WO2020098087A1 - Silicon oxide composite negative electrode material of lithium-ion battery and preparation method therefor - Google Patents

Silicon oxide composite negative electrode material of lithium-ion battery and preparation method therefor Download PDF

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WO2020098087A1
WO2020098087A1 PCT/CN2018/123632 CN2018123632W WO2020098087A1 WO 2020098087 A1 WO2020098087 A1 WO 2020098087A1 CN 2018123632 W CN2018123632 W CN 2018123632W WO 2020098087 A1 WO2020098087 A1 WO 2020098087A1
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silicon oxide
negative electrode
chloride
ion battery
electrode material
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PCT/CN2018/123632
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French (fr)
Chinese (zh)
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晏荦
曹付海
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东莞市凯金新能源科技股份有限公司
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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
    • H01M4/36—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
    • 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
    • H01M4/36—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
    • 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
    • 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 technical field of negative electrode materials for lithium ion secondary batteries, in particular to a silicon oxide composite negative electrode material for lithium ion batteries and a preparation method thereof.
  • Lithium-ion batteries have become the focus of current research in the world due to their large specific capacity, long service life, high safety, and portability, and are widely used in various electronic devices, electric vehicles, and portable energy storage devices.
  • the lithium-ion batteries that have been commercialized on a large scale mainly use graphite-based carbon materials as negative electrode materials, but their theoretical specific capacity is only 372mAh / g, which is difficult to meet current needs. Therefore, the development of higher capacity density negative electrode materials It is an urgent problem to be solved for lithium ion secondary batteries.
  • some researchers use the pre-lithium method, which first reacts with the silicon oxide material to produce Li2O and Li2SiO4 during the material preparation process, so that during the charging and discharging process, no or little lithium ion is consumed, and the efficiency of the first week of the material is improved, such as (Yom, J, H, Hwang, S, W, Cho, S, M, et.al.Improvement of of irreversible, behavior, of, SiO, nanodes, for lithium, batteries, solid, state, reaction, at high temperature [J]. Journal of Power Sources, 2016, 311: 159- 166.).
  • Chinese patent CN104577066A discloses a preparation method of SiO-SiO2-C.
  • This method uses SiO and SiO2 as raw materials, uses magnesite reduction to prepare silicon-oxygen materials, and uses high-temperature carbonization modification such as natural graphite and glucose to prepare composite materials. Its purpose is mainly to improve composite materials through magnesia reduction and carbonization coating.
  • the efficiency of the first week The results show that its efficiency in the first week is 79.2%, and its capacity is only 1176.1mAh / g, the efficiency has a small increase, but the capacity decline is large, so it has little significance.
  • Chinese patent CN1110003730644A discloses a method for preparing silicon-silicon oxide-carbon composite material. Under the protection of argon, this method first mechanically milled silicon monoxide, silicon and graphite, and then stirred and mixed with asphalt with tetrahydrofuran as a solvent. Finally, the high temperature treatment obtained a negative electrode composite material. The result showed that its efficiency was only 74.3%, and the capacity Only 966.3mAh / g, the result is very poor, and it is difficult to achieve industrial production using mechanical ball milling.
  • the Chinese patent CN103022446A patent discloses a method for preparing a silicon oxide / carbon negative electrode composite material.
  • This method uses silicon oxide, metal particles, and graphite as raw materials to prepare negative electrode materials after high-temperature heat treatment after mixing.
  • the results show that the efficiency of the negative electrode composite material in the first week has increased significantly, reaching 88%, almost all reduced, and the capacity is only 606.2mAh / g. After 50 weeks of circulation, the capacity retention rate was 100.6%. However, the capacity loss of the prepared material is too large, and the high capacity characteristic of the material cannot be fully utilized, so the practical application is poor.
  • the purpose of the present invention is to provide a silicon oxide composite negative electrode material for lithium ion batteries and a preparation method thereof in view of the above-mentioned deficiencies in the prior art, using silicon oxide, active metals, carbon-coated materials, and molten salt as raw materials. It is obtained by mixing, metal thermal reduction, pickling and impurity removal, and crushing.
  • the oxygen content of the finished material is low, which significantly improves the reversible capacity and efficiency of the lithium ion battery in the first week, and has fewer impurities, high application value, and small silicon crystal size. Improves the material's cyclic expansion and significantly improves the material's cycle life.
  • a method for preparing a silicon oxide composite anode material for a lithium ion battery includes the following steps:
  • S3 Mix the obtained low-oxygen-value silicon oxide material with carbon-coated material or use gas-phase coating, heat up to 500-1100 ° C under a protective atmosphere for roasting and carbonization treatment, and cool to obtain low-oxygen-value silicon oxide / carbon
  • the composite negative electrode material is coated, crushed, crushed and sieved to obtain a silicon oxide composite negative electrode material for lithium ion batteries.
  • the silicon oxide is powdered, and the particle diameter D50 is 1.0-15.0 ⁇ m.
  • the active metal is in the form of powder with a particle size D50 of 0.1-500 ⁇ m; the active metal is an active metal powder capable of reducing silicon oxide, which is lithium, iron, aluminum, nickel, tin, magnesium, chromium, titanium, One or more combinations of cobalt and zinc.
  • the molten salt is in the form of solid particles or powder, with a particle size D50 of 0.5-1000 ⁇ m, and the molten salt is calcium chloride, lithium chloride, magnesium chloride, aluminum chloride, ferric chloride, cobalt chloride, chlorine Barium chloride, ferric chloride, potassium chloride, sodium chloride, nickel chloride, potassium bromide, cesium bromide, sodium bromide, rubidium bromide, potassium carbonate, potassium sulfate, lithium carbonate, sodium carbonate, sodium sulfate , One or more of lithium hydroxide, magnesium carbonate, magnesium sulfate, magnesium bromide, calcium carbonate, titanium chloride, chromium chloride, manganese chloride, copper chloride, zinc chloride, tin chloride, etc. ; The mass ratio of the added silicon oxide and molten salt is 1: 0.1 ⁇ 1:20.
  • the carbon coating material is coal pitch, petroleum pitch, starch, polyvinyl chloride, glucose, epoxy resin, polystyrene, phenolic resin, urea-formaldehyde resin, polyurethane, polythiophenes, polyhydric alcohols, etc.
  • the particle size is 10 to 1000 ⁇ m; the added mass ratio of the silicon oxide to the carbon coating material is 1: 0.05 to 1: 1.
  • the mixing speed of the mixing in the steps S1 and S3 is 100-2000 rpm and the mixing time is 0.2-5.0 h; the heating rate of the roasting in the steps S2 and S4 is 0.1-20 ° C / min.
  • the concentration of the acid liquid in the step S2 is 0.1-10.0 mol / L
  • the acid liquid is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, carbonic acid, and oxalic acid.
  • the mass ratio of mixture to acid after roasting and cooling is 1: 0.5 ⁇ 1: 15.
  • the gas-phase coating in step S3 is one or more of methane, ethane, propane, ethylene, acetylene, etc., and the gas flow rate is 1L / min ⁇ 8L / min, ventilation The reaction time is 0.5 ⁇ 2h.
  • a silicon oxide composite anode material for a lithium ion battery obtained by using the foregoing manufacturing method of a silicon oxide composite anode material for a lithium ion battery is formed by using silicon oxide as a matrix and a conductive carbon material as a coating layer Silicone oxide composite anode material with silicon / carbon material core-shell structure.
  • the particle diameter D50 of the silicon oxide composite negative electrode material of the lithium ion battery is 0.1-100 ⁇ m.
  • the present invention has the following beneficial effects:
  • the silicon oxide composite negative electrode material of the lithium ion battery of the present invention uses silicon oxide as the main electrode active material of the lithium ion battery.
  • Li2O is generated during the first lithium insertion process, and Li4SiO4 can effectively buffer the volume expansion effect of the negative electrode material, while the oxygen content Low, can significantly reduce the lithium ion consumption of Li2O and Li4SiO4 generated during the first week cycle of lithium-ion batteries, and significantly improve the reversible capacity and efficiency of lithium-ion batteries in the first week.
  • the present invention uses the molten salt method to control the progress of the reaction with molten salt as a carrier, so that two immovable solid reactions are converted into reactions in a molten salt liquid environment, which significantly improves the reaction efficiency, while reducing the reaction temperature and saving
  • the molten salt method also fully demonstrates its control effect on the formation of impurities and the growth of grains during the preparation of the material. Significantly lower the reaction temperature of the preparation material while improving the reaction efficiency.
  • the preparation method is simple, the cost is low, and there is no pollution.
  • the resulting silicon oxide composite anode material lithium ion secondary battery has high capacity, low oxygen value, no impurities, small grains, and high
  • the present invention uses active metal to reduce silicon oxide, and uses molten salt as a carrier to control the reaction, and then performs carbon coating treatment, the oxygen content is low, and the oxygen content can be effectively controlled by adjusting the amount of active metal reducing agent added; the preparation process No silicate impurities are generated or a small amount cannot be washed off, and the silicon-oxygen ratio can be adjusted at will, which significantly improves its practical application value; the finished product has a small silicon grain size, which can effectively improve the cyclic expansion of the material and significantly improve the material Cycle life.
  • Figure 1 is an electron micrograph of the silicon oxide composite negative electrode material in Example 1 of the present invention.
  • Example 2 is the first charge-discharge curve of the silicon oxide composite anode material in Example 1 of the present invention
  • Example 3 is the first charge-discharge curve of the silicon oxide composite negative electrode material in Example 2 of the present invention.
  • Example 4 is an XRD pattern of the silicon oxide composite negative electrode material in Example 1 of the present invention.
  • S1 mixed silicon oxide with a median particle size (D50) of 0.5 to 2.5 ⁇ m, aluminum metal powder with a median particle size (D50) of 5 to 30 ⁇ m, and CaCl 2 -AlCl 3 mixed molten salt of 50 to 200 ⁇ m
  • D50 median particle size
  • Al metal powder with a median particle size (D50) of 5 to 30 ⁇ m
  • mixing speed is 900rpm
  • mixing time is 2h, in which the molar ratio of silicon oxide and aluminum metal powder material is 1: 0.2, the mass ratio of silicon oxide and mixed molten salt is 1: 3, mixing The mass ratio of molten salt CaCl 2 -AlCl 3 is 6: 4.
