CN103560247B - Vehicle-mounted and energy-storage lithium ion battery cathode material and preparation method thereof - Google Patents

Vehicle-mounted and energy-storage lithium ion battery cathode material and preparation method thereof Download PDF

Info

Publication number
CN103560247B
CN103560247B CN201310554920.3A CN201310554920A CN103560247B CN 103560247 B CN103560247 B CN 103560247B CN 201310554920 A CN201310554920 A CN 201310554920A CN 103560247 B CN103560247 B CN 103560247B
Authority
CN
China
Prior art keywords
lithium ion
ion battery
energy storage
vehicle
storage lithium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201310554920.3A
Other languages
Chinese (zh)
Other versions
CN103560247A (en
Inventor
岳敏
闫慧青
钟正
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bethel (Jiangsu) new Mstar Technology Ltd
Original Assignee
Shenzhen BTR New Energy Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen BTR New Energy Materials Co Ltd filed Critical Shenzhen BTR New Energy Materials Co Ltd
Priority to CN201310554920.3A priority Critical patent/CN103560247B/en
Publication of CN103560247A publication Critical patent/CN103560247A/en
Priority to KR1020140071407A priority patent/KR20150053693A/en
Priority to JP2014156362A priority patent/JP6152076B2/en
Application granted granted Critical
Publication of CN103560247B publication Critical patent/CN103560247B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 relates to a vehicle-mounted and energy-storage lithium ion battery cathode material, a battery and a preparation method of the material. Compared with the prior art, the preparation method has the advantage that nanometer conductive carbon is coated on and embedded in the surface of a graphite particle by adopting a mechanical and physical grinding modifying method. According to the preparation method, the use efficiency of a conductive agent and the stability of the conductive agent on the surface of a material can be improved, and thus the compatibility of a cathode active material and electrolyte is improved, and the low-temperature performance and the rate capability of a lithium ion battery is improved. The first-time charge and discharge efficiency of the vehicle-mounted and energy-storage lithium ion battery cathode material reaches up to above 94.0 percent, and the 25-DEG C low-temperature raising rate is higher than 98.0 percent and is increased by above 8.0 percent in comparison with that in the prior art. The preparation method provided by the invention is simple to operate, easy to control and low in production cost, and is suitable for industrialized production.

