WO2019114555A1 - 一种锂离子电池负极材料及其制备方法 - Google Patents

一种锂离子电池负极材料及其制备方法 Download PDF

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WO2019114555A1
WO2019114555A1 PCT/CN2018/118101 CN2018118101W WO2019114555A1 WO 2019114555 A1 WO2019114555 A1 WO 2019114555A1 CN 2018118101 W CN2018118101 W CN 2018118101W WO 2019114555 A1 WO2019114555 A1 WO 2019114555A1
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sio
metal
optionally
acid
negative electrode
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PCT/CN2018/118101
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French (fr)
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梁腾宇
庞春雷
任建国
岳敏
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深圳市贝特瑞新能源材料股份有限公司
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Priority to EP18887516.5A priority Critical patent/EP3726628A4/en
Priority to JP2019544907A priority patent/JP6942192B2/ja
Priority to US16/760,550 priority patent/US11967708B2/en
Priority to KR1020207006458A priority patent/KR102402341B1/ko
Priority to KR1020227016060A priority patent/KR20220070044A/ko
Publication of WO2019114555A1 publication Critical patent/WO2019114555A1/zh

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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the field of lithium ion battery anode materials, and relates to a lithium ion battery anode material and a preparation method thereof, for example, to a lithium ion battery oxysilicon oxide anode material and a preparation method thereof.
  • Lithium-ion batteries have become the ideal portable battery due to their high operating voltage, light weight, low self-discharge, long cycle life, no memory effect, no environmental pollution and good safety performance.
  • commercial lithium-ion batteries mainly use graphite as a negative electrode material, and its theoretical specific capacity is only, which cannot meet the increasing needs of the future energy storage field, and it is urgent to develop a new generation of high-performance negative electrode materials.
  • Si has a high lithium insertion capacity of up to 4200 mAh ⁇ g -1 , but in the process of deintercalating lithium from Si, the volume effect is as high as 300%, so that the lattice structure of Si is found to collapse, the Si particles are pulverized, and the active substances and the set
  • the detachment of the fluid causes the capacity to rapidly decay during the cycle, which hinders Si from being put into the practical application as a negative electrode of the lithium ion battery.
  • SiO x is a structure surrounded by a skeleton composed of amorphous nano-Si and amorphous SiO 2 which is composed of low-value oxide of Si, which alleviates the volume effect of Si, and makes SiO x have lower expansion and longer life than Si material.
  • the advantages are conducive to the development of lithium-ion batteries with higher capacity density and longer service life, which have been commercialized.
  • Formula (1) and formula (2) are irreversible reactions, and the formation of Li 2 O and Li 4 SiO 4 consumes a large amount of lithium ions, resulting in a low first coulombic efficiency of SiO x .
  • SiO x is required to reduce the content of oxygen in the system, reducing the irreversible capacity never by the formula (1) and (2) caused by the reaction. Since the SiO material requires a low-value oxide skeleton of Si to alleviate the expansion, the oxygen content is reduced and the system of SiO x itself cannot be destroyed.
  • Patent CN201310154328 discloses a method for preparing a lithium ion battery negative electrode material with high coulombic efficiency for the first time.
  • the method uses LiH to pre-embed lithium into SiO x material, which significantly improves the first coulombic efficiency of SiO x material.
  • LiH is a flammable and explosive substance in contact with water, which has a large safety hazard and is difficult to achieve large-scale industrial production.
  • Patent CN201110149645 discloses a method for preparing porous silicon by thermal reduction of magnesium, the technical point of which is to completely reduce SiO x by using a relatively large amount of magnesium to prepare a porous silicon material.
  • This material belongs to Si material and has completely destroyed the oxide skeleton of SiO x itself. It cannot guarantee the advantage of low expansion and is not the same system as SiO x anode material.
  • Patent CN201610863902.7 discloses a preparation method of a composite containing silicon oxide, the technical point of which is that the SiO vapor and the metal vapor are reacted in a gas phase and condensed under a negative pressure environment. This method requires a vacuum environment and a temperature at which SiO can be vaporized, and has high requirements on equipment and energy. Therefore, a solution that can be implemented with simple equipment under normal pressure is required.
  • Si materials have a very high capacity advantage compared to graphite, but their expansion of up to 300% inhibits the practical application of Si materials.
  • Si materials with high specific surface area such as porous silicon, although the space is relieved to some extent by the space reserved, the increase of the specific surface area will increase the side reaction with the electrolyte, which will cause it to consume more activity.
  • the material forms an SEI film and poor electrical contact between the particles.
  • the SiO x material is a structure in which a low-value oxide skeleton of Si encapsulates nano Si and amorphous SiO 2 .
  • Si is dispersed in the entire framework with a smaller crystallite size, and the smaller Si size of the Si itself expands less, and the rigid skeleton not only inhibits the expansion of the nano Si, but also prevents it from circulating. Agglomeration of nanoparticles. Therefore, SiO x materials have superior cycling and expansion advantages compared to Si materials, especially late cycle.
  • the purpose of the present application is to provide a lithium ion battery anode material and a preparation method thereof, in particular, a lithium ion battery oxysilicon oxide anode material and a preparation method thereof.
  • the battery made of the lithium ion battery anode material of the present application has a high first-time capacity, high first-time coulomb efficiency, good cycle performance, and small volume effect.
  • the present application provides a negative electrode material for a lithium ion battery, particularly a silicon oxide anode material, wherein the negative electrode material includes SiO y and M compounds, and M is a metal;
  • SiO y (0.2 ⁇ y ⁇ 0.9) maintains a good oxide skeleton and has the advantage of low expansion.
  • the "M compound” means a substance which is converted into a metal M after a redox reaction.
  • SiO y (0.2 ⁇ y ⁇ 0.9) is taken as a main component, and y is, for example, 0.25, 0.3, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.8 or 0.85.
  • the battery made of the negative electrode material of the lithium ion battery of the present application has high first capacity, high coulombic efficiency, good cycle performance, small volume effect, charge and discharge at 0.005V ⁇ 1.5V, and the first capacity is above 1250mAh/g.
  • the Coulomb efficiency is above 80%
  • the 50-week capacity retention rate is above 90%
  • the volume effect is small
  • the expansion rate of the pole piece is below 50%.
  • the silicon oxide anode material with different first-time capacity and first coulombic efficiency can be obtained by adjusting the process parameters according to actual needs.
  • the M is a reactive metal having a Pauling electronegativity of ⁇ 1.8.
  • any one or a combination of at least two of metal Na, metal K, metal Mg, metal Ca or metal Al may be included.
