CN103915629A - Preparation method of cladding material of lithium ion battery - Google Patents

Preparation method of cladding material of lithium ion battery Download PDF

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Publication number
CN103915629A
CN103915629A CN201410113231.3A CN201410113231A CN103915629A CN 103915629 A CN103915629 A CN 103915629A CN 201410113231 A CN201410113231 A CN 201410113231A CN 103915629 A CN103915629 A CN 103915629A
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China
Prior art keywords
lithium ion
ion battery
preparation
gel
emulsion
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CN201410113231.3A
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Inventor
涂健
胡海波
刘凯
刘志航
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Hunan Lifang New Energy Science and Technology Co Ltd
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Hunan Lifang New Energy Science and Technology Co Ltd
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Priority to CN201410113231.3A priority Critical patent/CN103915629A/en
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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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of a lithium ion battery, and particularly relates to a preparation method of a cladding material of a lithium ion battery. The preparation method comprises the following steps: stirring a core layer material in a stirring tank; making a cladding layer material into a solution, sol, gel or an emulsion; placing the cladding layer material into an atomizing machine, spraying the cladding layer material onto the surface of the core layer material, and continuously stirring the material; and drying, calcining and crushing the material to obtain the cladding material of the lithium ion battery. Compared with a solid-solid mixing way of the prior art, the mixing way provided by the invention ensures more uniformity in cladding; compared with a liquid-liquid mixing way and a conventional solid-liquid mixing way, the mixing way provided by the invention has the advantages that only the solvent in the sprayed solution is consumed, so that the application amount of the solvent is greatly reduced, and the energy consumption of the subsequent drying process can be reduced.

Description

The preparation method of clad material for a kind of lithium ion battery
Technical field
The invention belongs to technical field of lithium ion, relate in particular to the preparation method of a kind of lithium ion battery clad material.
Background technology
Lithium ion battery generally has sandwich layer and coating layer with clad material, and the effect of coating layer is mainly the surface of stablizing sandwich layer, prevents that the surface texture of sandwich layer is destroyed, as at LiNi 0.5mn 1.5o 4surface clad oxide just can improve its structural stability (technical scheme as disclosed in CN102709525A) under high voltage, coating layer is set on graphite composite powder surface also can improves its structural stability (technical scheme as disclosed in the Chinese patent application of CN102255077A); Coating layer can also play and improve the effect of conductivity, as at LiFePO 4coated with carbon bed just can improve its electric conductivity.
But lithium ion battery of the prior art generally comprises solid-solid phase mixing, liquid-liquid phase mixing and solid-liquid phase by the preparation method of clad material and mixes three kinds of modes.
Wherein, Gu-solid phase mixing is that nanometer materials are all pulverized or be prepared into core material and coating layer material, then solid phase mixing, compressing tablet is to increase the contact force between core material and coating layer material again, then carry out sintering, pulverizing, to obtain clad material (technical scheme as disclosed in the Chinese patent application of CN101339987A).The existing problem of the method is that core material is difficult to mix with coating layer material, and because the contact force between solid phase is less, the adhesion defective tightness after sintering between coating layer and sandwich layer, causes coated inhomogeneous, the consistency of material is poor, and its advantage is that power consumption is relatively less.
It is that core material and coating layer material are made to solution or gel that liquid-liquid phase is mixed, and then mixes, then obtains clad material, the disclosed technical scheme of Chinese patent application as 201310069290.0 after being dried, calcining, pulverizing.The existing problem of the method is to consume a large amount of solvents, in dry run, can consume a large amount of energy, some material is limited by physicochemical properties, cannot be prepared into the aqueous solution, need to use a large amount of organic solvents, also may cause the pollution (as coated fluoride time) of environment.
It is the precursor solution that core material is placed in to coating layer material that solid-liquid phase mixes, then add precipitation reagent, make coating layer material be coated on core material surface, after dry, sintering, pulverizing, obtain clad material, technical scheme as disclosed in CN102709525A.The shortcoming of this method is that it need to consume a large amount of solvents, in dry run, can consume a large amount of energy.
