WO2008025188A1 - A silicon-carbon composite negative material for lithium ion battery and the preparation method of the same - Google Patents

A silicon-carbon composite negative material for lithium ion battery and the preparation method of the same Download PDF

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Publication number
WO2008025188A1
WO2008025188A1 PCT/CN2007/000130 CN2007000130W WO2008025188A1 WO 2008025188 A1 WO2008025188 A1 WO 2008025188A1 CN 2007000130 W CN2007000130 W CN 2007000130W WO 2008025188 A1 WO2008025188 A1 WO 2008025188A1
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silicon
carbon
lithium
ion battery
phase particles
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PCT/CN2007/000130
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French (fr)
Chinese (zh)
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Min Yue
Wanhong Zhang
Jia Mei
Minghua Deng
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Btr Energy Materials Co., Ltd.
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Priority to JP2009524864A priority Critical patent/JP5180211B2/en
Priority to KR1020097003478A priority patent/KR101085611B1/en
Publication of WO2008025188A1 publication Critical patent/WO2008025188A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

Definitions

  • the invention relates to a battery anode material and a preparation method thereof, in particular to a silicon carbon composite anode material for a lithium ion battery and a preparation method thereof.
  • Lithium-ion batteries have developed rapidly since Sony Corporation took the lead in developing and commercializing lithium-ion batteries in 1990.
  • the miniaturization and individual development of electronic equipment requires the battery to have a smaller volume and higher specific energy output; aerospace energy
  • the battery is required to have a cycle life, better low temperature charge and discharge performance and higher safety performance; electric vehicles require batteries with high capacity, low cost, high stability and safety performance.
  • the successful development of lithium-ion batteries should be attributed to the breakthrough of electrode materials, especially carbon anode materials.
  • the embedded graphite-lithium intercalation compound Li-GIC has a high specific capacity, close to the theoretical specific capacity of LiC 6 of 372 mAh/g , and has a good charge and discharge voltage platform and a low intercalation and deintercalation potential.
  • the positive electrode materials of lithium source such as LiCo0 2 , ⁇ 0 2 and 1 ⁇ ] ⁇ 1 ⁇ 2 2 0 4 have good matching, and the assembled battery has high average voltage and stable discharge. Therefore, a large number of commercial lithium ion batteries use graphite.
  • a carbon-like material is used as a negative electrode material.
  • silicon-based materials have attracted much attention due to their high theoretical lithium storage capacity, such as single crystal Si : 4200mAlVg, low lithium insertion potential, and higher stability than other metals and materials. . If Si-based materials can be successfully applied, as a negative electrode material for lithium-ion batteries, it will definitely have an epoch-making significance for the development of lithium-ion batteries, and will also have a major impact on the development of information and energy industries. However, like the metal, the silicon-based material has a serious volume effect under high degree of deintercalation of lithium, which causes unstable cycle stability of the electrode, and its initial irreversible capacity is high, which limits its use as a lithium ion battery.
  • Maxwell's composite system of 3 ⁇ 4 ⁇ extragranular amorphous carbon particles prepared by CVD method improves the structure and electrical conductivity of silicon materials, and can inhibit the insertion and extraction process of lithium to a certain extent.
  • the volume effect which improves the cycle performance of this type of material.
  • the CVD method is controlled by a lot of uncertainties, so it is difficult to achieve mass production.
  • CSWang et al. used a 3 ⁇ 4/carbon binary system composite material prepared by mechanical ball milling of graphite and silicon powder to have a high first lithium insertion capacity, but its charge and discharge performance is unstable, especially the initial cycle capacity attenuation is very high. J.
  • Electrochem. Soc., 8(1998): 2751-2758 ) 0 SBNg, etc. similar to the network structure of graphite-silicon/Si(OCH 3 ) 4 composite prepared by sol-gel method, although relatively stable
  • the mechanical properties are beneficial to the improvement of the cycle performance.
  • the presence of the Si-0 network structure also hinders the diffusion behavior of lithium, which reduces the amount of lithium intercalation and does not fully exert the high capacity characteristics of Si (J. Power Sources, 94 (2001): 63-67).
  • HeJ uses a volume compensation method to prepare a silicon-containing composite material, which maintains the high specific capacity characteristics of silicon and simultaneously controls the volume change of the whole electrode.
  • ⁇ has added cycle stability.
  • the anode material has a higher specific capacity than the carbon anode material commonly used in the current k ⁇ lithium ion battery, and satisfies various types. Summary of the invention
  • the object of the present invention is to provide a lithium-ion battery silicon-carbon composite anode material and a preparation method thereof, and the technical problem to be solved is to improve the specific capacity of the battery, and have both excellent cycle performance and rate discharge performance.
  • the invention adopts the following technical solutions: a lithium-ion battery silicon-carbon composite anode material, wherein the lithium-ion battery silicon-carbon composite anode material is based on composite particles of silicon phase particles and carbon phase particles, and the matrix is spherical or spheroidal.
  • the substrate is coated with a carbon coating layer.
  • the carbon coating layer of the present invention is an organic pyrolytic carbon coating layer.
  • the carbon coating layer of the present invention contains conductive carbon.
  • the surface of the carbon coating layer of the present invention contains a lithium compound.
  • the ratio of the ratio of the ratio of the conductive material to the negative electrode material is 0. 5 ⁇ 5wt%.
  • the silicon-carbon composite negative electrode material having an average particle diameter of 5 to 60 m, a specific surface area of 1. 0 ⁇ 4. 0 m 2 / g, a tap density of 0. 7 ⁇ 2. 0g / cm 3 .
  • the silicon phase particles of the present invention are elemental silicon, a silicon oxide compound Si0x, a silicon-containing solid solution or a silicon-containing intermetallic compound, and the silicon phase particles constitute 1 to 50% by weight of the composite particle substrate, wherein 0 ⁇ x 2 .
  • the ratio of the silicon phase particles of the present invention to the matrix of the composite particles is 5 to 30% by weight.
  • the proportion of the silicon phase particles of the present invention to the composite particle substrate is further preferably from 10 to 20% by weight.
  • the silicon-containing solid solution or the silicon-containing intermetallic compound of the present invention is composed of any one or two elements of a lanthanum element in the periodic table of silicon and a chemical element, or any one or three elements of a transition metal element, a lanthanum Either or both of the elements, or one or both of the Group IVA elements other than silicon.
  • the carbon phase particles of the present invention are any one or a mixture of one or more of natural flake graphite, microcrystalline graphite, A graphite, and mesophase carbon micro-port coke.
  • the organic pyrolytic carbon of the present invention is composed of water-soluble polyvinyl alcohol, styrene-butadiene rubber latex, carboxymethyl cellulose, Organic solvent-based polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, phenolic resin, epoxy resin, glucose, sucrose, fructose, cellulose, starch or asphalt as precursors Body, pyrolytic carbon formed by high temperature carbonization.
  • the conductive carbon of the present invention is acetylene black, carbon nanotubes, nanocarbon microspheres, carbon fibers or conductive carbon black.
  • the lithium-containing compound of the present invention is lithium oxide, lithium carbonate, lithium fluoride, lithium chloride, lithium nitrate or lithium hydroxide.
  • a method for preparing a silicon-carbon composite anode material for a lithium ion battery comprises the following steps: 1. pulverizing the silicon phase particles to 0 ⁇ 1 ⁇ 1 ⁇ ⁇ to obtain ultrafine silicon phase particles; and having a particle size of ⁇ 75 m, ⁇ " The carbon phase particles having a particle size of 0.1 to 5 ⁇ m; and the silicon phase particles and the carbon phase particles are prepared by pulverizing, grading, shaping, and purifying the raw material by more than 95%. Mixing the granules into a composite granule matrix; 3.
  • the composite granule matrix with the precursor of the organic matter pyrolysis carbon of the composite granule matrix 1 to 25 wt% or wet stirring for 1 to 12 h, and then at 100 to 400 ° C TF Vapor deposition or coating granulation;
  • the coated particles are carbonized, heated in a protective atmosphere at 450 to 1500 ° C, held for 1 to 10 hours, and then cooled to room temperature to form a carbon coating;
  • the crushed and dispersed to 5 ⁇ 40 ⁇ , the lithium ion battery silicon carbon composite anode material was obtained.
  • the powder which is broken up to 5 ⁇ 40 ⁇ m is mixed with the powder of l ⁇ 30wt% of the powder, and then carbonized, heated in a protective atmosphere at 450 to 1500 ° C, and kept at 1 to After 10 hours, and then reduced to room temperature, the obtained powder is mixed with 0.5 to 5 % of conductive carbon, mixed in a mixer or surface coating modification machine for 1 to 6 hours, and dispersed using ultrasonic waves. ⁇ 30 minutes, crushed to 5 ⁇ 60 ⁇ ⁇ .
  • the immersion ratio is 0. 1 ⁇ 2, impregnated, the solid-liquid ratio is 0. 1 ⁇ 2, impregnated, the solid solution ratio is 0. 1 ⁇ 2, impregnated Time 1 to 48 hours.
  • the silicon phase particles of the method of the invention are elemental silicon, silicon oxide compound SiOx, silicon-containing solid solution or silicon-containing intermetallic compound, and the silicon phase particles account for 1 to 50 wt% of the composite particle matrix, wherein 0 ⁇ x 2, silicon-containing solid solution or
  • the silicon-containing intermetallic compound is any one or two of the lanthanum elements in the periodic table of silicon and the chemical element, any one or three of the transition metal elements, or any of the lanthanum elements or Two elements, or silicon Any one or two elements of the external IVA.
  • the carbon phase particles of the method of the present invention are a mixture of any one or more of natural flake graphite, microcrystalline graphite, artificial graphite, mesocarbon microbeads and coke, and the carbon phase particles occupy 50 to 99 of the composite particle matrix.
  • the ratio of the coating layer of the method of the invention to the composite material is 1 ⁇ 25wt% 0
  • the precursor of the organic pyrolytic carbon of the method of the invention is water-soluble polyvinyl alcohol, styrene-butadiene rubber emulsion, carboxymethyl cellulose, organic solvent-based polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Polyvinylidene fluoride, polyacrylonitrile organic, phenolic resin, epoxy resin, glucose, sucrose, fructose, cellulose or starch.
  • the conductive carbon of the method of the present invention is acetylene black, carbon nanotubes, nanocarbon microspheres, carbon fibers or conductive carbon black.
  • the lithium-containing compound of the method of the present invention is lithium oxide, lithium carbonate, lithium fluoride, lithium chloride, lithium nitrate or lithium hydroxide.
  • the silicon phase particle ball milling of the process of the present invention is carried out in a protective atmosphere, and the protective atmosphere is a mixture of any one or more of argon gas, hydrogen gas or nitrogen gas.
  • the silicon phase particles and the carbon phase particles are mixed and granulated, they are mixed and granulated in a mixing granulator for 1 to 6 hours.
  • the invention has a composite material of silicon phase particles and carbon phase particles as a matrix, and is spherical or spheroidal, and the lithium ion battery silicon carbon composite anode material coated with the coating layer has a high Electrochemical reversible absorption and desorption of lithium capacity and excellent cycle stability, the resulting negative electrode material has a reversible specific capacity of more than 450 mA / g, the first cycle coulombic efficiency is greater than 85%, cycle, sub-capacity retention rate is greater than 80%, significantly reducing silicon-containing activity
  • the volume effect of the substance in the absorption and desorption of lithium improves the diffusion behavior of lithium in the active material, improves the first efficiency and cycle stability compared with elemental silicon, reduces the consumption of the cathode material, and can insert and remove the lithium potential higher than the mesophase carbon.
  • a common anode material for lithium ion batteries such as microspheres, which prevents precipitation of metallic lithium on the surface of the negative electrode, has excellent high current discharge capability, and has a simple preparation process and an easy operation point, and is suitable for use in various portable devices, power tools, and the like.
  • Ion battery anode material BRIEF DESCRIPTION OF THE DRAWINGS:
  • Fig. 1 is an electron micrograph (1000 magnifications) of a silicon-carbon composite negative electrode material for a lithium ion battery according to a first embodiment of the present invention.
  • Fig. 2 is an electron micrograph (5000 magnifications) of a silicon-carbon composite negative electrode material of a lithium ion battery according to Embodiment 1 of the present invention.
  • Fig. 3 is a graph showing the first charge and discharge of the material of Example 1 of the present invention. _
  • Fig. 4 is an XRD chart of the material of Example 1 of the present invention.
  • the lithium-ion battery silicon-carbon composite anode material of the present invention is based on silicon phase particles and carbon phase particles, and is coated with a composite carbon coating layer.
  • the silicon phase particles in the matrix are elemental silicon, siloxane SiOx, wherein 0 ⁇ x 2, silicon-containing solid solution or silicon-containing intermetallic compound, wherein silicon-containing solid solution or silicon-containing intermetallic compound is composed of silicon and chemical element period Any one or two of the Group IIA elements, any one or three of the transition metal elements, any one or both of the lanthanum elements, or an IVA other than silicon Any one or two elements, the silicon phase particles account for 1 ⁇ 50wt% of the composite particle matrix ; the carbon phase particles in the matrix are any one of natural flake graphite, microcrystalline graphite, graphite, mesophase charcoal micro cokekind or more than one type of mixing.
  • the thickness of the coating layer is 0.1 to 5 ⁇ ⁇
  • the ratio of the organic pyrolytic carbon to the anode material is 0.5 to 20% by weight
  • the ratio of the conductive carbon to the anode material is 0.5 to 5 wt%.
  • the organic pyrolytic carbon in the coating layer is composed of water-soluble polyvinyl alcohol, styrene-butadiene rubber emulsion, carboxymethyl cellulose, organic solvent-based polystyrene, polymethyl methacrylate, polytetrafluoroethylene, poly Pyrocarbon, polyacrylonitrile, phenolic resin, epoxy resin, glucose, sucrose, fructose, cellulose, starch or asphalt as precursor, pyrocarbon formed by high temperature carbonization; conductive carbon in the coating is acetylene Black, carbon nanotubes, nanocarbon microspheres, carbon fiber or conductive carbon black Super-P.
  • the surface of the composite material of the negative electrode material is surface-treated with a lithium-containing compound of lithium, lithium carbonate, lithium fluoride, lithium chloride, lithium nitrate or lithium hydroxide.
  • the lithium ion battery silicon-carbon composite anode material of the present invention has the following technical features: an average particle diameter of 5 to 60 u, a specific surface area of 1.0 to 4.0 m 2 /g, and a tap density of 0.7 to 2.0 g cm 3 .
  • the average particle size described above is The Malvern laser particle size analyzer measured the specific surface area measured by the BET method using nitrogen displacement, and the tap density was measured using a Quantachrome AutoTap tap density meter.
  • the above material and ratio are used to prepare the lithium ion battery silicon carbon composite anode material of the invention, comprising the following steps: 1. one or more of the silicon phase particles in an air or non-oxidizing atmosphere such as argon, hydrogen or nitrogen. In a mixed gas, the ball is ground to 0.1 ⁇ 1 ⁇ ⁇ to obtain ultrafine silicon phase particles. 2. The carbon phase of the raw material having a particle size of ⁇ 75 m and a carbon content of 95% or more is pulverized, classified, shaped and purified to obtain more than 99.9% of carbon. a carbon phase particle having a particle diameter of 0.1 to 5 ⁇ m; 3.
  • the matrix and the composite particle matrix ⁇ 25w1% organic pyrolytic carbon precursor are ball or wet stirred for 1 ⁇ 12h, then vaporized or coated granulated at 100 ⁇ 40 (TC cake; fifth, the coated particles Carbonization treatment, heating 450 to 1500 ° C in a protective atmosphere, holding for 1 to 10 hours, then lowering to room temperature, forming a carbon coating layer, crushing and breaking up to 5 ⁇ 40 ⁇ ⁇ ; six, breaking up the broken to 5-
  • the powder of 40 U m is mixed with the asphalt of 1 ⁇ 30wt% of the powder. Mixing and coating in the machine; 7.
  • Silicon Si can reversibly occlude and release lithium by forming an intermetallic compound with lithium, such as 1 ⁇ 2 2 81 5 or the like.
  • the theoretical capacity of charge and discharge of Si can be as high as 4200 mAh/g, 9783 mA / cm 3 , and the specific gravity is calculated according to 2.33, which is much higher than the current graphite materials, the theoretical capacity is 372 mA / g or 844 mAh / g, specific gravity calculated according to 2.27.
  • the negative electrode material made of Si is accompanied by a serious volume change during absorption and release of Li, up to 300%, which is liable to cause cracks in the Si negative electrode. Powdering, the capacity is abruptly attenuated during the charge and discharge cycle, so pure Si cannot be directly used as a negative electrode material for a lithium ion secondary battery.
  • the Si phase particles are preferably of a smaller particle diameter.
  • silicon phase particles having a particle size of from 1 to 40 m are ball-milled to 0.1 to 1 ⁇ m in a protective atmosphere to prepare ultrafine silicon phase particles as a negative electrode active material in the composite material.
  • the average particle size of the Si phase particles When the average particle size of the Si phase particles is greater than 1 ⁇ m, the volume absorption effect of the matrix is weakened, which affects the cycle performance of the composite; if the average particle size of the Si phase particles is less than 0.1 m, the preparation is more difficult and easy.
  • the surface of the active particles is oxidized, which increases the chance of agglomeration between the particles and affects the specific capacity of the negative electrode material.
  • the particle diameter of the Si phase particles is measured by a scanning electron microscope SEM, and other methods such as a median diameter in the volume particle size distribution measured by a laser particle size analyzer may be used as the average particle diameter. In the examples, the average particle size of the particles was measured using a British Malvern Mastersizer 2000 laser particle size analyzer.
  • the Si phase particles account for 1 to 50% by weight of the composite particle matrix.
  • the proportion of the Si phase particles exceeds 50% by weight, the matrix cannot effectively buffer and absorb the volume effect of Si; on the other hand, if the proportion of the Si phase particles is less than 1% by weight, the capacity of the anode material cannot be effectively increased.
  • the ratio of Si phase particles is 5 to 30 wt%, and more female is 10 to 20 wt%.
  • the Si phase particles may be elemental silicon, siloxane SiOx, 0 ⁇ x 2, silicon solid solution or silicon-containing intermetallic compound.
  • the silicon solid solution or the silicon-containing intermetallic compound is any one or two of the lanthanum elements in the periodic table of silicon and the chemical element, any one or three of the transition metal elements, and any of the lanthanum elements.
  • these elements are preferably Mg, Ca and Ba of the lanthanum element, Ti, Cr, Mn, Fe, Co, Ni of the transition metal element. Cu, Mo, Ag, Ce, and Nd, lanthanum elements Al, Ga, ⁇ ⁇ , and Ge, Sn, and Sb of the IVA group elements.
  • more cranes Mg, Ca, Fe, Co, Ni and Cu.
  • the method of the present invention performs mixing granulation, composite coating and surface modification treatment on graphite and Si phase particles.
