CN101916846A - Lithium ion battery cathode composite material and preparation method thereof - Google Patents
Lithium ion battery cathode composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a lithium ion battery cathode composite material and a preparation method thereof. The invention aims to lower the cost of the cathode material of the lithium ion battery and enhance the conductivity thereof. Graphite is used as the substrate of the material, and an organic polymer and/or high molecular conducting polymer are/is coated outside the substrate. The preparation method comprises the following steps: purifying or graphitizing natural crystalline flake graphite, microcrystal graphite, crystallized veined graphite or needle coke and petroleum coke to obtain the graphite substrate, mixing the graphite substrate and the organic high molecular polymer and/or high molecular conducting polymer liquid phase, spray-drying, and carrying out oven-drying to obtain the lithium ion battery cathode composite material. Compared with the prior art, the invention has the advantages of simplified technique, firmer and more compact coating layer, and stable circulation of the lithium ion battery; the powder resistivity is below 7*10<-6> omega m; and when the material is used for manufacturing the pole piece of the battery, the use amounts of adhesive and conducting agent are reduced in the pole piece manufacturing process, thereby lowering the battery cost.
Description
Technical field
The present invention relates to a kind of carbon negative electrode material of lithium ion cell and preparation method thereof, particularly a kind of compound lithium ion battery cathode material and its preparation method.
Background technology
The method of prior art for preparing lithium ion battery negative material, it is high-purity spherical graphite with the profile subglobular, carbon content is up to making raw material more than 99.9%, adopt complicated preparation technology, comprise processing graphite such as heterogeneous method for coating, doping method, the complex process of these methods makes the cost of the negative material of lithium ion battery increase inevitably.Adopt the negative material of lithium ion battery of the method preparation of prior art simultaneously, compacted density is not high, the conductivity of negative material under high density compacting condition reduces, and has influenced the cycle life and the stability of lithium ion battery, has also influenced the process of lithium ion battery to the high-energy-density development.
Summary of the invention
The purpose of this invention is to provide a kind of composite cathode material of lithium ion battery and preparation method thereof, the technical problem that solve is to reduce the cost of the negative material of lithium ion battery, improves its conductivity, improves the life-span and the cyclical stability of lithium ion battery.
The present invention is by the following technical solutions: a kind of composite cathode material of lithium ion battery, described composite cathode material of lithium ion battery is that the graphite of 1.0～4.5 class sphere, bulk and/or sheet is matrix by spherical, axial ratio, matrix is coated with organic polymer and/or conductive polymer polymer, coating thickness between 1～10nm, the mean particle size D of described composite material
50Be 3.0～50.0 μ m, specific area is 0.50～6.5m
2/ g, powder body compacted density are 1.90～2.15g/cm
3, magnetisable material Fe, Ni, Cr and Zn are less than 0.1ppm; Described organic high molecular polymer is more than one in polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly(ethylene oxide), Kynoar, acrylic resin and the polyacrylonitrile; Described conductive polymer polymer is a polythiophene, and polyaniline, polyacetylene, polyaniline, polypyrrole, coalescence benzene poly-are bitten in fen, polyaniline, polyhenylene, polyphenylene ethylene and the poly-two alkynes more than one.
A kind of preparation method of composite cathode material of lithium ion battery may further comprise the steps: one, with phosphorus content 85～99.8%, mean particle size D
50Sphere, the axial ratio that is 3.0～50 μ m is natural flake graphite, micro crystal graphite, crystallization veiny graphite or needle coke, the petroleum coke raw material of 1.0～4.5 class sphere, bulk and/or sheet, through purification processes or graphitization processing, obtain the graphite matrix of phosphorus content more than 99.8%; Two, graphite matrix is mixed with graphite matrix 0.1～10wt% organic high molecular polymer and/or conductive polymer polymer liquid phase, the speed of 2000～8000r/min is mixed stirring 10～120min, solvent is water, absolute ethyl alcohol, glycerol, isopropyl alcohol, acetone, n-formyl sarcolysine base pyrrolidones, oxolane or dimethylacetylamide, its quality is 0.8～2.5 times of graphite matrix quality, mixing temperature is 10～90 ℃, obtains mixture; Described organic high molecular polymer is more than one in polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly(ethylene oxide), Kynoar, acrylic resin and the polyacrylonitrile; Described conductive polymer polymer is a polythiophene, and polyaniline, polyacetylene, polyaniline, polypyrrole, coalescence benzene poly-are bitten in fen, polyaniline, polyhenylene, polyphenylene ethylene and the poly-two alkynes more than one; Three, be 180～360 ℃ with mixture in inlet temperature, outlet temperature is 70～130 ℃, and pressure is to carry out spray drying under the condition of 10～100Pa; Four, under 80～300 ℃ of conditions, 1～30h is handled in oven dry; Or with the programming rate of 1～20 ℃/min, heat treatment 1～40h under 300～900 ℃ of conditions, the cooling rate with 1～20 ℃/min is cooled to room temperature then, obtains composite cathode material of lithium ion battery.