Summary of the invention
The object of the invention is to: for the deficiencies in the prior art, and provide a kind of lithium ion battery to use the preparation method of clad material, the method can make core material evenly mix with coating layer material, and closely, energy consumption is less simultaneously in contact; In the time using the coated solution of non-aqueous solution (as the organic solvent of coated fluoride use), its quantity of solvent is relatively less, and the environmental pollution causing is also less.
In order to reach above-mentioned requirements, the present invention adopts following technical scheme:
A preparation method for clad material for lithium ion battery, comprises the following steps:
Step 1, is placed in agitator tank by core material and stirs;
Step 2, makes solution, colloidal sol, gel or emulsion by coating layer material;
Step 3, solution, colloidal sol, gel or emulsion that step 2 is made are placed in spraying machine, the surface of core material will be sprayed to after this solution, colloidal sol, gel or emulsion atomization, continue to stir, make the surface of core material by solvent complete wetting, and make the surface uniform absorption of coating layer material at core material;
Step 4, obtains lithium ion battery clad material after being dried, calcining, pulverizing.
Wherein, solution is (as the lithium hydroxide) for the material of those solubilities, when use, coating layer material is added in solvent and is dissolved.
Wherein, colloidal sol can adopt these conventional method preparations of dispersoid and coagel, and wherein, dispersion method comprises again polishing, peptisation, ultrasonic wave dispersion method and arc process etc., and coacervation comprises again chemical coagulation method and physical condensation method.The colloidal sol of making can also adopt the method such as dialysis and ultrafiltration method to purify, to reduce the impurity wherein comprising.Certainly, also can directly adopt colloidal sol, gel and the emulsion of commercially available coating layer material.The example of colloidal sol is as Ludox
Gel can obtain by the gelation of colloidal sol, certainly, also can adopt the gel of commercially available coating layer material.The example of gel is as gel aluminum hydroxide.
Emulsion can, by excessive coating layer material is added in solvent and formed, can certainly adopt commercially available emulsion.The example of emulsion is as lime white.
Improve by the preparation method's of clad material one as lithium ion battery of the present invention, the speed of the stirring described in step 1 is 100-1000r/min.Mixing speed is too large, is unfavorable for surperficial infiltration and the absorption at core material of solution, colloidal sol, gel or emulsion, and then causes coated inhomogeneous; Mixing speed is too little, can cause again too much solution, colloidal sol, gel or emulsion to be deposited in subregion, other regions solution, colloidal sol, gel or emulsion are less, the surface of the core material in the less region of solution, colloidal sol, gel or emulsion can not be infiltrated by solvent completely, cause coated inhomogeneous, the waste of solvent and coating layer material can be caused again in the more region of solution, colloidal sol, gel or emulsion, but also can cause dry energy consumption of later stage to strengthen.So the selection of mixing speed, generally can be relevant with core material diameter, liquid-drop diameter size and the drop spray rate of clad material.
Improve by the preparation method's of clad material one as lithium ion battery of the present invention, solvent is water described in step 2, and its cost is lower, and boiling point is lower, easily dry.In addition its less pollution to environment, relatively environmental protection.
Improve by the preparation method's of clad material one as lithium ion battery of the present invention, in step 3, the spray rate of solution, colloidal sol, gel or emulsion is 0.01-0.3kg/min, spray rate is too fast, can make the too many solution of core material adsorption, colloidal sol, gel or emulsion, even be condensed into drop and low, cause the waste of solvent and coating layer material, and can strengthen dry energy consumption of later stage; Spray rate is too slow, and core material again can not be completely by wet with solvent, causes coated inhomogeneous on core material surface of coating layer material.The spray rate of solution, colloidal sol, gel or emulsion should adapt with the mixing speed of core material, and the surface of core material can be infiltrated by solvent completely, but do not form again can be mobile drop.Pressure when sprinkling is 0.2-0.5MPa.