  • the lithium-ion battery silicon-carbon composite anode material of the invention is based on a composite material of silicon phase particles and carbon phase particles, and is coated with a composite.
  • the carbon coating layer has a spherical or nearly spherical itU characteristic
  • the outer cladding layer is a layer of organic pyrolytic carbon and conductive carbon to improve the compatibility of the graphite material with the electrolyte.
  • the cladding layer constrains the volumetric effect of the Si phase particles, improves the electrical conductivity, and can reversibly insert and deintercalate lithium, thereby increasing the capacity of the negative electrode material and the high current charge and discharge capability.
  • the larger crystal layer spacing of the cladding layer reduces the expansion and contraction of the bow during the repeated charge and discharge, avoids the ringing and spalling of the crucible anode material structure, and improves the cycle performance.
  • Example 3 is a first charge-discharge curve of a silicon-carbon composite material prepared in Example 1 of the present invention. Compared with a graphite-based material, a high potential of Si is increased on a charge-discharge curve, about 0.5 V vs. Li/Li + lithium storage. On the platform, the lithium absorption capacity of composite materials has been greatly improved.
  • Example 4 is an X-ray diffraction pattern XRD of a silicon-carbon composite material prepared in Example 1 of the present invention, and a standard powder diffraction data PDF card of the International X-ray Powder Diffraction Commission, which contains a carbon PDF card number in the diffraction pattern of the composite material.
  • the diffraction peaks of 41-1487 and silicon PDF card No. 27-1402 indicate that the silicon-carbon composite material of the present invention is composed of carbon and silicon.
  • the carbon phase particles in the above matrix are a mixture of any one or more of natural flake graphite, microcrystalline graphite, Ai graphite, mesocarbon microbeads and coke, and the carbon phase particles occupy 99 ⁇ of the composite particle matrix 50 wt%.
  • the carbon phase particles are mainly used to absorb and buffer the volume effect of the Si phase particles upon absorption and desorption of lithium, and provide a certain lithium intercalation capacity.
  • the above materials are all flexible carbon materials, have good elasticity and have high lithium insertion. Capacity.
  • the carbon phase particles are less than 50% by weight, the Si phase particles are not effectively dispersed, the volume effect of the carbon phase particles absorbing and buffering the active material Si is poor, and the cycle performance of the material is unfavorable; and when the proportion of the carbon phase particles is greater than 99% At the time, the proportion of active Si is reduced, thereby affecting the increase in the specific capacity of the material.
  • the composite carbon coating layer has a thickness of 0.1 to 5 ⁇ m, and is calculated by a Malvern laser particle size analyzer to measure the average particle diameter of the particles before and after coating.
  • the composite carbon coating layer contains organic pyrocarbon and conductive carbon, and the proportion of the negative electrode material is 1 to 25 wt%, wherein the ratio of the organic pyrolytic carbon to the coating layer is 0.5 to 20 wt%, and the conductive carbon accounts for the coating layer. The ratio is 0.5 to 5 wt%.
  • the thickness of the composite carbon coating layer is less than 0.1 ⁇ m or the proportion of the anode material is less than 1%, a complete coating layer cannot be formed, thereby affecting the cycle stability of the anode material; and when the coating layer is too thick, for example, larger than When 5 ⁇ ⁇ or the proportion of the coating layer to the negative electrode material is more than 25% by weight, the specific capacity and the first efficiency of the negative electrode material are affected, which is also disadvantageous for the improvement of the electrochemical performance of the negative electrode material.
  • the organic pyrolytic carbon in the coating layer is made of water-soluble polyvinyl alcohol, styrene-butadiene rubber latex, carboxymethyl cellulose, organic solvent-based polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Polyvinylidene fluoride, polyacrylonitrile organic matter, phenolic resin, epoxy resin, glucose, sucrose, fructose, cellulose, starch or earned as a precursor, pyrocarbon formed by high temperature carbonization.
  • Such organic substances are uniformly coated on the surface of the composite particle matrix as a precursor of late-stage pyrolytic carbon or as a binder, dispersant or suspending agent of the solution system when mixed with the composite particle matrix, and in the later pyrolysis carbonization process.
  • Thermal decomposition reaction and thermal polycondensation reaction occur.
  • compounds composed of elements such as H, 0, and N contained in organic compounds are decomposed, and carbon atoms are continuously cyclized and aromatized.
  • atoms such as H, 0, and N are continuously reduced, and C is not Gland paste and enrichment.
  • the organic matter is subjected to a liquid phase carbonization process to form an easily graphitizable carbon, that is, a soft carbon, or only a solid phase carbonization process to form a hardly graphitizable carbon, that is, a hard carbon.
  • pyrolytic carbon is non-graphitizable carbon, and the material contains many small molecules, and the micropores formed during pyrolysis escape can better absorb and buffer the volume effect of the active material during charging and discharging, and the heat
  • the larger spacing of the carbon-decomposing layers is beneficial to the extraction and extraction of lithium ions.
  • the tongue L-layer structure of the pyrolytic carbon material also prevents the graphite layer from being etched by the solvated lithium ion co-inlay, thereby improving the cycle stability.
  • the conductive carbon in the coating layer is acetylene black, carbon nanotubes, nano carbon microspheres, carbon fiber or conductive carbon black Superb W 200
  • the method of mixing and coating the composite particle substrate with the precursor of the organic pyrolytic carbon and the conductive carbon is not particularly limited, and any known mixing and granulating equipment can be surfaced.
  • the mixed coating is mixed ball milling, wet stirring for l ⁇ 12h, followed by vapor deposition and coating granulation.
  • the vapor deposition and coating granulation are selected from 100 ° C to 400 ° C, when the treatment is lower than 100 ° C.
  • the powder drying speed is slower, the coating effect is poor, and it is easy to cause mutual adhesion between the particles, which affects the production efficiency and product quality.
  • the coating is carbonized or oxidized, which also affects the coating. effect.
  • the above mixture is carbonized, kept at 450 ° C to 1500 ° C for 1 to 10 hours, and then lowered to room temperature.
  • the secondary coating treatment is carried out, and the secondary coating material is asphalt, and the coating amount is l ⁇ 30wt%.
  • the above carbonization treatment is carried out in a non-oxidizing atmosphere, for example, under a nitrogen gas, an argon gas, a helium gas, a helium gas or a mixed gas of the above gas, a vacuum or a reducing atmosphere.
  • the carbonization i is carried out at 450 ° C to 1500 ° C for 10 hours and then lowered to room temperature.
  • the present invention is carried out on the surface of the composite material.
  • the coated or immersed conductive carbon is treated, and the conductive carbon accounts for 0.5 to 5 wt% of the negative electrode material.
  • the amount of conductive carbon is less than 0.5 wt ° /.
  • the conductivity of the material cannot be effectively improved; and when the proportion of the conductive carbon is more than 5% by weight, the specific capacity of the material and the charge and discharge efficiency are adversely affected.
  • a suitable amount of conductive addition is selected between 0.5 and 5%.
  • the coating method of the silicon-carbon composite material and the conductive carbon after the mixed coating treatment is not particularly limited, and any known mixing equipment can be used, such as a high-speed mixer, a planetary mixer, etc., and the mixing treatment time is 1 to 6 hours.
  • the suspension of the above composite material and conductive carbon is ultrasonically treated, and the ultrasonic treatment time is 1 ⁇ !
  • the basis of the graphite crystallites in the negative electrode material, the relative amount of the end faces, the difference in reactivity, the crystallite size, the electrolyte composition, and the kinetic properties of the reductive decomposition determine the compactness of the passivation film on the surface of the electrode.
  • the method of the invention adopts an inorganic or organic solution system containing a lithium compound to treat the silicon-carbon composite anode material, and forms a dense lithium ion-conducting solid electrolyte membrane on the surface of the anode material to improve the first charge and discharge efficiency and cycle of the anode material. stability.
  • a lithium-ion battery silicon-carbon composite anode material is most sought for by impregnating a lithium-containing compound.
  • the silicon-carbon composite negative electrode material for a lithium ion battery obtained by the above treatment has an average particle diameter of 5 to 60 ⁇ m, a specific surface area of 1.0 to 4.0 m 2 /g, and a tap density of 0.7 to 2.0 g cm 3 .
  • the average particle size described above was measured by a Malvern laser particle size analyzer, and the specific surface area was measured by a BET method using nitrogen displacement, and the tap density was measured using a Quantachrome AutoTap tap density meter.
  • Example 1 preparing a silicon carbon Si-GC-Li 2 C0 3 composite anode material: a silicon powder having a particle size of 75 ⁇ m was mechanically high-energy ball-milled to 0.5 nm in an argon atmosphere to obtain an ultrafine silicon powder; ⁇ ⁇ , more than 95% of natural graphite pulverization, grading, shaping and purification treatment to obtain more than 99.9% of spherical graphite with a particle size of 1 ⁇ m; the obtained ultrafine silicon powder 20wt% 3 ⁇ 4 80wt% spherical graphite in double The granules were mixed and granulated in a screw mixer for a few hours to form a composite particle matrix; and the composite particle matrix was 10 wt/min.
  • the phenolic resin is mixed and wet-mixed for 10 hours, and then dried at 300 ° C.
  • the composite material coated with the phenolic resin is carbonized, heated to 1,100 ° C in an argon atmosphere, kept for 3 hours, then cooled to room temperature, and crushed.
  • the crushed powder is mixed with 10 ⁇ 1% asphalt, carbonized, heated at 1200 ° C in an argon atmosphere, kept for 2 hours, then cooled to room temperature, broken up to 20 nm And then mixed with 0.5wt% carbon nanotubes in a high-speed mixer for 4 hours, while using ultrasonic treatment 5 with a frequency of 28kHz and a power of 3600W; impregnating 1% Li 2 C0 3 solution for 1 hour, solid-liquid ratio 0.1, and finally A silicon-carbon composite negative electrode material was obtained, and the average particle diameter was 20.1 rn, the specific surface area was 3.5 m 2 /g, and the tap density was 1.3 cm 3 .
  • the obtained composite material was prepared as follows: 5 g of composite negative electrode material, 2.5 g of styrene-butadiene rubber latex SBR, 1.5 g of carboxymethyl cellulose CMC, 1 g of conductive agent Superb, and an appropriate amount of pure water dispersing agent were mixed uniformly.
  • the charge and discharge test was carried out at a rate of 1 C, and the charge and discharge voltage was limited to 4.2-3.0 volts, and the capacity retention rate Qoo C of the test battery cycle was 200 times.
  • Example 2 preparing a silicon carbon Si-Mg-GC-LiOH composite anode material: a Si-Mg powder having a particle size of 75 ⁇ m, containing Si 50 wt%, and mechanically high-energy ball milling to 0.1 m in an argon atmosphere to prepare an ultra Fine Si-Mg powder; pulverized, graded and purified natural graphite with a particle size of 70 ⁇ ⁇ and a carbon content of 95% or more to prepare spherical graphite with a particle size of 3 ⁇ ⁇ ; Si-Mg powder 30wt% and 70wt% spherical graphite were mixed in a mixing granulator for 1 hour to form a composite particle matrix; the composite particle matrix was mixed with 2.5wt% T latex and wet-dried for 4 hours, then dried at 200 °C.
  • the obtained negative electrode material was prepared in the same manner as in Example 1 to carry out an electrochemical performance test.
  • Example 3 preparing a silicon-carbon Si-Fe-GC-LiF composite anode material: a Si-Fe powder having a particle size of 75 ⁇ , containing 75 wt% of Si, mechanically high-energy ball milling to 1 ⁇ m in an argon atmosphere, Ultrafine Si-Fe powder; pulverized, graded, and purified natural graphite with a particle size of 70 ⁇ ⁇ and a carbon content of 95% or more 99.9% or more, spherical graphite having a particle diameter of 5; and the obtained ultrafine Si-Fe powder is 2 wt%/. And 98wt ° /.
  • the spherical graphite is mixed in a mixing granulator for 6 hours to form a composite particle matrix; the composite particle substrate is mixed with a lwt% polyvinyl alcohol solution and wet-stirred for 10 hours, and then dried at 200 ° C for granulation;
  • the composite material is carbonized, heated to 1500 ° C in an argon atmosphere, kept for 1 hour, then cooled to room temperature, crushed and broken up to 5 u rn; mixed powder and 10 ⁇ % asphalt mixed coating, carbonization Treatment, heating at 1200 ° C in an argon atmosphere, holding for 10 hours, then dropping to room temperature, crushing and breaking up to 15 ⁇ m, and then mixing with a 5% carbon fiber high speed mixer for 6 hours; using a frequency of 40 kHz and a power of 50 W In the ultrasonic treatment 30, the granulation was then dried at 100 ° C, and the 0.2% LiF solution was immersed for 48 hours, and the solid-liquid ratio was 2, and finally a silicon-carbon composite negative
  • the obtained negative electrode was prepared in the same manner as in Example 1 to carry out an electrochemical performance test.
  • Example 4 preparing a silicon-carbon Si-Ca-GC-LiCl composite anode material: Si-Ca powder having a particle size of 75 ⁇ m, mechanically high-energy ball milling to 0.6 ⁇ ⁇ in a 60 wt% argon atmosphere, to obtain ultrafine Si-Ca powder; pulverized, graded, and purified natural graphite with a particle size of 70 P m and a carbon content of 95% or more to obtain spherical graphite having a carbon content of 99.9% or more and a particle diameter of 5 ⁇ m; Si-Ca powder 40% and 60 t% spherical graphite were mixed in a conical mixer for 4 hours to form a composite particle matrix; the composite particle substrate was mixed with 10 wt% phenolic resin and wet-stirred for 4 h, and then 400 dried and granulated; The coated composite was carbonized
  • the obtained negative electrode material was prepared in the same manner as in Example 1 to carry out an electrochemical performance test.
  • Example 5 preparing a silicon carbon SiO-GC-Li 2 0 composite anode material: SiO powder having a particle size of 75 ⁇ m was mechanically high-energy ball-milled to 0.8 ⁇ m in an argon atmosphere to obtain an ultrafine SiO powder; ⁇ m, J graphite with a carbon content of 95% or more, pulverized, shaped and purified to obtain spherical graphite with a carbon content of 99.9% or more and a particle size of 3 ⁇ m; the ultrafine SiO powder obtained is 15 wt% and 85 ⁇ % spherical graphite mixture was mixed and granulated in a double-helical mixer for 5 hours to form a composite particle matrix; the composite particles were mixed with 2.5 wt% polystyrene and wet-stirred for 4 h, then dried at 250 ° C for granulation; The composite material
  • Example 6 Preparation of a silicon-carbon Si-GG-LiN0 3 composite anode material: Si-Ni powder having a particle size of 75 ⁇ m, mechanically high-energy ball milling to 0.6 ⁇ m in a 40% by weight argon atmosphere, to obtain ultrafine Si -Ni powder; The natural graphite with a particle size of 70 U m and a cerium content of 95% or more is prepared by pulverizing, grading, shaping and purifying!
  • spherical graphite with a particle size of 3 m 50% by weight of the obtained ultrafine Si-Ni powder and 50% of spherical graphite are mixed and granulated in a double spiral mixer for 6 hours to form a composite particle matrix
  • the composite particles were mixed with 2.5 wt% butadiene latex for 4 h, and then dried at 200 ° C for granulation; the coated composite was carbonized, heated to 700 ° C in an argon atmosphere, and kept for 5 hours.
  • the crushed powder is mixed with 12wt% of asphalt, carbonized, heated at 1200 ° C in an argon atmosphere, kept for 10 hours, then cooled to room temperature, broken Disperse to 5 ⁇ ⁇ , then mix with 1% conductive carbon black Super-P in a high-speed mixer for 2 hours, while using a frequency of 35kFfe, power of 2500W ultrasonic treatment 15 impregnation of 10% LiN0 3 solution for 36 hours, solid-liquid ratio 2, the silicon-carbon composite anode material is finally obtained.
  • the average particle diameter was measured to be 5.2 m, the specific surface area was 4.0 m 2 /g, and the tap density was 2.0 gcm 3 .
  • the obtained negative electrode material was prepared in the same manner as in Example 1 to carry out an electrochemical performance test.
  • Example 7 Preparation of Silica Carbon SiO 2 -GC Composite Anode Material:
  • the SiO 2 powder having a particle size of 75 m was mechanically high-energy ball-milled to 0.8 ⁇ m in air to prepare an ultrafine SiO 2 powder; the particle size was 70 m, and the carbon content was More than 95% of the artificial graphite is pulverized and purified to obtain more than 99.9% of graphite fine powder having a particle diameter of 3 ⁇ ;
  • the obtained ultrafine Si0 2 powder 10% and 90% by weight of spherical graphite are mixed in a double-helical mixer Mixed granulation for 5 hours to form a composite granule matrix; mixing the composite granules with 25% phenolic resin in a wet method for 4 hours, and then drying and granulating at 250 ° C; the coated composite material is carbonized, and contains hydrogen gas.
  • the mixture was heated to 1300 ° C in a reducing atmosphere, kept for 2 hours, then cooled to room temperature, crushed and dispersed to 40 ⁇ ⁇ ; the crushed powder was mixed with 5 wt% of asphalt, carbonized, and heated in an argon atmosphere at 1100. °C, keep warm for 10 hours, then drop to room temperature, crush and break up to 60 m, and finally get silicon-carbon composite anode material.
  • the average particle diameter was measured to be 60.4 ⁇ m, the specific surface area was 2.8 m 2 /g, and the tap density was 0.98 g/cm 3 .
  • Example 8 Preparation of a silicon-carbon Si-GC composite anode material: Si powder having a particle size of 75 ⁇ m was mechanically high-energy ball-milled to 0.5 m in an argon atmosphere to obtain an ultrafine Si powder; mm 70 u rn, carbon content 95 More than % of natural graphite is crushed, graded, shaped and purified to produce spherical graphite with a carbon content of 99.9% or more and a particle size of 3 ⁇ m; and the prepared ultrafine Si powder 5 ⁇ % and 95% by weight of spherical graphite are mixed in a double helix Mixing and granulating for 5 hours in a blender to prepare a composite particle matrix; mixing the composite particles with 2.5 wt% T"3 ⁇ 4t latex SBR, 1.5% carboxymethylcellulose CMC 1.5% wet mixing ball for 1 h, then drying at 250 ° C Granular;
  • the obtained negative electrode material was prepared in the same manner as in Example 1 to carry out an electrochemical performance test.
  • Example 9 preparing a silicon carbon Si-GC composite anode material: a Si powder having a particle size of 75 ⁇ m was mechanically high-energy ball-milled to 0.5 ⁇ m in an argon atmosphere to prepare an ultrafine Si powder; a particle size of 70 ⁇ m, carbon More than 95% of the cumin graphite pulverization, grading, shaping and purification treatment to obtain more than 99.9% of spherical graphite with a particle size of 3 ⁇ m; the ultrafine Si powder obtained is 1% and 99wt. /.
