CN1913200A - 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

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CN1913200A
CN1913200A CNA2006100622556A CN200610062255A CN1913200A CN 1913200 A CN1913200 A CN 1913200A CN A2006100622556 A CNA2006100622556 A CN A2006100622556A CN 200610062255 A CN200610062255 A CN 200610062255A CN 1913200 A CN1913200 A CN 1913200A
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carbon
silicon
ion battery
lithium ion
cathode material
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CN1913200B (en
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岳敏
张万红
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BTR New Material Group Co Ltd
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BEITERUI ELECTRONIC MATERIALS Co Ltd SHENZHEN CITY
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Priority to KR1020097003478A priority patent/KR101085611B1/en
Priority to PCT/CN2007/000130 priority patent/WO2008025188A1/en
Priority to JP2009524864A priority patent/JP5180211B2/en
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    • 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
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    • H—ELECTRICITY
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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 SiO2?10wt％ 530 450 84.9
Embodiment 8 Si?5wt％ 538 458 89.6
Embodiment 9 Si?1wt％ 421 386 92.1
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 (25)

1. silicon-carbon composite cathode material of lithium ion battery, it is characterized in that: 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, and matrix is spherical in shape or class is spherical, and matrix is coated with carbon coating layer.
2. according to claims 1 described silicon-carbon composite cathode material of lithium ion battery, it is characterized in that: described carbon coating layer is an organic substance pyrolytic carbon coating layer.
3. according to claims 2 described silicon-carbon composite cathode material of lithium ion battery, it is characterized in that: described carbon coating layer contains conductive carbon.
4. according to claims 3 described silicon-carbon composite cathode material of lithium ion battery, it is characterized in that: lithium compound is contained on described carbon coating layer surface.
5. according to claims 4 described silicon-carbon composite cathode material of lithium ion battery, it is characterized in that: described coating thickness is 0.1～5 μ m, 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%.
6. according to arbitrary described silicon-carbon composite cathode material of lithium ion battery in claims 1 to 5, it is characterized in that: the average grain diameter of described silicon-carbon composite cathode material is 5～60 μ m, specific area 1.0～4.0m 2/ g, tap density 0.7～2.0g/cm 3
7. according to claims 6 described silicon-carbon composite cathode material of lithium ion battery; it is characterized in that: described silicon phase particle 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, wherein 0＜x≤2.
8. according to claims 7 described silicon-carbon composite cathode material of lithium ion battery, it is characterized in that: described silicon phase particle accounts for the ratio of composite particles matrix preferably at 5～30wt%.
9. according to claims 8 described silicon-carbon composite cathode material of lithium ion battery, it is characterized in that: described silicon phase particle accounts for the ratio of composite particles matrix further preferably at 10～20wt%.
10. according to claims 9 described silicon-carbon composite cathode material of lithium ion battery, it is characterized in that: compound between described 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.
11. according to claims 10 described silicon-carbon composite cathode material of lithium ion battery, it is characterized in that: described carbon phase particle is any one or more than one the mixing in natural flake graphite, micro crystal graphite, Delanium, MCMB and the coke.
12. according to claims 11 described silicon-carbon composite cathode material of lithium ion battery, it is characterized in that: described organic substance pyrolytic carbon 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.
13. according to claims 12 described silicon-carbon composite cathode material of lithium ion battery, it is characterized in that: described conductive carbon is acetylene black, carbon nano-tube, nano-sized carbon microballoon, carbon fiber or conductive carbon black.
14. according to claims 13 described silicon-carbon composite cathode material of lithium ion battery, it is characterized in that: described lithium-containing compound is lithia, lithium carbonate, lithium fluoride, lithium chloride, lithium nitrate or lithium hydroxide.
15. the preparation method of a 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.
16. the preparation method of silicon-carbon composite cathode material of lithium ion battery according to claim 15; it is characterized in that: 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%; in mixer or surface coating modification machine, mixed 1～6 hour; and use ultrasonic wave to disperse 1～30 minute, be crushed to 5～60 μ m.
17. the preparation method of silicon-carbon composite cathode material of lithium ion battery according to claim 16, it is characterized in that: with the described compound dipping lithium-containing compound that is crushed to 5～60 μ m, 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.
18. according to claim 15; the preparation method of 16 or 17 described silicon-carbon composite cathode material of lithium ion battery; it is characterized in that: described silicon phase particle is an elemental silicon; silicon oxide compound SiOx; compound between 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; in the transition metal any or three kinds of elements; 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.
19. the preparation method of silicon-carbon composite cathode material of lithium ion battery according to claim 18; it is characterized in that: described carbon phase particle 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.
20. the preparation method of silicon-carbon composite cathode material of lithium ion battery according to claim 19 is characterized in that: the ratio that described coating layer accounts for composite material is 1～25wt%.
21. the preparation method of silicon-carbon composite cathode material of lithium ion battery according to claim 20, it is characterized in that: the presoma of described organic substance pyrolytic carbon 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.
22. the preparation method of silicon-carbon composite cathode material of lithium ion battery according to claim 21 is characterized in that: described conductive carbon is acetylene black, carbon nano-tube, nano-sized carbon microballoon, carbon fiber or conductive carbon black.
23. the preparation method of silicon-carbon composite cathode material of lithium ion battery according to claim 22 is characterized in that: described lithium-containing compound is lithia, lithium carbonate, lithium fluoride, lithium chloride, lithium nitrate or lithium hydroxide.
24. the preparation method of silicon-carbon composite cathode material of lithium ion battery according to claim 23 is characterized in that: described silicon phase particle ball milling carries out in protective atmosphere, and protective atmosphere is any or several mixing in argon gas, hydrogen or the nitrogen.
25. the preparation method of silicon-carbon composite cathode material of lithium ion battery according to claim 24 is characterized in that: described during with silicon phase particle and carbon phase particle mixing granulation, mixing granulation is 1～6 hour in the mixing granulation machine.
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JP2010501970A (en) 2010-01-21
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