Improve by the preparation method's of clad material one as lithium ion battery of the present invention, the speed of the stirring described in step 3 is 100-1000r/min.The stirring of step 3 is in order further to improve coated uniformity.
Improve by the preparation method's of clad material one as lithium ion battery of the present invention, the diameter of the drop of solution, colloidal sol, gel or the emulsion spraying in step 3 is 0.1-3 μ m.The diameter of the drop spraying is too large, is difficult for spraying evenly; The diameter of the drop spraying is too little, and solution, colloidal sol, gel or emulsion are difficult for again passing through shower nozzle.
Improve by the preparation method's of clad material one as lithium ion battery of the present invention, in step 4, dry temperature is 90-120 DEG C, and the dry lasting time is 10-60min, and dry is in order to remove desolventizing; The temperature of calcining is 300-500 DEG C, and calcining the lasting time is 1-3h, and calcining is in order to improve the adhesion between core material and coating layer material.
Improve by the preparation method's of clad material one as lithium ion battery of the present invention, described core material is positive electrode active materials or negative active core-shell material, and described positive electrode active materials is LiCoO 2, LiNiO 2, LiMn 2o 4, LiFePO 4or LiNi xco ymn zo 2, wherein, x > 0, y > 0, z > 0, x+y+z=1, described negative active core-shell material is graphite, silicon or silicon alloy.It should be noted that, just provide positive electrode active materials and negative active core-shell material that machine is conventional here, but be not that method of the present invention can only be used for these materials to be coated.As long as in lithium ion battery and need coated solid particulate materials, all can use method of the present invention to be coated.Therefore, the present invention has very wide range of application.
Improve by the preparation method's of clad material one as lithium ion battery of the present invention, described coating layer material is metal oxide, metal fluoride, metal phosphate or carbon.Here only provide several conventional coating layer materials, but be not to use these several materials as coating layer material, as long as being coated on the solid particle outside solid particle, all can be used as coating layer material.
Improve by the preparation method's of clad material one as lithium ion battery of the present invention, described metal oxide is Al 2o 3, MgO, Fe 2o 3, SiO 2or TiO 2, described metal phosphate is calcium phosphate, manganese phosphate or ferric phosphate.
With respect to prior art, the present invention at least tool has the following advantages:
First, because coating layer material is solution, colloidal sol, gel or emulsion state, and this solution, colloidal sol, gel and emulsion are the surfaces that is adsorbed on core material by the mode of spraying, so can mix with solid-state core material, and coating layer material can closely bind with core material after calcining, reach liquid-liquid phase and mix close mixed effect;
The second, compared with solid-solid phase mixing mode, of the present invention coated more even; Mix with conventional solid-liquid phase and mix and compare with liquid-liquid phase, the quantity of solvent using in the solution that the quantity of solvent that the present invention consumes is just sprayed, therefore can greatly reduce the use amount of solvent, can reduce the energy consumption in follow-up dry run, and the temperature that follow-up calcining only need reduce just can realize combining closely of coating layer material and core material, thereby further reduce energy consumption, reduce production costs; Even in the time using the solution, colloidal sol, gel of coating layer material of non-aqueous solution or emulsion (organic solvent using as coated fluoride), its quantity of solvent also greatly reduces, therefore pollution on the environment is also less;
The 3rd, the present invention is directly sprayed at coating layer material the surface of core material, therefore can not introduce impurity, thereby not need to arrange removal step, has simplified operation sequence, has reduced energy consumption;
The 4th, the present invention can also reduce the side reaction that in dry run, material may occur with solvent, and reduces in dry run the reunion of nanometer materials in solvent.
Embodiment
Below in conjunction with specific embodiment, content of the present invention is further illustrated, but invention protection range of the present invention is not limited only to the described content of embodiment.