  • the spherical graphite mixture was mixed and granulated in a double-helical mixer for 5 hours to prepare a composite particle matrix; the composite particles were mixed with 2.5 wty. Ding 3 ⁇ 4 latex SBR, 1.5% carboxymethyl cellulose CMC 1.5% wet mixing ball mill 12h, while using frequency 28kHz, power 3600W, ultrasonic treatment 5, then dry granulation at 250 °C; Carbonized, heated to 450 ° C in an argon atmosphere, held for 10 hours, then reduced to room temperature, broken up to 15 m; mixed powder and 6 % asphalt mixed coating, carbonization, in argon The gas atmosphere was heated at 1100 ° C, kept for 10 hours, then cooled to room temperature, crushed and broken up to 17 ⁇ ⁇ , and finally a silicon-carbon composite anode material was obtained. The average particle size was measured to be 17.5 m, the specific surface area was 3.2 m 2 /g, and the tap density was 1.03 g cm 3 .
  • the average particle size was measured to be 17.5 ⁇ m, the specific surface area was 2.1 m 2 /g, and the tap density was 1.23 g C m 3 .
  • the obtained negative electrode material was prepared in the same manner as in Example 1 to carry out an electrochemical performance test.
  • the obtained negative electrode material was prepared in the same manner as in Example 1 to carry out an electrochemical performance test.
  • the graphite anode material prepared by the invention has a reversible specific capacity of more than 450 mAh/g, and the capacity retention rate of the cycle of 200 times is greater than 80%.
  • the lithium-ion battery silicon-carbon composite anode material of the invention can be widely used as a negative electrode material for lithium ion batteries of portable electric instruments and tools such as mobile phones, notebook computers and camcorders, and greatly improves the specific capacity of the battery, and satisfies the requirements.
  • Electrical appliances have light weight requirements for power supplies and are suitable for use in various fields. Electrochemical performance of polar materials
  • Si phase grain in the matrix Si phase grain in the matrix, first charge capacity, first hit capacity, 200 cycles of volume, and its content, mAh/g mAh/g, volume retention, %

Abstract

A silicon-carbon composite negative material for lithium ion battery and the preparation method of the same of which the technical problem to be solved is to improve the specific capacity of the battery. The material of the invention is based on the composite particles of silicon-phase particles and carbon-phase particles which are spheric or quasi-spheric and coated with carbon coating layer. The preparation is as following: crushing the silicon-phase particles; mixing and coating the composite particles, obtained by mixing the silion-phase particles and the carbon-phase particles, with the precursor of pyrolytic carbon of organic matter; carbonizing treatment; and crashing and breaking. Comparing with prior art, the reversible specific capacity of the composite negative electrode material which is coated with coating layer and based on the composite material of the silicon-phase particles and the carbon-phase particles is larger than 450mAh /g, the coulomb efficiency higher than 85% at first cycle, the conservation rate for capacity is larger than 80% in 200 times of circulation. The volume effect of the silicon-containing active material during the intercalation and de-intercalation process can be decreased, the diffusion action of the lithium in the active material is improved, and the material obtained can be used as negative electrode material for lithium ion battery suitably in the application of the portable device and electric tools.

Description

技术领域 Technical field
― 本发明涉及一种电池负极材料及其制备方法，特别是一种锂离子电池的硅碳复 合负极材料及其制备方法。  The invention relates to a battery anode material and a preparation method thereof, in particular to a silicon carbon composite anode material for a lithium ion battery and a preparation method thereof.
背景技术 Background technique
自从 1990年日本 Sony公司率先研制成功锂离子电池并将其商品化以来，锂离 子电池得到了迅猛发展。 如今锂离子电池已经广泛地应用于民用及军用的各个领 域。随着碰的不纖步， 人们对电池的性能提出了更多更高的要求： 电子设备的 小型化和个性化发展， 需要电池具有更小的体积和更高的比能量输出；航空航天能 源要求电池具有循环寿命，更好的低温充放电性能和更高的安全性能； 电动汽车需 要大容量、低成本、 高稳定性和安全性能的电池。锂离子电池的研制成功， 应首先 归功于电极材料， 特别是碳负极材料的突破， 在众多的碳材料中， 石墨化碳材料由 于具有良好的层状结构， 非常适合于锂离子的嵌入和脱嵌， 形成的石墨一锂层间化 合物 Li-GIC具有较高的比容量， 接近 LiC6的理论比容量 372mAh/g; 同时具有良 好的充放电电压平台和较低的嵌脱锂电位， 与提供锂源的正极材料， 如 LiCo02、 ^^02及1^]\½204等匹配性较好，所组成的电池平均电压高，放电平稳， 因此目前 商品化锂离子电池大量采用石墨类碳材料作为负极材料。 Lithium-ion batteries have developed rapidly since Sony Corporation took the lead in developing and commercializing lithium-ion batteries in 1990. Today, lithium-ion batteries have been widely used in various fields of civil and military applications. With the lack of fiber, people have put forward more and higher requirements on the performance of the battery: The miniaturization and individual development of electronic equipment requires the battery to have a smaller volume and higher specific energy output; aerospace energy The battery is required to have a cycle life, better low temperature charge and discharge performance and higher safety performance; electric vehicles require batteries with high capacity, low cost, high stability and safety performance. The successful development of lithium-ion batteries should be attributed to the breakthrough of electrode materials, especially carbon anode materials. Among many carbon materials, graphitized carbon materials are very suitable for the insertion and removal of lithium ions due to their good layered structure. The embedded graphite-lithium intercalation compound Li-GIC has a high specific capacity, close to the theoretical specific capacity of LiC 6 of 372 mAh/g , and has a good charge and discharge voltage platform and a low intercalation and deintercalation potential. The positive electrode materials of lithium source, such as LiCo0 2 , ^^0 2 and 1^]\1⁄2 2 0 4 have good matching, and the assembled battery has high average voltage and stable discharge. Therefore, a large number of commercial lithium ion batteries use graphite. A carbon-like material is used as a negative electrode material.
但是目前石墨类材料已接近理论容量，为了实现大电流密度下的安全可操作性， 减少首次不可逆容量损失， 满足未来市场锂离子电池高比能量、 高比功率的要求， 新型锂离子电极材料的开发极具迫切性， 目前学术界对该类电极材料的研究十分活 跃， 负极材料中的研究发现如 Al、 Sn、 Sb、 Si等， 这些能够与锂形成合金的金属 及其合金作为锂离子电池负极材料， 即是指 Al、 Sn、 Sb、 Si或其合金作为负极材 料，其可逆储锂的量远远大于石墨类负极材料。但该类负极材料高的体积效应造成 较差的循环稳定性， 使这些体系距实用化程度仍存在一定的距离。 因此， 如何使这 些高储锂性能的材料实用化已成为当前锂离子电池研究的热点问题。 However, at present, graphite materials are close to the theoretical capacity, in order to achieve safe operability at high current density, reduce the first irreversible capacity loss, meet the requirements of high specific energy and high specific power of lithium ion batteries in the future market, and new lithium ion electrode materials. The development is extremely urgent. At present, the research on this kind of electrode materials is very active in the academic community. The research in the negative electrode materials, such as Al, Sn, Sb, Si, etc., these metals and their alloys which can form alloys with lithium as lithium ion batteries Anode material, that is, Al, Sn, Sb, Si or an alloy thereof as a cathode material The amount of reversible lithium storage is much larger than that of graphite-based anode materials. However, the high volume effect of such negative electrode materials results in poor cycle stability, and these systems still have a certain distance from the practical degree. Therefore, how to make these high lithium storage materials practical has become a hot issue in current lithium ion battery research.
在非碳基负极材料的研究中， 硅基材料因具有高的理论储锂容量， 如单晶 Si: 4200mAlVg, 低的嵌锂电位， 较其它金属及材料有更高的稳定性而备受瞩目。 Si基 材料如能成功应用， 作为锂离子电池的负极材料， 必将对锂离子电池的发展产生划 时代的意义，也会对信息、能源行业的发展产生重大影响。但是与金属謝料一样， 硅基材料在高程度脱嵌锂^ ί牛下，存在严重的体积效应，造成电极的循环稳定性不 稳定， 且其初次不可逆容量高， 限制了其作为锂离子电池负极材料的应用。 因此， 目前许多研究者都致力于这种高储锂性能材料的改性与优化设计。 如日立属下的 Maxwell公司采用 CVD法制备的¾ ^粒外包裹无定形炭层颗粒的复合体系， 改善 了硅材料的结构和导电性能，在一定程度上能抑制住锂嵌入和脱出过程中的体积效 应， 从而使该类材料的循环性能得到了提高。 但 CVD法的过禾 M隹以控制， 不确定 因素多， 因此很难实现批量生产。 C.S.Wang等人采用石墨与硅粉通过机械球磨的 方法制备的 ¾ /碳二元体系复合物材料具有较高的首次嵌锂容量， 但其充放电性能 不稳定， 尤其是初始几个循环容量衰减很快 （J. Electrochem. Soc.， 8(1998): 2751-2758 ) 0 S.B.Ng 等采用溶胶-凝胶法制备的类似网状结构的石墨一硅 / Si(OCH3)4复合材料虽然具有相对稳定的机械性能， 有利于循环性能的提高， 但另 一方面， Si-0网状结构的存在也阻碍锂的扩散行为， 使锂的嵌入量减少， 不能充分 发挥出 Si的高容量特性 (J. Power Sources, 94(2001): 63-67)。 In the study of non-carbon based anode materials, silicon-based materials have attracted much attention due to their high theoretical lithium storage capacity, such as single crystal Si : 4200mAlVg, low lithium insertion potential, and higher stability than other metals and materials. . If Si-based materials can be successfully applied, as a negative electrode material for lithium-ion batteries, it will definitely have an epoch-making significance for the development of lithium-ion batteries, and will also have a major impact on the development of information and energy industries. However, like the metal, the silicon-based material has a serious volume effect under high degree of deintercalation of lithium, which causes unstable cycle stability of the electrode, and its initial irreversible capacity is high, which limits its use as a lithium ion battery. Application of negative electrode materials. Therefore, many researchers are currently working on the modification and optimization of this high lithium storage performance material. For example, Maxwell's composite system of 3⁄4 ^ extragranular amorphous carbon particles prepared by CVD method improves the structure and electrical conductivity of silicon materials, and can inhibit the insertion and extraction process of lithium to a certain extent. The volume effect, which improves the cycle performance of this type of material. However, the CVD method is controlled by a lot of uncertainties, so it is difficult to achieve mass production. CSWang et al. used a 3⁄4/carbon binary system composite material prepared by mechanical ball milling of graphite and silicon powder to have a high first lithium insertion capacity, but its charge and discharge performance is unstable, especially the initial cycle capacity attenuation is very high. J. Electrochem. Soc., 8(1998): 2751-2758 ) 0 SBNg, etc., similar to the network structure of graphite-silicon/Si(OCH 3 ) 4 composite prepared by sol-gel method, although relatively stable The mechanical properties are beneficial to the improvement of the cycle performance. On the other hand, the presence of the Si-0 network structure also hinders the diffusion behavior of lithium, which reduces the amount of lithium intercalation and does not fully exert the high capacity characteristics of Si (J. Power Sources, 94 (2001): 63-67).
针对硅由于在电化学锂嵌脱时产生的严重体积效应， 禾 IJ用体积补偿的方式， 制 备出一种含硅复合材料，保持硅的高比容量特性， 同时使整体电极的体积变化控制 在合理水平， ±曾加循环稳定性。 以提高锂离子电池的负极材料的能量密度， 使该负 极材料比目前商 k±锂离子电池中常用的碳负极材料具有更高的比容量，满足各类 发明内容 In view of the serious volume effect of silicon during electrochemical lithium insertion and removal, HeJ uses a volume compensation method to prepare a silicon-containing composite material, which maintains the high specific capacity characteristics of silicon and simultaneously controls the volume change of the whole electrode. A reasonable level, ± has added cycle stability. In order to improve the energy density of the anode material of the lithium ion battery, the anode material has a higher specific capacity than the carbon anode material commonly used in the current k± lithium ion battery, and satisfies various types. Summary of the invention
本发明的目的是提供一种锂离子电池硅碳复合负极材料及其制备方法，要解决 的技术问题是提高电池的比容量， 具兼有优异的循环性能和倍率放电性能。  The object of the present invention is to provide a lithium-ion battery silicon-carbon composite anode material and a preparation method thereof, and the technical problem to be solved is to improve the specific capacity of the battery, and have both excellent cycle performance and rate discharge performance.
本发明釆用以下技术方案： 一种锂离子电池硅碳复合负极材料， 所述锂离子电 池硅碳复合负极材料以硅相粒子和碳相粒子的复合颗粒为基体，基体呈球形或类球 形， 基体外包覆有碳包覆层。  The invention adopts the following technical solutions: a lithium-ion battery silicon-carbon composite anode material, wherein the lithium-ion battery silicon-carbon composite anode material is based on composite particles of silicon phase particles and carbon phase particles, and the matrix is spherical or spheroidal. The substrate is coated with a carbon coating layer.
本发明的碳包覆层是有机物热解炭包覆层。  The carbon coating layer of the present invention is an organic pyrolytic carbon coating layer.
本发明的碳包覆层含有导电碳。  The carbon coating layer of the present invention contains conductive carbon.
本发明的碳包覆层表面含有锂化合物。  The surface of the carbon coating layer of the present invention contains a lithium compound.
本发明的包覆层厚度为 0. 1-5 μ m, 有机物热解炭占负极材料的比例为 0. 5〜 20wt%, 导电碳占负极材料的比例是 0. 5〜5wt%。  5〜5重量%。 The ratio of the ratio of the ratio of the conductive material to the negative electrode material is 0. 5~5wt%.
本发明的硅碳复合负极材料的平均粒径为 5〜60 m,比表面积 1. 0〜4. 0 m2/g, 振实密度 0. 7〜2. 0g/cm3。 0 〜2. 0g/cm 3。 The silicon-carbon composite negative electrode material having an average particle diameter of 5 to 60 m, a specific surface area of 1. 0~4. 0 m 2 / g, a tap density of 0. 7~2. 0g / cm 3 .
本发明的硅相粒子是单质硅、硅氧化合物 Si0x、含硅固溶体或含硅金属间化合 物， 硅相粒子占复合颗粒基体的 1〜50 wt%, 其中 0<x 2。  The silicon phase particles of the present invention are elemental silicon, a silicon oxide compound Si0x, a silicon-containing solid solution or a silicon-containing intermetallic compound, and the silicon phase particles constitute 1 to 50% by weight of the composite particle substrate, wherein 0 < x 2 .
本发明的娃相粒子占复合颗粒基体的比例 ί½在 5〜30wt%。  The ratio of the silicon phase particles of the present invention to the matrix of the composite particles is 5 to 30% by weight.
本发明的硅相粒子占复合颗粒基体的比例进一步优选在 10〜20wt%。  The proportion of the silicon phase particles of the present invention to the composite particle substrate is further preferably from 10 to 20% by weight.
本发明的含硅固溶体或含硅金属间化合物，是由硅与化学元素周期表中 ΠΑ族 元素中的任一种或两种元素、过渡金属元素中的任一种或三种元素、 ΠΙΑ族元素中 的任一种或两种元素， 或除硅之外的 IVA族元素中的任一种或两种元素构成。  The silicon-containing solid solution or the silicon-containing intermetallic compound of the present invention is composed of any one or two elements of a lanthanum element in the periodic table of silicon and a chemical element, or any one or three elements of a transition metal element, a lanthanum Either or both of the elements, or one or both of the Group IVA elements other than silicon.
本发明的碳相粒子是天然鳞片石墨、微晶石墨、 A 石墨、 中间相炭微辦口焦 炭中的任意一种或一种以上的混合。  The carbon phase particles of the present invention are any one or a mixture of one or more of natural flake graphite, microcrystalline graphite, A graphite, and mesophase carbon micro-port coke.
本发明的有机物热解炭是由水溶性的聚乙烯醇、 丁苯橡胶乳、 羧甲基纤维素， 有机溶剂系的聚苯乙烯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯、聚丙烯腈、 酚醛树脂、环氧树脂， 葡萄糖、 蔗糖、果糖、 纤维素、 淀粉或沥青为前驱体， 经高 温碳化所形成的热解炭。 The organic pyrolytic carbon of the present invention is composed of water-soluble polyvinyl alcohol, styrene-butadiene rubber latex, carboxymethyl cellulose, Organic solvent-based polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, phenolic resin, epoxy resin, glucose, sucrose, fructose, cellulose, starch or asphalt as precursors Body, pyrolytic carbon formed by high temperature carbonization.
本发明的导电碳为乙炔黑、 碳纳米管、 纳米碳微球、 碳纤维或导电碳黑。  The conductive carbon of the present invention is acetylene black, carbon nanotubes, nanocarbon microspheres, carbon fibers or conductive carbon black.
本发明的含锂化合物为氧化锂、碳酸锂、氟化锂、氯化锂、硝酸锂或氢氧化锂。 一种锂离子电池硅碳复合负极材料的制备方法， 包括以下步骤： 一、将硅相粒 子粉碎至 0· 1〜1 μ ηι, 制得超细硅相粒子； 将粒度 <75 m， ^"量 95%以上的原料 碳粉碎分级、 整形和纯化处理制备得到 ^量 99. 9%以上， 粒径为 0. 1〜5 μ m的碳 相粒子； ：、将硅相粒子和碳相粒子混^ 粒， 制成复合颗粒基体； 三、将复合颗 粒基体与占复合颗粒基体 l〜25wt%的有机物热解炭的前驱体混合或湿法搅拌 1〜 12h, 然后在 100〜400°C TF气相沉积或包覆造粒； 四、 将包覆后的颗粒进行碳 化处理， 在保护气氛中加热 450至 1500°C， 保温 1至 10小时， 然后降至室温， 形 成碳包覆层； 五、 破碎打散至 5〜40 μπι， 制得锂离子电池硅碳复合负极材料。  The lithium-containing compound of the present invention is lithium oxide, lithium carbonate, lithium fluoride, lithium chloride, lithium nitrate or lithium hydroxide. A method for preparing a silicon-carbon composite anode material for a lithium ion battery comprises the following steps: 1. pulverizing the silicon phase particles to 0·1~1 μ ηι to obtain ultrafine silicon phase particles; and having a particle size of <75 m, ^" The carbon phase particles having a particle size of 0.1 to 5 μ m; and the silicon phase particles and the carbon phase particles are prepared by pulverizing, grading, shaping, and purifying the raw material by more than 95%. Mixing the granules into a composite granule matrix; 3. Mixing the composite granule matrix with the precursor of the organic matter pyrolysis carbon of the composite granule matrix 1 to 25 wt% or wet stirring for 1 to 12 h, and then at 100 to 400 ° C TF Vapor deposition or coating granulation; Fourth, the coated particles are carbonized, heated in a protective atmosphere at 450 to 1500 ° C, held for 1 to 10 hours, and then cooled to room temperature to form a carbon coating; The crushed and dispersed to 5~40 μπι, the lithium ion battery silicon carbon composite anode material was obtained.
