CN104167543A - Graphite flake/self-assembled nanometer cobaltosic oxide lithium ion negative electrode material, its preparation method and lithium battery using it - Google Patents

Graphite flake/self-assembled nanometer cobaltosic oxide lithium ion negative electrode material, its preparation method and lithium battery using it Download PDF

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CN104167543A
CN104167543A CN201410132597.5A CN201410132597A CN104167543A CN 104167543 A CN104167543 A CN 104167543A CN 201410132597 A CN201410132597 A CN 201410132597A CN 104167543 A CN104167543 A CN 104167543A
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graphite flake
self
lithium
cobaltosic oxide
graphite
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CN104167543B (en
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徐军明
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Hangzhou Dianzi University
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The embodiment of the invention discloses a graphite flake/self-assembled nanometer cobaltosic oxide lithium ion negative electrode material, its preparation method and a lithium battery using it. The preparation method comprises the following steps: weighing expanded graphite and DMF according to a ratio of 0.5-5g/L, and carrying out ultrasonic treatment to obtain a graphite flake solution; adding a proper amount of deionized water; weighing cobalt acetate tetrahydrate according to a ratio of the cobalt acetate tetrahydrate to the solvent DMF of 10-60g/L, and dissolving the cobalt acetate tetrahydrate in the solvent; stirring for dissolving, adding the above obtained solution into a hydrothermal tank, and carrying out heat insulation; and cooling to room temperature, cleaning the above obtained black sediment through using an alcohol solution by a centrifuge, and baking the cleaned black sediment until the obtained sample is dry. Co3O4 nanoparticles in the composite material prepared through the method are cubic particles with good crystallization and uniform size, the side length of the nanoparticles is about 4nm, the density of the nanoparticles is 2*10<13>/cm<2>, a gap between two adjacent nanoparticles is 1-10nm, and the nanoparticles are uniformly distributed on two surfaces of a graphite flake, so an extremely good lithium storage performance can be obtained.

Description

A kind of graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium, preparation method and apply its lithium battery
Technical field
The invention belongs to lithium-ion energy storage Material Field, relate to a kind of graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium and preparation method, this material can be used for making lithium ion cell electrode.
Background technology
Graphene (mono-layer graphite sheet) and the less graphite flake of the number of plies have good conductivity and the specific area of super large, adopt grapheme material to replace the electrode of traditional material with carbon element for lithium ion battery and ultracapacitor, it has shown good capacity characteristic and charge-discharge characteristic.But single Graphene is made electrode and is also existed some problems, the shortcoming such as reunion, cyclical stability be poor as existed.Therefore preparing metal oxide on Graphene surface is nearest study hotspot as electrode.Utilize the good conductivity of Graphene and the specific area of super large as carrier, nano level transition metal oxide is dispersed between the surface and lamella of Graphene, this compound is applied to lithium ion battery negative material and ultracapacitor will have good cycle performance and good high rate performance.
Nano-cobaltic-cobaltous oxide Co 3o 4possess some special knowledge as lithium ion battery negative material, shown very high capacity and good cycle performance.Recently existing Co 3o 4the report of the nano wire of nanometer rods, nano wire, nanotube and different arrays, but Co 3o 4chang Yin has very large change in volume and makes partial reaction irreversible in charge and discharge process, and the loss of capacity occurs, thereby affects the cycle performance of battery.This is because Co 3o 4poorly conductive, thereby cause in charge and discharge process, there is efflorescence and agglomeration, institute thinks improves its conductivity, can attempt Co 3o 4be dispersed in the high conductivity of utilizing graphite on graphite flake layer.
For improving the performance of graphite flake/oxide composite lithium-bearing material, target is that oxide particle size is as far as possible little, even, and the density on graphite flake is as far as possible high.Dwindle yardstick and can greatly reduce lithium ion diffusion time therein, thereby be conducive to improve high rate performance, the size of dwindling material also can increase and electrolytical contact area, thereby also can increase the path of lithium ion to material internal diffusion, further shorten its diffusion time, the size that reduces material also can strengthen the transmission of electronics at material internal.Improve oxide can improve storage lithium ion quantity in the density on Graphene surface, increase the cooperative effect of oxide and Graphene, be conducive to improve capacity characteristic.
