CN1913200B - Silicon carbone compound negative polar material of lithium ion battery and its preparation method - Google Patents

Silicon carbone compound negative polar material of lithium ion battery and its preparation method Download PDF

Info

Publication number
CN1913200B
CN1913200B CN200610062255A CN200610062255A CN1913200B CN 1913200 B CN1913200 B CN 1913200B CN 200610062255 A CN200610062255 A CN 200610062255A CN 200610062255 A CN200610062255 A CN 200610062255A CN 1913200 B CN1913200 B CN 1913200B
Authority
CN
China
Prior art keywords
carbon
silicon
powder
lithium
compound
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
CN200610062255A
Other languages
Chinese (zh)
Other versions
CN1913200A (en
Inventor
岳敏
张万红
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.)
BTR New Material Group Co Ltd
Original Assignee
BEITERUI ELECTRONIC MATERIALS Co Ltd SHENZHEN CITY
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 BEITERUI ELECTRONIC MATERIALS Co Ltd SHENZHEN CITY filed Critical BEITERUI ELECTRONIC MATERIALS Co Ltd SHENZHEN CITY
Priority to CN200610062255A priority Critical patent/CN1913200B/en
Priority to PCT/CN2007/000130 priority patent/WO2008025188A1/en
Priority to JP2009524864A priority patent/JP5180211B2/en
Priority to KR1020097003478A priority patent/KR101085611B1/en
Publication of CN1913200A publication Critical patent/CN1913200A/en
Application granted granted Critical
Publication of CN1913200B publication Critical patent/CN1913200B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • H01M4/62—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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

This invention discloses a silicon carbon compound negative material and its preparation method for Li ionic batteries, which takes silicon and carbon phase compound particles as the base of sphericity or its like covered by a carbon layer. The preparation method includes: crushing the carbon phase particles to be mixed with silicon phase particles and sized to become a compound particle matrix to be covered with the precursor of the organic pyrolyzed carbon then to be carbonized and crushed. Compared with the current technology, this invention takes the compound material of Si and C phase particles as the matrix covered by a compound negative material, in which, the reversible specific volume of which is greater than 450mAh/g, the first circulation coulomb efficiency is greater than 85% and the volume holding rate for 200 times is greater than 80% to greatly reduce the volume effect of the Si activated material when absorbing and discharging Li and improve the diffusion performance of Li in activated materials.

