CA3203658C - Silicon-based lithium storage material and preparation method thereof - Google Patents

Silicon-based lithium storage material and preparation method thereof

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CA3203658C
CA3203658C CA3203658A CA3203658A CA3203658C CA 3203658 C CA3203658 C CA 3203658C CA 3203658 A CA3203658 A CA 3203658A CA 3203658 A CA3203658 A CA 3203658A CA 3203658 C CA3203658 C CA 3203658C
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silicon
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lithium storage
based lithium
carbon coating
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CA3203658A1 (en
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Fei Ma
Yuhu WU
Zhihong Wu
Xiaoyang Ding
Fengfeng Li
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Shanghai Shanshan Technology Co Ltd
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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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • 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
    • 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
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

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Abstract

La présente demande concerne un matériau de stockage de lithium à base de silicium et un procédé de préparation associé. Le matériau de stockage de lithium à base de silicium comprend un premier composant comprenant du Si avec une valence comprise entre 0 et 4, où 0≤C Si(1-4)/C Si(0)≤1. Le matériau comprend également un deuxième composant comprenant un élément dopant R, lequel comprend au moins l’un des éléments du groupe principal 1, 2 ou 13. Le matériau comprend en outre un revêtement en carbone, qui comprend un revêtement en carbone amorphe et un revêtement en carbone graphié qui sont disposés alternativement. Le matériau de stockage au lithium à base de silicium améliore les caractéristiques du matériau de stockage au lithium à base de silicium en tant que substance active d’une batterie secondaire au lithium ionique dans un état de stockage à haute température, et améliore les caractéristiques du cycle et l’efficacité coulombique initiale charge-décharge de la batterie.This application relates to a silicon-based lithium storage material and an associated preparation process. The silicon-based lithium storage material comprises a first component comprising silicon with a valence between 0 and 4, where 0 ≤ C<sub>Si(1-4)</sub>/C<sub>Si(0)</sub> ≤ 1. The material also comprises a second component comprising a dopant element R, which includes at least one of the elements from main group 1, 2, or 13. The material further comprises a carbon coating, which includes an amorphous carbon coating and a graphitized carbon coating arranged alternately. The silicon-based lithium storage material improves the characteristics of the silicon-based lithium storage material as an active substance in a secondary lithium-ion battery in a high-temperature storage state, and improves the cycle characteristics and the initial charge-discharge coulombic efficiency of the battery.

Description

SILICON-BASED LITHIUM STORAGE MATERIAL AND
PREPARATION METHOD THEREOF
FIELD
The present invention relates to the field of lithium ion batteries, and in particular to a silicon-based lithium storage material and a preparation method thereof.
BACKGROUND
In recent years, higher requirements for the energy density of lithium-ion batteries have been put forward, resulting in the need of anode materials with a higher capacity. At present, silicon-oxygen anodes began to be used in power batteries, with a rapidly growing trend. Existing technologies for preparing anode materials of lithium battery starting from silicon oxide are mostly those that use raw materials containing silicon particles (Si) and silicon oxide (5i02) to obtain the anode materials of lithium battery under high-temperature and vacuum conditions.
The silicon-based lithium storage materials prepared by the method have a low first-time Coulomb efficiency and a poor cycle characteristics, and it is difficult for the method to form a silicon-based lithium storage material containing uniformly doped elements (such as sulfur, phosphorus, etc.).
Therefore, it is necessary to provide a new silicon-based lithium storage material and a preparation method thereof.
The present invention provides a new silicon-based lithium storage material and a preparation method thereof, to obtain a silicon-based lithium storage material with a homogeneous doped system, which improves characteristics of the silicon- based lithium storage material as an active substance in a lithium ion secondary battery at a high-temperature storage condition, and also improves the cycle characteristics and the initial charge-discharge coulombic efficiency of the secondary battery.
One aspect of the present invention provides a silicon-based lithium storage material, comprising: a first component, comprising Si with a valence of 0-4, with the proviso that 0<Csi(l-4)/Csi(o)<1, where Cs(l4) is the molar amount of element silicon with a valence of 1-4, and Csi(o) is the molar amount of element silicon with a valence of 0; and a second component, comprising a doping element R, where the doping element R at least includes one of elements of main group I, II, and III, and with the proviso that O<CR/Csi(o-4)<1.5, where CR is the molar amount of the doping element R, and Cs(o4) is the molar amount of element silicon with a valence of 0- 4.
In some embodiments of the present invention, the elements of main group I, II, and III include Li, Na, Mg, Ca, or Al.
In some embodiments of the present invention, the surface of the material further comprises a carbon coating. 2 In some embodiments of the present invention, the mass percentage content of the carbon coating is greater than 0 and less than 10%.
In some embodiments of the present invention, the carbon coating comprises at least one of an amorphous carbon coating or a graphitized carbon coating.
In some embodiments of the present invention, the carbon coating comprises more than one amorphous carbon coating and more than one graphitized carbon coating, wherein the more than one amorphous carbon coating is arranged alternately with the more than one graphitized carbon coating.
In some embodiments of the present invention, the amorphous carbon coating is doped with a nitrogen atom, and the graphitized carbon coating is doped with a nitrogen atom.
In some embodiments of the present invention, Si with a valence of 0-4 and the doping element R are uniformly distributed.
The present invention also provides a method for preparing a silicon-based lithium storage material, comprising: providing a first mixture, where the first mixture at least comprises an elementary substance silicon and a silicon with an oxidation state of +4, and also a doping element R, where the doping element R at least includes one of elements of main group I, II, and III, with the proviso that O<CR/Csi(o-4)<1.5, where CR is the molar amount of the doping element R, and Cs(o4) is the molar amount of element silicon 3 CA03203658 2023- 6- 28 with a valence of 0-4; and heating the first mixture to a molten state under the protection of a non- oxidizing gas, and then cooling to room temperature at a cooling rate of 5 C/S-30 C/S.
