WO2021077586A1 - 一种用于电极材料的硅氧颗粒及其制备方法和应用 - Google Patents

一种用于电极材料的硅氧颗粒及其制备方法和应用 Download PDF

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WO2021077586A1
WO2021077586A1 PCT/CN2019/126660 CN2019126660W WO2021077586A1 WO 2021077586 A1 WO2021077586 A1 WO 2021077586A1 CN 2019126660 W CN2019126660 W CN 2019126660W WO 2021077586 A1 WO2021077586 A1 WO 2021077586A1
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silica particles
carbon layer
particles according
silicon oxide
particles
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PCT/CN2019/126660
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English (en)
French (fr)
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李喆
王岑
汪芳
张和宝
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安普瑞斯（南京）有限公司
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Priority to EP19950036.4A priority Critical patent/EP3955345A4/en
Priority to KR1020217037928A priority patent/KR20210153710A/ko
Priority to JP2021570239A priority patent/JP7420836B2/ja
Priority to US17/617,746 priority patent/US20220246924A1/en
Publication of WO2021077586A1 publication Critical patent/WO2021077586A1/zh

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    • H—ELECTRICITY
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    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4417—Methods specially adapted for coating powder
    • 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
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0428—Chemical vapour deposition
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
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    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 the field of batteries, in particular to a silicon oxide particle used for lithium ion electrode materials, and a preparation method and application thereof.
  • the negative electrode material of commercial lithium-ion batteries is mainly graphite, but due to the low theoretical capacity, it limits the further improvement of the energy density of lithium-ion batteries. Due to the high capacity advantages of silicon anode materials that other anode materials cannot match, it has become a research and development hotspot in recent years, and has gradually moved from laboratory research and development to commercial applications.
  • the elemental silicon anode material has a serious volume effect in the process of lithium insertion and removal, and the volume change rate is about 300%, which will cause powdering of the electrode material and separation of the electrode material from the current collector.
  • the new SEI film will be formed when the fresh interface is exposed to the electrolyte, which will continue to consume the electrolyte and reduce the cycle performance of the electrode material. .
  • One of the objectives of the present invention is to provide a silicon-oxygen composite material with high capacity, high coulombic efficiency, long cycle life, and low expansion rate for lithium ion batteries and a preparation method thereof in view of the deficiencies of the prior art.
  • the present invention provides a silica particle for electrode material, which has a dense structure and no pores above sub-micrometer level; it is characterized in that the silica particle includes:
  • the general formula of the silicon oxide particles is SiOx; the silicon oxide particles are derived from, for example, amorphous silicon oxide powder raw materials through disproportionation reaction to form silicon nano-crystal grains/amorphous nano-crystals existing in the SiOx matrix Cluster
  • each silicon oxide particle is a secondary particle formed by a composite of a plurality of silicon oxide particles and a carbon film, and there is no single silicon oxide primary particle or a silicon oxide primary particle coated with a carbon film.
  • the carbon layer material is composed of glucose, sucrose, chitosan, starch, citric acid, gelatin, alginic acid, carboxymethyl cellulose, coal pitch, petroleum pitch, phenolic resin, tar, naphthalene oil, anthracene oil, Combination of one or more precursor materials of polyacrylic acid, polyacrylate, polystyrene, polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, epoxy resin, polyacrylonitrile, polymethyl methacrylate Obtained by carbonization treatment.
  • the silicon oxide particles 0.5 ⁇ x ⁇ 1.5, preferably 0.8 ⁇ x ⁇ 1.2. More preferably, 0.9 ⁇ x ⁇ 1.1.
  • the mass ratio of the silica particles to the silica particles is 80-99.9% by weight, preferably 90-99.5% by weight. More preferably, the mass ratio of the silica particles to the silica particles is 94-98 wt%.
  • the silica particles may further include conductive additives uniformly dispersed in the inner and/or outer surface carbon layer of the silica particles.
  • the conductive additive may be selected from one or a combination of Super P, Ketjen black, vapor-grown carbon fiber, acetylene black, conductive graphite, carbon nanotube, and graphene.
  • the conductive additive accounts for 0.01-10 wt% of the silica particles, preferably 0.03-5 wt%.
  • the silica particles further include one or more additional carbon layers coated on the outer surface of the silica particles, preferably one layer.
  • the additional carbon layer is obtained by carbonizing a combination of one or more precursor materials selected from coal pitch, petroleum pitch, polyvinyl alcohol, epoxy resin, polyacrylonitrile, and polymethyl methacrylate.
  • the additional carbon layer is composed of any one of methane, ethane, ethylene, acetylene, propane, propylene, butane, butene, butadiene, benzene, toluene, xylene, styrene or phenol, or Various combinations are obtained by chemical vapor deposition.
  • the mass ratio of the additional carbon layer to the silicon-oxygen particles is 0.1-10 wt%, preferably 0.3-6 wt%.
  • the D50 of the silica particles is 1-40 ⁇ m, preferably 3-20 ⁇ m.
  • the specific surface area of the silica particles is 0.1-10 m 2 /g, more preferably 0.3-6 m 2 /g.
  • the tap density of the silica particles is ⁇ 0.6 g/cm 3 , preferably ⁇ 0.8 g/cm 3 .
  • the present invention also proposes the application of the silicon-oxygen particles as described above in electrode materials.
  • the present invention also provides a negative electrode material, which includes any of the aforementioned silicon oxide particles.
  • the negative electrode material is prepared by mixing silicon oxide particles and carbon-based powder materials, and the carbon-based powder materials can be selected from natural graphite, artificial graphite, surface-modified natural graphite, hard carbon, soft carbon or mesocarbon micro Any combination of one or more of the balls.
  • the present invention also proposes a pole piece or battery including any of the foregoing negative electrode materials. Specifically, it may be a lithium ion battery.
  • the present invention also proposes a method for preparing silicon oxide particles as described above, which includes: mixing the silicon oxide particles with the carbon layer precursor material and then performing carbonization in a non-oxidizing atmosphere, and the carbonized product is dispersed , Sieving, demagnetization treatment.
  • the method for preparing silicon oxide particles as described above may also include the addition of conductive additives.
  • the silicon oxide particles, conductive additives, and carbon layer precursor materials are mixed and granulated in a non-oxidizing atmosphere. Carbonization is carried out in the process, and the carbonized product is broken up, sieved, and demagnetized.
  • the aforementioned method further includes the step of coating one or more additional carbon layers, preferably one layer.
  • the granulation equipment can optionally have both heating and stirring functions, including but not limited to a VC mixer, a mechanical fusion machine, a coating kettle or a reaction kettle.
  • the linear velocity at the maximum diameter of the stirring component in the VC mixer, mechanical fusion machine, coating kettle or reaction kettle is 1-30m/s; the temperature can be selected from 100-1050°C, and the time is 0.5-10 hours, and protected by an inert atmosphere.
  • the carbon precursor material is softened and uniformly coated on the surface of the silicon oxide particles during the continuous high-speed stirring process.
  • the multiple silicon oxide primary particles coated with the carbon precursor are bonded and agglomerated with each other.
  • silicon oxide/carbon precursor composite secondary particles Form a certain size of silicon oxide/carbon precursor composite secondary particles.
  • the above-mentioned secondary particles will become denser under long-term and high-frequency shearing, extrusion, and collision in VC mixer, mechanical fusion machine, coating kettle or reaction kettle, and at the same time, the carbon precursor will be partially removed under heating conditions.
  • the molecular volatiles are partially cross-linked and carbonized, so that the secondary particles are shaped.
  • the granulation equipment may also be a spray drying equipment.
  • the spray drying equipment processes the slurry containing silicon oxide particles and carbon precursors
  • the nozzle of the equipment atomizes the slurry into small droplets, and the solvent in the droplets acts on the hot air at a certain temperature in the equipment
  • the lower evaporates rapidly, and is collected by a cyclone to obtain dry silicon oxide/carbon precursor composite secondary particles.
  • the carbonization equipment includes a tube furnace, an atmosphere box furnace, a pusher kiln, a roller kiln or a rotary kiln.
  • the temperature of the carbonization reaction is 600-1200°C, and the time is 0.5-24 hours;
  • the non-oxidizing atmosphere is provided by at least one of the following gases: nitrogen, argon, hydrogen, and helium.