Description

Silicon-carbon composite cathode material of lithium ion battery and preparation method thereof
Technical field
The present invention relates to a kind of cell negative electrode material and preparation method thereof, particularly silicon-carbon composite cathode material of a kind of lithium ion battery and preparation method thereof.
Background technology
Since nineteen ninety Japan Sony company take the lead in succeeding in developing lithium ion battery and with its commercialization since, lithium ion battery has obtained fast development.Nowadays lithium ion battery has been widely used in civilian and military every field.Along with the continuous progress of science and technology, people have proposed more higher requirements to the performance of battery: the miniaturization of electronic equipment and individualized development need battery to have the specific energy output of littler volume and Geng Gao; The Aero-Space energy requires battery to have cycle life, better the security performance of low temperature charge-discharge performance and Geng Gao; Electric automobile needs the battery of big capacity, low cost, high stability and security performance.Succeeding in developing of lithium ion battery, should at first give the credit to electrode material, the particularly breakthrough of carbon negative pole material, in numerous material with carbon elements, graphitized carbon material is owing to have good layer structure, be very suitable for the embedding of lithium ion and take off embedding, the graphite of formation-lithium intercalation compound Li-GIC has higher specific capacity, near LiC 6Theoretical specific capacity 372mAh/g; Have favorable charge-discharge voltage platform and lower doff lithium current potential simultaneously, with the positive electrode that the lithium source is provided, as LiCoO 2, LiNiO 2And LiMn 2O 4Better etc. matching, as to be formed battery average voltage height, discharge is steady, and therefore the commercialization lithium ion battery adopts the graphite-like material with carbon element as negative material in a large number at present.
But graphite type material is near theoretical capacity at present, in order to realize the safe operability under the high current density, reduce irreversible capacity loss first, satisfy future market lithium ion battery high-energy-density, the requirement of high-specific-power, the exploitation of new type lithium ion electrode material has urgency, academia is very active to the research of such electrode material at present, discovering in the negative material as Al, Sn, Sb, Si etc., these can form the metal of alloy and alloy thereof as lithium ion battery negative material with lithium, promptly be meant Al, Sn, Sb, Si or its alloy are as negative material, and the amount of its reversible lithium storage is far longer than the graphite-like negative material.But the bulk effect that such negative material is high causes relatively poor cyclical stability, makes these systems still have certain distance apart from degree of being practical.Therefore, how to make these high material practicability of storing up the lithium performances become the hot issue of current Study on Li-ion batteries using.
In the research of non-carbon back negative material, silica-base material is because of having high theoretical lithium storage content, and as single crystalline Si: 4200mAh/g, low embedding lithium current potential has higher stability and gets most of the attention than other metal and material.The Si sill if can successful Application, as the negative material of lithium ion battery, will produce epoch making significance to the development of lithium ion battery, also can produce significant impact to the development of information, energy industry.But the same with metal_based material, there is serious bulk effect in silica-base material under high level removal lithium embedded condition, causes the cyclical stability instability of electrode, and its first irreversible capacity height, has limited its application as lithium ion battery negative material.Therefore, present many researchers are devoted to the modification and the optimal design of this high storage lithium performance materials.Adopt the compound system of the silicon grain outer wrapping amorphous carbon layer particle of CVD method preparation as the subordinate's of Hitachi Maxwell company, the structure and the electric conductivity of silicon materials have been improved, can restrain lithium to a certain extent and embed and deviate from bulk effect in the process, thereby the cycle performance of such material is improved.But the process of CVD method is difficult to control, and uncertain factor is many, therefore is difficult to realize producing in batches.People such as C.S.Wang adopt graphite and silica flour to have the higher lithium of embedding first capacity by the silicon/carbon binary system composite materials of the method preparation of mechanical ball milling, but its charge-discharge performance instability, especially initial several cycles capacity attenuation very fast (J.Electrochem.Soc., 8 (1998): 2751-2758).S.B.Ng etc. adopt the similar cancellated graphite-silicon/Si (OCH of sol-gel process preparation 3) 4Though composite material has metastable mechanical performance, help the raising of cycle performance, but then, the cancellated existence of Si-O also hinders the dispersal behavior of lithium, the embedded quantity of lithium is reduced, can not give full play of high capacity characteristics (J.Power Sources, 94 (2001): 63-67) of Si.
At the serious bulk effect of silicon owing to generation when the electrochemical lithium embedding is taken off, utilize the mode of volume compensation, prepare a kind of silicon composite that contains, keep the height ratio capacity characteristic of silicon, make the change in volume of overall electrode be controlled at reasonable level simultaneously, increase cyclical stability.Energy density with the negative material that improves lithium ion battery makes this negative material have higher specific capacity than carbon negative pole material commonly used in the present commercial lithium ion battery, satisfies the energy density requirement that all kinds of portable power consumption equipments improve day by day to battery.
Summary of the invention
The purpose of this invention is to provide a kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof, the technical problem that solve is to improve the specific capacity of battery, and tool has excellent cycle performance and multiplying power discharging property concurrently.
The present invention is by the following technical solutions: a kind of silicon-carbon composite cathode material of lithium ion battery, described silicon-carbon composite cathode material of lithium ion battery is a matrix with the composite particles of silicon phase particle and carbon phase particle, matrix is spherical in shape or class is spherical, and matrix is coated with carbon coating layer.
Carbon coating layer of the present invention is an organic substance pyrolytic carbon coating layer.
Carbon coating layer of the present invention contains conductive carbon.
Lithium compound is contained on carbon coating layer of the present invention surface.
Coating thickness of the present invention is 0.1～5 μ m, and the ratio that the organic substance pyrolytic carbon accounts for negative material is 0.5～20wt%, and the ratio that conductive carbon accounts for negative material is 0.5～5wt%.
The average grain diameter of silicon-carbon composite cathode material of the present invention is 5～60 μ m, specific area 1.0～4.0m 2/ g, tap density 0.7～2.0g/cm 3
Silicon phase particle of the present invention is a compound between elemental silicon, silicon oxide compound SiOx, siliceous solid solution or siliceous metal, and silicon phase particle accounts for 1～50wt% of composite particles matrix, wherein 0＜x≤2.
Silicon phase particle of the present invention accounts for the ratio of composite particles matrix preferably at 5～30wt%.
Silicon phase particle of the present invention accounts for the ratio of composite particles matrix further preferably at 10～20wt%.
Compound between siliceous solid solution of the present invention or siliceous metal, be by any one or two kinds of elements in the IIA family element in the silicon and the periodic table of chemical element, any or the three kinds of elements in the transition metal, any one or two kinds of elements in the IIIA family element, or any one or two kinds of elements in the IVA family element outside the silica removal constitute.
Carbon phase particle of the present invention is any one or more than one the mixing in natural flake graphite, micro crystal graphite, Delanium, MCMB and the coke.
Organic substance pyrolytic carbon of the present invention is by water miscible polyvinyl alcohol, butadiene-styrene rubber breast, carboxymethyl cellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, phenolic resins, the epoxy resin of organic solvent system, glucose, sucrose, fructose, cellulose, starch or pitch are presoma, through the formed pyrolytic carbon of high temperature cabonization.
Conductive carbon of the present invention is acetylene black, carbon nano-tube, nano-sized carbon microballoon, carbon fiber or conductive carbon black.
Lithium-containing compound of the present invention is lithia, lithium carbonate, lithium fluoride, lithium chloride, lithium nitrate or lithium hydroxide.
A kind of preparation method of silicon-carbon composite cathode material of lithium ion battery may further comprise the steps: one, silicon phase particle is crushed to 0.1～1 μ m, makes ultra-fine silicon phase particle; With granularity＜75 μ m, material carbon crushing and classification, shaping and the purification process of carbon content more than 95% prepares carbon content more than 99.9%, and particle diameter is the carbon phase particle of 0.1～5 μ m; Two, with silicon phase particle and carbon phase particle mixing granulation, make the composite particles matrix; Three, the composite particles matrix is mixed or wet method stirs 1～12h vapour deposition or coat granulation under 100～400 ℃ of conditions then with the presoma of the organic substance pyrolytic carbon that accounts for composite particles matrix 1～25wt%; Four, the particle after will coating carries out carbonization treatment, and heating is 450 to 1500 ℃ in protective atmosphere, be incubated 1 to 10 hour, reduces to room temperature then, the formation carbon coating layer; Five, fragmentation is broken up to 5～40 μ m, makes silicon-carbon composite cathode material of lithium ion battery.
The inventive method with described fragmentation break up to the powder of 5～40 μ m with account for powder 1～30wt% pitch and mix coating; carry out carbonization treatment then; heating is 450 to 1500 ℃ in protective atmosphere; be incubated 1 to 10 hour; reduce to room temperature then, the gained powder mixes coating with the conductive carbon that accounts for powder 0.5～5wt%, mixes 1～6 hour in mixer or surface coating modification machine; and use ultrasonic wave to disperse 1～30 minute, be crushed to 5～60 μ m.
The inventive method is with the described compound dipping lithium-containing compound that is crushed to 5～60 μ m, and it is in 0.2～10wt% lithium-containing compound solution that the compound powder is immersed in concentration, solid-to-liquid ratio 0.1～2, dip time 1～48 hour.
The silicon phase particle of the inventive method is a compound between elemental silicon, silicon oxide compound SiOx, siliceous solid solution or siliceous metal; silicon phase particle accounts for 1～50wt% of composite particles matrix; 0＜x≤2 wherein; compound between siliceous solid solution or siliceous metal; be by any one or two kinds of elements in the IIA family element in the silicon and the periodic table of chemical element, any or the three kinds of elements in the transition metal, any one or two kinds of elements in the IIIA family element, or any one or two kinds of elements in the IVA family element outside the silica removal constitute.
The carbon phase particle of the inventive method is any one in natural flake graphite, micro crystal graphite, Delanium, MCMB and coke or more than one mixing, and carbon phase particle accounts for 50～99wt% of described composite particles matrix.
The ratio that the coating layer of the inventive method accounts for composite material is 1～25wt%.
The presoma of the organic substance pyrolytic carbon of the inventive method is water miscible polyvinyl alcohol, butadiene-styrene rubber breast, carboxymethyl cellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile organic substance, phenolic resins, the epoxy resin of organic solvent system, glucose, sucrose, fructose, cellulose or starch.
The conductive carbon of the inventive method is acetylene black, carbon nano-tube, nano-sized carbon microballoon, carbon fiber or conductive carbon black.
The lithium-containing compound of the inventive method is lithia, lithium carbonate, lithium fluoride, lithium chloride, lithium nitrate or lithium hydroxide.
The silicon phase particle ball milling of the inventive method carries out in protective atmosphere, and protective atmosphere is any or several mixing in argon gas, hydrogen or the nitrogen.
The inventive method with silicon phase particle and carbon phase particle mixing granulation the time, mixing granulation is 1～6 hour in the mixing granulation machine.
The present invention compared with prior art, composite material by silicon phase particle and carbon phase particle is a matrix, spherical in shape or class is spherical, the silicon-carbon composite cathode material of lithium ion battery that is coated with coating layer has very high electrochemical reversible suction and puts lithium capacity and good cyclical stability, resulting negative material reversible specific capacity is greater than 450mAh/g, coulombic efficiency circulate first greater than 85%, circulate 200 capability retentions greater than 80%, obviously alleviate siliceous active material and inhale bulk effect when putting lithium, improve the dispersal behavior of lithium in active material, compare with elemental silicon and to have improved efficient and cyclical stability first, reduced the consumption of positive electrode, but the doff lithium current potential is higher than lithium ion battery negative materials commonly used such as carbonaceous mesophase spherules, prevent lithium metal separating out in negative terminal surface, have good large current discharging capability, and it is simple to have preparation technology, advantages such as easy operating are applicable to all kinds of portable device, the lithium ion battery negative material that electric tool etc. use.
