WO2021057923A1 - 复合负极材料及其制备方法和锂离子电池 - Google Patents

复合负极材料及其制备方法和锂离子电池 Download PDF

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WO2021057923A1
WO2021057923A1 PCT/CN2020/117889 CN2020117889W WO2021057923A1 WO 2021057923 A1 WO2021057923 A1 WO 2021057923A1 CN 2020117889 W CN2020117889 W CN 2020117889W WO 2021057923 A1 WO2021057923 A1 WO 2021057923A1
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silicon
negative electrode
carbon
electrode material
peak
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PCT/CN2020/117889
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English (en)
French (fr)
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庞春雷
孔一鸣
梁腾宇
任建国
贺雪琴
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贝特瑞新材料集团股份有限公司
惠州市鼎元新能源科技有限公司
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Priority to JP2021569999A priority Critical patent/JP7317145B2/ja
Priority to US17/616,080 priority patent/US20220320505A1/en
Priority to EP20869082.6A priority patent/EP3965192A4/en
Priority to KR1020217029916A priority patent/KR20210129691A/ko
Publication of WO2021057923A1 publication Critical patent/WO2021057923A1/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
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    • 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
    • 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
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    • 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
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    • 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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    • H01M4/00—Electrodes
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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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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/62—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
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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    • 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

  • This application belongs to the technical field of battery materials, and relates to a negative electrode material and a preparation method thereof and a lithium ion battery, and in particular to a composite negative electrode material and a preparation method thereof, and a lithium ion battery.
  • Lithium ion battery is a kind of secondary battery (rechargeable battery), which mainly relies on the movement of lithium ions between the positive and negative electrodes to work.
  • Li + intercalates and deintercalates back and forth between the two electrodes: when charging, Li + is deintercalated from the positive electrode and inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true during discharge.
  • the negative electrode of a lithium ion battery is made by mixing the negative active material carbon material or non-carbon material, binder and additives to form a paste glue that is uniformly applied to both sides of the copper foil, dried and rolled.
  • the key to the successful manufacture of lithium-ion batteries lies in the preparation of negative electrode materials that can reversibly de-intercalate lithium ions.
  • the negative electrode materials that have been actually used in lithium-ion batteries are generally carbon materials, such as graphite, soft carbon (such as coke, etc.), hard carbon, and so on.
  • the anode materials being explored include nitrides, PAS, tin-based oxides, tin alloys, nano-anode materials, and other intermetallic compounds.
  • the composite negative electrode material includes the negative electrode material and the metal film and metal oxide film coated on the surface thereof, and the coated metal film or metal oxide film adopts magnetron sputtering Prepared by shot coating method.
  • the modified silicon-based negative electrode material includes a silicon-based negative electrode substrate in which lithium ions are also embedded.
  • the preparation method includes the steps of preparing a lithium-containing aromatic compound solution and the steps of performing lithium intercalation treatment on the silicon-based negative electrode substrate.
  • the silicon oxide composite material is composed of silicon oxide powder and a conductive carbon layer uniformly and densely coated on the surface of the silicon oxide powder.
  • the purpose of the present application is to provide a composite negative electrode material, a preparation method thereof, and a lithium ion battery.
  • the composite negative electrode material provided by the present application has the advantages of high cycle capacity retention, good rate performance, and low high-temperature aging loss.
  • the present application provides a composite negative electrode material, the composite negative electrode material includes silicon-containing particles and a carbon coating layer, and the carbon coating layer covers at least part of the surface of the silicon-containing particles;
  • the composite negative electrode material has a characteristic silicon peak A between 450 cm -1 and 550 cm -1 , a characteristic carbon peak B between 1300 cm -1 and 1400 cm -1, and a characteristic peak B between 1530 cm -1 and 1630 cm -1 There is a characteristic peak C of carbon, and a characteristic peak D of the graphene structure between 2500 cm -1 and 2750 cm -1.
  • the Raman spectrum peak of the composite negative electrode material provided in the present application has the characteristic peak D of the graphene structure, indicating that the carbon coating layer contains a small amount of graphene structure, and the carbon coating layer containing the graphene structure can improve the electrical conductivity of the product.
  • the rate performance and the uniformly grown graphene structure can further improve the stability of the solid-liquid interface between the surface of the product particles and the electrolyte, form a uniform SEI film, improve the high-temperature storage performance of the product, and reduce the high-temperature aging loss.
  • the silicon peak intensity I A of the peak A to the peak D graphene structure characteristic peak intensity ratio I A I D / I D is greater than 0.1 and It is less than 30, and the ratio I D /I B of the peak intensity I D of the characteristic peak D of the graphene structure to the peak intensity I B of the characteristic carbon peak B is greater than 0 and less than 1.
  • the composite negative electrode material satisfies at least one of the following conditions a to f:
  • the silicon-containing particles include at least one of Si, SiO x and silicate, wherein 0 ⁇ x ⁇ 2;
  • the average particle size of the silicon-containing particles is 0.1um to 20um;
  • the specific surface area of the silicon-containing particles is greater than 150 cm 2 /g;
  • the carbon coating layer is an inorganic carbon material layer
  • the thickness of the carbon coating layer is 10 nm to 300 nm;
  • the mass fraction of the carbon coating layer is 1% to 65%.
  • this application provides a method for preparing a composite negative electrode material.
  • the method includes the following steps:
  • a reaction gas is introduced to react with silicon-containing particles, and the reaction temperature is 700°C to 1450°C.
  • the reaction gas includes a carbon-containing gas, so that at least part of the surface of the silicon-containing particles forms a carbon coating layer , To obtain the composite negative electrode material.
  • the silicon-containing particulate material is heated to a preset temperature, and then the carbon-containing gas is used to react on the surface of the silicon-containing particles.
  • the site grows on at least part of the surface of the silicon-containing particles, and the carbon coating layer containing the graphene structure can increase the conductivity of the product and increase the rate performance; instead of directly using graphene for coating, it greatly reduces the difficulty of preparation.
  • the entire preparation process has simple operation, short flow, mature technology, low production difficulty, and controllable cost, which is conducive to application in large-scale industrial production.
  • the method satisfies at least one of the following conditions a to f:
  • the silicon-containing particles include at least one of Si, SiO x and silicate, wherein 0 ⁇ x ⁇ 2;
  • the average particle size of the silicon-containing particles is 0.1um to 20um;
  • the specific surface area of the silicon-containing particles is greater than 150 cm 2 /g;
  • the carbon coating layer is an inorganic carbon material layer
  • the thickness of the carbon coating layer is 10 nm to 300 nm;
  • the mass fraction of the carbon coating layer is 1% to 65%.
  • the method satisfies at least one of the following conditions a to b:
  • the protective atmosphere includes at least one of nitrogen, helium, neon, argon, krypton and xenon;
  • the carbon-containing gas includes at least one of methane, acetylene, ethylene, propyne, propylene, toluene vapor, benzene vapor, acetone vapor, and formaldehyde vapor.
  • the reaction gas further includes an auxiliary gas, and the auxiliary gas includes hydrogen.
  • the molar ratio of the carbon-containing gas to the auxiliary gas is (2-10):1.
  • the method satisfies at least one of the following conditions a to d:
  • the method of the reaction is chemical vapor deposition
  • the method of the reaction is chemical vapor deposition, and the reaction temperature of the chemical vapor deposition is 700°C to 1150°C;
  • the method of the reaction is chemical vapor deposition, and the holding time of the chemical vapor deposition is 3h-16h;
  • the method of the reaction is chemical vapor deposition, and the reaction pressure of the chemical vapor deposition is 1.0 atm to 10.0 atm.
  • the method includes the following steps:
  • the chemical vapor deposition is carried out by introducing a reaction gas, the reaction gas including a carbon-containing gas, so that at least part of the surface of the silicon-containing particles forms a carbon coating layer to obtain a composite negative electrode material.
  • the method includes the following steps:
  • the carbon-containing gas and hydrogen are introduced into the silicon-containing particles at a molar ratio of (2-10):1 to perform chemical vapor deposition reaction, the reaction pressure is controlled to be 1.0atm-10.0atm, and the temperature is maintained for 3h-16h, so that the silicon-containing A carbon coating layer is formed on at least part of the surface of the particles to obtain the composite negative electrode material.
  • the present application provides a lithium ion battery, the lithium ion battery comprising the composite negative electrode material of the first aspect described above or the composite negative electrode material prepared according to the preparation method of the second aspect described above.
  • the composite anode material provided by this application has unique Raman spectral peaks and graphene structure characteristic peak D, indicating that the carbon coating layer contains a small amount of graphene structure, and the carbon coating layer containing the graphene structure can improve the product Conductivity, increase rate performance, and the uniformly grown graphene structure can further improve the stability of the solid-liquid interface between the particle surface of the product and the electrolyte, form a uniform SEI film, and improve the high-temperature storage performance of the product.
  • the composite anode material has a cycle capacity retention High rate, good rate performance, low temperature aging loss and other advantages.
  • the carbon-containing gas is subjected to chemical vapor deposition on the surface of the silicon-containing particles by using a carbon-containing gas to form a carbon coating layer in situ, and
  • the carbon coating layer contains a small amount of graphene instead of directly using graphene for coating, which greatly reduces the difficulty of preparation.
  • the entire preparation process has simple operation, short flow, mature technology, low production difficulty, and controllable cost, which is conducive to application in large-scale industrial production.
  • Fig. 1 is a process flow diagram of a method for preparing a composite negative electrode material provided by this application;
  • Example 2 is a Raman spectrum of the composite anode material prepared in Example 1;
  • Figure 3 is a cycle performance curve of the composite negative electrode material prepared in Example 1;
  • Example 4 is a Raman spectrum of the composite anode material prepared in Example 2.
  • Figure 5 is a cycle performance curve of the composite negative electrode material prepared in Example 2.
  • Figure 6 is a Raman spectrum of the composite negative electrode material prepared in Comparative Example 1;
  • FIG. 7 is a cycle performance curve of the composite negative electrode material prepared in Comparative Example 1.