In some embodiments of the present invention, the elements of main group I, II, and III include Li, Na, Mg, Ca, or Al.
In some examples of the present invention, the temperature when heating to a molten state is 1500 C-3000 C.
In some embodiments of the present invention, the method for cooling the molten first mixture to room temperature at a cooling rate of 5-30 C/S comprises: pouring the molten first mixture onto a fast roller, and separating the molten first mixture from the roller by a centrifugal action of the roller to obtain a flaky cooled product.
In some embodiments of the present invention, the method further comprises pulverizing the flaky cooled product to form a powder with a median particle size of 1-8 [tm.
In some embodiments of the present invention, the method further comprises: depositing a carbon coating on the surface of the pulverized silicon-based lithium storage material.
In some embodiments of the present invention, the method for depositing a carbon 4 CA03203658 2023- 6- 28 coating comprises: in a non-oxidizing atmosphere, passing a carbon source substance through a pre-decomposition zone to form a decomposition product, wherein the carbon source substance includes one or more of a gaseous carbon source substance, a vaporized carbon source substance or an atomized carbon source substance; adjusting the flow rate VG of the decomposition product into a reaction chamber of a depositing-coating zone, and a ratio Mc/M of the molar flow rate of the decomposition product to the mass of the pulverized silicon-based lithium storage material, to subject the pulverized silicon-based lithium storage material and the decomposition product to a depositing and coating reaction in the depositing-coating zone, forming an amorphous carbon coating or a graphitized carbon coating or a composite coating comprising an amorphous carbon coating and a graphitized carbon coating on the surface of the pulverized silicon- based lithium storage material, with the proviso that 0.01<VG<100 and 0.001<Mc/M <1, where VG is in a unit of m/min, Mc is in a unit of mol/min, in terms of carbon atoms, and M is the mass of the pulverized silicon-based lithium storage material, in a unit of kg.
In some embodiments of the present invention, under a first condition: 1O<VG<100 and 0.001<Mc/M<0.1, a graphitized carbon coating is formed on the surface of the silicon-based lithium storage material; under a second condition: 0.01<VG<5 and 0.2<Mc/M<1, an amorphous carbon coating is formed on the surface of the silicon- based lithium storage material.
In some embodiments of the present invention, the values of VG and Mc/M are adjusted to alternate between the first condition and the second condition, with the formation of an alternating coating of an amorphous carbon coating and a graphitized carbon coating on the surface of the silica-based storage lithium CA03203658 2023- 6- 28 material.
In some embodiments of the present invention, the gaseous carbon source substance includes methane, ethane, ethylene, acetylene, propane, and propylene, the vaporized carbon source substance includes n-hexane, ethanol, and benzene, and the atomized carbon source substance includes polyethylene and polypropylene.
In some embodiments of the present invention, a N-containing substance is introduced during the depositing and coating reaction, the N-containing substance includes one or more of NH3, acetonitrile, aniline, or butylamine.
According to the method for preparing the silicon-based lithium storage material described in the embodiments of the present invention, a homogeneous doped system is formed by the combination of high-temperature melting, rapid condensation control technology and doping control of element R, so as to realize a uniform modification of the valence state, structure, crystal shape, and magnetic environment of the silicon-based lithium storage material, improve its characteristics under a high-temperature storage condition after it is intercalated by an active lithium (as an active substance of a lithium-ion secondary battery) and obtain the best result, and meanwhile improve cycle characteristics and initial charge-discharge coulombic efficiency of the battery.
Additional features in the present invention will be described partly below.
With the description, the contents described in the following embodiments will be obvious to those skilled in the art. The inventive conception of the present 6 CA03203658 2023- 6- 28 invention can be fully explained by practicing or using the methods, means, and combinations thereof set forth in the detailed examples discussed below.
DETAILED DESCRPTION
The following description provides specific application scenarios and requirements of the present invention, with the purpose of enabling those skilled in the art to manufacture and use the content in the present invention. For those skilled in the art, various local modifications to the disclosed embodiments are obvious, and the general principles defined herein can be applied to other embodiments and uses without departing from the spirit and scope of the present invention.
Therefore, this disclosure is not limited to the illustrated embodiments, but the widest scope consistent with the claims.
The technical solution of the present invention will be described in detail below in conjunction with embodiments.
An embodiment of the present invention provides a silicon-based lithium storage material, comprising: a first component, comprising Si with a valence of 0-4, with the proviso that O<Csi(l-4)/Csi (0)<1, where Cs(l4) is the molar amount of element silicon with a valence of 1-4, and Csi(0) is the molar amount of element silicon with a valence of 0; and a second component, comprising a doping element R, where the doping element R includes at least one of elements of main group I, II, and III, and with the proviso that 0<CR/Csi(o-4)<1.5, where CR is the molar amount of the doping 7 CA03203658 2023- 6- 28 element R, and Cs(o4) is the molar amount of element silicon with a valence of 0- 4.
In some embodiments of the present invention, Si with a valence of 0-4 includes a Si particle in an elemental state, a silicon oxide SiOx (0<x<2) and a silicate such as a compound represented by a general formula MySiO3, where 1<y<2, and M is an element of main group 1,11 and III, such as Li, Na, Mg, Ca, or Al, etc. Also, O<Csi(l- 4)/Csin<1, where Cs(l4) refers to the molar amount of silicon with a valence of 1- 4, Co refers to the molar amount of silicon atom present in a form of elementary substance and with a valence of 0, and Csio_oCsin refers to a molar ratio (a ratio of the number of an atom) of a silicon with a valence of 1-4 to elementary substance silicon. The value of Cs(l4)/Cs(o) can be achieved by adjusting the contents of the silicon particle, the silicon oxide, and the silicate contained in the silicon- based lithium storage material.