Description of drawings:
Fig. 1 is the electromicroscopic photograph (1000 times) of the silicon-carbon composite cathode material of lithium ion battery of the embodiment of the invention 1.
Fig. 2 is the electromicroscopic photograph (5000 times) of the silicon-carbon composite cathode material of lithium ion battery of the embodiment of the invention 1.
Fig. 3 is the first charge-discharge curve chart of the material of the embodiment of the invention 1.
Fig. 4 is the XRD figure of the material of the embodiment of the invention 1.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.
Silicon-carbon composite cathode material of lithium ion battery of the present invention is to be matrix with silicon phase particle and carbon phase particle, is coated with the composite carbon coating layer.Silicon phase particle in the matrix is elemental silicon, silicon oxide compound SiOx, compound between 0＜x≤2, siliceous solid solution or siliceous metal wherein, compound between siliceous solid solution wherein or siliceous metal, be by any one or two kinds of elements in the IIA family element in the silicon and the periodic table of chemical element, any or the three kinds of elements in the transition metal, any one or two kinds of elements in the IIIA family element, or any one or two kinds of elements formations in the IVA family element outside the silica removal, silicon phase particle accounts for 1～50wt% of composite particles matrix; Carbon phase particle in the matrix is any one or more than one the mixing in natural flake graphite, micro crystal graphite, Delanium, MCMB and the coke.Coating thickness is 0.1～5 μ m, and the ratio that the organic substance pyrolytic carbon accounts for negative material is 0.5～20wt%, and the ratio that conductive carbon accounts for negative material is 0.5～5wt%.Organic substance pyrolytic carbon in the coating layer is by water miscible polyvinyl alcohol, butadiene-styrene rubber breast, carboxymethyl cellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, phenolic resins, the epoxy resin of organic solvent system, glucose, sucrose, fructose, cellulose, starch or pitch are presoma, through the formed pyrolytic carbon of high temperature cabonization; Conductive carbon in the coating layer is acetylene black, carbon nano-tube, nano-sized carbon microballoon, carbon fiber or conductive carbon black Super-P.The lithium-containing compound of the surperficial oxide containing lithium of negative material composite particles, lithium carbonate, lithium fluoride, lithium chloride, lithium nitrate or lithium hydroxide.
Silicon-carbon composite cathode material of lithium ion battery of the present invention has following technical characterictic: average grain diameter is 5～60 μ m, specific area 1.0～4.0m 2/ g, tap density 0.7～2.0g/cm 3Above-described average grain diameter is measured by the Malvern laser particle analyzer, and specific area adopts the BET method of nitrogen replacement to measure, and tap density adopts Quantachrome AutoTap tap density instrument to record.
Adopt above-mentioned material and ratio to prepare silicon-carbon composite cathode material of lithium ion battery of the present invention, may further comprise the steps: one, with silicon phase particle at air or nonoxidizing atmosphere, as ball milling to 0.1～1 μ m in any or several mist in argon gas, hydrogen or the nitrogen, make ultra-fine silicon phase particle; Two, with granularity＜75 μ m, material carbon phase crushing and classification, shaping and the purification process of carbon content more than 95% prepares carbon content more than 99.9%, and particle diameter is the carbon phase particle of 0.1～5 μ m; Three, silicon phase particle and the carbon phase particle that makes mixed in the mixing granulation machine 1～6 hour, make the composite particles matrix; Four, with the composite particles matrix with account for composite particles matrix 1～25wt% organic substance pyrolytic carbon presoma ball milling or wet method mixes 1～12h, vapour deposition or coat granulation under 100～400 ℃ of conditions then; Five, the particle after will coating carries out carbonization treatment, and heating is 450 to 1500 ℃ in protective atmosphere, be incubated 1 to 10 hour, reduces to room temperature then, the formation carbon coating layer, and fragmentation is broken up to 5～40 μ m; Six, fragmentation is broken up to the powder of 5～40 μ m and in mixer, mix coating with the pitch that accounts for powder 1～30wt%; Seven, carry out carbonization treatment behind the coating pitch, heating is 450 to 1500 ℃ in protective atmosphere, is incubated 1 to 10 hour, reduces to room temperature then, is crushed to 5～60 μ m; Eight, the compound that obtains is mixed coating with the conductive carbon that accounts for powder 0.5～5wt%, mixed 1～6 hour in mixer or surface coating modification machine, ultrasonic wave disperseed 1～30 minute, and ultrasonic frequency 40kHz～28kHz, ultrasonic power are 50W～3600W; Nine, dipping lithium-containing compound: it is in 0.2～10wt% lithium-containing compound solution that the compound powder is immersed in concentration, solid-to-liquid ratio 0.1～2, and dip time 1-48 hour, adjust granularity to 5～60 μ m, obtain silicon-carbon composite cathode material of lithium ion battery.
Silicon Si is by forming intermetallic compound with lithium, as Li 22Si 5Deng making lithium reversibly occlusion and release.Use the negative material of Si as lithium rechargeable battery, the theoretical capacity that discharges and recharges of Si can be up to 4200mAh/g, 9783mAh/cm 3, proportion calculates according to 2.33, is higher than the graphite type material of using now far away, theoretical capacity 372mAh/g or 844mAh/g, and proportion calculates according to 2.27.But the negative material of making by Si, be accompanied by serious change in volume in the absorption of Li when discharging,, cause very easily that the Si negative pole cracks, efflorescence up to 300%, capacity is sharply decayed in the charge and discharge cycles process, and therefore pure Si can not directly be used as ion secondary battery cathode material lithium.
In research, find product of the present invention and preparation method, when containing the Si Dispersion of Particles when material with carbon element matrix or Si phase particle surface are contained the solid solution of Si or intermetallic compound and surround, the change in volume that the occlusion of lithium Li and release are followed is cushioned or restricts, can prevent the electrode efflorescence, improve cycle life.For this effect is given full play to more, the preferred smaller particle size of Si phase particle.The present invention is silicon phase particle ball milling to 0.1～1 μ m in protective atmosphere of 1～40 μ m with granularity, makes ultra-fine silicon phase particle, as the negative electrode active material in the composite material.When the average grain diameter of Si phase particle during greater than 1 μ m, the volume sink effect of matrix weakens, and influences the raising of the cycle performance of composite material; If the average grain diameter of Si phase particle is during less than 0.1 μ m, the preparation difficulty strengthens, and causes the active particle surface oxidation easily, increases the chance of reuniting mutually between particle, influences the specific capacity of negative material.The particle diameter of Si phase particle adopts scanning electron microscopy SEM to measure, and also can use additive method, and the meso-position radius in the volume particle size distribution that records such as laser particle analyzer is as average grain diameter.Adopted Britain Malvern Mastersizer 2000 laser particle size analyzers to measure the average grain diameter of particle among the embodiment.
Si phase particle accounts for 1～50wt% of composite particles matrix in the silicon-carbon composite cathode material of the present invention.When the ratio of Si phase particle surpassed 50wt%, matrix can not effectively cushion and absorb the bulk effect of Si; Otherwise if the ratio of Si phase particle is during less than 1wt%, the capacity of negative material can not effectively promote.The ratio of Si phase particle is preferably at 5～30wt%, more preferably at 10～20wt%.
Si phase particle can be elemental silicon, silicon oxide compound SiOx, compound between 0＜x≤2, silicon solid solution or siliceous metal.Compound is by any one or two kinds of elements in the IIA family element in the silicon and the periodic table of chemical element, any or the three kinds of elements in the transition metal, any one or two kinds of elements in the IIIA family element between silicon solid solution or siliceous metal, or any one or two kinds of elements in the IVA family element outside the silica removal constitute.These elements are as active element that can reversible lithium storage, can increase the specific capacity of negative material, some element is then for storing up the nonactive element of lithium, put the caused bulk effect of lithium and/or, improve the cyclical stability of material but can be used as buffering and absorb the active material suction as the element that improves conductivity of composite material.Factors such as lithium capacity, buffer Si bulk effect, the effect of improving conductivity of composite material and resource thereof are put in the suction of considering element, these elements are preferably Mg, Ca and the Ba of IIA family element, the Ti of transition metal, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ag, Ce and Nd, IIIA family element al, Ga and In, and Ge, Sn and the Sb of IVA family element.In these elements, more preferably Mg, Ca, Fe, Co, Ni and Cu.
In order to prepare silicon-carbon composite cathode material of lithium ion battery of the present invention, improve the chemical property of negative material, method of the present invention to graphite and Si mutually particle carried out mixing granulation, compound coating and surface modification treatment.
As shown in Figure 1 and Figure 2, the microscopic characteristics of scanning electron microscope observation composite material, silicon-carbon composite cathode material of lithium ion battery of the present invention, composite material with silicon phase particle and carbon phase particle is a matrix, be coated with the composite carbon coating layer, microscopic feature with sphere or almost spherical, external coating are that one deck organic substance pyrolytic carbon and conductive carbon are formed coating layer, have improved the compatibility of graphite material and electrolyte.Coating layer has retrained the bulk effect of Si phase particle, improves electric conductivity, and can reversible doff lithium, has increased the capacity and the high current charge-discharge ability of negative material.The crystal layer spacing that coating layer is bigger has reduced the expansion amount of contraction that causes in the repeated charge process, has avoided the broken ring of negative material structure and peels off, and has improved cycle performance.
Fig. 3 is the first charge-discharge curve of the silico-carbo composite material of the embodiment of the invention 1 preparation, compares with graphite type material, has increased the high potential of Si on the charging and discharging curve, about 0.5V vs.Li/Li +Storage lithium platform, the lithium capacity is put in the suction of composite material raising by a relatively large margin.
Fig. 4 is the x-ray diffraction pattern XRD of the silico-carbo composite material of the embodiment of the invention 1 preparation, contrast the standard powder diffraction data PDF card of the international X-ray powder diffraction committee, the diffraction maximum that in the diffraction pattern of composite material, contains carbon PDF card number 41-1487 and silicon PDF card number 27-1402, illustrate that Si-C composite material of the present invention is by carbon and silicon, form.
Carbon phase particle in the above-mentioned matrix is any one or more than one the mixing in natural flake graphite, micro crystal graphite, Delanium, MCMB and the coke, and carbon phase particle accounts for 99～50wt% of described composite particles matrix.Carbon phase particle is mainly as absorbing and the buffer Si bulk effect of particle when lithium is put in suction mutually, and certain embedding lithium capacity is provided.Above-mentioned material is flexible material with carbon element, has preferably elasticity and has higher embedding lithium capacity.When carbon phase particle during less than 50wt%, Si phase particle can not effectively disperse, carbon phase particle absorb and the bulk effect effect of buffering active material Si relatively poor, unfavorable to the cycle performance of material; And when the ratio of carbon phase particle greater than 99% the time, the ratio of active Si reduces, thereby influences the raising of the specific capacity of material.
Above-mentioned composite carbon coating thickness is 0.1～5 μ m, calculates after the particle average grain diameter before and after being coated by the test of Malvern laser particle analyzer.The composite carbon coating layer contains organic substance pyrolytic carbon, conductive carbon, and the ratio of shared negative material is 1～25wt%, and wherein to account for the ratio of coating layer be 0.5～20wt% to the organic substance pyrolytic carbon, and the ratio that conductive carbon accounts for coating layer is 0.5～5wt%.When the composite carbon coating thickness, can not form complete coating layer, thereby influence the cyclical stability of negative material during less than 1wt% less than 0.1 μ m or the ratio that accounts for negative material; And blocked up when coating layer, when for example the ratio that accounts for negative material greater than 5 μ m or coating layer is greater than 25wt%, can influence the specific capacity of negative material and efficient first again, be unfavorable for the raising of the chemical property of negative material equally.