  • the mass percentage of the M compound is 1% to 60%, for example, 1%, 3%, 5%, 8%, based on 100% of the total mass of the negative electrode material. 10%, 12.5%, 15%, 20%, 25%, 27.5%, 30%, 33%, 36%, 40%, 45%, 50%, 55% or 60%, etc. If the mass percentage is less than 1%, the first coulombic efficiency of the prepared SiO y is too small compared to the SiO x ; if the mass percentage is more than 60%, SiO x will be completely reduced to elemental Si, oxymethylene oxide. The oxide skeleton of the material itself is completely destroyed, and the low expansion property of the oxysilylene material is lost.
  • a specific surface area of the negative electrode material is ⁇ 50m 2 / g, e.g. 1m 2 / g, 3m 2 / g, 5m 2 / g, 7m 2 / g, 10m 2 / g, 15m 2 / g, 20m 2 / g, 22 m 2 /g, 25 m 2 /g, 30 m 2 /g, 32 m 2 /g, 35 m 2 /g, 40 m 2 /g, 45 m 2 /g Hu 50 m 2 /g, etc., optionally 1.0 m 2 /g ⁇ 15.0m 2 /g. If the specific surface area is greater than 50 m 2 /g, it will result in a low first coulombic efficiency, optionally ⁇ 15 m 2 /g.
  • the size of the Si crystallite grains in the SiO y is ⁇ 100 nm, for example, 1 nm, 5 nm, 10 nm, 12 nm, 15 nm, 20 nm, 25 nm, 28 nm, 30 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 70 nm, 80 nm, 90 nm or 100 nm, etc., if the size of the Si crystallite grains is larger than 100 nm, the cycle performance is poor, and it is optionally ⁇ 20 nm.
  • the anode material further comprises any one or at least two of an amorphous carbon coating layer, graphite, carbon black, carbon nanotubes, graphene, silicon, and a metal compound. Combination of species.
  • the metal compound comprises any one of metal oxide, metal silicide or metal silicate or a combination of at least two, optionally including K 2 O, Na 2 O, MgO, CaO, Al 2 O 3 , Mg 2 Si, Ca 2 Si, Al 4 Si 3 , K 2 SiO 3 , K 4 SiO 4 , K 2 Si 2 O 5 , Na 2 SiO 3 , Na 4 SiO 4 , Na 2 Si 2 O 5 , Any one or a combination of at least two of Mg 2 SiO 4 , MgSiO 3 , Ca 2 SiO 4 , CaSiO 3 , Al 4 (SiO 4 ) 3 or Al 2 (SiO 3 ) 3 .
  • the present application provides a method for preparing a lithium ion battery anode material according to the first aspect, which is also a modification method, the method comprising:
  • the raw material containing the SiO x material is subjected to a redox reaction with the metal M, and the O/Si ratio x of the SiO x material is adjusted to y, and the metal M is oxidized to obtain the M compound;
  • the y value is controllable, and can be realized by adjusting process parameters according to different actual needs.
  • the method includes the following steps:
  • the mass percentage of the metal M is 3% to 40%, based on 100% of the total mass of the raw material containing the SiO x material and the metal M;
  • the mass percentage of the metal M in the step (1) is 3% to 40%, for example, 3%, 4%, 6%, 10%, 13%, 15%, 20%, 22.5%, 25 %, 30%, 35% or 40%, etc.
  • the mass percentage of the metal M is controlled to be 3% to 40%, and the mixing ratio is recorded as m, and the ratio m can control the O/Si ratio x of the SiO x material to be adjusted to y, 0.5. ⁇ x ⁇ 1.5, 0.2 ⁇ y ⁇ 0.9, and y ⁇ x.
  • the method further comprises the steps of performing liquid-solid separation after the acid treatment, and washing and drying the separated solid phase.
  • the manner of liquid-solid separation includes, but is not limited to, any one of centrifugation or filtration separation.
  • the manner of drying includes, but is not limited to, any of high temperature drying or freeze drying.
  • the method further comprises, as the raw material of the step (1), the product of the step (1) and/or the product of the step (2), repeating the following steps: step (1) , or step (1) and step (2) in sequence.
  • step (1) the first coulombic efficiency of the finally obtained negative electrode material
  • the number of repetitions can be selected from 0 to 5 times, for example, 0 times, 1 time, 2 times, 3 times, 4 times or 5 times. “0 times” means no repeated operation, and can be selected once.
  • the Si crystallite grain size in the raw material containing the SiO x material in the step (1) is ⁇ 100 nm, for example, 1 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 40 nm, 45 nm, 55 nm, 60 nm, 70 nm, 80 nm, 90 nm or 100 nm, etc., optionally ⁇ 20 nm.
  • the raw material comprising the SiO x material in the step (1) further comprises an additive and a SiO x material forming a SiO x -based composite material, the additive being amorphous carbon coated. Any one or a combination of at least two of layers, graphite, carbon black, carbon nanotubes, graphene, silicon or metal salts.
  • the amorphous carbon coating layer has a mass percentage of 1% to 20%, such as 1%, 2%, 3%, 5%, based on 100% of the total mass of the SiO x -based composite material. , 8%, 10%, 12%, 15%, 18%, 19% or 20%, etc.
  • the raw material containing the SiO x material is any one or a combination of two of SiO x powder or SiO x matrix composite.
  • the metal M in the step (1) is a living metal, and its Pauling electronegativity is ⁇ 1.8.
  • any one or a combination of at least two of metal Na, metal K, metal Mg, metal Ca or metal Al may be included.
  • the metal M has a particle diameter D50 ⁇ 300 ⁇ m, such as 300 ⁇ m, 275 ⁇ m, 260 ⁇ m, 240 ⁇ m, 220 ⁇ m, 200 ⁇ m, 180 ⁇ m, 150 ⁇ m, 120 ⁇ m, 100 ⁇ m or 50 ⁇ m, 20 ⁇ m or 10 ⁇ m, and the like.
  • the apparatus used in the mixing in the step (1) is any one of a VC mixer, a multi-dimensional mixer, a mechanical fusion machine, a powder mixer or a ball mill.
  • the non-oxidizing atmosphere in the step (1) comprises any one of a nitrogen atmosphere, an argon atmosphere, a helium atmosphere or a helium atmosphere, or a combination of at least two.
  • the gas pressure during the heat treatment in the step (1) is 0.01 MPa to 1 MPa, for example, 0.01 MPa, 0.02 MPa, 0.05 MPa, 0.08 MPa, 0.1 MPa, 0.15 MPa, 0.2 MPa, 0.3 MPa, 0.35 MPa, 0.4 MPa.