Description

A kind of vehicle-mounted with energy storage lithium ion battery negative material and preparation method thereof
Technical field
The present invention relates to field of lithium ion battery material, in particular it relates to plant vehicle-mounted and energy storage lithium-ion electric Pond negative material and preparation method thereof.
Background technology
At present, based on graphite type material, graphite is as the theory ratio of negative material for commercial li-ion cell negative electrode material Capacity reaches 372mah/g, but it exist charge-discharge magnification poor performance and electrolyte phase capacitive is poor, poor performance at low temperatures the shortcomings of, These all directly influence the development process in power and energy-storage battery field for the lithium ion battery.
By coating modification process is carried out to graphite type material, can make the reversible capacity of material, cycle performance and with electricity The compatibility of solution liquid is significantly lifted, but because covering material Colophonium or resin or polymer substance electric conductivity compare graphite Difference, therefore the electric conductivity phase strain differential of electrode material, and low temperature high rate performance is bad；Work through numerous studies and find, conductive The addition of agent can effectively improve the electric conductivity of coated graphite material, and electrode material is carried with the compatibility of electrolyte simultaneously High.
The addition of conductive material can improve the electric conductivity of graphite material to a certain extent, but there is conductive agent dispersion Difficulty, the problems such as under low production efficiency, and scattered conductive agent, as used not in time, there is also secondary agglomeration phenomenon, thus The impact service efficiency of conductive agent and the homogeneity of material, lead to the circulation of lithium ion battery and high rate performance to reduce.
Cn 101887967 a discloses a kind of preparation method from cell negative electrode material for lithium, comprises the following steps: liquid Mutually mixing, drying, carbonization treatment, high-temperature process, compound.The preparation method of this negative material includes carbonization treatment and high temperature simultaneously Process, described compound inclusion mixes successively and merges, high energy consumption, high cost, complex operation, is unfavorable for industrialized production.
Therefore, develop a kind of electric conductivity, cycle performance and high rate performance excellent, and preparation method is simple, produces into This low lithium is the technical barrier of art from cell negative electrode material.
Content of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of vehicle-mounted and energy storage lithium ion battery The preparation method of negative material, comprises the following steps:
(1) using organic carbon source, graphite type material is coated, obtain compound；
(2) compound is carried out carbonization treatment in 500-1800 DEG C, obtain the outer stone having disordered structure material with carbon element clad Ink material；
(3) material that step (2) obtains is carried out mechanical-physical with conductive material and grind modification；
(4) sieve, remove magnetic, obtain lithium ion battery negative material.
Preferably, described graphite type material is the group of a kind or at least 2 kinds in native graphite, Delanium or carbosphere Close；Preferably, the fixing carbon content of described graphite type material is more than or equal to 99.9%, and axial ratio is 1.0-2.5, particle mean size For 1-30 μm, dmax40.0 μm, specific surface area is 2.0-20.0m2/ g, powder body compacted density is 1.45-2.05g/cm3；Interlayer Away from (d002) it is 0.3354-0.3363nm；Diamond structure (3r) content is 1.0-35.0%, id/ig(area ratio) is 0.1-1.0； i110/i004For 0.05-0.95, lc is 200.0-1000.0nm；La is 800.0-1800.0nm, and magnetisable material content is 0.5ppm Below；Metallic foreign body granular size is less than 100.0 μm；Powder conductivity rate under compacted density is for 1.5g/cc is 50.0- 800.0s/cm.
Preferably, described organic carbon source is in selected from coal tar pitch and petroleum asphalt, mesophase pitch, macromolecular material or polymer 1 kind or at least 2 kinds of combination.
Preferably, described conductive material is conductive nano agent and/or electrically conductive graphite；Preferably, described conductive nano agent is 1 kind in cnts, carbon fiber, nano-graphite or Graphene or at least 2 kinds of combination；Preferably, described conductive nano agent is flat All size (d50) it is 10-600.0nm, specific surface area ssa is 2.0-60.0m2/g；Preferably, described conductive nano agent is average A size of 10.0-300.0nm；Preferably, a diameter of 1-300nm of described cnt and carbon fiber, length is 1-20 μm；Preferably, The graphite flake number of plies of described Graphene is 1-100；Preferably, described conductive nano agent is presented in nano conductive liquid；Excellent Selection of land, in described nano conductive liquid, the content of conductive nano agent is 0.5-20wt%；Preferably, disperse in described nano conductive liquid Solvent is the combination of a kind or at least 2 kinds in water, methanol, ethanol, acetone or chloroform.
Preferably, described conductive material is conductive natural graphite powder, conduction graphous graphite powder or conductive nano white carbon black (super-p) a kind in or at least 2 kinds of combination；Preferably, described conductive material is in the form of sheets or block, and Ratio of long radius to short radius is 1.3-4.5, mean diameter is 0.5-12.0 μm, and specific surface area ssa is 2.0-60.0m2/g.
Preferably, step (1) is described coats as solid phase cladding or liquid phase coating.
Solid phase of the present invention coats as art known technology, and one of ordinary skill in the art can select to close as needed Suitable technical parameter.The nonrestrictive example of described solid phase cladding includes: organic carbon source and graphite type material are placed in mixing In machine, control temperature at 15 DEG C -80 DEG C, with rotating speed 400-2000rpm, process 1-300min, obtain compound；Described mixer For modified vc mixer, cone-type mixer or kneading machine at a high speed.
Liquid phase coating of the present invention is art known technology, and one of ordinary skill in the art can select to close as needed Suitable technical parameter.The nonrestrictive example of described liquid phase coating includes: organic carbon source is added in solvent, using at a high speed Blender carries out liquid-phase mixing, and speed of agitator is 3000-5000rpm, and mixing time is 20-60min, and temperature is 80-90 DEG C, so Afterwards graphite substrate material is added in said mixture, organic carbon source is 1:9-2:8 with the mass ratio of graphite substrate material, continues Continue and liquid-phase mixing is carried out using homogenizer, speed of agitator is 3000-5000rpm, mixing time is 120-180min, used Solvent is 2～1.2 with the mass ratio of graphite substrate material, is dried, obtains compound, and described solvent is ethanol or methanol；Described In liquid phase coating, drying is carried out using spray dryer, and the inlet temperature of spray dryer is 150-350 DEG C, and outlet temperature is 20-250 DEG C, pressure is 10-100mpa, and loading frequency is 10-100hz, and speed of agitator is 3000-5000rpm, and mixing time is 120-180min, solvent for use is 2～1.2 with the mass ratio of graphite substrate material, is dried, obtains compound, described solvent is Ethanol or methanol.