According to having at present at Graphene surface preparation Co 3o 4report.Commonly use and prepare compound by graphene oxide (GO).The chemical modification of Graphene is introduced functional group on its surface, and logical peroxide bridge and functional group can be with the method for chemical bond at its surface deposition nano-oxides.This method by GO method and nearest redox graphene is prepared composite material and is existed complex process, the high shortcoming of cost, and meanwhile, the chemical modification of GO can reduce the conductivity of Graphene, thereby has weakened its performance as electrode.There is the deposition Co of preparation 3o 4size is larger, and size is not very even, and in the not high problem of the coverage rate on Graphene surface, these all can certain influence electrode material characteristic.
Summary of the invention
For addressing the above problem, the object of the present invention is to provide a kind of preparation method of graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium, on the graphite flake that the method employing is obtained at simple ultrasonic method, prepare nano-scale little, density is high, there is the cobaltosic oxide particle of a fixed gap, although the number of plies of graphite flake is more than Graphene, the compound of preparation has still obtained good storage lithium performance.The Co obtaining on graphite flake surface 3o 4nano particle is cube, and evenly, density is greater than 2 × 10 to size 13individual/cm 2, the length of side is about 4nm, and space each other, at 1-10nm, is evenly distributed on two surfaces of graphite flake, can eliminate the direct contact between graphite flake, there will not be agglomeration.Co 3o 4because diameter is little, evenly, lithium performance is stored up in can be best obtain to size.Graphite flake does not pass through any processing simultaneously, therefore can ensure maximum conductivity.
Another object of the present invention is to provide the graphite flake/self-assembled nanometer cobaltosic oxide being prepared by above method ion cathode material lithium.
Another object of the present invention is to provide the lithium battery that uses this graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium to make negative pole.
For achieving the above object, technical scheme of the present invention is:
A preparation method for graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium, comprises the following steps:
S10, takes expanded graphite and dimethyl formamide DMF by 0.5-5g/L proportioning, expanded graphite is put into DMF and carry out ultrasonic 1-4 hour, obtains graphite flake solution;
S20, adds deionized water, and the ratio of deionized water and DMF is 1:1-1:9, stirs;
S30, takes four hydration cobalt acetates, and wherein cobalt is II valency, and four hydration cobalt acetates are 10-60g/L with respect to the concentration of solvent DMF, and four hydration cobalt acetates are dissolved in to solvent, stirs;
S40, puts into hydro-thermal tank by above solution, and wherein the filling volume ratio of hydro-thermal tank is 1/5-1/2, is warmed up to 100-150 DEG C with the programming rate of 1 DEG C/point-10 DEG C/point, temperature retention time 1.5h-10h, after cooling with stove;
S50, after cool to room temperature, pours out solution, black deposit is cleaned with centrifuge, cleans and adopts alcoholic solution, and the number of times of cleaning is at 3-5 time;
S60 is baked to sample drying by the black deposit having cleaned at 40-80 DEG C.
And, a kind of graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium, described graphite flake/self-assembled nanometer cobaltosic oxide composite material ion cathode material lithium is by preparing as said method, and the carbon-coating number of the graphite flake in composite material is less than 100 layers, the Co on graphite flake surface 3o 4nano particle is the isometric particle of advantages of good crystallization, and evenly, density is greater than 2 × 1O to size 13individual/cm 2, the length of side is about 4nm left and right, and space each other, at 1-10nm, is evenly distributed on two surfaces of graphite flake.
And a kind of lithium battery, comprises negative pole, the material of described negative pole is graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium as above.
Compared with prior art, beneficial effect of the present invention is as follows:
(1) Co on graphite flake surface 3o 4nano particle is closely and is uniformly distributed, this Co 3o 4particle advantages of good crystallization, is isometric particle, and evenly, the length of side is about 4nm to size, and density is greater than 2 × 10 13individual/cm 2, space each other, at 1-10nm, is evenly distributed on two surfaces of graphite flake.
(2) prepare the method for graphite flake simple, graphite flake is made up of the carbon-coating that is less than 100 layers, can obviously see (002) diffraction maximum of graphite linings in X-ray diffraction.Owing to specially not adding oxidant, the degree of oxidation of graphite flake is low.Thereby in processing procedure below, do not need to adopt to add the reducing agents such as hydrazine to reduce processing, and can ensure the structural intergrity that graphite flake is initial, thereby ensure best electrical conductance.And the number of plies that reduces graphite flake can further improve storage lithium performance.