  • an embodiment of the present application provides a composite negative electrode material.
  • the composite negative electrode material includes silicon-containing particles and a carbon coating layer.
  • the carbon coating layer covers the silicon-containing particles. At least part of the surface.
  • the composite negative electrode material having between 450 ⁇ 550cm -1 silicon characteristic peaks A, Room B having characteristic peaks in carbon 1300 ⁇ 1400cm -1, at 1530 ⁇ 1630cm -1 among carbon peaks characteristic C, There is a characteristic peak D of graphene structure between 2500 and 2750 cm -1.
  • characteristic peak A is a characteristic peak of silicon
  • characteristic peak B and characteristic peak C are characteristic peaks of carbon
  • characteristic peak D is a characteristic peak of graphene structure.
  • the carbon coating layer containing the graphene structure is grown in situ on at least part of the surface of the silicon-containing particles.
  • the carbon coating layer containing the graphene structure can increase the electrical conductivity of the product and increase the rate performance.
  • the uniformly grown graphene structure can further Improve the stability of the solid-liquid interface between the particle surface of the product and the electrolyte to form a uniform SEI film, improve the high-temperature storage performance of the product, and reduce the high-temperature aging loss.
  • the composite negative electrode material with special Raman spectrum characteristics provided in this application has the advantages of high cycle capacity retention, good rate performance, and low high-temperature aging loss.
  • the silicon peak intensity I A of the peak A to the peak D graphene structure characteristic peak intensity ratio I A I D / I D is greater than 0.1 and less than 30, for example, I a / I D is 0.2,0.5,1,5,10,15,20,25 or the like 29, and the peak intensity I D D graphene structure characteristic peak and characteristic peak of the carbon B
  • the ratio I D /I B of the peak intensity I B is greater than 0 and less than 1, for example, I D /I B is 0.1, 0.2, 0.32, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9.
  • I A / I D may represent the uniformity of the growth of graphene structure, the smaller the value, the more uniform the growth of graphene structure , But if the value is less than 0.1, it means that the thickness of the carbon coating layer is too large, which will affect the transmission of lithium ions and cause performance degradation. Therefore, this application realizes the product graphene by controlling 0.1 ⁇ I A /I D ⁇ 30 The structure grows uniformly and the thickness of the carbon coating layer is appropriate, resulting in better product performance.
  • Characteristic peaks B and peaks C is a carbon material characteristic peaks, characteristic peaks D graphene structure characteristic peaks, characteristic peaks B may represent a carbon material is amorphous or defect structure sheet edge, so the I D / I B may be used to characterize
  • the ratio of the graphene structure to the defect structure in the product, I D /I B ⁇ 1 indicates that the composite anode material of this application is obtained by in-situ growth, and the carbon coating layer contains a large amount of fine graphene structure instead of directly using graphite
  • the olefin sheet coats the silicon-containing particles, which greatly reduces the difficulty of preparation and has the advantages of high productivity and controllable cost.
  • the carbon coating layer is an inorganic carbon material layer.
  • the carbon coating layer covers the surface of the silicon-containing particles.
  • the surface referred to in this application is not only the flat surface of the particles.
  • the carbon coating layer can also be filled in the cracks, pores and other structures on the surface of the particles. , It is not limited here.
  • the mass fraction of the carbon coating layer is 1%-65%, for example, 1%, 10%, 20%, 30%, 40%, 50%, 60% Or 65%, etc., but not limited to the listed values, and other unlisted values within this range of values are also applicable.
  • the mass fraction of the carbon coating layer is less than 1%, the coating amount will be insufficient, and the product performance cannot be fully utilized.
  • the mass fraction of the carbon coating layer higher than 65% will cause the carbon coating amount to be too high and affect At the same time, the capacity hinders the transmission of lithium ions and reduces the overall performance of the negative electrode material.
  • the thickness of the carbon coating layer is 10 nm to 300 nm, for example, it may be 10 nm, 20 nm, 50 nm, 80 nm, 100 nm, 150 nm, 200 nm, 250 nm, or 300 nm, etc., However, it is not limited to the listed values, and other unlisted values within this range of values are also applicable. If the carbon coating layer is too thick, the lithium ion transmission efficiency is reduced, which is not conducive to the large-rate charge and discharge of the material, and the overall performance of the negative electrode material is reduced. The carbon coating layer is too thin, which is not conducive to increasing the conductivity of the negative electrode material and suppressing the volume expansion of the material The performance is weak, resulting in a long-cycle performance price difference.
  • the silicon-containing particles include at least one of Si, SiO x and silicate, where 0 ⁇ x ⁇ 2.
  • the silicon-containing particles in this application do not limit the specific spatial structure, particle size, morphology, doping, silicon-carbon composite, etc., and different silicon-containing particles only need to fine-tune the specific preparation parameters to obtain the composite anode material proposed in this application.
  • the average particle size of the silicon-containing particles is 0.1um-20um, for example, it can be 0.1um, 0.5um, 1um, 3um, 5um, 10um, 13um, 15um, 18um, 20um, etc.
  • the average particle size of the silicon-containing particles is controlled within the above range, which is beneficial to the improvement of the cycle performance of the negative electrode material.
  • the silicon-containing particles of surface area greater than 150cm 2 / g for example, be 150cm 2 / g, 180cm 2 / g, 200cm 2 / g, 250cm 2 / g, 300cm 2 / g, 400cm 2 /g or 500cm 2 /g, etc.
  • the specific surface area of the silicon-containing particles within the above range is beneficial to improve the primary efficiency of the lithium battery made of the negative electrode material, and is beneficial to improve the cycle performance of the negative electrode material.
  • x is 0.1, 0.2, 0.5, 0.8, 1, 1.2, 1.5, 1.7, or 1.9.
  • the present application provides a method for preparing a composite negative electrode material, the method includes the following steps:
  • a reaction gas is introduced to react with silicon-containing particles, and the reaction temperature is 700°C to 1450°C.
  • the reaction gas includes a carbon-containing gas, so that at least part of the surface of the silicon-containing particles forms a carbon coating layer , To obtain the composite negative electrode material.
  • the method provided in the present application reacts carbon-containing gas with silicon-containing particles at 700°C to 1450°C, and carbon is grown in situ on at least part of the surface of the silicon-containing particles to form a carbon coating layer.
  • the carbon coating layer has graphene.
  • the structure can improve the conductivity of the product and the rate performance.
  • the uniformly grown graphene structure can further improve the stability of the solid-liquid interface between the surface of the product particles and the electrolyte, forming a uniform SEI film, improving the high-temperature storage performance of the product, and reducing the high-temperature aging loss .
  • the silicon-containing particles include at least one of Si, SiO x and silicate, where 0 ⁇ x ⁇ 2.
  • the silicon-containing particles in this application do not limit the specific spatial structure, particle size, morphology, doping, silicon-carbon composite, etc., and different silicon-containing particles only need to fine-tune the specific preparation parameters to obtain the composite anode material proposed in this application.
  • the average particle size of the silicon-containing particles is 0.1um-20um, for example, it can be 0.1um, 0.5um, 1um, 3um, 5um, 10um, 13um, 15um, 18um, 20um, etc.
  • the average particle size of the silicon-containing particles is controlled within the above range, which is beneficial to the improvement of the cycle performance of the negative electrode material.
  • the silicon-containing particles of surface area greater than 150cm 2 / g for example, be 150cm 2 / g, 180cm 2 / g, 200cm 2 / g, 250cm 2 / g, 300cm 2 / g, 400cm 2 /g or 500cm 2 /g, etc.
  • the specific surface area of the silicon-containing particles within the above range is beneficial to improve the primary efficiency of the lithium battery made of the negative electrode material, and is beneficial to improve the cycle performance of the negative electrode material.
  • x is 0.1, 0.2, 0.5, 0.8, 1, 1.2, 1.5, 1.7, or 1.9.
  • the reaction gas and the silicon-containing particulate material undergo a chemical vapor deposition reaction.
  • the preparation method provided in this application can be prepared by simple chemical vapor deposition to obtain the composite negative electrode material described in this application.
  • the composite negative electrode material in the Raman spectrum, has a characteristic silicon peak A between 450 and 550 cm -1 , a characteristic carbon peak B between 1300 and 1400 cm -1, and a characteristic peak B between 1530 and 1630 cm -1 carbon peaks between -1 C, at between 2500 ⁇ 2750cm -1 characteristic peak having a graphene structure D.
  • the ratio I D /I B of the peak intensity I D of the carbon characteristic peak B to the peak intensity I B of the carbon characteristic peak B is greater than 0 and less than 1.
  • the protective atmosphere includes at least one of nitrogen, helium, neon, argon, krypton, and xenon.
  • the carbon-containing gas includes at least one of methane, acetylene, ethylene, propyne, propylene, toluene vapor, benzene vapor, acetone vapor, and formaldehyde vapor.
  • the reaction gas further includes auxiliary gas.
  • the auxiliary gas includes hydrogen.
  • Hydrogen can control the reaction rate of certain carbon-containing gases (such as acetylene), making it easier to produce graphene structures at large flow rates, so as to improve production efficiency.
  • the molar ratio of the carbon-containing gas and the auxiliary gas is (2-10):1, such as 2:1, 3:1, 4:1, 5:1, 6:1, 7: 1, 8:1, 9:1 or 10:1, etc., but not limited to the listed values, other unlisted values within this range of values are also applicable.
  • the feed rate of the reaction gas is 0.1 to 6.0 L/min, for example, 0.1 L/min, 0.3 L/min, 0.5 L/min, 1.0 L/min, 2.0 L/min , 3.0L/min, 4.0L/min, 5.0L/min or 6.0L/min, etc., but not limited to the listed values, other unlisted values within this range of values are also applicable.
  • the feed rate of the reactive gas is too fast, the graphene structure will not be generated; if the feed rate of the reactive gas is too slow, the deposition efficiency will be too low, which will affect the productivity and practical value.
