be embodiment 4-1 negative material and comparative example 1-1 untreated graphite EDS face and some region element test result.
Table 3
By Fig. 1-a, 1-b, shown in 1-c and 1-d.The body graphite material (untreated graphite) using with comparative example 1-1 is compared, embodiment 4-1 negative material particle surface has covered the coating of thin layer, coating is the surface that nanometer state is uniformly distributed in material, the surface transition of nano grain surface edge and bulk material is mild, show coating layer compact structure, possess good processing intensity.By EDS collection of illustrative plates (Fig. 1-c and Fig. 1-d) and table 3, can obviously test out material host element titanium coated in the present invention etc., the content of face test and some test titanium is close, has proved that from another point of view coating layer of the present invention is evenly coated simultaneously.In the follow-up stirring/operation such as be coated with/roll, can not come off like this and the degradation phenomena such as reunion.
Negative material and the untreated graphite sample of comparative example 1-2 embodiment 4-2 made carry out X-ray diffraction test (XRD) simultaneously, and test angle is 10 °～85 °, and stepping is 2 °/min, obtains result as shown in Figure 2.As seen from Figure 2, embodiment negative material possesses the feature spectrogram of graphite body and clad material (lithium titanate) simultaneously, shows that the structure of material in coated process is not changed, and coating has been generated as spinel type lithium titanate.The two brings out the best in each other, and in performance, may reach complementary object.
Embodiment 6 button cells are made and result
Embodiment 6-1 embodiment 4-3 negative material button cell is made
Taking 70g deionized water uses in dispersion machine container in experiment, open and stir, 2g sodium carboxymethylcellulose (CMC) the powder adhesive that adds metering in the situation that stirring, after dissolving completely Deng adhesive, take again 2g conductive carbon powder, and join in above-mentioned solution, after high speed dispersion 60min, getting final comminuting matter 90g prepared by embodiment 4-3 joins in above-mentioned solution, disperse to reduce mixing speed after 1～1.5h, then take 4.1g butadiene-styrene rubber (SBR) solution (solid content 48.0%) and join in slurry, after dispersion 40min, discharging is standby.
Get thickness and be 12 μ m Copper Foils as collector, the slurry of above-mentioned preparation is evenly coated on Copper Foil and in convection oven and dried, baking temperature is 85 ℃, and baking time is 1h.
Above-mentioned Copper Foil compacting is made to pole piece, and pole piece active material compacted density is 1.5g/cm 3, active matter thickness is about 85 μ m, and gross thickness is about 97 μ m.Then preparing CR2032 type button cell, is metal lithium sheet (produce Tianjin, 99.9%) to electrode.
At normal temperatures, with 2000 type battery test systems (Wuhan product), battery is carried out to volume test, voltage is respectively 0.05V～2.00V, and current density is 1mA/cm 2, result is as shown in Fig. 3-b.
The average grain diameter that embodiment 6-2 comparative example 1-2 is used is 25 μ m Delanium button cells
Take 70g deionized water in dispersion machine container, open and stir, the 2gCMC powder adhesive that adds metering in the situation that stirring, after dissolving completely Deng adhesive, take again 2g conductive carbon powder, and join in above-mentioned solution, after high speed dispersion 60min, getting respectively comparative example 1-2 graphite material (average grain diameter D50:17 μ m) 90g joins in above-mentioned solution, disperse to reduce mixing speed after 1～1.5h, then take 4.1gSBR solution (solid content 48%) and join in slurry, after dispersion 40min, discharging is standby.
Get thickness and be 12 μ m Copper Foils as collector, the slurry of above-mentioned preparation is evenly coated on Copper Foil and in convection oven and dried, baking temperature is 85 ℃, and baking time is 1h.
Above-mentioned Copper Foil compacting is made to pole piece, and pole piece active material compacted density is 1.5g/cm 3, active matter thickness is about 85 μ m, and gross thickness is about 105 μ m.Then preparing CR2032 type button cell, is metal lithium sheet (produce Tianjin, 99.9%) to electrode.
At normal temperatures, with 2000 type battery test systems (Wuhan product), battery is carried out to volume test, voltage is respectively 0.05V～2.00V, and current density is 1mA/cm 2, result is as shown in Fig. 3-a.
