CN104167543B - Its lithium battery of a kind of graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium, preparation method and application - Google Patents
Its lithium battery of a kind of graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium, preparation method and application Download PDFInfo
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- CN104167543B CN104167543B CN201410132597.5A CN201410132597A CN104167543B CN 104167543 B CN104167543 B CN 104167543B CN 201410132597 A CN201410132597 A CN 201410132597A CN 104167543 B CN104167543 B CN 104167543B
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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
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- 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
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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
- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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 kind of graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium, its lithium battery of preparation method and application, wherein embodiment of the method is as follows: weigh expanded graphite and DMF by 0.5 5g/L proportioning, obtains graphite flake solution through ultrasonic；Add appropriate amount of deionized water；Weigh and be dissolved in solvent relative to concentration is 10 60g/L four hydration cobalt acetates of solvent DMF；After stirring and dissolving, above solution is put into the insulation of hydro-thermal tank；After being cooled to room temperature, after being cleaned by black deposit alcoholic solution with centrifuge, it is baked to sample drying.Co in composite prepared by the method for the embodiment of the present invention3O4Nano particle is the isometric particle of advantages of good crystallization, and size is uniform, and the length of side is about about 4nm, and density is more than 2 × 1013Individual/cm2, space each other, at 1 10nm, is evenly distributed on two surfaces of graphite flake, thus can obtain fabulous storage lithium performance.
Description
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 the specific surface area of good electric conductivity and super large, using grapheme material to replace traditional material with carbon element for lithium ion battery and the electrode of ultracapacitor, it has shown good capacity characteristic and charge-discharge characteristic.But single Graphene there is also some problems as electrode, as there is the shortcoming such as reunion, cyclical stability difference.Therefore preparing metal oxide as electrode at graphenic surface is nearest study hotspot.Utilize the specific surface area of the excellent electric conductivity of Graphene and super large as carrier, being dispersed between the surface of Graphene and lamella by nano level transition metal oxide, this compound is applied to lithium ion battery negative material and ultracapacitor and will have good cycle performance and good high rate performance.
Nano-cobaltic-cobaltous oxide Co3O4Possess some special knowledge as lithium ion battery negative material, shown the highest capacity and good cycle performance.Have Co recently3O4The report of the nano wire of nanometer rods, nano wire, nanotube and different array, but Co3O4Chang Yin has the biggest Volume Changes to make partial reaction irreversible in charge and discharge process, the loss of capacity occurs, thus affects the cycle performance of battery.This is because Co3O4Poorly conductive, thus cause in charge and discharge process, there is efflorescence and agglomeration, so for improving its electric conductivity, can attempt Co3O4It is dispersed on graphite flake layer the high conductivity utilizing graphite.
For improving the performance of graphite flake/oxide composite lithium-bearing material, target is that oxide particle size is the least, uniform, the height as far as possible of the density on graphite flake.Reduce yardstick and can significantly reduce lithium ion diffusion time wherein, thus be conducive to improving high rate performance, the size reducing material can also increase the contact area with electrolyte, thus the path that lithium ion spreads can also be increased to material internal, shortening its diffusion time further, the size reducing material can also strengthen the electronics transmission at material internal.Improve oxide and can improve the quantity of storage lithium ion in the density of graphenic surface, increase the cooperative effect of oxide and Graphene, be conducive to improving capacity characteristic.
Co is prepared at graphenic surface according to the most existing3O4Report.Commonly use and prepare compound by graphene oxide (GO).The chemical modification of Graphene introduces functional group, logical peroxide bridge and functional group on its surface can be with the method for chemical bond at its surface deposition nano-oxide.This method by GO method and nearest redox graphene is prepared composite and be there is complex process, cost high shortcoming, and meanwhile, the chemical modification of GO can reduce the electric conductivity of Graphene, thus reduces its performance as electrode.There is deposition Co of preparation3O4Size is relatively big, and size is not very uniform, and the problem that coverage rate at graphenic surface is the highest, these all can necessarily affect electrode material characteristic.