(3) graphite flake in composite material has two dimensional surface shape structure, has larger specific area, and good conductivity and thermal conduction characteristic are conducive to the fast transport of electronics.Oxide nano particles directly contacts with graphite flake, ensures that electronics can promptly transmit between graphite flake and oxide.Between oxide, there is certain space, graphite flake/Co 3o 4be compounded in while preparing electrode, can produce each other space, for electrolyte ion provides passage at whole composite material, promoted the fast transport of ion.Ensure the power characteristic that this material is good.
(4) graphite flake and oxide nano particles interact, and have avoided the accumulation again of graphite flake and the reunion of oxide nano particles.Co 3o 4particle is little, and charging and discharging in lithium process, the change in size of whole particle is little.And the space between oxide nano particles can provide space in the change in volume charging and discharging in lithium process for oxide, thereby improve the cyclical stability of material.
(5) prepared oxide is distributed in upper and lower two surfaces of graphite flake, and between particle, space is very little, and oxide particle density is very high, is conducive to improve the storage lithium performance of material.
(6) the Multi-layer graphite layer structure of graphite flake still keeps the original structure of graphite, therefore, can store certain lithium ion.
(7) composite material 50mA/g of the present invention charges and discharge first lithium capacity and reaches 1400mAh/g, and stable capacity can reach 1030mAh/g; It is 900mAh/g that 100mA/g charges and discharge lithium capacity; Efficiency for charge-discharge is high.
(8) this method preparation process is simple, is suitable for volume production.
Brief description of the drawings
Fig. 1 is graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium preparation method's of the embodiment of the present invention flow chart of steps;
Fig. 2 is graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium scanning electron microscope (SEM) photograph of the embodiment of the present invention;
Fig. 3 is graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium transmission electron microscope picture of the embodiment of the present invention;
Fig. 4 is graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium XRD collection of illustrative plates of the embodiment of the present invention;
Fig. 5 is the charging and discharging curve figure of the test battery of the composite material making of the embodiment of the present invention;
Fig. 6 be the test battery made of the composite material of the embodiment of the present invention fill lithium cycle performance collection of illustrative plates.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
On the contrary, the present invention contain any defined by claim in marrow of the present invention and scope, make substitute, amendment, equivalent method and scheme.Further, for the public is had a better understanding to the present invention, in below details of the present invention being described, detailed some specific detail sections of having described.Do not have for a person skilled in the art the description of these detail sections can understand the present invention completely yet.
Referring to Fig. 1, be depicted as the preparation method of a kind of graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium of the embodiment of the present invention, comprise the following steps:
S10, takes expanded graphite and dimethyl formamide DMF by 0.5-5g/L proportioning, expanded graphite is put into DMF and carry out ultrasonic 1-2 hour, obtains graphite flake solution;
S20, adds deionized water, and the ratio of deionized water and DMF is 1:1-1:9, stirs;
S30, takes four hydration cobalt acetates, and wherein cobalt is II valency, is called for short four hydration cobalt acetates (II), and four hydration cobalt acetates (II) are 10-60g/L with respect to the concentration of solvent DMF, and four hydration cobalt acetates are dissolved in to solvent, and stirring and dissolving is even;
S40, puts into hydro-thermal tank by above solution, and wherein the filling volume ratio of hydro-thermal tank is 1/5-1/2, be the 20%-50% that reaction solution volume accounts for hydro-thermal tank cumulative volume, programming rate with 1 DEG C/point-10 DEG C/point is warmed up to 100-150 DEG C, temperature retention time 1.5h-10h, after cooling with stove;
S50, after cool to room temperature, pours out solution, black deposit is cleaned with centrifuge, cleans and adopts alcoholic solution, and the number of times of cleaning is at 3-5 time;
S60 is baked to the black deposit having cleaned graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium sample drying at 40-80 DEG C.
Known by above preparation process explanation, the method that the present invention adopts prepares graphite flake/self-assembled nanometer cobaltosic oxide composite material, and preparation process is simple and controlled and repeatable good, is suitable for volume production.