  • the method of the reaction is chemical vapor deposition
  • the reaction temperature of the chemical vapor deposition is 700°C to 1450°C, for example, 700°C, 800°C, 900°C, 1000°C, 1050°C, 1100°C, 1150°C, 1200°C, 1250°C, 1300°C, 1350°C, 1400°C or 1450°C, etc., but are not limited to the listed values, and other unlisted values within this range of values are equally applicable.
  • the reaction temperature is lower than 700°C, which affects the in-situ growth of the carbon coating layer containing the graphene structure, which will cause the graphene structure characteristic peak D to be unable to be observed in the Raman test of the product.
  • the reaction temperature of the chemical vapor deposition is 700°C to 1150°C, such as 700°C, 800°C, 900°C, 1000°C, 1050°C, or 1150°C, but is not limited to the listed values. , Other unlisted values within this value range also apply.
  • the reaction temperature if the reaction temperature is too high, it will cause the carbon coating layer to react with the silicon-containing core to produce electrochemically inert silicon carbide, which will degrade the electrochemical performance of the product; if the reaction temperature is too low, the graphene structure will not be formed. .
  • the holding time of the chemical vapor deposition is 3h-16h, for example, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h or 16h, etc., However, it is not limited to the listed values, and other unlisted values within this range of values are also applicable.
  • the reaction pressure of the chemical vapor deposition is 1.0atm-10.0atm, such as 1.0atm, 2.0atm, 4.0atm, 6.0atm, 7.0atm, 8.0atm, 9.0atm or 10.0atm, etc., but not It is not limited to the listed values, and other unlisted values within this range of values are also applicable.
  • the reaction pressure is too high, the reaction rate will be too slow, affecting productivity and practicability, and there is a safety risk; if the reaction pressure is too low, it will lead to an inert atmosphere that cannot ensure the reaction environment. If the pressure is lower than 1atm, it may even cause air to be sucked into the reaction chamber with high-temperature combustible gas, causing serious safety risks.
  • reaction gas flow rate, reaction temperature, reaction pressure, and holding time can make these operating conditions coordinate with each other, better improve the performance of the product, and ensure the appearance of the characteristic peak D representing the graphene structure.
  • the method includes the following steps S100-S200:
  • a reaction gas is introduced to perform chemical vapor deposition, and the reaction gas includes a carbon-containing gas, so that at least a part of the surface of the silicon-containing particles forms a carbon coating layer to obtain a composite negative electrode material.
  • the reaction is carried out in a chemical vapor deposition (CVD) device.
  • CVD chemical vapor deposition
  • the chemical vapor deposition apparatus includes, for example, a rotary chemical vapor deposition (CVD) reactor, a plasma enhanced chemical vapor deposition (CVD) reactor, a chemical vapor deposition (CVD) tube furnace, or a fluidized bed Any one or a combination of at least two of them.
  • CVD rotary chemical vapor deposition
  • CVD plasma enhanced chemical vapor deposition
  • CVD chemical vapor deposition
  • CVD chemical vapor deposition
  • the carbon coating layer is an inorganic carbon material layer. It should be noted that the carbon coating layer covers the surface of the silicon-containing particles. The surface referred to in this application is not only the flat surface of the particles. The carbon coating layer can also be filled in the cracks, pores and other structures on the surface of the particles. , It is not limited here.
  • the mass fraction of the carbon coating layer is 1%-65%, for example, 1%, 10%, 20%, 30%, 40%, 50%, 60% Or 65%, etc., but not limited to the listed values, and other unlisted values within this range of values are also applicable.
  • the mass fraction of the carbon coating layer is less than 1%, the coating amount will be insufficient, and the product performance cannot be fully utilized.
  • the mass fraction of the carbon coating layer higher than 65% will cause the carbon coating amount to be too high and affect At the same time, the capacity hinders lithium ion transmission and reduces the overall performance of the negative electrode material.
  • the thickness of the carbon coating layer is 10 nm to 300 nm, for example, it may be 10 nm, 20 nm, 50 nm, 80 nm, 100 nm, 150 nm, 200 nm, 250 nm, or 300 nm, etc., However, it is not limited to the listed values, and other unlisted values within this range of values are also applicable. If the carbon coating layer is too thick, the lithium ion transmission efficiency is reduced, which is not conducive to the large-rate charge and discharge of the material, and the overall performance of the negative electrode material is reduced. The carbon coating layer is too thin, which is not conducive to increasing the conductivity of the negative electrode material and suppressing the volume expansion of the material The performance is weak, resulting in a long-cycle performance price difference.
  • the preparation method further includes: natural cooling after the chemical vapor deposition reaction.
  • the method includes the following steps:
  • the carbon-containing gas and hydrogen are introduced into the silicon-containing particles at a molar ratio of (2-10):1 to perform chemical vapor deposition reaction, the reaction pressure is controlled to be 1.0atm-10.0atm, and the temperature is maintained for 3h-16h, so that the silicon-containing A carbon coating layer is formed on at least part of the surface of the particles to obtain the composite negative electrode material.
  • the present application provides a lithium ion battery, the lithium ion battery comprising the composite negative electrode material described in the first aspect or the composite negative electrode material produced by the preparation method described in the second aspect.
  • the composite negative electrode material was prepared according to the following method:
  • the Raman spectroscopy test is carried out (using Japan HORIBA XPLORA laser confocal Raman spectrometer, using laser wavelength 532nm, test range 100cm -1 to 2800cm -1 , other embodiments
  • the Raman spectrometer of this model and the comparative example were used for testing, and the test conditions were the same as in Example 1) and carbon content test (using the G4 ICARUS HF infrared sulfur carbon analyzer of Germany Bruker for testing, other examples and comparative examples This type of tester is used to test the carbon content).
  • the negative electrode material prepared in this embodiment includes a SiO core and an inorganic carbon material coating layer covering the surface of the SiO core, and the mass fraction of the carbon coating layer is 2.53%.
  • the silicon characteristic peak A is at 504 cm -1
  • the carbon characteristic peak B is at 1352 cm -1
  • the carbon characteristic peak C is at 1601 cm -1
  • the graphene structure characteristic peak D is at -1 2695cm
  • peak intensity I A 90.2
  • I B 109.0
  • I D 54.5
  • I D / I B is 0.50.
  • Figure 2 is the Raman spectrum of the composite negative electrode material prepared in this embodiment. From the figure, it can be seen that the product has characteristic peaks of the graphene structure.
  • Figure 3 is the cycle performance curve of the composite negative electrode material prepared in this example. It can be seen from the figure that the product has better cycle performance and better rate performance (1C/0.1C).
  • the composite negative electrode material was prepared according to the following method:
  • porous silicon powder (specific surface area>150cm 2 /g) and add it to a 5L experimental batch rotary CVD furnace, and pass nitrogen into the furnace for atmosphere replacement. After the oxygen content in the exhaust gas is less than 200ppm, continue When nitrogen is introduced, the temperature is increased. After the temperature is increased to 935°C, 1.0L/min of methane is introduced using nitrogen as the carrier gas, and the reaction pressure is maintained at 2.0atm. After the reaction continues for 10 hours, the methane gas is cut off and the temperature begins to cool down naturally.
  • the composite negative electrode material Take 150g of porous silicon powder (specific surface area>150cm 2 /g) and add it to a 5L experimental batch rotary CVD furnace, and pass nitrogen into the furnace for atmosphere replacement. After the oxygen content in the exhaust gas is less than 200ppm, continue When nitrogen is introduced, the temperature is increased. After the temperature is increased to 935°C, 1.0L/min of methane is introduced using nitrogen as the carrier gas, and the reaction pressure is maintained at 2.0atm.
  • the negative electrode material prepared in this embodiment includes a porous silicon core and an inorganic carbon material coating layer covering the surface of the porous silicon core, and the mass fraction of the carbon coating layer is 41.2%.
  • the silicon characteristic peak A is at 501 cm -1
  • the carbon characteristic peak B is at 1348 cm -1
  • the carbon characteristic peak C is at 1591 cm -1
  • the graphene structure characteristic peak D is at At 2682 cm -1
  • the peak intensity I A /I D is 4.35
  • I D /I B is 0.34.
  • Figure 4 is the Raman spectrum of the composite negative electrode material prepared in this embodiment. From this figure, it can be seen that the product has characteristic peaks of graphene structure.
  • Figure 5 is the cycle performance curve of the composite negative electrode material prepared in this example. It can be seen from the figure that the product has better cycle performance and better rate performance (1C/0.1C).
  • the negative electrode material prepared in this embodiment includes a SiO core and an inorganic carbon material coating layer covering the surface of the SiO core, and the mass fraction of the carbon coating layer is 4.3%.
  • Raman spectrum of the negative electrode material prepared in the present embodiment the silicon characteristic peaks at 503cm -1 A, the carbon B characteristic peaks at 1351cm -1, the carbon peaks at 1597cm -1 in the C, D graphene structure characteristic peaks At 2691 cm -1 , the peak intensity I A /I D is 6.73, and I D /I B is 0.34.
  • the composite negative electrode material prepared in this embodiment includes a silicon oxide/silicon/lithium metasilicate core and an inorganic carbon material coating layer covering the surface of the silicon oxide/silicon/lithium metasilicate core.
  • the quality of the carbon coating layer The score is 2.5%.
  • the silicon characteristic peak A is at 501 cm -1
  • the carbon characteristic peak B is at 1347 cm -1
  • the carbon characteristic peak C is at 1598 cm -1
  • the graphene structure characteristic peak D is at At 2692 cm -1
  • the peak intensity I A /I D is 8.59
  • I D /I B is 0.24.
  • the negative electrode material prepared in this embodiment includes a SiO core and an inorganic carbon material coating layer covering the surface of the SiO core, and the mass fraction of the carbon coating layer is 4.1%.
  • the silicon characteristic peak A is at 501 cm -1
  • the carbon characteristic peak B is at 1347 cm -1
  • the carbon characteristic peak C is at 1592 cm -1
  • the graphene structure characteristic peak D is at At 2685 cm -1
  • the peak intensity I A /I D is 6.68
  • I D /I B is 0.30.
  • reaction pressure is 13 atm
  • other raw materials and operating conditions are the same as those in Embodiment 1.