本发明方法将所述破碎打散至 5〜40 μ m的粉体与占粉体 l〜30wt%沥青混合包 覆， 然后进行碳化处理， 在保护气氛中加热 450至 1500°C， 保温 1至 10小时， 然 后降至室温， 所得粉体与占粉体 0. 5〜5 %的导电碳混合包覆， 在混合机或表面包 覆改性机中混合 1〜6小时， 并使用超声波分散 1〜30分钟， 破碎至 5〜60μ πι。  In the method of the invention, the powder which is broken up to 5~40 μm is mixed with the powder of l~30wt% of the powder, and then carbonized, heated in a protective atmosphere at 450 to 1500 ° C, and kept at 1 to After 10 hours, and then reduced to room temperature, the obtained powder is mixed with 0.5 to 5 % of conductive carbon, mixed in a mixer or surface coating modification machine for 1 to 6 hours, and dispersed using ultrasonic waves. ~30 minutes, crushed to 5~60μ πι.
本发明方法将所述破碎至 5〜60 u m的复合物浸渍含锂化合物， 将复合物粉体 到浓度为 0. 2〜10wt%含锂化合物溶液中， 固液比 0. 1〜2， 浸渍时间 1〜48小 时。  The immersion ratio is 0. 1~2, impregnated, the solid-liquid ratio is 0. 1~2, impregnated, the solid solution ratio is 0. 1~2, impregnated Time 1 to 48 hours.
本发明方法的硅相粒子是单质硅、硅氧化合物 Si0x、含硅固溶体或含硅金属间 化合物， 硅相粒子占复合颗粒基体的 l〜50 wt%， 其中 0<x 2， 含硅固溶体或含硅 金属间化合物， 是由硅与化学元素周期表中 ΠΑ族元素中的任一种或两种元素、过 渡金属元素中的任一种或三种元素、 ΠΙΑ族元素中的任一种或两种元素，或除硅之 外的 IVA 素中的任一种或两种元素构成。 The silicon phase particles of the method of the invention are elemental silicon, silicon oxide compound SiOx, silicon-containing solid solution or silicon-containing intermetallic compound, and the silicon phase particles account for 1 to 50 wt% of the composite particle matrix, wherein 0<x 2, silicon-containing solid solution or The silicon-containing intermetallic compound is any one or two of the lanthanum elements in the periodic table of silicon and the chemical element, any one or three of the transition metal elements, or any of the lanthanum elements or Two elements, or silicon Any one or two elements of the external IVA.
本发明方法的碳相粒子是天然鳞片石墨、微晶石墨、人造石墨、 中间相炭微球 和焦炭中的任意一或一种以上的混合， 碳相粒子占所述复合颗粒基体的 50〜99 本发明方法的包覆层占复合材料的比例是 l〜25wt%0 The carbon phase particles of the method of the present invention are a mixture of any one or more of natural flake graphite, microcrystalline graphite, artificial graphite, mesocarbon microbeads and coke, and the carbon phase particles occupy 50 to 99 of the composite particle matrix. The ratio of the coating layer of the method of the invention to the composite material is 1~25wt% 0
本发明方法的有机物热解炭的前驱体是水溶性的聚乙烯醇、丁苯橡胶乳、羧甲 基纤维素，有机溶剂系的聚苯乙烯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯、 聚丙烯腈有机物、 酚醛树脂、 环氧树脂， 葡萄糖、 蔗糖、 果糖、 纤维素或淀粉。  The precursor of the organic pyrolytic carbon of the method of the invention is water-soluble polyvinyl alcohol, styrene-butadiene rubber emulsion, carboxymethyl cellulose, organic solvent-based polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Polyvinylidene fluoride, polyacrylonitrile organic, phenolic resin, epoxy resin, glucose, sucrose, fructose, cellulose or starch.
本发明方法的导电碳为乙炔黑、 碳纳米管、 纳米碳微球、 碳纤维或导电碳黑。 本发明方法的含锂化合物为氧化锂、碳酸锂、氟化锂、 氯化锂、硝酸锂或氢氧 化锂。  The conductive carbon of the method of the present invention is acetylene black, carbon nanotubes, nanocarbon microspheres, carbon fibers or conductive carbon black. The lithium-containing compound of the method of the present invention is lithium oxide, lithium carbonate, lithium fluoride, lithium chloride, lithium nitrate or lithium hydroxide.
本发明方法的硅相粒子球磨在保护气氛中进行，保护气氛为氩气、氢气或氮气 中的任一种或几种的混合。  The silicon phase particle ball milling of the process of the present invention is carried out in a protective atmosphere, and the protective atmosphere is a mixture of any one or more of argon gas, hydrogen gas or nitrogen gas.
本发明方法的将硅相粒子和碳相粒子混合造粒时， 在混合造粒机中混合造粒 1〜6小时。  In the method of the present invention, when the silicon phase particles and the carbon phase particles are mixed and granulated, they are mixed and granulated in a mixing granulator for 1 to 6 hours.
本发明与现有技 目比， 由硅相粒子和碳相粒子的复合材料为基体， 呈球形或 类球形，夕卜包覆有包覆层的锂离子电池硅碳复合负极材料具有很高的电化学可逆吸 放锂容量和优良的循环稳定性， 所得到的负极材料可逆比容量大于 450mA /g, 首 次循环库仑效率大于 85%，循环，次容量保持率大于 80%，明显减轻含硅活性物 质吸放锂时的体积效应， 改善锂在活性材料中的扩散行为， 与单质硅相比提高了首 次效率和循环稳定性，减少了正极材料的消耗，可嵌脱锂电位高于中间相碳微球等 常用锂离子电池负极材料， 防止金属锂在负极表面的析出， 具有优良的大电流放电 能力， 且具有制备工艺简单、 易于操作 点， 适用于各类便携式器件、 电动工具 等使用的锂离子电池负极材料。 附图说明: Compared with the prior art, the invention has a composite material of silicon phase particles and carbon phase particles as a matrix, and is spherical or spheroidal, and the lithium ion battery silicon carbon composite anode material coated with the coating layer has a high Electrochemical reversible absorption and desorption of lithium capacity and excellent cycle stability, the resulting negative electrode material has a reversible specific capacity of more than 450 mA / g, the first cycle coulombic efficiency is greater than 85%, cycle, sub-capacity retention rate is greater than 80%, significantly reducing silicon-containing activity The volume effect of the substance in the absorption and desorption of lithium improves the diffusion behavior of lithium in the active material, improves the first efficiency and cycle stability compared with elemental silicon, reduces the consumption of the cathode material, and can insert and remove the lithium potential higher than the mesophase carbon. A common anode material for lithium ion batteries such as microspheres, which prevents precipitation of metallic lithium on the surface of the negative electrode, has excellent high current discharge capability, and has a simple preparation process and an easy operation point, and is suitable for use in various portable devices, power tools, and the like. Ion battery anode material. BRIEF DESCRIPTION OF THE DRAWINGS:
图 1是本发明实施例 1的锂离子电池硅碳复合负极材料的电镜照片 (1000倍)。 图 2是本发明实施例 1的锂离子电池硅碳复合负极材料的电镜照片 (5000倍)。 图 3是本发明实施例 1的材料的首次充放电曲线图。 _  BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an electron micrograph (1000 magnifications) of a silicon-carbon composite negative electrode material for a lithium ion battery according to a first embodiment of the present invention. Fig. 2 is an electron micrograph (5000 magnifications) of a silicon-carbon composite negative electrode material of a lithium ion battery according to Embodiment 1 of the present invention. Fig. 3 is a graph showing the first charge and discharge of the material of Example 1 of the present invention. _
图 4是本发明实施例 1的材料的 XRD图。  Fig. 4 is an XRD chart of the material of Example 1 of the present invention.
具体实贿式 Specific bribery
下面结合附图和实施例对本发明作进一步详细说明。  The present invention will be further described in detail below with reference to the accompanying drawings and embodiments.
本发明的锂离子电池硅碳复合负极材料是以硅相粒子和碳相粒子为基体，夕卜包 覆有复合碳包覆层。基体中的硅相粒子是单质硅、硅氧化合物 SiOx， 其中 0<x 2、 含硅固溶体或含硅金属间化合物，其中的含硅固溶体或含硅金属间化合物，是由硅 与化学元素周期表中 IIA族元素中的任一种或两种元素、过渡金属元素中的任一种 或三种元素、 ΠΙΑ族元素中的任一种或两种元素，或除硅之外的 IVA 素中的任 一种或两种元素构成， 硅相粒子占复合颗粒基体的 l〜50wt%; 基体中的碳相粒子 是天然鳞片石墨、微晶石墨、 石墨、 中间相炭微 Π焦炭中的任意一种或一种 以上的混合。 包覆层厚度为 0.1〜5 μ ηι， 有机物热解炭占负极材料的比例为 0.5〜 20wt%， 导电碳占负极材料的比例是 0.5〜5wt%。 包覆层中的有机物热解炭是由水 溶性的聚乙烯醇、丁苯橡胶乳、羧甲基纤维素， 有机溶剂系的聚苯乙烯、聚甲基丙 烯酸甲酯、 聚四氟乙烯、 聚偏氟乙烯、 聚丙烯腈、 酚醛树脂、 环氧树脂， 葡萄糖、 蔗糖、 果糖、 纤维素、 淀粉或沥青为前驱体， 经高温碳化所形成的热解炭； 包覆层 中的导电碳为乙炔黑、 碳纳米管、 纳米碳微球、 碳纤维或导电碳黑 Super-P。 负极 材料复合颗粒表面表面 化锂、碳酸锂、 氟化锂、氯化锂、硝酸锂或氢氧化锂的 含锂化合物。 The lithium-ion battery silicon-carbon composite anode material of the present invention is based on silicon phase particles and carbon phase particles, and is coated with a composite carbon coating layer. The silicon phase particles in the matrix are elemental silicon, siloxane SiOx, wherein 0<x 2, silicon-containing solid solution or silicon-containing intermetallic compound, wherein silicon-containing solid solution or silicon-containing intermetallic compound is composed of silicon and chemical element period Any one or two of the Group IIA elements, any one or three of the transition metal elements, any one or both of the lanthanum elements, or an IVA other than silicon Any one or two elements, the silicon phase particles account for 1~50wt% of the composite particle matrix ; the carbon phase particles in the matrix are any one of natural flake graphite, microcrystalline graphite, graphite, mesophase charcoal micro coke Kind or more than one type of mixing. The thickness of the coating layer is 0.1 to 5 μ η, the ratio of the organic pyrolytic carbon to the anode material is 0.5 to 20% by weight, and the ratio of the conductive carbon to the anode material is 0.5 to 5 wt%. The organic pyrolytic carbon in the coating layer is composed of water-soluble polyvinyl alcohol, styrene-butadiene rubber emulsion, carboxymethyl cellulose, organic solvent-based polystyrene, polymethyl methacrylate, polytetrafluoroethylene, poly Pyrocarbon, polyacrylonitrile, phenolic resin, epoxy resin, glucose, sucrose, fructose, cellulose, starch or asphalt as precursor, pyrocarbon formed by high temperature carbonization; conductive carbon in the coating is acetylene Black, carbon nanotubes, nanocarbon microspheres, carbon fiber or conductive carbon black Super-P. The surface of the composite material of the negative electrode material is surface-treated with a lithium-containing compound of lithium, lithium carbonate, lithium fluoride, lithium chloride, lithium nitrate or lithium hydroxide.
本发明的锂离子电池硅碳复合负极材料具有以下技术特征： 平均粒径为 5〜60 u , 比表面积 1.0-4.0 m2/g, 振实密度 0.7〜2.0g cm3。 以上所述的平均粒径由 Malvern激光粒度仪测出， 比表面积采用氮气置换的 BET法测出， 振实密度采用 Quantachrome AutoTap振实密度仪测得。 The lithium ion battery silicon-carbon composite anode material of the present invention has the following technical features: an average particle diameter of 5 to 60 u, a specific surface area of 1.0 to 4.0 m 2 /g, and a tap density of 0.7 to 2.0 g cm 3 . The average particle size described above is The Malvern laser particle size analyzer measured the specific surface area measured by the BET method using nitrogen displacement, and the tap density was measured using a Quantachrome AutoTap tap density meter.
采用上述材料和比例制备本发明的锂离子电池硅碳复合负极材料，包括以下步 骤- 一、将硅相粒子在空气或非氧化气氛， 如氩气、氢气或氮气中的任一种或几种 的混合气体中球磨至 0.1〜1 μ ηι, 制得超细硅相粒子； 二、将粒度 <75 m，碳含量 95%以上的原料碳相粉碎分级、 整形和纯化处理制备得到碳 99.9%以上， 粒径 为 0.1〜5 μ m的碳相粒子；三、将制得的硅相粒子和碳相粒子在混合造粒机中混合 1〜6小时， 制成复合颗粒基体； 四、将复合颗粒基体与占复合颗粒基体 〜 25w1% 有机物热解炭前驱体球磨或湿法搅拌混合 l〜12h， 然后在 100〜40(TC餅下气相 沉积或包覆造粒;五、将包覆后的颗粒进行碳化处理,在保护气氛中加热 450至 1500 °C，保温 1至 10小时，然后降至室温，形成碳包覆层，破碎打散至 5〜40μ ιη;六、 将破碎打散至 5-40 U m的粉体与占粉体 l〜30wt%的沥青在混合机中混合包覆； 七、 包覆沥青后进行碳化处理， 在保护气氛中加热 450至 1500 , 保温 1至 10小 时， 然后降至室温， W 5-60 u rn; 八、 将得到的复合物与占粉体 0.5〜5wl 的导电碳混合包覆，在混合机或表面包覆改 机中混合 Γ〜ό小时，超声波分散 1〜 30 ^ΗΦ, 超声波频率 40kHz〜28kHz, 超声波功率为 50W〜3600W; 九、浸渍含锂 化合物： 将复合物粉«A到浓度为 0.2〜10wt%含锂化合物溶液中， 固液比 0.1〜 2，浸渍时间 1一 48小时， 调整粒度至 5〜60μ ηι, 得到锂离子电池硅碳复合负极材 料。 The above material and ratio are used to prepare the lithium ion battery silicon carbon composite anode material of the invention, comprising the following steps: 1. one or more of the silicon phase particles in an air or non-oxidizing atmosphere such as argon, hydrogen or nitrogen. In a mixed gas, the ball is ground to 0.1~1 μ ηι to obtain ultrafine silicon phase particles. 2. The carbon phase of the raw material having a particle size of <75 m and a carbon content of 95% or more is pulverized, classified, shaped and purified to obtain more than 99.9% of carbon. a carbon phase particle having a particle diameter of 0.1 to 5 μm; 3. mixing the obtained silicon phase particles and carbon phase particles in a mixing granulator for 1 to 6 hours to form a composite particle matrix; The matrix and the composite particle matrix ~ 25w1% organic pyrolytic carbon precursor are ball or wet stirred for 1~12h, then vaporized or coated granulated at 100~40 (TC cake; fifth, the coated particles Carbonization treatment, heating 450 to 1500 ° C in a protective atmosphere, holding for 1 to 10 hours, then lowering to room temperature, forming a carbon coating layer, crushing and breaking up to 5~40μ ιη ; six, breaking up the broken to 5- The powder of 40 U m is mixed with the asphalt of 1~30wt% of the powder. Mixing and coating in the machine; 7. Carbonized after coating the asphalt, heating 450 to 1500 in a protective atmosphere, keeping warm for 1 to 10 hours, then lowering to room temperature, W 5-60 u rn; VIII, the obtained composite Mix with 0.5~5wl of conductive carbon in powder, mix it in mixer or surface coating machine for Γ~ό hours, ultrasonic dispersion 1~ 30 ^ΗΦ, ultrasonic frequency 40kHz~28kHz, ultrasonic power 50W~3600W ; nine, impregnating a lithium-containing compound: the composite powder «a concentration of 0.2~10wt% to the lithium-containing compound solution, solid-liquid ratio 0.1~ 2, 1 a 48 hours immersion time, to adjust the particle size 5~60μ ηι, to give Lithium ion battery silicon carbon composite anode material.
硅 Si通过与锂形成金属间化合物， 如 ½2815等能使锂可逆地吸留和释放。 使 用 Si作为锂离子二次电池的负极材料， Si的充放电理论容量可高达 4200mAh/g, 9783mA /cm3, 比重按照 2.33计算， 远远高于现今 的石墨类材料， 理论容量 372mA /g或 844mAh/g, 比重按照 2.27计算。 但是由 Si制成的负极材料， 在 Li 的吸收与释放时伴随着严重的体积变化， 高达 300%， 极易造成 Si负极产生裂紋、 粉化， 在充放电循环过程中容量急剧衰减， 因此纯 Si并不能直接用作锂离子二次 电池负极材料。 Silicon Si can reversibly occlude and release lithium by forming an intermetallic compound with lithium, such as 1⁄2 2 81 5 or the like. Using Si as the anode material for lithium ion secondary batteries, the theoretical capacity of charge and discharge of Si can be as high as 4200 mAh/g, 9783 mA / cm 3 , and the specific gravity is calculated according to 2.33, which is much higher than the current graphite materials, the theoretical capacity is 372 mA / g or 844 mAh / g, specific gravity calculated according to 2.27. However, the negative electrode material made of Si is accompanied by a serious volume change during absorption and release of Li, up to 300%, which is liable to cause cracks in the Si negative electrode. Powdering, the capacity is abruptly attenuated during the charge and discharge cycle, so pure Si cannot be directly used as a negative electrode material for a lithium ion secondary battery.
寸本发明的产品和制备方法的研究中发现， 当含 Si颗粒分散在碳材料基体 或者 Si相颗粒表面被含 Si的固溶体或金属间化合物包围时，锂 Li的吸留和释放伴 随的体积变化被缓冲或制约， 可以防止电极粉化， 提高循环寿命。 为了使这种效果 更加充分发挥， Si相粒子优选较小的粒径。本发明将粒度为 l〜40 m的硅相粒子 在保护气氛中球磨至 0.1〜1 μ ηι， 制得超细硅相粒子， 作为复合材料中的负极活性 物质。当 Si相粒子的平均粒径大于 1 μ m时，基体的体积吸收效应减弱， 影响复合 材料的循环性能的提高； 若 Si相粒子的平均粒径小于 0.1 m时， 制备难度加大， 并且容易造成活性粒子表面氧化， 增大粒子间相互团聚的机会， 影响负极材料的比 容量。 Si相粒子的粒径采用扫描电子显微镜 SEM测定， 也可以使用其他方法， 比 如激光粒度测试仪测得的体积粒度分布中的中位径作为平均粒径。实施例中采用了 英国 Malvern Mastersizer 2000激光粒度分析仪测定粒子的平均粒径。  In the study of the product and the preparation method of the present invention, it was found that the volume change accompanying the occlusion and release of lithium Li when the Si-containing particles are dispersed in the carbon material matrix or the surface of the Si phase particles is surrounded by the Si-containing solid solution or intermetallic compound. It is buffered or restricted to prevent electrode dusting and improve cycle life. In order to make this effect more fully exerted, the Si phase particles are preferably of a smaller particle diameter. In the present invention, silicon phase particles having a particle size of from 1 to 40 m are ball-milled to 0.1 to 1 μm in a protective atmosphere to prepare ultrafine silicon phase particles as a negative electrode active material in the composite material. When the average particle size of the Si phase particles is greater than 1 μm, the volume absorption effect of the matrix is weakened, which affects the cycle performance of the composite; if the average particle size of the Si phase particles is less than 0.1 m, the preparation is more difficult and easy. The surface of the active particles is oxidized, which increases the chance of agglomeration between the particles and affects the specific capacity of the negative electrode material. The particle diameter of the Si phase particles is measured by a scanning electron microscope SEM, and other methods such as a median diameter in the volume particle size distribution measured by a laser particle size analyzer may be used as the average particle diameter. In the examples, the average particle size of the particles was measured using a British Malvern Mastersizer 2000 laser particle size analyzer.