  • the dispersing equipment includes any one of a jet mill, a ball mill, a turbo mill, a Raymond mill, a coulter mill, and a toothed disk mill.
  • the equipment for coating the additional carbon layer can optionally have both heating and stirring functions, including but not limited to any one of a mechanical fusion machine, a VC mixer, a high-speed disperser, a coating kettle or a reaction kettle.
  • the coating additional carbon layer may be selected from a chemical vapor deposition method, which includes the step of: performing chemical vapor deposition in an organic gas and/or steam at a temperature of 700°C to 1050°C.
  • the present invention has the following advantages:
  • the silicon oxide particles are tightly connected through the carbon layer to form aggregated particles, which reduces the proportion of primary particles of small size while not increasing the secondary particles of large size too much, and obtains secondary particles with a narrower particle size distribution. Due to the preparation process of the secondary particles, the applicable range of the raw material of the silicon oxide particles is increased, and the technical solution of the present invention also greatly reduces the specific surface area of the material, thereby reducing the material in the battery, such as lithium ion secondary battery. The contact area between the electrolyte and the electrolyte reduces the loss of lithium ions caused by the continuous generation of SEI on the surface of the electrolyte during each charge and discharge process, which makes the battery coulombic efficiency higher and cycle performance better.
  • the carbon layer connection and coating provide excellent electron and lithium ion transmission channels at the same time, ensuring that the silicon oxide inside the particles fully participates in the electrochemical reaction, reducing the polarization of the battery, and improving the rate performance; when the interior and surface of the secondary particles are dispersed When there are conductive additives, the conductivity of the material is further mentioned, and the rate performance of the battery is better.
  • the capacity and expansion rate of the silicon-oxygen composite material are higher than that of the carbon-based negative electrode mixed with it, after the battery pole piece is made, the micro-area where the usual silicon-oxygen composite material is located has a higher meeting capacity and larger expansion.
  • the particles prepared by the present invention have a narrower particle size distribution and a smaller proportion of large particles. Therefore, when the particles of the present invention are made into battery pole pieces, the surface capacity and expansion of the pole pieces The distribution is relatively more uniform, and the expansion rate of the pole piece will be smaller.
  • the outer surface of the particles is further coated with a continuous carbon protective layer, which increases the conductivity of the material and further reduces the specific surface area of the composite material, reduces the formation of SEI, and is beneficial to improving the coulombic efficiency and battery cycle retention rate. Since the structure of the material of the present invention is more stable and the expansion is smaller, more silicon oxide particles can be added to the negative electrode material to achieve the purpose of increasing the energy density of the battery.
  • Figure 1 is a high-power scanning electron micrograph of the secondary particles prepared in Example 1.
  • FIG. 2 is a schematic diagram of the structure of the secondary particles prepared in Example 1.
  • FIG. 2 is a schematic diagram of the structure of the secondary particles prepared in Example 1.
  • FIG. 3 is a schematic diagram of the structure of the secondary particles prepared in Example 2.
  • FIG. 3 is a schematic diagram of the structure of the secondary particles prepared in Example 2.
  • FIG. 4 is a schematic diagram of the structure of the secondary particles prepared in Example 4.
  • FIG. 4 is a schematic diagram of the structure of the secondary particles prepared in Example 4.
  • FIG. 5 is a graph showing the particle size distribution of the silicon oxide raw materials used in Comparative Examples 2 and 6, and the secondary particles prepared in Comparative Examples 1, 2, and 6.
  • Fig. 6 is a low-power scanning electron micrograph of the secondary particles prepared in Example 6.
  • FIG. 7 is a high-power scanning electron micrograph of the secondary particles prepared in Example 6.
  • Example 8 is an electron micrograph of a cross section of a negative electrode of a battery containing secondary particles prepared in Example 6 after formation.
  • FIG. 9 is a high-power scanning electron micrograph of the secondary particles prepared in Example 14.
  • FIG. 9 is a high-power scanning electron micrograph of the secondary particles prepared in Example 14.
  • Figure 10 is a scanning electron microscope photograph of particles prepared in Comparative Example 1.
  • Figure 11 is a scanning electron micrograph of particles prepared in Comparative Example 2.
  • Figure 1 is a high-magnification scanning electron micrograph of the secondary particles prepared in Example 1
  • Figure 2 is a schematic diagram of the structure.
  • the particles prepared in Example 1 are dense secondary particles.
  • the coated carbon layer B is composited.
  • the silicon oxide material undergoes a heat treatment above 800°C, a disproportionation reaction will occur: 2SiO ⁇ Si+SiO 2 , forming silicon nanocrystalline grains/clusters uniformly dispersed in SiOx. According to the results of the X-ray diffraction pattern, substituting the Sherrer equation, it can be calculated that the Si(111) crystal plane in the material obtained in Example 1 corresponds to a crystal grain size of 2.9 nm.
  • Hitachi SU8010 field emission scanning electron microscope to observe the surface morphology of the sample.
  • Quantachrome Nova4200e specific surface area tester was used to test the specific surface area of the material.
  • the elementar vario EL cube elemental analyzer is used to determine the carbon content in the material.
  • the Rigaku MiniFlex600 X-ray diffractometer was used to test the crystal structure of the material.
  • Half-cell evaluation the above-prepared silicon-oxygen-containing secondary particle negative electrode sheet, diaphragm, lithium sheet, and stainless steel gasket were sequentially stacked, and 200 ⁇ L of electrolyte was added dropwise, and then sealed to produce a 2016-type lithium-ion half-cell.
  • Example 2 The process of Example 2 is similar to that of Example 1. The difference is that in the process of material synthesis, in addition to taking 100kg of silica powder and 12kg of coal pitch powder into the VC mixer, an additional 0.3kg of Ketjen Black and 0.2 kg of multi-walled carbon nanotube conductive additive powder. Therefore, the final product is silicon oxide/amorphous carbon composite secondary particles containing conductive additives.
  • the structure is shown in Figure 3. This material is composed of silicon oxide primary particles A, conductive additives C and the two connected and coated in The carbon layer B is compounded together, and the conductive additive C is uniformly dispersed on the inner and outer surfaces of the secondary particles.
  • the crystal grain size corresponding to the crystal plane is 2.9 nm.
  • Example 2 Take 100kg of the secondary particles prepared in Example 1, and take 1kg of petroleum pitch powder, add them to the VC mixer, and mix them mechanically at a line speed of 3m/s for 10 minutes, and then reduce the speed to 2m/s in a nitrogen atmosphere. While stirring, the equipment was heated to 300°C and kept for 1 h, and then slowly cooled to room temperature. The above-mentioned pitch-coated material was kept at 400°C for 2h in an argon inert atmosphere, then heated to 900°C and carbonized for 4h, naturally cooled to room temperature, crushed, sieved and demagnetized to obtain a second layer of amorphous Carbon-coated silicon oxide/amorphous carbon composite particles.
  • the crystal grain size corresponding to the crystal plane is 2.9 nm.
  • FIG. 4 is a schematic diagram of the structure of the secondary particles prepared in this embodiment. As shown in Figure 4, the material is composed of primary silicon oxide particles A, conductive additives C, and a carbon layer B that connects and coats the two. , The conductive additive C is uniformly dispersed inside the secondary particles, and there is a second continuous carbon coating layer D on the outer surface of the secondary particles.
  • the crystal grain size corresponding to the crystal plane is 2.9 nm.
  • Example 3 The half-cell and full-cell evaluation methods are the same as in Example 1, and the results are summarized in Table 1. It can be seen that, as in Example 3, the performance of the product can be significantly improved after multiple coatings.
  • sucrose solution Dissolve 0.2 kg of sucrose in 8 kg of deionized water to obtain a sucrose solution, then add 0.6 g of single-walled carbon nanotubes to the sucrose solution and stir and disperse the carbon nanotube slurry, and then add 2 kg of silicon oxide powder while stirring (same implementation Example 1), followed by ultrasonic dispersion for 1 hour while stirring, to obtain a composite slurry of sucrose/single-walled carbon nanotubes/silica particles.
  • the composite slurry is spray-dried, the air inlet temperature is 150°C, and the spray nozzle atomization pressure is 0.2Mpa, to obtain dry powder of sucrose/single-walled carbon nanotube/silica composite secondary particles.