  • the temperature of the heat treatment in the step (1) is 550 ° C to 1100 ° C, for example, 550 ° C, 600 ° C, 650 ° C, 675 ° C, 700 ° C, 725 ° C, 735 ° C, 750 ° C, 770 ° C, 780 ° C , 800 ° C, 850 ° C, 880 ° C, 900 ° C, 925 ° C, 950 ° C, 1000 ° C, 1050 ° C or 1100 ° C and so on.
  • the heat preservation time in the step (1) is 0.5 h to 24 h, for example, 0.5 h, 1 h, 2 h, 3 h, 4 h, 6 h, 8 h, 9 h, 10 h, 12 h, 13.5 h, 15 h, 18 h, 19 h, 20h, 22h or 24h, etc.
  • the apparatus used for the heat treatment is any one of a box furnace, a rotary furnace, a tube furnace, a heating mixer, a roller kiln, a pusher kiln, an autoclave or a vacuum furnace.
  • the acid used is an acid capable of dissolving the M compound, including any one or at least two of hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, formic acid or acetic acid.
  • hydrochloric acid sulfuric acid, nitric acid, perchloric acid, formic acid or acetic acid.
  • the acid treatment time is 0.2h-24h, such as 0.2h, 0.5h, 1h, 3h, 5h, 6h, 8h, 10h, 12h, 15h, 18h, 20h, 21.5h or 24h, etc. Choose from 0.2h to 4h.
  • the residual M compound accounts for 1% to 60% of the total mass of the lithium ion battery material, and the reason for limiting to the range is: avoiding the total surface area of the material being excessively caused by the M compound being completely dissolved, The material capacity caused by the excessive dissolution of the M compound is prevented from being too low. Whether it is completely dissolved or dissolved too little will reduce the final electrochemical performance of the material.
  • the method includes the following steps:
  • the mass percentage of the metal M is 3% to 40%, based on 100% of the total mass of the raw material containing the SiO x material and the metal M;
  • the acid obtained by the step (1) is acid-treated with an acid to partially dissolve the M compound, and the treatment time is controlled during the acid treatment, so that the residual amount of the M compound accounts for 1% to 60% of the total mass of the material, avoiding The M compound is completely dissolved to cause the specific surface area of the material to be too large, and then liquid-solid separation, washing to neutral, and drying to obtain a lithium ion battery material including SiO y and M compounds;
  • This application uses active metal to reduce and deoxidize SiO x (0.5 ⁇ x ⁇ 1.5) anode materials to prepare lithium ion battery anode materials, which effectively and inexpensively reduces the oxygen content in SiO x system to y (0.2 ⁇ y ⁇ 0.9), the first coulombic efficiency is improved, and the obtained negative electrode material further contains M compound, and SiO y contains Si crystallite grains.
  • the negative electrode material prepared by the method of the present application maintains the structure of the SiO x system itself, and inherits the advantage that the SiO x material itself has excellent cycle expansion performance.
  • the anode material of the present application includes SiO y (0.2 ⁇ y ⁇ 0.9) and M compound, M is a metal, and SiO y contains Si crystallite grains, and the anode material has a high first coulombic efficiency, which is reduced
  • the O content of the negative electrode reduces the amount of irreversible phase Li 2 O and Li 4 SiO 4 formed during the first lithium insertion, and the material has excellent cyclic expansion properties, which is favorable for the development of high energy density batteries.
  • Fig. 1 is a graph showing the 50-cycle cycle capacity retention ratio of the button battery of Example 1 and Comparative Example.
  • the O content of the material is characterized by first treating the material with concentrated HCl for 24 h, then separating the acid solution and drying the filter residue. The X-ray diffraction pattern was examined to confirm that there was no diffraction peak of any metal salt, and the residue was characterized using an N/H/O analyzer.
  • the Si crystallite size of the material is characterized by X-ray diffractometry, scanning the 2-Theta range from 10° to 90°, and then fitting the 2-Theta range from 26° to 30° to obtain Si.
  • the half-peak width of the (111) peak was calculated using the Scherrer formula to obtain the Si crystallite grain size.
  • the first capacity and the first efficiency test of the material were characterized by button cells.
  • the counter electrode was a lithium metal sheet with a charge and discharge rate of 0.1 C and a charge and discharge voltage range of 0.005 V to 1.5 V.
  • the cycle charge/discharge rate is 0.1 C for the first week, 0.2 C for the second week, 0.5 C for the third week, 1.0 C for the fourth week to the 50th week, and 0.1 C discharge to 0.005 V for the 51st week. Decompose the battery to test the thickness of the pole piece.
  • the charge and discharge voltage range of all cycle weeks is 0.005V to 1.5V.
  • the 50-week capacity retention ratio is the ratio of the charging capacity at the 50th week to the charging capacity at the 1st week.
  • the pole piece expansion ratio (the thickness of the pole piece after the cycle - the thickness of the pole piece before the cycle) / (the thickness of the pole piece before the cycle - the thickness of the copper foil).
  • Mg powder 120 g. That is, the ratio of Mg to the mixture was 12%, and the mixture was placed in a VC mixer for 30 minutes, and then placed in a box furnace of 0.1 MPa Ar atmosphere at 1000 ° C for 12 hours to obtain a product (reduced SiO y material and Mg compound).
  • step (2) The product obtained in the step (1) is subjected to acid treatment for 2 hours using HCl, and then the acid solution is separated by filtration, and then the filter residue is dried at a high temperature to obtain a negative electrode material of a lithium ion battery.
  • the O content was characterized by using an N/H/O analyzer.
  • y 0.37.
  • the Si crystallite size of the SiO y was characterized by X-ray diffractometry to be 9.8 nm.
  • the material was mixed with graphite and assembled into a button cell, which had a 50-week capacity retention rate of 95% and a pole piece expansion ratio of 49%.
  • the O content was characterized by using an N/H/O analyzer.
  • y 0.78.
  • the Si crystallite size of the SiO y was characterized by X-ray diffractometry to be 4.5 nm.
  • the material was mixed with graphite and assembled into a button cell, and its 50-week capacity retention rate was 97%, and the pole piece expansion ratio was 42%.
  • the mixture of SiO x and Mg mixed by a VC mixer was placed in a box furnace of 0.1 MPa N 2 atmosphere and treated at 1000 ° C for 12 h.
  • the content of O was characterized by using an N/H/O analyzer.
  • y 0.79.