  • the mixed materials are roasted in a box furnace, protected by a nitrogen atmosphere, the roasting temperature is 500 ° C, the heating rate is 3 ° C / min, the temperature is kept for 2 hours, and the material is completely removed after cooling.
  • the obtained material was added into 2mol / L hydrochloric acid to mix and stir.
  • the mass ratio of the obtained material to hydrochloric acid was 1: 3, the stirring speed was 1500rpm, and the time was 5h. After the pickling was completed, it was filtered with a filter press, and the air box was dried.
  • S3 Blend the dried material with petroleum pitch with a median particle size (D50) of 100-500 ⁇ m, the blending mass ratio is 1: 0.2, and put the mixed material into a box furnace for roasting. Nitrogen atmosphere protection, calcination temperature 800 °C, heating rate 2 °C / min, heat preservation 3h, low oxygen value silicon oxide / carbon coated composite anode material. The above-mentioned materials are crushed, crushed and sieved to finally obtain a finished silicon oxide composite negative electrode material for a lithium ion battery.
  • the median particle size (D50) of the material is 0.1 to 100 m.
  • the preparation method of the silicon oxide composite negative electrode material of the lithium ion battery of this embodiment specifically includes: the silicon oxide with a particle size median diameter (D50) of 4-8 ⁇ m and a particle size median diameter (D50) of 80-120 ⁇ m
  • Aluminum metal powder, MgCl 2 -KCl mixed molten salt of 50 ⁇ 200 ⁇ m is used for VC mixing work, mixing speed is 800rpm, mixing time is 2h, in which the molar ratio of silicon oxide to aluminum metal powder material is 1: 0.8, suboxide
  • the added mass ratio of silicon to the mixed molten salt is 1: 8, and the mass ratio between the mixed molten salt MgCl 2 -KCl is 2: 8.
  • the mixed materials are put into a box furnace for roasting, protected by an argon atmosphere, the roasting temperature is 750 ° C, the heating rate is 10 ° C / min, and the temperature is kept for 8 hours. After cooling, the material is completely taken out.
  • the mass ratio of the obtained material to hydrochloric acid is 1: 6, the stirring speed is 1500rpm, the time is 5h.
  • the filter press is used for filtering, and the air box is dried.
  • the dried material is blended with coal pitch with a median particle size (D50) of 100 to 500 ⁇ m, the blending mass ratio is 1: 0.2, the mixed materials are placed in a box furnace for roasting, argon atmosphere Protection, roasting temperature 900 °C, heating rate 2 °C / min, heat preservation 5h, get low oxygen value silicon oxide / carbon coated composite anode material, crush, crush and sieve the above materials to obtain the median particle size
  • the particle size (D50) is 0.1 ⁇ 100 ⁇ m, which is the silicon oxide composite negative electrode material of the finished lithium ion battery.
  • the mixed materials are put into a box furnace for roasting, protected by an argon atmosphere, the roasting temperature is 300 ° C, the heating rate is 3 ° C / min, the temperature is kept for 2 hours, and the material is completely taken out after cooling.
  • the mass ratio of the obtained material to hydrochloric acid is 1: 3, the stirring speed is 1500rpm, and the time is 5h. After the pickling is completed, it is filtered with a filter press, and the air box is dried.
  • the dried material is blended with coal pitch with a median particle size (D50) of 100 ⁇ 500 ⁇ m, the blending mass ratio is 1: 0.2, the mixed materials are placed in a box furnace for roasting, and protected by argon atmosphere , The calcination temperature is 950 °C, the heating rate is 5 °C / min, and the heat is kept for 4h. After cooling, the material is completely taken out to obtain a low oxygen value silicon oxide / carbon coated composite negative electrode material. The above materials are finally crushed, crushed and sieved.
  • the median particle size (D50) of the material is 0.1-100 ⁇ m, which is the silicon oxide composite negative electrode material of the finished lithium ion battery.
  • the mixed materials are put into a box furnace for roasting, protected by an argon atmosphere, the roasting temperature is 500 ° C, the heating rate is 5 ° C / min, and the temperature is kept for 2 hours. After cooling, the material is completely taken out.
  • the mass ratio of the obtained material to hydrochloric acid is 1: 5, the stirring speed is 1500rpm, the time is 5h.
  • the dried material is blended with coal pitch with a median particle size (D50) of 100 to 500 ⁇ m, the blending mass ratio is 1: 0.2, the mixed materials are placed in a box furnace for roasting, argon atmosphere Protection, roasting temperature 1100 °C, heating rate 5 °C / min, heat preservation 5h, take out the material completely after cooling, get low oxygen value silicon oxide / carbon coated composite anode material, crush, crush and screen the above materials
  • the median particle size (D50) of the obtained material is 0.1-100 ⁇ m, which is the silicon oxide composite negative electrode material of the finished lithium ion battery.
  • the mixed materials were roasted in a box furnace, protected by a nitrogen atmosphere.
  • the roasting temperature was 600 ° C, the heating rate was 3 ° C / min, and the temperature was kept for 2 hours. After cooling, the material was completely removed. Add the obtained material to 2mol / L hydrochloric acid to mix and stir. The mass ratio of the obtained material to hydrochloric acid is 1: 3, the stirring speed is 1500rpm, and the time is 5h. After the pickling is completed, it is filtered with a filter press, and the air box is dried. The dried material is placed in a rotary furnace for roasting, protected by an argon atmosphere. The roasting temperature is 700 ° C, and the heating rate is 7 ° C / min.
  • the methane gas is started to flow and the flow rate is controlled to 3 L / min The reaction time is 1h.
  • the material is completely taken out to obtain a low-oxygen-silicon oxide / carbon-coated composite negative electrode material.
  • the above-mentioned material is crushed, crushed and sieved to finally obtain a material with a median particle size (D50) of 0.1 to 100 ⁇ m is the silicon dioxide composite anode material of the finished lithium ion battery.
  • the mixed materials are put into a box furnace for roasting, protected by an argon atmosphere, the roasting temperature is 750 ° C, the heating rate is 5 ° C / min, the temperature is kept for 2 hours, and the material is completely taken out after cooling.
  • the mass ratio of the obtained material to hydrochloric acid is 1: 5, the stirring speed is 1500rpm, the time is 5h. After the pickling is completed, it is filtered with a filter press, and the air box is dried.
  • the dried material is blended with starch with a median particle size (D50) of 100 to 500 ⁇ m, the blending mass ratio is 1: 0.2, the mixed materials are placed in a box furnace for roasting, and protected by an argon atmosphere , The calcination temperature is 800 °C, the heating rate is 5 °C / min, and the temperature is kept for 3 hours. After cooling, the material is completely taken out to obtain a low oxygen value silicon oxide / carbon coated composite negative electrode material.
  • the median particle size (D50) of the material is 0.1-100 ⁇ m, which is the silicon oxide composite negative electrode material of the finished lithium ion battery.
  • the preparation method of the silicon oxide composite negative electrode material of the lithium ion battery of this embodiment specifically includes: the silicon oxide with a median particle size (D50) of 0.5 to 2.5 ⁇ m and a median particle size (D50) of 5 to 30 ⁇ m
  • the aluminum metal powder is mixed with VC, the mixing speed is 800rpm, the mixing time is 2h, and the molar ratio of the addition of silicon oxide and aluminum metal powder material is 1: 0.2.
  • the mixed materials were put into a box furnace for roasting, protected by a nitrogen atmosphere. The roasting temperature was 250 ° C, the heating rate was 3 ° C / min, and the temperature was kept for 2 hours. After cooling, the material was completely taken out. Add the obtained material to 2mol / L hydrochloric acid to mix and stir.
  • the mass ratio of the obtained material to hydrochloric acid is 1: 3, the stirring speed is 1500rpm, and the time is 5h.
  • the dried material is blended with coal pitch with a median particle size (D50) of 100 to 500 ⁇ m, the blending mass ratio is 1: 0.2, the mixed materials are placed in a box furnace for roasting, argon atmosphere Protection, roasting temperature 800 °C, heating rate 2 °C / min, heat preservation 3h, take out the material completely after cooling, get low oxygen value silicon oxide / carbon coated composite anode material, crush, crush and sieve the above materials
  • the median particle size (D50) of the obtained material is 0.1-100 ⁇ m, which is the silicon oxide composite negative electrode material of the finished lithium ion battery.
  • the preparation method of the silicon oxide composite negative electrode material of the lithium ion battery of this embodiment specifically includes: the silicon oxide with a median particle size (D50) of 2.5-5 ⁇ m and a median particle size (D50) of 30-80 ⁇ m Zinc metal powder, VC mixing work, mixing speed is 800rpm, mixing time is 2h, in which the molar ratio of silicon oxide to zinc metal powder material is 1: 0.4.
  • the mixed materials are put into a box furnace for roasting, protected by an argon atmosphere, the roasting temperature is 750 ° C, the heating rate is 5 ° C / min, the temperature is kept for 2 hours, and the material is completely taken out after cooling. Add the obtained material to 3mol / L hydrochloric acid to mix and stir.
  • the mass ratio of the obtained material to hydrochloric acid is 1: 5, the stirring speed is 1500rpm, the time is 5h. After the pickling is completed, it is filtered with a filter press, and the air box is dried.
  • the dried material is blended with coal pitch with a median particle size (D50) of 100 to 500 ⁇ m, the blending mass ratio is 1: 0.2, the mixed materials are placed in a box furnace for roasting, argon atmosphere Protection, roasting temperature 700 °C, heating rate 2 °C / min, heat preservation 5h, take out the material completely after cooling, get the low oxygen value silicon oxide / carbon coated composite anode material, crush, crush and sieve the above materials
  • the median particle size (D50) of the obtained material is 0.1-100 ⁇ m, which is the silicon oxide composite negative electrode material of the finished lithium ion battery.
  • a Malvern laser particle size analyzer MS3000 was used to test the material particle size range and distribution.
  • the Tristar 3000 fully automatic specific surface area and porosity analysis of American Mac Instruments was used to test the specific surface area of the material.
  • Hitachi S4800 scanning electron microscope was used to observe the sample morphology and particle size.