From Fig. 3-a and Fig. 3-b.Embodiment and comparative example are the button cell result of obvious graphite cathode material, and the specific capacity of the two approaches, and are 345mAh/g left and right, and efficiency approximately 92% first.The coated negative material specific capacity of processing of the present invention has no decline.Negative electrode prepared by the present invention first efficiency should be higher than raw material graphite, after this is likely the lithium titanate by clad nano yardstick, the surface of graphite obtains certain modification, is likely also that the efficiency first of metatitanic acid material itself is higher and possess certain specific capacity and cause performance boost.
Simultaneously from Fig. 3-b, at about 1.55V, there is a new platform in negative material of the present invention, the charge and discharge platform voltage of the lithium titanate material just that this platform is corresponding, shows that negative material of the present invention (clad material) is in the chemical property feature that reaches meeting embodiment self in a certain amount of situation.This likely has certain Economic Application and is worth.
The full battery of embodiment 7 is made and result.
The making of embodiment and the full battery of comparative example and result are mainly investigated the low temperature of full battery, multiplying power and circulation safe performance.Wherein assessing applicable kind is winding-structure 454261 type aluminum plastic film flexible-packed batteries, and the cell thickness of making is 4.5mm, and length is 4.2mm, and width is 6.1mm.Battery design capacity is 1.5Ah.
The positive electrode that the inventive example and comparative example are used is cobalt acid lithium, the preparation of positive electrode pole piece (adopts N-methyl pyrrole to omit alkane ketone as solvent by preparing slurry conventionally, polyvinylidene fluoride is as bonding agent), be coated with (adopting aluminium foil as collector) and cold pressing, the technique such as cutting makes, in pole piece, effectively positive active material content is 95%, and pole coating weight is 0.21g/cm 3, pole coating width is 38mm, the pole piece active material gross area is 0.050m 2, pole piece compacted density is counted 4.1g/cm with active material 3.
The preparation method of negative plate is conventionally via preparing slurry, and coating, colds pressing, and the operation preparation such as cuts, and the effective negative electrode active material content of pole piece after preparation is 95%, and pole coating weight is 0.089g/cm 2, pole coating width is 40mm, the pole piece active material gross area is 0.051m 2, pole piece compacted density is counted 1.5g/cm with active material 3.
By positive plate, barrier film, negative plates etc. are reeled in order and are prepared into naked battery core, naked battery core packs into after the assay was approved in the aluminum plastic film in made hole and seals 1 (approximately 135 ℃ * 5s, width 5～8mm), fluid injection (electrolyte: LIB302,3.2g/ only), change into (0-3.85V, 0.2C), heat-sealing 2 (approximately 135 ℃ * 5s, width 5-8mm) and volume test (3.0-4.2V, 0.5C), select up-to-standard battery core for follow-up Performance Evaluation.
Embodiment 7-1 embodiment 4-1,4-2,4-3 and 4-4 negative material are made the full battery of negative pole and are made
Use embodiment 4-1,4-2, the prepared negative material of 4-3 and 4-4 is prepared corresponding negative plate.The battery core of preparation be take negative material as grouping information, difference called after embodiment 4-1, and 4-2,4-3 and 4-4, the anodal material using is identical pole piece.
Embodiment 7-2 contrast groups lithium battery
Get comparative example 1-1,1-2,1-3 undressed average grain diameter used is 5 μ m, the standby full battery of 10 μ m and 25 μ m graphite-mades.By its actual Capacity design and be coated with into the pole piece of corresponding weight, by the method identical with example, be prepared into qualified lithium battery electric core for follow-up assessment.