  • the Si crystallite size of the SiO y was characterized by X-ray diffractometry to be 4.6 nm.
  • the material was mixed with graphite and assembled into a button cell, and its 50-week capacity retention rate was 97%, and the pole piece expansion ratio was 42%.
  • the O content was characterized by using an N/H/O analyzer.
  • y 0.35.
  • the Si crystallite size of the SiO y was characterized by X-ray diffractometry to be 5.2 nm.
  • the material was mixed with graphite and assembled into a button cell, and its 50-week capacity retention rate was 94%, and the pole piece expansion ratio was 48%.
  • the mixture of SiO x and Mg mixed by a VC mixer was placed in a vacuum of 0.02 MPa Ar atmosphere at 1000 ° C for 12 h.
  • the content of O was characterized by using an N/H/O analyzer.
  • y 0.37.
  • the Si crystallite size of the SiO y was characterized by X-ray diffractometry to be 9.5 nm.
  • the material was mixed with graphite and assembled into a button cell, which had a 50-week capacity retention rate of 95% and a pole piece expansion ratio of 49%.
  • the mixture of SiO x and Mg mixed by a VC mixer was placed in a vacuum of 0.1 MPa Ar atmosphere at 800 ° C for 12 h.
  • the O content was characterized by using an N/H/O analyzer.
  • y 0.51.
  • the Si crystallite size of the SiO y was characterized by X-ray diffractometry to be 6.6 nm.
  • the material was mixed with graphite and assembled into a button cell, and its 50-week capacity retention rate was 97%, and the pole piece expansion ratio was 45%.
  • the product obtained in the step (1) of Example 2 was used as the starting material of the step (1), and the operation of the step (1) was repeated once, and then the step (2) was completed to obtain the product SiO y .
  • the O content was characterized by using an N/H/O analyzer.
  • y 0.53.
  • the Si crystallite size of the SiO y was characterized by X-ray diffractometry to be 5.2 nm.
  • the material was mixed with graphite and assembled into a button cell, and its 50-week capacity retention rate was 96%, and the pole piece expansion ratio was 44%.
  • SiO y having different y values can be obtained by different processing conditions from different x SiO x raw materials and different metal (Mg, Al, etc.) addition ratios.
  • the obtained SiO y has high first efficiency, high first capacity, excellent cycle performance, and small volume effect.
  • 500g SiO x matrix composite material which is a composite material formed by amorphous carbon coating layer and commercially available SiO, and amorphous carbon accounts for 3wt% of the composite material, and 500g Mg powder is tested, that is, the proportion of Mg in the mixture. It is 50% by weight.
  • the content of O was characterized by using an N/H/O analyzer.
  • y 0.
  • the Si crystallite size of the SiO y was characterized by X-ray diffractometry to be 63.5 nm.
  • the material was mixed with graphite and assembled into a button cell, and its 50-week capacity retention rate was 82%, and the pole piece expansion ratio was 71%.