  • the negative electrode material prepared in this embodiment includes a SiO core and an inorganic carbon material coating layer covering the surface of the SiO core, and the mass fraction of the carbon coating layer is 0.7%.
  • the silicon characteristic peak A is at 505 cm -1
  • the carbon characteristic peak B is at 1352 cm -1
  • the carbon characteristic peak C is at 1597 cm -1
  • the graphene structure characteristic peak D is at At 2701 cm -1
  • the peak intensity I A /I D is 19.2
  • I D /I B is 0.61.
  • reaction temperature is 1450° C.
  • other raw materials and operating conditions are the same as those in Embodiment 1.
  • the negative electrode material prepared in this embodiment includes a SiO core and an inorganic carbon material coating layer covering the surface of the SiO core, and the mass fraction of the carbon coating layer is 4.3%.
  • the silicon characteristic peak A is at 502 cm -1
  • the carbon characteristic peak B is at 1342 cm -1
  • the carbon characteristic peak C is at 1601 cm -1
  • the graphene structure characteristic peak D is at At 2694 cm -1
  • the peak intensity I A /I D is 5.4
  • I D /I B is 0.24.
  • the negative electrode material prepared in this embodiment includes a SiO core and an inorganic carbon material coating layer covering the surface of the SiO core, and the mass fraction of the carbon coating layer is 6.4%.
  • Raman spectrum of the negative electrode material prepared in the present embodiment the silicon characteristic peaks at 503cm -1 A, the carbon B characteristic peaks at 1341cm -1, the carbon peaks at 1602cm -1 in the C, D graphene structure characteristic peaks At 2696 cm -1 , the peak intensity I A /I D is 4.5, and I D /I B is 0.16.
  • the negative electrode material was prepared according to the following method:
  • the mass fraction of the carbon coating layer of the negative electrode material is 4.21% (that is, the carbon content), and the characteristic peak D of the graphene structure is not observed in the Raman test result.
  • Figure 5 is the Raman spectrum of the composite negative electrode material prepared in the comparative example. It can be seen from the figure that the product has no graphene structure.
  • Figure 6 is the cycle performance curve of the composite negative electrode material prepared in the comparative example. It can be seen from the figure that both the cycle performance and rate performance of the product have deteriorated.
  • the negative electrode material obtained in this comparative example was subjected to a Raman test, and as a result, the characteristic peak D of the graphene structure was not observed.
  • the negative electrode material prepared in each example and comparative example was mixed with a commercial graphite negative electrode in a ratio of 10:90 as the negative electrode active material, and the graphite was selected as the artificial graphite S360 series produced by Shenzhen Beterui New Energy Materials Co., Ltd.
  • the negative electrode material prepared in each example and comparative example is used as the negative electrode active material.
  • the negative electrode material prepared in each example and comparative example was mixed with a commercial graphite negative electrode in a ratio of 10:90 as the negative electrode active material, and the graphite was selected as the artificial graphite S360 series produced by Shenzhen Beterui New Energy Materials Co., Ltd., the negative electrode
  • the mass ratio of the negative active material, the conductive agent (Super P) and the binder (CMC+SBR) in the electrode sheet coating is 95.8:1.0:3.2
  • the positive electrode active material NCA ternary material, Shenzhen Produced by Beiterui New Energy Materials Co., Ltd., product name: N8-S
  • conductive agent (Super P) conductive agent
  • PVDF binder
  • the blue battery test system is used to conduct electrochemical tests on the above-mentioned batteries.
  • the button cell is cycled at 0.1C, 0.2C, and 0.5C for one week, and then charged and discharged at 1C for 47 weeks, and the capacity of the 50th week is divided by the capacity of the first week to obtain the 50-week cycle capacity retention rate of the product. , 0.1C capacity divided by 1C capacity is used to evaluate product rate performance.
  • the composite negative electrode material prepared in Examples 1 to 5 embodiment has a unique Raman spectrum peak, peak D is a characteristic peaks graphene structure, and I A / I D and I D / I B is better, so that the composite negative electrode material provided by the foregoing embodiment has the advantages of high cycle capacity retention, good rate performance, and low high-temperature aging loss.
  • the reaction pressure of Example 6 is too high, resulting in too low reaction rate and low carbon content.
  • the reaction pressure of Example 1 is 1.2 atm.
  • the capacity retention rate and cycle retention of the battery made of the composite anode material according to Example 1 are The performances such as rate and aging loss are better than those of Example 6. It can be seen that it is more appropriate to control the reaction pressure in the range of 1.0 atm to 10.0 atm, which can not only ensure the performance of the product, but also reduce production safety risks.
  • the reaction temperature of Example 7 is too high to the boundary value, which causes a small amount of carbon coating layer to react with silicon-containing particles to produce a small amount of electrochemically inert silicon carbide.