In some embodiments of the present invention, the doping element is marked as R, then the doping element R may be an element capable of accepting electrons, and at least include one of elements of main group I, II, and III. The elements of main group I, II, and III, for example, are Li, Na, Mg, Ca, Al and so on. The elements of main group I, II, and III can be combined with other elements capable of accepting electrons to form an electrically neutral material. The other elements capable of accepting electrons include N, P, 0, C, S, Se, and so on. The doping element R may be present in an atomic state or an ionic state in the silicon-based lithium storage material, and atoms of the doping element may combine with each other to form an ionic state, such as elementary substance Mg or elementary substance Al; for another example, the elements of main group I, II, and III combine with one or more of N, P, 0, C, S, Se to form a metal oxide or metal salt, such as Mg0, Na2O, 8 CaO, Na3PO4, MgS03, etc. The doping element may combine with Si with a valence of 0-4 to form a silicon oxide, a silicate, etc., such as MgSiO3, CaSiO3, Li2SiO3 or Na2SiO3, etc. Also, O<CR/Csi(o-4)<1.5, where CR refers to the molar amount of the doping element R, and Cs(o4) refers to the molar amount of silicon with a valence of 0-4. By adjusting the doping amount of the doping element R, it is possible to change the characteristics of the silicon-based lithium storage material under a high-temperature storage condition after being intercalated with an active lithium and obtain the best results. In some embodiments, the value of CR/Csi(o-4) is, for example, 0.2, 0.5, 0.8, 1, or 1.2 etc.
In some embodiments of the present invention, Si with a valence of 0-4 and the doping element R are uniformly distributed.
In some embodiments of the present invention, the surface of the silicon-based lithium storage material further comprises a carbon coating. In some embodiments of the present invention, the mass percentage content of the carbon coating is greater than 0 and less than 10%, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9% etc. The coating thickness of the carbon coating is, for example, 1 nm to 500 nm. The carbon coating may further improve the conductive properties of the material.
In some embodiments of the present invention, the carbon coating comprises at least one of an amorphous carbon coating or a graphitized carbon coating. That is, the surface of the silicon-based lithium storage material may comprise an amorphous carbon coating or a graphitized carbon coating or both an amorphous carbon coating and a graphitized carbon coating. In some embodiments of the 9 CA03203658 2023- 6- 28 present invention, the surface of the silicon-based lithium storage material is directly coated by the amorphous carbon coating, and the surface of the amorphous carbon coating is then coated by the graphitized carbon coating. In other embodiments of the present invention, the surface of the silicon-based lithium storage material is directly coated by the graphitized carbon coating, and the surface of the graphitized carbon layer is then coated by the amorphous carbon coating. The "coated (or coating)" described in the embodiments of the present invention may be "partially coated" or "completely coated". The degree of coating in "coated (or coating)" also varies with the manufacturing process of the silicon- based lithium storage material.
For example, the total coating thickness of the amorphous carbon coating and the graphitized carbon coating on the surface of the silicon-based lithium storage material is 500 nm, wherein the surface of the silicon-based lithium storage material is coated by the amorphous carbon coating with a total thickness of 400 nm (the amorphous carbon coating with a total thickness of 400 nm may comprises a number of single-layer amorphous carbon coatings with a single layer thickness of 1-20 nm), and the surface of the amorphous carbon coating is coated by the graphitized carbon coating with a total thickness of 100 nm (the graphitized carbon coating with a total thickness of 100 nm may comprises a number of single- layer graphitized carbon coatings with a single layer thickness of 1-20 nm). The coating degree of the amorphous carbon coating or the graphitized carbon coating is relatively high, close to complete coating. In the embodiments of the present invention, when the thickness of the amorphous carbon coating or the graphitized carbon coating reaches about 5 nm, it can be considered that a completely coated structure is formed.
For another example, the total coating thickness of the amorphous carbon coating and the graphitized carbon coating on the surface of the silicon-based lithium storage material is 30 nm, wherein the surface of the silicon-based lithium storage material is sequentially coated with a graphitized carbon coating of 5 nm, an amorphous carbon coating of 3 nm, a graphitized carbon coating of 4 nm, an amorphous carbon coating of 2 nm, a graphitized carbon coating of 10 nm, and an amorphous carbon coating of 6 nm.
In the above embodiment, the carbon coating includes more than one layer of the amorphous carbon coating and more than one layer of the graphitized carbon coating, wherein the more than one layer of the amorphous carbon coating is arranged alternately with the more than one layer of the graphitized carbon coating.
In the structure in which the amorphous carbon coating and the graphitized carbon coating are alternately arranged, the surface of the silicon-based lithium storage material may be directly coated with either the amorphous carbon coating or the graphitized carbon coating.
Since the amorphous carbon coating has a loose amorphous carbon structure, and plays a buffering role in the expansion of the silicon-based lithium storage material when being intercalated with lithium, while the graphitized carbon coating has a crystalline carbon structure with a high graphitization, and has a certain binding effect on the expansion of the silicon-based lithium storage material when being intercalated with lithium, and prevents the cracking of the coating and the deactivation of the active substance material in the silicon-based lithium storage material during the deintercalation of lithium. Therefore, the alternate arrangement of the amorphous carbon structure and graphitized carbon coating structure can better adjust the charge-discharge performance of the silicon-based lithium storage 11 CA03203658 2023- 6- 28 material and improve the cycle life of the battery.