Preferably, the described carbonization treatment temperature of step (2) is 600-1600 DEG C, particularly preferably 700～1500 DEG C.
Preferably, the described mechanical-physical of step (3) grinds modification is that ball-milling treatment, fusion treatment or high speed nanometer are divided Dissipate and process；Preferably, described ball milling modification process time is more than 5.0min, and processing speed is 200-4000r/min；Described ball Mill the modification time can for 6.0min, 8.0min, 10.0min, 15.0min, 20.0min, 50.0min, 100.0min, 200.0min、300.0min、500.0min、800.0min、1000.0min、1100.0min、1150.0min、1180.0min、 1190.0min, 1195.0min or 1199.0min etc., preferably 5.0-1200.0min；Described ball milling modification processing speed can be 210r/min、220r/min、250r/min、300r/min、500r/min、1000r/min、1500r/min、2000r/min、 2500r/min, 3000r/min, 3500r/min, 3800r/min, 3900r/min or 3950r/min etc.；Preferably, described ball A diameter of 0.1-3.0mm of the ball that mill modification adopts, the species of ball is alumina balls or corundum ball；Preferably, described melt Conjunction process time is 20.0-800.0min, and rotating speed is 800-3000r/min, and cavity gap is 0.1-2.0cm, and temperature is 10-80 ℃；Preferably, the described fusion treatment time is 20.0-300.0min；Preferably, described fusion treatment rotating speed is 800-2600r/ min；Preferably, the cavity gap of described fusion treatment is 0.1-1.0cm；Preferably, described fusion treatment temperature is 20-60 ℃；Preferably, the described high speed nano-dispersed time is 20.0-1200.0min, and rotating speed is 200-8000r/min；Preferably, institute State high speed nano-dispersed and adopt dispersant；Preferably, described conductive material and the mass ratio of dispersant are 1:0.1-1:1, especially Preferably 1:0.3-1:0.8；Preferably, described dispersant be sodium carboxymethyl cellulose, sodium lignin sulfonate, magnesium lignosulfonate, 1 kind in Sodium Polystyrene Sulfonate, ammonium polystyrene sulphonate, sodium metnylene bis-naphthalene sulfonate or polyacrylamide or at least 2 kinds Combination.
Preferably, the described magnetic induction except magnetic of step (4) is 3000-30000gs, and treatment temperature is 10-80 DEG C, removes The magnetic time is 10-120s.
The second object of the present invention is to provide a kind of vehicle-mounted and energy storage lithium ion battery negative material, described negative pole material Material is prepared by the method for the invention, and, electronic conductivity high and low temperature high rate performance good with electrolyte wellability and cycle performance are excellent Different.
Described vehicle-mounted and energy storage lithium ion battery negative material has disordered structure material with carbon element by outside graphite type material, matrix Clad and conductive material form, and conductive material is evenly coated with being embedded into graphite granule surface.
Preferably, the described vehicle-mounted content with conductive material in energy storage lithium ion battery negative material is 0.1- 20.0wt%, further preferred 0.5-18.0wt%, particularly preferred 1-15.0wt%.
Preferably, the described vehicle-mounted content with disordered structure material with carbon element clad in energy storage lithium ion battery negative material For 0.1-20.0wt%, further preferred 0.5-18.0wt%, particularly preferred 1-15.0wt%；
Preferably, described vehicle-mounted with energy storage lithium ion battery negative material in disordered structure material with carbon element clad and graphite The mass ratio of class material is 0.1:100-20.0:100, further preferred 0.5:100-18.0:100, particularly preferred 0.5:100- 15.0:100.
Preferably, the described vehicle-mounted quality with graphite type material in energy storage lithium ion battery negative material and conductive material Than for 10:0.01-10:10.0, further preferred 10:0.1-10:8.0, particularly preferred 10:0.5-10:6.0.
The third object of the present invention is to provide a kind of vehicle-mounted and energy storage lithium ion battery, described vehicle-mounted and energy storage lithium Ion battery comprises of the present invention vehicle-mounted and energy storage lithium ion battery negative material.
Compared with prior art, the present invention adopts mechanical-physical to grind modified method, by conductive nano agent and/or conduction Uniformly coating is embedded into graphite granule surface to graphite, and nano-sized carbon coating is embedded into graphite granule surface, is not in secondary group Poly- phenomenon, increased the active force between conductive agent and graphite granule, lifts the service efficiency of conductive agent and in material surface Stability, thus improving the compatibility of negative electrode active material and electrolyte, improve low temperature and the high rate performance of lithium ion battery. The head of negative material of the present invention is imitated as more than 94.0%, higher by more than 2.0% than prior art sample, and 25 DEG C of low temperature rise rates are high In 98.0%, improve more than 8.0% than prior art.The inventive method is simple to operate, easily controllable, low production cost, suitable work Industry metaplasia is produced.
Brief description
Fig. 1 is the sem figure of the embodiment of the present invention 3.
Fig. 2 is the electrical conductivity comparison diagram of the embodiment of the present invention 2 and comparing embodiment 1.
Fig. 3 is the embodiment of the present invention and comparing embodiment cryogenic property comparison diagram.
Specific embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that described enforcement Example is only to aid in understanding the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
By phosphorus content be more than 99.9%, granularity be 3-40 μm of spherical natural graphite, be placed in vc reactor, introduce with Native graphite mass ratio is that the asphalt of 5:100 carries out solid phase mixing, and rotating speed is 1200rpm, and incorporation time is 90min, obtains To compound；By above-mentioned compound under nitrogen protection, carry out carbonization treatment, 1200 DEG C of temperature, afterwards product is cooled down To room temperature, obtain the outer native graphite having disordered structure material with carbon element clad.There is outward the natural of disordered structure material with carbon element clad Graphite is mixed homogeneously using mechanical ball milling by the mass ratio of 100:2 with conductive nano agent Graphene, and the rotating speed of wherein ball mill is 200rpm, process time is 480min.Gains are carried out sieving, remove magnetic, except magnetic number of times is 3 times, magnetic induction is 10000gs, treatment temperature is 10 DEG C, and electromagnetic hammer cycle is 20 times/second, obtains the lithium-ion electric that particle mean size is 11.2 μm Pond graphite cathode material.
Embodiment 2