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Abstract

本文公开了一种锂离子电池负极材料及其制备方法，所述负极材料中包括SiOy(0.2＜y＜0.9)和M化合物，M为金属。本申请的方法为：使包含SiOx材料的原料与金属M发生氧化还原反应，SiOx(0.5＜x＜1.5)材料的O/Si比x调整为y(0.2＜y＜0.9)，同时金属M被氧化得到M化合物。

Description

一种锂离子电池负极材料及其制备方法 技术领域
本申请属于锂离子电池负极材料领域，涉及一种锂离子电池负极材料及其制备方法，例如涉及一种锂离子电池氧化亚硅负极材料及其制备方法。
背景技术
现有随着电动汽车以及其他电子产品的快速发展，对电能储存提出了越来越高的要求。锂离子电池以其工作电压高、重量轻、自放电小、循环寿命长、无记忆效应、无环境污染以及安全性能好等特点，成为了目前理想的便携式电池。目前商业化的锂离子电池主要采用石墨作为负极材料，其理论比容量仅为，不能满足未来储能领域日益增长的需要，亟需开发新一代的高性能负极材料。Si有很高的嵌锂容量，高达4200mAh·g -1，但Si的脱嵌锂过程中，体积效应高达300％，使Si的晶格结构发现坍塌，Si颗粒发生粉化，活性物质与集流体发生脱离，导致在循环过程中容量发生迅速地衰减，从而阻碍了Si作为锂离子电池负极投入到实际应用中。SiO x为非晶纳米Si和非晶SiO 2被Si的低值氧化物组成的骨架所包围的结构，缓解了Si的体积效应，使SiO x相比Si材料有较低膨胀和较长寿命的优势，有利于开发更高容量密度和更长使用寿命的锂离子电池，现已实现商品化。
但SiO x的首次库仑效率较低，约75％。一般认为，SiO x在首次嵌锂时，发生了如下反应：
SiO+2Li ++2e -→Li 2O+Si                   (1)
4SiO+4Li ++4e -→Li 4SiO 4+3Si              (2)
Si+4.4Li ++4.4e -→Li 4.4Si                 (3)
式(1)和式(2)为不可逆反应，生成Li 2O和Li 4SiO 4消耗了较多的锂离子，从而导致SiO x的首次库仑效率较低。欲提升SiO x的首次库仑效率，则需要减少SiO x体系中氧的含量，从来减少由式(1)和式(2)反应所造成的不可逆容量。由于SiO材料需要Si的低值氧化物骨架以缓解膨胀，故减少氧含量的同时，不能破坏SiO x本身的体系。
专利CN201310154328公开了一种首次库仑效率高的锂离子电池负极材料的制备方法，该方法使用了LiH对SiO x材料预嵌入锂，显著提升了SiO x材料的首次库仑效率。但是LiH的为遇水易燃易爆物，有较大安全隐患，不易实现大规模工业化生产。
专利CN201110149645公开了一种镁热还原制备多孔硅的方法，其技术要点在使用较大量的镁将SiO x彻底还原，制备多孔硅材料。此材料属于Si材料，已经完全破坏SiO x本身的氧化物骨架，不能保障其低膨胀的优势，与SiO x负极材料非同一体系。
专利CN201610863902.7公开了一种含硅氧化物的复合物的制备方法，其技术要点为在负压的环境下，使SiO蒸气与金属蒸气以气相方式反应并凝结得到。此方法需要真空环境及能使SiO气化的温度，对设备及能源的要求较高，故需要一种常压下用简易设备可以实施的方案。
Si材料相比石墨，有非常高的容量优势，但其高达300％的膨胀抑制了Si材料的实际应用。多孔硅等高比表面积的Si材料，虽然以预留空间的方式一定程度上缓解了膨胀，但其比表面积的增大会使其与电解液的副反应增多，反而会导致其消耗更多的活性物质形成SEI膜，以及使颗粒之间电接触不良。SiO x材料为Si的低值氧化物骨架包裹纳米Si和非晶SiO 2的结构。Si以较小的微晶晶粒尺寸分散在整个骨架中，较小晶粒尺寸的纳米Si自身的膨胀较小，而且刚 性的骨架不但抑制了纳米Si的膨胀，还防止了其在循环过程中纳米粒子发生的团聚。故SiO x材料相比Si材料有着优良的循环和膨胀优势，尤其是后期循环。
因此，保持SiO x负极材料本身的体系结构，保证其较低的体积效应及较好的循环性能的前提下，用简单常见的设备、温和的反应条件，安全、廉价地大幅提升其首次库伦效率，并能实现其产业化，为所属领域的技术难题。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请的目的在于提供一种锂离子电池负极材料及其制备方法，尤其是一种锂离子电池氧化亚硅负极材料及其制备方法。采用本申请的锂离子电池负极材料制成的电池的首次容量高，首次库伦效率高，且循环性能好，体积效应小。
第一方面，本申请提供一种锂离子电池负极材料，尤其是一种氧化亚硅负极材料，所述负极材料中包括SiO y和M化合物，M为金属；
其中，0.2＜y＜0.9。
本申请中，SiO y(0.2＜y＜0.9)保持了很好的氧化物骨架，具有低膨胀的优势。
本申请中，所述“M化合物”指：金属M发生氧化还原反应之后转变为的物质。
本申请中，SiO y(0.2＜y＜0.9)作为主要成分，y例如0.25、0.3、0.4、0.45、0.5、0.55、0.6、0.65、0.7、0.8或0.85等。
采用本申请的锂离子电池负极材料制成的电池的首次容量高，首次库伦效率高，且循环性能好，体积效应小，在0.005V～1.5V下充放电，首次容量在 1250mAh/g以上，首次库伦效率在80％以上，50周容量保持率在90％以上，且体积效应小，极片的膨胀率在50％以下。且可以根据实际需要，通过调整工艺参数得到不同首次容量和首次库伦效率的氧化亚硅负极材料。
可选地，所述M为活泼金属，其鲍林电负性＜1.8。可选包括金属Na、金属K、金属Mg、金属Ca或金属Al中的任意一种或至少两种的组合。
作为本申请的可选技术方案，以所述负极材料的总质量为100％计，所述M化合物的质量百分含量为1％～60％，例如1％、3％、5％、8％、10％、12.5％、15％、20％、25％、27.5％、30％、33％、36％、40％、45％、50％、55％或60％等。若质量百分含量小于1％，所制得的SiO y的首次库伦效率相比SiO x提升幅度过小；若质量百分含量大于60％，SiO x将被彻底还原成单质Si，氧化亚硅材料本身的氧化物骨架被完全破坏，将失去氧化亚硅材料低膨胀的特性。
可选地，所述负极材料的比表面积为≤50m 2/g，例如1m 2/g、3m 2/g、5m 2/g、7m 2/g、10m 2/g、15m 2/g、20m 2/g、22m 2/g、25m 2/g、30m 2/g、32m 2/g、35m 2/g、40m 2/g、45m 2/g胡50m 2/g等，可选为1.0m 2/g～15.0m 2/g。若比表面积大于50m 2/g，会导致其首次库伦效率较低，可选为≤15m 2/g。