  • the reaction temperature of Example 1 is 900°C, and the reaction is relatively mild.
  • the first-turn reversible specific capacity, capacity retention rate, cycle retention rate and aging loss of the battery made of the composite negative electrode material of Example 1 are better than those of Example 7. It can be seen that the reaction temperature is controlled at 700°C to 1150. The °C range is more suitable, which can guarantee the electrochemical capacity and rate performance of the product.
  • Example 8 The auxiliary gas hydrogen is not used in Example 8. Compared with Example 3, Example 8 needs to use a lower acetylene flow rate to produce the graphene structure, which makes the reaction time required in Example 8 longer and lowers the production efficiency. It can be seen that the addition of auxiliary gas can control the reaction rate of acetylene gas and improve the efficiency of graphene structure generation.
  • Example 1 the methane in Example 1 was replaced with acetylene and the reaction temperature was too low, resulting in the failure of the graphene structure to be generated.
  • the carbon coating layer containing the graphene structure can improve the stability of the solid-liquid interface between the surface of the composite negative electrode material particle and the electrolyte, forming a uniform SEI film, making the first circle of the battery made of the composite negative electrode material containing the graphene structure reversible
  • Various properties such as specific capacity, capacity retention rate, cycle retention rate and aging loss have all been improved.
  • the applicant declares that this application uses the above-mentioned embodiments to illustrate the detailed methods of this application, but this application is not limited to the above-mentioned detailed methods, which does not mean that this application must rely on the above-mentioned detailed methods to be implemented.
  • any improvement to this application, the equivalent replacement of each raw material of the product of this application, the addition of auxiliary components, the selection of specific methods, etc. fall within the scope of protection and disclosure of this application.

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Abstract

本申请提供了一种复合负极材料及其制备方法和锂离子电池。所述复合负极材料包括含硅颗粒和碳包覆层，所述碳包覆层包覆所述含硅颗粒的至少部分表面，在拉曼光谱中，所述复合负极材料在450cm -1～550cm -1间具有硅特征峰A，在1300cm -1～1400cm -1间具有碳特征峰B，在1530cm -1～1630cm -1间有碳特征峰C，在2500cm -1～2750cm -1间具有石墨烯结构特征峰D。所述制备方法包括：在保护性气氛下，通入反应气体与含硅颗粒进行反应，反应温度为700℃～1450℃，所述反应气体包括含碳气体，使得所述含硅颗粒的至少部分表面形成碳包覆层，得到所述复合负极材料。所述复合负极材料具有循环容量保持率高、倍率性能好、高温老化损失小等优点。

Description

复合负极材料及其制备方法和锂离子电池
本申请要求于2019年9月26日提交中国专利局，申请号为2019109183208、发明名称为“一种复合负极材料及其制备方法和锂离子电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请属于电池材料技术领域，涉及一种负极材料及其制备方法和锂离子电池，尤其涉及一种复合负极材料及其制备方法和锂离子电池。
背景技术
锂离子电池是一种二次电池(充电电池)，它主要依靠锂离子在正极和负极之间移动来工作。在充放电过程中，Li +在两个电极之间往返嵌入和脱嵌：充电时，Li +从正极脱嵌，经过电解质嵌入负极，负极处于富锂状态；放电时则相反。
锂离子电池的负极是由负极活性物质碳材料或非碳材料、粘合剂和添加剂混合制成糊状胶合剂均匀涂抹在铜箔两侧，经干燥、辊压而成。锂离子电池能否成功地制成，关键在于能否制备出可逆地脱/嵌锂离子的负极材料。一般来说，选择一种好的负极材料应遵循以下原则：比能量高；相对锂电极的电极电位低；充放电反应可逆性好；与电解液和粘结剂的兼容性好；比表面积小(<10m 2/g)，真密度高(>2.0g/cm 3)；嵌锂过程中尺寸和机械稳定性好；资源丰富，价格低廉；在空气中稳定、无毒副作用。目前，已实际用于锂离子电池的负极材料一般都是碳素材料，如石墨、软碳(如焦炭等)、硬碳等。正在探索的负极材料有氮化物、PAS、锡基氧化物、锡合金、纳米负极材料，以及其他的一些金属间化合物等。
近年来，对高性能锂离子电池的需求日益迫切，以电子消费品、电动汽车等为代表的产品市场不断扩大，对高性能锂离子电池负极材料的需要也越来越迫切。
一种锂离子电池复合负极材料镀膜的改性方法，该方案中，复合负极材料包括负极材料及其表面包覆的金属膜、金属氧化膜，包覆的金属膜或金属氧化膜采用磁控溅射镀膜法制备。
另一种改性硅基负极材料及其制备方法与应用，该方案中，改性硅基负极材料包括硅基负极基材，在所述硅基负极基材中还嵌有锂离子。其制备方法包括配制含锂的芳烃化合物溶液的步骤和对硅基负极基材进行嵌锂处理的步骤。
又一种锂离子电池氧化亚硅复合负极材料、制备方法及其用途。所述氧化亚硅复合材料由氧化亚硅粉末和均匀致密涂覆在氧化亚硅粉末表面的导电碳层组成。
然而上述方案均存在着负极材料的循环性能和倍率性能有待提高的问题。
申请内容
基于此，本申请的目的在于提供一种复合负极材料及其制备方法和锂离子电池。 本申请提供的复合负极材料具有循环容量保持率高、倍率性能好、高温老化损失小等优点。
为达此目的，本申请采用以下技术方案：
第一方面，本申请提供一种复合负极材料，所述复合负极材料包括含硅颗粒和碳包覆层，所述碳包覆层包覆所述含硅颗粒的至少部分表面；
在拉曼光谱中，所述复合负极材料在450cm -1～550cm -1间具有硅特征峰A，在1300cm -1～1400cm -1间具有碳特征峰B，在1530cm -1～1630cm -1间有碳特征峰C，在2500cm -1～2750cm -1间具有石墨烯结构特征峰D。
本申请提供的复合负极材料的拉曼光谱峰中具有石墨烯结构特征峰D，说明其碳包覆层中含有少量石墨烯结构，含石墨烯结构的碳包覆层可提高产品电导率、提高倍率性能，均匀生长的上述石墨烯结构能够进一步提升产品颗粒表面与电解液的固液界面稳定，形成均一的SEI膜，提高产品的高温保存性能，降低高温老化损失。
在一种可行的实施方式中，在拉曼光谱中，所述硅特征峰A的峰强度I A与所述石墨烯结构特征峰D的峰强度I D的比值I A/I D大于0.1且小于30，且所述石墨烯结构特征峰D的峰强度I D与所述碳特征峰B的峰强度I B的比值I D/I B大于0且小于1。
在一种可行的实施方式中，所述复合负极材料满足以下条件a～f的至少一者：
a.所述含硅颗粒包括Si、SiO x和硅酸盐中的至少一种，其中，0<x<2；
b.所述含硅颗粒的平均粒径为0.1um～20um；
c.所述含硅颗粒的比表面积大于150cm 2/g；
d.所述碳包覆层为无机碳材料层；
e.所述碳包覆层的厚度为10nm～300nm；
f.在所述复合负极材料中，所述碳包覆层的质量分数为1％～65％。
第二方面，本申请提供一种复合负极材料的制备方法，所述方法包括以下步骤：
在保护性气氛下，通入反应气体与含硅颗粒进行反应，反应温度为700℃～1450℃，所述反应气体包括含碳气体，使得所述含硅颗粒的至少部分表面形成碳包覆层，得到所述复合负极材料。
本申请提供的复合负极材料的制备方法，将含硅颗粒材料加热至预设温度后，通过含碳气体，使得含碳气体在含硅颗粒表面进行反应，含有石墨烯结构的碳包覆层原位生长在含硅颗粒的至少部分表面，含石墨烯结构的碳包覆层可提高产品电导率、提高倍率性能；而非直接使用石墨烯进行包覆，大幅降低了制备难度。整个制备过程操作简单，流程短，工艺成熟，生产难度低，成本可控，有利于在工业化大生产中进行应用。
在一种可行的实施方式中，所述方法满足以下条件a～f的至少一者：
a.所述含硅颗粒包括Si、SiO x和硅酸盐中的至少一种，其中，0<x<2；
b.所述含硅颗粒的平均粒径为0.1um～20um；
c.所述含硅颗粒的比表面积大于150cm 2/g；
d.所述碳包覆层为无机碳材料层；
e.所述碳包覆层的厚度为10nm～300nm；
f.在所述复合负极材料中，所述碳包覆层的质量分数为1％～65％。
在一种可行的实施方式中，在拉曼光谱中，所述复合负极材料在450cm -1～550cm -1间具有硅特征峰A，在1300cm -1～1400cm -1间具有碳特征峰B，在1530cm -1～1630cm -1间有碳特征峰C，在2500cm -1～2750cm -1间具有石墨烯结构特征峰D；所述硅特征峰A的峰强度I A与所述石墨烯结构特征峰D的峰强度I D的比值I A/I D大于0.1且小于30，且所述石墨烯结构特征峰D的峰强度I D与所述碳特征峰B的峰强度I B的比值I D/I B大于0且小于1。
在一种可行的实施方式中，所述方法满足以下条件a～b的至少一者：
a.所述保护性气氛包括氮气、氦气、氖气、氩气、氪气和氙气中的至少一种；
b.所述含碳气体包括甲烷、乙炔、乙烯、丙炔、丙烯、甲苯蒸气、苯蒸气、丙酮蒸气和甲醛蒸气中的至少一种。
在一种可行的实施方式中，所述反应气体还包括辅助气体，所述辅助气体包括氢气。
在一种可行的实施方式中，所述含碳气体和所述辅助气体的摩尔比为(2～10)：1。
在一种可行的实施方式中，所述方法满足以下条件a～d的至少一者：
a.所述反应的方式为化学气相沉积；
b.所述反应的方式为化学气相沉积，所述化学气相沉积的反应温度为700℃～1150℃；
c.所述反应的方式为化学气相沉积，所述化学气相沉积的保温时间为3h～16h；
d.所述反应的方式为化学气相沉积，所述化学气相沉积的反应气压为1.0atm～10.0atm。
在一种可行的实施方式中，所述方法包括以下步骤：
在保护性气氛下，将含硅颗粒加热至700℃～1450℃；
通入反应气体进行化学气相沉积，所述反应气体包括含碳气体，使得含硅颗粒的至少部分表面形成碳包覆层，得到复合负极材料。