In some embodiments of the present invention, the thickness of each amorphous carbon coating ranges from 1 nm to 20 nm, and the thickness of each graphitized carbon coating ranges from 1 nm to 20 nm. For example, the sum of the thickness of the amorphous carbon coating and the thickness of the graphitized carbon coating on the surface of the silicon-based lithium storage material is 300 nm, then the surface of the silicon-based lithium storage material comprises an amorphous carbon coating with a thickness of 10 nm and a graphitized carbon coating with a thickness of 10 nm, which are alternately arranged for 15 times.
In some embodiments of the present invention, when the outermost layer of the silicon-based lithium storage material is an amorphous carbon coating, a specific surface area of the silicon-based lithium storage material is generally higher (1-20 m2/g), and when the outermost layer of the silicon-based lithium storage material is a graphitized carbon coating, a specific surface area of the silicon-based lithium storage material is generally lower (0.1-15 m2/g).
In some embodiments of the present invention, the amorphous carbon coating is doped with nitrogen atoms, and the graphitized carbon coating is doped with nitrogen atoms. The nitrogen atom may be derived from a N-containing substance, such as one or more of NH3, acetonitrile, aniline or butylamine. Introducing nitrogen atoms to the amorphous carbon coating and the graphitized carbon coating can further improve the charge-discharge capability of the silicon-based lithium storage material, because nitrogen doping can further improve conductivity of the material, so as to reduce internal resistance of the battery, thereby ensuring charge 12 CA03203658 2023- 6- 28 and discharge capacity of the battery with a large current.
Not necessarily, when the silicon-based lithium storage material is used as an anode material, in order to obtain a higher first-time Coulomb efficiency, a temperature raising process may be performed in advance under the protection of an inert gas. When a crystal grain of elementary substance silicon with a valence of 0 is present in the silicon-based lithium storage material, the crystal grain of elementary substance silicon and the crystal grain of a surrounding compound are in a homogeneous system. All the crystal grain sizes are <300 nm analyzed by Scherrer calculation with the powder X-ray diffraction method.
The material has 1-2 crystallization transition peaks between 800-1000 C, and the corresponding crystallization transition activation energy is 100-250 KJ/mol analyzed by differential thermal scanning calorimetry (DSC). Si 2P results analyzed by XPS test contains peaks between 98eV (Si (0) peak) and 102.5eV (Si (4+) peak).
In some embodiments of the present invention, a magnetic susceptibility of the silicon-based lithium storage material has 1-2 peaks around 0 Oe, with a peak intensity of 2x10-8 to 3 x10-5. The magnetic susceptibility is i3M/i3H, where H represents an applied magnetic field (H, in a unit of Oe) obtained by a vibrating the sample magnetometer, and M represents a magnetic induction strength (M, in a unit of emu/g) when the applied magnetic field is within the range of +30000 to -30000.
The silicon-based lithium storage material is a homogeneous doped system, so as 13 CA03203658 2023- 6- 28 to realize a uniform modification of the valence state, structure, crystal shape, and magnetic environment of the silicon-based lithium storage material, improve its characteristics under a high-temperature storage condition after it is intercalated with an active lithium as an active substance of a lithium-ion secondary battery and obtain the best result, and meanwhile improve cycle characteristics and initial charge-discharge coulombic efficiency of the battery.
The present invention also provides a method for preparing a silicon-based lithium storage material, comprising:
Step 51: providing a first mixture, where the first mixture comprises at least an elementary substance silicon and a silicon with an oxidation state of +4, and also a doping element R, where the doping element R at least includes one of the elements of main group I, II, and III, with the proviso that O<CR/Csi(0_4)<1.5, where CRis the molar amount of the doping element R, and Csi(0_4) is the molar amount of element silicon with a valence of 0-4; and Step S2: heating the first mixture to a molten state under the protection of a non- oxidizing gas, and then cooling to room temperature at a cooling rate of 5 C/S- 30 C/S.
In the embodiment of the present invention, the elementary substance silicon is, for example, polysilicon. The silicon with an oxidation state of +4 is, for example, silica, and the raw material containing silica is, for example, quartz, and optionally, for example, 13-type quartz. The silicon with an oxidation state of +4 may also be a silicate, for example, a compound represented by a general formula MySiO3, where 1<y<2, and M is an element of main group I, II, and III such as Li, Na, Mg, Ca, etc. 14 The first mixture comprises a doping element R, where the doping element Rat least includes one of N, P, 0, C, S, and Se, and may also includes elements of main group I, II, and III such as Li, Na, Mg, Ca, etc.; the raw material providing the doping element may be an metal elementary substance such as Mg, or may be a metal oxide, a metal hydroxide, or a metal salt, such as Mg0, Na2O, CaO, Na3PO4 MgS03, Li0H, Li2CO3, MgCO3, MgSiO3, CaSiO3, Li2SiO3 or Na2SiO3, etc.
Acomposition ratio of each raw material in the first mixture is adjusted, to meet the proviso that O<CR/Csi(o-4)<1.5, where CR is the molar amount of the doping element R, and Cs(o4) is the molar amount of element silicon with a valance of 0- 4, for example, the sum of the molar amount of the silicon atoms in elementary substance silicon and silicon with an oxidation state of +4. In some embodiments of the present invention, the raw material includes polysilicon, I3-type quartz and Li2CO3. In other embodiments of the present invention, the raw material includes polysilicon, I3-type quartz and Li0H. In still other embodiments of the present invention, the raw material includes polysilicon, I3-type quartz, and MgCO3.
The non-oxidizing gas described in the embodiments of the present invention is, for example, an inert gas, such as helium, neon, and argon etc. In some embodiments of the present invention, the temperature when heating to a molten state is 1500 C-3000 C, for example, 2000 C, 2500 C, etc. After heating to the molten state, the molten mixture is cooled rapidly to room temperature at a cooling rate of 5 C/S-30 C/S ( C/S: Celsius/second). The rapid cooling process may make the prepared material have the best cycle performance after being made into a battery.