可选地，所述SiO y中的Si微晶晶粒的尺寸在≤100nm，例如1nm、5nm、10nm、12nm、15nm、20nm、25nm、28nm、30nm、40nm、45nm、50nm、55nm、60nm、70nm、80nm、90nm或100nm等，若Si微晶晶粒的尺寸大于100nm，会导致其循环性能较差，可选为≤20nm。
作为本申请所述方法的可选技术方案，所述负极材料中还包含无定形碳包覆层、石墨、碳黑、纳米碳管、石墨烯、硅、金属化合物中的任意一种或至少两种的组合。
可选地，所述金属化合物包括金属氧化物、金属硅化物或金属硅酸盐中的任意一种或至少两种的组合，可选包括K 2O、Na 2O、MgO、CaO、Al 2O 3、Mg 2Si、Ca 2Si、Al 4Si 3、K 2SiO 3、K 4SiO 4、K 2Si 2O 5、Na 2SiO 3、Na 4SiO 4、Na 2Si 2O 5、Mg 2SiO 4、MgSiO 3、Ca 2SiO 4、CaSiO 3、Al 4(SiO 4) 3或Al 2(SiO 3) 3中的任意一种或至少两种的组合。
第二方面，本申请提供如第一方面所述锂离子电池负极材料的制备方法，这种方法也是一种改性方法，所述方法包括：
使包含SiO x材料的原料与金属M发生氧化还原反应，SiO x材料的O/Si比x调整为y，同时金属M被氧化得到M化合物；
其中，0.5＜x＜1.5，0.2＜y＜0.9，且y＜x，例如x＝0.6，y＝0.25；x＝0.75，y＝0.4；x＝0.8，y＝0.4；x＝0.9，y＝0.45；x＝1.0，y＝0.5；x＝1.2，y＝0.8；x＝1.5，y＝0.85等。
本申请中，y值可控，可根据不同的实际需要，通过调整工艺参数实现。
作为本申请所述方法的可选技术方案，所述方法包括以下步骤：
(1)使包含SiO x材料的原料与金属M混合均匀，然后在非氧化性气氛下进行热处理并保温，得到还原产物SiO y和氧化产物M化合物；
其中，以包含SiO x材料的原料与金属M的总质量为100％计，所述金属M的质量百分含量为3％～40％；
(2)使用酸对步骤(1)得到的产物进行酸处理以使M化合物发生溶解而部分去除，得到包括SiO y和M化合物的锂离子电池材料；
其中，0.5＜x＜1.5，0.2＜y＜0.9，且y＜x。
本申请中，步骤(1)所述金属M的质量百分含量为3％～40％，例如3％、4％、6％、10％、13％、15％、20％、22.5％、25％、30％、35％或40％等。此可 选技术方案中，控制所述金属M的质量百分含量为3％～40％，该混合比例记为m，该比例m可以控制SiO x材料的O/Si比x调整为y，0.5＜x＜1.5，0.2＜y＜0.9，且y＜x。
作为本申请所述方法的可选技术方案，所述方法还包括在酸处理之后，进行液固分离，并对分离固相进行洗涤和干燥的步骤。
可选地，所述液固分离的方式包括但不限于离心分离或过滤分离中的任意一种。
可选地，所述干燥的方式包括但不限于高温烘干或冷冻干燥中的任意一种。
作为本申请所述方法的可选技术方案，所述方法还包括将步骤(1)的产物和/或步骤(2)的产物，作为步骤(1)的原料，重复以下步骤：步骤(1)，或依次的步骤(1)和步骤(2)。通过重复上述的步骤，可以使最终得到的负极材料的首次库伦效率更高，重复的次数可选为0～5次，例如0次、1次、2次、3次、4次或5次，其中“0次”指不进行重复操作，可选为1次。
可选地，步骤(1)所述包含SiO x材料的原料中的Si微晶晶粒尺寸≤100nm，例如1nm、5nm、10nm、15nm、20nm、25nm、30nm、40nm、45nm、55nm、60nm、70nm、80nm、90nm或100nm等，可选为≤20nm。
作为本申请所述方法的可选技术方案，步骤(1)所述包含SiO x材料的原料中还包含添加物与SiO x材料形成SiO x基复合材料，所述添加物为无定形碳包覆层、石墨、碳黑、纳米碳管、石墨烯、硅或金属盐中的任意一种或至少两种的组合。
可选地，以SiO x基复合材料的总质量为100％计，所述无定形碳包覆层的质量百分含量为1％～20％，例如1％、2％、3％、5％、8％、10％、12％、15％、 18％、19％或20％等。
可选地，所述包含SiO x材料的原料为SiO x粉末或SiO x基复合材料中的任意一种或两种的组合。
可选地，步骤(1)所述金属M为活泼金属，为其鲍林电负性＜1.8。可选包括金属Na、金属K、金属Mg、金属Ca或金属Al中的任意一种或至少两种的组合。
可选地，所述金属M的粒径D50≤300μm，例如300μm、275μm、260μm、240μm、220μm、200μm、180μm、150μm、120μm、100μm或50μm、20μm或10μm等。
可选地，步骤(1)所述混合采用的设备为VC混合机、多维混合机、机械融合机、粉末搅拌机或球磨机中的任意一种。
可选地，步骤(1)所述非氧化性气氛包括氮气气氛、氩气气氛、氖气气氛或氦气气氛中的任意一种或至少两种的组合。
可选地，步骤(1)所述热处理时的气压为0.01MPa～1MPa，例如0.01MPa、0.02MPa、0.05MPa、0.08MPa、0.1MPa、0.15MPa、0.2MPa、0.3MPa、0.35MPa、0.4MPa、0.5MPa、0.6MPa、0.7MPa、0.8MPa或1MPa等，可选为0.1MPa。
可选地，步骤(1)所述热处理的温度为550℃～1100℃，例如550℃、600℃、650℃、675℃、700℃、725℃、735℃、750℃、770℃、780℃、800℃、850℃、880℃、900℃、925℃、950℃、1000℃、1050℃或1100℃等。
可选地，步骤(1)所述保温的时间为0.5h～24h，例如0.5h、1h、2h、3h、4h、6h、8h、9h、10h、12h、13.5h、15h、18h、19h、20h、22h或24h等。
可选地，所述热处理采用的设备为箱式炉、回转炉、管式炉、加热混合 机、辊道窑、推板窑、高压釜或真空炉中的任意一种。
可选地，步骤(2)所述酸处理过程中，使用的酸为能使M化合物溶解的酸，包括盐酸、硫酸、硝酸、高氯酸、甲酸或乙酸中的任意一种或至少两种的组合。
可选地，所述酸处理的时间为0.2h～24h，例如0.2h、0.5h、1h、3h、5h、6h、8h、10h、12h、15h、18h、20h、21.5h或24h等，可选为0.2h～4h。
可选地，所述酸处理之后，残余的M化合物占锂离子电池材料总质量的1％～60％，限定到此范围的原因是：避免M化合物全部溶解造成材料的比表面积过大，也避免了M化合物溶解过少而导致的材料容量过低。不管是全部溶解，还是溶解过少都会降低材料最终的电化学性能。
作为本申请所述方法的可选技术方案，所述方法包括以下步骤：
(1)使包含SiO x材料的原料与金属M混合均匀，然后在非氧化性气氛下550℃热处理并保温0.5h～24h，得到还原产物SiO y和氧化产物M化合物；
其中，以包含SiO x材料的原料与金属M的总质量为100％计，所述金属M的质量百分含量为3％～40％；