Graphitization processing of the present invention is just phosphorus content 85～99.8%, mean particle size D
50Sphere, the axial ratio that is 3.0～50 μ m is natural flake graphite, micro crystal graphite, crystallization veiny graphite or the needle coke of 1.0～4.5 class sphere, bulk and/or sheet or the petroleum coke raw material programming rate with 1～20 ℃/min, to 1800～2800 ℃, high-temperature process 1～144h naturally cools to room temperature then.
Purification processes of the present invention is with alkali or acid soak natural flake graphite, micro crystal graphite, crystallization veiny graphite material 0.5～6h, and soaking temperature is 30～95 ℃, puts into 100～300 ℃ of baking ovens again and toasts 2～10h.
Alkali of the present invention is more than one of lithium hydroxide, NaOH and potassium hydroxide.
Acid of the present invention is more than one in hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, nitric acid and the boric acid.
Feed nitrogen, argon gas or inert gas in the heat treatment process of the present invention, flow is 1～150L/h.
Method of the present invention is sieved the composite cathode material of lithium ion battery that obtains with 100～400 mesh sieves.
Magnetic is removed in method screening of the present invention back, and magnetic flux density is 3000～30000Gs, and treatment temperature is 10～80 ℃, magnetic Jie net sheet number is 15～40, the electromagnetic hammer cycle is 3～180 times/second, and processing speed is 100～2000kg/h, rises or be cooled to room temperature then naturally.
A kind of preparation method of composite cathode material of lithium ion battery may further comprise the steps: one, with phosphorus content 85～99.8%, mean particle size D
50Sphere, the axial ratio that is 3.0～50 μ m is that the natural flake graphite, micro crystal graphite, crystallization veiny graphite of 1.0～4.5 class sphere, bulk and/or sheet is as graphite matrix; Two, graphite matrix is mixed with graphite matrix 0.1～10wt% organic high molecular polymer and/or conductive polymer polymer liquid phase, the speed of 2000～8000r/min is mixed stirring 10～120min, solvent is water, absolute ethyl alcohol, glycerol, isopropyl alcohol, acetone, oxolane, n-formyl sarcolysine base pyrrolidones or dimethylacetylamide, its quality is 0.8～2.5 times of graphite matrix quality, mixing temperature is 10～90 ℃, obtains mixture; Described organic high molecular polymer is more than one in polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly(ethylene oxide), Kynoar, acrylic resin and the polyacrylonitrile; Described conductive polymer polymer is a polythiophene, and polyaniline, polyacetylene, polyaniline, polypyrrole, coalescence benzene poly-are bitten in fen, polyaniline, polyhenylene, polyphenylene ethylene and the poly-two alkynes more than one; Three, be 180～360 ℃ with mixture in inlet temperature, outlet temperature is 70～130 ℃, and pressure is to carry out spray drying under the condition of 10～100Pa; Four, under 80～300 ℃ of conditions, 1-30h is handled in oven dry; Or with the programming rate of 1～20 ℃/min, heat treatment 1～40h under 300～900 ℃ of conditions, the cooling rate with 1～20 ℃/min is cooled to room temperature then, obtains composite cathode material of lithium ion battery.
The present invention compared with prior art, adopting phosphorus content is natural flake graphite, micro crystal graphite, crystallization veiny graphite and/or the Delanium of 85～99.8% sphere, class sphere, bulk and/or sheet in a big way, the preparation composite cathode material of lithium ion battery, work simplification, coating layer is more firmly fine and close, and powder resistivity is 7 * 10
-6Below the Ω m, the life-span height of lithium ion battery, stable circulation with the pole piece of the material battery of the present invention preparation, can reduce the consumption of making binding agent and conductive agent in the pole piece process, thereby the battery manufacturing cost is reduced.