In some embodiments of the present invention, the method for cooling the molten first mixture to room temperature at a cooling rate of 5 C/S-30 C/S comprises: pouring the molten first mixture onto a rapidly rotating roller, and separating the molten first mixture from the roller by a centrifugal action of the roller, to obtain a flaky cooled product. The rapidly rotating may be adjusted according to the gear position or the rotation speed setting of the used equipment with rollers, and is not specifically limited in the present invention. In some embodiments of the present invention, the method further comprises pulverizing the flaky cooled product to form a powder with a median particle size of 1-8 gm.
After melting and rapidly cooling the first mixture, the atoms in the silicon- based lithium storage material are recombined, to meet the proviso that O<Csi(l-4) /Csin<1, where Cs(l4) is the molar amount of element silicon with a valence of 1-4, and Csi(0) is the molar amount of element silicon with a valence of 0.
In some embodiments of the present invention, the silicon-based lithium storage material method further comprises: depositing a carbon coating on the surface of the pulverized silicon-based lithium storage material. The method for depositing a carbon coating comprises the following steps: in a non-oxidizing atmosphere, passing a carbon source substance through a pre- decomposition zone to form a decomposition product, wherein the carbon source substance includes at least one of a gaseous carbon source substance, a vaporized carbon source substance, or an atomized carbon source substance; adjusting the flow rate VG of the decomposition products into a reaction chamber of a depositing-coating zone, and a ratio Mc/M of the molar flow rate of the 16 CA03203658 2023- 6- 28 decomposition product to the mass of the pulverized silicon-based lithium storage material, to subject the pulverized silicon-based lithium storage material and the decomposition product to a depositing and coating reaction in the depositing- coating zone, forming an amorphous carbon coating or a graphitized carbon coating or a composite coating comprising an amorphous carbon coating and a graphitized carbon coating on the surface of the pulverized lithium storage material, with the proviso that 0.01<VG<100 and 0.001<Mc/M<1, where VG is in a unit of m/min, Mc is in a unit of mol/min, in terms of carbon atoms, and M is the mass of the pulverized silicon-based lithium storage material, in a unit of kg.
Acoating equipment such as a revolver, a rotary furnace and the like can be used to prepare the carbon coating. The coating equipment may be configured to comprise a pre-decomposition zone and a depositing-coating zone, wherein both the pre-decomposition zone and the depositing-coating zone comprises a reaction chamber. The pre-decomposition zone is used to pre-decompose the carbon source substance. For example, the carbon source substance is introduced into the pre- decomposition zone of the coating equipment, and then subjected to pyrolysis, cracking, polycondensation reactions and the like in a non-oxidizing atmosphere, to become a gaseous substance. The carbon source comprises a low-molecular- weight substance and a high-molecular-weight substance, wherein the low- molecular-weight substance becomes a medium/large-molecular-weight substance via pyrolysis, polycondensation, and addition reactions and the like; the high- molecular-weight substance is cracked into a medium/small-molecular-weight substance, which is also accompanied by pyrolysis, polycondensation, addition reactions and the like.
The gas that provides the non-oxidizing atmosphere includes, for example, any one 17 CA03203658 2023- 6- 28 or more of hydrogen, nitrogen, or inert gas, and is used as a protective gas, a carrier gas, and a diluent gas for the reaction in the pre-decomposition zone.
The gaseous carbon source substance includes a hydrocarbon that is gaseous at room temperature and an aldehyde that is gaseous at room temperature. The gaseous carbon source substance includes methane, ethane, ethylene, acetylene, propane, and propylene. The vaporized carbon source substance is the carbonaceous material that is liquid at room temperature, and is gaseous at a temperature above room temperature but lower than the temperature of the pre- decomposition zone. The vaporized carbon source substance includes n-hexane, ethanol, and benzene.
The atomized carbon source substance is a substance that is difficult to evaporate by heating, and can be made into small droplets by an atomizing device, for example, a substance that is liquid at a temperature lower than the temperature of the pre-decomposition zone. The atomized carbon source substance includes polyethylene and polypropylene.
In some embodiments of the present invention, the flow rate VG of the decomposition product into the reaction chamber of the deposition coating zone and a ratio Mc/M of the molar flow rate of the decomposition product to the mass of the pulverization treated silicon-based lithium storage material are adjusted, to subject the pulverized silicon-based lithium storage material and the decomposition product to a depositing and coating reaction in the depositing- coating zone, forming an amorphous carbon coating and/or a graphitized carbon coating on the surface of the pulverized silicon-based lithium storage material, with 18 CA03203658 2023- 6- 28 the proviso that 0.01<VG<100 and 0.001<Mc/M <1, where VG is in a unit of m/min, Mc is in a unit of mol/min, in terms of carbon atoms, and M is the mass of the pulverized silicon-based lithium storage material, in a unit of kg. Under a first condition: 1O<VG<100 and 0.001<Mc/M<0.1, a graphitized carbon coating is formed on the surface of the pulverized silicon-based lithium storage material; under a second condition: 0.01<VG<5 and 0.2<Mc/M<1, an amorphous carbon coating is formed on the surface of the pulverized silicon-based lithium storage material. That is to say, in the preparation process of the silicon-based lithium storage material described in the embodiments of the present invention, the thickness of the formed amorphous carbon coating and/or graphitized carbon coating and the situation of the alternate coating may be adjusted by adjusting the flow rate and mass of the reactants and the reaction time. When the thickness of one coating reaches a set value, the flow rate and mass of the reactant is rapidly adjusted, thereby switching to another coating. Of course, in the actual process, when the speed of adjusting flow rate and mass of the reactants is set to be slower, and a composite coating comprising both the amorphous carbon coating and the graphitized carbon coating may be present.