Organic substance pyrolytic carbon in the above-mentioned coating layer is by water miscible polyvinyl alcohol, butadiene-styrene rubber breast, carboxymethyl cellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile organic substance, phenolic resins, the epoxy resin of organic solvent system, glucose, sucrose, fructose, cellulose, starch or pitch etc. are presoma, through the formed pyrolytic carbon of high temperature cabonization.This type organic evenly is coated on the composite particles matrix surface as the presoma of later stage pyrolytic carbon or as binding agent, dispersant or the suspending agent of solution system when mixing with the composite particles matrix, and pyrolysis and thermal polycondensation reaction take place in the pyrolysis charring process in later stage.In the high temperature pyrolysis process, the compound that elements such as contained H, O, N are formed in the organic compound is decomposed, and the continuous cyclisation of carbon atom, aromatisation, result are that atoms such as H, O, N constantly reduce, and C constantly concentrates and enrichment.It is soft charcoal that above-mentioned organic substance forms easy graphitized charcoal through the liquid phase carbonization process, and perhaps only through the solid phase carbonization process, forming difficult graphitized charcoal is hard charcoal.This class pyrolytic carbon is ungraphitised carbon, contain the micropore that forms when more micromolecular compound pyrolysis is overflowed in the material, can absorb and cushion the bulk effect of active material in the charge and discharge process better, and the pyrolytic carbon layer spacing helps the embedding of lithium ion more greatly and deviates from.The Turbostratic of pyrolyzed carbon materials also prevented the solvation lithium ion altogether the graphite linings that causes of embedding peel off, improved cyclical stability.Conductive carbon in the coating layer is acetylene black, carbon nano-tube, nano-sized carbon microballoon, carbon fiber or conductive carbon black Super-P.
The composite particles matrix is mixed the method that coats do not limit especially with presoma, the conductive carbon of organic substance pyrolytic carbon, any known mixing granulator equipment all can use.Mixing to coat adopts mixing and ball milling, wet method to stir 1～12h, carry out vapour deposition afterwards and coat granulation, the temperature of vapour deposition and coating granulation is chosen in 100 ℃～400 ℃, when treatment temperature is lower than 100 ℃, powder drying speed is slower, covered effect is relatively poor, is easy to cause inter-adhesive between the particle, influences production efficiency and product quality; When treatment temperature is higher than 400 ℃, can cause coating layer carbonization or oxidation, also can influence covered effect.Subsequently, above-mentioned compound is carried out carbonization treatment, temperature is incubated 1～10 hour at 450 ℃～1500 ℃, reduces to room temperature then.For guaranteeing the coating layer densification, carry out secondary and coat processing, the secondary clad material is a pitch, covering amount is 1～30wt%.Above-mentioned carbonization treatment is carried out in nonoxidizing atmosphere, for example, carries out in mist, vacuum or the reducing atmosphere of nitrogen, argon gas, helium, neon or above-mentioned gas.Carburizing temperature is carried out at 450 ℃～1500 ℃, is incubated 1～10 hour, reduces to room temperature then.
Because composite material surface has coated agraphitic organic substance pyrolytic carbon, its electric conductivity descends, in order to improve the electric conductivity of negative material, guarantee the stable circulation of negative material and giving full play to of specific capacity, the present invention has carried out on the surface of composite material coating or conductive doped carbon is handled, and conductive carbon accounts for 0.5～5wt% of negative material.When the amount of conductive carbon during less than 0.5wt%, can't form continuous conductive network, the electric conductivity of material can not effectively improve; And, can the specific capacity and the efficiency for charge-discharge of material be had a negative impact again when the ratio of conductive carbon during greater than 5wt%.Suitable conduction addition is chosen between 0.5～5wt%.
The Si-C composite material after the mixing coating is handled and the method for coating of conductive carbon are not particularly limited, and any known mixing apparatus all can use, and as homogenizer, planetary stirring machine etc., the mixed processing time is 1～6 hour.For conductive carbon is uniformly dispersed, used the suspension of above-mentioned composite material of ultrasonic Treatment and conductive carbon, ultrasonic treatment time 1 minute～30 minutes, ultrasonic frequency 40kHz～28kHz, ultrasonic power are 50W～3600W.
In the first charge-discharge process of lithium ion battery, irreversible electrochemical reduction decomposition reaction will take place in solvent and electrolytic salt, generating products such as alkyl lithium carbonate, alkoxyl lithium carbonate is deposited on the negative material surface and constitutes one deck to electronic isolation and to the solid electrolyte film SEI film of ion conducting, the character of this layer passivating film affects the chemical property of negative material strongly, the generation of the electrode surface passivating film that one deck is thin and fine and close can stop the common embedding of solvation lithium ion, is the assurance that battery has higher cycle efficieny first and less loop attenuation.Kinetic property of the relative quantity of the basal plane of graphite microcrystal, end face, reactive difference and crystallite size, electrolyte component, reduction decomposition etc. has determined the compactness of the electrode surface passivating film that generated in the negative material.
Method of the present invention adopts the inorganic or organic solution system of lithium-containing compound to handle silicon-carbon composite cathode material, and the solid electrolyte film of lithium ion conducting that generates one deck densification on the negative material surface is to improve the first charge-discharge efficiency and the cyclical stability of negative material.Adopt the method for dipping lithium-containing compound finally to obtain silicon-carbon composite cathode material of lithium ion battery.
The lithium ion battery silicon-carbon composite cathode material that obtains after above-mentioned processing, its average grain diameter are 5～60 μ m, and specific area is 1.0～4.0m 2/ g, tap density is 0.7～2.0g/cm 3Above-described average grain diameter is measured by the Malvern laser particle analyzer, and specific area adopts the BET method of nitrogen replacement to measure, and tap density adopts Quantachrome AutoTap tap density instrument to record.
Embodiment 1, preparation silicon-carbon Si-G-C-Li 2CO 3Composite negative pole material: with granularity is silica flour mechanical high-energy ball milling to 0.5 μ m in argon gas atmosphere of 75 μ m, makes superfine silica powder; With granularity 70 μ m, the native graphite of carbon content more than 95% pulverized classification, shaping and purification process and prepared carbon content more than 99.9%, and particle diameter is the spherical graphite of 1 μ m; With the superfine silica powder 20wt% that makes and 80wt% spherical graphite mixing granulation 6 hours in twin-shaft mixer, make the composite particles matrix; The composite particles matrix is mixed wet method stir 10h, 300 ℃ of drying-granulatings then with 10wt% phenolic resins; Compound material behind the coating phenolic resins is carried out carbonization treatment, be heated to 1100 ℃ in argon gas atmosphere, be incubated 3 hours, reduce to room temperature then, fragmentation is broken up to 10 μ m; Powder after the fragmentation is mixed coating, charing processing with 10wt% pitch, heating is 1200 ℃ in argon gas atmosphere, be incubated 2 hours, reduce to room temperature then, fragmentation is broken up to 20 μ m, mixed in homogenizer 4 hours with the carbon nano-tube of 0.5wt% afterwards, adopting frequency 28kHz, power simultaneously is the ultrasonic Treatment 5 minutes of 3600W; The Li of dipping 1% 2CO 3Solution 1 hour, solid-to-liquid ratio 0.1 finally obtains silicon-carbon composite cathode material, and recording its average grain diameter is 20.1 μ m, and specific area is 3.5m 2/ g, tap density is 1.3g/cm 3
The gained composite material prepares electrode as follows: take by weighing 95 gram composite negative pole materials, 2.5 gram butadiene-styrene rubber breast SBR, 1.5 gram carboxyl methyl celluloses, 1 gram conductive agent Super-P, adds an amount of pure water dispersant even after, make electrode, with lithium is to electrode, 1MLiPF 6, EC: DMC: EMC=1: 1: 1, v/v solution was electrolyte, and microporous polypropylene membrane is a barrier film, is assembled into simulated battery, with 0.5mA/cm 2Current density carry out constant current charge-discharge experiment, charging/discharging voltage is 0.02～1.5 volt, test compound material reversible specific capacity.Cycle performance adopts the finished product battery testing, with LiCoO 2Be positive pole, 1M LiPF 6, EC: DMC: EMC=1: 1: 1, v/v solution was electrolyte, and microporous polypropylene membrane is a barrier film, is assembled into the finished product battery, discharged and recharged test with the speed of 1C, charging/discharging voltage is limited in 4.2～3.0 volts, the capability retention C that the test battery circulation is 200 times 200/ C 1
Embodiment 2, and preparation silicon-carbon Si-Mg-G-C-LiOH composite negative pole material: with granularity is the Si-Mg powder of 75 μ m, contains Si 50wt%, and mechanical high-energy ball milling to 0.1 μ m makes ultra-fine Si-Mg powder in argon gas atmosphere; With granularity 70 μ m, the native graphite of carbon content more than 95% pulverized classification, shaping and purification process and prepared carbon content more than 99.9%, and particle diameter is the spherical graphite of 3 μ m; The ultra-fine Si-Mg powder 30wt% and the 70wt% spherical graphite that make are mixed granulation in 1 hour in the mixing granulation machine, make the composite particles matrix; The composite particles matrix is mixed wet method with 2.5wt% butadiene-styrene rubber breast stir 4h, 200 ℃ of drying and granulatings then; Compound material after coating is carried out carbonization treatment, be heated to 700 ℃ in argon gas atmosphere, be incubated 5 hours, reduce to room temperature then, fragmentation is broken up to 10 μ m; Powder after the fragmentation is mixed coating, charing processing with 12wt% pitch, heating is 1200 ℃ in argon gas atmosphere, be incubated 8 hours, reduce to room temperature then, fragmentation is broken up to 15 μ m, mixed in homogenizer 1 hour with 1% nano-sized carbon microballoon afterwards, adopting frequency 40kHz, power simultaneously is the ultrasonic Treatment 20 minutes of 50W; The LiOH solution of dipping 5% 12 hours, solid-to-liquid ratio is 1, finally obtains silicon-carbon composite cathode material.Recording its average grain diameter is 15.4 μ m, and specific area is 2.8m 2/ g, tap density is 1.2g/cm 3
The gained negative material prepares electrode according to the method identical with embodiment 1, carries out electrochemical property test.
Embodiment 3, and preparation silicon-carbon Si-Fe-G-C-LiF composite negative pole material: with granularity is the Si-Fe powder of 75 μ m, contains Si 75wt%, and mechanical high-energy ball milling to 1 μ m makes ultra-fine Si-Fe powder in argon gas atmosphere; With granularity 70 μ m, the native graphite of carbon content more than 95% pulverized classification, shaping and purification process and prepared carbon content more than 99.9%, and particle diameter is the spherical graphite of 5 μ m; The ultra-fine Si-Fe powder 2wt% and the 98wt% spherical graphite that make are mixed granulation in 6 hours in the mixing granulation machine, make the composite particles matrix; The composite particles matrix is mixed wet method stir 10h, 200 ℃ of drying and granulatings then with the 1wt% poly-vinyl alcohol solution; Compound material after coating is carried out carbonization treatment, be heated to 1500 ℃ in argon gas atmosphere, be incubated 1 hour, reduce to room temperature then, fragmentation is broken up to 5 μ m; Powder after the fragmentation is mixed coating, charing processing with 10wt% pitch, heating is 1200 ℃ in argon gas atmosphere, is incubated 10 hours, reduces to room temperature then, and fragmentation is broken up to 15 μ m, mixes 6 hours afterwards with in the 5% carbon fiber homogenizer; Adopting frequency 40kHz, power simultaneously is the ultrasonic Treatment 30 minutes of 50W, 100 ℃ of drying and granulatings then, and the LiF solution of dipping 0.2% 48 hours, solid-to-liquid ratio is 2, finally obtains silicon-carbon composite cathode material.Recording its average grain diameter is 15.6 μ m, and specific area is 1.8m 2/ g, tap density is 1.0g/cm 3
The gained negative material prepares electrode according to the method identical with embodiment 1, carries out electrochemical property test.