  • the crystal grain size corresponding to the (111) crystal plane is 2.9 nm.
  • FIG. 5 shows the particle size distribution diagram of the silica powder raw material and the silica composite material (ie, secondary particles) in this embodiment.
  • FIG. 6 and FIG. 7 show scanning electron micrographs of the secondary particles prepared in this example
  • FIG. 8 is a cross-sectional electron micrograph of the negative pole piece of a lithium ion battery containing the secondary particles prepared in this example.
  • the particles obtained in this embodiment are secondary particles of uniform size, without monodisperse primary particles.
  • Fig. 7 and Fig. 8 at the same time, it can be seen that the particles prepared in this embodiment are dense secondary particles.
  • the carbon content is 3.0wt%, and the crystal grain size corresponding to the Si(111) crystal plane is 4.1nm.
  • the half-cell and full-cell evaluation methods are the same as in Example 1.
  • the results are summarized in Table 1.
  • the weight energy density of the full battery reached 311Wh/kg, the cycle retention rate reached 90.7%, and the battery expansion rate was 7.6%.
  • the obtained battery has excellent performance.
  • Example 9 The process steps of Example 9 are similar to those of Example 8. The only difference is that in the granulation step, the holding temperature in the VC mixer is 400° C., and the holding time is 3 h.
  • the crystal grain size corresponding to the crystal plane is 3.9 nm.
  • Example 10 The process steps of Example 10 are similar to those of Example 8, with the only difference being that in the granulation step, the holding temperature in the VC mixer is 150° C., and the holding time is 6 hours.
  • the crystal grain size corresponding to the crystal plane is 3.9 nm.
  • Example 11 The process steps of Example 11 are similar to those of Example 9, with the only difference being that the amount of petroleum pitch added is 9 kg.
  • the crystal grain size corresponding to the crystal plane is 3.9 nm.
  • Example 12 The process steps of Example 12 are similar to those of Example 9, with the only difference being that the amount of petroleum pitch added is 3 kg.
  • the crystal grain size corresponding to the crystal plane is 3.9 nm.
  • FIG. 9 is a high-power scanning electron micrograph of the secondary particles prepared in Example 14.
  • FIG. 9 is a high-power scanning electron micrograph of the secondary particles prepared in Example 14.
  • silicon oxide block (average particle size about 2cm) in a box furnace, pass in an argon protective atmosphere, heat up at 3°C/min to 1000°C for high temperature heat treatment for 2 hours to obtain a disproportionated modified silicon oxide block body.
  • Figure 10 is an electron microscope picture of the silicon oxide composite material in Comparative Example 1. It can be seen that there are many fine powder particles in the composite material, mostly monodisperse primary particles, and the particles have sharp edges and corners. It can be seen from the particle size distribution diagram of the silica composite material in Comparative Example 1 in FIG. 5 that the particle size distribution of the product of Comparative Example 1 is wider than that of Example 6, and the proportion of small particles is higher.
  • the particle size distribution curve in Figure 5 is a weight/volume distribution curve. The height of the small particle segment curve is relatively high, indicating that the weight/volume ratio of small particles is relatively high. The ratio of the number of small particles and the ratio of specific surface area are orders of magnitude. increase. Therefore, it can be seen from the figure that compared with Example 6, the number of small particles in Comparative Example 1 is much higher, and the specific surface area also increases greatly.
  • Example 1 Refer to the half-cell and full-cell evaluation methods of Example 1 to evaluate the performance of the battery prepared by the particles of this comparative example, and the results are summarized in Table 1.
  • a precursor 1 put 100 kg of silica powder (same as Example 6) and 10 kg of petroleum pitch powder in a VC mixer, adjust the linear speed to 10 m/s, and mix for 0.5 h to obtain a precursor 1.
  • Add the precursor 1 to the vacuum kneader control the temperature of the material to be above 250°C by heating and circulating the heat transfer oil, kneading for 6 hours until the material becomes viscous, and then quickly transfer to the flaking mill for flaking treatment before the material is cooled.
  • the thickness of the rolled sheet is 2.0 ⁇ 5.0mm. After the rolled sheet is cooled, it is mechanically crushed.
  • the median particle size is controlled to be 2.0 ⁇ 15.0 ⁇ m.
  • the crushed material is subjected to isostatic pressure treatment with a controlled pressure of 20MPa and a temperature of 250°C. , The pressure treatment for 0.1h was carried out, and the precursor 2 was obtained.
  • the precursor 2 is placed in a roller kiln, and a nitrogen protective gas is introduced to raise the temperature to 1000°C at 3°C/min, keep the temperature for 7 hours, and cool to room temperature naturally.
  • the coulter is crushed for 1 hour, the maximum linear speed of the coulter is 3m/s, and then sieved, demagnetized, and dried to obtain silica particles.
  • the crystal grain size corresponding to the crystal plane is 4.0 nm.
  • Figure 11 is an electron microscope picture of the silica particles in Comparative Example 2. It can be seen that there are many fine powder particles in the composite material, and more monodisperse primary particles. There are some loose particles with larger and smaller primary particles that have a larger specific surface area. Secondary particles. It can be seen from the particle size distribution diagram of the silica particles in Comparative Example 2 in FIG. 5 that the particle size distribution of the product of Comparative Example 2 is wider than that of Example 1, and the proportions of small particles and large particles are both higher.
  • Example 1 Refer to the half-cell and full-cell evaluation methods of Example 1 to evaluate the performance of the battery prepared by the particles of this comparative example, and the results are summarized in Table 1.
  • Comparative Example 3 The process steps of Comparative Example 3 are similar to those of Examples 8-10. The only difference is that after mixing with a VC mixer at room temperature, the granulation process of heating and stirring is not carried out, and the material is discharged directly, and the material is subsequently carbonized and crushed. , Screening, demagnetization treatment.
  • the crystal grain size corresponding to the crystal plane is 3.9 nm.
  • the prior art As far as the prior art is concerned, its preparation process is complicated, such as kneading, sheet rolling, and compression molding processes that are difficult to achieve large-scale production.
  • the carbon precursor is bound to adhere and agglomerate adjacent silicon oxide particles after being carbonized, and subsequent crushing, pulverization and other processes will damage the carbon coating layer.
  • the material prepared in the prior art has a wide particle size distribution, and the proportions of large and small particles are relatively high.
  • the coulombic efficiency, expansion rate, and cycle retention rate of the prepared battery are all unsatisfactory, and the area capacity and micro-area expansion distribution are uneven.
  • the secondary particles used in the negative electrode material prepared by the present invention are compact, narrow in particle size distribution, and small in specific surface area.