In other words, the crystal structure of the coating can be controlled by adjusting VG(m/min) and Mc/M (Mc is in a unit of mol/min, in terms of carbon atoms, and Mis the mass of the pulverized silicon-based lithium storage material, in a unit of kg), thereby obtaining an amorphous carbon coating and/or a graphitized carbon coating. At the same time, in combination with adjusting the reaction time, the mass percentage content of the carbon coating can be adjusted.
Adjusting the operation speed of the pulverized silicon-based lithium storage material and the flow rate of the decomposition product into the reaction chamber 19 CA03203658 2023- 6- 28 can ensure that a uniform and continuous amorphous carbon coating and graphitized carbon coating are obtained during the reaction process, and meanwhile can minimize the loss of materials.
In some embodiments of the present invention, adjusting the value of VG and Mc/M to alternate between the first condition and the second condition achieves that an alternating coating of an amorphous carbon coating and a graphitized carbon coating are formed on the surface of the pulverized silica-based storage lithium material. Since the amorphous carbon coating has a loose amorphous carbon structure, and plays a buffering role in the expansion of the silicon-based lithium storage material when being intercalated with lithium, while the graphitized carbon coating has a crystalline carbon structure with a high graphitization, has a certain binding effect on the expansion of the silicon-based lithium storage material when being intercalated with lithium, and prevents the cracking of the coating and the deactivation of the active substance in the silicon-based lithium storage material during the deintercalation of lithium, the alternating arrangement of the amorphous carbon structure and graphitized carbon coating structure can better adjust the charge-discharge performance of the silicon-based lithium storage material and improve the cycle life of the battery.
In some embodiments of the present invention, a molar flow rate Mc of the pyrolysis product after thermally decomposing the atomized carbon source in the pre-decomposition zone, can be determined by measuring the CO2 content after an oxidative combustion. For the gaseous and vaporous carbon source, a molar flow rate Mc of the pyrolysis product can be directly determined according to the molecular structure of the intake gas.
In some embodiments of the present invention, during the depositing and coating reaction, an N-containing substance may be further introduced, and the N- containing substance includes one or more of NH3, acetonitrile, aniline, or butylamine.
In the embodiment of the present invention, the temperature range for pre- decomposing the carbon source substance is set to 500-1500 C, and preferably 700 C-1300 C, so that the carbon source substance can turn into gaseous in the pre-decomposition zone, and be quickly subjected to pyrolysis or polycondensation reactions, forming a pre-decomposition zone product that can quickly be subjected to the subsequent coating reaction. In the pre- decomposition zone, the desired temperature can be realized by means of a conventional heating method or microwave or a radio frequency method. However, the microwave heating method can ionize the C-containing substance, and reduce the pre- decomposition temperature and improve the pre-decomposition efficiency compared with other heating methods.
In some embodiments of the present invention, after passing through the pre- decomposition zone, the gaseous carbon source substance is subjected to dehydrogenation, free radical addition reactions and the like, tobecome a straight- chain or aromatic compound with a larger relative molecular mass and a lower Gibbs free energy. After passing through the pre-decomposition zone, the vaporized carbon source substance is subjected to dehydrogenation (cracking), free radical addition reactions and the like, to become a straight-chain or aromatic compound. After passing through the pre-decomposition zone, the atomized carbon source substance is subjected to cracking, free radical addition reactions and the like, to become a straight-chain or aromatic compound. 21 In the embodiments of the present invention, after the pre-decomposition reaction, the mixed gas that passes through the pre-decomposition zone is a decomposition product, and the decomposition product comprises a non-oxidizing gas that are introduced into the reaction atmosphere and a pre-decomposed carbon source substance. The pre-decomposition reaction step can make the reaction temperature control in the preparation method of the silicon-based lithium storage material more flexible, is beneficial to control the reaction progress (such as the decomposition, addition etc.) of the carbon source substance, and has little interference to the temperature in the coating zone.
After that, the decomposition product is introduced into the depositing and coating zone of the coating equipment, so that the pulverized silicon-based lithium storage material and the pre-decomposed carbon source substance can be subjected to a depositing and coating reaction, so as to form an amorphous carbon coating and a graphitized carbon coating on the surface of the pulverized silicon- based lithium storage material, wherein the surface of the pulverized silicon-based lithium storage material is directly coated by the amorphous carbon coating or the graphitized carbon coating.
In some embodiments of the present invention, the depositing and coating reaction is carried out at a temperature of 500 C-1100 C. Preferably, the depositing and coating reaction is carried out at a temperature of 650 C-1000 C. During the depositing and coating reaction, if the temperature is too low, the C/H ratio of the coating on the surface of the anode material is too high, resulting in poor conductivity and having a negative effect on performance; if the temperature is too high, the silicon oxide in the pulverized silicon-based lithium storage material may 22 CA03203658 2023- 6- 28 be excessively disproportionated, having a negative effect on the capacity and cycle performance of the silicon-based lithium storage material.
During the depositing and coating reaction, a N-containing substance may also be introduced. The N-containing substance includes one or more of NH3, acetonitrile, aniline, or butylamine. By introducing the N-containing substance, it is possible to obtain an amorphous carbon coating and/or graphitized carbon coating doped with Natoms. The amorphous carbon coating and/or graphitized carbon coating doped with N atoms can further improve the charge-discharge capability of the silicon- based lithium storage material, because the amorphous carbon coating and the graphitized carbon coating after being doped with N can further improve the conductivity of the material, thereby reducing the internal resistance of the battery, and thus ensuring the ability of the battery to charge and discharge with high current.