Summary of the invention
For solving the problems referred to above, it is an object of the invention to provide the preparation method of a kind of graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium, it is little that the method employing prepares nano-scale on the graphite flake that simple ultrasonic method obtains, 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 still obtains excellent storage lithium performance.The Co obtained on graphite flake surface3O4Nano particle is cube, and size is uniform, and density is more than 2 × 1013Individual/cm2, 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, not have agglomeration.Co3O4Owing to diameter is little, size is uniform, it is possible to best acquisition storage lithium performance.Graphite flake is not through any process simultaneously, therefore can guarantee that the electric conductivity of maximum.
A further object of the present invention is to provide the graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium prepared by above method.
A further object of the present invention is to provide the lithium battery using this graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium to make negative pole.
For achieving the above object, the technical scheme is that
The preparation method of a kind of graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium, comprises the following steps:
S10, weighs expanded graphite and dimethylformamide DMF by 0.5-5g/L proportioning, expanded graphite is put into DMF and carries out ultrasonic 1-4 hour, obtain graphite flake solution；
S20, adds deionized water, and deionized water is 1:1-1:9 with the ratio of DMF, stirs；
S30, weighs four hydration cobalt acetates, and wherein cobalt is II valency, and four hydration cobalt acetates are 10-60g/L relative to the concentration of solvent DMF, four hydration cobalt acetates is dissolved in solvent, stirs；
S40, puts into hydro-thermal tank by above solution, and wherein the filling volume fraction 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/minute-10 DEG C/minute, temperature retention time 1.5h-10h, after with stove cool down；
S50, after being cooled to room temperature, pours out solution, is cleaned by black deposit with centrifuge, cleans and uses alcoholic solution, and the number of times of cleaning is at 3-5 time；
S60, is baked to sample drying by the black deposit 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 prepared by such as said method, and the carbon-coating number of the graphite flake in composite is less than 100 layers, the Co on graphite flake surface3O4Nano particle is the isometric particle of advantages of good crystallization, and size is uniform, and density is more than 2 × 1O13Individual/cm2, the length of side is about about 4nm, and space each other, at 1-10nm, is evenly distributed on two surfaces of graphite flake.
And, a kind of lithium battery, including negative pole, the material of described negative pole is graphite flake as above/self-assembled nanometer cobaltosic oxide ion cathode material lithium.
Compared with prior art, beneficial effects of the present invention is as follows:
(1) Co on graphite flake surface3O4Nano particle in being closely uniformly distributed, this Co3O4Grain crystalline is good, and for isometric particle, size is uniform, and the length of side is about 4nm, and density is more than 2 × 1013Individual/cm2, space each other, at 1-10nm, is evenly distributed on two surfaces of graphite flake.
(2) method preparing graphite flake is simple, and graphite flake is made up of the carbon-coating less than 100 layers, can be clearly visible (002) diffraction maximum of graphite linings in X-ray diffraction.Owing to the most specially adding oxidant, the degree of oxidation of graphite flake is low.Thus in processing procedure below, it is not necessary to use reducing agents such as adding hydrazine to carry out reduction treatment, and can guarantee that the structural intergrity that graphite flake is initial, thus ensure optimal electrical conductance.And the number of plies reducing graphite flake can improve storage lithium performance further.
(3) graphite flake in composite has two dimensional surface shape structure, has bigger specific surface area, the quick transmission of good electric conductivity and thermal conduction characteristic, beneficially electronics.Oxide nano particles directly contacts with graphite flake, it is ensured that electronics can promptly transmit between graphite flake and oxide.There is between oxide certain space, graphite flake/Co3O4It is compounded in when preparing electrode, space can be produced each other, provide passage for electrolyte ion at whole composite, promote the quick transmission of ion.Ensure that the power characteristic that this material is good.
(4) graphite flake and oxide nano particles interact, it is to avoid again the piling up and the reunion of oxide nano particles of graphite flake.Co3O4Particle is little, and during charge and discharge lithium, the change in size of whole particle is little.And the space between oxide nano particles can be that oxide Volume Changes during charge and discharge lithium provides space, thus improve the cyclical stability of material.
(5) oxide prepared by is distributed in upper and lower two surfaces of graphite flake, and between particle, space is the least, and oxide particle density is the highest, is conducive to improving the storage lithium performance of material.