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Abstract

一种用于电极材料的硅氧颗粒，所述硅氧颗粒包括：氧化亚硅颗粒（A），其通式为SiOx；碳层（B），多个所述氧化亚硅颗粒（A）由所述碳层（B）粘结，且碳层（B）粘结的多个所述氧化亚硅颗粒（A）由所述碳层（B）包覆。该硅氧颗粒致密、粒径分布窄、比表面积小，具有高容量、高库伦效率、低膨胀、循环保持率高等优点。

Description

一种用于电极材料的硅氧颗粒及其制备方法和应用 技术领域
本发明涉及电池领域，特别涉及一种用于锂离子电极材料的硅氧颗粒及其制备方法和应用。
背景技术
由于近年来各种便携式电子设备、电动汽车以及储能系统的快速发展和广泛应用，对于能量密度高、循环寿命长的锂离子电池的需求日益迫切。目前商业化的锂离子电池的负极材料主要为石墨，但由于理论容量低，限制了锂离子电池能量密度的进一步提高。由于硅负极材料具有其它负极材料无法匹敌的高容量优势，近些年来成为了研发热点，并逐渐从实验室研发走向商业应用。其中，单质硅负极材料在嵌脱锂过程中存在严重的体积效应，体积变化率约为300％，会造成电极材料粉化以及电极材料与集流体分离。另外，由于硅负极材料在电池充放电过程中不断地膨胀收缩而持续破裂，产成的新鲜界面暴露于电解液中会形成新的SEI膜，从而持续消耗电解液，降低了电极材料的循环性能。
现有硅负极材料库伦效率低、膨胀大、循环保持率低、极化大、制备工艺复杂，因而难以实现在电池中的商业化应用，是所属领域的技术难题。
发明内容
本发明的目的之一是针对现有技术的不足，提供一种用于锂离子电池的容量高、库伦效率高、循环寿命长、膨胀率低的硅氧复合材料及其制备方法。
具体地，本发明提出了一种用于电极材料的硅氧颗粒，该颗粒结构致密，无亚微米级以上的孔隙；其特征在于，所述硅氧颗粒包括：
氧化亚硅颗粒，其通式为SiOx；所述氧化亚硅颗粒由例如是无定形态的氧化亚硅粉末原料经歧化反应而来，形成存在于SiOx基体内的硅纳米晶粒/无定形纳米团簇；
碳层，多个所述氧化亚硅颗粒由所述碳层粘结，且碳层粘结的多个所述氧化亚硅颗粒由所述碳层包覆。具体而言，每个硅氧颗粒均为多个 氧化亚硅颗粒和碳膜复合而成的二次颗粒，不存在单个的氧化亚硅一次颗粒或者包覆碳膜的氧化亚硅一次颗粒。
具体地，所述碳层材料由葡萄糖、蔗糖、壳聚糖、淀粉、柠檬酸、明胶、海藻酸、羧甲基纤维素、煤沥青、石油沥青、酚醛树脂、焦油、萘油、蒽油、聚丙烯酸、聚丙烯酸酯、聚苯乙烯、聚乙烯吡咯烷酮、聚氧化乙烯、聚乙烯醇、环氧树脂、聚丙烯腈、聚甲基丙烯酸甲酯中的一种或多种前驱体材料的组合经碳化处理得到。
具体地，所述氧化亚硅颗粒中，0.5≤x≤1.5，优选为0.8≤x≤1.2。更优选地，0.9≤x≤1.1。
进一步地，所述氧化亚硅颗粒的中值粒径D50为0.05-20μm，优选为0.3-10μm。更优选地，所述氧化亚硅颗粒的D50为3-8μm，D90＝3.5-15μm。
具体地，氧化亚硅颗粒占所述硅氧颗粒质量比为80-99.9wt％，优选为90-99.5wt％。更优选地，氧化亚硅颗粒占所述硅氧颗粒质量比为94-98wt％。
进一步地，所述硅氧颗粒还可包括均匀分散于所述硅氧颗粒中内部和/或外表面碳层的导电添加剂。
具体地，所述导电添加剂可选自Super P、科琴黑、气相生长碳纤维、乙炔黑、导电石墨、碳纳米管、石墨烯中的一种或多种的组合。
具体地，所述的导电添加剂占所述硅氧颗粒质量比为0.01-10wt％，优选为0.03-5wt％。
进一步地，所述硅氧颗粒还包括在硅氧颗粒外表面包覆的一层或多层附加碳层，优选为一层。
具体地，所述附加碳层由煤沥青、石油沥青、聚乙烯醇、环氧树脂、聚丙烯腈、聚甲基丙烯酸甲酯中的一种或多种前驱体材料的组合经碳化处理得到。
可选地，所述附加碳层由甲烷、乙烷、乙烯、乙炔、丙烷、丙烯、丁烷、丁烯、丁二烯、苯、甲苯、二甲苯、苯乙烯或苯酚中的任意一种或者多种的组合经化学气相沉积得到。
进一步地，所述附加碳层占所述硅氧颗粒质量比为0.1-10wt％，优 选为0.3-6wt％。
进一步地，如前任一所述的硅氧颗粒，所述硅氧颗粒的D50为1-40μm，优选为3-20μm。
进一步地，所述硅氧颗粒的粒径分布窄，其跨度值(SPAN)＝(D90-D10)/D50，≤1.4，优选为≤1.35。
优选地，所述硅氧颗粒的比表面积为0.1-10m 2/g，更优选为0.3-6m 2/g。
进一步地，所述硅氧颗粒的振实密度≥0.6g/cm 3，优选为≥0.8g/cm 3。
更具体地，如前任一所述的硅氧颗粒，所述硅氧颗粒优选为：D50＝3.5-10μm，SPAN＝0.9-1.35，比表面积为0.8-2.7m 2/g。
更优选地，所述硅氧颗粒的D10＝3.5-5.5μm，D50＝6.0-10μm，SPAN＝0.9-1.2，比表面积为0.9-1.6m 2/g，振实密度0.95-1.2g/cm 3，碳含量为2-6.5wt％。最优选地，D10＝4.0-5.0μm，D50＝6.5-9μm，SPAN＝0.9-1.1，比表面积为0.9-1.4m 2/g，振实密度1.0-1.2g/cm 3，碳含量为2.5-5.5wt％。
本发明还提出了如前任一所述的硅氧颗粒在电极材料中的应用。
本发明还提出了一种负极材料，包括如前任一所述的硅氧颗粒。其中，所述负极材料由硅氧颗粒和碳基粉末材料混合制备，所述碳基粉末材料可选自天然石墨、人造石墨、表面改性的天然石墨、硬碳、软碳或者中间相炭微球中的一种或多种的任意组合。
本发明还提出了包括如前任一所述负极材料的极片或电池。具体地可以是锂离子电池。
本发明还提出了一种如前所述的硅氧颗粒的制备方法，包括：将氧化亚硅颗粒同碳层前驱体材料混合造粒后在非氧化性气氛中进行碳化，碳化产物经打散、过筛、除磁处理。
进一步地，如前所述的硅氧颗粒的制备方法，还可包括导电添加剂的加入，具体地，将氧化亚硅颗粒、导电添加剂、及碳层前驱体材料混合造粒后在非氧化性气氛中进行碳化，碳化产物经打散、过筛、除磁处理。
进一步地，前述方法进一步包括包覆一层或多层附加碳层的步骤，优选为一层。
具体地，所述造粒的设备可选择同时具有加热和搅拌功能，包括但不限于VC混合机、机械融合机、包覆釜或反应釜。具体地，造粒过程中所述VC混合机、机械融合机、包覆釜或反应釜中搅拌部件最大直径处的线速度为1-30m/s；温度可选自100-1050℃，时间为0.5-10小时，并由惰性气氛保护。在此过程中，碳前驱体材料软化，在不停的高速搅拌过程中均匀涂覆在氧化亚硅颗粒表面，同时，涂覆有碳前驱体的多个氧化亚硅一次颗粒相互粘接团聚，形成一定尺寸的氧化亚硅/碳前驱体复合二次颗粒。上述二次颗粒在VC混合机、机械融合机、包覆釜或反应釜中长时间高频次的剪切、挤压、碰撞下会越发致密，同时在加热条件下碳前驱体会部分脱去小分子挥发物，部分交联、碳化，从而使二次颗粒定形。
具体地，所述造粒的设备还可以是喷雾干燥设备。此时，所述喷雾干燥设备处理含有氧化亚硅颗粒、碳前驱体的浆料时，设备的喷头将浆料雾化成小液滴，液滴中的溶剂在设备中一定温度的热空气的作用下迅速蒸发，经旋风收集后得到干燥的氧化亚硅/碳前驱体复合二次颗粒。
进一步地，所述碳化的设备包括管式炉、气氛箱式炉、推板窑、辊道窑或回转炉。
具体地，所述碳化反应的温度为600-1200℃，时间为0.5-24小时；
具体地，所述非氧化性气氛由下述至少一种气体提供：氮气、氩气、氢气、氦气。
具体地，所述打散设备包括采用气流粉碎机、球磨机、涡轮式粉碎机、雷蒙磨、犁刀粉碎机、齿盘磨中的任意一种。