In the preparation method of the silicon-based lithium storage material described in the embodiments of the present invention, a homogeneous doped system is formed by the combination of high-temperature melting, rapid condensation control technology and doping control of an element R, so as to realize a uniform modification of the valence state, structure, crystal shape, and magnetic environment of the silicon-based lithium storage material, improve its characteristics under a high-temperature storage condition after it is intercalated with an active lithium as an active substance of a lithium-ion secondary battery and obtain the best result, and meanwhile improve cycle characteristics and initial charge-discharge coulombic efficiency of the battery. 23 The magnetic susceptibility of the silicon-based lithium storage material prepared by the method described in the embodiments of the present invention has 1-2 peaks around 0 Oe, with a peak intensity of 2 x10'-3 x10-5. The magnetic susceptibility is i3M/i3H, where H represents an applied magnetic field (H, in a unit of Oe) obtained by the vibrating sample magnetometer, and M represents a magnetic induction strength (M, in a unit of emu/g) when the applied magnetic field is within the range of +30000 to -30000. By using the method described in the embodiments of the present invention, the magnetic environment of the silicon-based lithium storage material is improved, and the magnetic induction intensity is greatly reduced.
Example 1 The first mixture was prepared, and it comprised a component A (polysilicon), a component B (13-type quartz), and a component C (MgCO3), wherein the doping element R was based on element Mg in the component C. The molar ratio of the component B to the component A (marked as Si(+4)/Si(0), representing a molar ratio of silicon with a valance of +4 in the component B to silicon with a valance of 0 in the component A) was 5: 3, and the molar ratio of element Mg in the component C to element Si in the component A and the component B (CR/Csi(0_4)) was 0.5.
The first mixture was heated to 2600 C and into a molten state under the protection of argon gas and then cooled to room temperature at a cooling rate of 20 C/S (the molten first mixture was poured onto a fast roller and separated from the roller by a centrifugal action of the roller, to obtain a flaky cooled product). The flaky cooled product was then subjected to a pulverization to form a powder with a median particle size of 4 um, and then an amorphous carbon coating and a graphitized carbon coating with a thickness of 300 nm were deposited on the surface of the powder. The silicon-based lithium storage material prepared had a 24 CA03203658 2023- 6- 28 first-time lithium deintercalation capacity of 980 mAh/g, a first-time coulombic efficiency of 81%, and a capacity retention after 100 cycles at room temperature of 41%.
Example 2 to Example 11 For specific process description, please refer to Example 1. Specific process data and performance parameters of the silicon-based lithium storage material prepared were shown in Table 1.
Comparative Example 1 1 kg of silicon oxide SiOx (x=0.9) with a median particle size of 5 lam were used as the silicon-based material, nitrogen was used as the protective gas, and the reaction temperature was set 900 C, an amorphous carbon coating and a graphitized carbon coating with a thickness of 300 nm were deposited on the surface of the silicon-based material, to form a silicon-based anode material.
The first-time lithium deintercalation capacity of the material was 760 mAh/g, the first- time coulombic efficiency was 64%, and the a capacity retention after 100 cycles at room temperature was 35%.
Table 1 preparation process of the silicon-based lithium storage material and performance parameters of the prepared silicon-based lithium storage material in Examples 1-11 Raw Capacity material First-time retention lithium First-time after 100 Si(+4) Melting Cooling providing CR/ deintercal- coulombic cycles at temperature rate the doping ation efficiency room !Si(0) ( umin) ( C/min) Csio-4) capacity temperat element R (%) -ure (mAh/g) (%) Example 1 3/5 2600 5 MgCO3 0.3 980 81 41 Example 2 3/5 2600 10 Li2CO3 0.3 1052 83 43 Example 3 3/5 2600 20 Li2CO3 0.3 1290 86 59 Example 4 3/5 2600 30 Li2CO3 0.3 1340 88 64 Example 5 3/5 2600 30 Li2CO3 0.5 1300 91 66 Example 6 5/5 2600 20 Li2CO3 0.5 1400 90 67 Example 7 5/5 2300 20 Li2CO3 0.5 1360 89 73 Example 8 5/5 2300 20 LiOH 0.2 1500 85 79 Example 9 5/5 2300 20 LiH 0.1 1420 89 80 Example 10 5/5 2300 20 Mg 0.2 1480 85 84 Example 11 5/5 2300 20 Al 0.3 1420 84 83 When the silicon-based lithium storage material prepared by the method described in the examples of the present invention is used as an anode material of a lithium battery, its first-time lithium deintercalation capacity, first-time coulombic efficiency and capacity retention after 100 cycles at room temperature are far higher than those of the silicon-based anode material in the comparative example.
In summary, after reading this detailed disclosure, those skilled in the art may understand that the foregoing detailed disclosure may be presented by way of example only, and may not be limiting. Although not explicitly stated here, those 26 CA03203658 2023- 6- 28 skilled in the art can understand that the present invention is intended to include various reasonable changes, improvements, and modifications to the embodiments.
These changes, improvements, and modifications are intended to be proposed by the present disclosure, and are within the spirit and scope of the exemplary embodiments of the present disclosure.
It should be understood that the term "and/or" used herein includes any or all combinations of one or more of the associated listed items.
It should also be understood that the terms "comprising" "comprise(s)", "including", and/or "include(s)", when used herein, indicate the presence of the recited features, wholes, steps, operations, elements and/or components, but it does not exclude the presence or addition of one or more other features, wholes, steps, operations, elements, components, and/or groups thereof.
It should also be understood that although the terms first, second, third, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another.