(2)使用酸对步骤(1)得到的产物进行酸处理，以使M化合物发生溶解而部分去除，酸处理时控制处理时间，使M化合物残留量占材料总质量1％～60％，避免M化合物全部溶解造成材料的比表面积过大，然后液固分离，洗涤至中性，干燥，得到包括SiO y和M化合物的锂离子电池材料；
其中，0.5＜x＜1.5，0.2＜y＜0.9，且y＜x。
与相关技术相比，本申请如有如下有益效果：
(1)本申请使用了活泼金属对SiO x(0.5＜x＜1.5)负极材料进行还原脱氧制备锂离子电池负极材料，有效且廉价地减少了SiO x体系中氧的含量到y(0.2＜ y＜0.9)，使其首次库仑效率得到提升，同时得到的负极材料中还包含M化合物，SiO y中包含Si微晶晶粒。采用本申请的方法制备得到的负极材料保持了SiO x体系本身的结构，继承了SiO x材料本身循环膨胀性能优良的优点。
(2)本申请的方法采用的原料及设备均常见易得，且反应条件温和，故本申请的方法简单经济，容易实现产业化。
(3)本申请的负极材料包括SiO y(0.2＜y＜0.9)和M化合物，M为金属，SiO y中包含Si微晶晶粒，该负极材料具备较高的首次库伦效率，因减少了负极的O含量，从而减少了首次嵌锂时不可逆相Li 2O和Li 4SiO 4的生成量，并且该材料具备优良的循环膨胀性能，有利于高能量密度电池的开发。
在阅读并理解了详细描述和附图后，可以明白其他方面。
附图说明
图1是实施例1与对比例的扣式电池50周循环容量保持率图。
具体实施方式
下面结合附图并通过具体实施方式来进一步说明本申请的技术方案。
材料表征方法：
材料的O含量的表征方法为，先对材料使用浓HCl处理24h，然后将酸液分离并烘干滤渣。检查其X射线衍射图谱，确认没有任何金属盐类的衍射峰后，使用N/H/O分析仪对该滤渣进行表征。
材料SiO x中的x，使用上述方法表征得到的O含量，根据x＝O含量×16/(28+O含量×16)计算得到。
材料SiO y中的y，使用上述方法表征得到的O含量，y＝O含量×16/(28+O含量×16)计算得到。
材料的Si微晶晶粒尺寸的表征方法均为使用X射线衍射仪，对2-Theta范 围为10°～90°进行扫描，然后对2-Theta范围为26°～30°进行拟合得到Si(111)峰的半峰宽，使用谢乐公式计算得到Si微晶晶粒尺寸。
材料的首次容量和首次效率测试均使用扣式电池进行表征，对电极为金属锂片，充放电倍率均为0.1C，充放电电压范围为0.005V～1.5V。
材料的循环及膨胀性能均使用扣式电池进行表征，与石墨按材料∶石墨＝1∶9(质量比)比例混合后，在铜箔上涂布制成极片并测定其极片厚度。然后以金属锂片作为对电极，组装成扣式电池。
循环充放电倍率为：第1周为0.1C，第2周为0.2C，第3周为0.5C，第4周～第50周为1.0C，第51周以0.1C放电至0.005V，然后分解电池测试极片厚度。所有循环周数的充放电电压范围均为0.005V～1.5V。
50周容量保持率为第50周的充电容量与第1周的充电容量的比值。
极片膨胀率为(循环后极片厚度-循环前极片厚度)/(循环前极片厚度-铜箔厚度)。
实施例1
SiO y的制备：
(1)取880g SiO x基复合材料(其是由无定形碳包覆层和市售SiO x(x＝1)形成的复合材料，且无定形碳占复合材料的3wt％)与120g Mg粉，即Mg占混合物的比例为12％，投入VC混合机内混合30min后，投入0.1MPa Ar气氛的箱式炉中于1000℃处理12h，得到产物(还原SiO y材料和Mg的化合物)。
(2)使用HCl对步骤(1)得到的产物进行酸处理2h，然后过滤将酸液分离，然后将滤渣高温烘干，得到锂离子电池负极材料。
表征结果：
使用N/H/O分析仪表征得到O含量，本实施例得到的锂离子电池负极材料 中，y＝0.37。
X射线衍射仪表征得到SiO y的Si微晶晶粒尺寸为9.8nm。
其将材料组装成扣式电池进行表征，其首次容量为1281mAh/g，首次效率为83.1％。
将材料混合石墨后组装成扣式电池，其50周容量保持率为95％，极片膨胀率为49％。
实施例2
SiO y的制备：
除以下内容外，其他条件与实施例1相同：
取960g SiO x基复合材料(其是由无定形碳包覆层和市售SiO x(x＝1)形成的复合材料，且无定形碳占复合材料的3wt％)与40g Mg粉进行试验，即Mg占混合物的比例为4％。
表征结果：
使用N/H/O分析仪表征得到O含量，本实施例得到的锂离子电池负极材料中，y＝0.78。
X射线衍射仪表征得到SiO y的Si微晶晶粒尺寸为4.5nm。
其将材料组装成扣式电池进行表征，其首次容量为1465mAh/g，首次效率为80.1％。
将材料混合石墨后组装成扣式电池，其50周容量保持率为97％，极片膨胀率为42％。
实施例3
SiO y的制备：
除以下内容外，其他条件与实施例2相同：
SiO x与Mg经过VC混合机混合后的混合物，投入0.1MPa N 2气氛的箱式炉中于1000℃处理12h。
表征结果：
使用N/H/O分析仪表征得到O含量，本实施例得到的锂离子电池负极材料中，y＝0.79。
X射线衍射仪表征得到SiO y的Si微晶晶粒尺寸为4.6nm。
其将材料组装成扣式电池进行表征，其首次容量为1471mAh/g，首次效率为79.9％。
将材料混合石墨后组装成扣式电池，其50周容量保持率为97％，极片膨胀率为42％。
实施例4
SiO y的制备：
除以下内容外，其他条件与实施例1相同：
取960g SiO x基复合材料(其是由无定形碳包覆层和市售SiO x(x＝1)形成的复合材料，且无定形碳占复合材料的3wt％)与40g Al粉进行试验，即Al占混合物的比例为4％。
表征结果：
使用N/H/O分析仪表征得到O含量，本实施例得到的锂离子电池负极材料中，y＝0.35。
X射线衍射仪表征得到SiO y的Si微晶晶粒尺寸为5.2nm。
其将材料组装成扣式电池进行表征，其首次容量为1379mAh/g，首次效率为86.4％。
将材料混合石墨后组装成扣式电池，其50周容量保持率为94％，极片膨胀率为48％。
实施例5
SiO y的制备：
除以下内容外，其他条件与实施例1相同：
SiO x与Mg经过VC混合机混合后的混合物，投入0.02MPa Ar气氛的真空中于1000℃处理12h。
表征结果：
使用N/H/O分析仪表征得到O含量，本实施例得到的锂离子电池负极材料中，y＝0.37。
X射线衍射仪表征得到SiO y的Si微晶晶粒尺寸为9.5nm。
其将材料组装成扣式电池进行表征，其首次容量为1307mAh/g，首次效率为83.3％。
将材料混合石墨后组装成扣式电池，其50周容量保持率为95％，极片膨胀率为49％。
实施例6
SiO y的制备：
除以下内容外，其他条件与实施例1相同：
SiO x与Mg经过VC混合机混合后的混合物，投入0.1MPa Ar气氛的真空中于800℃处理12h。
表征结果：
使用N/H/O分析仪表征得到O含量，本实施例得到的锂离子电池负极材料中，y＝0.51。
X射线衍射仪表征得到SiO y的Si微晶晶粒尺寸为6.6nm。