在一种可行的实施方式中，所述方法包括以下步骤：
在保护性气氛下，将含硅颗粒加热至700℃～1150℃；
将含碳气体与氢气按照摩尔比为(2～10)：1通入所述含硅颗粒中进行化学气相沉积反应，控制反应气压1.0atm～10.0atm，保温3h～16h，使得所述含硅颗粒的至少部分表面形成碳包覆层，得到所述复合负极材料。
第三方面，本申请提供一种锂离子电池，所述锂离子电池包含如上述第一方面的复合负极材料或根据上述第二方面的制备方法制得的复合负极材料。
与现有技术相比，本申请具有以下有益效果：
(1)本申请提供的复合负极材料具有独特的拉曼光谱峰具有石墨烯结构特征峰D，说明其碳包覆层中含有少量石墨烯结构，含石墨烯结构的碳包覆层可提高产品电导率、提高倍率性能，均匀生长的上述石墨烯结构能够进一步提升产品颗粒表面与电解液的固液界面稳定，形成均一的SEI膜，提高产品的高温保存性能，该复合负极材料具有循环容量保持率高、倍率性能好、高温老化损失小等优点。
(2)本申请提供的制备方法，将含硅颗粒材料加热至预设温度后，通过含碳气体，使得含碳气体在含硅颗粒表面进行化学气相沉积，原位生成碳包覆层，并且碳包覆层中含有少量石墨烯，而非直接使用石墨烯进行包覆，大幅降低了制备难度。整个制备过程操作简单，流程短，工艺成熟，生产难度低，成本可控，有利于在工业化大生产中进行应用。
附图说明
图1为本申请提供的复合负极材料的制备方法的工艺流程图；
图2为实施例1制备的复合负极材料的拉曼光谱；
图3为实施例1制备的复合负极材料的循环性能曲线；
图4为实施例2制备的复合负极材料的拉曼光谱；
图5为实施例2制备的复合负极材料的循环性能曲线；
图6为对比例1制备的复合负极材料的拉曼光谱；
图7为对比例1制备的复合负极材料的循环性能曲线。
具体实施方式
为更好地说明本申请，便于理解本申请的技术方案，下面对本申请进一步详细说明。但下述的实施例仅仅是本申请的简易例子，并不代表或限制本申请的权利保护范围，本申请保护范围以权利要求书为准。
以下为本申请典型但非限制性实施例：
第一方面，本申请实施例提供一种复合负极材料，所述复合负极材料包括所述复合负极材料包括含硅颗粒和碳包覆层，所述碳包覆层包覆所述含硅颗粒的至少部分表面。在拉曼光谱中，所述复合负极材料在450～550cm -1间具有硅特征峰A，在1300～1400cm -1间具有碳特征峰B，在1530～1630cm -1间有碳特征峰C，在2500～2750cm -1间具有石墨烯结构特征峰D。
本申请提供的复合负极材料的拉曼光谱中，特征峰A为硅特征峰，特征峰B和特征峰C为碳特征峰，特征峰D为石墨烯结构特征峰。上述含有石墨烯结构的碳包覆层原位生长在含硅颗粒的至少部分表面，含石墨烯结构的碳包覆层可提高产品电导率、提高倍率性能，均匀生长的上述石墨烯结构能够进一步提升产品颗粒表面与电解液的固液界面稳定，形成均一的SEI膜，提高产品的高温保存性能，降低高温老化损失。
本申请提供的这种具有特殊拉曼光谱特征的复合负极材料具有循环容量保持率高、倍率性能好、高温老化损失小等优点。
以下作为本申请可选的技术方案，但不作为对本申请提供的技术方案的限制，通过以下优选的技术方案，可以更好的达到和实现本申请的技术目的和有益效果。
作为本申请可选的技术方案，在拉曼光谱中，所述硅特征峰A的峰强度I A与所述石墨烯结构特征峰D的峰强度I D的比值I A/I D大于0.1且小于30，例如I A/I D为0.2、0.5、1、5、10、15、20、25或29等，且所述石墨烯结构特征峰D的峰强度I D与所述碳特征峰B的峰强度I B的比值I D/I B大于0且小于1，例如I D/I B为0.1、0.2、0.32、 0.4、0.5、0.6、0.7、0.8或0.9等。
在本申请中，特征峰A为硅特征峰，特征峰D为石墨烯结构特征峰，故I A/I D可表示石墨烯结构生长的均匀性，该值越小，石墨烯结构生长越均匀，但若该值低于0.1，说明碳包覆层厚度过大，反而会影响锂离子的传输，导致性能劣化，故本申请通过控制0.1<I A/I D<30，实现了产品石墨烯结构生长均匀且碳包覆层厚度适宜，得到了较好的产品性能。特征峰B和特征峰C为碳材料特征峰，特征峰D为石墨烯结构特征峰，特征峰B可表示碳材料中无定形或片层边缘的缺陷结构，故I D/I B可用于表征产品中石墨烯结构与缺陷结构的比例，I D/I B<1说明本申请的复合负极材料是利用原位生长得到的，碳包覆层中含有大量细密石墨烯结构，而非直接使用石墨烯片对含硅颗粒进行包覆，大幅降低了制备难度，具备生产性强、成本可控的优点。
作为本申请可选的技术方案，所述碳包覆层为无机碳材料层。
需要说明的是，碳包覆层包覆在含硅颗粒的表面，本申请中所指的表面不仅仅是颗粒的平整表面，碳包覆层还可以填充于颗粒表面的裂缝、孔道等结构内，在此不做限定。
在其中一些实施例中，在所述复合负极材料中，碳包覆层的质量分数为1％～65％，例如1％、10％、20％、30％、40％、50％、60％或65％等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。本申请中，碳包覆层的质量分数低于1％会导致包覆量不足，无法充分发挥该产品性能，碳包覆层的质量分数高于65％会导致碳包覆量过高，影响容量的同时阻碍锂离子传输，降低负极材料的综合性能。
在其中一些实施例中，在所述复合负极材料中，所述碳包覆层的厚度为10nm～300nm，例如可以是10nm、20nm、50nm、80nm、100nm、150nm、200nm、250nm或300nm等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。碳包覆层过厚，锂离子传输效率降低，不利于材料大倍率充放电，降低负极材料的综合性能，碳包覆层过薄，不利于增加负极材料的导电性且对材料的体积膨胀抑制性能较弱，导致长循环性能价差。
作为本申请可选的技术方案，所述含硅颗粒包括Si、SiO x和硅酸盐中的至少一种，其中，0<x<2。本申请中所述含硅颗粒不限定特定的空间结构、粒度、形貌、掺杂、硅碳复合等，不同的含硅颗粒仅需微调制备具体参数即可得到本申请提出的复合负极材料。
在其中一些实施例中，所述含硅颗粒的平均粒径为0.1um～20um，例如可以是0.1um、0.5um、1um、3um、5um、10um、13um、15um、18um、20um等。含硅颗粒的平均粒径控制在上述范围内，有利于负极材料循环性能的提升。
在其中一些实施例中，所述含硅颗粒的比表面积大于150cm 2/g，例如可以是150cm 2/g、180cm 2/g、200cm 2/g、250cm 2/g、300cm 2/g、400cm 2/g或500cm 2/g等。所述含硅颗粒的比表面积在上述范围内，有利于提高由该负极材料制成的锂电池的首次效率，有利于提高负极材料的循环性能。
在其中一些实施例中，所述SiO x中0<x<2，例如x为0.1、0.2、0.5、0.8、1、1.2、1.5、1.7或1.9等。
第二方面，本申请提供一种复合负极材料的制备方法，所述方法包括以下步 骤：
在保护性气氛下，通入反应气体与含硅颗粒进行反应，反应温度为700℃～1450℃，所述反应气体包括含碳气体，使得所述含硅颗粒的至少部分表面形成碳包覆层，得到所述复合负极材料。
本申请提供的方法将含碳气体与含硅颗粒在700℃～1450℃下进行反应，碳原位生长在含硅颗粒的至少部分表面，形成碳包覆层，该碳包覆层具有石墨烯结构，可提高产品电导率、提高倍率性能，均匀生长的石墨烯结构能够进一步提升产品颗粒表面与电解液的固液界面稳定，形成均一的SEI膜，提高产品的高温保存性能，降低高温老化损失。
作为本申请可选的技术方案，所述含硅颗粒包括Si、SiO x和硅酸盐中的至少一种，其中，0<x<2。本申请中所述含硅颗粒不限定特定的空间结构、粒度、形貌、掺杂、硅碳复合等，不同的含硅颗粒仅需微调制备具体参数即可得到本申请提出的复合负极材料。
在其中一些实施例中，所述含硅颗粒的平均粒径为0.1um～20um，例如可以是0.1um、0.5um、1um、3um、5um、10um、13um、15um、18um、20um等。含硅颗粒的平均粒径控制在上述范围内，有利于负极材料循环性能的提升。
在其中一些实施例中，所述含硅颗粒的比表面积大于150cm 2/g，例如可以是150cm 2/g、180cm 2/g、200cm 2/g、250cm 2/g、300cm 2/g、400cm 2/g或500cm 2/g等。所述含硅颗粒的比表面积在上述范围内，有利于提高由该负极材料制成的锂电池的首次效率，有利于提高负极材料的循环性能。
在其中一些实施例中，所述SiO x中0<x<2，例如x为0.1、0.2、0.5、0.8、1、1.2、1.5、1.7或1.9等。
本申请提供的制备方法中，反应气体与含硅颗粒材料进行的是化学气相沉积反应，本申请提供的制备方法通过简单的化学气相沉积即可制备得到本申请所述复合负极材料。
制得的所述复合负极材料，在拉曼光谱中，所述复合负极材料在450～550cm -1间具有硅特征峰A，在1300～1400cm -1间具有碳特征峰B，在1530～1630cm -1间有碳特征峰C，在2500～2750cm -1间具有石墨烯结构特征峰D。优选地，所述硅特征峰A的峰强度I A与所述石墨烯结构特征峰D的峰强度I D的比值I A/I D大于0.1且小于30，且所述石墨烯结构特征峰D的峰强度I D与所述碳特征峰B的峰强度I B的比值I D/I B大于0且小于1。
作为本申请可选的技术方案，所述保护性气氛包括氮气、氦气、氖气、氩气、氪气和氙气中的至少一种。
在其中一些实施例中，所述含碳气体包括甲烷、乙炔、乙烯、丙炔、丙烯、甲苯蒸气、苯蒸气、丙酮蒸气和甲醛蒸气中的至少一种。
在其中一些实施例中，所述反应气体中还包括辅助气体。
在其中一些实施例中，所述辅助气体包括氢气。氢气可以控制某些含碳气体(例如乙炔)的反应速度，使其更容易在大流量下产生石墨烯结构，以提高生产效率。
在其中一些实施例中，所述含碳气体和辅助气体的摩尔比为(2～10):1，例如 2:1、3:1、4:1、5:1、6:1、7:1、8:1、9:1或10:1等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
作为本申请可选的技术方案，所述反应气体的通入速度为0.1～6.0L/min，例如0.1L/min、0.3L/min、0.5L/min、1.0L/min、2.0L/min、3.0L/min、4.0L/min、5.0L/min或6.0L/min等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。本申请中，如果反应气体的通入速度过快，会导致石墨烯结构无法生成；如果反应气体的通入速度过慢，会导致沉积效率过低，影响生产性和实用价值。但是该优选条件是以5L容积的小型实验炉进行实验得到的，对于其他容积与之相差太大的反应器可能并不适用。因此，本申请并不限定反应气体的通入速度为上述优选范围，可根据制备条件适应性地调整。
作为本申请可选的技术方案，所述反应的方式为化学气相沉积，所述化学气相沉积的反应温度为700℃～1450℃，例如700℃、800℃、900℃、1000℃、1050℃、1100℃、1150℃、1200℃、1250℃、1300℃、1350℃、1400℃或1450℃等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。反应温度低于700℃，影响原位生长出含石墨烯结构的碳包覆层，会导致无法在产品的拉曼测试中观测到石墨烯结构特性峰D。
在其中一些实施例中，所述化学气相沉积的反应温度为700℃～1150℃，例如700℃、800℃、900℃、1000℃、1050℃或1150℃等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。本申请中，如果反应温度过高，会导致碳包覆层与含硅内核发生反应生成电化学惰性的碳化硅，使产品电化学性能劣化；如果反应温度过低，会导致石墨烯结构无法生成。
在其中一些实施例中，所述化学气相沉积的保温时间为3h～16h，例如3h、4h、5h、6h、7h、8h、9h、10h、11h、12h、13h、14h、15h或16h等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
在其中一些实施例中，所述化学气相沉积的反应气压为1.0atm～10.0atm，例如1.0atm、2.0atm、4.0atm、6.0atm、7.0atm、8.0atm、9.0atm或10.0atm等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。本申请中，如果反应气压过高，会导致反应速率过慢，影响生产性和实用性，同时存在安全风险；如果反应气压过低，会导致无法确保反应环境的惰性气氛，如果压力低于于1atm，甚至可能会导致空气倒吸入有高温可燃气体的反应室，引发严重安全风险。
本申请中，采用上述反应气体流速、反应温度、反应气压以及保温时间可以使这些操作条件相互配合，更好地提升产品的性能，并确保代表石墨烯结构的特征峰D的出现。