  • FIG. 1 is a scanning electron micrograph of the silicon oxide composite negative electrode material prepared in Example 1. Through analysis, FIG. 1 clearly reflects the particle size and surface condition of the material, indicating the modified form of the material.
  • FIG. 4 is the X-ray diffraction pattern of Comparative Example 1. It can be seen from the figure that after the treated silicon oxide material, the peak of amorphous silicon oxide is still very strong, while the silicon crystal size is small, the actual generated There is very little silicon.
  • the negative electrode material, the conductive agent, and the binder were mixed in a solvent at a mass ratio of 92: 2: 6, the solid content was controlled to 55%, and the copper foil collector was coated and dried.

Abstract

Disclosed is a preparation method for a silicon oxide composite negative electrode material of a lithium-ion battery, comprising the following steps: mixing silicon oxide, a reactive metal, and a fused salt to obtain a mixture; carrying out a roasting reaction in a protective atmosphere, cooling and pickling to remove impurities; mixing the obtained low-oxygen-value silicon oxide material and a carbon coating material or adopting gas phase coating, roasting and carbonizing, cooling, crushing and screening, thereby obtaining the silicon oxide composite negative electrode material for the lithium-ion battery. Compared with the prior art, the silicon oxide composite negative electrode material is prepared by taking the silicon oxide, the reactive metal, the carbon coating material, and the fused salt as raw materials, mixing, performing metal hot reduction, pickling to remove impurities and grinding, the oxygen content of the finished material is low, and the first-cycle reversible capacity and efficiency of the lithium-ion battery are obviously improved. Moreover, the negative electrode material is less in impurity, high in application value and small in silicon grain size, cycle expansion of the material is effectively improved, and the cycle life of the material is obviously prolonged.

Description

一种锂离子电池氧化亚硅复合负极材料及制法Silicon oxide composite negative electrode material for lithium ion battery and preparation method 技术领域Technical field
本发明涉及锂离子二次电池负极材料技术领域，特别涉及一种锂离子电池氧化亚硅复合负极材料及制法。The invention relates to the technical field of negative electrode materials for lithium ion secondary batteries, in particular to a silicon oxide composite negative electrode material for lithium ion batteries and a preparation method thereof.
背景技术Background technique
锂离子电池由于其比容量大，使用寿命长，安全性高，方便携带等诸多优点，已成为当前世界研究的热点，并广泛应用于各种电子设备，电动汽车以及便携储能设备中。目前，已经大规模商品化的锂离子电池主要采用以石墨为主的碳素材料作为负极材料，但是其理论比容量只有372mAh/g，难以满足当前需求，因此，开发更高容量密度的负极材料是锂离子二次电池急需解决的问题。Lithium-ion batteries have become the focus of current research in the world due to their large specific capacity, long service life, high safety, and portability, and are widely used in various electronic devices, electric vehicles, and portable energy storage devices. At present, the lithium-ion batteries that have been commercialized on a large scale mainly use graphite-based carbon materials as negative electrode materials, but their theoretical specific capacity is only 372mAh / g, which is difficult to meet current needs. Therefore, the development of higher capacity density negative electrode materials It is an urgent problem to be solved for lithium ion secondary batteries.
硅最大理论比容量较高(4200mAh/g)，脱嵌锂电位低，资源广泛，从而成为最有希望改善当前锂离子负极材料性能的材料之一，但是硅材料也有难以克服的缺陷，主要表现在脱嵌锂过程中，有高达300％多的体积膨胀，导致充放电过程中，活性材料容易粉化、脱落，循环性能极差，商业化生产受阻。而在众多硅以及硅化物材料中，氧化亚硅材料理论比容量较高(大于2000mAh/g)，虽然相较于硅材料容量有所降低，但其循环性能却有很大改善，主要原因在于氧化亚硅材料在首次充放电过程中锂离子会与硅氧材料反应生成Li2O和Li2SiO4，有效缓解活性材料的体积膨胀，很大程度的提高其循环性能。但是，在生成Li2O和Li2SiO4时消耗掉较多锂离子，因此，氧化亚硅负极材料的首周效率，容量都不高，这点严重影响氧化亚硅负极材料的商业 化应用。因此如何在保证氧化亚硅负极材料循环性能的基础上提高锂离子电池氧化亚硅负极材料的首周容量、效率是当前氧化亚硅负极材料研究的重难点。The maximum theoretical specific capacity of silicon (4200mAh / g), low lithium release potential, and extensive resources make it one of the most promising materials for improving the performance of current lithium ion anode materials, but silicon materials also have insurmountable defects, the main performance In the process of deintercalating lithium, there is a volume expansion of more than 300%, which causes the active material to be easily pulverized and peeled off during the charge and discharge process, the cycle performance is extremely poor, and commercial production is hindered. Among many silicon and silicide materials, the theoretical specific capacity of oxysilicon material is higher (greater than 2000mAh / g). Although the capacity is reduced compared to silicon material, its cycle performance has been greatly improved, mainly because In the first charge and discharge process of the silicon oxide material, lithium ions will react with the silicon oxide material to form Li2O and Li2SiO4, which effectively relieves the volume expansion of the active material and greatly improves its cycle performance. However, more lithium ions are consumed when generating Li2O and Li2SiO4. Therefore, the first week efficiency and capacity of the silicon oxide anode material are not high, which seriously affects the commercial application of the silicon oxide anode material. Therefore, how to improve the capacity and efficiency of silicon oxide anode materials for lithium-ion batteries on the basis of ensuring the cycle performance of silicon oxide anode materials is the most difficult problem in the current research on silicon oxide anode materials.
目前有研究人员采用预锂方法，即在材料制备过程中首先与硅氧材料反应生成Li2O和Li2SiO4，这样在充放电过程中，不会消耗或很少消耗锂离子，提高材料首周效率，如(Yom J H,Hwang S W,Cho S M,et al.Improvement of irreversible behavior of SiO anodes for lithium ion batteries by a solid state reaction at high temperature[J].Journal of Power Sources,2016,311:159-166.)。通过氧化亚硅与金属锂的质量比关系研究预锂后氧化亚硅负极材料首周效率的变化规律，结果显示当其质量比达到7:1时效率达到82.1％，但其容量只有1220mAh/g。预锂化方法提高氧化亚硅负极材料首周效率是一种较为直接的方法，但是预锂实验条件要求苛刻，操作难度大，且成本高，很难大规模生产，因此目前仅限于实验室研究。At present, some researchers use the pre-lithium method, which first reacts with the silicon oxide material to produce Li2O and Li2SiO4 during the material preparation process, so that during the charging and discharging process, no or little lithium ion is consumed, and the efficiency of the first week of the material is improved, such as (Yom, J, H, Hwang, S, W, Cho, S, M, et.al.Improvement of of irreversible, behavior, of, SiO, nanodes, for lithium, batteries, solid, state, reaction, at high temperature [J]. Journal of Power Sources, 2016, 311: 159- 166.). Through the relationship between the mass ratio of silicon oxide and lithium metal, the change rule of the first week efficiency of the silicon oxide anode material after pre-lithium is studied. The results show that when the mass ratio reaches 7: 1, the efficiency reaches 82.1%, but its capacity is only 1220mAh / g . The pre-lithiation method to improve the efficiency of silicon oxide anode materials in the first week is a more direct method, but the pre-lithium experimental conditions are demanding, the operation is difficult, and the cost is high, which is difficult to mass production, so it is currently limited to laboratory research .
目前也有还有很多研究人员通过活性金属还原的方法制备硅氧材料，如中国专利CN104577066A公开了一种SiO-SiO2-C的制备方法。该方法以SiO，SiO2为原料，采用镁热法还原制备硅氧材料，并使用天然石墨和葡萄糖等高温碳化修饰，制备复合材料，其目的主要是通过镁热还原，以及碳化包覆提高复合材料的首周效率。结果显示，其首周效率为79.2％，而其容量只有1176.1mAh/g，效率有少量提升，但是容量下降较大，因此意义不大。中国专利CN1110003730644A公开了一种硅-硅氧化物-碳复合材料的制备方法。该方法首先在氩气保护下，将一氧化硅、硅和石墨进行机械球磨，然后再与沥青以四氢呋喃为溶剂搅拌混合，最后高温处理得到负极复合材料，结果显示其 效率只有74.3％，而容量只有966.3mAh/g，结果很差，且采用机械球磨很难实现工业化生产。中国专利CN103022446A专利公开了一种硅氧化物/碳负极复合材料的制备方法。该方法以硅氧化物，金属颗粒，石墨为原料，混合后高温热处理制备负极材料，结果显示，负极复合材料首周效率提升明显，达到88％，几乎全部还原，而容量只有606.2mAh/g,循环50周后容量保持率100.6％。但是制备材料容量损失过大，未能充分利用材料高容量的特点，因此实际应用性差。At present, there are still many researchers preparing silicon oxide materials by the method of active metal reduction. For example, Chinese patent CN104577066A discloses a preparation method of SiO-SiO2-C. This method uses SiO and SiO2 as raw materials, uses magnesite reduction to prepare silicon-oxygen materials, and uses high-temperature carbonization modification such as natural graphite and glucose to prepare composite materials. Its purpose is mainly to improve composite materials through magnesia reduction and carbonization coating. The efficiency of the first week. The results show that its efficiency in the first week is 79.2%, and its capacity is only 1176.1mAh / g, the efficiency has a small increase, but the capacity decline is large, so it has little significance. Chinese patent CN1110003730644A discloses a method for preparing silicon-silicon oxide-carbon composite material. Under the protection of argon, this method first mechanically milled silicon monoxide, silicon and graphite, and then stirred and mixed with asphalt with tetrahydrofuran as a solvent. Finally, the high temperature treatment obtained a negative electrode composite material. The result showed that its efficiency was only 74.3%, and the capacity Only 966.3mAh / g, the result is very poor, and it is difficult to achieve industrial production using mechanical ball milling. The Chinese patent CN103022446A patent discloses a method for preparing a silicon oxide / carbon negative electrode composite material. This method uses silicon oxide, metal particles, and graphite as raw materials to prepare negative electrode materials after high-temperature heat treatment after mixing. The results show that the efficiency of the negative electrode composite material in the first week has increased significantly, reaching 88%, almost all reduced, and the capacity is only 606.2mAh / g. After 50 weeks of circulation, the capacity retention rate was 100.6%. However, the capacity loss of the prepared material is too large, and the high capacity characteristic of the material cannot be fully utilized, so the practical application is poor.