(6) the Multi-layer graphite Rotating fields of graphite flake still keeps the original structure of graphite, therefore, it is possible to store certain lithium ion.
(7) the composite 50mA/g of present invention charge and discharge lithium capacity first reaches 1400mA h/g, stablizes capacity up to 1030mA h/g；100mA/g charge and discharge lithium capacity is 900mA h/g；Efficiency for charge-discharge is high.
(8) this method preparation process is simple, is suitable for volume production.
Accompanying drawing explanation
Fig. 1 is the flow chart of steps of the graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium preparation method of the embodiment of the present invention；
Fig. 2 is the 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 the 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 the graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium XRD spectrum of the embodiment of the present invention；
Fig. 5 is the charging and discharging curve figure of the test battery of the composite making of the embodiment of the present invention；
Fig. 6 be the embodiment of the present invention composite make test battery fill lithium cycle performance collection of illustrative plates.
Detailed description of the invention
In order to make the purpose 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 contains any replacement made in the spirit and scope of the present invention, amendment, equivalent method and scheme being defined by the claims.Further, in order to make the public that the present invention to be had a better understanding, in below the details of the present invention being described, detailed describe some specific detail sections.The description not having these detail sections for a person skilled in the art can also understand the present invention completely.
See Fig. 1, show 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, weighs expanded graphite and dimethylformamide DMF by 0.5-5g/L proportioning, expanded graphite is put into DMF and carries out ultrasonic 1-2 hour, obtain graphite flake solution；
S20, adds deionized water, and deionized water is 1:1-1:9 with the ratio of DMF, stirs；
S30, weighs four hydration cobalt acetates, and wherein cobalt is II valency, is called for short four hydrations cobalt acetate (II), and four hydrations cobalt acetate (II) are 10-60g/L relative to the concentration of solvent DMF, and four hydration cobalt acetates are dissolved in solvent, and stirring and dissolving is uniform；
S40, puts into hydro-thermal tank by above solution, and wherein the filling volume fraction of hydro-thermal tank is 1/5-1/2, i.e. reaction solution volume accounts for the 20%-50% of hydro-thermal tank cumulative volume, be warmed up to 100-150 DEG C with the programming rate of 1 DEG C/minute-10 DEG C/minute, temperature retention time 1.5h-10h, after with stove cool down；
S50, after being cooled to room temperature, pours out solution, is cleaned by black deposit with centrifuge, cleans and uses alcoholic solution, and the number of times of cleaning is at 3-5 time；
S60, is baked to graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium sample drying at 40-80 DEG C by the black deposit cleaned.
By procedure declaration made above, the method that the present invention uses prepares graphite flake/self-assembled nanometer cobaltosic oxide composite material, preparation process simple and controlled and repeatable well, be suitable for volume production.
Simultaneously, corresponding with method, further embodiment of this invention provides the graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium prepared by said method, see Fig. 2 to Fig. 4, it is respectively the scanning electron microscope (SEM) photograph of the graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium of the embodiment of the present invention, transmission electron microscope picture and XRD.See Fig. 2 and 3 visible, the Co on graphite flake surface3O4Nano particle is the isometric particle of advantages of good crystallization, and size is uniform, and the length of side is about 4nm, and density is more than 2 × 1013Individual/cm2, space each other, at 1-10nm, is evenly distributed on two surfaces of graphite flake.The method preparing graphite flake is simple, sees Fig. 4, can see (002) diffraction maximum of graphite linings in X-ray diffraction.In the embodiment of the present invention, owing to the most specially adding oxidant, the degree of oxidation of graphite flake is low, thus in processing procedure below, need not use reducing agents such as adding hydrazine to carry out reduction treatment, and can guarantee that the structural intergrity that graphite flake is initial, thus ensure optimal electrical conductance.Graphite flake in composite has two dimensional surface shape structure, has bigger specific surface area, the quick transmission of good electric conductivity and thermal conduction characteristic, beneficially electronics.Oxide nano particles directly contacts with graphite flake, it is ensured that electronics can promptly transmit between graphite flake and oxide.There is between oxide certain space, graphite flake/Co3O4It is compounded in when preparing electrode, space can be produced each other, provide passage for electrolyte ion at whole composite, promote the quick transmission of ion, it is ensured that the power characteristic that this material is good.Graphite flake and oxide nano particles interact, it is to avoid again the piling up and the reunion of oxide nano particles of graphite flake.Co3O4Particle is little, and during Volume Changes, the change in size of whole particle is little.Space between oxide can be oxide Volume variation during charge and discharge lithium, thus improves the cyclical stability of material.Prepared oxide is distributed in upper and lower two surfaces of graphite flake, and between particle, space is the least, and oxide particle density is the highest, is conducive to improving the storage lithium performance of material.