A certain amount of acrylic resin is added to the water, liquid-phase mixing is carried out using homogenizer, speed of agitator is 3000rpm, mixing time is 60min, and temperature is 90 DEG C, then by phosphorus content be more than 99.9%, granularity be 3-40 μm of bulk Native graphite is added in said mixture, and wherein acrylic resin and the mass ratio of native graphite are 15:100, continue to adopt Homogenizer carries out liquid-phase mixing, and speed of agitator is 3000rpm, and mixing time is 180min, solvent for use water and block sky So the mass ratio of graphite is 200:100, is dried using spray dryer, and inlet temperature is 350 DEG C, and outlet temperature is 150 DEG C, pressure is 100mpa, and loading frequency is 10hz, obtains compound；Under nitrogen protection, carbonization treatment, temperature 500 are carried out DEG C, afterwards product is cooled to room temperature, obtains the outer native graphite having disordered structure material with carbon element clad.There is outward unordered knot The block native graphite of structure material with carbon element clad is mixed homogeneously using fusion by the mass ratio of 100:9 with cnt, wherein merges machine Rotating speed is 2600rpm, and process time is 90min.Gains are carried out sieving, remove magnetic, except magnetic number of times is 3 times, magnetic induction For 10000gs, treatment temperature is 10 DEG C, and electromagnetic hammer cycle is 20 times/second, obtains the lithium ion that particle mean size is 8.9 μm Battery graphite cathode material.
Embodiment 3
By phosphorus content be more than 99.9%, granularity be 3-40 μm of Delanium, be placed in cone-type mixer, introduce and people Make graphite quality and carry out solid phase mixing than the mesophase pitch for 4:100, rotating speed is 50rpm, incorporation time is 300min, obtains Compound；By above-mentioned compound under nitrogen protection, carry out carbonization treatment, 1800 DEG C of temperature, afterwards product is cooled to Room temperature, obtains the outer Delanium having disordered structure material with carbon element clad.There is outward the artificial stone of disordered structure material with carbon element clad Ink is mixed homogeneously using fusion machine by the mass ratio of 100:9:0.1 with conductive natural graphite powder, sp, and the rotating speed merging machine is 800rpm, process time is 300min.Gains are carried out sieving, remove magnetic, except magnetic number of times is 3 times, magnetic induction is 10000gs, treatment temperature is 10 DEG C, and electromagnetic hammer cycle is 20 times/second, obtains the lithium-ion electric that particle mean size is 14.5 μm Pond graphite cathode material.
Embodiment 4
By phosphorus content be more than 99.9%, granularity be 3-40 μm of block native graphite, be placed in vc reactor, introduce and Native graphite mass ratio is that the coal tar pitch of 20:100 carries out solid phase mixing, and rotating speed is 2000rpm, and incorporation time is 60min, obtains Compound；By above-mentioned compound under nitrogen protection, carry out carbonization treatment, 950 DEG C of temperature, afterwards product is cooled to room Temperature, obtains the outer native graphite having disordered structure material with carbon element clad.Have outward disordered structure material with carbon element clad native graphite, Sp and dispersant press the mass ratio of 100:8:3 using high speed nano-dispersed mix homogeneously, and the rotating speed of its high speed nano-dispersed is 8000rpm, process time is 60min, and dispersant is polyacrylamide.Gains are carried out sieving, remove magnetic, except magnetic number of times is 3 Secondary, magnetic induction is 10000gs, and treatment temperature is 10 DEG C, and electromagnetic hammer cycle is 20 times/second, and obtaining particle mean size is 17.0 μm of graphite negative material of lithium ion battery.
Embodiment 5
By phosphorus content be more than 99.9%, granularity be 3-40 μm of carbosphere, be placed in cone-type mixer, introduce micro- with carbon Ball mass ratio is that the coal tar pitch of 0.1:100 carries out solid phase mixing, and rotating speed is 120rpm, and incorporation time is 90min, is mixed Material；By above-mentioned compound under nitrogen protection, carry out carbonization treatment, 1500 DEG C of temperature, afterwards product be cooled to room temperature, Obtain the outer carbosphere having disordered structure material with carbon element clad.There are outward the carbosphere of disordered structure material with carbon element clad, conductive sky So graphite powder and dispersant press the mass ratio of 100:20:8 using high speed nano-dispersed mix homogeneously, its high speed nano-dispersed Rotating speed is 5000rpm, and process time is 90min, and dispersant is sodium carboxymethyl cellulose.Gains are carried out sieving, remove magnetic, removes Magnetic number of times is 3 times, and magnetic induction is 10000gs, and treatment temperature is 10 DEG C, and electromagnetic hammer cycle is 20 times/second, is put down All granularity is 9.8 μm of graphite negative material of lithium ion battery.
Embodiment 6
A certain amount of poly(ethylene oxide) is added in dimethyl acetylamide, liquid-phase mixing is carried out using homogenizer, Speed of agitator be 5000rpm, mixing time be 20min, temperature be 80 DEG C, then by phosphorus content be more than 99.9%, granularity be 3- 40 μm of spherical natural graphite is added in said mixture, and wherein poly(ethylene oxide) and the mass ratio of spherical natural graphite are 18:100, continues to carry out liquid-phase mixing using homogenizer, and speed of agitator is 5000rpm, and mixing time is 120min, used Solvent dimethyl acetylamide is 12:100 with the mass ratio of spherical natural graphite, is dried using spray dryer, import temperature Spend for 280 DEG C, outlet temperature is 120 DEG C, pressure is 80mpa, loading frequency is 30hz, obtains compound；Under nitrogen protection, Carry out carbonization treatment, 700 DEG C of temperature, afterwards product is cooled to room temperature, obtain there is disordered structure material with carbon element clad outward Native graphite.There are outward the native graphite of disordered structure material with carbon element clad and conductive graphous graphite powder, carbon fiber by 100:5:3 Mass ratio adopt ball mill mix homogeneously, the rotating speed of ball mill is 1200rpm, and process time is 120min.Gains are entered Row sieves, removes magnetic, and except magnetic number of times is 3 times, magnetic induction is 10000gs, and treatment temperature is 10 DEG C, and electromagnetic hammer cycle is 20 times/second, obtain the graphite negative material of lithium ion battery that particle mean size is 13.8 μm.
Embodiment 7
By phosphorus content be more than 99.9%, granularity be 3-40 μm of Delanium, be placed in vc reactor, introduce with artificial Graphite quality carries out solid phase mixing than the coal tar pitch for 6:100, and rotating speed is 800rpm, and incorporation time is 120min, is mixed Material；By above-mentioned compound under nitrogen protection, carry out carbonization treatment, 900 DEG C of temperature, afterwards product be cooled to room temperature, Obtain the outer Delanium having disordered structure material with carbon element clad.There is outward the Delanium of disordered structure material with carbon element clad and lead Electric natural graphite powder presses the mass ratio of 100:15 using merging mix homogeneously, and the rotating speed wherein merging machine is 1800rpm, during process Between be 120min.Gains are carried out sieving, remove magnetic, except magnetic number of times is 3 times, magnetic induction is 10000gs, and treatment temperature is 10 DEG C, electromagnetic hammer cycle is 20 times/second, obtains the graphite negative material of lithium ion battery that particle mean size is 15.3 μm.
Embodiment 8