Embodiment 1
The present embodiment provides the preparation method of a kind of lithium ion battery clad material, is specially a kind of at LiCoO 2the coated Al in surface 2o 3method, comprise the following steps:
Step 1, by LiCoO 2be placed in agitator tank and stir, mixing speed is 400r/min;
Step 2, splashes into the aluminum potassium sulfate aqueous solution in aqueous sodium carbonate, generates after aluminum hydroxide precipitation, by dialysis, aluminum hydroxide precipitation is carried out to purified treatment, then dry at 15 DEG C, generates gel aluminum hydroxide after gelation;
Step 3, the gel aluminum hydroxide that step 2 is made is placed in spraying machine, will after gel atomization, be sprayed to LiCoO 2surface, spray rate is 0.2kg/min, the diameter of the drop of the gel spraying be 1 μ m continue stir, mixing speed is 400r/min, makes LiCoO 2the water complete wetting that comprised in gel aluminum hydroxide of surface, and make aluminium hydroxide at LiCoO 2surface uniform absorption;
Step 4 is dried 30min, then at 400 DEG C, calcines 2h, makes aluminium hydroxide be converted into aluminium oxide at 105 DEG C, makes the adhesion between aluminium oxide and cobalt acid lithium increase simultaneously, obtains LiCoO after pulverizing 2surface is coated with Al 2o 3anode material for lithium-ion batteries.
Embodiment 2
The present embodiment provides the preparation method of a kind of lithium ion battery clad material, is specially a kind of at LiNiO 2the method of the coated MgO in surface, comprises the following steps:
Step 1, by LiNiO 2be placed in agitator tank and stir, mixing speed is 500r/min;
Step 2, reacts magnesium chloride solution the synthetic magnesium hydroxide hydrosol with ammoniacal liquor; Again the magnesium hydroxide hydrosol is placed in to absolute ethyl alcohol, at room temperature stirs 2h and get final product to obtain magnesium hydroxide gel;
Step 3, the magnesium hydroxide gel that step 2 is made is placed in spraying machine, will after the atomization of magnesium hydroxide gel, be sprayed to LiNiO 2surface, spray rate is 0.1kg/min, the diameter of the drop of the gel spraying be 2 μ m continue stir, mixing speed is 500r/min, makes LiNiO 2the surface water and the ethanol complete wetting that in magnesium hydroxide gel, are comprised, and make magnesium hydroxide at LiNiO 2surface uniform absorption;
Step 4 is dried 40min, then at 300 DEG C, calcines 3h, makes magnesium hydroxide be converted into magnesium oxide at 110 DEG C, makes the adhesion between magnesium oxide and lithium nickelate increase simultaneously, obtains LiNiO after pulverizing 2surface is coated with the anode material for lithium-ion batteries of MgO.
Embodiment 3
The present embodiment provides the preparation method of a kind of lithium ion battery clad material, is specially a kind of at LiMn 2o 4the coated TiO in surface 2method, comprise the following steps:
Step 1, by LiMn 2o 4be placed in agitator tank and stir, mixing speed is 600r/min;
Step 2, purchases commercially available Nanometer Titanium Dioxide Hydrosol;
Step 3, is placed in spraying machine by the Nanometer Titanium Dioxide Hydrosol of step 2, will after colloidal sol atomization, be sprayed to LiMn 2o 4surface, spray rate is 0.05kg/min, the diameter of the drop of the solution spraying be 3 μ m continue stir, mixing speed is 600r/min, makes LiMn 2o 4the water complete wetting that comprised in Nanometer Titanium Dioxide Hydrosol of surface, and make titanium dioxide at LiMn 2o 4surface uniform absorption;
Step 4 is dried 10min, then at 500 DEG C, calcines 1h at 120 DEG C, and the adhesion between titanium dioxide and LiMn2O4 is increased, and obtains LiMn after pulverizing 2o 4surface is coated with TiO 2anode material for lithium-ion batteries.