Therefore, the first element in some embodiments may be referred to as the second element in other embodiments without departing from the teachings of the present invention. The same reference numerals or the same reference signs denote the same elements throughout the specification. 27

Claims (19)

Claims
1. A silicon-based lithium storage material, characterized in that, comprising: a first component, comprising Si with a valence of 0-4, with the proviso that O<Csi(l-4)/Csi(o)<1, where Csi(1-4) is the molar amount of element silicon with a valence of 1-4, and Csi(o) is the molar amount of element silicon with a valence of 0; and a second component, comprising a doping element R, where the doping element R at least includes one of elements of main group I, II, and III, with the proviso that O<CR/Csi(0-4)<1 .5, where CR is the molar amount of the doping element R, and Csi(0_4) is the molar amount of element silicon with a valence of 0- 4.
2. The silicon-based lithium storage material of claim 1, characterized in that, the elements of main group I, II, and III include Li, Na, Mg, Ca, or Al.
3. The silicon-based lithium storage material of claim 1, characterized in that, the surface of the material further comprises a carbon coating.
4. The silicon-based lithium storage material of claim 3, characterized in that, the mass percentage content of the carbon coating is greater than 0 and less than 1 0%.
5. The silicon-based lithium storage material of claim 3, characterized in that, the 28 carbon coating comprises at least one of an amorphous carbon coating or a graphitized carbon coating.
6. The silicon-based lithium storage material of claim 3, characterized in that, the carbon coating comprises more than one amorphous carbon coating and more than one graphitized carbon coating, wherein the more than one amorphous carbon coating is arranged alternately with the more than one graphitized carbon coating.
7. The silicon-based lithium storage material of claim 5 or 6, characterized in that, the amorphous carbon coating is doped with a nitrogen atom, and the graphitized carbon coating is doped with a nitrogen atom.
8. The silicon-based lithium storage material of claim 1, characterized in that, Si with a valence of 0-4 and the doping element R are uniformly distributed.
9. A method for preparing a silicon-based lithium storage material, comprising: providing a first mixture, where the first mixture at least comprises an elementary substance silicon and a silicon with an oxidation state of +4, and also a doping element R, where the doping element R at least includes one of elements of main group I, II, and III, with the proviso that O<CR/Csj(o-4)<1 .5, where CR is the molar amount of the doping element R, and Csi(o-4) is the molar amount of element silicon with a valence of 0-4; and heating the first mixture to a molten state under the protection of a non- oxidizing gas, and then cooling to room temperature at a cooling rate of 5 C/S-30 C/S. 29
10. The method for preparing a silicon-based lithium storage material of claim 9, characterized in that, the elements of main group I, II, and III include Li, Na, Mg, Ca, or Al.
11. The method for preparing a silicon-based lithium storage material of claim 9, characterized in that, the temperature when heating to a molten state is 1500C- 3000C.
12. The method for preparing a silicon-based lithium storage material of claim 9, characterized in that, the method for cooling the molten first mixture to room temperature at a cooling rate of 5-30C/S comprises: pouring the molten first mixture onto a fast roller, and separating the molten first mixture from the roller by a centrifugal action of the roller to obtain a flaky cooled product.
13. The method for preparing a silicon-based lithium storage material of claim 12, characterized in that, the method further comprises pulverizing the flaky cooled product to form a powder with a median particle size of 1-8 ilm.
14. The method for preparing a silicon-based lithium storage material of claim 13, characterized in that, the method further comprises depositing a carbon coating on the surface of the pulverized silicon-based lithium storage material.
15. The method for preparing a silicon-based lithium storage material of claim 14, characterized in that, the method for depositing a carbon coating comprises: in a non-oxidizing atmosphere, passing a carbon source substance through a pre- decomposition zone to form a decomposition product, wherein the carbon source substance includes one or more of a gaseous carbon source substance, a vaporized carbon source substance or an atomized carbon source substance; and adjusting the flow rate VG of the decomposition product into a reaction chamber of a depositing-coating zone, and a ratio Mc/M of the molar flow rate of the decomposition product to the mass of the pulverized silicon-based lithium storage material, to subject the pulverized silicon-based lithium storage material and the decomposition product to a depositing and coating reaction in the depositing- coating zone, forming an amorphous carbon coating or a graphitized carbon coating or a composite coating comprising both an amorphous carbon coating and a graphitized carbon coating on the surface of the pulverization-treated silicon- based lithium storage material, with the proviso that 0.01<VG<100 and 0.001<Mc/M <1, where VG is in a unit of m/min, Mc is in a unit of mol/min, in terms of carbon atoms, and M is the mass of the pulverized silicon-based lithium storage material, in a unit of kg.
16. The method for preparing a silicon-based lithium storage material of claim 15, characterized in that, under a first condition: 1O<VG<100 and 0.001<Mc/M<0.1, a graphitized carbon coating is formed on the surface of the silicon-based lithium storage material; under a second condition: 0.01<VG<5 and 0.2<Mc/M<1, an amorphous carbon coating is formed on the surface of the silicon-based lithium storage material.
17. The method for preparing a silicon-based lithium storage material of claim 16, characterized in that, the value of VG and Mc/M are adjusted to alternate between the first condition and the second condition, thereby forming an alternating coating of an amorphous carbon coating and a graphitized carbon coating on the surface of 31 the silica-based storage lithium material.
18. The method for preparing a silicon-based lithium storage material of claim 15, characterized in that, the gaseous carbon source substance includes methane, ethane, ethylene, acetylene, propane, and propylene, the vaporized carbon source substance includes n-hexane, ethanol, and benzene, and the atomized carbon source substance include polyethylene and polypropylene.
19. The method for preparing a silicon-based lithium storage material of claim 15, characterized in that, a N-containing substance is introduced during the depositing and coating reaction, and the N-containing substance includes one or more of NH3, acetonitrile, aniline, or butylamine. 32
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