Description of drawings
Fig. 1 is the SEM figure of the embodiment of the invention 1.
Fig. 2 is the electrochemical property test figure as a result of the embodiment of the invention 1.
Fig. 3 is the cycle performance figure under high compacted density of the embodiment of the invention 1.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.Composite cathode material of lithium ion battery of the present invention, the graphite that by spherical, axial ratio is 1.0～4.5 class sphere, bulk and/or sheet is matrix, matrix is coated with organic polymer and/or conductive polymer polymer, and coating thickness is between 1～10nm.The mean particle size D of composite material
50Be 3～50 μ m, specific area is 0.50～6.5m
2/ g, powder body compacted density are 1.90～2.15g/cm
3, magnetisable material Fe, Ni, Cr and Zn are less than 0.1ppm (quality).Graphite is Delanium or native graphite.Adopting the gram volume of Delanium is more than the 350mAh/g, and adopting the gram volume of native graphite is more than the 360mAh/g.
Organic high molecular polymer is more than one in PVAC polyvinylalcohol, polyvinylchloride, polyethylene glycol PEG, poly(ethylene oxide) PEO, Kynoar PVDF, acrylic resin PAA and the polyacrylonitrile (PAN).
The conductive polymer polymer is a polythiophene, and polyaniline, polyacetylene, polyaniline, polypyrrole, coalescence benzene poly-are bitten in fen PTh, polyaniline Pn, polyhenylene, polyphenylene ethylene and the poly-two alkynes more than one.
The preparation method of composite cathode material of lithium ion battery of the present invention may further comprise the steps:
One, graphitization processing or graphite purification processes are with phosphorus content 85～99.8%, mean particle size D
50Sphere, the axial ratio that is 3.0～50 μ m is natural flake graphite, micro crystal graphite, crystallization veiny graphite or needle coke, the petroleum coke raw material of 1.0～4.5 class sphere, bulk and/or sheet, through purification processes or graphitization processing, obtain the graphite matrix of phosphorus content more than 99.9%.The graphite of phosphorus content 99.9% is not graphitization processing or graphite purification processes also.
Graphitization processing is to be that 85～99.8% natural flake graphite, micro crystal graphite, crystallization veiny graphite or phosphorus content are 85～99.8% needle cokes or the petroleum coke raw material programming rate with 1～20 ℃/min with phosphorus content, to 1800～2800 ℃, high-temperature process 1～144h, naturally cool to room temperature then in equipment, adopting Equipment for Heating Processing is the SHL-2500 type graphitizing furnace of Qingdao auspicious American aircraft electricity Co., Ltd.
Purification processes adopts the chemical purification method, to remove phosphorus content is impurity element in 85～99.8% natural flake graphites, micro crystal graphite, the crystallization veiny graphite material, with alkali or acid soak material 0.5～6h, soaking temperature is 30～95 ℃, make the impurity dissolving in the material, with the pure water washing, put into 100～300 ℃ of baking ovens again and toast 2～10h then.The consumption of alkali or acid is advisable to soak natural flake graphite, micro crystal graphite, crystallization veiny graphite material fully.
Alkali is more than one of lithium hydroxide, NaOH and potassium hydroxide.
Acid is more than one in hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, nitric acid and the boric acid.
Two, graphite matrix is mixed with graphite matrix 0.1～10wt% organic high molecular polymer and/or conductive polymer polymer liquid phase, adopt the GX-200 type high-speed stirred bucket of Wuxi new light powder processing Co., Ltd, the speed of 2000～8000r/min is mixed stirring 10～120min, solvent for use is water or organic solvent, the quality of solvent is 0.8～2.5 times of graphite matrix quality, mixing temperature is 10～90 ℃, obtains mixture.
Organic high molecular polymer is more than one in PVAC polyvinylalcohol, polyvinylchloride, polyethylene glycol PEG, poly(ethylene oxide) PEO, Kynoar PVDF, acrylic resin PAA and the polyacrylonitrile (PAN).
The conductive polymer polymer is a polythiophene, and polyaniline, polyacetylene, polypyrrole, coalescence benzene poly-are bitten in fen PTh, polyaniline Pn, polyhenylene, polyphenylene ethylene and the poly-two alkynes more than one.