Embodiment 4, and preparation silicon-carbon Si-Ca-G-C-LiCl composite negative pole material: with granularity is the Si-Ca powder of 75 μ m, contains Si 60wt% mechanical high-energy ball milling to 0.6 μ m in argon gas atmosphere, makes ultra-fine Si-Ca powder; With granularity 70 μ m, the native graphite of carbon content more than 95% pulverized classification, shaping and purification process and prepared carbon content more than 99.9%, and particle diameter is the spherical graphite of 5 μ m; The ultra-fine Si-Ca powder 40wt% that makes and 60wt% spherical graphite be blended in the cone-type mixer mixed 4 hours, make the composite particles matrix; The composite particles matrix is mixed wet method stir 4h, 400 ℃ of drying and granulatings then with 10wt% phenolic resins; Compound material after coating is carried out carbonization treatment, be heated to 800 ℃ in argon gas atmosphere, be incubated 5 hours, reduce to room temperature then, fragmentation is broken up to 18 μ m; Powder after the fragmentation is mixed coating, charing processing with 30wt% pitch, heating is 1200 ℃ in argon gas atmosphere, be incubated 1 hour, reduce to room temperature then, fragmentation is broken up to 15 μ m, mixed in homogenizer 2 hours with 1% acetylene black afterwards, adopting frequency 40kHz, power simultaneously is the ultrasonic Treatment 20 minutes of 50W; The LiCl solution of dipping 10% 24 hours, solid-to-liquid ratio is 0.5.Finally obtain silicon-carbon composite cathode material.Recording its average grain diameter is 24.8 μ m, and specific area is 3.8m 2/ g, tap density is 0.94g/cm 3
The gained negative material prepares electrode according to the method identical with embodiment 1, carries out electrochemical property test.
Embodiment 5, preparation silicon-carbon SiO-G-C-Li 2The O composite negative pole material: with granularity is SiO powder mechanical high-energy ball milling to 0.8 μ m in argon gas atmosphere of 75 μ m, makes ultra-fine SiO powder; With granularity 70 μ m, the Delanium of carbon content more than 95% pulverized classification, shaping and purification process and prepared carbon content more than 99.9%, and particle diameter is the spherical graphite of 3 μ m; The ultra-fine SiO powder 15wt% that makes and 85wt% spherical graphite are blended in the twin-shaft mixer mixing granulation 5 hours, make the composite particles matrix; Composite particles is mixed wet method stir 4h, 250 ℃ of drying and granulatings then with the 2.5wt% polystyrene; Compound material after coating is carried out carbonization treatment, be heated to 1300 ℃ in argon gas atmosphere, be incubated 2 hours, reduce to room temperature then, fragmentation is broken up to 5 μ m; Powder after the fragmentation is mixed coating, charing processing with 8wt% pitch, heating is 1100 ℃ in argon gas atmosphere, is incubated 10 hours, reduces to room temperature then, and fragmentation is broken up to 5 μ m, floods 5% Li afterwards 2O solution 48 hours, solid-to-liquid ratio are 1, finally obtain silicon-carbon composite cathode material.Recording its average grain diameter is 5.8 μ m, and specific area is 3.8m 2/ g, tap density is 0.96g/cm 3
The gained negative material prepares electrode according to the method identical with embodiment 1, carries out electrochemical property test.
Embodiment 6, preparation silicon-carbon Si-G-C-LiNO 3Composite negative pole material: with granularity is the Si-Ni powder of 75 μ m, contains Si 40wt% mechanical high-energy ball milling to 0.6 μ m in argon gas atmosphere, makes ultra-fine Si-Ni powder; With granularity 70 μ m, the native graphite of carbon content more than 95% pulverized classification, shaping and purification process and prepared carbon content more than 99.9%, and particle diameter is the spherical graphite of 3 μ m; With the ultra-fine Si-Ni powder 50wt% that makes and 50wt% spherical graphite mixing granulation 6 hours in double worm mixer, make the composite particles matrix; Composite particles is mixed wet method with 2.5wt% butadiene-styrene rubber breast stir 4h, 200 ℃ of drying and granulatings then; Compound material after coating is carried out carbonization treatment, be heated to 700 ℃ in argon gas atmosphere, be incubated 5 hours, reduce to room temperature then, fragmentation is broken up to 10 μ m; Powder after the fragmentation is mixed coating, charing processing with 12wt% pitch, heating is 1200 ℃ in argon gas atmosphere, be incubated 10 hours, reduce to room temperature then, fragmentation is broken up to 5 μ m, mixed in homogenizer 2 hours with 1% conductive carbon black Super-P afterwards, adopting frequency 35kHz, power simultaneously is the ultrasonic Treatment 15 minutes of 2500W; The LiNO of dipping 10% 3Solution 36 hours, solid-to-liquid ratio are 2, finally obtain silicon-carbon composite cathode material.Recording its average grain diameter is 5.2 μ m, and specific area is 4.0m 2/ g, tap density is 2.0g/cm 3
The gained negative material prepares electrode according to the method identical with embodiment 1, carries out electrochemical property test.
Embodiment 7, preparation silicon-carbon SiO 2-G-C composite negative pole material: with granularity is the SiO of 75 μ m 2Powder is mechanical high-energy ball milling to 0.8 μ m in air, makes ultra-fine SiO 2Powder; With granularity 70 μ m, the Delanium of carbon content more than 95% pulverized, purification process makes carbon content more than 99.9%, and particle diameter is the graphite microparticles of 3 μ m; With the ultra-fine SiO that makes 2Powder 10wt% and 90wt% spherical graphite were blended in the twin-shaft mixer mixing granulation 5 hours, made the composite particles matrix; Composite particles is mixed wet method stir 4h, 250 ℃ of drying and granulatings then with 25wt% phenolic resins; Compound material after coating is carried out carbonization treatment, be heated to 1300 ℃ in containing the reducing atmosphere of hydrogen, be incubated 2 hours, reduce to room temperature then, fragmentation is broken up to 40 μ m; Powder after the fragmentation is mixed coating, charing processing with 5wt% pitch, heating is 1100 ℃ in argon gas atmosphere, is incubated 10 hours, reduces to room temperature then, and fragmentation is broken up to 60 μ m, finally obtains silicon-carbon composite cathode material.Recording its average grain diameter is 60.4 μ m, and specific area is 2.8m 2/ g, tap density is 0.98g/cm 3
The gained negative material prepares electrode according to the method identical with embodiment 1, carries out electrochemical property test.
Embodiment 8, and preparation silicon-carbon Si-G-C composite negative pole material: with granularity is Si powder mechanical high-energy ball milling to 0.5 μ m in argon gas atmosphere of 75 μ m, makes ultra-fine Si powder; With granularity 70 μ m, the native graphite of carbon content more than 95% pulverized classification, shaping and purification process and prepared carbon content more than 99.9%, and particle diameter is the spherical graphite of 3 μ m; The ultra-fine Si powder 5wt% that makes and 95wt% spherical graphite are blended in the twin-shaft mixer mixing granulation 5 hours, make the composite particles matrix; With composite particles and 2.5wt% butadiene-styrene rubber breast SBR, 1.5% carboxyl methyl cellulose, 1.5% wet-mixed ball milling 1h, 250 ℃ of drying and granulatings then; Compound material after coating is carried out carbonization treatment, be heated to 450 ℃ in argon gas atmosphere, be incubated 10 hours, reduce to room temperature then, fragmentation is broken up to 15 μ m; Powder after the fragmentation is mixed coating, charing processing with 1wt% pitch, heating is 1100 ℃ in argon gas atmosphere, is incubated 10 hours, reduces to room temperature then, and fragmentation is broken up to 17 μ m, finally obtains silicon-carbon composite cathode material.Recording its average grain diameter is 17.2 μ m, and specific area is 3.3m 2/ g, tap density is 1.05g/cm 3
The gained negative material prepares electrode according to the method identical with embodiment 1, carries out electrochemical property test.
Embodiment 9, and preparation silicon-carbon Si-G-C composite negative pole material: with granularity is Si powder mechanical high-energy ball milling to 0.5 μ m in argon gas atmosphere of 75 μ m, makes ultra-fine Si powder; With granularity 70 μ m, the native graphite of carbon content more than 95% pulverized classification, shaping and purification process and prepared carbon content more than 99.9%, and particle diameter is the spherical graphite of 3 μ m; The ultra-fine Si powder 1wt% that makes and 99wt% spherical graphite are blended in the twin-shaft mixer mixing granulation 5 hours, make the composite particles matrix; With composite particles and 2.5wt% butadiene-styrene rubber breast SBR, 1.5% carboxyl methyl cellulose, 1.5% wet-mixed ball milling 12h, adopting frequency 28kHz, power simultaneously is 3600W, ultrasonic Treatment 5 minutes, then 250 ℃ of drying and granulatings; Compound material after coating is carried out carbonization treatment, be heated to 450 ℃ in argon gas atmosphere, be incubated 10 hours, reduce to room temperature then, fragmentation is broken up to 15 μ m; Powder after the fragmentation is mixed coating, charing processing with 6wt% pitch, heating is 1100 ℃ in argon gas atmosphere, is incubated 10 hours, reduces to room temperature then, and fragmentation is broken up to 17 μ m, finally obtains silicon-carbon composite cathode material.Recording its average grain diameter is 17.5 μ m, and specific area is 3.2m 2/ g, tap density is 1.03g/cm 3
The gained negative material prepares electrode according to the method identical with embodiment 1, carries out electrochemical property test.
Embodiment 10, and preparation silicon-carbon Si-Sn-Cu-G-C composite negative pole material: with granularity is the Si-Sn-Cu powder of 75 μ m, Si: Sn: Cu weight ratio=65: 30: 5, and mechanical high-energy ball milling to 0.5 μ m makes superfine alloy Si powder in argon gas atmosphere; With granularity 70 μ m, the native graphite of carbon content more than 95% pulverized classification, shaping and purification process and prepared carbon content more than 99.9%, and particle diameter is the spherical graphite of 3 μ m; The superfine alloy Si powder 40wt% that makes and 60wt% spherical graphite are blended in the twin-shaft mixer mixing granulation 5 hours, make the composite particles matrix; With composite particles and 2.5wt% butadiene-styrene rubber breast SBR, 1.5% carboxyl methyl cellulose, 1.5% wet-mixed ball milling 12h, adopting frequency 28kHz, power simultaneously is 3600W, ultrasonic Treatment 5 minutes, then 250 ℃ of drying and granulatings; Compound material after coating is carried out carbonization treatment, be heated to 450 ℃ in argon gas atmosphere, be incubated 10 hours, reduce to room temperature then, fragmentation is broken up to 15 μ m; Powder after the fragmentation is mixed coating, charing processing with 6wt% pitch, heating is 1100 ℃ in argon gas atmosphere, is incubated 10 hours, reduces to room temperature then, and fragmentation is broken up to 17 μ m, finally obtains silicon-carbon composite cathode material.Recording its average grain diameter is 17.5 μ m, and specific area is 2.1m 2/ g, tap density is 1.23g/cm 3
The gained negative material prepares electrode according to the method identical with embodiment 1, carries out electrochemical property test.
Embodiment 11, preparation silicon-carbon Si-Ni-Co-Ag-G-C composite negative pole material: with granularity is the Si-Ni-Mg-Ag powder of 75 μ m, Si: Ni: Co: Ag weight ratio=55: 30: 10: 5, mechanical high-energy ball milling to 0.5 μ m makes superfine alloy Si powder in argon gas atmosphere; With granularity 70 μ m, the native graphite of carbon content more than 95% pulverized classification, shaping and purification process and prepared carbon content more than 99.9%, and particle diameter is the spherical graphite of 3 μ m; The superfine alloy Si powder 40wt% that makes and 60wt% spherical graphite are blended in the twin-shaft mixer mixing granulation 5 hours, make the composite particles matrix; With composite particles and 2.5wt% butadiene-styrene rubber breast SBR, 1.5% carboxyl methyl cellulose, 1.5% wet-mixed ball milling 12h, adopting frequency 28kHz, power simultaneously is 3600W, ultrasonic Treatment 5 minutes, then 250 ℃ of drying and granulatings; Compound material after coating is carried out carbonization treatment, be heated to 450 ℃ in argon gas atmosphere, be incubated 10 hours, reduce to room temperature then, fragmentation is broken up to 15 μ m; Powder after the fragmentation is mixed coating, charing processing with 6wt% pitch, heating is 1100 ℃ in argon gas atmosphere, is incubated 10 hours, reduces to room temperature then, and fragmentation is broken up to 17 μ m, finally obtains silicon-carbon composite cathode material.Recording its average grain diameter is 17.5 μ m, and specific area is 1.9m 2/ g, tap density is 1.41g/cm 3
The gained negative material prepares electrode according to the method identical with embodiment 1, carries out electrochemical property test.
Comparative example uses D 50The natural spherical plumbago of=16 μ m is as negative material, and is not treated, directly as negative material, prepares electrode and battery according to the method identical with embodiment 1, carries out electrochemical property test.
The chemical property of the negative material that the foregoing description and comparative example record is listed in table 1.
From embodiment as can be seen, the prepared graphite cathode material reversible specific capacity of the present invention is greater than 450mAh/g, and 200 capability retentions that circulate are greater than 80%.
Silicon-carbon composite cathode material of lithium ion battery of the present invention can be widely used in the lithium ion battery negative material of portable electric instruments such as mobile phone, notebook computer, camcorder apparatus, instrument, greatly improved the specific capacity of battery, satisfy electrical appliance to the power supply lightweight requirements, be applicable to the various electrical domains of using.
The chemical property of table 1 negative material
Si phase particle and content thereof in the matrix Initial charge capacity mAh/g Discharge capacity mAh/g first 200 circulation volume conservation rate %
Embodiment 1 Si 20wt％ 765 650 82.3
Embodiment 2 Si-Mg 30wt％ 770 680 87.1
Embodiment 3 Si-Fe 2wt％ 526 452 83.5
Embodiment 4 Si-Ca 40wt％ 806 690 82.1
Embodiment 5 SiO 15wt％ 658 558 82.5
Embodiment 6 Si-Ni 50wt％ 772 654 81.8
Embodiment 7 SiO 2 10wt％ 530 450 84.9
Embodiment 8 Si 5wt％ 538 458 89.6
Embodiment 9 Si 1wt％ 421 386 92.1
Si phase particle and content thereof in the matrix Initial charge capacity mAh/g Discharge capacity mAh/g first 200 circulation volume conservation rate %
Embodiment 10 Si-Sn-Cu 40wt％ 965 788 81.2
Embodiment 11 Si-Ni-Co-Ag 40wt％ 915 775 84.3
Comparative example - 401 345 70.0