Low temperature (20 ℃) test of the qualified lithium battery of embodiment 8 preparations
Press GB2423.1-89 electric and electronic product Essential Environment testing regulations test A: low-temperature test method.After liquid lithium ionic cell finishes by 5.7.2 regulation charging, battery is put into the cryogenic box constant temperature 16-24h of (20 ± 2) ℃, then with 1C/5A electric current constant-current discharge to final voltage, should be not less than 3h discharge time.After off-test, battery is taken out under the condition of ambient temperature (20 ± 5) ℃ and shelves 2h, range estimation battery outward appearance should be without distortion, without explosion.Under-20 ℃ of conditions of embodiment 4-4 and comparative example 1-3, discharge curve as shown in Figure 4.As seen from Figure 4, the battery that adopts the coated negative electrode of lithium titanate (LTO) material to make, its low temperature performance has greatly improved (under voltage 2.8V, depth of discharge brings up to 79% by 45%), so greatly widen the temperature limit of lithium battery, tentatively can meet the requirement of electric vehicle material.
Qualified lithium battery multiplying power (0.2C, 0.5C, 1.0C, the 2.0C) test of embodiment 9 preparations
Get the embodiment battery core being up to the standards and carry out 0.2C, 0.5C, 1.0C according to GBT standard, the test of 2.0C discharge-rate, adopts embodiment 4-1,4-3, the full battery of 4-4 negative material and employing comparative example 1-1, the high rate performance test result of the full battery of the untreated graphite of 1-2 as shown in Figure 5.It is one that the curve of embodiment 4-1 and comparative example 1-2 overlaps.
As seen from Figure 5, with contrast groups battery, compare, what adopt that the high rate performance of negative material of the present invention has is better than raw material group, have a little less than raw material group, its reason is likely that the discharge condition of graphite material and lithium titanate material is different, itself there is small capacitor and inductor phenomenon in negative plate inside, lithium intercalated graphite/lithium titanate material forms ion/electron channel each other mutually, thereby cause performance generally inconsistent, but adopt in general the high rate performance of negative material of the present invention to be better than the prepared lithium battery of undressed raw material.
60 ℃ of 1C/1C circulation results of qualified lithium battery of embodiment 10 preparations
As seen from Figure 6, the lithium battery high temperature cyclic performance that adopts embodiment 4-4 negative material to prepare is better than lithium battery prepared by undressed comparative example 1-3 graphite material.It is likely that reduce on the electrolytical surface of graphite composite powder contact that has been coated lithium titanate material, is likely also that lithium titanate coating participates in having formed more stable SEI film, thereby negative material is more tended towards stability.
In sum, adopt method of the present invention to prepare the technique of negative material simple, material wide material sources, adopt simultaneously lithium battery high temperature prepared by negative material of the present invention and high rate performance all improvement to a certain extent, initial stage conception of the present invention and target have been reached, believing along with the going deep into of material characterizing method and research, can progressively disclose merits and demerits of the present invention, is the application extension space of lithium battery.

Claims (17)

1. an anode material for lithium-ion secondary battery, is characterized in that, this negative material is formed with lithium titanate coating layer on the negative material particle surface of surface treated graphite-like basis.
2. negative material according to claim 1, is characterized in that, described graphite-like basis negative material is selected from Delanium, native graphite, their mixture, or their modifier.
3. negative material according to claim 1 and 2, is characterized in that, described surface treated graphite-like basis negative material, and its average grain diameter (D50) is 5-25 μ m, specific area is 1.5-6.5m 2/ g.
4. according to the negative material described in claim 1-3 any one, it is characterized in that, coated rear negative material surface lithium titanate particle average grain diameter (D50) is < 1 μ m, accounts for the 0.1-2wt% of negative material total weight.
5. according to the negative material described in claim 1-4 any one, it is characterized in that, wherein, the specific capacity of described negative material is 320-365mAh/g, and coulombic efficiency is 89-94% first.
6. a preparation method for negative material, the method comprises the steps:
(1) surface treatment procedure of graphite-like basis negative material
Graphite-like basis negative material is carried out to surface treatment with acid solution, obtain surface treated graphite-like basis negative material;
(2) lithium titanate coating layer original position generates operation
Lithium titanate precursor powder, the surface treated graphite-like of step (1) gained basis negative material, dispersant and solvent is even; dehydration; then under protective atmosphere (preferably argon gas); 650-750 ℃ of temperature conditions sintering, obtains being formed with the negative material of lithium titanate coating layer on the negative material particle surface of surface treated graphite-like basis.