具体地，包覆所述附加碳层的设备可选择同时具有加热和搅拌功能，包括但不限于机械融合机、VC混合机、高速分散机、包覆釜或反应釜中的任意一种。
进一步地，所述包覆附加碳层可选自化学气相沉积方法，该方法包括步骤：在700℃至1050℃的温度下于有机气体和/或蒸汽中实施化学气相沉积。
和现有技术相比，本发明具有如下优点：
本发明将氧化亚硅颗粒通过碳层紧密连接为集合颗粒体，在不过多增加大尺寸二次颗粒的同时，减少了尺寸小的一次颗粒占比，得到粒径分布更窄的二次颗粒，由于具备二次颗粒的制备过程，因此提高了氧化亚硅颗粒原料的适用范围，而且本发明的技术方案还极大降低了材料的比表面积，从而降低了材料在电池、如锂离子二次电池中同电解液的接触面积，减少了每一次充放电过程中电解液在材料表面不断生成SEI造成的锂离子损失，使得电池库伦效率更高，循环性能更好。
碳层连接和包覆同时提供了优良的电子和锂离子传输通道，保证了颗粒内部的氧化亚硅充分参与电化学反应，降低电池的极化，提高倍率性能；当二次颗粒内部和表面分散有导电添加剂时，则进一步提到了材料的导电性，电池的倍率性能更佳。
由于硅氧复合材料的容量和膨胀率均高于与其掺混使用的碳基负极，因此在制成电池极片后，通常的硅氧复合材料所在的微区会面容量较高，膨胀较大。相比其他方法制得的硅氧复合材料，本发明制备得到的颗粒粒径分布窄，大颗粒占比更少，因此本发明的颗粒在制成电池极片时，极片上的面容量和膨胀分布相对更加均匀，极片的膨胀率会更小。
本发明还通过颗粒外表面进一步包覆连续的碳保护层，在增加材料导电性的同时进一步降低复合材料的比表面积，减少SEI的形成，有利于提高库伦效率和电池循环保持率。由于本发明的材料的结构更加稳定且膨胀更小，可以在负极材料中添加更多的硅氧颗粒以达到提高电池能量密度的目的。
附图说明
图1是实施例1制备的二次颗粒的高倍扫描电子显微镜照片。
图2是实施例1制备的二次颗粒的结构示意图。
图3是实施例2制备的二次颗粒的结构示意图。
图4是实施例4制备的二次颗粒的结构示意图。
图5为对比例2及实施例6所用的氧化亚硅原料，以及对比例1、2、实施例6制得的二次颗粒的粒径分布图。
图6是实施例6制备的二次颗粒的低倍扫描电子显微镜照片。
图7是实施例6制备的二次颗粒的高倍扫描电子显微镜照片。
图8是含有实施例6制备的二次颗粒的电池在化成之后的负极横切面电子显微镜照片。
图9是实施例14制备的二次颗粒的高倍扫描电子显微镜照片。
图10为对比例1制备的颗粒的扫描电子显微镜照片。
图11为对比例2制备的颗粒的扫描电子显微镜照片。
具体实施方式
以下结合实施例，对本发明的具体实施方式进行更加详细的说明，以便能够更好地理解本发明的方案以及其各个方面的优点。然而，以下描述的具体实施方式和实施例仅是说明的目的，而不是对本发明的限制。
实施例1
1、制备方法
1.1二次颗粒的制备
取100kg氧化亚硅粉末(即：一次颗粒，D10＝0.60μm，D50＝1.78μm，D90＝3.59μm，SPAN＝1.68，SiOx通式中x＝1，比表面积8.9m 2/g)与12kg煤沥青粉末加入VC混合机中，在搅拌部件最大直径处线速度为16m/s的速度下混合30min，使两种原料混合均匀。随后，将转速降低，使前述线速度降至8m/s，同时通入氮气作为惰性保护气，然后开始以3℃/min的速度升温，升温至300℃后保持4h，随后自然冷却至室温，完成氧化亚硅和沥青的造粒工艺。在此过程中，随着VC混合机内温度的升高沥青逐渐软化，在不停的高速搅拌中均匀包覆在每一个氧化亚硅粉末表面，同时，包覆有沥青的氧化亚硅一次颗粒相互粘接团聚，形成一定尺寸的氧化亚硅/沥青复合二次颗粒。上述二次颗粒在VC混合机中经过长时间的剪切、挤压、碰撞后会越发致密，同时在300℃的温度下沥青会部分脱去小分子挥发物，部分交联、碳化，从而使二次颗粒定形。
取上述中间品装入石墨匣钵，置于辊道窑中，通入氮气保护性气体以3℃/min升温至900℃，保温4h，然后自然冷却至室温，完成碳化处理。此步骤中，沥青在无氧氛围的高温处理下碳化。将上述碳化品进行 气流粉碎处理，通过调节粉碎气流压力，将碳化后得到的复合材料软团聚体打散成细腻的二次颗粒粉末，而同时不会破坏二次颗粒结构。最后过筛和除磁处理，得到最终可用于负极材料的产品。
图1为实施例1制备的二次颗粒的高倍扫描电子显微镜照片，图2为其结构示意图，实施例1制备的颗粒为致密的二次颗粒，由氧化亚硅一次颗粒A和将其连接并包覆的碳层B复合而成。
1.2极片的制备
取上述二次颗粒9份，人造石墨43.5份，天然石墨43.5份，导电添加剂Super P 1份、多壁碳纳米管0.5份，粘结剂羧甲基纤维素钠CMC 1份、改性聚丙烯酸酯1.5份，在水性体系下匀浆、涂布、烘干、碾压，得到含硅氧二次颗粒的负极极片。
2、产品检测
经检测，二次颗粒的粒径为D10＝1.89μm，D50＝4.02μm，D90＝7.16μm，SPAN＝1.31，比表面积为2.7m 2/g，振实密度0.88g/cm 3，碳含量为4.9wt％。氧化亚硅材料经过800℃以上的热处理后会发生歧化反应：2SiO→Si+SiO 2，形成均匀分散于SiOx内的硅纳米晶粒/簇。根据X射线衍射图谱结果，代入Sherrer方程可算得实施例1所得材料中的Si(111)晶面对应的晶粒尺寸为2.9nm。
以上检测项目所采用的仪器设备分别是：
采用日立SU8010场发射扫描电子显微镜观察样品的表面形貌等。
采用丹东百特Bettersize2000LD激光粒度仪测试材料粒径以及粒径分布。
采用康塔Quantachrome Nova4200e比表面积测试仪测试材料的比表面积。
采用丹东百特BT-301振实密度仪测试材料的振实密度。
采用elementar vario EL cube元素分析仪测定材料中碳含量。
采用Rigaku MiniFlex600 X射线衍射仪测试材料的晶体结构。
3、性能测试
半电池评估：将上述制得的含硅氧二次颗粒负极极片与隔膜、锂片、不锈钢垫片依次叠放并滴加200μL电解液后封口制成2016式锂离子半 电池。用武汉市蓝电电子股份有限公司的小(微)电流量程设备测试容量及放电效率。测得上述负极的半电池的首次可逆脱锂比容量为1593.3mAh/g，首次充放电库伦效率为78.6％。
全电池评估：上述制得的含硅氧二次颗粒负极极片经过分切、真空烘烤、与配对的正极片(三元镍钴锰材料，LiNi 0.8Co 0.1Mn 0.1O 2)和隔膜一起进行卷绕并装进相应大小的铝塑壳中后，注入一定量电解液并封口，化成后即可得到一个完整的含硅氧二次颗粒负极的锂离子全电池。用深圳市新威尔电子有限公司的电池测试仪测试该全电池在0.2C下的容量、平均电压和在1C充放电速率下循环500次的容量保持率数据，测试的电压范围为4.2-2.75V。将电池称重后，结合以上电化学数据，计算得到全电池的重量能量密度为301Wh/kg，首次库伦效率为84.1％，500次充放电循环后的容量保持率为85.3％。500次循环之后，将电池充满电，测量电池厚度，同电池循环前的初始厚度对比，得到电池膨胀率为9.0％；然后将电池在惰性氛围下拆解，测量嵌满锂的负极极片厚度，同电池组装前的负极极片厚度对比，得到负极极片的满电膨胀率为29.4％。以上测试结果汇总于表1。
实施例2