Claims (1)

1. the preparation method of a silicon-carbon composite cathode material of lithium ion battery, may further comprise the steps: with granularity is the Si-Ca powder of 75 μ m, contains Si 60wt% mechanical high-energy ball milling to 0.6 μ m in argon gas atmosphere, makes ultra-fine Si-Ca powder; With granularity 70 μ m, the native graphite of carbon content more than 95% pulverized classification, shaping and purification process and prepared carbon content more than 99.9%, and particle diameter is the spherical graphite of 5 μ m; The ultra-fine Si-Ca powder 40wt% that makes and 60wt% spherical graphite be blended in the cone-type mixer mixed 4 hours, make the composite particles matrix; The composite particles matrix is mixed wet method stir 4h, 400 ℃ of drying and granulatings then with 10wt% phenolic resins; Compound material after coating is carried out carbonization treatment, be heated to 800 ℃ in argon gas atmosphere, be incubated 5 hours, reduce to room temperature then, fragmentation is broken up to 18 μ m; Powder after the fragmentation is mixed coating, charing processing with 30wt% pitch, heating is 1200 ℃ in argon gas atmosphere, be incubated 1 hour, reduce to room temperature then, fragmentation is broken up to 15 μ m, mixed in homogenizer 2 hours with 1% acetylene black afterwards, adopting frequency 40kHz, power simultaneously is the ultrasonic Treatment 20 minutes of 50W; The LiCl solution of dipping 10% 24 hours, solid-to-liquid ratio is 0.5, makes silicon-carbon composite cathode material of lithium ion battery; The average grain diameter of described silicon-carbon composite cathode material is 24.8 μ m, specific area 3.8m 2/ g, tap density 0.94g/cm 3
CN200610062255A 2006-08-22 2006-08-22 Silicon carbone compound negative polar material of lithium ion battery and its preparation method Active CN1913200B (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN200610062255A CN1913200B (en) 2006-08-22 2006-08-22 Silicon carbone compound negative polar material of lithium ion battery and its preparation method
PCT/CN2007/000130 WO2008025188A1 (en) 2006-08-22 2007-01-12 A silicon-carbon composite negative material for lithium ion battery and the preparation method of the same
JP2009524864A JP5180211B2 (en) 2006-08-22 2007-01-12 Silicon / carbon composite cathode material for lithium ion battery and method for producing the same
KR1020097003478A KR101085611B1 (en) 2006-08-22 2007-01-12 A silicon-carbon composite negative material for lithium ion battery and the preparation method of the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200610062255A CN1913200B (en) 2006-08-22 2006-08-22 Silicon carbone compound negative polar material of lithium ion battery and its preparation method