Architectural characteristic by above graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium, further embodiment of this invention provides a kind of lithium battery, including negative pole, wherein the material of negative pole is graphite flake as above/self-assembled nanometer cobaltosic oxide ion cathode material lithium.Using general method to test after making the test battery of composite, see first three the charging and discharging curve figure of the lithium battery that Fig. 5 is the embodiment of the present invention, charge cutoff voltage is 3V, and discharge cut-off voltage is about 0.05V, it can be seen that significantly Co in figure3O4Charge-discharge characteristic.Fig. 6 be the lithium battery of the embodiment of the present invention fill lithium cycle performance collection of illustrative plates, as can be seen from the figure the composite 50mA/g of embodiment of the present invention charge and discharge lithium capacity first reaches 1400mA h/g, stablizes capacity up to 1030mA h/g；100mA/g charge and discharge lithium capacity is 900mA h/g, and charge and discharge efficiency is high.
Below by the preparation process by alum ink sheet for multiple specific embodiments/self-assembled nanometer cobaltosic oxide ion cathode material lithium.Hydro-thermal tank used 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 by ratio adjustment and account for the 20%-50% of hydro-thermal tank cumulative volume.
Embodiment 1
Weigh expanded graphite 4mg and DMF8ml, expanded graphite is put into DMF and carries out ultrasonic 1 hour, obtain graphite flake solution.Weigh deionized water 0.9ml, add graphite flake solution, stir.Weighing four hydration cobalt acetate (II) 80mg, four hydrations cobalt acetate (II) are dissolved in mixed solvent, stirring is to being completely dissolved.Above solution is put into the hydro-thermal tank that volume is 20ml, and reaction solution accounts for the cumulative volume of hydro-thermal tank and is about 44.5%, meets the filling volume fraction requirement of hydro-thermal tank, is warmed up to 120 DEG C with the programming rate of 1 DEG C/minute, temperature retention time 1.5h, after with stove cool down.Being carried out by microparticle with centrifuge, clean and use alcoholic solution, the number of times of cleaning is at 3 times.At 40 DEG C, it is baked to sample drying, i.e. obtains graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium sample.
Embodiment 2
Weigh expanded graphite 40mg and DMF8ml, expanded graphite is put into DMF and carries out ultrasonic 2 hours, obtain graphite flake solution.Weigh deionized water 8ml, add graphite flake solution, stir.Weighing four hydration cobalt acetate (II) 480mg, four hydrations cobalt acetate (II) are dissolved in mixed solvent, stirring is to being completely dissolved.Above solution is put into the hydro-thermal tank of 50ml, and reaction solution accounts for the cumulative volume of hydro-thermal tank and is about 32%, meets the filling volume fraction requirement of hydro-thermal tank, is warmed up to 150 DEG C with the programming rate of 5 DEG C/minute, temperature retention time 5h, after with stove cool down.Being carried out by microparticle with centrifuge, clean and use alcoholic solution, the number of times of cleaning is at 4 times.At 80 DEG C, it is baked to sample drying, i.e. obtains graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium sample.
Embodiment 3
Weigh expanded graphite 30mg and DMF16ml, expanded graphite is put into DMF and carries out ultrasonic 3 hours, obtain graphite flake solution.Weigh deionized water 8ml, add graphite flake solution, stir.Weighing four hydration cobalt acetate (II) 400mg, cobalt acetate (II) is dissolved in mixed solvent, stirring is to being completely dissolved.Above solution is put into the hydro-thermal tank of 100ml, and reaction solution accounts for the cumulative volume of hydro-thermal tank and is about 24%, meets the filling volume fraction requirement of hydro-thermal tank, is warmed up to 130 DEG C with the programming rate of 10 DEG C/minute, temperature retention time 10h, after with stove cool down.Being carried out by microparticle with centrifuge, clean and use alcoholic solution, the number of times of cleaning is at 5 times.At 60 DEG C, it is baked to sample drying, i.e. obtains graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium sample.