Used organic solvent is absolute ethyl alcohol, glycerol, isopropyl alcohol or acetone, oxolane, n-formyl sarcolysine base pyrrolidones NMP or dimethylacetylamide.
Three, with mixture moment gas phase drying, adopt the GZ-500 type Highspeedcentrifugingandsprayingdrier of Wuxi City weather-drying instrument factory, in inlet temperature is 180～360 ℃, outlet temperature is 70～130 ℃, at pressure is under the condition of 10～100Pa, carry out spray drying, feed rate is 160kg～1000kg/h.
Four, dry processing, adopt Shanghai, Shanghai to get over the 1010AS type digital display type Constant Temp. Oven of laboratory apparatus Co., Ltd, under 80～300 ℃ of conditions, 1-30h is handled in oven dry.
Or heat-treat, adopt Jiangsu to fly the RGD-300-8 type tunnel cave of the company that reaches, programming rate with 1～20 ℃/min, heat treatment 1～40h under 300～900 ℃ of conditions, feed nitrogen, argon gas or inert gas in the heat treatment process, flow is 1～150L/h, and the cooling rate with 1～20 ℃/min is cooled to room temperature then.
Five,, remove magnetic with 100～400 mesh sieve branches.Removing magnetic adopts the SD-F of Japanese HOSOKAWA MICRON GROUP to remove the magnetic machine, magnetic flux density is 3000～30000Gs, treatment temperature is 10～80 ℃, magnetic Jie net sheet number is 15～40, the electromagnetic hammer cycle is 3～180 times/second, processing speed is 100～2000kg/h, rises or be cooled to room temperature naturally, obtains composite cathode material of lithium ion battery.
Six, the packing of product is put in storage.
Adopt method of the present invention, at first, used raw-material phosphorus content is natural flake graphite, micro crystal graphite, crystallization veiny graphite and/or the Delanium of 85～99.9% sphere, class sphere, bulk and/or sheet in a big way, and the prior art for preparation method adopts phosphorus content at 99% above spherical graphite, so the present invention just greatly reduces cost in the selection of raw material.
Secondly, method preparation technology of the present invention is simple, and the preparation process complexity of prior art generally prepares the multistage pulverizing of spherical graphite needs, purifying, spheroidization processing procedure, and product yield is low, is below 50%, and yield of the present invention is more than 55%.
In the preparation process of the present invention, directly use the gas phase wink-dry to realize coating, replace the gas phase method for coating of prior art, not only preparation technology simplifies, and coating layer is more firmly fine and close.
Method of the present invention has adopted 1800～2800 ℃ of 300～900 ℃ of lower heat treatment temperatures and graphitization temperatures, prior art needs carburizing temperature more than 1000 ℃, graphitization temperature reaches 3000 ℃, and the present invention has reduced energy resource consumption, and product cost is reduced.
The composite cathode material of lithium ion battery of method preparation of the present invention, the KYKY2800B sem observation pattern that adopts Beijing instrument Development Co., Ltd of section to produce adopts the transmission electron microscope H-9500 of Guangzhou F door scientific instrument Co., Ltd to obtain coating thickness.Adopt the U.S. OPTIMA of Perkinelmer Inc. 2100 DV inductive coupling plasma emission spectrographs to record magnetisable material.Resistivity with the FZ-9601 powder resistivity test machine test compound material of Shanghai good luck detecting instrument Co., Ltd.The resistivity measurement method is according to YS/T 587.7-2006 carbon anode after-smithing petroleum coke detection method, and the conductivity of the high more material of resistivity is poor more, and resistivity is low more, and the conductivity of material is good more.
Adopt composite cathode material of lithium ion battery of the present invention to make the negative pole of Experimental cell, by negative material: the mass ratio of binding agent Kynoar PVDF is 98: 2, described negative material, PVDF are dissolved in the mixed pulp of the mass concentration 10% that obtains behind the N-methyl pyrrolidone NMP, evenly be coated on the thick Copper Foil of 10 μ m, compacting in flakes, make diameter 1cm carbon membrane then, oven dry 12h is standby under 120 ℃ in drying box.Pole piece with above-mentioned preparation is a work electrode, metal lithium sheet is as auxiliary electrode and reference electrode, and electrolyte adopts the EC/DMC/EMC solution of 1mol/L LiPF6, and volume ratio is 1: 1: 1, prepare simulated battery in being full of the glove box of argon gas, internal diameter is Φ 12mm.The charge-discharge test of battery is on the CT2001C battery testing system of the blue electric battery test system of Wuhan gold promise, charging/discharging voltage scope: 0.01V～2.0V, electric current is 0.2C, test capacity and efficient, and method of testing is according to GB/T 24533-2009 silicon/carbon/graphite in lithium ion batteries class negative material.