Publications (2)

Publication Number Publication Date
CN1913200A CN1913200A (en) 2007-02-14
CN1913200B true CN1913200B (en) 2010-05-26

Family

ID=37722051

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200610062255A Active CN1913200B (en) 2006-08-22 2006-08-22 Silicon carbone compound negative polar material of lithium ion battery and its preparation method

Country Status (4)

Country Link
JP (1) JP5180211B2 (en)
KR (1) KR101085611B1 (en)
CN (1) CN1913200B (en)
WO (1) WO2008025188A1 (en)

Families Citing this family (135)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101436657B (en) * 2007-11-13 2011-01-26 比亚迪股份有限公司 Composite material for lithium ion battery cathode and preparation method thereof, cathode and battery
CN101439972B (en) * 2007-11-21 2013-01-09 比亚迪股份有限公司 Silicon-carbon composite material, preparation thereof, battery cathode and lithium ionic cell
CN100565980C (en) * 2008-05-30 2009-12-02 成都中科来方能源科技有限公司 A kind of composite cathode material for lithium ion cell and preparation method thereof
CN101339987A (en) * 2008-07-21 2009-01-07 长沙市海容电子材料有限公司 Silicon-carbon composite cathode material of lithium ion battery and preparation thereof
CN101323447B (en) * 2008-07-21 2012-02-22 深圳市贝特瑞新能源材料股份有限公司 Graphite powder of lithium ionic cell cathode and preparation thereof
FR2936102B1 (en) * 2008-09-12 2010-10-29 Commissariat Energie Atomique PROCESS FOR THE PREPARATION OF A COMPOSITE MATERIAL SILICON / CARBON, MATERIAL THUS PREPARED AND ELECTRODE IN PARTICULAR NEGATIVE ELECTRODE, COMPRISING THIS MATERIAL.
KR101607232B1 (en) * 2009-04-09 2016-03-29 삼성전자주식회사 Process for preparing anode active composite material
CN101710617B (en) * 2009-05-12 2011-10-26 大连丽昌新材料有限公司 High-energy silicon-carbon composite negative electrode material for lithium ion battery and manufacturing process thereof
CN101908625B (en) 2009-06-03 2014-02-05 法拉赛斯能源公司 Composite for li-ion cells and preparation process thereof
CN102005569A (en) * 2009-08-28 2011-04-06 上海宝钢化工有限公司 Composite cathode material for lithium ion battery and preparation method thereof
CN102630355A (en) 2009-11-03 2012-08-08 安维亚***公司 High capacity anode materials for lithium ion batteries
CN101841035B (en) * 2009-12-07 2013-02-13 大连丽昌新材料有限公司 High-energy compound material used for cathode of lithium ion battery and process for preparing same
US10461366B1 (en) * 2010-01-18 2019-10-29 Enevate Corporation Electrolyte compositions for batteries
KR101137374B1 (en) 2010-01-28 2012-04-20 삼성에스디아이 주식회사 Negative active material containing super-conductive nanoparticle coated with high capacity negative material and lithium battery comprising same
CN102195038B (en) * 2010-03-05 2015-04-15 宁波杉杉新材料科技有限公司 Lithium ion battery as well as negative material and preparation method thereof
KR101252932B1 (en) * 2010-03-11 2013-04-09 주식회사 엘지화학 Particulate polymer-silicon composites for an anode of lithium secondary batteries and the method of preparation of the same
CN101859886A (en) * 2010-05-27 2010-10-13 深圳市德兴富电池材料有限公司 Lithium ion battery anode material and preparation method thereof
WO2011157013A1 (en) * 2010-06-18 2011-12-22 深圳市贝特瑞新能源材料股份有限公司 Composite hard carbon material of negative electrode for lithium ion battery and method for preparing the same
JP5177183B2 (en) * 2010-07-29 2013-04-03 株式会社豊田自動織機 Method for producing negative electrode active material for non-aqueous secondary battery
CN101944596A (en) * 2010-07-30 2011-01-12 中国科学院化学研究所 Preparation method of silicon and carbon composite microspheres and application thereof
CN101931076B (en) * 2010-07-30 2014-01-29 中国科学院化学研究所 Method for preparing silicon carbide composite particles and application thereof as cathode material of lithium ion battery
CN101916847A (en) * 2010-08-19 2010-12-15 深圳市贝特瑞新能源材料股份有限公司 Anode material for lithium ion power battery and preparation method thereof
KR101036288B1 (en) * 2010-09-13 2011-05-23 주식회사 예일전자 Sio-c composite powder for lithium secondary battery and method for manufacturing the same
KR101920942B1 (en) 2010-09-17 2018-11-21 후루카와 덴키 고교 가부시키가이샤 Porous silicon particles and complex porous silicon particles, and method for producing both
WO2012036265A1 (en) * 2010-09-17 2012-03-22 古河電気工業株式会社 Porous silicon particles and complex porous silicon particles, and method for producing both
CN102479939B (en) * 2010-11-25 2016-08-03 上海交通大学 Electrode and manufacture method thereof for lithium ion battery
CN103229336A (en) * 2010-12-07 2013-07-31 株式会社大阪钛技术 Powder for negative electrode material for lithium ion secondary battery, negative electrode of lithium ion secondary battery and negative electrode of capacitor respectively using same, lithium ion secondary battery and capacitor
JP5881943B2 (en) * 2010-12-10 2016-03-09 日立化成株式会社 Lithium secondary battery
FR2970245B1 (en) 2011-01-07 2013-01-25 Commissariat Energie Atomique SILICON / CARBON COMPOSITE MATERIAL, PROCESS FOR THE SYNTHESIS AND USE OF SUCH A MATERIAL
WO2012132387A1 (en) * 2011-03-28 2012-10-04 株式会社豊田自動織機 Electrode material, method for producing same, electrode, secondary battery, and vehicle
CN102593426A (en) * 2011-05-07 2012-07-18 天津锦美碳材科技发展有限公司 Method for preparing silicon oxide (SiOx) / carbon (C) composite materials and prepared silicon carbon cathode materials for lithium ion battery
KR101342601B1 (en) 2011-06-30 2013-12-19 삼성에스디아이 주식회사 Negative active material, manufacturing method thereof, and lithium battery containing the material
CN102916167B (en) * 2011-08-04 2016-08-03 上海交通大学 Mesoporous silicon compound as lithium ion battery negative material and preparation method thereof
CN102299307B (en) 2011-09-03 2014-01-01 深圳市贝特瑞新能源材料股份有限公司 Electrode anode material and preparation method thereof
JP2013058452A (en) * 2011-09-09 2013-03-28 Mitsubishi Chemicals Corp Composite carbon material for nonaqueous secondary battery and method for manufacturing the same, negative electrode, and nonaqueous secondary battery
EP2573845B1 (en) * 2011-09-26 2018-10-31 VARTA Micro Innovation GmbH Structural active material for battery electrodes
CN103137952A (en) * 2011-11-22 2013-06-05 宁波杉杉新材料科技有限公司 Lithium ion battery silicon-based composite anode material and preparation method thereof
CN102637872A (en) * 2012-01-07 2012-08-15 天津市贝特瑞新能源材料有限责任公司 High-capacity silicon-carbon composited anode material, preparation method and application thereof
JP5830419B2 (en) * 2012-03-21 2015-12-09 古河電気工業株式会社 Porous silicon particles, porous silicon composite particles, and production methods thereof
CN103378368B (en) * 2012-04-17 2016-06-15 万向电动汽车有限公司 A kind of silicon cathode lithium ion battery and manufacture method
CN102709532B (en) * 2012-06-01 2015-06-03 中国东方电气集团有限公司 Carbon-silicon composite anode material for preparing lithium ion battery and preparation method for carbon-silicon composite anode material
JP5941437B2 (en) * 2012-06-29 2016-06-29 Ｊｆｅケミカル株式会社 Composite particles for negative electrode of lithium ion secondary battery and method for producing the same, negative electrode for lithium ion secondary battery, and lithium ion secondary battery
US9580322B2 (en) 2012-08-28 2017-02-28 Knu-Industry Cooperation Foundation Method of preparing negative active material for rechargeable lithium battery, and negative active material and rechargeable lithium battery prepared from the same
US9368792B2 (en) 2012-08-28 2016-06-14 Kangwon National University University-Industry Cooperation Foundation Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same
CN102903898B (en) * 2012-10-19 2015-10-28 山东大学 A kind of graphite and transition metal oxide composite cathode material and preparation method thereof
CN103208615B (en) * 2012-10-25 2014-06-04 郴州杉杉新材料有限公司 Silicon-carbon composite material, and preparation method and application thereof
KR101610995B1 (en) * 2012-11-30 2016-04-08 주식회사 엘지화학 Silicon based composite and manufacturing method thereof
CN103050666B (en) * 2012-12-12 2015-04-22 中南大学 Preparation method of silicon and carbon-coated graphene composite cathode material
CN103035919A (en) * 2012-12-14 2013-04-10 深圳市斯诺实业发展有限公司永丰县分公司 Method for preparing modified graphite negative electrode material of lithium ion power battery
KR101460774B1 (en) * 2013-01-15 2014-11-17 강원대학교산학협력단 Negative active material for rechargeable lithium battery, method of preparing the same, and negative electrode and rechargeable lithium battery including the same
US9831491B2 (en) 2013-02-19 2017-11-28 Lg Chem, Ltd. Si/C composite, method of preparing the same, and anode active material for lithium secondary battery including the Si/C composite
KR101630008B1 (en) * 2013-02-19 2016-06-13 주식회사 엘지화학 Si/C COMPOSITE, PREPARATION METHOD OF THEREOF, AND ANODE ACTIVE MATERIAL FOR LITHIUM SECONDARY BATTERY COMPRISING THE SAME
CN103199252B (en) * 2013-03-08 2015-10-28 深圳市贝特瑞新能源材料股份有限公司 Lithium-ion battery silicon-carbon anode material and preparation method thereof
CN104282881B (en) * 2013-07-11 2017-03-08 万向一二三股份公司 A kind of soft bag lithium ionic cell silicium cathode and its manufacture method
KR102202366B1 (en) * 2013-08-20 2021-01-13 강원대학교산학협력단 Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same
WO2015025443A1 (en) * 2013-08-21 2015-02-26 信越化学工業株式会社 Negative-electrode active substance, negative electrode active substance material, negative electrode, lithium ion secondary battery, negative electrode active substance manufacturing method, and lithium ion secondary battery manufacturing method
JP2015084320A (en) * 2013-09-17 2015-04-30 株式会社東芝 Active material for batteries, electrode, nonaqueous electrolyte battery and battery pack
CN103779536B (en) * 2013-11-06 2017-01-04 南京安普瑞斯有限公司 Silicon-containing cathode of lithium ion battery and preparation method thereof
CN103647056B (en) * 2013-11-29 2017-02-08 深圳市贝特瑞新能源材料股份有限公司 SiOx based composite negative electrode material, preparation method and battery
CN103682286B (en) * 2013-12-18 2015-09-02 南京毕汉特威高分子材料有限公司 Silicon/high molecular composite microsphere and silicon-carbon composite anode material for lithium ion battery and preparation method thereof
CN103779601B (en) * 2013-12-19 2016-08-31 宁波维科电池股份有限公司 A kind of silicon cathode lithium ion battery and manufacture method
CN103769592B (en) * 2014-01-15 2016-02-03 北京科技大学 A kind of preparation method of spherical TiC/Fe cermet composite particles
JP6082355B2 (en) * 2014-02-07 2017-02-15 信越化学工業株式会社 Negative electrode active material for negative electrode material of non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
KR101924035B1 (en) * 2014-05-09 2018-11-30 주식회사 엘지화학 Silicon-carbon composite, preparation method thereof, and anode active material comprising the same
CN104332608B (en) * 2014-08-19 2017-06-06 新乡市远东电子科技股份有限公司 A kind of lithium ion battery silicon composite cathode material and preparation method thereof
CN104332616B (en) * 2014-09-09 2017-01-25 深圳市本征方程石墨烯技术股份有限公司 Graphene coated graphite composite lithium ion battery negative material and its preparation method
JP6020533B2 (en) * 2014-10-29 2016-11-02 日立化成株式会社 Lithium ion secondary battery
KR101888230B1 (en) 2014-11-27 2018-08-13 주식회사 엘지화학 Silicon-based anode active material and its fabrication method
WO2016085282A1 (en) * 2014-11-27 2016-06-02 주식회사 엘지화학 Silicon-based negative electrode active material and method for manufacturing same
CN104577084A (en) 2015-01-20 2015-04-29 深圳市贝特瑞新能源材料股份有限公司 Nano silicon composite negative electrode material for lithium ion battery, preparation method and lithium ion battery
CN104953100A (en) * 2015-06-17 2015-09-30 田东 Preparation method of carbon/graphite/tin composite anode material
KR102479726B1 (en) 2015-10-22 2022-12-21 삼성전자주식회사 Electrode active material, electrode and secondary battery including the same, and method of preparing the electrode active material
JP6975435B2 (en) * 2015-11-06 2021-12-01 国立大学法人 新潟大学 Non-aqueous electrolyte secondary battery Negative electrode manufacturing method
KR20180097594A (en) 2015-12-28 2018-08-31 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Silicon-based materials and methods of making and using the same
CN105655555B (en) * 2016-01-13 2018-07-06 浙江天能能源科技股份有限公司 A kind of Si-C composite material, preparation method and applications
CN105576209B (en) * 2016-02-04 2017-11-24 中南大学 A kind of high-capacity lithium ion cell silicon based anode material and preparation method thereof, lithium ion battery
WO2017149977A1 (en) * 2016-02-29 2017-09-08 パナソニックＩｐマネジメント株式会社 Non-aqueous electrolyte secondary battery
CN105958072B (en) * 2016-06-20 2019-02-05 傅云峰 A kind of preparation method of natural flake graphite base negative electrode material
US10968106B2 (en) * 2016-08-11 2021-04-06 Wacker Chemie Ag Production of Si/C composite particles
DE102016221782A1 (en) * 2016-11-07 2018-05-09 Wacker Chemie Ag Carbon coated silicon particles for lithium ion batteries
CN106784741B (en) * 2017-02-17 2021-01-08 贝特瑞新材料集团股份有限公司 Carbon-silicon composite material, preparation method thereof and lithium ion battery containing composite material
CN108511740A (en) * 2017-03-13 2018-09-07 万向二三股份公司 A kind of high-specific-capacity silicon carbon electrode coating preparation method
CN108807861B (en) * 2017-05-03 2021-11-30 安普瑞斯（南京）有限公司 Silicon-carbon composite material for lithium ion battery and preparation method thereof
CN106898762B (en) * 2017-05-05 2019-03-26 天津师范大学 A kind of preparation method of lithium ion battery high-capacity cathode material
CN107093529B (en) * 2017-05-08 2019-04-30 华东理工大学 A method of transition metal oxide/carbon composite is prepared using solar energy
KR102285979B1 (en) * 2017-09-11 2021-08-04 주식회사 엘지에너지솔루션 Negative electrode active material, negative electrode comprising the negative electrode active material, and lithium secondarty battery comprising the negative electrode
GB201803983D0 (en) 2017-09-13 2018-04-25 Unifrax I Llc Materials
KR102285980B1 (en) * 2017-11-09 2021-08-04 주식회사 엘지에너지솔루션 Negative electrode active material, negative electrode comprising the negative electrode active material, and lithium secondarty battery comprising the negative electrode
CN113437274A (en) * 2017-12-12 2021-09-24 贝特瑞新材料集团股份有限公司 Lithium ion battery cathode material and preparation method thereof
JP6467031B2 (en) * 2017-12-27 2019-02-06 信越化学工業株式会社 Anode material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery
CN108598430B (en) * 2018-04-27 2021-03-09 北方奥钛纳米技术有限公司 Preparation method of silicon-carbon negative electrode material and porous silicon-carbon microsphere negative electrode material
CN110838574A (en) * 2018-08-16 2020-02-25 深圳市贝特瑞新能源材料股份有限公司 High-capacity composite negative electrode material for lithium ion battery, preparation method of high-capacity composite negative electrode material and lithium ion battery comprising composite material
CN109411714B (en) * 2018-09-12 2022-12-09 西安交通大学 High-capacity high-stability silicon-carbon negative electrode material and preparation method thereof
KR102243610B1 (en) * 2018-12-17 2021-04-27 주식회사 티씨케이 Negative active material, method for preparing the same and lithium secondary battery comprising the same
CN109713265B (en) * 2018-12-21 2021-01-12 桑德新能源技术开发有限公司 Silicon-carbon negative electrode material and preparation method thereof
CN109970052B (en) * 2019-02-27 2022-10-25 福建翔丰华新能源材料有限公司 Method for granulating and secondary coating modification of natural graphite
CN111834615B (en) * 2019-04-23 2021-11-16 四川佰思格新能源有限公司 Composite negative electrode material, preparation method and lithium ion battery
CN110391406A (en) * 2019-07-01 2019-10-29 深圳市比克动力电池有限公司 A kind of lithium ion battery silicon oxygen negative electrode material and preparation method thereof, lithium ion battery
CN110416543A (en) * 2019-08-07 2019-11-05 宁德新能源科技有限公司 Negative electrode material and electrochemical appliance and electronic device comprising it
US11316142B2 (en) * 2019-09-17 2022-04-26 GM Global Technology Operations LLC Methods for fabricating silicon-based electrodes comprising naturally occurring carbonaceous filaments and battery cells utilizing the same
US11094996B2 (en) * 2019-09-18 2021-08-17 GM Global Technology Operations LLC Additive to ceramic ion conducting material to mitigate the resistive effect of surface carbonates and hydroxides
CN110642247B (en) * 2019-09-30 2021-05-25 广东凯金新能源科技股份有限公司 Artificial graphite negative electrode material, preparation method thereof and lithium ion battery
CN112661131B (en) * 2019-10-16 2022-12-06 中国科学院福建物质结构研究所 Preparation method and application of carbon-coated silicon composite material
CN110854367B (en) * 2019-11-21 2022-05-03 陕西煤业化工技术研究院有限责任公司 Silicon-carbon anode material slurry and preparation method thereof
CN112909224A (en) * 2019-12-04 2021-06-04 华为技术有限公司 Lithium ion battery electrode material and preparation method thereof
CN112670489A (en) * 2019-12-16 2021-04-16 宁波杉杉新材料科技有限公司 Silicon-carbon composite material, electrode, lithium ion battery and preparation method and application thereof
CN111153394B (en) * 2020-01-16 2023-01-20 昆明理工大学 Preparation method of carbon-silicon negative electrode material of lithium ion battery
CN111244417B (en) * 2020-01-17 2022-04-15 天津大学 Preparation method of micron silicon-carbon composite negative electrode material with long cycle life
CN111517317B (en) * 2020-01-21 2023-02-17 西安隆基锂电新材料有限公司 Silicon-carbon composite negative electrode material and preparation method thereof
JP2023524933A (en) * 2020-03-18 2023-06-14 ワッカー ケミー アクチエンゲゼルシャフト Method for producing carbon-coated silicon particles
CN111740111B (en) * 2020-06-24 2022-09-27 东莞东阳光科研发有限公司 Lithium-sulfur battery positive electrode material and preparation method and application thereof
CN112028078B (en) * 2020-08-19 2023-02-14 上海纳米技术及应用国家工程研究中心有限公司 Method for improving stability of lithium battery silicon negative electrode material
CN111960421B (en) * 2020-08-27 2021-11-05 北京理工大学 Preparation method of coated carbon-silicon negative electrode material
CN112374482B (en) * 2020-10-08 2023-06-20 常州硅润新材料科技有限公司 Silicon-oxygen-fluorine-carbon negative electrode material of lithium ion battery prepared by mechanochemical method
CN112310368B (en) * 2020-10-16 2023-09-12 欣旺达电动汽车电池有限公司 Negative electrode active material, preparation method and application thereof, and lithium ion battery
CN114497469B (en) * 2020-11-11 2023-12-22 成都爱敏特新能源技术有限公司 Silicon monoxide-cobalt fluoride-graphene composite negative electrode material and preparation method thereof
CN112938959B (en) * 2021-01-29 2023-11-07 乌海宝杰新能源材料有限公司 Preparation method of power battery negative electrode material
CN113003559A (en) * 2021-02-06 2021-06-22 常德速碳新能源科技有限公司 Preparation method of carbon negative electrode material for lithium ion battery
CN113013390B (en) * 2021-02-20 2022-07-22 珠海冠宇电池股份有限公司 Negative plate and lithium ion battery
CN113161521B (en) * 2021-03-10 2022-11-01 广东海洋大学 Natural graphite-based silicon-carbon composite negative electrode material and preparation method and application thereof
CN113044828A (en) * 2021-03-17 2021-06-29 昆山宝创新能源科技有限公司 Porous conductive silica material, preparation method thereof and lithium ion battery
CN113675405B (en) * 2021-08-18 2022-08-05 合肥工业大学 Fluffy carbon-coated silicon composite material and preparation method and application thereof
CN113745483B (en) * 2021-09-07 2023-04-07 宁波特粒科技有限公司 Hollow silicon-carbon-based composite material, preparation method thereof and negative electrode energy storage material for non-aqueous electrolyte secondary battery
CN114105133B (en) * 2021-10-19 2023-09-05 湖南金硅科技有限公司 Graphite-silicon/silicon oxide-carbon composite material and preparation method and application thereof
CN114141993A (en) * 2021-11-25 2022-03-04 广东凯金新能源科技股份有限公司 Processing technology of composite modified graphite negative electrode with good cycling stability
CN114275785A (en) * 2021-12-24 2022-04-05 安徽科达新材料有限公司 High-first-efficiency silicon monoxide negative electrode and preparation method thereof
CN114497481B (en) * 2021-12-31 2024-02-20 长沙矿冶研究院有限责任公司 Conductive polymer coated nano silicon powder, preparation method and application thereof, and silicon-carbon negative electrode material
CN114464804A (en) * 2022-02-10 2022-05-10 珠海冠宇电池股份有限公司 Cathode material and lithium ion battery containing same
CN114559033B (en) * 2022-03-04 2023-03-10 厦门大学 Carbon-coated copper nanoparticles and preparation method thereof
CN115050925B (en) * 2022-07-01 2023-09-01 山东仁丰特种材料股份有限公司 Electrode material, preparation method, electrode plate and battery
WO2024040605A1 (en) * 2022-08-26 2024-02-29 宁德时代新能源科技股份有限公司 Silicon-carbon composite material and preparation method therefor, secondary battery and electric device
CN115621534B (en) * 2022-12-16 2023-04-07 宁德新能源科技有限公司 Electrochemical device and electronic device
CN116022783B (en) * 2023-01-09 2023-08-08 南阳天成新能源科技有限公司 Modified graphite negative electrode material and preparation method and application thereof
CN116253558B (en) * 2023-03-20 2024-02-13 深圳市诺安智能股份有限公司 Preparation method of graphene-coated electronic compound and preparation method of film
CN117019154B (en) * 2023-09-07 2024-04-09 深圳市贝特瑞新能源技术研究院有限公司 Photocatalyst based on microcrystalline graphite and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1681145A (en) * 2004-04-05 2005-10-12 中国科学院物理研究所 Negative electrode active material and use of secondary lithium battery
CN1710734A (en) * 2005-06-30 2005-12-21 复旦大学 Method for modifying carbon negative polar material