By phosphorus content be more than 99.9%, granularity be 3-40 μm of block native graphite, be placed in kneading machine, introducing and block Shape native graphite mass ratio is that the asphalt of 10:100 carries out solid phase mixing, and rotating speed is 180rpm, and incorporation time is 60min, Temperature is 80 DEG C, obtains compound；By above-mentioned compound under nitrogen protection, carry out carbonization treatment, 1300 DEG C of temperature, afterwards will Product is cooled to room temperature, obtains the outer native graphite having disordered structure material with carbon element clad.There is outward disordered structure material with carbon element The native graphite of clad is mixed using high speed nano-dispersed by the mass ratio of 100:12:5 with conductive graphous graphite powder, dispersant Uniformly, the rotating speed of its high speed nano-dispersed is 2500rpm, and process time is 240min, and dispersant is ammonium polystyrene sulphonate. Gains are carried out sieving, remove magnetic, except magnetic number of times is 3 times, magnetic induction is 10000gs, and treatment temperature is 10 DEG C, electromagnetic hammer Cycle is 20 times/second, obtains the graphite negative material of lithium ion battery that particle mean size is 12.1 μm.
Comparing embodiment 1
By phosphorus content be more than 99.9%, granularity be 3-40 μm of block native graphite, be placed in vc reactor, introduce and Native graphite mass ratio is that the asphalt of 8:100 carries out solid phase mixing, and rotating speed is 1200rpm, and incorporation time is 120min, obtains To compound；By above-mentioned compound under nitrogen protection, carry out carbonization treatment, 1200 DEG C of temperature, afterwards product is cooled down To room temperature, obtain the outer native graphite having disordered structure material with carbon element clad.Gains are carried out sieving, remove magnetic, except magnetic number of times For 3 times, magnetic induction is 10000gs, and treatment temperature is 10 DEG C, and electromagnetic hammer cycle is 20 times/second, obtains particle mean size For 12.5 μm of graphite negative material of lithium ion battery.
Comparing embodiment 2
By phosphorus content be more than 99.9%, granularity be 3-40 μm of spherical natural graphite and conductive nano agent sp by 100:3's Mass ratio adopts mechanical ball milling mix homogeneously, and the wherein rotating speed of ball mill is 1200rpm, and process time is 120min.By gained Thing carries out sieving, removes magnetic, and except magnetic number of times is 3 times, magnetic induction is 10000gs, and treatment temperature is 10 DEG C, electromagnetic hammer strike time Number is 20 times/second, obtains the graphite negative material of lithium ion battery that particle mean size is 14.6 μm.
The present invention adopts mechanically modifying method, it will be seen from figure 1 that conductive agent is dispersed in coated graphite material list Face, can greatly improve service efficiency and the stability in material surface of conductive agent, thus improving negative electrode active material and electricity The compatibility performance of solution liquid, improves low temperature and the high rate performance of lithium ion battery.
The inventive method preparation vehicle-mounted with energy storage lithium ion battery negative material, due to the addition and uniformly of conductive agent Dispersion, figure it is seen that the electrical conductivity of the coated graphite material being processed using mechanically modifying is substantially better than and is not added with conductive agent Comparing embodiment 1, electrical conductivity increases by 60-180s/cm on a year-on-year basis.
The present invention adopts mechanically modifying method, from figure 3, it can be seen that the dispersed of conductive agent substantially increases conductive agent Service efficiency and the stability in material surface, improve the cryogenic property of lithium ion battery, the low temperature properties of all embodiments Comparing embodiment 1 and 2 can be superior to, all 25 DEG C of low temperature rise rates of embodiment be higher than 98.0%, than prior art improve 8.0% with On.
The vehicle-mounted and energy storage lithium ion battery negative material of the inventive method preparation, pattern adopts s:4800 surface sweeping Electronic Speculum Instrument records, and electrical conductivity is recorded using mcp-pd51 powder conductivity rate measurement system.
Application routine evaluations detection method detects the vehicle-mounted and energy storage lithium of the method preparation of embodiment and comparing embodiment The half-cell performance of ion battery cathode material.
The half-cell result of each embodiment and comparing embodiment is shown in list below 1.
Table 1
Used by the present invention, full battery testing method is: with embodiment 1-8 and comparing embodiment 1-2 as negative material, cmc and Sbr is binding agent, and super-p is conductive agent, and three's mass ratio is negative material: binding agent: conductive agent=95.8:3.2:1.0, Smear is carried out for collector with Copper Foil, drying, tabletting, cut-parts obtain negative plate.Again with licoo2For positive electrode, with pvdf For binding agent, super-p is conductive agent, and three's mass ratio is positive electrode: binding agent: conductive agent=94.5:1.5:4.0, with aluminum Paper tinsel carries out smear for collector, obtains positive plate through conventional method drying, tabletting, cut-parts.By the above-mentioned positive/negative plate matching, With (pe or pp) as barrier film, by positive pole/barrier film/negative pole, top-down order is put well, is then wound into rate cylinder 18650 battery cores.Battery core loads in box hat, injects appropriate electrolyte from battery core liquid injection port after sealing in the argon glove box being dried (lmol/l lipf6/dmc+emc+ec, 1:1:1).Open formation, 0.1c speed is charged to 50%s DEG C, after placing 4-6h, then with 1c Charge and discharge 3 weeks, is obtained 25 DEG C of battery capacities, then is filled using room temperature 0.5c, and low temperature (- 30 DEG C, -20 DEG C, -10 DEG C) 0.5c is put, low temperature After the completion of test, by battery discharge and recharge at normal temperatures once, calculate low temperature rise rate.Concrete outcome is as shown in table 2.
Adopt and calculate low temperature with the following method and bring back to life rate:
25 DEG C of battery rise capacity × 100% after the front 25 DEG C of battery capacity/low-temperature tests of the low temperature rate of bringing back to life=low-temperature test.
Table 2
Negative material -10℃/25℃ -20℃/25℃ -30℃/25℃ 25 DEG C of rise rates
Embodiment 1 92.90% 81.50% 65.70% 98.7%
Embodiment 2 94.90% 84.00% 68.40% 98.6%
Embodiment 3 95.20% 86.50% 72.90% 98.7%
Embodiment 4 96.70% 89.80% 74.20% 98.8%
Embodiment 5 96.10% 87.20% 73.90% 98.9%
Embodiment 6 94.90% 85.90% 68.70% 98.6%
Embodiment 7 95.00% 84.80% 67.90% 98.9%
Embodiment 8 92.80% 82.20% 66.90% 98.4%
Comparing embodiment 1 82.80% 65.30% 45.30% 85.0%
Comparing embodiment 2 89.60% 72.80% 48.90% 89.3%
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment, But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention, The interpolation of the equivalence replacement to each raw material of product of the present invention and auxiliary element, selection of concrete mode etc., all fall within the present invention's Within the scope of protection domain and disclosure.