可见，以上方法制备出来的材料性能都较差，材料中存在无法除去的硅酸盐杂质，同时制备材料硅晶粒尺寸较大，材料循环膨胀加重，严重影响了硅氧材料的使用寿命。It can be seen that the properties of the materials prepared by the above methods are poor. There are silicate impurities in the materials that cannot be removed. At the same time, the silicon grain size of the prepared material is large, and the material cyclic expansion is increased, which seriously affects the service life of the silicon oxide material.
为此，确有必要开发一种锂离子电池氧化亚硅复合负极材料以得到高容量、高首效、长寿命、环境友好的负极材料克服本技术领域的技术难题。For this reason, it is indeed necessary to develop a silicon oxide composite negative electrode material for lithium ion batteries to obtain high capacity, high first-effect, long-life, and environmentally friendly negative electrode materials to overcome the technical problems in this technical field.
发明内容Summary of the invention
本发明的目的在于，针对现有技术的上述不足，提供一种锂离子电池氧化亚硅复合负极材料及其制法，以氧化亚硅、活性金属、碳包覆材料、熔盐为原料，经过混合、金属热还原、酸洗除杂、粉碎而获得，成品材料的氧含量低，显著提升了锂离子电池首周可逆容量和效率，且杂质少，应用价值高，硅晶粒尺寸小，有效改善了材料的循环膨胀，显著提高了材料的循环寿命。The purpose of the present invention is to provide a silicon oxide composite negative electrode material for lithium ion batteries and a preparation method thereof in view of the above-mentioned deficiencies in the prior art, using silicon oxide, active metals, carbon-coated materials, and molten salt as raw materials. It is obtained by mixing, metal thermal reduction, pickling and impurity removal, and crushing. The oxygen content of the finished material is low, which significantly improves the reversible capacity and efficiency of the lithium ion battery in the first week, and has fewer impurities, high application value, and small silicon crystal size. Improves the material's cyclic expansion and significantly improves the material's cycle life.
本发明为达到上述目的所采用的技术方案是：The technical solutions adopted by the present invention to achieve the above objectives are:
一种锂离子电池氧化亚硅复合负极材料的制法，包括下列步骤：A method for preparing a silicon oxide composite anode material for a lithium ion battery includes the following steps:
S1：将氧化亚硅、活性金属、熔盐进行混合，得到混合料；S1: Mixing silicon oxide, active metal and molten salt to obtain a mixture;
S2：将所得混合料在保护气氛下升温至200～800℃进行焙烧反应，之后经冷却、酸洗除杂，得到低氧值氧化亚硅材料；S2: The resulting mixture is heated to 200-800 ° C under a protective atmosphere for roasting reaction, and then cooled and pickled to remove impurities to obtain a low-oxygen silicon oxide material;
S3：将所得低氧值氧化亚硅材料与碳包覆材料进行混合或采用气相包覆，在保护气氛下升温至500～1100℃进行焙烧碳化处理，冷却，得到低氧值氧化亚硅/碳包覆复合负极材料，再进行破碎、粉碎并筛分，得到锂离子电池氧化亚硅复合负极材料。S3: Mix the obtained low-oxygen-value silicon oxide material with carbon-coated material or use gas-phase coating, heat up to 500-1100 ° C under a protective atmosphere for roasting and carbonization treatment, and cool to obtain low-oxygen-value silicon oxide / carbon The composite negative electrode material is coated, crushed, crushed and sieved to obtain a silicon oxide composite negative electrode material for lithium ion batteries.
优选地，所述的氧化亚硅为粉末状，粒径D50为1.0～15.0μm。Preferably, the silicon oxide is powdered, and the particle diameter D50 is 1.0-15.0 μm.
优选地，所述的活性金属为粉末状，粒径D50为0.1～500μm；活性金属为能够还原氧化亚硅的活性金属粉末，为锂、铁、铝、镍、锡、镁、铬、钛、钴、锌中的一种或多种组合。Preferably, the active metal is in the form of powder with a particle size D50 of 0.1-500 μm; the active metal is an active metal powder capable of reducing silicon oxide, which is lithium, iron, aluminum, nickel, tin, magnesium, chromium, titanium, One or more combinations of cobalt and zinc.
优选地，所述的熔盐为固体颗粒或粉末形式，粒径D50为0.5～1000μm，熔盐为氯化钙、氯化锂、氯化镁、氯化铝、二氯化铁、氯化钴、氯化钡、三氯化铁、氯化钾、氯化钠、氯化镍、溴化钾、溴化铯、溴化钠、溴化铷、碳酸钾、硫酸钾、碳酸锂、碳酸钠、硫酸钠、氢氧化锂、碳酸镁、硫酸镁、溴化镁、碳酸钙、氯化钛、氯化铬、氯化锰、氯化铜、氯化锌、氯化锡等中的一种或多种混合；所述的氧化亚硅与熔盐的添加质量比为1:0.1～1:20。Preferably, the molten salt is in the form of solid particles or powder, with a particle size D50 of 0.5-1000 μm, and the molten salt is calcium chloride, lithium chloride, magnesium chloride, aluminum chloride, ferric chloride, cobalt chloride, chlorine Barium chloride, ferric chloride, potassium chloride, sodium chloride, nickel chloride, potassium bromide, cesium bromide, sodium bromide, rubidium bromide, potassium carbonate, potassium sulfate, lithium carbonate, sodium carbonate, sodium sulfate , One or more of lithium hydroxide, magnesium carbonate, magnesium sulfate, magnesium bromide, calcium carbonate, titanium chloride, chromium chloride, manganese chloride, copper chloride, zinc chloride, tin chloride, etc. ; The mass ratio of the added silicon oxide and molten salt is 1: 0.1 ~ 1:20.
优选地，所述的碳包覆材料为煤沥青、石油沥青、淀粉、聚氯乙烯、葡萄糖、环氧树脂、聚苯乙烯、酚醛树脂、脲醛树脂、聚氨酯、聚噻吩类、多羟基醇类等中一种或多种混合并经高温处理得到，颗粒粒径为10～1000μm；所述的氧化亚硅与碳包覆材料的添加质量比为1:0.05～1:1。Preferably, the carbon coating material is coal pitch, petroleum pitch, starch, polyvinyl chloride, glucose, epoxy resin, polystyrene, phenolic resin, urea-formaldehyde resin, polyurethane, polythiophenes, polyhydric alcohols, etc. One or more of them are mixed and obtained by high temperature treatment, and the particle size is 10 to 1000 μm; the added mass ratio of the silicon oxide to the carbon coating material is 1: 0.05 to 1: 1.
优选地，所述的步骤S1、S3中混合的混合转速为100～2000rpm、混合时间为0.2～5.0h；所述的步骤S2、S4中焙烧的升温速率为0.1～20℃/min。Preferably, the mixing speed of the mixing in the steps S1 and S3 is 100-2000 rpm and the mixing time is 0.2-5.0 h; the heating rate of the roasting in the steps S2 and S4 is 0.1-20 ° C / min.
优选地，所述的步骤S2中酸洗除杂的酸液的浓度为0.1～10.0mol/L，酸液为盐酸、硫酸、硝酸、磷酸、醋酸、碳酸、草酸中的一种或多种混合；焙烧冷却后混合料与酸液的质量比为1:0.5～1:15。Preferably, the concentration of the acid liquid in the step S2 is 0.1-10.0 mol / L, and the acid liquid is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, carbonic acid, and oxalic acid. ; The mass ratio of mixture to acid after roasting and cooling is 1: 0.5 ～ 1: 15.
优选地，所述的步骤S3中气相包覆：采用的反应气体为甲烷、乙烷、丙烷、乙烯、乙炔等中的一种或多种气体，气体流量为1L/min～8L/min，通气反应时间0.5～2h。Preferably, the gas-phase coating in step S3: the reaction gas used is one or more of methane, ethane, propane, ethylene, acetylene, etc., and the gas flow rate is 1L / min ～ 8L / min, ventilation The reaction time is 0.5 ～ 2h.
一种采用前述的锂离子电池氧化亚硅复合负极材料的制法而得到的锂离子电池氧化亚硅复合负极材料，是以氧化亚硅为基体、导电碳材料为包覆层 而形成的氧化亚硅/碳材料核壳结构的氧化亚硅复合负极材料。该锂离子电池氧化亚硅复合负极材料的粒径D50为0.1～100μm。A silicon oxide composite anode material for a lithium ion battery obtained by using the foregoing manufacturing method of a silicon oxide composite anode material for a lithium ion battery is formed by using silicon oxide as a matrix and a conductive carbon material as a coating layer Silicone oxide composite anode material with silicon / carbon material core-shell structure. The particle diameter D50 of the silicon oxide composite negative electrode material of the lithium ion battery is 0.1-100 μm.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1.本发明的锂离子电池氧化亚硅复合负极材料采用氧化亚硅作为锂离子电池主要的电极活性材料，首次嵌锂过程中生成Li2O，Li4SiO4可以有效缓冲负极材料的体积膨胀效应，同时氧含量低，可以显著降低锂离子电池在首周循环过程中生成Li2O，Li4SiO4时的锂离子消耗，显著提升锂离子电池首周可逆容量和效率。1. The silicon oxide composite negative electrode material of the lithium ion battery of the present invention uses silicon oxide as the main electrode active material of the lithium ion battery. Li2O is generated during the first lithium insertion process, and Li4SiO4 can effectively buffer the volume expansion effect of the negative electrode material, while the oxygen content Low, can significantly reduce the lithium ion consumption of Li2O and Li4SiO4 generated during the first week cycle of lithium-ion batteries, and significantly improve the reversible capacity and efficiency of lithium-ion batteries in the first week.