实施例2的工艺过程类似于实施例1，区别在于在材料合成过程中，除了取100kg氧化亚硅粉与12kg煤沥青粉末加入VC混合机中，还额外加入了0.3kg的科琴黑和0.2kg的多壁碳纳米管导电添加剂粉末。因此最终产品为含有导电添加剂的氧化亚硅/无定形碳复合二次颗粒，其结构如图3所示，该材料由氧化亚硅一次颗粒A，导电添加剂C和将两者连接并包覆在一起的碳层B复合而成，导电添加剂C均匀地分散于二次颗粒内部和外表面。最终产品的D10＝1.78μm，D50＝3.89μm，D90＝7.01μm，SPAN＝1.34，比表面积为3.0m 2/g，振实密度0.84g/cm 3，碳含量为5.3wt％，Si(111)晶面对应的晶粒尺寸为2.9nm。
半电池和全电池评估方法同实施例1，结果汇总于表1，可见在加入导电添加剂后，电池性能有了一定的改善。
实施例3
取实施例1所制得的二次颗粒100kg，以及取石油沥青粉末1kg， 加入VC混合机，在线速度3m/s的条件下机械混合10分钟后，降速至2m/s，在氮气保护氛围下，一边搅拌一边将设备升温至300℃后保持1h，随后缓慢冷却至室温。将上述沥青包覆的材料在氩气惰性气氛中，在400℃下保温2h，随后升温至900℃碳化4h，自然冷却至室温后破碎、过筛和除磁处理，得到具有第二层无定形碳包覆层的氧化亚硅/无定形碳复合颗粒。该最终产品的D10＝2.13μm，D50＝4.65μm，D90＝7.87μm，SPAN＝1.23，比表面积为2.4m 2/g，振实密度0.95g/cm 3，碳含量为5.8wt％，Si(111)晶面对应的晶粒尺寸为2.9nm。
半电池和全电池评估方法同实施例1，结果汇总于表1。
实施例4
取实施例2所制得的二次颗粒100kg，采用实施例3的二次包覆工艺处理，得到具有第二层无定形碳包覆层的氧化亚硅/多壁碳纳米管/科琴黑/无定形碳复合颗粒。图4为本实施例制备的二次颗粒结构示意图，如图4所示，该材料由氧化亚硅一次颗粒A，导电添加剂C和将两者连接并包覆在一起的碳层B复合而成，导电添加剂C均匀的分散于二次颗粒内部，二次颗粒外表面还有第二层连续的碳包覆层D。该最终产品的D10＝2.01μm，D50＝4.45μm，D90＝7.76μm，SPAN＝1.29，比表面积为2.7m 2/g，振实密度0.89g/cm 3，碳含量为6.2wt％，Si(111)晶面对应的晶粒尺寸为2.9nm。
半电池和全电池评估方法同实施例1，结果汇总于表1，可见，和实施例3相同，多次包覆后，能显著提高产品的性能。
实施例5
取0.2kg蔗糖溶解于8kg去离子水中得到蔗糖溶液，再向蔗糖溶液中加入含有0.6g单壁碳纳米管的碳纳米管浆料搅拌分散，随后边搅拌边加入2kg氧化亚硅粉末(同实施例1)，继而边搅拌边超声分散1h，得到蔗糖/单壁碳纳米管/氧化亚硅颗粒复合浆料。将上述复合浆料进行喷雾干燥处理，进风温度150℃，喷头雾化压力0.2Mpa，得到蔗糖/单壁碳纳米管/氧化亚硅复合二次颗粒干粉。将上述粉末装入石墨匣钵，置于箱式气氛炉中，通入氮气作为惰性保护气，以3℃/min升温至900℃，保温6h，自然冷却至室温，完成碳化处理。将上述碳化品进行 齿盘磨打散处理，齿盘磨转子外边缘最大线速度3m/s。取上述二次颗粒1kg，以及取石油沥青粉末0.04kg，简单搅拌混合后加入机械融合机中，控制转子外边缘线速度在15m/s，融合0.5h，将处理后产品在氮气惰性气氛中，在400℃下保温2h，随后升温至900℃碳化4h，自然冷却至室温后破碎、过筛和除磁处理，得到具有第二层无定形碳包覆层的氧化亚硅/单壁碳纳米管/无定形碳复合颗粒。该最终产品的D10＝1.90μm，D50＝4.87μm，D90＝8.62μm，SPAN＝1.38，比表面积为3.7m 2/g，振实密度0.82g/cm 3，碳含量约为4.8wt％，Si(111)晶面对应的晶粒尺寸为2.9nm。
半电池和全电池评估方法同实施例1，结果汇总于表1，综合来看，喷雾干燥方式制得的电池性能虽然相比于现有技术有了一定的提高，但相较于其他实施例，其部分指标并不突出。
实施例6
取100kg氧化亚硅粉末(D10＝1.07μm，D50＝4.68μm，D90＝8.84μm，SPAN＝1.66，SiOx通式中x＝1，比表面积2.9m 2/g)与5kg石油沥青粉末加入立式包覆釜中，在搅拌部件最大直径处线速度7m/s的速度下混合1h，使两种原料混合均匀。随后，将线速度降低至3m/s，同时通入氮气作为惰性保护气，然后开始以3℃/min的速度升温至500℃后保持3h，随后自然冷却至室温。取上述中间品装入石墨匣钵，置于辊道窑中，通入氮气保护性气体以3℃/min升温至1020℃，保温2h，自然冷却至室温。将上述碳化品进行犁刀打散处理1h，犁刀线速度3m/s。最后进行过筛和除磁处理，得到的最终产品的D10＝4.32μm，D50＝7.06μm，D90＝10.90μm，SPAN＝0.93，比表面积为1.1m 2/g，振实密度1.09g/cm 3，碳含量为3.2wt％，Si(111)晶面对应的晶粒尺寸为4.1nm。
图5展示了本实施例中氧化亚硅粉末原料以及氧化亚硅复合材料(即二次颗粒)的粒径分布图。此外，图6、图7所示为本实施例所制备的二次颗粒的扫描电子显微镜照片，图8为含有本实施例制备的二次颗粒的锂离子电池负极极片的横切面电子显微镜照片。从图6中可以看出本实施例所得颗粒为大小均一的二次颗粒，无单分散的一次小颗粒。同时参见图7、图8，可见本实施例制备的颗粒为致密的二次颗粒。
半电池和全电池评估方法同实施例1，结果汇总于表1。
实施例7
取100kg氧化亚硅粉末(同实施例6)与9kg聚乙烯醇粉末加入立式包覆釜中，在搅拌部件最大直径处线速度5m/s的速度下混合2h，使两种原料混合均匀。随后，将线速度降低至3m/s，同时通入氮气作为惰性保护气，然后开始以2℃/min的速度升温至300℃后保持6h，随后自然冷却至室温。取上述中间品装入石墨匣钵，置于辊道窑中，通入氮气保护性气体以3℃/min升温至1020℃，保温2h，自然冷却至室温。将上述碳化品进行犁刀打散处理1h，犁刀线速度3m/s。最后进行过筛和除磁处理，得到的最终产品的D10＝3.97μm，D50＝6.91μm，D90＝10.40μm，SPAN＝0.93，比表面积为1.2m 2/g，振实密度1.05g/cm 3，碳含量为3.0wt％，Si(111)晶面对应的晶粒尺寸为4.1nm。
半电池和全电池评估方法同实施例1，结果汇总于表1。
实施例8
取100kg氧化亚硅粉末(D10＝0.87μm，D50＝3.88μm，D90＝7.73μm，SPAN＝1.77，SiOx通式中x＝1，比表面积3.8m 2/g)与7kg石油沥青粉末加入VC混合机中，在搅拌部件最大直径处线速度8m/s的速度下混合1h，使两种原料混合均匀。随后，将线速度降低至4m/s，同时通入氮气作为惰性保护气，然后开始以3℃/min的速度升温至900℃后保持1h，随后自然冷却至室温。取上述中间品装入石墨匣钵，置于推板窑中，通入氮气保护性气体以3℃/min升温至1000℃，保温3h，自然冷却至室温。将上述碳化品进行犁刀打散处理1h，犁刀线速度3m/s。最后进行过筛和除磁处理，得到的最终产品的D10＝4.51μm，D50＝7.15μm，D90＝11.07μm，SPAN＝0.92，比表面积为1.0m 2/g，振实密度1.12g/cm 3，碳含量为4.0wt％，Si(111)晶面对应的晶粒尺寸为3.9nm。
半电池和全电池评估方法同实施例1，结果汇总于表1，全电池的重量能量密度达到311Wh/kg，循环保持率达到90.7％，电池膨胀率为7.6％，综合来看本实施例制备得到的电池具有优秀的性能。
实施例9