在其中一些实施例中，如图1所示，所述方法包括以下步骤S100～S200：
S100、在保护性气氛下，将含硅颗粒加热至700℃～1450℃；
S200、通入反应气体进行化学气相沉积，所述反应气体包括含碳气体，使得含硅颗粒的至少部分表面形成碳包覆层，得到复合负极材料。
作为本申请优选的技术方案，所述反应在化学气相沉积(CVD)装置中进行。
在其中一些实施例中，所述化学气相沉积装置包括如回转式化学气相沉积(CVD) 反应炉、等离子增强化学气相沉积(CVD)反应炉、化学气相沉积(CVD)管式炉或流化床中的任意一种或至少两种的组合。
作为本申请可选的技术方案，所述碳包覆层为无机碳材料层。需要说明的是，碳包覆层包覆在含硅颗粒的表面，本申请中所指的表面不仅仅是颗粒的平整表面，碳包覆层还可以填充于颗粒表面的裂缝、孔道等结构内，在此不做限定。
在其中一些实施例中，在所述复合负极材料中，碳包覆层的质量分数为1％～65％，例如1％、10％、20％、30％、40％、50％、60％或65％等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。本申请中，碳包覆层的质量分数低于1％会导致包覆量不足，无法充分发挥该产品性能，碳包覆层的质量分数高于65％会导致碳包覆量过高，影响容量的同时阻碍锂离子传输，降低负极材料的综合性能。
在其中一些实施例中，在所述复合负极材料中，所述碳包覆层的厚度为10nm～300nm，例如可以是10nm、20nm、50nm、80nm、100nm、150nm、200nm、250nm或300nm等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。碳包覆层过厚，锂离子传输效率降低，不利于材料大倍率充放电，降低负极材料的综合性能，碳包覆层过薄，不利于增加负极材料的导电性且对材料的体积膨胀抑制性能较弱，导致长循环性能价差。
在其中一些实施例中，所述制备方法还包括：化学气相沉积反应后自然冷却。
作为本申请所述制备方法的进一步可选技术方案，所述方法包括以下步骤：
在保护性气氛下，将含硅颗粒加热至700℃～1150℃；
将含碳气体与氢气按照摩尔比为(2～10)：1通入所述含硅颗粒中进行化学气相沉积反应，控制反应气压1.0atm～10.0atm，保温3h～16h，使得所述含硅颗粒的至少部分表面形成碳包覆层，得到所述复合负极材料。
第三方面，本申请提供一种锂离子电池，所述锂离子电池包含上述第一方面所述的复合负极材料或上述第二方面所述的制备方法制得的复合负极材料。
下面分多个实施例对本发明实施例进行进一步的说明。其中，本发明实施例不限定于以下的具体实施例。在保护范围内，可以适当的进行变更实施。
实施例1
本实施例按照如下方法制备复合负极材料：
取SiO粉末1.5kg，加入到5L实验型间歇式回转CVD炉中，向炉内通入氮气进行气氛置换，待排出气体中氧含量低于200ppm后，在持续通入氮气的情况下开始升温，升温至900℃后，以氮气为载气通入0.8L/min的甲烷，保持反应气压为1.2atm，持续反应6h后，切断甲烷气体，开始自然降温，得到所述复合负极材料。
将所述负极材料出料后打散过筛，进行拉曼光谱测试(采用日本HORIBA的XPLORA型激光共焦拉曼光谱仪，使用激光波长532nm，测试范围100cm -1至2800cm -1，其他实施例和对比例均采用该型号的拉曼光谱仪进行测试，测试条件也与实施例1相同)和碳含量测试(采用德国布鲁克的G4 ICARUS HF型红外 硫碳分析仪进行测试，其他实施例和对比例均采用该型号的测试仪测试碳含量)。
本实施例制备的负极材料包括SiO内核和包覆在SiO内核表面的无机碳材料包覆层，碳包覆层的质量分数为2.53％。本实施例制备的负极材料的拉曼光谱中的硅特征峰A在504cm -1处，碳特征峰B在1352cm -1处，碳特征峰C在1601cm -1处，石墨烯结构特征峰D在2695cm -1处，峰强度I A＝90.2，I B＝109.0，I D＝54.5，I A/I D为1.65，I D/I B为0.50。
本实施例制备的复合负极材料的性能测试结果见表1。
图2为本实施例制备的复合负极材料的拉曼光谱，由该图可以看出产品出现石墨烯结构的特征峰。
图3为本实施例制备的复合负极材料的循环性能曲线，由该图可以看出产品具有较好的循环性能，且倍率性能(1C/0.1C)较好。
实施例2
本实施例按照如下方法制备复合负极材料：
取多孔硅粉末150g(比表面积>150cm 2/g)，加入到5L实验型间歇式回转CVD炉中，向炉内通入氮气进行气氛置换，待排出气体中氧含量低于200ppm后，在持续通入氮气的情况下开始升温，升温至935℃后，以氮气为载气通入1.0L/min的甲烷，保持反应气压为2.0atm，持续反应10h后，切断甲烷气体，开始自然降温，得到所述复合负极材料。
将所述负极材料出料后打散过筛，进行测试。
本实施例制备的负极材料包括多孔硅内核和包覆在多孔硅内核表面的无机碳材料包覆层，碳包覆层的质量分数为41.2％。本实施例制备的负极材料的拉曼光谱中的硅特征峰A在501cm -1处，碳特征峰B在1348cm -1处，碳特征峰C在1591cm -1处，石墨烯结构特征峰D在2682cm -1处，峰强度I A/I D为4.35，I D/I B为0.34。
本实施例制备的复合负极材料的性能测试结果见表1。
图4为本实施例制备的复合负极材料的拉曼光谱，由该图可以看出产品出现石墨烯结构特征峰。
图5为本实施例制备的复合负极材料的循环性能曲线，由该图可以看出产品具有较好的循环性能，且倍率性能(1C/0.1C)较好。
实施例3
取SiO粉末1.5kg，加入到5L实验型间歇式回转CVD炉中，向炉内通入氮气进行气氛置换，待排出气体中氧含量低于200ppm后，在持续通入氮气的情况下开始升温，升温至700℃后，以氮气为载气通入1.8L/min的乙炔和氢气的混合气(乙炔与氢气的摩尔比为2:1)，保持反应气压为1.0atm，持续反应16h后，切断混合气，开始自然降温，得到所述复合负极材料。
本实施例制备的负极材料包括SiO内核和包覆在SiO内核表面的无机碳材料包覆层，碳包覆层的质量分数为4.3％。本实施例制备的负极材料的拉曼光谱中 的硅特征峰A在503cm -1处，碳特征峰B在1351cm -1处，碳特征峰C在1597cm -1处，石墨烯结构特征峰D在2691cm -1处，峰强度I A/I D为6.73，I D/I B为0.34。
本实施例制备的复合负极材料的性能测试结果见表1。
实施例4
取Si-O-C-Li复合物2kg，加入到5L实验型间歇式回转CVD炉中，向炉内通入氩气进行气氛置换，待排出气体中氧含量低于200ppm后，在持续通入氮气的情况下开始升温，升温至1150℃后，以氩气为载气通入0.8L/min的乙炔和氢气的混合气(乙炔与氢气的摩尔比为4:1)，保持反应气压为10.0atm，持续反应3h后，切断混合气，开始自然降温，得到所述复合负极材料。
本实施例制备的复合负极材料包括氧化亚硅/硅/偏硅酸锂内核和包覆在氧化亚硅/硅/偏硅酸锂内核表面的无机碳材料包覆层，碳包覆层的质量分数为2.5％。本实施例制备的负极材料的拉曼光谱中的硅特征峰A在501cm -1处，碳特征峰B在1347cm -1处，碳特征峰C在1598cm -1处，石墨烯结构特征峰D在2692cm -1处，峰强度I A/I D为8.59，I D/I B为0.24。
本实施例制备的复合负极材料的性能测试结果见表1。
实施例5
本实施例除了乙炔与氢气的摩尔比为10:1之外，其他操作条件和原料种类均与实施例3相同。
本实施例制备的负极材料包括SiO内核和包覆在SiO内核表面的无机碳材料包覆层，碳包覆层的质量分数为4.1％。本实施例制备的负极材料的拉曼光谱中的硅特征峰A在501cm -1处，碳特征峰B在1347cm -1处，碳特征峰C在1592cm -1处，石墨烯结构特征峰D在2685cm -1处，峰强度I A/I D为6.68，I D/I B为0.30。
本实施例制备的复合负极材料的性能测试结果见表1。
实施例6
本实施例除了反应气压为13atm之外，其他原料和操作条件均与实施例1相同。
本实施例制备的负极材料包括SiO内核和包覆在SiO内核表面的无机碳材料包覆层，碳包覆层的质量分数为0.7％。本实施例制备的负极材料的拉曼光谱中的硅特征峰A在505cm -1处，碳特征峰B在1352cm -1处，碳特征峰C在1597cm -1处，石墨烯结构特征峰D在2701cm -1处，峰强度I A/I D为19.2，I D/I B为0.61。
本实施例制备的复合负极材料的性能测试结果见表1。
实施例7
本实施例除了反应温度为1450℃之外，其他原料和操作条件均与实施例1相同。
本实施例制备的负极材料包括SiO内核和包覆在SiO内核表面的无机碳材料 包覆层，碳包覆层的质量分数为4.3％。本实施例制备的负极材料的拉曼光谱中的硅特征峰A在502cm -1处，碳特征峰B在1342cm -1处，碳特征峰C在1601cm -1处，石墨烯结构特征峰D在2694cm -1处，峰强度I A/I D为5.4，I D/I B为0.24。
本实施例制备的复合负极材料的性能测试结果见表1。
实施例8
本实施例除了不通入氢气而仅仅通入乙炔，且反应气体通入速度为0.1L/min，持续反应24h之外，其他原料和操作条件均与实施例3相同。
本实施例制备的负极材料包括SiO内核和包覆在SiO内核表面的无机碳材料包覆层，碳包覆层的质量分数为6.4％。本实施例制备的负极材料的拉曼光谱中的硅特征峰A在503cm -1处，碳特征峰B在1341cm -1处，碳特征峰C在1602cm -1处，石墨烯结构特征峰D在2696cm -1处，峰强度I A/I D为4.5，I D/I B为0.16。
本实施例制备的复合负极材料的性能测试结果见表1。
对比例1
本对比例按照如下方法制备负极材料：
取SiO粉末1.5kg，加入到实验型间歇式回转CVD炉中，向炉内通入氮气进行气氛置换，待排出气体中氧含量低于200ppm后，在持续通入氮气的情况下开始升温，升温至680℃后，以氮气为载气通入1.5L/min的乙炔，保持反应气压为1.4atm，持续反应5h后，切断乙炔气体，开始自然降温，得到负极材料。
将所述负极材料出料后打散过筛，进行测试。
该负极材料的碳包覆层的质量分数为4.21％(即碳含量)，拉曼测试结果未观察到石墨烯结构特征峰D。
本对比例制备的负极材料的性能测试结果见表1。
图5为本对比例制备的复合负极材料的拉曼光谱，由该图可以看出产品无石墨烯结构。
图6为本对比例制备的复合负极材料的循环性能曲线，由该图可以看出产品循环性能和倍率性能均出现劣化。
对比例2
本对比例除了反应温度为500℃之外，其他原料和操作条件均与实施例1相同。
本对比例得到的负极材料经拉曼测试，结果未观察到石墨烯结构特征峰D。
本对比例制备的负极材料的性能测试结果见表1。
性能测试方法
将各实施例和对比例制备的负极材料与商业石墨负极以10:90的比例进行混合作为负极活性物质，选用石墨为深圳市贝特瑞新能源材料股份有限公司生产的人造石墨S360系列，电极片涂层中活性物质、导电剂(Super P)和粘结剂 (CMC+SBR)的质量比为92:4:4，对电极为锂片；使用1mol/L的LiPF 6/EC+DMC+EMC(v/v＝1:1:1)电解液、Celgard2400隔膜组装扣式电池。用该种电池进行循环测试。
各实施例和对比例制备的负极材料作为负极活性物质，电极片涂层中活性物质、导电剂(Super P)和粘结剂(CMC+SBR)的质量比为92:4:4，对电极为锂片；使用1mol/L的LiPF 6/EC+DMC+EMC(v/v＝1:1:1)电解液、Celgard2400隔膜组装扣式电池。用该种电池进行首圈充放电测试。
将各实施例和对比例制备的负极材料与商业石墨负极以10：90的比例进行混合作为负极活性物质，选用石墨为深圳市贝特瑞新能源材料股份有限公司生产的人造石墨S360系列，负极电极片涂层中负极活性物质、导电剂(Super P)和粘结剂(CMC+SBR)的质量比为95.8:1.0:3.2，正极电极片涂层中正极活性物质(NCA三元材料，深圳市贝特瑞新能源材料股份有限公司生产，产品名称：N8-S)、导电剂(Super P)、粘结剂(PVDF)的质量比为97.3：1.0：1.7，使用隔膜为Celgard2400隔膜、使用1mol/L的LiPF 6/EC+DMC+EMC(v/v＝1:1:1)电解液，装配18650型电池，用于高温老化损失测试。
采用蓝电电池测试系统对上述电池进行电化学测试。
在常温下，扣式电池以0.1C、0.2C、0.5C各循环一周，后以1C充放电循环47周，以第50周的容量除以第1周容量，得产品50周循环容量保持率，0.1C容量除以1C容量用于评估产品倍率性能。
将18650电池经过化成后，使用0.3C在2.5～4.2V电压区间进行充放电记录可逆容量后，再0.3C充电至4.2V，以满电状态在60℃温度静置3天，3天后以0.3C放电至2.5V以存放后可放出的容量和记录的可逆容量计算差值，计算的差值除以记录的可逆容量即为产品的老化损失。
上述性能测试的结果见表1.