2.本发明利用熔盐法，以熔盐为载体控制反应的进行，使两种不可移动的固体反应转化为熔盐液体环境下的反应，显著提高了反应效率，同时降低了反应温度，节省了成本，同时熔盐法也充分展示其对材料制备过程中杂质生成以及晶粒增大方面的控制作用。显著降低制备材料反应温度的同时提高反应效率，制备方法简单，成本低，且无污染，所得氧化亚硅复合负极材料锂离子二次电池高容量、低氧值，无杂质，小晶粒、高首效，长寿命，各方面性能优异，提高了氧化亚硅的首次比容量，首次充放电效率和循环寿命。2. The present invention uses the molten salt method to control the progress of the reaction with molten salt as a carrier, so that two immovable solid reactions are converted into reactions in a molten salt liquid environment, which significantly improves the reaction efficiency, while reducing the reaction temperature and saving At the same time, the molten salt method also fully demonstrates its control effect on the formation of impurities and the growth of grains during the preparation of the material. Significantly lower the reaction temperature of the preparation material while improving the reaction efficiency. The preparation method is simple, the cost is low, and there is no pollution. The resulting silicon oxide composite anode material lithium ion secondary battery has high capacity, low oxygen value, no impurities, small grains, and high The first effect, long life, excellent performance in all aspects, improved the first specific capacity of silicon oxide, the first charge and discharge efficiency and cycle life.
3.本发明采用活性金属还原氧化亚硅、并以熔盐作为载体控制反应进行，然后进行碳包覆处理，氧含量低，通过调节活性金属还原剂的添加量可以有效控制氧含量；制备过程中不生成或生成少量无法洗掉的硅酸盐类杂质，且硅氧比可以随意调节，显著提高其实际应用价值；成品材料硅晶粒尺寸小，可以有效改善材料的循环膨胀，显著提高材料的循环寿命。3. The present invention uses active metal to reduce silicon oxide, and uses molten salt as a carrier to control the reaction, and then performs carbon coating treatment, the oxygen content is low, and the oxygen content can be effectively controlled by adjusting the amount of active metal reducing agent added; the preparation process No silicate impurities are generated or a small amount cannot be washed off, and the silicon-oxygen ratio can be adjusted at will, which significantly improves its practical application value; the finished product has a small silicon grain size, which can effectively improve the cyclic expansion of the material and significantly improve the material Cycle life.
上述是发明技术方案的概述，以下结合附图与具体实施方式，对本发明做进一步说明。The above is an overview of the technical solution of the invention, and the present invention will be further described below with reference to the drawings and specific implementations.
附图说明BRIEF DESCRIPTION
图1为本发明实施例1中氧化亚硅复合负极材料电镜图片；Figure 1 is an electron micrograph of the silicon oxide composite negative electrode material in Example 1 of the present invention;
图2为本发明实施例1中氧化亚硅复合负极材料首次充放电曲线；2 is the first charge-discharge curve of the silicon oxide composite anode material in Example 1 of the present invention;
图3为本发明实施例2中氧化亚硅复合负极材料首次充放电曲线；3 is the first charge-discharge curve of the silicon oxide composite negative electrode material in Example 2 of the present invention;
图4为本发明实施例1中氧化亚硅复合负极材料的XRD图谱；4 is an XRD pattern of the silicon oxide composite negative electrode material in Example 1 of the present invention;
图5为本发明对比例1中氧化亚硅复合负极材料的XRD图谱。5 is an XRD pattern of the silicon oxide composite negative electrode material in Comparative Example 1 of the present invention.
具体实施方式：detailed description:
为了使本发明的目的和技术方案及优点更加清楚明白，以下结合实施例作详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the objectives, technical solutions and advantages of the present invention clearer, the following detailed description will be made in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, and are not intended to limit the present invention.
实施例1Example 1
本实施例的锂离子电池氧化亚硅复合负极材料的制法具体包括：The manufacturing method of the silicon oxide composite negative electrode material of the lithium ion battery of this embodiment specifically includes:
S1：将粒度中值粒径(D50)为0.5～2.5μm的氧化亚硅、粒度中值粒径(D50)为5～30μm的铝金属粉末、50～200μm的CaCl 2-AlCl 3混合熔盐进行VC混合工作，混合转速为900rpm，混合时间为2h，其中氧化亚硅与铝金属粉末材料的添加摩尔比为1:0.2，氧化亚硅与混合熔盐的添加质量比为1:3，混合熔盐CaCl 2-AlCl 3之间的质量比为6:4。 S1: mixed silicon oxide with a median particle size (D50) of 0.5 to 2.5 μm, aluminum metal powder with a median particle size (D50) of 5 to 30 μm, and CaCl 2 -AlCl 3 mixed molten salt of 50 to 200 μm Carry out VC mixing work, mixing speed is 900rpm, mixing time is 2h, in which the molar ratio of silicon oxide and aluminum metal powder material is 1: 0.2, the mass ratio of silicon oxide and mixed molten salt is 1: 3, mixing The mass ratio of molten salt CaCl 2 -AlCl 3 is 6: 4.
S2：将混合后的物料放在箱式炉中焙烧，氮气氛围保护，焙烧温度为500℃，升温速率为3℃/min，保温2h，待冷却完全取出材料。将所得材料加入到2mol/L的盐酸中混合搅拌，所得材料与盐酸的质量比为1:3，搅拌转速1500rpm，时间5h，酸洗完成后采用压滤机过滤，鼓风风箱烘干。S2: The mixed materials are roasted in a box furnace, protected by a nitrogen atmosphere, the roasting temperature is 500 ° C, the heating rate is 3 ° C / min, the temperature is kept for 2 hours, and the material is completely removed after cooling. The obtained material was added into 2mol / L hydrochloric acid to mix and stir. The mass ratio of the obtained material to hydrochloric acid was 1: 3, the stirring speed was 1500rpm, and the time was 5h. After the pickling was completed, it was filtered with a filter press, and the air box was dried.
S3：将烘干后的材料与粒度中值粒径(D50)为100～500μm的石油沥青共混，共混质量比为1:0.2，将混合好的材料放入箱式炉中进行焙烧，氮气氛围保护，焙烧温度800℃，升温速率为2℃/min，保温3h，得低氧值氧化亚硅/碳包覆复合负极材料。将上述材料经破碎、粉碎并筛分最终得成品锂离 子电池氧化亚硅复合负极材料，材料的粒度中值粒径(D50)为0.1～100μm。S3: Blend the dried material with petroleum pitch with a median particle size (D50) of 100-500 μm, the blending mass ratio is 1: 0.2, and put the mixed material into a box furnace for roasting. Nitrogen atmosphere protection, calcination temperature 800 ℃, heating rate 2 ℃ / min, heat preservation 3h, low oxygen value silicon oxide / carbon coated composite anode material. The above-mentioned materials are crushed, crushed and sieved to finally obtain a finished silicon oxide composite negative electrode material for a lithium ion battery. The median particle size (D50) of the material is 0.1 to 100 m.
实施例2Example 2
本实施例的锂离子电池氧化亚硅复合负极材料的制法具体包括：将粒度中值粒径(D50)为4～8μm的氧化亚硅，粒度中值粒径(D50)为80～120μm的铝金属粉末，50～200μm的MgCl 2-KCl混合熔盐进行VC混合工作，混合转速为800rpm，混合时间为2h，其中氧化亚硅与铝金属粉末材料的添加摩尔比为1:0.8，氧化亚硅与混合熔盐的添加质量比为1:8，混合熔盐MgCl 2-KCl之间的质量比为2:8。将混合后的物料放入箱式炉中焙烧，氩气氛围保护，焙烧温度为750℃，升温速率为10℃/min，保温8h，待冷却完全取出材料。将所得材料加入到3mol/L的盐酸中混合搅拌，所得材料与盐酸的质量比为1:6，搅拌转速1500rpm，时间5h，酸洗完成后采用压滤机过滤，鼓风风箱烘干，将烘干后的材料与粒度中值粒径(D50)为100～500μm的煤沥青共混，共混质量比为1:0.2，将混合好的物料放入箱式炉中进行焙烧，氩气氛围保护，焙烧温度900℃，升温速率为2℃/min，保温5h，得低氧值氧化亚硅/碳包覆复合负极材料，将上述材料经破碎、粉碎并筛分最终得材料的粒度中值粒径(D50)为0.1～100μm，即为成品锂离子电池氧化亚硅复合负极材料。 The preparation method of the silicon oxide composite negative electrode material of the lithium ion battery of this embodiment specifically includes: the silicon oxide with a particle size median diameter (D50) of 4-8 μm and a particle size median diameter (D50) of 80-120 μm Aluminum metal powder, MgCl 2 -KCl mixed molten salt of 50 ～ 200μm is used for VC mixing work, mixing speed is 800rpm, mixing time is 2h, in which the molar ratio of silicon oxide to aluminum metal powder material is 1: 0.8, suboxide The added mass ratio of silicon to the mixed molten salt is 1: 8, and the mass ratio between the mixed molten salt MgCl 2 -KCl is 2: 8. The mixed materials are put into a box furnace for roasting, protected by an argon atmosphere, the roasting temperature is 750 ° C, the heating rate is 10 ° C / min, and the temperature is kept for 8 hours. After cooling, the material is completely taken out. Add the obtained material to 3mol / L hydrochloric acid to mix and stir. The mass ratio of the obtained material to hydrochloric acid is 1: 6, the stirring speed is 1500rpm, the time is 5h. After the pickling is completed, the filter press is used for filtering, and the air box is dried. The dried material is blended with coal pitch with a median particle size (D50) of 100 to 500 μm, the blending mass ratio is 1: 0.2, the mixed materials are placed in a box furnace for roasting, argon atmosphere Protection, roasting temperature 900 ℃, heating rate 2 ℃ / min, heat preservation 5h, get low oxygen value silicon oxide / carbon coated composite anode material, crush, crush and sieve the above materials to obtain the median particle size The particle size (D50) is 0.1 ～ 100μm, which is the silicon oxide composite negative electrode material of the finished lithium ion battery.