Claims (37)

1. a kind of vehicle-mounted preparation method with energy storage lithium ion battery negative material, comprises the following steps:
(1) using organic carbon source, graphite type material is coated, obtain compound；
The fixing carbon content of described graphite type material is more than or equal to 99.9%, and axial ratio is 1.0-2.5, and particle mean size is 1-30 μm, dmax40.0 μm, specific surface area is 2.0-20.0m2/ g, powder body compacted density is 1.45-2.05g/cm3；Interlamellar spacing is 0.3354-0.3363nm；Diamond structure content is 1.0-35.0%, id/igFor 0.1-1.0；i110/i004For 0.05-0.95, lc For 200.0-1000.0nm；La is 800.0-1800.0nm, and magnetisable material content is below 0.5ppm；Metallic foreign body granular size For less than 100.0 μm；Powder conductivity rate under compacted density is for 1.5g/cc is 50.0-800.0s/cm；
(2) compound is carried out carbonization treatment in 900-1600 DEG C, obtain the outer graphite material having disordered structure material with carbon element clad Material；
(3) material that step (2) obtains is carried out at ball milling modification process, fusion treatment or high speed nano-dispersed with conductive material Reason；
Described conductive material is conductive nano agent or conductive nano agent and electrically conductive graphite；Described conductive material is in the form of sheets or block, Ratio of long radius to short radius is 1.3-4.5, and mean diameter is 0.5-12.0 μm, and specific surface area ssa is 2.0-60.0m2/g；Described conductive nano Agent is the combination of a kind or at least 2 kinds in CNT, carbon fiber, nano-graphite or Graphene；Described conductive nano agent flat All a size of 10-600.0nm, specific surface area ssa is 2.0-60.0m2/g；Described conductive nano agent is in the form of nano conductive liquid Exist；In described nano conductive liquid, dispersion solvent is the combination of a kind or at least 2 kinds in water, methanol, ethanol, acetone or chloroform；
(4) sieve, remove magnetic, obtain lithium ion battery negative material.
2. the method for claim 1 is it is characterised in that described graphite type material is native graphite, Delanium or carbon 1 kind in microsphere or at least 2 kinds of combination.
3. the method for claim 1 it is characterised in that described organic carbon source be selected from coal tar pitch and petroleum asphalt, mesophase drip The combination of a kind or at least 2 kinds in green grass or young crops or macromolecular material.
4. the method for claim 1 is it is characterised in that the average-size of described conductive nano agent is 10.0- 300.0nm.
5. the method for claim 1 is it is characterised in that a diameter of 1-300nm of described CNT and carbon fiber, long Spend for 1-20 μm.
6. the method for claim 1 is it is characterised in that the graphite flake number of plies of described Graphene is 1-100.
7. the method for claim 1 it is characterised in that in described nano conductive liquid conductive nano agent content be 0.5- 20wt%.
8. the method for claim 1 is it is characterised in that described cladding of step (1) coats or liquid phase coating for solid phase.
9. the method for claim 1, it is characterised in that described ball milling modification process time is more than 5.0min, is processed Speed is 200-4000r/min.
10. the method for claim 1 is it is characterised in that described ball milling modification process time is 5.0-1200.0min.
11. the method for claim 1 are it is characterised in that described ball milling modification processes a diameter of 0.1- of the ball adopting 3.0mm, the species of ball is alumina balls or zirconia ball.
12. the method for claim 1 it is characterised in that the described fusion treatment time be 20.0-800.0min, rotating speed For 800-3000r/min, cavity gap is 0.1-2.0cm, and temperature is 10-80 DEG C.
13. the method for claim 1 are it is characterised in that the described fusion treatment time is 20.0-300.0min.
14. the method for claim 1 are it is characterised in that described fusion treatment rotating speed is 800-2600r/min.
15. the method for claim 1 are it is characterised in that the cavity gap of described fusion treatment is 0.1-1.0cm.
16. the method for claim 1 are it is characterised in that described fusion treatment temperature is 20-60 DEG C.
17. the method for claim 1 are it is characterised in that described high speed nano-dispersed process time is 20.0- 1200.0min, rotating speed is 200-8000r/min.
18. the method for claim 1 adopt dispersant it is characterised in that described high speed nano-dispersed is processed.
19. methods as claimed in claim 18 are it is characterised in that described conductive material is 1:0.1- with the mass ratio of dispersant 1:1.
20. methods as claimed in claim 18 are it is characterised in that described conductive material is 1:0.3- with the mass ratio of dispersant 1:0.8.
21. methods as claimed in claim 18 are it is characterised in that described dispersant is sodium carboxymethyl cellulose, sulfomethylated lignin Sour sodium, magnesium lignosulfonate, Sodium Polystyrene Sulfonate, ammonium polystyrene sulphonate, sodium metnylene bis-naphthalene sulfonate or polyacrylamide In a kind or at least 2 kinds of combination.
22. the method for claim 1 are it is characterised in that the described magnetic induction except magnetic of step (4) is 3000- 30000gs, treatment temperature is 10-80 DEG C, except the magnetic time is 10-120s.
23. a kind of vehicle-mounted with energy storage lithium ion battery negative materials it is characterised in that described vehicle-mounted with energy storage lithium-ion electric Method preparation described in any one of claim 1-22 for the pond negative material.
24. as claimed in claim 23 vehicle-mounted with energy storage lithium ion battery negative materials it is characterised in that described vehicle-mounted with Energy storage lithium ion battery negative material is by having disordered structure material with carbon element clad and conductive material group outside graphite type material, matrix Become, and conductive material is evenly coated with being embedded into graphite granule surface.
25. as claimed in claim 23 vehicle-mounted with energy storage lithium ion battery negative materials it is characterised in that described vehicle-mounted with In energy storage lithium ion battery negative material, the content of conductive material is 0.1-20.0wt%.
26. as claimed in claim 24 vehicle-mounted with energy storage lithium ion battery negative materials it is characterised in that described vehicle-mounted with In energy storage lithium ion battery negative material, the content of conductive material is 0.5-18.0wt%.
27. as claimed in claim 23 vehicle-mounted with energy storage lithium ion battery negative materials it is characterised in that described vehicle-mounted with In energy storage lithium ion battery negative material, the content of conductive material is 1-15.0wt%.
28. as claimed in claim 23 vehicle-mounted with energy storage lithium ion battery negative materials it is characterised in that described vehicle-mounted with In energy storage lithium ion battery negative material, the content of disordered structure material with carbon element clad is 0.1-20.0wt%.
29. as claimed in claim 23 vehicle-mounted with energy storage lithium ion battery negative materials it is characterised in that described vehicle-mounted with In energy storage lithium ion battery negative material, the content of disordered structure material with carbon element clad is 0.5-18.0wt%.
30. as claimed in claim 23 vehicle-mounted with energy storage lithium ion battery negative materials it is characterised in that described vehicle-mounted with In energy storage lithium ion battery negative material, the content of disordered structure material with carbon element clad is 1-15.0wt%；
31. as claimed in claim 23 vehicle-mounted with energy storage lithium ion battery negative materials it is characterised in that described vehicle-mounted with In energy storage lithium ion battery negative material, disordered structure material with carbon element clad and the mass ratio of graphite type material are 0.1:100- 20.0:100.
32. as claimed in claim 23 vehicle-mounted with energy storage lithium ion battery negative materials it is characterised in that described vehicle-mounted with In energy storage lithium ion battery negative material, disordered structure material with carbon element clad and the mass ratio of graphite type material are 0.5:100- 18.0:100.
33. as claimed in claim 23 vehicle-mounted with energy storage lithium ion battery negative materials it is characterised in that described vehicle-mounted with In energy storage lithium ion battery negative material, disordered structure material with carbon element clad and the mass ratio of graphite type material are 0.5:100- 15.0:100.
34. as claimed in claim 23 vehicle-mounted with energy storage lithium ion battery negative materials it is characterised in that described vehicle-mounted with In energy storage lithium ion battery negative material, graphite type material and the mass ratio of conductive material are 10:0.01-10:10.0.
35. as claimed in claim 23 vehicle-mounted with energy storage lithium ion battery negative materials it is characterised in that described vehicle-mounted with In energy storage lithium ion battery negative material, graphite type material and the mass ratio of conductive material are 10:0.1-10:8.0.
36. as claimed in claim 23 vehicle-mounted with energy storage lithium ion battery negative materials it is characterised in that described vehicle-mounted with In energy storage lithium ion battery negative material, graphite type material and the mass ratio of conductive material are 10:0.5-10:6.0.
37. a kind of vehicle-mounted with energy storage lithium ion batteries it is characterised in that described vehicle-mounted comprise with energy storage lithium ion battery as Vehicle-mounted and energy storage lithium ion battery negative material described in claim 23.
CN201310554920.3A 2013-11-08 2013-11-08 Vehicle-mounted and energy-storage lithium ion battery cathode material and preparation method thereof Active CN103560247B (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201310554920.3A CN103560247B (en) 2013-11-08 2013-11-08 Vehicle-mounted and energy-storage lithium ion battery cathode material and preparation method thereof
KR1020140071407A KR20150053693A (en) 2013-11-08 2014-06-12 Anode Materials of Lithium Ion Battery for Vehicle and Energy Storage, and Preparation Method thereof
JP2014156362A JP6152076B2 (en) 2013-11-08 2014-07-31 Lithium ion battery negative electrode material for in-vehicle use and energy storage, and manufacturing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310554920.3A CN103560247B (en) 2013-11-08 2013-11-08 Vehicle-mounted and energy-storage lithium ion battery cathode material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103560247A CN103560247A (en) 2014-02-05
CN103560247B true CN103560247B (en) 2017-02-01