本发明的硅碳复合负极材料中 Si相粒子占复合颗粒基体的 1〜50 wt%。 当 Si 相粒子的比例超过 50wt%时， 基体不能有效缓冲和吸收 Si的体积效应； 反之若 Si 相粒子的比例小于 lwt%时， 负极材料的容量不能有效提升。 Si相粒子的比例鶴 在 5〜30wt%， 更雌在 10〜20wt%。  In the silicon-carbon composite negative electrode material of the present invention, the Si phase particles account for 1 to 50% by weight of the composite particle matrix. When the proportion of the Si phase particles exceeds 50% by weight, the matrix cannot effectively buffer and absorb the volume effect of Si; on the other hand, if the proportion of the Si phase particles is less than 1% by weight, the capacity of the anode material cannot be effectively increased. The ratio of Si phase particles is 5 to 30 wt%, and more female is 10 to 20 wt%.
Si相粒子可以是单质硅、 硅氧化合物 SiOx, 0<x 2、 硅固溶体或含硅金属间 化合物。硅固溶体或含硅金属间化合物是由硅与化学元素周期表中 ΠΑ族元素中的 任一种或两种元素、过渡金属元素中的任一种或三种元素、 ΙΠΑ族元素中的任一种 或两种元素，或除硅之外的 IVA方 素中的任一种或两种元素构成。这些元素作为 能够可逆储锂的活性元素， 能够增大负极材料的比容量，而有些元素则为不能够储 锂的非活性元素，但是可以作为缓冲和吸收活性材料吸放锂所弓 ί起的体积效应和 I 或作为改善复合材料导电性的元素， 改进材料的循环稳定性。考虑元素的吸放锂容 量、 缓冲 Si体积效应、 改进复合材料导电性的效果及其资源等因素， 这些元素优 选为 ΠΑ族元素的 Mg、 Ca和 Ba，过渡金属元素的 Ti、 Cr、 Mn、 Fe、 Co、 Ni、 Cu、 Mo、 Ag、 Ce和 Nd， ΠΙΑ族元素 Al、 Ga禾 Π Ιη， 以及 IVA族元素的 Ge、 Sn和 Sb。 在这些元素中， 更鶴 Mg、 Ca、 Fe、 Co、 Ni和 Cu。 The Si phase particles may be elemental silicon, siloxane SiOx, 0<x 2, silicon solid solution or silicon-containing intermetallic compound. The silicon solid solution or the silicon-containing intermetallic compound is any one or two of the lanthanum elements in the periodic table of silicon and the chemical element, any one or three of the transition metal elements, and any of the lanthanum elements. One or two elements, or any one or two elements other than silicon. These elements, as active elements capable of reversible lithium storage, can increase the specific capacity of the negative electrode material, while some elements are inactive elements that cannot store lithium, but can be used as a buffering and absorbing active material to absorb lithium. Volumetric effects and I or as an element to improve the electrical conductivity of the composite, improve the cyclic stability of the material. Consider the element's absorption and discharge capacity The amount, the buffering volume effect of Si, the effect of improving the conductivity of the composite material and its resources, etc., these elements are preferably Mg, Ca and Ba of the lanthanum element, Ti, Cr, Mn, Fe, Co, Ni of the transition metal element. Cu, Mo, Ag, Ce, and Nd, lanthanum elements Al, Ga, Ι η, and Ge, Sn, and Sb of the IVA group elements. Among these elements, more cranes Mg, Ca, Fe, Co, Ni and Cu.
为了制备本发明的锂离子电池硅碳复合负极材料， 改善负极材料的电化学性 能， 本发明的方法对石墨和 Si相粒子进行了混合造粒、 复合包覆及表面改性处理。  In order to prepare the lithium ion battery silicon carbon composite anode material of the present invention and improve the electrochemical performance of the anode material, the method of the present invention performs mixing granulation, composite coating and surface modification treatment on graphite and Si phase particles.
如图 1、 图 2所示，—扫描电镜观测复合材料的微观特性， 本发明的锂离子电池 硅碳复合负极材料， 以硅相粒子和碳相粒子的复合材料为基体， 外包覆有复合碳包 覆层， 具有球形或近似球形的 itU特征，夕卜包覆层是一层有机物热解炭和导电碳组 成包覆层， 改善了石墨材料与电解液的相容性。 包覆层约束了 Si相粒子的体积效 应，提高导电性能， 并能够可逆嵌脱锂， 增大了负极材料的容量和大电流充放电能 力。包覆层较大的晶体层间距减少了反复充放电过程中弓 I起的膨胀收缩量，避免 Γ 负极材料结构的破环和剥落， 改善了循环性能。  As shown in FIG. 1 and FIG. 2, the microscopic characteristics of the composite material are observed by scanning electron microscopy. The lithium-ion battery silicon-carbon composite anode material of the invention is based on a composite material of silicon phase particles and carbon phase particles, and is coated with a composite. The carbon coating layer has a spherical or nearly spherical itU characteristic, and the outer cladding layer is a layer of organic pyrolytic carbon and conductive carbon to improve the compatibility of the graphite material with the electrolyte. The cladding layer constrains the volumetric effect of the Si phase particles, improves the electrical conductivity, and can reversibly insert and deintercalate lithium, thereby increasing the capacity of the negative electrode material and the high current charge and discharge capability. The larger crystal layer spacing of the cladding layer reduces the expansion and contraction of the bow during the repeated charge and discharge, avoids the ringing and spalling of the crucible anode material structure, and improves the cycle performance.
图 3为本发明实施例 1制备的硅一碳复合材料的首次充放电曲线，与石墨类材 料相比， 充放电曲线上增加了 Si的高电位， 约 0.5V vs. Li/Li+储锂平台， 复合材料 的吸放锂容量有了较大幅度的提高。 3 is a first charge-discharge curve of a silicon-carbon composite material prepared in Example 1 of the present invention. Compared with a graphite-based material, a high potential of Si is increased on a charge-discharge curve, about 0.5 V vs. Li/Li + lithium storage. On the platform, the lithium absorption capacity of composite materials has been greatly improved.
图 4为本发明实施例 1制备的硅一碳复合材料的 X-射线衍射图 XRD， 对照国 际 X-射线粉末衍射委员会的标准粉末衍射资料 PDF卡， 在复合材料的衍射图中含 有碳 PDF*** 41-1487和硅 PDF*** 27-1402的衍射峰， 说明本发明的硅碳复合 材料是由碳和硅， 所组成。  4 is an X-ray diffraction pattern XRD of a silicon-carbon composite material prepared in Example 1 of the present invention, and a standard powder diffraction data PDF card of the International X-ray Powder Diffraction Commission, which contains a carbon PDF card number in the diffraction pattern of the composite material. The diffraction peaks of 41-1487 and silicon PDF card No. 27-1402 indicate that the silicon-carbon composite material of the present invention is composed of carbon and silicon.
上述基体中的碳相粒子是天然鳞片石墨、微晶石墨、 Ai 石墨、 中间相炭微球 和焦炭中的任意一种或一种以上的混合， 碳相粒子占所述复合颗粒基体的 99〜50 wt%。碳相粒子主要用作吸收和缓冲 Si相粒子在吸放锂时的体积效应，并且提供一 定的嵌锂容量。上述材料均为柔性的碳材料， 具有较好的弹性并且具有较高的嵌锂 容量。当碳相粒子小于 50wt%时， Si相粒子不能够有效分散，碳相粒子吸收和缓冲 活性材料 Si的体积效应效果较差， 对材料的循环性能不利； 而当碳相粒子的比例 大于 99%时， 活性 Si的比例减少， 从而影响材料的比容量的提高。 The carbon phase particles in the above matrix are a mixture of any one or more of natural flake graphite, microcrystalline graphite, Ai graphite, mesocarbon microbeads and coke, and the carbon phase particles occupy 99~ of the composite particle matrix 50 wt%. The carbon phase particles are mainly used to absorb and buffer the volume effect of the Si phase particles upon absorption and desorption of lithium, and provide a certain lithium intercalation capacity. The above materials are all flexible carbon materials, have good elasticity and have high lithium insertion. Capacity. When the carbon phase particles are less than 50% by weight, the Si phase particles are not effectively dispersed, the volume effect of the carbon phase particles absorbing and buffering the active material Si is poor, and the cycle performance of the material is unfavorable; and when the proportion of the carbon phase particles is greater than 99% At the time, the proportion of active Si is reduced, thereby affecting the increase in the specific capacity of the material.
上述复合碳包覆层厚度为 0.1〜5 μ m， 由 Malvern激光粒度仪测试包覆前后的 颗粒平均粒径后计算得出。复合碳包覆层含有有机物热解炭、 导电碳， 所占负极材 料的比例是 l〜25wt%， 其中有机物热解炭占包覆层的比例为 0.5〜20wt%， 导电碳 占包覆层的比例是 0.5〜5wt%。 当复合碳包覆层厚度小于 0.1 μ m或占负极材料的 比例小于 1^%时， 不能形成完整的包覆层， 从而影响负极材料的循环稳定性； 而 当包覆层过厚， 例如大于 5 μ ιη或者包覆层占负极材料的比例大于 25wt%时， 又会 影响负极材料的比容量和首次效率， 同样不利于负极材料的电化学性能的提高。  The composite carbon coating layer has a thickness of 0.1 to 5 μm, and is calculated by a Malvern laser particle size analyzer to measure the average particle diameter of the particles before and after coating. The composite carbon coating layer contains organic pyrocarbon and conductive carbon, and the proportion of the negative electrode material is 1 to 25 wt%, wherein the ratio of the organic pyrolytic carbon to the coating layer is 0.5 to 20 wt%, and the conductive carbon accounts for the coating layer. The ratio is 0.5 to 5 wt%. When the thickness of the composite carbon coating layer is less than 0.1 μm or the proportion of the anode material is less than 1%, a complete coating layer cannot be formed, thereby affecting the cycle stability of the anode material; and when the coating layer is too thick, for example, larger than When 5 μ ιη or the proportion of the coating layer to the negative electrode material is more than 25% by weight, the specific capacity and the first efficiency of the negative electrode material are affected, which is also disadvantageous for the improvement of the electrochemical performance of the negative electrode material.
上述包覆层中的有机物热解炭是由水溶性的聚乙烯醇、丁苯橡胶乳、羧甲基纤 维素， 有机溶剂系的聚苯乙烯、 聚甲基丙烯酸甲酯、 聚四氟乙烯、聚偏氟乙烯、聚 丙烯腈有机物、酚醛树脂、 环氧树脂， 葡萄糖、蔗糖、 果糖、 纤维素、 淀粉或赚 等为前驱体，经高温碳化所形成的热解炭。这类有机物在与复合颗粒基体混合时作 为后期热解炭的前驱体或者作为溶液体系的粘结剂、分散剂或悬浮剂均匀包覆在复 合颗粒基体表面，而在后期的热解炭化过程中发生热分解反应和热縮聚反应。在高 温热解过程中， 有机化合物中所含的 H、 0、 N等元素组成的化合物被分解， 碳原 子不断环化、 芳构化， 结果是 H、 0、 N等原子不断减少， C不腺糊和富集。 上 述有机物经过液相炭化过程形成易石墨化炭即软炭， 或者只经过固相炭化过程，形 成难石墨化炭即硬炭。这类热解炭均为非石墨化碳，材料中含有较多的小分子化合 物热解逸出时形成的微孔，可以更好地吸收和缓冲充放电过程中活性物质的体积效 应，而且热解碳层间距较大有利于锂离子的 和脱出。热解炭材料的舌 L层结构也 防止了溶剂化锂离子共嵌弓 I起的石墨层剥离，提高了循环稳定性。包覆层中的导电 碳为乙炔黑、 碳纳米管、 纳米碳微球、 碳纤维或导电碳黑 Superb W 200 The organic pyrolytic carbon in the coating layer is made of water-soluble polyvinyl alcohol, styrene-butadiene rubber latex, carboxymethyl cellulose, organic solvent-based polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Polyvinylidene fluoride, polyacrylonitrile organic matter, phenolic resin, epoxy resin, glucose, sucrose, fructose, cellulose, starch or earned as a precursor, pyrocarbon formed by high temperature carbonization. Such organic substances are uniformly coated on the surface of the composite particle matrix as a precursor of late-stage pyrolytic carbon or as a binder, dispersant or suspending agent of the solution system when mixed with the composite particle matrix, and in the later pyrolysis carbonization process. Thermal decomposition reaction and thermal polycondensation reaction occur. In the high-temperature pyrolysis process, compounds composed of elements such as H, 0, and N contained in organic compounds are decomposed, and carbon atoms are continuously cyclized and aromatized. As a result, atoms such as H, 0, and N are continuously reduced, and C is not Gland paste and enrichment. The organic matter is subjected to a liquid phase carbonization process to form an easily graphitizable carbon, that is, a soft carbon, or only a solid phase carbonization process to form a hardly graphitizable carbon, that is, a hard carbon. Such pyrolytic carbon is non-graphitizable carbon, and the material contains many small molecules, and the micropores formed during pyrolysis escape can better absorb and buffer the volume effect of the active material during charging and discharging, and the heat The larger spacing of the carbon-decomposing layers is beneficial to the extraction and extraction of lithium ions. The tongue L-layer structure of the pyrolytic carbon material also prevents the graphite layer from being etched by the solvated lithium ion co-inlay, thereby improving the cycle stability. The conductive carbon in the coating layer is acetylene black, carbon nanotubes, nano carbon microspheres, carbon fiber or conductive carbon black Superb W 200
将复合颗粒基体与有机物热解炭的前驱体、 导电碳混合包覆的方法不特别限 定，任何公知的混炼造粒设备均可麵。混合包覆采用混合球磨、湿法搅拌 l〜12h， 之后进行气相沉积和包覆造粒， 气相沉积和包覆造粒的 选择在 100°C〜400°C， 当处理 低于 100°C时， 粉体干燥速度较慢， 包覆效果较差， 易于造成颗粒之间 的相互粘连， 影响生产效率和产品质量； 当处理 高于 400 时， 成包覆层 碳化或氧化， 也会影响包覆效果。 随后， 对上述混合料进行碳化处理， 在450 °C〜1500°C， 保温 1〜10小时， 然后降至室温。 为保证包覆层致密， 进行二次包覆 处理， 二次包覆材料为沥青， 包覆量为 l〜30wt%。 上述的碳化处理在非氧化气氛 中进行， 例如， 在氮气、氩气、 氦气、 氖气或上述气体的混合气体、真空或还原气 氛中进行。 碳化 i 在 450°C〜1500°C进行， 保温卜 10小时， 然后降至室温。  The method of mixing and coating the composite particle substrate with the precursor of the organic pyrolytic carbon and the conductive carbon is not particularly limited, and any known mixing and granulating equipment can be surfaced. The mixed coating is mixed ball milling, wet stirring for l~12h, followed by vapor deposition and coating granulation. The vapor deposition and coating granulation are selected from 100 ° C to 400 ° C, when the treatment is lower than 100 ° C. The powder drying speed is slower, the coating effect is poor, and it is easy to cause mutual adhesion between the particles, which affects the production efficiency and product quality. When the treatment is higher than 400, the coating is carbonized or oxidized, which also affects the coating. effect. Subsequently, the above mixture is carbonized, kept at 450 ° C to 1500 ° C for 1 to 10 hours, and then lowered to room temperature. In order to ensure the dense coating layer, the secondary coating treatment is carried out, and the secondary coating material is asphalt, and the coating amount is l~30wt%. The above carbonization treatment is carried out in a non-oxidizing atmosphere, for example, under a nitrogen gas, an argon gas, a helium gas, a helium gas or a mixed gas of the above gas, a vacuum or a reducing atmosphere. The carbonization i is carried out at 450 ° C to 1500 ° C for 10 hours and then lowered to room temperature.
由于复合材料表面包覆了非石墨的有机物热解炭，其导电性能下降， 为了提高 负极材料的导电性能，保证负极材料的循环稳定及比容量的充分发挥， 本发明在复 合材料的表面进行了包覆或渗杂导电碳处理， 导电碳占负极材料的 0.5〜5wt%。 当 导电碳的量小于 0.5wt°/。时， 无法形成连续的导电网络， 材料的导电性能不能有效 提高； 而当导电碳的比例大于 5wt%时， 又会对材料的比容量和充放电效率产生不 利影响。 合适的导电加入量选择在 0.5〜5^%之间。  Since the surface of the composite material is coated with non-graphite organic pyrolytic carbon, the electrical conductivity is lowered. In order to improve the electrical conductivity of the negative electrode material and ensure the cycle stability of the negative electrode material and the full capacity of the specific material, the present invention is carried out on the surface of the composite material. The coated or immersed conductive carbon is treated, and the conductive carbon accounts for 0.5 to 5 wt% of the negative electrode material. When the amount of conductive carbon is less than 0.5 wt ° /. When a continuous conductive network cannot be formed, the conductivity of the material cannot be effectively improved; and when the proportion of the conductive carbon is more than 5% by weight, the specific capacity of the material and the charge and discharge efficiency are adversely affected. A suitable amount of conductive addition is selected between 0.5 and 5%.