实施例3Example 3
本实施例的锂离子电池氧化亚硅复合负极材料的制法具体包括：The manufacturing method of the silicon oxide composite negative electrode material of the lithium ion battery of this embodiment specifically includes:
将粒度中值粒径(D50)为0.5～2.5μm的氧化亚硅，粒度中值粒径(D50)为5～30μm的锌金属粉末，50～200μm的KCl-AlCl 3混合熔盐进行VC混合工作，混合转速为1500rpm，混合时间为2h，其中氧化亚硅与锌金属粉末材料的添加摩尔比为1:0.2，氧化亚硅与混合熔盐的添加质量比为1:3，混合熔 盐KCl-AlCl 3之间的质量比为3.5:6.5。将混合后的物料放入箱式炉中焙烧，氩气氛围保护，焙烧温度为300℃，升温速率为3℃/min，保温2h，待冷却完全取出材料。将所得材料加入到2mol/L的盐酸中混合搅拌，所得材料与盐酸的质量比为1:3，搅拌转速1500rpm，时间5h，酸洗完成后采用压滤机过滤，鼓风风箱烘干，将烘干后的材料与粒度中值粒径(D50)为100～500μm煤沥青共混，共混质量比为1:0.2，将混合好的物料放入箱式炉中进行焙烧，氩气氛围保护，焙烧温度950℃，升温速率为5℃/min，保温4h，待冷却完全取出材料，得低氧值氧化亚硅/碳包覆复合负极材料，将上述材料经破碎、粉碎并筛分最终得材料的粒度中值粒径(D50)为0.1～100μm，即为成品锂离子电池氧化亚硅复合负极材料。 Silica oxide with a median particle size (D50) of 0.5 to 2.5 μm, zinc metal powder with a median particle size (D50) of 5 to 30 μm, mixed molten salt of KCl-AlCl 3 with a particle size of 50 to 200 μm for VC mixing Working, mixing speed is 1500rpm, mixing time is 2h, in which the added molar ratio of silicon oxide and zinc metal powder material is 1: 0.2, the added mass ratio of silicon oxide and mixed molten salt is 1: 3, mixed molten salt KCl -The mass ratio between AlCl 3 is 3.5: 6.5. The mixed materials are put into a box furnace for roasting, protected by an argon atmosphere, the roasting temperature is 300 ° C, the heating rate is 3 ° C / min, the temperature is kept for 2 hours, and the material is completely taken out after cooling. Add the obtained material to 2mol / L hydrochloric acid to mix and stir. The mass ratio of the obtained material to hydrochloric acid is 1: 3, the stirring speed is 1500rpm, and the time is 5h. After the pickling is completed, it is filtered with a filter press, and the air box is dried. The dried material is blended with coal pitch with a median particle size (D50) of 100 ～ 500μm, the blending mass ratio is 1: 0.2, the mixed materials are placed in a box furnace for roasting, and protected by argon atmosphere , The calcination temperature is 950 ℃, the heating rate is 5 ℃ / min, and the heat is kept for 4h. After cooling, the material is completely taken out to obtain a low oxygen value silicon oxide / carbon coated composite negative electrode material. The above materials are finally crushed, crushed and sieved. The median particle size (D50) of the material is 0.1-100 μm, which is the silicon oxide composite negative electrode material of the finished lithium ion battery.
实施例4Example 4
本实施例的锂离子电池氧化亚硅复合负极材料的制法具体包括：The manufacturing method of the silicon oxide composite negative electrode material of the lithium ion battery of this embodiment specifically includes:
将粒度中值粒径(D50)为2.5～5μm的氧化亚硅，粒度中值粒径(D50)为30～80μm的锌金属粉末，50～200μm的CaCl 2-LiCl混合熔盐进行VC混合工作，混合转速为1000rpm，混合时间为1h，其中氧化亚硅与锌金属粉末材料的添加摩尔比为1:0.5，氧化亚硅与混合熔盐的添加质量比为1:5，混合熔盐CaCl 2-LiCl之间的质量比为3.5:6.5。将混合后的物料放入箱式炉中焙烧，氩气氛围保护，焙烧温度为500℃，升温速率为5℃/min，保温2h，待冷却完全取出材料。将所得材料加入到3mol/L的盐酸中混合搅拌，所得材料与盐酸的质量比为1:5，搅拌转速1500rpm，时间5h，酸洗完成后采用压滤机过滤，鼓风风箱烘干，将烘干后的材料与粒度中值粒径(D50)为100～500μm的煤沥青共混，共混质量比为1:0.2，将混合好的物料放入箱式炉中进行焙烧， 氩气氛围保护，焙烧温度1100℃，升温速率为5℃/min，保温5h，待冷却完全取出材料，得低氧值氧化亚硅/碳包覆复合负极材料，将上述材料经破碎、粉碎并筛分最终得材料的粒度中值粒径(D50)为0.1～100μm，即为成品锂离子电池氧化亚硅复合负极材料。 Silica oxide with median particle size (D50) of 2.5-5 μm, zinc metal powder with median particle size (D50) of 30-80 μm, mixed molten salt of CaCl 2 -LiCl with 50-200 μm for VC mixing work , Mixing speed is 1000rpm, mixing time is 1h, the molar ratio of the addition of silicon oxide and zinc metal powder material is 1: 0.5, the mass ratio of the addition of silicon oxide and mixed molten salt is 1: 5, mixed molten salt CaCl 2 -The mass ratio between LiCl is 3.5: 6.5. The mixed materials are put into a box furnace for roasting, protected by an argon atmosphere, the roasting temperature is 500 ° C, the heating rate is 5 ° C / min, and the temperature is kept for 2 hours. After cooling, the material is completely taken out. Add the obtained material to 3mol / L hydrochloric acid to mix and stir. The mass ratio of the obtained material to hydrochloric acid is 1: 5, the stirring speed is 1500rpm, the time is 5h. After the pickling is completed, it is filtered with a filter press, and the air box is dried The dried material is blended with coal pitch with a median particle size (D50) of 100 to 500 μm, the blending mass ratio is 1: 0.2, the mixed materials are placed in a box furnace for roasting, argon atmosphere Protection, roasting temperature 1100 ℃, heating rate 5 ℃ / min, heat preservation 5h, take out the material completely after cooling, get low oxygen value silicon oxide / carbon coated composite anode material, crush, crush and screen the above materials The median particle size (D50) of the obtained material is 0.1-100 μm, which is the silicon oxide composite negative electrode material of the finished lithium ion battery.
实施例5Example 5
本实施例的锂离子电池氧化亚硅复合负极材料的制法具体包括：The manufacturing method of the silicon oxide composite negative electrode material of the lithium ion battery of this embodiment specifically includes:
将粒度中值粒径(D50)为0.5～2.5μm的氧化亚硅，粒度中值粒径(D50)为5～30μm的锂金属粉末，50～200μm的MgCl 2-KCl混合熔盐进行VC混合工作，混合转速为800rpm，混合时间为2h，其中氧化亚硅与锂金属粉末材料的添加摩尔比为1:0.2，氧化亚硅与混合熔盐的添加质量比为1:3，混合熔盐MgCl 2-KCl之间的质量比为6:4。将混合后的物料放入箱式炉中焙烧，氮气氛围保护，焙烧温度为600℃，升温速率为3℃/min，保温2h，待冷却完全取出材料。将所得材料加入到2mol/L的盐酸中混合搅拌，所得材料与盐酸的质量比为1:3，搅拌转速1500rpm，时间5h，酸洗完成后采用压滤机过滤，鼓风风箱烘干，将烘干后的材料放入回转炉中焙烧，氩气氛围保护，焙烧温度700℃，升温速率为7℃/min，当温度达到700℃时，开始通入甲烷气体，控制流量为3L/min，反应时间1h，待冷却完全取出材料，得低氧值氧化亚硅/碳包覆复合负极材料，将上述材料经破碎、粉碎并筛分最终得材料的粒度中值粒径(D50)为0.1～100μm，即为成品锂离子电池氧化亚硅复合负极材料。 Siliceous oxide with a median particle size (D50) of 0.5 to 2.5 μm, lithium metal powder with a median particle size (D50) of 5 to 30 μm, mixed molten salt of MgCl 2 -KCl with a particle size of 50 to 200 μm for VC mixing Work, mixing speed is 800rpm, mixing time is 2h, in which the molar ratio of silicon oxide and lithium metal powder material is 1: 0.2, the mass ratio of silicon oxide and mixed molten salt is 1: 3, mixed molten salt MgCl The mass ratio between 2 -KCl is 6: 4. The mixed materials were roasted in a box furnace, protected by a nitrogen atmosphere. The roasting temperature was 600 ° C, the heating rate was 3 ° C / min, and the temperature was kept for 2 hours. After cooling, the material was completely removed. Add the obtained material to 2mol / L hydrochloric acid to mix and stir. The mass ratio of the obtained material to hydrochloric acid is 1: 3, the stirring speed is 1500rpm, and the time is 5h. After the pickling is completed, it is filtered with a filter press, and the air box is dried. The dried material is placed in a rotary furnace for roasting, protected by an argon atmosphere. The roasting temperature is 700 ° C, and the heating rate is 7 ° C / min. When the temperature reaches 700 ° C, the methane gas is started to flow and the flow rate is controlled to 3 L / min The reaction time is 1h. After cooling, the material is completely taken out to obtain a low-oxygen-silicon oxide / carbon-coated composite negative electrode material. The above-mentioned material is crushed, crushed and sieved to finally obtain a material with a median particle size (D50) of 0.1 to 100μm is the silicon dioxide composite anode material of the finished lithium ion battery.