Simultaneously, corresponding with method, further embodiment of this invention provides graphite flake/self-assembled nanometer cobaltosic oxide of preparing by said method ion cathode material lithium, referring to Fig. 2 to Fig. 4, be respectively the scanning electron microscope (SEM) photograph of graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium of the embodiment of the present invention, transmission electron microscope picture and XRD figure.Referring to Fig. 2 and 3 visible, the Co on graphite flake surface 3o 4nano particle is the isometric particle of advantages of good crystallization, and evenly, the length of side is about 4nm to size, and density is greater than 2 × 10 13individual/cm 2, space each other, at 1-10nm, is evenly distributed on two surfaces of graphite flake.The method of preparing graphite flake is simple, referring to Fig. 4, can see (002) diffraction maximum of graphite linings in X-ray diffraction.In the embodiment of the present invention, owing to specially not adding oxidant, the degree of oxidation of graphite flake is low, thereby in processing procedure below, do not need to adopt to add the reducing agents such as hydrazine to reduce processing, and can ensure the structural intergrity that graphite flake is initial, thereby ensure best electrical conductance.Graphite flake in composite material has two dimensional surface shape structure, has larger specific area, and good conductivity and thermal conduction characteristic are conducive to the fast transport of electronics.Oxide nano particles directly contacts with graphite flake, ensures that electronics can promptly transmit between graphite flake and oxide.Between oxide, there is certain space, graphite flake/Co 3o 4be compounded in while preparing electrode, can produce each other space, for electrolyte ion provides passage at whole composite material, promoted the fast transport of ion, ensured the power characteristic that this material is good.Graphite flake and oxide nano particles interact, and have avoided the accumulation again of graphite flake and the reunion of oxide nano particles.Co 3o 4particle is little, and in the process of change in volume, the change in size of whole particle is little.Space between oxide can be for oxide be at the Volume variation charging and discharging in lithium process, thereby has improved the cyclical stability of material.Prepared oxide is distributed in upper and lower two surfaces of graphite flake, and between particle, space is very little, and oxide particle density is very high, is conducive to improve the storage lithium performance of material.
By the architectural characteristic of above graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium, further embodiment of this invention provides a kind of lithium battery, comprise negative pole, wherein the material of negative pole is graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium as above.After adopting general method to make the test battery of composite material, test, first three of the lithium battery that is the embodiment of the present invention referring to Fig. 5 time charging and discharging curve figure, charge cutoff voltage is 3V, discharge cut-off voltage is about 0.05V, in figure, can see obvious Co 3o 4charge-discharge characteristic.Fig. 6 be the embodiment of the present invention lithium battery fill lithium cycle performance collection of illustrative plates, as can be seen from the figure the composite material 50mA/g of the embodiment of the present invention charges and discharge first lithium capacity and reaches 1400mAh/g, stable capacity can reach 1030mAh/g; It is 900mAh/g that 100mA/g charges and discharge lithium capacity, charges and discharge efficiency high.
Below by the preparation process of alum ink sheet/self-assembled nanometer cobaltosic oxide ion cathode material lithium by multiple specific embodiments.The hydro-thermal tank using in specific embodiment is market and buys, and its typical volume is 20ml, 50ml, 100ml and 250ml.In specific embodiment, the cumulative volume of mixed solution can cover reaction solution volume and account for the 20%-50% of hydro-thermal tank cumulative volume in the adjustment of proportioning ratio.
Embodiment 1
Take expanded graphite 4mg and DMF8ml, expanded graphite is put into DMF and carry out ultrasonic 1 hour, obtain graphite flake solution.Take deionized water 0.9ml, add graphite flake solution, stir.Take four hydration cobalt acetate (II) 80mg, four hydration cobalt acetates (II) are dissolved in to mixed solvent, be stirred to completely and dissolve.Above solution is put into the hydro-thermal tank that volume is 20ml, and the cumulative volume that reaction solution accounts for hydro-thermal tank is about 44.5%, meets the filling volume proportion requirement of hydro-thermal tank, is warmed up to 120 DEG C with the programming rate of 1 DEG C/point, temperature retention time 1.5h, after cooling with stove.Microparticle is cleaned with centrifuge, clean and adopt alcoholic solution, the number of times of cleaning is at 3 times.At 40 DEG C, be baked to sample drying, obtain graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium sample.