7. preparation method according to claim 6, it is characterized in that, the method also comprises lithium titanate precursor preparation section: by the metatitanic acid of 5.0-8.0 weight portion or metatitanic acid, and the lithium salts of 1.0-5.0 weight portion is scattered in the solvent of 10-50 weight portion, then in solvent, add the glucose of 1.0-2.0 weight portion to disperse to size mixing and obtain slurry, then at 150-500 ℃, sinter the slurry of preparation into presoma powder.
8. method according to claim 7, is characterized in that, described lithium salts is one or both in monohydrate lithium hydroxide or lithium carbonate, and described solvent is deionized water or alcohol-water mixture; Described alcohol is selected from C 10following water-soluble lower alcohol, particular methanol, ethanol or isopropyl alcohol; Deionized water/alcohol ratio range is (10～50): (90～50).
9. according to the method described in claim 6-8 any one, it is characterized in that, in step (1), described surface treatment is that graphite-like basis negative material is joined in aqueous acid, stir process 2-12 hour under 50-70 ℃ of temperature conditions is then dry after dehydration, washing.
10. according to the method described in claim 6-9 any one, it is characterized in that, in step (1), described acid is sulfuric acid, nitric acid, acid or glacial acetic acid, preferably nitric acid; The concentration of described aqueous acid is 3-8mol/L, by weight, and aqueous acid: graphite-like basis negative material=1:5-10.
11. according to the method described in claim 6-10 any one, it is characterized in that, in step (2), by weight, the ratio of lithium titanate precursor powder and surface treated graphite-like basis negative material is 1-10:90-95; Described dispersant is polyketone resin or polyacetal resin, and in lithium titanate precursor powder solid content, the addition of dispersant is 0.2-3wt%; Described solvent is isopropyl alcohol or absolute ethyl alcohol; By weight, the ratio of dispersant and solvent is 2-10:80-90.
12. according to the method described in claim 6-11 any one, it is characterized in that, in step (2), 650～750 ℃ of temperature conditions sintering 6-8 hour, then cooling, sieve.
13. according to the method described in claim 6-12 any one, it is characterized in that, the lithium titanate grain diameter in described lithium titanate coating layer is < 1 μ m, accounts for the 0.1-2.0wt% of negative material total weight.
14. 1 kinds of ion secondary battery cathode material lithiums, it prepares by the preparation method described in claim 6-13 any one.
15. 1 kinds of lithium rechargeable batteries, is characterized in that, adopt the negative material described in claim 1-5 any one or claim 14 to prepare.
16. 1 kinds of energy-accumulating power stations or removable storage device, is characterized in that, adopts the lithium rechargeable battery described in claim 15 to prepare.
The application of negative material described in 17. claim 1-5 any one or claim 14 in manufacturing lithium ion battery, removable storage device or energy-accumulating power station.
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CN108598421A (en) * 2018-04-25 2018-09-28 桑顿新能源科技有限公司 A kind of start and stop battery
CN109888229A (en) * 2019-03-01 2019-06-14 中山市华舜科技有限责任公司 A kind of preparation method of the lithium ion battery negative material based on lithium titanate coated graphite composite material
CN110518226A (en) * 2019-09-10 2019-11-29 石家庄尚太科技有限公司 A kind of silicon-carbon composite cathode material and preparation method thereof
CN110931757A (en) * 2019-12-16 2020-03-27 成都爱敏特新能源技术有限公司 Graphite composite material and preparation method thereof
CN112018366A (en) * 2020-09-10 2020-12-01 安徽科达新材料有限公司 Graphite negative electrode material of lithium ion battery and preparation method thereof
CN113363444A (en) * 2021-06-15 2021-09-07 广东凯金新能源科技股份有限公司 Nano lithium titanate-coated modified graphite negative electrode material, and preparation method and application thereof
CN114497507A (en) * 2022-01-29 2022-05-13 辽宁中宏能源新材料股份有限公司 Quick-filling graphite composite material and preparation method thereof
CN114792802A (en) * 2022-04-29 2022-07-26 内蒙古杉杉科技有限公司 Modified high-initial-efficiency composite graphite negative electrode material

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