Embodiment 4
The present embodiment provides the preparation method of a kind of lithium ion battery clad material, is specially a kind of method at Graphite Coating silicon, comprises the following steps:
Step 1, is placed in agitator tank by graphite and stirs, and mixing speed is 700r/min;
Step 2, by nano level SiO 2be dispersed in water, form SiO 2emulsion;
Step 3, the SiO that step 2 is made 2emulsion be placed in spraying machine, by SiO 2emulsion atomization after be sprayed to the surface of graphite, spray rate is 0.3kg/min, the diameter of the drop of the emulsion spraying is that 0.5 μ m continues to stir, mixing speed is 700r/min, makes the surface of graphite by SiO 2emulsion in the water complete wetting that comprises, and make the surface uniform absorption of silicon dioxide at graphite;
Step 4 is dried 20min, then at 300 DEG C, calcines 3h, the adhesion between silicon dioxide and graphite is increased at 115 DEG C, and after pulverizing, obtaining Graphite Coating has SiO 2lithium ion battery negative material.
Embodiment 5
The present embodiment provides the preparation method of a kind of lithium ion battery clad material, is specially a kind of at LiFeO 4the method of coated with carbon, comprises the following steps:
Step 1, by LiFeO 4be placed in agitator tank and stir, mixing speed is 300r/min;
Step 2, glucose is soluble in water, obtain the saturated solution of glucose;
Step 3, the saturated solution of the glucose that step 2 is made is placed in spraying machine, will after solution atomization, be sprayed to LiFeO 4surface, spray rate is 0.3kg/min, the diameter of the drop of the solution spraying be 1.5 μ m continue stir, mixing speed is 800r/min, makes LiFeO 4the water complete wetting that comprised in glucose solution of surface, and make glucose at LiFeO 4surface uniform absorption;
Step 4, at 95 DEG C, being dried 60min, then at 350 DEG C, calcining 2.5h, make conversion of glucose is carbon, makes the adhesion between carbon and LiFePO4 increase simultaneously, obtains LiFeO after pulverizing 4surface is coated with the anode material for lithium-ion batteries of carbon.
Embodiment 6
The present embodiment provides the preparation method of a kind of lithium ion battery clad material, is specially a kind of at LiNi 1/3co 1/3mn 1/3o 2the method of the coated calcium phosphate in surface, comprises the following steps:
Step 1, by LiNi 1/3co 1/3mn 1/3o 2be placed in agitator tank and stir, mixing speed is 100r/min;
Step 2, by commercially available Calcium phosphate gel be added to the water dilution ten times after, obtain Calcium phosphate gel;
Step 3, the Calcium phosphate gel that step 2 is made is placed in spraying machine, will after Calcium phosphate gel atomization, be sprayed to LiNi 1/3co 1/3mn 1/3o 2surface, spray rate is 0.25kg/min, the diameter of the drop of the colloidal sol spraying be 0.5 μ m continue stir, mixing speed is 200r/min, makes LiNi 1/3co 1/3mn 1/3o 2the water complete wetting that comprised in Calcium phosphate gel of surface, and make calcium phosphate at LiNi 1/3co 1/3mn 1/3o 2surface uniform absorption;
Step 4 is dried 10min, then at 500 DEG C, calcines 1h, makes calcium phosphate and LiNi at 120 DEG C 1/3co 1/3mn 1/3o 2between adhesion increase, after pulverizing, obtain LiNi 1/3co 1/3mn 1/3o 2surface is coated with the anode material for lithium-ion batteries of calcium phosphate.
Embodiment 7
The present embodiment provides the preparation method of a kind of lithium ion battery clad material, is specially a kind of at LiNi 0.5co 0.2mn 0.3o 2the coated Fe in surface 2o 3method, comprise the following steps:
Step 1, by LiNi 0.5co 0.2mn 0.3o 2be placed in agitator tank and stir, mixing speed is 300r/min;
Step 2, gets fresh Fe (OH) 3precipitation, adds FeCl 3solution, forms Fe (OH) 3colloidal sol (peptisation), then purify this colloidal sol through dialysis;
Step 3, the Fe that step 2 is made (OH) 3colloidal sol is placed in spraying machine, by Fe (OH) 3after colloidal sol atomization, be sprayed to LiNi 0.5co 0.2mn 0.3o 2surface, spray rate is 0.18kg/min, the diameter of the drop of the colloidal sol spraying be 0.2 μ m continue stir, mixing speed is 250r/min, makes LiNi 0.5co 0.2mn 0.3o 2surface by Fe (OH) 3the water complete wetting comprising in colloidal sol, and make Fe (OH) 3at LiMn 2o 4surface uniform absorption;
Step 4 is dried 60min, then at 450 DEG C, calcines 1.5h, makes Fe (OH) at 90 DEG C 3become Fe 2o 3, make Fe simultaneously 2o 3with LiNi 0.5co 0.2mn 0.3o 2between adhesion increase, after pulverizing, obtain LiNi 0.5co 0.2mn 0.3o 2surface is coated with Fe 2o 3anode material for lithium-ion batteries.