Embodiment 2
Take expanded graphite 40mg and DMF8ml, expanded graphite is put into DMF and carry out ultrasonic 2 hours, obtain graphite flake solution.Take deionized water 8ml, add graphite flake solution, stir.Take four hydration cobalt acetate (II) 480mg, four hydration cobalt acetates (II) are dissolved in to mixed solvent, be stirred to completely and dissolve.The hydro-thermal tank of above solution being put into 50ml, the cumulative volume that reaction solution accounts for hydro-thermal tank is about 32%, meets the filling volume proportion requirement of hydro-thermal tank, is warmed up to 150 DEG C with the programming rate of 5 DEG C/point, temperature retention time 5h, after cooling with stove.Microparticle is cleaned with centrifuge, clean and adopt alcoholic solution, the number of times of cleaning is at 4 times.At 80 DEG C, be baked to sample drying, obtain graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium sample.
Embodiment 3
Take expanded graphite 30mg and DMF16ml, expanded graphite is put into DMF and carry out ultrasonic 3 hours, obtain graphite flake solution.Take deionized water 8ml, add graphite flake solution, stir.Take four hydration cobalt acetate (II) 400mg, cobalt acetate (II) is dissolved in to mixed solvent, be stirred to completely and dissolve.The hydro-thermal tank of above solution being put into 100ml, the cumulative volume that reaction solution accounts for hydro-thermal tank is about 24%, meets the filling volume proportion requirement of hydro-thermal tank, is warmed up to 130 DEG C with the programming rate of 10 DEG C/point, temperature retention time 10h, after cooling with stove.Microparticle is cleaned with centrifuge, clean and adopt alcoholic solution, the number of times of cleaning is at 5 times.At 60 DEG C, be baked to sample drying, obtain graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium sample.
Embodiment 4
Take expanded graphite 120mg and DMF48ml, expanded graphite is put into DMF and carry out ultrasonic 4 hours, obtain graphite flake solution.Take deionized water 36ml, add graphite flake solution, stir.Take cobalt acetate (II) 300mg, four hydration cobalt acetates (II) are dissolved in to mixed solvent, be stirred to completely and dissolve.The hydro-thermal tank of above solution being put into 250ml, the cumulative volume that reaction solution accounts for hydro-thermal tank is about 33.6%, meets the filling volume proportion requirement of hydro-thermal tank, is warmed up to 140 DEG C with the programming rate of 5 DEG C/point, temperature retention time 4h, after cooling with stove.Microparticle is cleaned with centrifuge, clean and adopt alcoholic solution, the number of times of cleaning is at 5 times.At 40 DEG C, be baked to sample drying, obtain graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium sample.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (3)

1. a preparation method for graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium, is characterized in that, comprises the following steps:
S10, takes expanded graphite and dimethyl formamide DMF by 0.5-5g/L proportioning, expanded graphite is put into DMF and carry out ultrasonic 1-4 hour, obtains graphite flake solution;
S20, adds deionized water, and the ratio of deionized water and DMF is 1:1-1:9, stirs;
S30, takes four hydration cobalt acetates, and wherein cobalt is II valency, and four hydration cobalt acetates are 10-60g/L with respect to the concentration of solvent DMF, and four hydration cobalt acetates are dissolved in to solvent, and stirring and dissolving is even;
S40, puts into hydro-thermal tank by above solution, and wherein the filling volume ratio of hydro-thermal tank is 1/5-1/2, is warmed up to 100-150 DEG C with the programming rate of 1 DEG C/point-10 DEG C/point, temperature retention time 1.5h-10h, after cooling with stove;
S50, after cool to room temperature, pours out solution, black deposit is cleaned with centrifuge, cleans and adopts alcoholic solution, and the number of times of cleaning is at 3-5 time;
S60 is baked to the black deposit having cleaned graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium sample drying at 40-80 DEG C.
2. graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium, it is characterized in that, described graphite flake/self-assembled nanometer cobaltosic oxide composite material ion cathode material lithium is prepared by the method for claim 1, the carbon-coating number of the graphite flake in composite material is less than 100 layers, the Co on graphite flake surface 3o 4nano particle is the isometric particle of advantages of good crystallization, and evenly, density is greater than 2 × 10 to size 13individual/cm 2, the length of side is about 4nm left and right, and space each other, at 1-10nm, is evenly distributed on two surfaces of graphite flake.
3. a lithium battery, comprises negative pole, it is characterized in that, the material of described negative pole is graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium as claimed in claim 2.
CN201410132597.5A 2014-04-03 2014-04-03 Its lithium battery of a kind of graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium, preparation method and application Expired - Fee Related CN104167543B (en)

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