实施例9的工艺步骤同实施例8类似，唯一的区别在于造粒步骤中， VC混合机中的保温温度为400℃，保温时间3h。最终产品的D10＝4.26μm，D50＝7.46μm，D90＝11.98μm，SPAN＝1.03，比表面积为1.2m 2/g，振实密度1.07g/cm 3，碳含量为3.9wt％，Si(111)晶面对应的晶粒尺寸为3.9nm。
半电池和全电池评估方法同实施例1，结果汇总于表1。
实施例10
实施例10的工艺步骤同实施例8类似，唯一的区别在于造粒步骤中，VC混合机中的保温温度为150℃，保温时间6h。最终产品的D10＝4.00μm，D50＝8.47μm，D90＝14.10μm，SPAN＝1.19，比表面积为1.4m 2/g，振实密度1.02g/cm 3，碳含量为3.9wt％，Si(111)晶面对应的晶粒尺寸为3.9nm。
半电池和全电池评估方法同实施例1，结果汇总于表1。
实施例11
实施例11的工艺步骤同实施例9类似，唯一的区别在于加入的石油沥青量为9kg。最终产品的D10＝4.78μm，D50＝8.90μm，D90＝14.90μm，SPAN＝1.14，比表面积为1.6m 2/g，振实密度1.01g/cm 3，碳含量为6.1wt％，Si(111)晶面对应的晶粒尺寸为3.9nm。
半电池和全电池评估方法同实施例1，结果汇总于表1。
实施例12
实施例12的工艺步骤同实施例9类似，唯一的区别在于加入的石油沥青量为3kg。最终产品的D10＝3.78μm，D50＝6.98μm，D90＝10.76μm，SPAN＝1.00，比表面积为1.1m 2/g，振实密度1.11g/cm 3，碳含量为2.7wt％，Si(111)晶面对应的晶粒尺寸为3.9nm。
半电池和全电池评估方法同实施例1，结果汇总于表1。
实施例13
取2kg氧化亚硅粉末(D10＝3.62μm，D50＝7.90μm，D90＝13.40μm，SPAN＝1.24，SiOx通式中x＝1，比表面积1.8m 2/g)与0.08kg煤沥青粉末、0.01kg气相生长碳纤维粉末加入机械融合机中，在转子外边缘处线速度为20m/s的速度下混合10分钟，使三种原料混合均匀。随后保持20m/s的线速度，升温至180℃后保持0.5h，随后自然冷却至室 温。取上述中间品装入石墨匣钵，置于管式炉中，通入氮气保护性气体以3℃/min升温至930℃，保温8h，自然冷却至室温。将上述碳化品进行齿盘磨打散处理，齿盘磨转子外边缘最大线速度3m/s。最后进行过筛和除磁处理，得到的最终产品的D10＝5.91μm，D50＝10.21μm，D90＝17.60μm，SPAN＝1.14，比表面积为1.1m 2/g，振实密度1.10g/cm 3，碳含量为3.2wt％，Si(111)晶面对应的晶粒尺寸为3.1nm。
半电池和全电池评估方法同实施例1，结果汇总于表1。
实施例14
取100kg氧化亚硅粉末(D10＝2.44μm，D50＝4.55μm，D90＝6.99μm，SPAN＝1.00，SiOx通式中x＝1，比表面积1.7m 2/g)与6kg煤沥青粉末加入立式包覆釜中，在搅拌部件最大直径处线速度6m/s的速度下混合1h，使两种原料混合均匀。随后，将线速度降低至2m/s，同时通入氮气作为惰性保护气，然后开始以3℃/min的速度升温至300℃后保持6h，随后自然冷却至室温。取上述中间品装入石墨匣钵，置于推板窑中，通入氮气保护性气体以3℃/min升温至950℃，保温5h，自然冷却至室温。将上述碳化品进行齿盘磨打散处理，齿盘磨转子外边缘最大线速度3m/s。最后进行过筛和除磁处理，得到的最终产品的D10＝4.92μm，D50＝8.32μm，D90＝14.70μm，SPAN＝1.18，比表面积为1.2m 2/g，振实密度1.07g/cm 3，碳含量为3.2wt％，Si(111)晶面对应的晶粒尺寸为3.7nm。图9是实施例14制备的二次颗粒的高倍扫描电子显微镜照片。
半电池和全电池评估方法同实施例1，结果汇总于表1。
实施例15
取100kg氧化亚硅粉末(同实施例14)与6kg煤沥青粉末、0.5kg Super P加入立式包覆釜中，在搅拌部件最大直径处线速度6m/s的速度下混合1h，使三种原料混合均匀。随后，将线速度降低至2m/s，同时通入氮气作为惰性保护气，然后开始以3℃/min的速度升温至300℃后保持6h，随后自然冷却至室温。取上述中间品装入石墨匣钵，置于推板窑中，通入氮气保护性气体以3℃/min升温至950℃，保温5h，自然冷却至室温。将上述碳化品进行齿盘磨打散处理，齿盘磨转子外边缘最大线速度3m/s。取打散后的材料2kg置于回转炉中，以3℃/min升温至 950℃，通入乙炔和氮气，流量分别为0.2L/min和0.3L/min，反应5h后冷却至室温取出。最后进行过筛和除磁处理，得到的最终产品的D10＝5.38μm，D50＝8.80μm，D90＝15.60μm，SPAN＝1.16，比表面积为1.8m 2/g，振实密度0.99g/cm 3，碳含量为5.2wt％，Si(111)晶面对应的晶粒尺寸为3.7nm。
半电池和全电池评估方法同实施例1，结果汇总于表1。
对比例1
将氧化亚硅块体(平均粒径约为2cm)置于箱式炉中，通入氩气保护气氛，以3℃/min升温至1000℃高温热处理2h，得到歧化改性的氧化亚硅块体。将歧化的氧化亚硅块体进行破碎、粉碎，所得材料的D10＝1.04μm，D50＝4.61μm，D90＝9.01μm，SPAN＝1.73。取2000g的氧化亚硅粉末置于回转炉中，以3℃/min升温至900℃，通入乙炔气体，流量为0.2L/min，整个反应过程炉内通入氮气保护性气氛，控制流量为0.1L/min，反应10h，得到前驱体；将上述前驱体投入到机械融合机中，控制转子外边缘处线速度为15m/s，融合10min，随后进行混合、筛分、除磁、干燥和打包，得到氧化亚硅复合材料的D10＝2.05μm，D50＝5.25μm，D90＝9.54μm，SPAN＝1.43，比表面积为5.2m 2/g，振实密度0.93g/cm 3，碳含量约为5.2wt％，Si(111)晶面对应的晶粒尺寸为4.0nm。
图10为对比例1中氧化亚硅复合材料电镜图片，可见复合材料中细粉颗粒较多，多为单分散一次颗粒，且颗粒的棱角分明，边缘锐利。由图5中对比例1中氧化亚硅复合材料的粒径分布图可见，对比例1产品的粒径分布相比实施例6较宽，小颗粒的占比较高。图5中的粒度分布曲线为重量/体积分布曲线，小颗粒段曲线高度较高，说明小颗粒的重量/体积占比较高，折算成小颗粒的数量占比和比表面积占比则是数量级的增加。因此从图中可以看出，对比例1相比实施例6，小颗粒数量占比高出极多，比表面积也增加较大。
参考实施例1半电池和全电池评估方法来评估本对比例颗粒制备的电池性能，结果汇总于表1。
对比例2
将氧化亚硅粉末(同实施例6)100kg与石油沥青粉末10kg置于VC混合机中，调节线速度为10m/s，混合0.5h，得到前驱体1。将前驱体1加入到真空捏合机内，通过加热循环导热油控制物料温度在250℃以上，混捏6h至物料呈粘稠状，然后在物料冷却之前迅速转移至轧片机进行轧片处理，控制轧片厚度为2.0～5.0mm，待轧片冷却后进行机械粉碎，控制粒度中值粒径为2.0～15.0μm，接着将粉碎物料进行恒温等静压处理，控制压强为20MPa，温度为250℃，实施0.1h加压处理，得到前驱体2。将前驱体2置于辊道窑中，通入氮气保护性气体以3℃/min升温至1000℃，保温7h，自然冷却至室温。然后进行犁刀破碎1h，犁刀最大线速度3m/s，随后进行筛分、除磁、干燥得到氧化亚硅颗粒。所得材料的D10＝3.22μm，D50＝6.77μm，D90＝13.36μm，SPAN＝1.50，比表面积为2.2m 2/g，振实密度0.99g/cm 3，碳含量约为6.3wt％，Si(111)晶面对应的晶粒尺寸为4.0nm。