实施例6Example 6
本实施例的锂离子电池氧化亚硅复合负极材料的制法具体包括：The manufacturing method of the silicon oxide composite negative electrode material of the lithium ion battery of this embodiment specifically includes:
将粒度中值粒径(D50)为2.5～5μm的氧化亚硅，粒度中值粒径(D50) 为30～80μm的锂金属粉末，50～200μm的CaCl 2-KCl混合熔盐进行VC混合工作，混合转速为800rpm，混合时间为2h，其中氧化亚硅与锂金属粉末材料的添加摩尔比为1:0.4，氧化亚硅与混合熔盐的添加质量比为1:5，混合熔盐CaCl 2-KCl之间的质量比为2.6:7.4。将混合后的物料放入箱式炉中焙烧，氩气氛围保护，焙烧温度为750℃，升温速率为5℃/min，保温2h，待冷却完全取出材料。将所得材料加入到3mol/L的盐酸中混合搅拌，所得材料与盐酸的质量比为1:5，搅拌转速1500rpm，时间5h，酸洗完成后采用压滤机过滤，鼓风风箱烘干，将烘干后的材料与粒度中值粒径(D50)为100～500μm的淀粉共混，共混质量比为1:0.2，将混合好的物料放入箱式炉中进行焙烧，氩气氛围保护，焙烧温度800℃，升温速率为5℃/min，保温3h，待冷却完全取出材料，得低氧值氧化亚硅/碳包覆复合负极材料，将上述材料经破碎、粉碎并筛分最终得材料的粒度中值粒径(D50)为0.1～100μm，即为成品锂离子电池氧化亚硅复合负极材料。 Silica oxide with median particle size (D50) of 2.5-5 μm, lithium metal powder with median particle size (D50) of 30-80 μm, mixed molten salt of CaCl 2 -KCl with 50-200 μm for VC mixing work , Mixing speed is 800rpm, mixing time is 2h, in which the molar ratio of silicon oxide and lithium metal powder material is 1: 0.4, the mass ratio of silicon oxide and mixed molten salt is 1: 5, mixed molten salt CaCl 2 -The mass ratio between KCl is 2.6: 7.4. The mixed materials are put into a box furnace for roasting, protected by an argon atmosphere, the roasting temperature is 750 ° C, the heating rate is 5 ° C / min, the temperature is kept for 2 hours, and the material is completely taken out after cooling. Add the obtained material to 3mol / L hydrochloric acid to mix and stir. The mass ratio of the obtained material to hydrochloric acid is 1: 5, the stirring speed is 1500rpm, the time is 5h. After the pickling is completed, it is filtered with a filter press, and the air box is dried. The dried material is blended with starch with a median particle size (D50) of 100 to 500 μm, the blending mass ratio is 1: 0.2, the mixed materials are placed in a box furnace for roasting, and protected by an argon atmosphere , The calcination temperature is 800 ℃, the heating rate is 5 ℃ / min, and the temperature is kept for 3 hours. After cooling, the material is completely taken out to obtain a low oxygen value silicon oxide / carbon coated composite negative electrode material. The median particle size (D50) of the material is 0.1-100 μm, which is the silicon oxide composite negative electrode material of the finished lithium ion battery.
对比例1Comparative Example 1
本实施例的锂离子电池氧化亚硅复合负极材料的制法具体包括：将粒度中值粒径(D50)为0.5～2.5μm的氧化亚硅，粒度中值粒径(D50)为5～30μm的铝金属粉末进行VC混合工作，混合转速为800rpm，混合时间为2h，其中氧化亚硅与铝金属粉末材料的添加摩尔比为1:0.2。将混合后的物料放入箱式炉中焙烧，氮气氛围保护，焙烧温度为250℃，升温速率为3℃/min，保温2h，待冷却完全取出材料。将所得材料加入到2mol/L的盐酸中混合搅拌，所得材料与盐酸的质量比为1:3，搅拌转速1500rpm，时间5h，酸洗完成后采用压滤机过滤，鼓风风箱烘干，将烘干后的材料与粒度中值粒径(D50) 为100～500μm的煤沥青共混，共混质量比为1:0.2，将混合好的物料放入箱式炉中进行焙烧，氩气氛围保护，焙烧温度800℃，升温速率为2℃/min，保温3h，待冷却完全取出材料，得低氧值氧化亚硅/碳包覆复合负极材料，将上述材料经破碎、粉碎并筛分最终得材料的粒度中值粒径(D50)为0.1～100μm，即为为成品锂离子电池氧化亚硅复合负极材料。The preparation method of the silicon oxide composite negative electrode material of the lithium ion battery of this embodiment specifically includes: the silicon oxide with a median particle size (D50) of 0.5 to 2.5 μm and a median particle size (D50) of 5 to 30 μm The aluminum metal powder is mixed with VC, the mixing speed is 800rpm, the mixing time is 2h, and the molar ratio of the addition of silicon oxide and aluminum metal powder material is 1: 0.2. The mixed materials were put into a box furnace for roasting, protected by a nitrogen atmosphere. The roasting temperature was 250 ° C, the heating rate was 3 ° C / min, and the temperature was kept for 2 hours. After cooling, the material was completely taken out. Add the obtained material to 2mol / L hydrochloric acid to mix and stir. The mass ratio of the obtained material to hydrochloric acid is 1: 3, the stirring speed is 1500rpm, and the time is 5h. After the pickling is completed, it is filtered with a filter press, and the air box is dried. The dried material is blended with coal pitch with a median particle size (D50) of 100 to 500 μm, the blending mass ratio is 1: 0.2, the mixed materials are placed in a box furnace for roasting, argon atmosphere Protection, roasting temperature 800 ℃, heating rate 2 ℃ / min, heat preservation 3h, take out the material completely after cooling, get low oxygen value silicon oxide / carbon coated composite anode material, crush, crush and sieve the above materials The median particle size (D50) of the obtained material is 0.1-100 μm, which is the silicon oxide composite negative electrode material of the finished lithium ion battery.
对比例2Comparative Example 2
本实施例的锂离子电池氧化亚硅复合负极材料的制法具体包括：将粒度中值粒径(D50)为2.5～5μm的氧化亚硅，粒度中值粒径(D50)为30～80μm的锌金属粉末，进行VC混合工作，混合转速为800rpm，混合时间为2h，其中氧化亚硅与锌金属粉末材料的添加摩尔比为1:0.4。将混合后的物料放入箱式炉中焙烧，氩气氛围保护，焙烧温度为750℃，升温速率为5℃/min，保温2h，待冷却完全取出材料。将所得材料加入到3mol/L的盐酸中混合搅拌，所得材料与盐酸的质量比为1:5，搅拌转速1500rpm，时间5h，酸洗完成后采用压滤机过滤，鼓风风箱烘干，将烘干后的材料与粒度中值粒径(D50)为100～500μm的煤沥青共混，共混质量比为1:0.2，将混合好的物料放入箱式炉中进行焙烧，氩气氛围保护，焙烧温度700℃，升温速率为2℃/min，保温5h，待冷却完全取出材料，得低氧值氧化亚硅/碳包覆复合负极材料，将上述材料经破碎、粉碎并筛分最终得材料的粒度中值粒径(D50)为0.1～100μm，即为成品锂离子电池氧化亚硅复合负极材料。The preparation method of the silicon oxide composite negative electrode material of the lithium ion battery of this embodiment specifically includes: the silicon oxide with a median particle size (D50) of 2.5-5 μm and a median particle size (D50) of 30-80 μm Zinc metal powder, VC mixing work, mixing speed is 800rpm, mixing time is 2h, in which the molar ratio of silicon oxide to zinc metal powder material is 1: 0.4. The mixed materials are put into a box furnace for roasting, protected by an argon atmosphere, the roasting temperature is 750 ° C, the heating rate is 5 ° C / min, the temperature is kept for 2 hours, and the material is completely taken out after cooling. Add the obtained material to 3mol / L hydrochloric acid to mix and stir. The mass ratio of the obtained material to hydrochloric acid is 1: 5, the stirring speed is 1500rpm, the time is 5h. After the pickling is completed, it is filtered with a filter press, and the air box is dried. The dried material is blended with coal pitch with a median particle size (D50) of 100 to 500 μm, the blending mass ratio is 1: 0.2, the mixed materials are placed in a box furnace for roasting, argon atmosphere Protection, roasting temperature 700 ℃, heating rate 2 ℃ / min, heat preservation 5h, take out the material completely after cooling, get the low oxygen value silicon oxide / carbon coated composite anode material, crush, crush and sieve the above materials The median particle size (D50) of the obtained material is 0.1-100 μm, which is the silicon oxide composite negative electrode material of the finished lithium ion battery.
采用以下方法对实施例1～6和对比例1～2的负极材料进行测试：The anode materials of Examples 1 to 6 and Comparative Examples 1 to 2 were tested using the following methods:
采用马尔文激光粒度测试仪MS3000测试材料粒径范围以及分布。A Malvern laser particle size analyzer MS3000 was used to test the material particle size range and distribution.
采用美国麦克仪器公司的Tristar3000全自动比表面积和孔隙度分析以测 试材料的比表面积。The Tristar 3000 fully automatic specific surface area and porosity analysis of American Mac Instruments was used to test the specific surface area of the material.
采用日立公司S4800扫描电子显微镜观察样品形貌、颗粒大小等。Hitachi S4800 scanning electron microscope was used to observe the sample morphology and particle size.
其中，附图1为实施例1制备的氧化亚硅复合负极材材料的扫描电镜图谱，通过分析在图1中清晰的反映出了材料的粒径以及表面状况，表明材料修饰后的形态。Among them, FIG. 1 is a scanning electron micrograph of the silicon oxide composite negative electrode material prepared in Example 1. Through analysis, FIG. 1 clearly reflects the particle size and surface condition of the material, indicating the modified form of the material.
采用X射线衍射仪X′Pert Pro，PANalytical测试材料结构。Using X-ray diffractometer X′Pert Pro, PANalytical to test the material structure.
其中，附图4为对比例1的X射线衍射图谱，从图中可知，经过处理后的氧化亚硅材料，无定型氧化亚硅的峰依然很强，而硅晶体尺寸较小，实际生成的硅很少。Among them, FIG. 4 is the X-ray diffraction pattern of Comparative Example 1. It can be seen from the figure that after the treated silicon oxide material, the peak of amorphous silicon oxide is still very strong, while the silicon crystal size is small, the actual generated There is very little silicon.
采用以下方法测试电化学循环性能：将负极材料、导电剂、粘结剂按照质量比92:2:6在溶剂中混合，控制固含量为55％，涂覆铜箔集流体上，烘干得负极极片；然后利用常规正极片、1mol/L的LiPF 6/EC+DMC(V/V＝1:1)电解液，CeLgard2400隔膜，外壳采用常规生产工艺装配18650圆柱电池，1C倍率下恒流充放电，充放电电压限制在2.75～4.2V。 The following methods were used to test the electrochemical cycle performance: the negative electrode material, the conductive agent, and the binder were mixed in a solvent at a mass ratio of 92: 2: 6, the solid content was controlled to 55%, and the copper foil collector was coated and dried. Negative pole piece; then use the conventional positive electrode piece, 1mol / L LiPF 6 / EC + DMC (V / V = 1: 1) electrolyte, CeLgard2400 separator, the shell adopts conventional production process to assemble 18650 cylindrical battery, constant current at 1C rate Charge and discharge, charge and discharge voltage is limited to 2.75 ~ 4.2V.