混合包覆处理后的硅碳复合材料与导电碳的包覆方法不作特别限定，任何公知 的混合设备均可使用， 如高速搅拌机、 行星式搅拌机等， 混合处理时间为 1〜6小 时。为使导电碳分散均匀， 了超声波处理上述复合材料与导电碳的悬浮液， 超 声波处理时间 1 ^！中〜 30 中，超声波频率 40kHz〜28kHz，超声波功率为 50W〜 在锂离子电池的首次充放电过程中，溶剂及电解质盐将发生不可逆的电化学还 原分解反应， 生纖基碳酸锂、烧氧基碳酸锂等产物沉积在负极材料表面构成一层 对电子绝缘、而对离子导通的固体电解质膜 SEI膜， 这层钝化膜的性质强烈影响着 负极材料的电化学性能，一层薄而致密的电极表面钝化膜的生成能够 IS±溶剂化锂 离子的共 «Λ， 是电池具有较高的首次循环效率和较小的循环衰减的保证。负极材 料中石墨微晶的基面、 端面的相对量、 反应性的差别以及微晶大小、 电解液组分、 还原分解的动力学性质等决定了所生成的电极表面钝化膜的致密性。 The coating method of the silicon-carbon composite material and the conductive carbon after the mixed coating treatment is not particularly limited, and any known mixing equipment can be used, such as a high-speed mixer, a planetary mixer, etc., and the mixing treatment time is 1 to 6 hours. In order to make the conductive carbon evenly dispersed, the suspension of the above composite material and conductive carbon is ultrasonically treated, and the ultrasonic treatment time is 1 ^! Medium ~ 30, ultrasonic frequency 40kHz~28kHz, ultrasonic power 50W~ During the first charge and discharge of lithium ion battery, the solvent and electrolyte salt will undergo irreversible electrochemical reduction decomposition reaction, fibril-based lithium carbonate, alkoxy A product such as lithium carbonate is deposited on the surface of the negative electrode material to form a solid electrolyte membrane SEI film which is electrically insulated and ion-conducting. The properties of this passivation film strongly influence The electrochemical properties of the negative electrode material, the formation of a thin and dense electrode surface passivation film can be IS ± solvated lithium ion, which is a guarantee of high first cycle efficiency and small cycle attenuation. The basis of the graphite crystallites in the negative electrode material, the relative amount of the end faces, the difference in reactivity, the crystallite size, the electrolyte composition, and the kinetic properties of the reductive decomposition determine the compactness of the passivation film on the surface of the electrode.
本发明的方法采用含锂化合物的无机或有机溶液体系处理硅碳复合负极材料， 在负极材料表面生成一层致密的锂离子导通的固体电解质膜以提髙负极材料的首 次充放电效率及循环稳定性。采用浸渍含锂化合物的方法最 寻到锂离子电池硅碳 复合负极材料。  The method of the invention adopts an inorganic or organic solution system containing a lithium compound to treat the silicon-carbon composite anode material, and forms a dense lithium ion-conducting solid electrolyte membrane on the surface of the anode material to improve the first charge and discharge efficiency and cycle of the anode material. stability. A lithium-ion battery silicon-carbon composite anode material is most sought for by impregnating a lithium-containing compound.
经上述处理后得到的锂离子电池用硅碳复合负极材料， 其平均粒径为 5〜60μ m， 比表面积为 1.0〜4.0m2/g， 振实密度为 0.7〜2.0g cm3。 以上所述的平均粒径由 Malvern激光粒度仪测出， 比表面积采用氮气置换的 BET法测出， 振实密度采用 Quantachrome AutoTap振实密度仪测得。 The silicon-carbon composite negative electrode material for a lithium ion battery obtained by the above treatment has an average particle diameter of 5 to 60 μm, a specific surface area of 1.0 to 4.0 m 2 /g, and a tap density of 0.7 to 2.0 g cm 3 . The average particle size described above was measured by a Malvern laser particle size analyzer, and the specific surface area was measured by a BET method using nitrogen displacement, and the tap density was measured using a Quantachrome AutoTap tap density meter.
实施例 1， 制备硅碳 Si-G-C-Li2C03复合负极材料： 将粒度为 75 μ m的硅粉在 氩气气氛中机械高能球磨至 0.5 n m， 制得超细硅粉； 将粒度 70 μ ηι， 95% 以上的天然石墨粉碎分级、 整形和纯化处理制备得到 量 99.9%以上， 粒径为 1 μ m的球形石墨； 将制得的超细硅粉 20wt%¾ 80wt%球形石墨在双螺旋搅拌机中 混合造粒 ό小时，制成复合颗粒基体；将复合颗粒基体与 10wt°/。酚醛树脂混合湿法 搅拌 10h, 然后 300°C干 粒； 将包覆酚醛树脂后的复合料进行碳化处理， 在氩 气气氛中加热至 1100°C， 保温 3小时， 然后降至室温， 破碎打散至 ΙΟμ ιη; 将破 碎后的粉体与 10\^1%沥青混合包覆、炭化处理，在氩气气氛中加热 1200°C，保温 2 小时， 然后降至室温， 破碎打散至 20 n m, 之后与 0.5wt%的碳纳米管在高速搅拌 机中混合 4小时， 同时采用频率 28kHz、 功率为 3600W的超声波处理 5 中； 浸 渍 1%的 Li2C03溶液 1小时， 固液比 0.1， 最终得到硅碳复合负极材料， 测得其平 均粒径为 20.1 rn, 比表面积为 3.5m2/g， 振实密度为 1.3^cm3。 所得复合材料按下述方法制备电极： 称取 5克复合负极材料， 2.5克丁苯橡 胶乳 SBR, 1.5克羧甲基纤维素 CMC, 1克导电剂 Superb 加入适量的纯水分散 剂混合均匀后， 制成电极， 以锂为对电极， l MLiPF6， EC:DMC:EMC=1:1:1， v/v 溶液为电解液， 聚丙烯微孔膜为隔膜， 组装 莫拟电池， 以 0.5mA/cm2的电流密度 进行恒流充放电实验， 充放电电压为 0.02〜1.5伏， 测试复合材料可逆比容量。 循 环性能采用成品电池测试， 以 LiCo02为正极， l MLiPF6， EC:DMC:EMC=1:1:1, v/v溶液为电解液，聚丙烯微孔膜为隔膜，组装成成品电池， 以 1C的速率进行充放 电试验，充放电电压限制在 4.2-3.0伏，测试电池循环 200次的容量保持率 Qoo C,。 Example 1, preparing a silicon carbon Si-GC-Li 2 C0 3 composite anode material: a silicon powder having a particle size of 75 μm was mechanically high-energy ball-milled to 0.5 nm in an argon atmosphere to obtain an ultrafine silicon powder; μ ηι, more than 95% of natural graphite pulverization, grading, shaping and purification treatment to obtain more than 99.9% of spherical graphite with a particle size of 1 μm; the obtained ultrafine silicon powder 20wt% 3⁄4 80wt% spherical graphite in double The granules were mixed and granulated in a screw mixer for a few hours to form a composite particle matrix; and the composite particle matrix was 10 wt/min. The phenolic resin is mixed and wet-mixed for 10 hours, and then dried at 300 ° C. The composite material coated with the phenolic resin is carbonized, heated to 1,100 ° C in an argon atmosphere, kept for 3 hours, then cooled to room temperature, and crushed. Disperse to ΙΟμ ιη; The crushed powder is mixed with 10\1% asphalt, carbonized, heated at 1200 ° C in an argon atmosphere, kept for 2 hours, then cooled to room temperature, broken up to 20 nm And then mixed with 0.5wt% carbon nanotubes in a high-speed mixer for 4 hours, while using ultrasonic treatment 5 with a frequency of 28kHz and a power of 3600W; impregnating 1% Li 2 C0 3 solution for 1 hour, solid-liquid ratio 0.1, and finally A silicon-carbon composite negative electrode material was obtained, and the average particle diameter was 20.1 rn, the specific surface area was 3.5 m 2 /g, and the tap density was 1.3 cm 3 . The obtained composite material was prepared as follows: 5 g of composite negative electrode material, 2.5 g of styrene-butadiene rubber latex SBR, 1.5 g of carboxymethyl cellulose CMC, 1 g of conductive agent Superb, and an appropriate amount of pure water dispersing agent were mixed uniformly. , made of electrode, with lithium as the counter electrode, l MLiPF 6 , EC:DMC:EMC=1:1:1, v/v solution is electrolyte, polypropylene microporous membrane is diaphragm, assembled mono-battery, to 0.5 The current density of mA/cm 2 was subjected to a constant current charge and discharge test, and the charge and discharge voltage was 0.02 to 1.5 volts, and the reversible specific capacity of the composite material was tested. The cycle performance is tested by the finished battery, with LiCo0 2 as the positive electrode, l MLiPF 6 , EC:DMC:EMC=1:1:1, v/v solution as electrolyte, polypropylene microporous membrane as diaphragm, assembled into finished battery, The charge and discharge test was carried out at a rate of 1 C, and the charge and discharge voltage was limited to 4.2-3.0 volts, and the capacity retention rate Qoo C of the test battery cycle was 200 times.
实施例 2，制备硅碳 Si-Mg-G-C-LiOH复合负极材料:将粒度为 75 μ m的 Si-Mg 粉， 含 Si 50wt%, 在氩气气氛中机械高能球磨至 0.1 m， 制得超细 Si-Mg粉； 将 粒度 70 μ ηι，碳含量 95%以上的天然石墨粉碎分级、整形和纯化处理制备得到 量 99.9%以上， 粒径为 3 μ ιη的球形石墨； 将制得的超细 Si-Mg粉 30wt%和 70wt% 球形石墨在混合造粒机中混合 1小时造粒，制成复合颗粒基体; 将复合颗粒基体与 2.5wt%T 胶乳混合湿法搅拌 4h，然后 200°C干燥制粒；将包覆后的复合料进行 碳化处理， 在氩气气氛中加热至 700 ， 保温 5小时， 然后降至室温， 破碎打散至 10 u rn; 将破碎后的粉体与 12wt% 青混合包覆、 炭化处理， 在氩气气氛中加热 1200°C， 保温 M、时， 然后降至室温， 破碎打散至 15 μ ιη， 之后与 1 %纳米碳微球 在高速搅拌机中混合 1小时， 同时采用频率 40kHz、 功率为 50W的超声波处理 20 中； 浸渍 5%的 LiOH溶液 12小时， 固液比为 1， 最终得到硅碳复合负极材料。 测得其平均粒径为 15.4 μ ιη， 比表面积为 2.8m2/g， 振实密度为 1.2g cm3。 Example 2, preparing a silicon carbon Si-Mg-GC-LiOH composite anode material: a Si-Mg powder having a particle size of 75 μm, containing Si 50 wt%, and mechanically high-energy ball milling to 0.1 m in an argon atmosphere to prepare an ultra Fine Si-Mg powder; pulverized, graded and purified natural graphite with a particle size of 70 μ ηι and a carbon content of 95% or more to prepare spherical graphite with a particle size of 3 μ ηη; Si-Mg powder 30wt% and 70wt% spherical graphite were mixed in a mixing granulator for 1 hour to form a composite particle matrix; the composite particle matrix was mixed with 2.5wt% T latex and wet-dried for 4 hours, then dried at 200 °C. Granulation; carbonization of the coated composite, heating to 700 in an argon atmosphere, holding for 5 hours, then lowering to room temperature, breaking up to 10 u rn; crushing powder with 12wt% green Mixed coating, carbonization, heating at 1200 ° C in an argon atmosphere, keeping M, keeping it to room temperature, breaking up to 15 μm, and then mixing with 1% nanocarbon microspheres in a high-speed mixer for 1 hour. At the same time, using ultrasonic treatment with a frequency of 40 kHz and a power of 50 W; immersing 5% of L The iOH solution was used for 12 hours, and the solid-liquid ratio was 1, and finally a silicon-carbon composite anode material was obtained. The average particle diameter was measured to be 15.4 μm, the specific surface area was 2.8 m 2 /g, and the tap density was 1.2 g cm 3 .
所得负极材料按照与实施例 1相同的方法制备电极， 进行电化学性能测试。 实施例 3， 制备硅碳 Si-Fe-G-C-LiF复合负极材料： 将粒度为 75 μ ηι的 Si-Fe 粉， 含 Si 75wt%, 在氩气气氛中机械高能球磨至 1 μ m， 制得超细 Si-Fe粉； 将粒 度 70 μ ηι，碳含量 95%以上的天然石墨粉碎分级、整形和纯化处理制备得到 量 99.9%以上， 粒径为 5 的球形石墨； 将制得的超细 Si-Fe粉 2wt°/。和 98wt°/。球形 石墨在混合造粒机中混合 6小时造粒，制成复合颗粒基体;将复合颗粒基体与 lwt% 聚乙烯醇溶液混合湿法搅拌 10h， 然后 200°C干燥制粒； 将包覆后的复合料进行碳 化处理， 在氩气气氛中加热至 1500°C， 保温 1小时， 然后降至室温， 破碎打散至 5 u rn; 将破碎后的粉体与 10^%沥青混合包覆、 炭化处理， 在氩气气氛中加热 1200°C , 保温 10小时， 然后降至室温， 破碎打散至 15 μ ιη， 之后与 5%碳纤维高 速搅拌机中混合 6小时；同时采用频率 40kHz、功率为 50W的超声波处理 30 中， 然后 100°C干燥制粒， 浸渍 0.2%的 LiF溶液 48小时， 固液比为 2, 最终得到硅碳 复合负极材料。 测得其平均粒径为 15.6 μ ιη， 比表面积为 1.8m2/g， 振实密度为 1.0g/cm3。 The obtained negative electrode material was prepared in the same manner as in Example 1 to carry out an electrochemical performance test. Example 3, preparing a silicon-carbon Si-Fe-GC-LiF composite anode material: a Si-Fe powder having a particle size of 75 μηη, containing 75 wt% of Si, mechanically high-energy ball milling to 1 μm in an argon atmosphere, Ultrafine Si-Fe powder; pulverized, graded, and purified natural graphite with a particle size of 70 μ ηι and a carbon content of 95% or more 99.9% or more, spherical graphite having a particle diameter of 5; and the obtained ultrafine Si-Fe powder is 2 wt%/. And 98wt ° /. The spherical graphite is mixed in a mixing granulator for 6 hours to form a composite particle matrix; the composite particle substrate is mixed with a lwt% polyvinyl alcohol solution and wet-stirred for 10 hours, and then dried at 200 ° C for granulation; The composite material is carbonized, heated to 1500 ° C in an argon atmosphere, kept for 1 hour, then cooled to room temperature, crushed and broken up to 5 u rn; mixed powder and 10 ^% asphalt mixed coating, carbonization Treatment, heating at 1200 ° C in an argon atmosphere, holding for 10 hours, then dropping to room temperature, crushing and breaking up to 15 μm, and then mixing with a 5% carbon fiber high speed mixer for 6 hours; using a frequency of 40 kHz and a power of 50 W In the ultrasonic treatment 30, the granulation was then dried at 100 ° C, and the 0.2% LiF solution was immersed for 48 hours, and the solid-liquid ratio was 2, and finally a silicon-carbon composite negative electrode material was obtained. The average particle diameter was measured to be 15.6 μm, the specific surface area was 1.8 m 2 /g, and the tap density was 1.0 g/cm 3 .
所得负极才才料按照与实施例 1相同的方法制备电极， 进行电化学性能测试。 实施例 4， 制备硅碳 Si-Ca-G-C-LiCl复合负极材料： 将粒度为 75 μ m的 Si-Ca 粉，含 Si 60wt% 氩气气氛中机械高能球磨至 0.6μ πι，制得超细 Si-Ca粉；将粒度 70 P m, 碳含量 95%以上的天然石墨粉碎分级、 整形和纯化处理制备得到碳含量 99.9%以上， 粒径为 5 μ m的球形石墨; 将制得的超细 Si-Ca粉 40 ％和 60 t%球 形石墨混合在锥形混合机中混合 4小时， 制成复合颗粒基体； 将复合颗粒基体与 10wt%酚醛树脂混合湿法搅拌 4h， 然后 400 干燥制粒； 将包覆后的复合料进行碳 化处理， 在氩气气氛中加热至 800 , 保温 5小时， 然后降至室温， 破碎打散至 18 μ ιη; 将破碎后的粉体与 30w /。沥青混合包覆、 炭化处理， 在氩气气氛中加热 1200 , 保温 1小时， 然后降至室温， 破碎打散至 15 μ ηι， 之后与 1 %的乙炔黑在 高速搅拌机中混合 2小时， 同时釆用频率 40kHz,功率为 50W的超声波处理 20分 钟； 浸渍 10%的 LiCl溶液 24小时， 固液比为 0.5。 最终得到硅碳复合负极材料。 测得其平均粒径为 24.8 μ m， 比表面积为 3.8m2/g， 振实密度为 0.94^cm3。 The obtained negative electrode was prepared in the same manner as in Example 1 to carry out an electrochemical performance test. Example 4, preparing a silicon-carbon Si-Ca-GC-LiCl composite anode material: Si-Ca powder having a particle size of 75 μm, mechanically high-energy ball milling to 0.6 μ π in a 60 wt% argon atmosphere, to obtain ultrafine Si-Ca powder; pulverized, graded, and purified natural graphite with a particle size of 70 P m and a carbon content of 95% or more to obtain spherical graphite having a carbon content of 99.9% or more and a particle diameter of 5 μm; Si-Ca powder 40% and 60 t% spherical graphite were mixed in a conical mixer for 4 hours to form a composite particle matrix; the composite particle substrate was mixed with 10 wt% phenolic resin and wet-stirred for 4 h, and then 400 dried and granulated; The coated composite was carbonized, heated to 800 in an argon atmosphere, held for 5 hours, then cooled to room temperature, broken up to 18 μm; and the broken powder was 30 w /. Asphalt mixed coating, carbonization, heating 1200 in an argon atmosphere, holding for 1 hour, then lowering to room temperature, crushing and breaking up to 15 μ ηι, and then mixing with 1% acetylene black in a high-speed mixer for 2 hours while 釆Ultrasonic treatment with a frequency of 40 kHz and a power of 50 W for 20 minutes; impregnation of 10% LiCl solution for 24 hours with a solid-liquid ratio of 0.5. Finally, a silicon-carbon composite anode material is obtained. The average particle diameter was 24.8 μm, the specific surface area was 3.8 m 2 /g, and the tap density was 0.94 cm 3 .
所得负极材料按照与实施例 1相同的方法制备电极， 进行电化学性能测试。 实施例 5， 制备硅碳 SiO-G-C-Li20复合负极材料： 将粒度为 75 μ m的 SiO粉 在氩气气氛中机械高能球磨至 0.8 μ m, 制得超细 SiO粉； 将粒度 70 μ m， 碳含量 95%以上的 J 石墨粉碎分级、 整形和纯化处理制备得到碳含量 99.9%以上， 粒径 为 3 μ m的球形石墨；将制得的超细 SiO粉 15wt%和 85\^%球形石墨混合在双螺旋 搅拌机中混合造粒 5小时， 制成复合颗粒基体； 将复合颗粒与 2.5wt%聚苯乙烯混 合湿法搅拌 4h， 然后 250°C干燥制粒； 将包覆后的复合料进行碳化处理， 在氩气气 氛中加热至 1300°C， 保温 2小时， 然后降至室温， 破碎打散至 5 μ ηι; 将破碎后的 粉体与 8wt%沥青混合包覆、 炭化处理， 在氩气气氛中加热 1100°C， 保温 10小时， 然后降至室温，破碎打散至 5 μ ιη，之后浸渍 5%的 Li20溶液 48小时，固液比为 1， 最终得到硅碳复合负极材料。 测得其平均粒径为 5.8 μ πι， 比表面积为 3.8m2/g， 振 实密度为 0.96^cm3。 The obtained negative electrode material was prepared in the same manner as in Example 1 to carry out an electrochemical performance test. Example 5, preparing a silicon carbon SiO-GC-Li 2 0 composite anode material: SiO powder having a particle size of 75 μm was mechanically high-energy ball-milled to 0.8 μm in an argon atmosphere to obtain an ultrafine SiO powder; μ m, J graphite with a carbon content of 95% or more, pulverized, shaped and purified to obtain spherical graphite with a carbon content of 99.9% or more and a particle size of 3 μm; the ultrafine SiO powder obtained is 15 wt% and 85\^ % spherical graphite mixture was mixed and granulated in a double-helical mixer for 5 hours to form a composite particle matrix; the composite particles were mixed with 2.5 wt% polystyrene and wet-stirred for 4 h, then dried at 250 ° C for granulation; The composite material is carbonized, heated to 1300 ° C in an argon atmosphere, kept for 2 hours, then reduced to room temperature, crushed and dispersed to 5 μ ηι ; the crushed powder is mixed with 8 wt% of asphalt, carbonized , heated at 1100 ° C in an argon atmosphere, held for 10 hours, then reduced to room temperature, crushed and dispersed to 5 μ η, then 5% Li 2 0 solution was immersed for 48 hours, the solid-liquid ratio was 1, and finally silicon carbon was obtained. Composite anode material. The average particle diameter was 5.8 μm, the specific surface area was 3.8 m 2 /g, and the tap density was 0.96 cm 3 .