图11为对比例2中氧化亚硅颗粒电镜图片，可见复合材料中细粉颗粒较多，较多单分散的一次颗粒，存在部分大、小一次颗粒复合而成的松散的比表面积较大的二次颗粒。由图5中对比例2中氧化亚硅颗粒的粒径分布图可见，对比例2产品的粒径分布相比实施例1较宽，小颗粒和大颗粒的占比均比较高。
参考实施例1半电池和全电池评估方法来评估本对比例颗粒制备的电池性能，结果汇总于表1。
对比例3
对比例3的工艺步骤同实施例8-10类似，唯一的区别在于室温下采用VC混合机混料结束后，不进行升温搅拌的造粒处理，直接出料，对物料进行后续的碳化、破碎、分筛、除磁处理。最终产品的D10＝1.93μm，D50＝8.68μm，D90＝16.22μm，SPAN＝1.65，比表面积为2.2m 2/g，振实密度1.02g/cm 3，碳含量为3.9wt％，Si(111)晶面对应的晶粒尺寸为3.9nm。
半电池和全电池评估方法同实施例1，结果汇总于表1。
表1性能检测数据汇总
Figure PCTCN2019126660-appb-000001
Figure PCTCN2019126660-appb-000002
对于现有技术而言，其制备工艺复杂，例如混捏、轧片和压制成型等工艺难以实现规模化生产。且碳前驱体碳化后势必会对相邻的氧化亚硅颗粒粘连和团聚，后续的破碎、粉碎等工艺会对碳包覆层造成破坏。现有技术制备的材料粒径分布较宽，大、小颗粒占比均较高，制成的电池的库伦效率、膨胀率、循环保持率均不理想，面容量、微区膨胀分布不均匀。而本发明所制得的用于负极材料的二次颗粒致密、粒径分布窄、比表面积小，经检测其具有高容量，高库伦效率，面容量分布均匀，低膨胀，循环保持率高等优点。以上所述，仅是本发明的较佳实施例，并非对本发明作任何形式上的限制，任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，依据本发明的技术实质，对以上实施例所作的任何简单的修改、等同替换与改进等，均仍属于本发明技术方案的保护范围之内。

Claims (26)

  1. 一种用于电极材料的硅氧颗粒，其特征在于，所述硅氧颗粒包括：
    氧化亚硅颗粒，其通式为SiOx；
    碳层，多个所述氧化亚硅颗粒由所述碳层粘结，且碳层粘结的多个所述氧化亚硅颗粒由所述碳层包覆。
  2. 根据权利要求1所述的硅氧颗粒，其特征在于，所述碳层由葡萄糖、蔗糖、壳聚糖、淀粉、柠檬酸、明胶、海藻酸、羧甲基纤维素、煤沥青、石油沥青、酚醛树脂、焦油、萘油、蒽油、聚丙烯酸、聚丙烯酸酯、聚苯乙烯、聚乙烯吡咯烷酮、聚氧化乙烯、聚乙烯醇、环氧树脂、聚丙烯腈、聚甲基丙烯酸甲酯中的一种或多种前驱体材料的组合经碳化处理得到。
  3. 根据权利要求1所述的硅氧颗粒，其特征在于，所述氧化亚硅颗粒中，0.5≤x≤1.5。
  4. 根据权利要求1所述的硅氧颗粒，其特征在于，所述氧化亚硅颗粒的中值粒径D50为0.05-20μm，优选为0.3-10μm。
  5. 根据权利要求1所述的硅氧颗粒，其特征在于，氧化亚硅颗粒占所述硅氧颗粒质量比为80-99.9wt％，优选为90-99.5wt％。
  6. 根据权利要求1所述的硅氧颗粒，其特征在于，还包括均匀分散于所述硅氧颗粒内部和外表面的导电添加剂。
  7. 根据权利要求6所述的硅氧颗粒，其特征在于，所述导电添加剂选自Super P、科琴黑、气相生长碳纤维、乙炔黑、导电石墨、碳纳米管、石墨烯中的一种或多种的组合。
  8. 根据权利要求6所述的硅氧颗粒，其特征在于，所述的导电添加剂占所述硅氧颗粒质量比为0.01-10wt％，优选为0.03-5wt％。
  9. 根据权利要求1或6所述的硅氧颗粒，其特征在于，还包括在 所述硅氧颗粒外表面包覆的一层或多层附加碳层，优选为一层。
  10. 根据权利要求9所述的硅氧颗粒，其特征在于，所述附加碳层由煤沥青、石油沥青、聚乙烯醇、环氧树脂、聚丙烯腈、聚甲基丙烯酸甲酯中的一种或多种前驱体材料的组合经碳化处理得到，或由甲烷、乙烷、乙烯、乙炔、丙烷、丙烯、丁烷、丁烯、丁二烯、苯、甲苯、二甲苯、苯乙烯或苯酚中的任意一种或者多种的组合经化学气相沉积得到。
  11. 根据权利要求9所述的硅氧颗粒，其特征在于，所述附加碳层占所述硅氧颗粒质量比为0.1-10wt％，优选为0.3-6wt％。
  12. 根据权利要求1-11任一所述的硅氧颗粒，其特征在于，所述硅氧颗粒的D50为1-40μm，优选为3-20μm，更优选为3.5-10μm。
  13. 根据权利要求12所述的硅氧颗粒，其特征在于，所述硅氧颗粒的粒径满足：(D90-D10)/D50≤1.4，优选为≤1.35。
  14. 根据权利要求12所述的硅氧颗粒，其特征在于，所述硅氧颗粒的比表面积为0.1-10m 2/g，优选为0.3-6m 2/g，更优选为0.8-2.7m 2/g。
  15. 根据权利要求14所述的硅氧颗粒，其特征在于，所述硅氧颗粒的振实密度≥0.6g/cm 3，优选为≥0.8g/cm 3。
  16. 如权利要求1-15任一所述的硅氧颗粒在电极材料中的应用。
  17. 一种负极材料，其特征在于，包括权利要求1-15任一所述的硅氧颗粒。
  18. 包括权利要求17所述负极材料的极片或电池。
  19. 如权利要求1所述的硅氧颗粒的制备方法，其特征在于，包括：
    将氧化亚硅颗粒同碳层的前驱体材料混合造粒后在非氧化性气氛中进行碳化，碳化产物经打散、过筛、除磁处理。
  20. 如权利要求19所述的硅氧颗粒的制备方法，其特征在于，
    所述氧化亚硅颗粒同碳层的前驱体材料混合造粒步骤还包括加入导电添加剂的步骤。
  21. 如权利要求19或20所述的硅氧颗粒的制备方法，其特征在于，
    该方法进一步包括包覆一层或多层附加碳层的步骤，优选为一层。
  22. 如权利要求19-21任一所述的硅氧颗粒的制备方法，其特征在于，
    所述造粒的设备包括VC混合机、机械融合机、包覆釜或反应釜；
    所述造粒过程中，设备中搅拌部件最大直径处的线速度为1-30m/s；温度为100-1050℃，时间为0.5-10小时，并由惰性气氛保护。
  23. 如权利要求19-21任一所述的硅氧颗粒的制备方法，其特征在于，
    所述造粒的设备还可以选自喷雾干燥设备；
    所述碳化的设备包括管式炉、气氛箱式炉、推板窑、辊道窑、回转炉；
    所述碳化反应的温度为600-1200℃，时间为0.5-24小时；
    所述非氧化性气氛由下述至少一种气体提供：氮气、氩气、氢气、氦气。
  24. 如权利要求19-21任一所述的硅氧颗粒的制备方法，其特征在于，
    所述打散工艺采用的设备包括采用气流粉碎机、球磨机、涡轮式粉碎机、雷蒙磨、犁刀粉碎机、齿盘磨中的任意一种。
  25. 如权利要求21所述的硅氧颗粒的制备方法，其特征在于，
    包覆所述附加碳层的设备包括机械融合机、VC混合机、高速分散机、包覆釜或反应釜中的任意一种。
  26. 如权利要求21所述的硅氧颗粒的制备方法，其特征在于，包覆所述附加碳层选自化学气相沉积方法，该方法包括步骤：在700℃至1050℃的温度下于有机气体和/或蒸汽中实施化学气相沉积。
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