The composite cathode material of lithium ion battery of using the present invention's preparation carries out the pole piece making of battery, owing in the composite cathode material of lithium ion battery preparation, be added with polymer, improve the cementability of negative material and collector, improve the conductivity of negative material simultaneously, so can reduce the consumption of making binding agent in the pole piece process, do not use conductive agent, thereby the lithium ion battery manufacturing cost is further reduced.
Composite cathode material of lithium ion battery control magnetisable material content of the present invention, magnetisable material in the charge and discharge process and side reaction between the electrolyte have been reduced, reduce the side reaction in the charge and discharge process, reduced the battery capacity loss, helped improving the cyclical stability of battery.
As shown in Figure 1, adopt high molecular polymer to coat after, coating layer is even, bonding between the particle do not occur.
As shown in Figure 2, through the material after coating, when reducing the binding agent consumption, gram volume is brought into play still at 370.9mAh/g.
As shown in Figure 3, be 1.75g/cm in the pole piece compacting
3Under the compacted density, the capability retention in 500 weeks of battery is 86.8%.
Comparative Examples adopts the natural graphite material that does not coat, and resistivity is 9 * 10
-6Ω m,, make Experimental cell as stated above, its electrical property is tested.
The process data of table 1 embodiment 1-7
The physicochemical property test result of table 2 negative material
From test result as can be seen, adopt the material of the inventive method preparation and the height of reversible capacity first of lithium ion battery, enclosed pasture efficient height has first improved the cycle performance of battery.
Claims (10)
1. composite cathode material of lithium ion battery, it is characterized in that: described composite cathode material of lithium ion battery is that the graphite of 1.0～4.5 class sphere, bulk and/or sheet is matrix by spherical, axial ratio, matrix is coated with organic polymer and/or conductive polymer polymer, coating thickness between 1～10nm, the mean particle size D of described composite material
50Be 3.0～50.0 μ m, specific area is 0.50～6.5m
2/ g, powder body compacted density are 1.90～2.15g/cm
3, magnetisable material Fe, Ni, Cr and Zn are less than 0.1ppm; Described organic high molecular polymer is more than one in polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly(ethylene oxide), Kynoar, acrylic resin and the polyacrylonitrile; Described conductive polymer polymer is a polythiophene, and polyaniline, polyacetylene, polyaniline, polypyrrole, coalescence benzene poly-are bitten in fen, polyaniline, polyhenylene, polyphenylene ethylene and the poly-two alkynes more than one.
2. the preparation method of a composite cathode material of lithium ion battery may further comprise the steps: one, with phosphorus content 85～99.8%, mean particle size D
50Sphere, the axial ratio that is 3.0～50 μ m is natural flake graphite, micro crystal graphite, crystallization veiny graphite or needle coke, the petroleum coke raw material of 1.0～4.5 class sphere, bulk and/or sheet, through purification processes or graphitization processing, obtain the graphite matrix of phosphorus content more than 99.8%; Two, graphite matrix is mixed with graphite matrix 0.1～10wt% organic high molecular polymer and/or conductive polymer polymer liquid phase, the speed of 2000～8000r/min is mixed stirring 10～120min, solvent is water, absolute ethyl alcohol, glycerol, isopropyl alcohol, acetone, n-formyl sarcolysine base pyrrolidones, oxolane or dimethylacetylamide, its quality is 0.8～2.5 times of graphite matrix quality, mixing temperature is 10～90 ℃, obtains mixture; Described organic high molecular polymer is more than one in polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly(ethylene oxide), Kynoar, acrylic resin and the polyacrylonitrile; Described conductive polymer polymer is a polythiophene, and polyaniline, polyacetylene, polyaniline, polypyrrole, coalescence benzene poly-are bitten in fen, polyaniline, polyhenylene, polyphenylene ethylene and the poly-two alkynes more than one; Three, be 180～360 ℃ with mixture in inlet temperature, outlet temperature is 70～130 ℃, and pressure is to carry out spray drying under the condition of 10～100Pa; Four, under 80～300 ℃ of conditions, 1～30h is handled in oven dry; Or with the programming rate of 1～20 ℃/min, heat treatment 1～40h under 300～900 ℃ of conditions, the cooling rate with 1～20 ℃/min is cooled to room temperature then, obtains composite cathode material of lithium ion battery.