所得负极材料按照与实施例 1相同的方法制备电极， 进行电化学性能测试。 实施例 6,制备硅碳 Si-G-G-LiN03复合负极材料:将粒度为 75 μ m的 Si-Ni粉， 含 Si 40wt% 氩气气氛中机械高能球磨至 0.6 μ m， 制得超细 Si-Ni粉; 将粒度 70 U m，齢量 95%以上的天然石墨粉碎分级、整形和纯化处理制备得到！ ^量 9.9% 以上， 粒径为 3 m的球形石墨； 将制得的超细 Si-Ni粉 50wt%和 50^%球形石墨 在双螺旋混合机中混合造粒 6小时， 制成复合颗粒基体； 将复合颗粒与 2.5wt%丁 胶乳混合湿法搅拌 4h,然后 200°C干燥制粒;将包覆后的复合料进行碳化处理， 在氩气气氛中加热至 700°C， 保温 5小时， 然后降至室温， 破碎打散至 Ιθμ ιη; 将 破碎后的粉体与 12wt%沥青混合包覆、 炭化处理， 在氩气气氛中加热 1200°C， 保 温 10小时， 然后降至室温， 破碎打散至 5 μ ιη， 之后与 1 %的导电碳黑 Super-P在 高速搅拌机中混合 2小时， 同时采用频率 35kFfe、 功率为 2500W的超声波处理 15 浸渍 10%的 LiN03溶液 36小时， 固液比为 2， 最终得到硅碳复合负极材料。 测得其平均粒径为 5.2 m, 比表面积为 4.0m2/g， 振实密度为 2.0gcm3。 所得负极材料按照与实施例 1相同的方法制备电极， 进行电化学性能测试。 实施例 7， 制备硅碳 Si02-G-C复合负极材料： 将粒度为 75 m的 Si02粉在空 气中机械高能球磨至 0.8 μ m， 制得超细 Si02粉； 将粒度 70 m， 碳含量 95%以上 的人造石墨粉碎、 纯化处理制得 量 99.9%以上， 粒径为 3 μ πι的石墨微粉； 将 制得的超细 Si02粉 10^%和 90wt%球形石墨混合在双螺旋搅拌机中混合造粒 5小 时，制成复合颗粒基体;将复合颗粒与 25^%酚醛树脂混合湿法搅拌 4h,然后 250°C 干燥制粒； 将包覆后的复合料进行碳化处理， 在含有氢气的还原气氛中加热至 1300°C ,保温 2小时，然后降至室温，破碎打散至 40μ πι;将破碎后的粉体与 5 wt% 沥青混合包覆、 炭化处理， 在氩气气氛中加热 1100°C， 保温 10小时， 然后降至室 温，破碎打散至 60 m，最终得到硅碳复合负极材料。测得其平均粒径为 60.4 μ πι， 比表面积为 2.8m2/g， 振实密度为 0.98g/cm3。 The obtained negative electrode material was prepared in the same manner as in Example 1 to carry out an electrochemical performance test. Example 6 Preparation of a silicon-carbon Si-GG-LiN0 3 composite anode material: Si-Ni powder having a particle size of 75 μm, mechanically high-energy ball milling to 0.6 μm in a 40% by weight argon atmosphere, to obtain ultrafine Si -Ni powder; The natural graphite with a particle size of 70 U m and a cerium content of 95% or more is prepared by pulverizing, grading, shaping and purifying! ^ 9.9% or more, spherical graphite with a particle size of 3 m; 50% by weight of the obtained ultrafine Si-Ni powder and 50% of spherical graphite are mixed and granulated in a double spiral mixer for 6 hours to form a composite particle matrix The composite particles were mixed with 2.5 wt% butadiene latex for 4 h, and then dried at 200 ° C for granulation; the coated composite was carbonized, heated to 700 ° C in an argon atmosphere, and kept for 5 hours. Then, it is cooled to room temperature, crushed and broken up to Ιθμ ιη; the crushed powder is mixed with 12wt% of asphalt, carbonized, heated at 1200 ° C in an argon atmosphere, kept for 10 hours, then cooled to room temperature, broken Disperse to 5 μ ιη, then mix with 1% conductive carbon black Super-P in a high-speed mixer for 2 hours, while using a frequency of 35kFfe, power of 2500W ultrasonic treatment 15 impregnation of 10% LiN0 3 solution for 36 hours, solid-liquid ratio 2, the silicon-carbon composite anode material is finally obtained. The average particle diameter was measured to be 5.2 m, the specific surface area was 4.0 m 2 /g, and the tap density was 2.0 gcm 3 . The obtained negative electrode material was prepared in the same manner as in Example 1 to carry out an electrochemical performance test. Example 7, Preparation of Silica Carbon SiO 2 -GC Composite Anode Material: The SiO 2 powder having a particle size of 75 m was mechanically high-energy ball-milled to 0.8 μm in air to prepare an ultrafine SiO 2 powder; the particle size was 70 m, and the carbon content was More than 95% of the artificial graphite is pulverized and purified to obtain more than 99.9% of graphite fine powder having a particle diameter of 3 μππ; the obtained ultrafine Si0 2 powder 10% and 90% by weight of spherical graphite are mixed in a double-helical mixer Mixed granulation for 5 hours to form a composite granule matrix; mixing the composite granules with 25% phenolic resin in a wet method for 4 hours, and then drying and granulating at 250 ° C; the coated composite material is carbonized, and contains hydrogen gas. The mixture was heated to 1300 ° C in a reducing atmosphere, kept for 2 hours, then cooled to room temperature, crushed and dispersed to 40 μ πι ; the crushed powder was mixed with 5 wt% of asphalt, carbonized, and heated in an argon atmosphere at 1100. °C, keep warm for 10 hours, then drop to room temperature, crush and break up to 60 m, and finally get silicon-carbon composite anode material. The average particle diameter was measured to be 60.4 μm, the specific surface area was 2.8 m 2 /g, and the tap density was 0.98 g/cm 3 .
所得负极材料按照与实施例 1相同的方法制备电极， 进行电化学性能测试。 实施例 8， 制备硅碳 Si-G-C复合负极材料： 将粒度为 75 μ m的 Si粉在氩气气 氛中机械高能球磨至 0.5 m， 制得超细 Si粉； mm 70 u rn, 碳含量 95%以上的 天然石墨粉碎分级、 整形和纯化处理制 到碳含量 99.9%以上， 粒径为 3 μ m的 球形石墨；将制得的超细 Si粉 5^%和 95wt%球形石墨混合在双螺旋搅拌机中混合 造粒 5小时， 制成复合颗粒基体； 将复合颗粒与 2.5wt%T"¾t胶乳 SBR、 1.5%羧 甲基纤维素 CMC1.5%湿法混合球磨 lh， 然后 250°C干燥制粒； 将包覆后的复合料 进行碳化处理， 在氩气气氛中加热至 450°C , 保温 10小时， 然后降至室温， 破碎 打散至 15 m; 将破碎后的粉体与 1 ％沥青混合包覆、 炭化处理， 在氩气气氛中 加热 1100°C， 保温 10小时， 然后降至室温， 破碎打散至 17 μ ηι， 最终得到硅碳复 合负极材料。 测得其平均粒径为 17.2 μ ηι, 比表面积为 3.3m2/g， 振实密度为 1.05^cm3 o The obtained negative electrode material was prepared in the same manner as in Example 1 to carry out an electrochemical performance test. Example 8 Preparation of a silicon-carbon Si-GC composite anode material: Si powder having a particle size of 75 μm was mechanically high-energy ball-milled to 0.5 m in an argon atmosphere to obtain an ultrafine Si powder; mm 70 u rn, carbon content 95 More than % of natural graphite is crushed, graded, shaped and purified to produce spherical graphite with a carbon content of 99.9% or more and a particle size of 3 μm; and the prepared ultrafine Si powder 5^% and 95% by weight of spherical graphite are mixed in a double helix Mixing and granulating for 5 hours in a blender to prepare a composite particle matrix; mixing the composite particles with 2.5 wt% T"3⁄4t latex SBR, 1.5% carboxymethylcellulose CMC 1.5% wet mixing ball for 1 h, then drying at 250 ° C Granular; the coated composite is carbonized, heated to 450 ° C in an argon atmosphere, held for 10 hours, then reduced to room temperature, broken up to 15 m ; the broken powder and 1% asphalt Mixed coating, carbonization treatment, heating at 1100 ° C in an argon atmosphere, holding for 10 hours, then dropping to room temperature, crushing and breaking up to 17 μ ηι, finally obtaining a silicon-carbon composite anode material. The average particle size was determined to be 17.2. μ ηι, specific surface area of 3.3 m 2 /g, tap density of 1.05^cm 3 o
所得负极材料按照与实施例 1相同的方法制备电极， 进行电化学性能测试。 实施例 9， 制备硅碳 Si-G-C复合负极材料： 将粒度为 75 μ ιη的 Si粉在氩气气 氛中机械高能球磨至 0.5 μ πι， 制得超细 Si粉； 将粒度 70 μ ιη， 碳含量 95%以上的 夭然石墨粉碎分级、 整形和纯化处理制备得到 量 99.9%以上， 粒径为 3 μ m的 球形石墨；将制得的超细 Si粉 1^%和 99wt。/。球形石墨混合在双螺旋搅拌机中混合 造粒 5小时， 制成复合颗粒基体； 将复合颗粒与 2.5wty。丁 ¾ 胶乳 SBR、 1.5%羧 甲基纤维素 CMC1.5%湿法混合球磨 12h， 同时采用频率 28kHz、 功率为 3600W、 超声波处理 5 ， 然后 250°C干燥制粒； 将包覆后的复合料进行碳化处理， 在氩 气气氛中加热至 450°C， 保温 10小时， 然后降至室温， 破碎打散至 15 m; 将破 碎后的粉体与 6 ％沥青混合包覆、炭化处理，在氩气气氛中加热 1100°C，保温 10 小时， 然后降至室温， 破碎打散至 17 μ ηι， 最终得到硅碳复合负极材料。测得其平 均粒径为 17.5 m， 比表面积为 3.2m2/g， 振实密度为 1.03g cm3。 The obtained negative electrode material was prepared in the same manner as in Example 1 to carry out an electrochemical performance test. Example 9, preparing a silicon carbon Si-GC composite anode material: a Si powder having a particle size of 75 μm was mechanically high-energy ball-milled to 0.5 μm in an argon atmosphere to prepare an ultrafine Si powder; a particle size of 70 μm, carbon More than 95% of the cumin graphite pulverization, grading, shaping and purification treatment to obtain more than 99.9% of spherical graphite with a particle size of 3 μm; the ultrafine Si powder obtained is 1% and 99wt. /. The spherical graphite mixture was mixed and granulated in a double-helical mixer for 5 hours to prepare a composite particle matrix; the composite particles were mixed with 2.5 wty. Ding 3⁄4 latex SBR, 1.5% carboxymethyl cellulose CMC 1.5% wet mixing ball mill 12h, while using frequency 28kHz, power 3600W, ultrasonic treatment 5, then dry granulation at 250 °C; Carbonized, heated to 450 ° C in an argon atmosphere, held for 10 hours, then reduced to room temperature, broken up to 15 m; mixed powder and 6 % asphalt mixed coating, carbonization, in argon The gas atmosphere was heated at 1100 ° C, kept for 10 hours, then cooled to room temperature, crushed and broken up to 17 μ ηι, and finally a silicon-carbon composite anode material was obtained. The average particle size was measured to be 17.5 m, the specific surface area was 3.2 m 2 /g, and the tap density was 1.03 g cm 3 .
所得负极材料按照与实施例 1相同的方法制备电极， 进行电化学性能测试。 实施例 10,制备硅碳 Si-Sn-Cu-G-C复合负极材料:将粒度为 75 μ m的 Si-Sn-Cu 粉， Si: Sn: Cu重量比 =65: 30： 5,在氩气气氛中机械高能球磨至 0.5 μ m, 制得 超细合金 Si粉; 将粒度 70 m， 碳含量 95%以上的天然石墨粉碎分级、 整形和纯 化处理制备得到^ * 99.9%以上， 粒径为 3 μ ηι的球形石墨； 将制得的超细合金 Si粉 40^%和 60wt%球形石墨混合在双螺旋搅拌机中混合造粒 5小时， 制成复合 颗粒基体； 将复合颗粒与 2.5wty0丁雜胶乳 SBR、 1.5%羧甲基纤维素 CMC1.5 湿法混合球磨 12h， 同时采用频率 28kHz、 功率为 3600W、超声波处理 5 中， 然 后 250°C干燥制粒；将包覆后的复合料进行碳化处理，在氩气气氛中加热至 450 ， 保温 10小时，然后降至室温，破碎打散至 15 m;将破碎后的粉体与 6wty。沥青混 合包覆、 炭化处理， 在氩气气氛中加热 1100°C， 保温 10小时， 然后降至室温， 破 碎打散至 17 μ ιη， 最终得到硅碳复合负极材料。 测得其平均粒径为 17.5 μ m， 比表 面积为 2.1m2/g， 振实密度为 1.23g Cm3。 所得负极材料按照与实施例 1相同的方法制备电极， 进行电化学性能测试。 实施例 11， 制备硅碳 Si-M-Co-Ag-G-C复合负极材料： 将粒度为 75 μ ιη的 Si-Ni-Mg-Ag粉， Si: Ni: Co: Ag重量比 =55: 30： 10: 5,在氩气气氛中机械高能 球磨至 0.5 m， 制得超细合金 Si粉; 将粒度 70 μ ηι, 碳含量 95%以上的天然石墨 粉碎分级、整形和纯化处理制备得到碳含量 99.9%以上，粒径为 3 μ ηι的球形石墨; 将制得的超细合金 Si粉 40wt%和 60wt%球形石墨混合在双螺旋搅拌机中混合造粒 5小时， 制成复合颗粒基体； 将复合颗粒与 2.5wt%T¾ 胶乳 SBR、 1.5%羧甲基 纤维素 CMC1.5%湿法混合球磨 12h， 同时采用频率 28kHz、 功率为 3600W、 超声 波处理 5 然后 250°C千燥制粒； 将包覆后的复合料进行碳化处理， 在氩气气 氛中加热至 450°C， 保温 10小时， 然后降至室温， 破碎打輕 15 μ πι; 将破碎后 的粉体与 6^%沥青混合包覆、 炭化处理， 在氩气气氛中加热 1100°C， 保温 10小 时， 然后降至室温， 破碎打散至 17ix m， 最终得到硅碳复合负极材料。测得其平均 粒径为 17.5 μ ιη, 比表面积为 1.9m2/g， 振实密度为 1.41g cm3。 The obtained negative electrode material was prepared in the same manner as in Example 1 to carry out an electrochemical performance test. Example 10, preparing a silicon carbon Si-Sn-Cu-GC composite anode material: Si-Sn-Cu powder having a particle size of 75 μm, Si: Sn: Cu weight ratio = 65: 30: 5, in an argon atmosphere Medium mechanical high energy ball milling to 0.5 μ m to produce ultra-fine alloy Si powder; natural graphite with a particle size of 70 m and a carbon content of 95% or more is prepared by pulverization, shaping and purification to obtain more than 99.9%, and the particle size is 3 μ.球形ι spherical graphite; the prepared ultra-fine alloy Si powder 40^% and 60wt% spherical graphite are mixed and granulated in a double-helical mixer for 5 hours to form a composite particle matrix; the composite particles and 2.5wty 0 -butadiene latex SBR, 1.5% carboxymethyl cellulose CMC1.5 wet mixing ball milling for 12h, using frequency 28kHz, power 3600W, ultrasonic treatment 5, then drying at 250 °C; carbonization of the coated composite , heated to 450 in an argon atmosphere, held for 10 hours, then reduced to room temperature, broken up to 15 m; the broken powder and 6wty. Asphalt mixed coating, carbonization treatment, heating at 1100 ° C in an argon atmosphere, holding for 10 hours, then dropping to room temperature, crushing and breaking up to 17 μ η, and finally obtaining a silicon-carbon composite anode material. The average particle size was measured to be 17.5 μm, the specific surface area was 2.1 m 2 /g, and the tap density was 1.23 g C m 3 . The obtained negative electrode material was prepared in the same manner as in Example 1 to carry out an electrochemical performance test. Example 11, Preparation of Silicon Carbon Si-M-Co-Ag-GC Composite Anode Material: Si-Ni-Mg-Ag powder having a particle size of 75 μm, Si: Ni: Co: Ag weight ratio = 55:30: 10: 5, mechanical high energy ball milling to 0.5 m in an argon atmosphere, to obtain ultra-fine alloy Si powder; natural particle size of 70 μ ηι, carbon content of 95% or more pulverized, shaped and purified to obtain a carbon content of 99.9 More than %, spherical graphite with a particle size of 3 μηη; 40% by weight of the prepared ultrafine alloy Si powder and 60% by weight of spherical graphite are mixed and granulated in a double-helical mixer for 5 hours to form a composite particle matrix; Blended with 2.5wt% T3⁄4 latex SBR, 1.5% carboxymethylcellulose CMC 1.5% wet milling for 12h, using frequency 28kHz, power 3600W, ultrasonic treatment 5 and then 250 °C dry granulation; The composite material is carbonized, heated to 450 ° C in an argon atmosphere, kept for 10 hours, then cooled to room temperature, crushed and lightened 15 μ πι ; the crushed powder is mixed with 6% of asphalt, carbonized Treatment, heating at 1100 ° C in an argon atmosphere, holding for 10 hours, then dropping to room temperature, breaking up and breaking up to 17ix m, the final silicon-carbon composite anode material. The average particle size was measured to be 17.5 μm, the specific surface area was 1.9 m 2 /g, and the tap density was 1.41 g cm 3 .