Family

ID=50014448

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310554920.3A Active CN103560247B (en) 2013-11-08 2013-11-08 Vehicle-mounted and energy-storage lithium ion battery cathode material and preparation method thereof

Country Status (3)

Country Link
JP (1) JP6152076B2 (en)
KR (1) KR20150053693A (en)
CN (1) CN103560247B (en)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103811718B (en) * 2014-02-20 2016-08-17 深圳市贝特瑞新能源材料股份有限公司 The preparation method of a kind of graphene-based composite negative pole material and prepared negative material and lithium ion battery
CN104124431B (en) * 2014-08-12 2016-11-23 长沙赛维能源科技有限公司 A kind of lithium ion battery graphite cathode material and preparation method thereof
WO2017216822A1 (en) * 2016-06-13 2017-12-21 Nec Corporation Fast chargeable lithium ion batteries with nano-carbon coated anode material and imide anion based lithium salt electrolyte
CN106410264B (en) * 2016-06-23 2018-09-04 河南大学 The molten salt preparation method of lithium ion battery negative material zinc titanate
CN106207180B (en) * 2016-07-19 2019-01-15 福建翔丰华新能源材料有限公司 A kind of preparation method of porous hollow graphite material
CN107758653A (en) * 2016-08-17 2018-03-06 宁波杉杉新材料科技有限公司 A kind of preparation method of lithium ion battery composite particles graphite cathode material
CN106848468B (en) * 2017-01-25 2019-05-14 天津市捷威动力工业有限公司 A kind of method and apparatus of the cleaning solution preparation hard charcoal coated graphite using recycling
CN108039493B (en) * 2017-11-22 2020-06-23 深圳市德方纳米科技股份有限公司 Conductive slurry for lithium ion battery and preparation method and application thereof
KR102040212B1 (en) 2017-12-14 2019-11-04 자동차부품연구원 Material for electrode of lithium ion secondary battery and methods of fabricating the same
CN108598437A (en) * 2018-05-03 2018-09-28 合肥宸翊商贸有限公司 Lithium ion battery negative material and preparation method thereof suitable for low temperature
CN110854371A (en) * 2019-11-26 2020-02-28 宁夏百川新材料有限公司 Carbon composite negative electrode material and preparation method thereof
CN112563473A (en) * 2020-12-28 2021-03-26 山东天瀚新能源科技有限公司 Anode material, anode pole piece, preparation method and application
CN114874576B (en) * 2021-02-05 2023-08-22 深圳市研一新材料有限责任公司 High-molecular polymer composite coating material, preparation method and application thereof
CN113078000B (en) * 2021-04-01 2022-08-30 浙江科技学院 Preparation method of flexible electrode material of high-load lignin carbon spheres
CN113265008B (en) * 2021-07-02 2022-03-01 重庆力宏精细化工有限公司 High-viscosity lithium carboxymethyl cellulose and preparation method and application thereof
CN116283292A (en) * 2021-12-21 2023-06-23 湖南中科星城石墨有限公司 Quick-charge graphite negative electrode material, preparation method thereof and lithium ion battery
CN114804095B (en) * 2022-04-27 2023-12-12 中南大学 Graphite negative electrode active material prepared from spheroidized graphite micropowder waste, and preparation method and application thereof
CN115117355B (en) * 2022-08-24 2022-11-15 湖南金阳烯碳新材料股份有限公司 Preparation method and application of negative electrode material for secondary battery
CN115117366B (en) * 2022-08-29 2022-11-18 天津凯普瑞特新能源科技有限公司 Carbon-coated aluminum foil, manufacturing process thereof and lithium ion battery
CN115692910B (en) * 2022-12-28 2023-03-03 湖南金阳烯碳新材料股份有限公司 Method for recovering waste negative electrode material of lithium ion battery

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1624955A (en) * 2003-12-01 2005-06-08 上海杉杉科技有限公司 Method for manufacturing carbon nagtive electrode material of lithium ion cell
CN1702893A (en) * 2005-04-20 2005-11-30 深圳市贝特瑞电子材料有限公司 Cathode material of Li-ion battery and preparation method, battery cathode, battery thereof
CN101147284A (en) * 2005-03-23 2008-03-19 日本瑞翁株式会社 Binder for electrode of nonaqueous electrolyte secondary battery, electrode, and nonaqueous electrolyte secondary battery
CN101412510A (en) * 2007-10-15 2009-04-22 台湾松下能源股份有限公司 Composite graphite for lithium secondary battery and manufacturing method thereof
CN101887967A (en) * 2010-06-18 2010-11-17 深圳市贝特瑞新能源材料股份有限公司 Lithium ion battery cathode material and preparation method thereof
CN102473898A (en) * 2009-07-01 2012-05-23 日本瑞翁株式会社 Electrode for secondary battery, slurry for secondary battery electrode, and secondary battery