3. the preparation method of composite cathode material of lithium ion battery according to claim 2 is characterized in that: described graphitization processing is just phosphorus content 85～99.8%, mean particle size D
50Sphere, the axial ratio that is 3.0～50 μ m is natural flake graphite, micro crystal graphite, crystallization veiny graphite or the needle coke of 1.0～4.5 class sphere, bulk and/or sheet or the petroleum coke raw material programming rate with 1～20 ℃/min, to 1800～2800 ℃, high-temperature process 1～144h naturally cools to room temperature then.
4. the preparation method of composite cathode material of lithium ion battery according to claim 2, it is characterized in that: described purification processes is with alkali or acid soak natural flake graphite, micro crystal graphite, crystallization veiny graphite material 0.5～6h, soaking temperature is 30～95 ℃, puts into 100～300 ℃ of baking ovens again and toasts 2～10h.
5. the preparation method of composite cathode material of lithium ion battery according to claim 4, it is characterized in that: described alkali is more than one of lithium hydroxide, NaOH and potassium hydroxide.
6. the preparation method of composite cathode material of lithium ion battery according to claim 4, it is characterized in that: described acid is more than one in hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, nitric acid and the boric acid.
7. according to the preparation method of each described composite cathode material of lithium ion battery in the claim 2 to 6, it is characterized in that: feed nitrogen, argon gas or inert gas in the described heat treatment process, flow is 1～150L/h.
8. the preparation method of composite cathode material of lithium ion battery according to claim 7 is characterized in that: with 100～400 mesh sieves the composite cathode material of lithium ion battery that obtains is sieved.
9. the preparation method of composite cathode material of lithium ion battery according to claim 8, it is characterized in that: remove magnetic, magnetic flux density is 3000～30000Gs, treatment temperature is 10～80 ℃, magnetic Jie net sheet number is 15～40, the electromagnetic hammer cycle is 3～180 times/second, and processing speed is 100～2000kg/h, rises or be cooled to room temperature then naturally.
10. the preparation method of a composite cathode material of lithium ion battery may further comprise the steps: one, with phosphorus content 85～99.8%, mean particle size D
50Sphere, the axial ratio that is 3.0～50 μ m is that the natural flake graphite, micro crystal graphite, crystallization veiny graphite of 1.0～4.5 class sphere, bulk and/or sheet is as graphite matrix; Two, graphite matrix is mixed with graphite matrix 0.1～10wt% organic high molecular polymer and/or conductive polymer polymer liquid phase, the speed of 2000～8000r/min is mixed stirring 10～120min, solvent is water, absolute ethyl alcohol, glycerol, isopropyl alcohol, acetone, oxolane, n-formyl sarcolysine base pyrrolidones or dimethylacetylamide, its quality is 0.8～2.5 times of graphite matrix quality, mixing temperature is 10～90 ℃, obtains mixture; Described organic high molecular polymer is more than one in polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly(ethylene oxide), Kynoar, acrylic resin and the polyacrylonitrile; Described conductive polymer polymer is a polythiophene, and polyaniline, polyacetylene, polyaniline, polypyrrole, coalescence benzene poly-are bitten in fen, polyaniline, polyhenylene, polyphenylene ethylene and the poly-two alkynes more than one; Three, be 180～360 ℃ with mixture in inlet temperature, outlet temperature is 70～130 ℃, and pressure is to carry out spray drying under the condition of 10～100Pa; Four, under 80～300 ℃ of conditions, 1-30h is handled in oven dry; Or with the programming rate of 1～20 ℃/min, heat treatment 1～40h under 300～900 ℃ of conditions, the cooling rate with 1～20 ℃/min is cooled to room temperature then, obtains composite cathode material of lithium ion battery.
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