Embodiment 4
Weigh expanded graphite 120mg and DMF48ml, expanded graphite is put into DMF and carries out ultrasonic 4 hours, obtain graphite flake solution.Weigh deionized water 36ml, add graphite flake solution, stir.Weighing cobalt acetate (II) 300mg, four hydrations cobalt acetate (II) are dissolved in mixed solvent, stirring is to being completely dissolved.Above solution is put into the hydro-thermal tank of 250ml, and reaction solution accounts for the cumulative volume of hydro-thermal tank and is about 33.6%, meets the filling volume fraction requirement of hydro-thermal tank, is warmed up to 140 DEG C with the programming rate of 5 DEG C/minute, temperature retention time 4h, after with stove cool down.Being carried out by microparticle with centrifuge, clean and use alcoholic solution, the number of times of cleaning is at 5 times.At 40 DEG C, it is baked to sample drying, i.e. obtains graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium sample.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, should be included within the scope of the present invention.
Claims (3)
1. a preparation method for graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium, it is special
Levy and be, comprise the following steps:
S10, weighs expanded graphite and dimethylformamide DMF by 0.5-5g/L proportioning, expanded graphite is put
Enter DMF to carry out ultrasonic 1-4 hour, obtain graphite flake solution；
S20, adds deionized water, and deionized water is 1:1-1:9 with the ratio of DMF, stirs；
S30, weighs four hydration cobalt acetates, and wherein cobalt is II valency, and four hydration cobalt acetates are relative to solvent DMF
Concentration be 10-60g/L, by four hydration cobalt acetates be dissolved in solvent, stirring and dissolving is uniform；
S40, puts into hydro-thermal tank by above solution, and wherein the filling volume fraction of hydro-thermal tank is 1/5-1/2, with 1 DEG C
/ the programming rate of points-10 DEG C/minute is warmed up to 100-150 DEG C, temperature retention time 1.5h-10h, after cool down with stove；
S50, after being cooled to room temperature, pours out solution, is cleaned by black deposit with centrifuge, and cleaning is adopted
With alcoholic solution, the number of times of cleaning is at 3-5 time；
S60, is baked to graphite flake/self-assembled nanometer four oxidation at 40-80 DEG C by the black deposit cleaned
Three cobalt ion cathode material lithium sample dryings.
2. graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium, it is characterised in that institute
State graphite flake/self-assembled nanometer cobaltosic oxide composite material ion cathode material lithium by as claimed in claim 1
Method prepare, the carbon-coating number of the graphite flake in composite be less than 100 layers, graphite flake surface
Co3O4Nano particle is the isometric particle of advantages of good crystallization, and size is uniform, and density is more than 2 × 1013Individual/cm2, limit
Long about about 4nm, space each other, at 1-10nm, is evenly distributed on two surfaces of graphite flake.
3. a lithium battery, including negative pole, it is characterised in that the material of described negative pole is such as claim 2
Described graphite flake/self-assembled nanometer cobaltosic oxide ion cathode material lithium.
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| CN102941042A (en) * | 2012-10-25 | 2013-02-27 | 北京理工大学 | Graphene/metal oxide hybrid aerogel, preparation method and applications thereof |
| CN103400967A (en) * | 2013-07-18 | 2013-11-20 | 上海交通大学 | Three-dimensional porous cobalt-based/graphene composite material and preparation method thereof |
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| WO2011122218A1 (en) * | 2010-03-29 | 2011-10-06 | 日本電気硝子株式会社 | Sealing material and paste material using same |
| CN102941042A (en) * | 2012-10-25 | 2013-02-27 | 北京理工大学 | Graphene/metal oxide hybrid aerogel, preparation method and applications thereof |
| CN103400967A (en) * | 2013-07-18 | 2013-11-20 | 上海交通大学 | Three-dimensional porous cobalt-based/graphene composite material and preparation method thereof |
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