其将材料组装成扣式电池进行表征，其首次容量为1321mAh/g，首次效率为81.8％。
将材料混合石墨后组装成扣式电池，其50周容量保持率为97％，极片膨胀率为45％。
实施例7
SiO y的制备：
将实施例2步骤(1)得到的产物作为步骤(1)的原料，重复1次步骤(1)的操作，然后完成步骤(2)得到产物SiO y。
表征结果：
使用N/H/O分析仪表征得到O含量，本实施例得到的锂离子电池负极材料中，y＝0.53。
X射线衍射仪表征得到SiO y的Si微晶晶粒尺寸为5.2nm。
其将材料组装成扣式电池进行表征，其首次容量为1395mAh/g，首次效率为81.4％。
将材料混合石墨后组装成扣式电池，其50周容量保持率为96％，极片膨胀率为44％。
从实施例1～实施例7可以看出，可以由不同x的SiO x原料和不同的金属(Mg、Al等)的添加比例，通过不同的处理条件，得到不同y值的SiO y。且得到的SiO y首次效率高，首次容量高，同时的循环性能优良，体积效应小。
对比例1
除以下内容外，其他条件与实施例1相同：
取500g SiO x基复合材料(其是由无定形碳包覆层和市售SiO形成的复合材料，且无定形碳占复合材料的3wt％)与500g Mg粉进行试验，即Mg占混合物的比例为50wt％。
表征结果：
使用N/H/O分析仪表征得到O含量，本实施例得到的锂离子电池负极材料中，y＝0。
X射线衍射仪表征得到SiO y的Si微晶晶粒尺寸为63.5nm。
其将材料组装成扣式电池进行表征，其首次容量为1235mAh/g，首次效率为88.4％。
将材料混合石墨后组装成扣式电池，其50周容量保持率为82％，极片膨胀率为71％。
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。

Claims (12)

  1. 一种锂离子电池负极材料，其中，所述负极材料中包括SiO y和M化合物，M为金属；
    其中，0.2＜y＜0.9。
  2. 根据权利要求1所述的负极材料，其中，以所述负极材料的总质量为100％计，所述M化合物的质量百分含量为1％～60％。
  3. 根据权利要求1所述的负极材料，其中，所述负极材料的比表面积为≤50m 2/g，可选为≤15m 2/g。
  4. 根据权利要求1所述的负极材料，其中，所述SiO y中的Si微晶晶粒的尺寸在≤100nm，可选为≤20nm；
    可选地，所述M为活泼金属，其鲍林电负性＜1.8，可选包括金属Na、金属K、金属Mg、金属Ca或金属Al中的任意一种或至少两种的组合。
  5. 根据权利要求1或4所述的负极材料，其中，所述负极材料中还包含无定形碳包覆层、石墨、碳黑、纳米碳管、石墨烯、硅、金属化合物中的任意一种或至少两种的组合；
    可选地，所述金属化合物包括金属氧化物、金属硅化物或金属硅酸盐中的任意一种或至少两种的组合，可选包括K 2O、Na 2O、MgO、CaO、Al 2O 3、Mg 2Si、Ca 2Si、Al 4Si 3、K 2SiO 3、K 4SiO 4、K 2Si 2O 5、Na 2SiO 3、Na 4SiO 4、Na 2Si 2O 5、Mg 2SiO 4、MgSiO 3、Ca 2SiO 4、CaSiO 3、Al 4(SiO 4) 3或Al 2(SiO 3) 3中的任意一种或至少两种的组合。
  6. 根据权利要求1-5任一项所述的锂离子电池材料的制备方法，其中，所述方法包括：
    使包含SiO x材料的原料与金属M发生氧化还原反应，SiO x材料的O/Si比x调整为y，同时金属M被氧化得到M化合物；
    其中，0.5＜x＜1.5，0.2＜y＜0.9，且y＜x。
  7. 根据权利要求6所述的方法，其中，所述方法包括以下步骤：
    (1)使包含SiO x材料的原料与金属M混合均匀，然后在非氧化性气氛下进行热处理并保温，得到还原产物SiO y和氧化产物M化合物；
    其中，以包含SiO x材料的原料与金属M的总质量为100％计，所述金属M的质量百分含量为3％～40％；
    (2)使用酸对步骤(1)得到的产物进行酸处理以使M化合物发生溶解而部分去除，得到包括SiO y和M化合物的锂离子电池材料；
    其中，0.5＜x＜1.5，0.2＜y＜0.9，且y＜x。
  8. 根据权利要求6或7所述的方法，其中，步骤(1)所述包含SiO x材料的原料中的Si微晶晶粒尺寸在≤100nm，可选为≤20nm。
  9. 根据权利要求7所述的方法，其中，所述方法还包括在酸处理之后，进行液固分离，并对分离固相进行洗涤和干燥的步骤；
    可选地，所述液固分离的方式包括离心分离或过滤分离中的任意一种；
    可选地，所述干燥的方式包括高温烘干或冷冻干燥中的任意一种。
  10. 根据权利要求7或9所述的方法，其中，所述方法还包括将步骤(1)的产物和/或步骤(2)的产物，作为步骤(1)的原料，重复以下步骤：步骤(1)，或依次的步骤(1)和步骤(2)；
    可选地，所述重复的次数为0～5次，可选为1次；
    可选地，步骤(1)所述包含SiO x材料的原料中还包含添加物与SiO x材料形成SiO x基复合材料，所述添加物为无定形碳包覆层、石墨、碳黑、纳米碳管、石墨烯、硅或金属盐中的任意一种或至少两种的组合；
    可选地，以SiO x基复合材料的总质量为100％计，所述无定形碳包覆层的 质量百分含量为1％～20％；
    可选地，所述包含SiO x材料的原料为SiO x粉末或SiO x基复合材料中的任意一种或两种的组合；
    可选地，步骤(1)所述金属M为活泼金属，其鲍林电负性＜1.8，可选包括金属Na、金属K、金属Mg、金属Ca或金属Al中的任意一种或至少两种的组合；
    可选地，所述金属M的粒径D50≤300μm；
    可选地，步骤(1)所述混合采用的设备为VC混合机、多维混合机、机械融合机、粉末搅拌机或球磨机中的任意一种。
  11. 根据权利要求6-10任一项所述的方法，其中，步骤(1)所述非氧化性气氛包括氮气气氛、氩气气氛、氖气气氛或氦气气氛中的任意一种或至少两种的组合；
    可选地，步骤(1)所述热处理时的气压为0.01MPa～1MPa，可选为0.1MPa；
    可选地，步骤(1)所述热处理的温度为550℃～1100℃；
    可选地，步骤(1)所述保温的时间为0.5h～24h；
    可选地，所述热处理采用的设备为箱式炉、回转炉、管式炉、加热混合机、辊道窑、推板窑、高压釜或真空炉中的任意一种。
  12. 根据权利要求6-11任一项所述的方法，其中，步骤(2)所述酸处理过程中，使用的酸为能使M化合物溶解的酸，包括盐酸、硫酸、硝酸、高氯酸、甲酸或乙酸中的任意一种或至少两种的组合；
    可选地，所述酸处理的时间为0.2h～24h，可选为0.2h～4h；
    可选地，所述酸处理之后，残余的M化合物占锂离子电池材料总质量的1％～60％。
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