实施例1-6及对比例1、2所制备负极材料的电化学测试结果及晶粒尺寸测试结果如表一所示：The electrochemical test results and grain size test results of the anode materials prepared in Examples 1-6 and Comparative Examples 1 and 2 are shown in Table 1:
表一Table I
Figure PCTCN2018123632-appb-000001
Figure PCTCN2018123632-appb-000001
Figure PCTCN2018123632-appb-000002
Figure PCTCN2018123632-appb-000002
根据上述说明书的揭示和教导，本发明所属领域的技术人员还可以对上述实施方式进行变更和修改。因此，上述实施例说明本发明的详细方法，但本发明并不局限于上面揭示和描述的具体实施方式，也不意味着本发明必须依赖上述详细方法才能实施，对发明的一些修改和变更等任何改进，对本发明产品各原料的等效替换及辅助成分的添加，具体方式的选择等，也应当落入本发明的权利要求的保护范围内。According to the disclosure and teaching of the above description, those skilled in the art to which the present invention belongs can also make changes and modifications to the above-mentioned embodiments. Therefore, the above embodiments illustrate the detailed method of the present invention, but the present invention is not limited to the specific embodiments disclosed and described above, nor does it mean that the present invention must rely on the above detailed method to implement, and some modifications and changes to the invention, etc. Any improvement, equivalent replacement of each raw material of the product of the present invention, addition of auxiliary components, choice of specific methods, etc., should also fall within the protection scope of the claims of the present invention.

Claims (10)

  1. 一种锂离子电池氧化亚硅复合负极材料的制法，其特征在于，包括下列步骤：A method for manufacturing a silicon oxide composite anode material for a lithium ion battery is characterized in that it includes the following steps:
    S1：将氧化亚硅、活性金属、熔盐进行混合，得到混合料；S1: Mixing silicon oxide, active metal and molten salt to obtain a mixture;
    S2：将所得混合料在保护气氛下升温至200～800℃进行焙烧反应，之后经冷却、酸洗除杂，得到低氧值氧化亚硅材料；S2: The resulting mixture is heated to 200-800 ° C under a protective atmosphere for roasting reaction, and then cooled and pickled to remove impurities to obtain a low-oxygen silicon oxide material;
    S3：将所得低氧值氧化亚硅材料与碳包覆材料进行混合或采用气相包覆，在保护气氛下升温至500～1100℃进行焙烧碳化处理，冷却，得到低氧值氧化亚硅/碳包覆复合负极材料，再进行破碎、粉碎并筛分，得到锂离子电池氧化亚硅复合负极材料。S3: Mix the obtained low-oxygen-value silicon oxide material with carbon-coated material or use gas-phase coating, heat up to 500-1100 ° C under a protective atmosphere for roasting and carbonization treatment, and cool to obtain low-oxygen-value silicon oxide / carbon The composite negative electrode material is coated, crushed, crushed and sieved to obtain a silicon oxide composite negative electrode material for lithium ion batteries.
  2. 如权利要求1所述的锂离子电池氧化亚硅复合负极材料的制法，其特征在于，所述的氧化亚硅为粉末状，粒径D50为1.0～15.0μm。The method for producing a silicon oxide composite negative electrode material for a lithium ion battery according to claim 1, wherein the silicon oxide is in powder form and has a particle diameter D50 of 1.0 to 15.0 μm.
  3. 如权利要求1所述的锂离子电池氧化亚硅复合负极材料的制法，其特征在于，所述的活性金属为粉末状，粒径D50为0.1～500μm；活性金属为能够还原氧化亚硅的活性金属粉末，为锂、铁、铝、镍、锡、镁、铬、钛、钴、锌中的一种或多种组合。The method for producing a silicon oxide composite negative electrode material for a lithium ion battery according to claim 1, wherein the active metal is in a powder form with a particle diameter D50 of 0.1 to 500 μm; the active metal is capable of reducing silicon oxide The active metal powder is one or more combinations of lithium, iron, aluminum, nickel, tin, magnesium, chromium, titanium, cobalt, and zinc.
  4. 如权利要求1所述的锂离子电池氧化亚硅复合负极材料的制法，其特征在于，所述的熔盐为固体颗粒或粉末形式，粒径D50为0.5～1000μm，熔盐为氯化钙、氯化锂、氯化镁、氯化铝、二氯化铁、氯化钴、氯化钡、三氯化铁、氯化钾、氯化钠、氯化镍、溴化钾、溴化铯、溴化钠、溴化铷、碳酸钾、硫酸钾、碳酸锂、碳酸钠、硫酸钠、氢氧化锂、碳酸镁、硫酸镁、溴化镁、碳酸钙、氯化钛、氯化铬、氯化锰、氯化铜、氯化锌、氯化锡等中的一种或多种混合；所述的氧化亚硅与熔盐的添加质量比为1:0.1～1:20。The method for preparing a silicon oxide composite negative electrode material for a lithium ion battery according to claim 1, wherein the molten salt is in the form of solid particles or powder, the particle diameter D50 is 0.5-1000 μm, and the molten salt is calcium chloride , Lithium chloride, magnesium chloride, aluminum chloride, ferric chloride, cobalt chloride, barium chloride, ferric chloride, potassium chloride, sodium chloride, nickel chloride, potassium bromide, cesium bromide, bromine Sodium chloride, rubidium bromide, potassium carbonate, potassium sulfate, lithium carbonate, sodium carbonate, sodium sulfate, lithium hydroxide, magnesium carbonate, magnesium sulfate, magnesium bromide, calcium carbonate, titanium chloride, chromium chloride, manganese chloride , One or more of copper chloride, zinc chloride, tin chloride, etc .; the mass ratio of the added silicon oxide and molten salt is 1: 0.1 ~ 1:20.
  5. 如权利要求1所述的锂离子电池氧化亚硅复合负极材料的制法，其特征在于，所述的碳包覆材料为煤沥青、石油沥青、淀粉、聚氯乙烯、葡萄糖、环氧树脂、聚苯乙烯、酚醛树脂、脲醛树脂、聚氨酯、聚噻吩类、多羟基醇类等中一种或多种混合并经高温处理得到，颗粒粒径为10～1000μm；所述的氧化亚硅与碳包覆材料的添加质量比为1:0.05～1:1。The method for producing a silicon oxide composite negative electrode material for a lithium ion battery according to claim 1, wherein the carbon coating material is coal pitch, petroleum pitch, starch, polyvinyl chloride, glucose, epoxy resin, One or more of polystyrene, phenolic resin, urea-formaldehyde resin, polyurethane, polythiophenes, polyhydric alcohols, etc. are mixed and subjected to high temperature treatment, and the particle size is 10 ～ 1000μm; The mass ratio of the coating material is 1: 0.05 ～ 1: 1.
  6. 如权利要求1所述的锂离子电池氧化亚硅复合负极材料的制法，其特征在于，所述的步骤S1、S3中混合的混合转速为100～2000rpm、混合时间为0.2～5.0h；所述的步骤S2、S4中焙烧的升温速率为0.1～20℃/min。The method for producing a silicon oxide composite negative electrode material for a lithium ion battery according to claim 1, wherein the mixing speed of the mixing in the steps S1 and S3 is 100-2000rpm and the mixing time is 0.2-5.0h; The heating rate of the baking in steps S2 and S4 is 0.1-20 ° C / min.
  7. 如权利要求1所述的锂离子电池氧化亚硅复合负极材料的制法，其特征在于，所述的步骤S2中酸洗除杂的酸液的浓度为0.1～10.0mol/L，酸液为盐酸、硫酸、硝酸、磷酸、醋酸、碳酸、草酸中的一种或多种混合；焙烧冷却后混合料与酸液的质量比为1:0.5～1:15。The method for producing a silicon oxide composite negative electrode material for a lithium ion battery according to claim 1, wherein the concentration of the acid solution in the step S2 is 0.1-10.0mol / L, and the acid solution is One or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, carbonic acid, and oxalic acid are mixed; after roasting and cooling, the mass ratio of the mixture to the acid solution is 1: 0.5 ～ 1: 15.
  8. 如权利要求1所述的锂离子电池氧化亚硅复合负极材料的制法，其特征在于，所述的步骤S3中气相包覆：采用的反应气体为甲烷、乙烷、丙烷、乙烯、乙炔等中的一种或多种气体，气体流量为1L/min～8L/min，通气反应时间0.5～2h。The method for manufacturing a silicon oxide composite anode material for a lithium ion battery according to claim 1, wherein the gas-phase coating in the step S3: the reaction gas used is methane, ethane, propane, ethylene, acetylene, etc. One or more of the gases, the gas flow rate is 1L / min ~ 8L / min, the ventilation reaction time is 0.5 ~ 2h.
  9. 一种采用如权利要求1-8任一所述的锂离子电池氧化亚硅复合负极材料的制法而得到的锂离子电池氧化亚硅复合负极材料，其特征在于，是以氧化亚硅为基体、导电碳材料为包覆层而形成的氧化亚硅/碳材料核壳结构的氧化亚硅复合负极材料。A silicon oxide composite anode material for a lithium ion battery obtained by using the method for manufacturing a silicon oxide composite anode material for a lithium ion battery according to any one of claims 1-8, characterized in that it uses silicon oxide as a matrix 2. The conductive carbon material is a SiO 2 / carbon material core-shell structure SiO 2 composite anode material formed by coating.
  10. 如权利要求9所述的锂离子电池氧化亚硅复合负极材料，其特征在于，该锂离子电池氧化亚硅复合负极材料的粒径D50为0.1～100μm。The silicon oxide composite negative electrode material for a lithium ion battery according to claim 9, wherein the particle size D50 of the silicon oxide composite negative electrode material for the lithium ion battery is 0.1 to 100 μm.
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CN104671247A (en) * 2015-02-11 2015-06-03 武汉科技大学 Method for preparing superfine nano-silicon by taking silicon-containing biomass as raw material as well as prepared superfine nano-silicon and application thereof

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