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004196609A (en) * 2002-12-19 2004-07-15 Jfe Chemical Corp Production method for composite graphite particle, composite graphite particle, cathode material for lithium ion secondary battery, and lithium ion secondary battery
JP2005097010A (en) * 2003-09-22 2005-04-14 Showa Denko Kk Carbon material, production method therefor and its application
JP4748949B2 (en) * 2004-03-31 2011-08-17 三洋電機株式会社 Nonaqueous electrolyte secondary battery
JP4537809B2 (en) * 2004-09-13 2010-09-08 リグナイト株式会社 Carbon / phenolic resin composite material, carbon / phenolic resin composite cured material, carbon / phenolic resin composite carbonized material, fuel cell separator, conductive resin composition, battery electrode, electric double layer capacitor
JP5143437B2 (en) * 2007-01-30 2013-02-13 日本カーボン株式会社 Method for producing negative electrode active material for lithium ion secondary battery, negative electrode active material, and negative electrode
JP2009158105A (en) * 2007-12-25 2009-07-16 Tokai Carbon Co Ltd Method of manufacturing composite carbon material for negative electrode material of lithium ion secondary battery
WO2010100764A1 (en) * 2009-03-02 2010-09-10 Showa Denko K.K. Composite graphite particles and lithium secondary battery using the same
JP5413645B2 (en) * 2009-03-13 2014-02-12 東海カーボン株式会社 Method for producing negative electrode material for lithium secondary battery
JP5150010B1 (en) * 2010-07-02 2013-02-20 シェンヅェン ビーティーアール ニュー エナジー マテリアルズ インコーポレイテッド Method for producing lithium ion battery negative electrode material
JP6102074B2 (en) * 2011-03-29 2017-03-29 三菱化学株式会社 Non-aqueous secondary battery negative electrode carbon material, negative electrode, and non-aqueous secondary battery
EP2698851B1 (en) * 2011-04-13 2018-12-12 Sei Corporation Electrode material for lithium secondary battery and lithium secondary battery
CN103620836B (en) * 2011-06-30 2016-03-23 三洋电机株式会社 Rechargeable nonaqueous electrolytic battery and manufacture method thereof
JP2013222641A (en) * 2012-04-18 2013-10-28 Showa Denko Kk Negative electrode material for lithium ion battery and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1624955A (en) * 2003-12-01 2005-06-08 上海杉杉科技有限公司 Method for manufacturing carbon nagtive electrode material of lithium ion cell
CN101147284A (en) * 2005-03-23 2008-03-19 日本瑞翁株式会社 Binder for electrode of nonaqueous electrolyte secondary battery, electrode, and nonaqueous electrolyte secondary battery
CN1702893A (en) * 2005-04-20 2005-11-30 深圳市贝特瑞电子材料有限公司 Cathode material of Li-ion battery and preparation method, battery cathode, battery thereof
CN101412510A (en) * 2007-10-15 2009-04-22 台湾松下能源股份有限公司 Composite graphite for lithium secondary battery and manufacturing method thereof
CN102473898A (en) * 2009-07-01 2012-05-23 日本瑞翁株式会社 Electrode for secondary battery, slurry for secondary battery electrode, and secondary battery
CN101887967A (en) * 2010-06-18 2010-11-17 深圳市贝特瑞新能源材料股份有限公司 Lithium ion battery cathode material and preparation method thereof

Also Published As

Publication number Publication date
KR20150053693A (en) 2015-05-18
CN103560247A (en) 2014-02-05
JP2015095455A (en) 2015-05-18
JP6152076B2 (en) 2017-06-21

Similar Documents

Publication Publication Date Title
CN103560247B (en) Vehicle-mounted and energy-storage lithium ion battery cathode material and preparation method thereof
CN109748587B (en) High-capacity quick-charging graphite negative electrode material and preparation method thereof
CN104085883B (en) A kind of man-made graphite cathode material for lithium ion battery and preparation method thereof
CN109671942A (en) A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof
CN103633295B (en) A kind of Si-C composite material, lithium ion battery and its preparation method and application
CN111224078A (en) Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery negative electrode
CN107369823A (en) A kind of lithium ion battery artificial composite cathode material of silicon/carbon/graphite and preparation method thereof
WO2016201940A1 (en) Preparation method for carbon/graphite composite anode material
CN102637847B (en) Method for preparing high-dispersity lithium battery anode and cathode slurry
CN107706387B (en) Composite negative electrode material, preparation method thereof and lithium ion battery
CN103346293A (en) Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery
KR20150098548A (en) A graphene-based composite material preparation method, anode materials and lithium ion battery
CN101764219A (en) Cathode materials for carbon nano-tube composite lithium ion battery and preparation method thereof
CN103855369A (en) Lithium battery negative electrode material and preparation method thereof
CN103346325A (en) Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery
CN105720258B (en) Lithium ion battery negative material and its preparation method and application, lithium ion battery
CN103840161A (en) Method for preparing lithium battery negative electrode material, and lithium battery negative electrode sheet
WO2016202164A1 (en) Preparation method for preparing composite carbon/graphite/tin negative-electrode material
CN102110813B (en) Graphite material at negative pole of lithium ion battery and preparation method thereof
CN106340653A (en) Wrinkle-like graphene composite conductive agent and preparation method
CN102683646B (en) Preparation method of composite negative electrode material of lithium ion battery
CN103915609A (en) Silicon-silicon oxide-carbon composite material, lithium ion secondary battery anode material, preparation methods of two and application of composite material
CN110350161A (en) A kind of preparation method of silicon-carbon cathode presoma
CN105244485A (en) High capacity and high magnification composite graphite material for lithium ion battery and preparation method thereof
CN112652753A (en) Lithium ion battery negative electrode material, lithium ion battery and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20180719

Address after: 213299 No. 399, Ming Hu Road, Jintan District, Changzhou City, Suzhou, Jiangsu.

Patentee after: Bethel (Jiangsu) new Mstar Technology Ltd

Address before: 518106 Shenzhen Guangming New Area Gongming Office, Shenzhen City, Guangdong Province

Patentee before: Shenzhen BTR New Energy Material Co., Ltd.

CP02 Change in the address of a patent holder
CP02 Change in the address of a patent holder

Address after: 213299 No. 399, Ming Hu Road, Jintan District, Changzhou, Jiangsu.

Patentee after: Bethel (Jiangsu) new Mstar Technology Ltd

Address before: 213299 No. 399, Ming Hu Road, Jintan District, Changzhou City, Suzhou, Jiangsu.

Patentee before: Bethel (Jiangsu) new Mstar Technology Ltd