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4104830B2 (en) * 2001-03-02 2008-06-18 三星エスディアイ株式会社 Carbonaceous material, lithium secondary battery, and method for producing carbonaceous material
JP3897709B2 (en) * 2002-02-07 2007-03-28 日立マクセル株式会社 Electrode material, method for producing the same, negative electrode for non-aqueous secondary battery, and non-aqueous secondary battery
JP5060010B2 (en) * 2002-10-18 2012-10-31 株式会社Ｇｓユアサ Nonaqueous electrolyte secondary battery
US20040137327A1 (en) * 2003-01-13 2004-07-15 Gross Karl J. Synthesis of carbon/silicon composites
JP2004259475A (en) * 2003-02-24 2004-09-16 Osaka Gas Co Ltd Lithium secondary battery negative electrode material and its manufacturing method as well as lithium secondary battery using the same
KR100595896B1 (en) * 2003-07-29 2006-07-03 주식회사 엘지화학 A negative active material for lithium secondary battery and a method for preparing same
JP4530647B2 (en) * 2003-11-17 2010-08-25 日本コークス工業株式会社 Negative electrode material for lithium secondary battery, method for producing the same, and lithium secondary battery
US7618678B2 (en) * 2003-12-19 2009-11-17 Conocophillips Company Carbon-coated silicon particle powders as the anode material for lithium ion batteries and the method of making the same
US7432015B2 (en) * 2004-02-25 2008-10-07 Samsung Sdi Co., Ltd. Negative active material for a rechargeable lithium battery, a method of preparing the same, and a rechargeable lithium battery comprising the same
JP2005243431A (en) * 2004-02-26 2005-09-08 Japan Storage Battery Co Ltd Nonaqueous electrolyte secondary battery
JP4401984B2 (en) * 2004-03-08 2010-01-20 三星エスディアイ株式会社 Negative electrode active material for lithium secondary battery, negative electrode active material for lithium secondary battery, and lithium secondary battery
JP4519592B2 (en) * 2004-09-24 2010-08-04 株式会社東芝 Negative electrode active material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery
WO2006068066A1 (en) * 2004-12-24 2006-06-29 Matsushita Electric Industrial Co., Ltd. Composite electrode active material for nonaqueous electrolyte secondary battery or nonaqueous electrolyte electrochemical capacitor, and method for producing same
JP4740753B2 (en) * 2005-01-28 2011-08-03 三星エスディアイ株式会社 Lithium battery for charging / discharging, and method for producing negative electrode active material contained in negative electrode of lithium battery for charging / discharging
KR100784996B1 (en) * 2005-01-28 2007-12-11 삼성에스디아이 주식회사 Anode active material, method of preparing the same, and anode and lithium battery containing the material
CN1326267C (en) * 2005-05-27 2007-07-11 深圳市贝特瑞电子材料有限公司 Cathode material of composite carbon in use for lithium ion battery and preparation method
CN1315207C (en) * 2005-06-22 2007-05-09 浙江大学 Composite negative pole material of Li-ion battery and its preparing process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1681145A (en) * 2004-04-05 2005-10-12 中国科学院物理研究所 Negative electrode active material and use of secondary lithium battery
CN1710734A (en) * 2005-06-30 2005-12-21 复旦大学 Method for modifying carbon negative polar material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
说明书第3页第1行－第6页倒数第2行.

Also Published As

Publication number Publication date
JP2010501970A (en) 2010-01-21
CN1913200A (en) 2007-02-14
WO2008025188A1 (en) 2008-03-06
JP5180211B2 (en) 2013-04-10
KR101085611B1 (en) 2011-11-22
KR20090058505A (en) 2009-06-09

Similar Documents

Publication Publication Date Title
CN1913200B (en) Silicon carbone compound negative polar material of lithium ion battery and its preparation method
CN100565980C (en) A kind of composite cathode material for lithium ion cell and preparation method thereof
CN101887966B (en) Preparation method of composite hard carbon cathode material of lithium ion battery
CN101916845B (en) Hard carbon material for power and energy-storage battery and preparation method thereof
CN112467108B (en) Porous silica composite material and preparation method and application thereof
CN1909268B (en) Lithium ion battery negative electrode material containing PC dissolvent electrolytic solution and its preparation method
CN101510602B (en) Method for preparing silicon composite cathode material of lithium ion battery
CN1315207C (en) Composite negative pole material of Li-ion battery and its preparing process
CN107579239A (en) A kind of graphene/solid electrolyte compound coating silicon composite cathode and preparation method thereof
CN110620224A (en) Negative electrode material for lithium battery, preparation method of negative electrode material and lithium battery
CN106935860A (en) A kind of carbon intercalation V2O3Nano material, its preparation method and application
CN103078090A (en) Lithium ion power battery composite cathode material and its preparation method
CN103346293A (en) Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery
CN103259005B (en) A kind of preparation method of high power capacity high rate lithium ionic cell cathode material
CN102082272A (en) Hard carbon coated lithium ion battery anode material and preparation method thereof
CN105789576A (en) Preparation method for silicon-based negative electrode material, negative electrode material and battery
CN109461921B (en) Preparation method of modified silicon-based alloy composite negative electrode material of lithium ion battery
CN101969111A (en) Silicon-carbon alloy cathode material for lithium ion batteries and preparation method thereof
CN109449421B (en) Silicon-based alloy composite negative electrode material of lithium ion battery and preparation method thereof
CN105047888A (en) Lithium ion battery anode material and preparation method thereof
WO2022002057A1 (en) Silicon-oxygen composite negative electrode material, negative electrode, lithium-ion battery, and preparation methods therefor
CN111333063B (en) Natural graphite-based silicon-carbon composite negative electrode material and preparation method and application thereof
CN1702894A (en) Cathode material of lithium ion cell and preparation method thereof
CN102709563A (en) Lithium ion battery silicon cathode material and preparation method thereof
CN109817962A (en) A kind of Silicon Based Anode Materials for Lithium-Ion Batteries and preparation method of phenolic resin modification

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
C56 Change in the name or address of the patentee

Owner name: SHENZHEN BTR NEW ENERGY MATERIAL CO., LTD.

Free format text: FORMER NAME: BEITERUI ELECTRONIC MATERIALS CO., LTD., SHENZHEN CITY

CP03 Change of name, title or address

Address after: 518106 Gongming office, Guangming District, Guangdong, Shenzhen Province, eighth village industrial town, Liantang Village

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

Address before: Nanshan District Xili Town, Shenzhen city Guangdong province 518055 Liuxian Avenue joygoal building

Patentee before: Beiterui Electronic Materials Co., Ltd., Shenzhen City

C56 Change in the name or address of the patentee
CP02 Change in the address of a patent holder

Address after: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth,

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

Address before: 518106 Gongming office, Guangming District, Guangdong, Shenzhen Province, eighth village industrial town, Liantang Village

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

CP01 Change in the name or title of a patent holder

Address after: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth,

Patentee after: Beitrei New Materials Group Co., Ltd

Address before: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth,

Patentee before: Shenzhen BTR New Energy Materials Inc.

CP01 Change in the name or title of a patent holder