所得负极材料按照与实施例 1相同的方法制备电极， 进行电化学性能测试。 比较例， 使用 D5(}=16 m的天然球形石墨作为负极材料， 不经处理， 直接用 作负极材料， 按照与实施例 1相同的方法制备电极和电池， 进行电化学性能测试。 The obtained negative electrode material was prepared in the same manner as in Example 1 to carry out an electrochemical performance test. For the comparative example, an electrode and a battery were prepared in the same manner as in Example 1 using a natural spherical graphite of D 5 (} = 16 m as a negative electrode material, and used as a negative electrode material without treatment, and subjected to electrochemical performance test.
上述实施例和比较例测得的负极材料的电化学性能列于表 1。  The electrochemical properties of the negative electrode materials measured in the above examples and comparative examples are shown in Table 1.
从实施例可以看出，本发明所制备的石墨负极材料可逆比容量大于 450mAh/g, 循环 200次容量保持率大于 80%o  It can be seen from the examples that the graphite anode material prepared by the invention has a reversible specific capacity of more than 450 mAh/g, and the capacity retention rate of the cycle of 200 times is greater than 80%.
本发明的锂离子电池硅碳复合负极材料可广泛用于移动电话、笔记本电脑、摄 录一体机等便携式电动仪器、工具的锂离子电池用负极材料， 极大地提高了电池的 比容量， 满足用电器对电源轻量化要求， 适用于各种鹏领域。 极材料的电化学性能 The lithium-ion battery silicon-carbon composite anode material of the invention can be widely used as a negative electrode material for lithium ion batteries of portable electric instruments and tools such as mobile phones, notebook computers and camcorders, and greatly improves the specific capacity of the battery, and satisfies the requirements. Electrical appliances have light weight requirements for power supplies and are suitable for use in various fields. Electrochemical performance of polar materials
基体中 Si相粒 首次充电容量 首碰电容量 200次循环容 子及其含量 mAh/g mAh/g 量保持率％ 实施例 1 Si20wt% ― 765 650 82.3 实施例 2 Si-Mg 30wt% 770 680 87.1 实施例 3 Si-Fe2wt% 526 452 83.5 实施例 4 Si-Ca40wt% 806 690 82.1 实施例 5 SiO 15wt% 658 558 82.5 实施例 6 Si- 50wt 772 654 81.8 实施例 7 Si02 10w1% 530 450 84.9 实施例 8 Si 5wt% 538 458 89.6 实施例 9 Si lwt% 421 386 92.1 Si phase grain in the matrix, first charge capacity, first hit capacity, 200 cycles of volume, and its content, mAh/g mAh/g, volume retention, % Example 1 Si20wt% ― 765 650 82.3 Example 2 Si-Mg 30wt% 770 680 87.1 Implementation Example 3 Si-Fe 2 wt% 526 452 83.5 Example 4 Si-Ca 40 wt% 806 690 82.1 Example 5 SiO 15 wt% 658 558 82.5 Example 6 Si- 50 wt 772 654 81.8 Example 7 Si0 2 10 w1% 530 450 84.9 Example 8 Si 5wt% 538 458 89.6 Example 9 Si lwt% 421 386 92.1
Si-Sn-Cu Si-Sn-Cu
实施例 10 965 788 81.2 Example 10 965 788 81.2
40wt%  40wt%
Si-Ni-Co-Ag Si-Ni-Co-Ag
实施例 11 915 775 84.3 Example 11 915 775 84.3
40wt% 比较例 - 401 345 70.0  40wt% Comparative Example - 401 345 70.0

Claims

1. 一种锂离子电池硅碳复合负极材料， 其特征在于： 所述锂离子电池硅碳复合负 极材料以硅相粒子和碳相粒子的复合颗粒为基体， 基体呈球形或类球形， 基体 外包覆有碳包覆层。 A lithium-ion battery silicon-carbon composite anode material, characterized in that: the lithium-ion battery silicon-carbon composite anode material is based on composite particles of silicon phase particles and carbon phase particles, and the matrix is spherical or spheroidal, Covered with a carbon coating.
2. 根据权利要求书 1所述的锂离子电池硅碳复合负极材料， 其特征在于： 所述碳 包覆层是有机物热解炭包覆权层。  The lithium ion battery silicon-carbon composite negative electrode material according to claim 1, wherein the carbon coating layer is an organic pyrolytic carbon coating right layer.
3. 根据权利要求书 2所述的锂离子电池硅碳复合负极材料， 其特征在于： 所述碳 包覆层含有导电碳。  The lithium ion battery silicon-carbon composite negative electrode material according to claim 2, wherein the carbon coating layer contains conductive carbon.
4. 根据权利要求书 3所述的锂离子电池硅碳复合负极材料， 其特征在于： 所述碳 包覆层表面含有锂化合物 求  The lithium-ion battery silicon-carbon composite anode material according to claim 3, wherein: the surface of the carbon coating layer contains a lithium compound
5. 根据权利要求书 4腿勺锂离子电池硅碳复合负极材料， 其特征在于： 所述包 覆层厚度为 0.1〜5 m， 有机物热解炭占负极材料的比例为 0.5〜20wt%， 导电 碳占负极材料的比例是 0.5〜5wt%。  5. The silicon-carbon composite negative electrode material for a lithium ion battery according to claim 4, wherein: the thickness of the coating layer is 0.1 to 5 m, and the ratio of the organic pyrolytic carbon to the negative electrode material is 0.5 to 20 wt%, and is electrically conductive. The ratio of carbon to the negative electrode material is 0.5 to 5 wt%.
6. 根据权利要求书 1至 5中任一所述的锂离子电池硅碳复合负极材料， 其特征在 于： 所述硅碳复合负极材料的平均粒径为 5〜60 m， 比表面积 1.0〜4.0 m2/g， 振实密度 0.7〜2.0g/cm3。 The lithium-ion battery silicon-carbon composite anode material according to any one of claims 1 to 5, wherein the silicon-carbon composite anode material has an average particle diameter of 5 to 60 m and a specific surface area of 1.0 to 4.0. m 2 /g, tap density 0.7 to 2.0 g/cm 3 .
7. 根据权利要求书 6所述的锂离子电池硅碳复合负极材料， 其特征在于： 戶 M硅 相粒子是单质硅、硅氧化合物 SiOx、含硅固溶体或含硅金属间化合物， 硅相粒 子占复合颗粒基体的 l〜50 wt%， 其中 0<x 2。  7. The lithium-ion battery silicon-carbon composite anode material according to claim 6, wherein: the silicon phase silicon particles are elemental silicon, silicon oxide SiOx, silicon-containing solid solution or silicon-containing intermetallic compound, silicon phase particles. It accounts for 1~50 wt% of the composite particle matrix, where 0<x 2 .
8. 根据权利要求书 7所述的锂离子电池硅碳复合负极材料， 其特征在于： 所述硅 相粒子占复合颗粒¾#的比例优选在 5〜30wt%。  The lithium-ion battery silicon-carbon composite anode material according to claim 7, wherein the ratio of the silicon phase particles to the composite particles 3⁄4# is preferably 5 to 30% by weight.
9. 根据权利要求书 8所述的锂离子电池硅碳复合负极材料， 其特征在于： 所述硅 相粒子占复合颗粒基体的比例进一步 在 10〜20wt%。  The lithium-ion battery silicon-carbon composite anode material according to claim 8, wherein the proportion of the silicon phase particles to the composite particle matrix is further 10 to 20% by weight.
10.根据权利要求书 9所述的锂离子电池硅碳复合负极材料， 其特征在于： 所述含 硅固溶体或含硅金属间化合物， 是由硅与化学元素周期表中 ΠΑ族元素中的任 一种或两种元素、 3«金属元素中的任一种或三种元素、 ΠΙΑ族元素中的任一 种或两种元素， 或除硅之外的 IVA族元素中的任一种或两种元素构成。 The lithium-ion battery silicon-carbon composite anode material according to claim 9, wherein: a silicon solid solution or a silicon-containing intermetallic compound, which is composed of any one or two of the lanthanum elements in the periodic table of silicon and the chemical element, any one or three of the metal elements, and the lanthanide element. Any one or two elements, or one or both of the IVA group elements other than silicon.
11.根据权利要求书 10所述的锂离子电池硅碳复合负极材料，其特征在于：所述碳 相粒子是天然鳞片石墨、 微晶石墨、 人造石墨、 中间相炭微球和焦炭中的任意 一种或一种以上的混合。  The lithium-ion battery silicon-carbon composite anode material according to claim 10, wherein the carbon phase particles are any of natural flake graphite, microcrystalline graphite, artificial graphite, mesocarbon microspheres and coke. One or more blends.
12.根据权利要求书 11戶 ¾的锂离子电池硅碳复合负极材料，其特征在于：所述有 机物热解炭是由水溶性的聚乙烯醇、 丁¾1胶乳、 羧甲基纤维素， 有机溶剂系 的聚苯乙烯、 聚甲基丙烯酸甲酯、 聚四氟乙烯、 聚偏氟乙烯、 聚丙烯腈、 酚醛 树脂、 环氧树脂， 葡萄糖、 蔗糖、 果糖、 纤维素、 淀粉或沥青为前驱体， 经高 温碳化所形成的热解炭。  12. A lithium-ion battery silicon-carbon composite anode material according to claim 11 wherein said organic pyrolytic carbon is derived from water-soluble polyvinyl alcohol, butyl rubber, carboxymethyl cellulose, organic solvent. Polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, phenolic resin, epoxy resin, glucose, sucrose, fructose, cellulose, starch or asphalt as precursors, Pyrolytic carbon formed by high temperature carbonization.
13.根据权利要求书 12 的锂离子电池硅碳复合负极材料，其特征在于：所述导 电碳为乙炔黑、 碳纳米管、 纳米碳微球、 碳纤维或导电碳黑。  A lithium ion battery silicon-carbon composite anode material according to claim 12, wherein said conductive carbon is acetylene black, carbon nanotubes, nanocarbon microspheres, carbon fibers or conductive carbon black.
14.根据权利要求书 13舰的锂离子电池硅碳复合负极材料，其特征在于：所述含 锂化合物为氧化锂、 碳酸锂、 氟化锂、 氯化锂、 硝酸锂或氢氧化锂。  A lithium ion battery silicon-carbon composite negative electrode material according to claim 13, wherein said lithium-containing compound is lithium oxide, lithium carbonate, lithium fluoride, lithium chloride, lithium nitrate or lithium hydroxide.
15.一种锂离子电池硅碳复合负极材料的制备方法， 包括以下步骤： 一、 将硅相粒 子粉碎至 0.1〜1 μ πι， 制得超细硅相粒子； 将粒度 <75 μ πι， ^"量 95%以上的 原料碳粉碎分级、 整形和纯化处理制备得到齢量 99.9%以上， 粒径为 0.1-5 U m的碳相粒子； 二、将硅相粒子和碳相粒子混合造粒， 制成复合颗粒基体； 三、将复合颗粒基体与占复合颗粒基体 1〜25 ％的有机物热解炭的前驱体混合 或湿法搅拌 l〜12h，然后在 100〜400 牛下气相沉积或包覆造粒； 四、将包 覆后的颗粒进行碳化处理， 在保护气氛中加热 450至 1500°C， 保温 1至 10小 时， 然后降至室温， 形成碳包覆层； 五、 破碎打散至 5〜40 ix m， 制得锂离子电 池硅碳复合负极材料。 A method for preparing a silicon-carbon composite anode material for a lithium ion battery, comprising the steps of: 1. pulverizing the silicon phase particles to 0.1 to 1 μππ to obtain ultrafine silicon phase particles; and having a particle size of <75 μ πι, ^ "More than 95% of the raw material carbon is crushed, graded, shaped and purified to obtain carbon phase particles with a mass of 99.9% or more and a particle size of 0.1-5 U m. 2. Mixing the silicon phase particles with the carbon phase particles , the composite particle matrix is prepared; 3. The composite particle matrix is mixed with the precursor of the organic matter pyrolysis carbon of 1 to 25% of the composite particle matrix or wet stirred for 1~12h, and then vapor deposited or packaged under 100~400 cattle. Coating the granules; 4. Carbonizing the coated granules, heating 450 to 1500 ° C in a protective atmosphere, holding for 1 to 10 hours, then lowering to room temperature to form a carbon coating; 5. Breaking and breaking up to 5~40 ix m, a lithium-ion battery silicon-carbon composite anode material is obtained.
16.根据权利要求 15所述的锂离子电池硅碳复合负极材料的制备方法， 其特征在 于： 将所述破碎打散至 5〜40 μ πι的粉体与占粉体 1〜30 %沥青混合包覆， 然 后进行碳化处理， 在保护气氛中加热 450至 1500°C， 保温 1至 10小时， 然后 降至室温， 所得粉体与占粉体 0. 5〜5wt%的导电碳混合包覆， 在混合机或表面 包覆改性机中混合 1〜6小时， 并使用超声波分散 1〜30分钟， 破碎至 5〜60μ m。 The method for preparing a lithium-ion battery silicon-carbon composite anode material according to claim 15, wherein: the powder which is broken up to 5 to 40 μm is mixed with the powder of 1 to 30% of the powder. 5〜5重量%的复合碳混合覆,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Mix in a mixer or surface coating modification machine for 1 to 6 hours, and use ultrasonic dispersion for 1 to 30 minutes, and crush to 5 to 60 μm.
17.根据权利要求 16所述的锂离子电池硅碳复合负极材料的制备方法， 其特征在 于： 将所述破碎至 5〜60 li m的复合物浸渍含锂化合物， 将复合物粉 到 浓度为 0.2〜10^%含锂化合物溶液中， 固液比 0.1〜2， 浸渍时间 1〜48小时。 The method for preparing a lithium-ion battery silicon-carbon composite anode material according to claim 16, wherein: the composite compound which is crushed to 5 to 60 li m is impregnated with a lithium-containing compound, and the composite powder is powdered to a concentration of 0.2 to 10% by weight of the lithium-containing compound solution, the solid-liquid ratio is 0.1 to 2, and the immersion time is 1 to 48 hours.
18.根据权利要求 15、 16或 17所述的锂离子电池硅碳复合负极材料的制备方法， 其特征在于： 所述硅相粒子是单质硅、硅氧化合物 SiOx、含硅固溶体或含硅金 属间化合物， 硅相粒子占复合颗粒基体的 l〜50 wty。， 其中 0<x 2， 含硅固溶 体或含硅金属间化合物， 是由硅与化学元素周期表中 ΠΑ族元素中的任一种或 两种元素、 过渡金属元素中的任一种或三种元素、 ΙΠΑ族元素中的任一种或两 种元素， 或除硅之外的 IVA族元素中的任一种或两种元素构成。 The method for preparing a lithium-ion battery silicon-carbon composite anode material according to claim 15, 16 or 17, wherein the silicon phase particles are elemental silicon, silicon oxide SiOx, silicon-containing solid solution or silicon-containing metal. The interphase compound, the silicon phase particles account for 1 to 50 wty of the composite particle matrix. , wherein 0<x 2, a silicon-containing solid solution or a silicon-containing intermetallic compound, is any one or two of the lanthanum elements in the periodic table of silicon and the chemical element, and one or three of the transition metal elements Any one or two elements of the element, the lanthanum element, or one or both of the group IVA elements other than silicon.
19.根据权利要求 18所述的锂离子电池硅碳复合负极材料的制备方法， 其特征在 于： 所述碳相粒子是天然鳞片石墨、 微晶石墨、 At石墨、 中间相炭微綱口焦 炭中的任意一或一种以上的混合， 碳相粒子占所述复合颗粒基体的 50〜99 wt%。  The method for preparing a lithium-ion battery silicon-carbon composite anode material according to claim 18, wherein: the carbon phase particles are natural flake graphite, microcrystalline graphite, At graphite, mesophase carbon micro-cylinder coke Any one or more of the mixtures, the carbon phase particles account for 50 to 99% by weight of the composite particle matrix.
20.根据权利要求 19所述的锂离子电池硅碳复合负极材料的制备方法， 其特征在 于： 所述包覆层占复合材料的比例是 l〜25wt%。  The method for preparing a lithium-ion battery silicon-carbon composite anode material according to claim 19, wherein the ratio of the coating layer to the composite material is from 1 to 25 wt%.
21.根据权利要求 20所述的锂离子电池硅碳复合负极材料的制备方法， 其特征在 于- 所述有机物热解炭的前驱体是水溶性的聚乙烯醇、 丁 胶乳、 羧甲基纤 维素， 有机溶剂系的聚苯乙烯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯、 聚丙烯腈有机物、酚醛树脂、环氧树脂， 葡萄糖、蔗糖、果糖、 纤维素或淀粉。The method for preparing a lithium-ion battery silicon-carbon composite anode material according to claim 20, wherein - the precursor of the organic pyrolytic carbon is water-soluble polyvinyl alcohol, butadiene latex, carboxymethyl cellulose , organic solvent-based polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, Polyacrylonitrile organic, phenolic resin, epoxy resin, glucose, sucrose, fructose, cellulose or starch.
22.根据又利要求 21 所述的锂离子电池硅碳复合负极材料的制备方法， 其特征在 于- 所述导电碳为乙炔黑、 碳纳米管、 纳米碳微球、 碳纤维或导电碳黑。 22. The method for preparing a lithium-ion battery silicon-carbon composite anode material according to claim 21, wherein the conductive carbon is acetylene black, carbon nanotubes, nanocarbon microspheres, carbon fibers or conductive carbon black.
23.根据权利要求 22所述的锂离子电池硅碳复合负极材料的制备方法， 其特征在 于： 所述含锂化合物为氧化锂、碳酸锂、氟化锂、氯化锂、硝酸锂或氢氧化锂。 The method for preparing a lithium-ion battery silicon-carbon composite anode material according to claim 22, wherein the lithium-containing compound is lithium oxide, lithium carbonate, lithium fluoride, lithium chloride, lithium nitrate or hydrogen hydroxide. lithium.
24.根据权利要求 23所述的锂离子电池硅碳复合负极材料的制备方法， 其特征在 于： 所述硅相粒子球磨在保护气氛中进行， 保护气氛为氩气、 氢气或氣气中的 任一种或几种的混合。 The method for preparing a silicon-carbon composite anode material for a lithium ion battery according to claim 23, wherein: the silicon phase particles are ball milled in a protective atmosphere, and the protective atmosphere is any of argon gas, hydrogen gas or gas gas. One or a mixture of several.
25.根据权利要求 24所述的锂离子电池硅碳复合负极材料的制备方法， 其特征在 于-所述将硅相粒子和碳相粒子混合造粒时，在混合造粒机中混合造粒.1〜6小 时。  The method for preparing a lithium-ion battery silicon-carbon composite anode material according to claim 24, wherein when the silicon phase particles and the carbon phase particles are mixed and granulated, the granulation is mixed and granulated in a mixing granulator. 1 to 6 hours.
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