表1
Figure PCTCN2020117889-appb-000001
Figure PCTCN2020117889-appb-000002
综合上述实施例和对比例可知，本申请实施例1～5制备的复合负极材料具有独特的拉曼光谱峰，特征峰D为石墨烯结构特征峰，且I A/I D和I D/I B较优，使得上述实施例提供的复合负极材料具有循环容量保持率高、倍率性能好、高温老化损失小等优点。
实施例6的反应气压过高，导致反应速率过低，碳含量较低，而实施例1的反应气压为1.2atm，根据实施例1的复合负极材料制成的电池的容量保持率、循环保持率及老化损失等各项性能均优于实施例6，由此可见，反应气压控制在1.0atm～10.0atm范围较为合适，既可以保障产品的性能，又能降低生产安全风险。
实施例7的反应温度过高达到边界值，导致少量碳包覆层与含硅颗粒反应，生成少量电化学惰性的碳化硅，而实施例1的反应温度为900℃，反应较为温和，根据实施例1的复合负极材料制成的电池的首圈可逆比容量、容量保持率、循环保持率及老化损失等各项性能均优于实施例7，由此可见，反应温度控制在700℃～1150℃范围较为合适，可以保障产品的电化学容量和倍率性能。
实施例8中未使用辅助气体氢气，相比于实施例3，实施例8需要使用较低的乙炔流量才能产生石墨烯结构，这使得实施例8所需的反应时间更长，生产效率降低，由此可见，加入辅助气体可以控制乙炔气体的反应速度，提高石墨烯结构的生成效率。
对比例1将实施例1中的甲烷换为乙炔并且反应温度过低，导致石墨烯结构无法生成。
对比例2的反应温度过低，导致石墨烯结构无法生成。
由于对比例1、2中的负极材料不具有石墨烯结构，其难以维持复合负极材料与电解液的固液界面的稳定性，虽然首圈可逆比容量与实施例1～8相近，但是电池在长期循环后，容量保持率、循环保持率均有所下降，恶化电池的老化损失。而含有石墨烯结构的碳包覆层可以提升复合负极材料颗粒表面与电解液的固液界面稳定，形成均一的SEI膜，使得由含石墨烯结构的复合负极材料制成的电池的首圈可逆比容量、容量保持率、循环保持率及老化损失等各项性能均较有所改进。申请人声明，本申请通过上述实施例来说明本申请的详细方法，但本申请并不局限于上述详细方法，即不意味着本申请必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请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，均落在本申请的保护范围和公开范围之内。

Claims (13)

  1. 一种复合负极材料，其特征在于，所述复合负极材料包括含硅颗粒和碳包覆层，所述碳包覆层包覆所述含硅颗粒的至少部分表面；
    在拉曼光谱中，所述复合负极材料在450cm -1～550cm -1间具有硅特征峰A，在1300cm -1～1400cm -1间具有碳特征峰B，在1530cm -1～1630cm -1间有碳特征峰C，在2500cm -1～2750cm -1间具有石墨烯结构特征峰D。
  2. 根据权利要求1所述复合负极材料，其特征在于，在拉曼光谱中，所述硅特征峰A的峰强度I A与所述石墨烯结构特征峰D的峰强度I D的比值I A/I D大于0.1且小于30，且所述石墨烯结构特征峰D的峰强度I D与所述碳特征峰B的峰强度I B的比值I D/I B大于0且小于1。
  3. 根据权利要求1或2所述复合负极材料，其特征在于，其满足以下条件a～f的至少一者：
    a.所述含硅颗粒包括Si、SiO x和硅酸盐中的至少一种，其中，0<x<2；
    b.所述含硅颗粒的平均粒径为0.1um～20um；
    c.所述含硅颗粒的比表面积大于150cm 2/g；
    d.所述碳包覆层为无机碳材料层；
    e.所述碳包覆层的厚度为10nm～300nm；
    f.在所述复合负极材料中，所述碳包覆层的质量分数为1％～65％。
  4. 一种复合负极材料的制备方法，其特征在于，所述方法包括以下步骤：
    在保护性气氛下，通入反应气体与含硅颗粒进行反应，反应温度为700℃～1450℃，所述反应气体包括含碳气体，使得所述含硅颗粒的至少部分表面形成碳包覆层，得到所述复合负极材料。
  5. 根据权利要求4所述的制备方法，其特征在于，其满足以下条件a～f的至少一者：
    a.所述含硅颗粒包括Si、SiO x和硅酸盐中的至少一种，其中，0<x<2；
    b.所述含硅颗粒的平均粒径为0.1um～20um；
    c.所述含硅颗粒的比表面积大于150cm 2/g；
    d.所述碳包覆层为无机碳材料层；
    e.所述碳包覆层的厚度为10nm～300nm；
    f.在所述复合负极材料中，所述碳包覆层的质量分数为1％～65％。
  6. 根据权利要求4或5所述的制备方法，其特征在于，
    在拉曼光谱中，所述复合负极材料在450cm -1～550cm -1间具有硅特征峰A，在1300cm -1～1400cm -1间具有碳特征峰B，在1530cm -1～1630cm -1间有碳特征峰C，在2500cm -1～2750cm -1间具有石墨烯结构特征峰D；
    所述硅特征峰A的峰强度I A与所述石墨烯结构特征峰D的峰强度I D的比值I A/I D大于0.1且小于30，且所述石墨烯结构特征峰D的峰强度I D与所述碳特征峰B的峰强度I B的比值I D/I B大于0且小于1。
  7. 根据权利要求4～6任一项所述的制备方法，其特征在于，其满足以下条件a～b的至少一者：
    a.所述保护性气氛包括氮气、氦气、氖气、氩气、氪气和氙气中的至少一种；
    b.所述含碳气体包括甲烷、乙炔、乙烯、丙炔、丙烯、甲苯蒸气、苯蒸气、丙酮蒸气和甲醛蒸气中的至少一种。
  8. 根据权利要求4～7任一项所述的制备方法，其特征在于，所述反应气体还包括辅助气体，所述辅助气体包括氢气。
  9. 根据权利要求8所述的制备方法，其特征在于，所述含碳气体和所述辅助气体的摩尔比为(2～10)：1。
  10. 根据权利要求4～6任一项所述的制备方法，其特征在于，其满足以下条件a～d的至少一者：
    a.所述反应的方式为化学气相沉积；
    b.所述反应的方式为化学气相沉积，所述化学气相沉积的反应温度为700℃～1150℃；
    c.所述反应的方式为化学气相沉积，所述化学气相沉积的保温时间为3h～16h；
    d.所述反应的方式为化学气相沉积，所述化学气相沉积的反应气压为1.0atm～10.0atm。
  11. 根据权利要求4～10任一项所述的制备方法，其特征在于，所述方法包括以下步骤：
    在保护性气氛下，将含硅颗粒加热至700℃～1450℃；
    通入反应气体进行化学气相沉积，所述反应气体包括含碳气体，使得含硅颗粒的至少部分表面形成碳包覆层，得到复合负极材料。
  12. 根据权利要求4～10任一项所述的制备方法，其特征在于，所述方法包括以下步骤：
    在保护性气氛下，将含硅颗粒加热至700℃～1150℃；
    将含碳气体与氢气按照摩尔比为(2～10)：1通入所述含硅颗粒中进行化学气相沉积反应，控制反应气压1.0atm～10.0atm，保温3h～16h，使得所述含硅颗粒的至少部分表面形成碳包覆层，得到所述复合负极材料。
  13. 一种锂离子电池，其特征在于，所述锂离子电池包含如权利要求1～3任一项所述的复合负极材料或根据权利要求4～12任一项所述的制备方法制得的复合负极材料。
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