Wherein, Fe (OH) in step 2 3the preparation of colloidal sol can also adopt hydro thermal method preparation, is added to the water by FeCl3, makes Fe (OH) after hydro-thermal reaction 3colloidal sol.
It should be noted that, the announcement of book and elaboration according to the above description, those skilled in the art in the invention can also change and revise above-mentioned execution mode.Therefore, the present invention is not limited to embodiment disclosed and described above, also should be in the protection range of claim of the present invention to equivalent modifications more of the present invention and change.In addition,, although used some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.

Claims (10)

1. a preparation method for clad material for lithium ion battery, is characterized in that, comprises the following steps:
Step 1, is placed in agitator tank by core material and stirs;
Step 2, makes solution, colloidal sol, gel or emulsion by coating layer material;
Step 3, solution, colloidal sol, gel or emulsion that step 2 is made are placed in spraying machine, the surface of core material will be sprayed to after this solution, colloidal sol, gel or emulsion atomization, continue to stir, make the surface of core material by the solvent complete wetting being comprised in solution, colloidal sol, gel or emulsion, and make the surface uniform absorption of coating layer material at core material;
Step 4, obtains lithium ion battery clad material after being dried, calcining, pulverizing.
2. the preparation method of clad material for lithium ion battery according to claim 1, is characterized in that: the speed of the stirring described in step 1 is 100-1000r/min.
3. the preparation method of clad material for lithium ion battery according to claim 1, is characterized in that: described in step 2, solvent is water, ethanol.
4. the preparation method of clad material for lithium ion battery according to claim 2, is characterized in that: in step 3, the spray rate of solution, colloidal sol, gel or emulsion is 0.01-0.3kg/min.
5. the preparation method of clad material for lithium ion battery according to claim 4, is characterized in that: the speed of the stirring described in step 3 is 100-1000r/min.
6. the preparation method of clad material for lithium ion battery according to claim 1, is characterized in that: the diameter of the drop of solution, colloidal sol, gel or the emulsion spraying in step 3 is 0.1-3 μ m.
7. the preparation method of clad material for lithium ion battery according to claim 1, is characterized in that: in step 4, dry temperature is 90-120 DEG C, and the dry lasting time is 10-60min; The temperature of calcining is 300-500 DEG C, and calcining the lasting time is 1-3h.
8. the preparation method of clad material for lithium ion battery according to claim 1, is characterized in that: described core material is positive electrode active materials or negative active core-shell material, and described positive electrode active materials is LiCoO 2, LiNiO 2, LiMn 2o 4, LiFePO 4or LiNi xco ymn zo 2, wherein, x > 0, y > 0, z > 0, x+y+z=1, described negative active core-shell material is graphite, silicon or silicon alloy.
9. the preparation method of clad material for lithium ion battery according to claim 1, is characterized in that: described coating layer material is metal oxide, metal phosphate or carbon.
10. the preparation method of clad material for lithium ion battery according to claim 9, is characterized in that: described metal oxide is Al 2o 3, MgO, Fe 2o 3, SiO 2or TiO 2, described metal phosphate is calcium phosphate, manganese phosphate or ferric phosphate.
CN201410113231.3A 2014-03-25 2014-03-25 Preparation method of cladding material of lithium ion battery Pending CN103915629A (en)

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