WO2020113982A1 - 一种负极材料、及其制备方法和用途 - Google Patents

一种负极材料、及其制备方法和用途 Download PDF

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WO2020113982A1
WO2020113982A1 PCT/CN2019/098884 CN2019098884W WO2020113982A1 WO 2020113982 A1 WO2020113982 A1 WO 2020113982A1 CN 2019098884 W CN2019098884 W CN 2019098884W WO 2020113982 A1 WO2020113982 A1 WO 2020113982A1
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negative electrode
lithium
electrode material
optionally
atmosphere
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PCT/CN2019/098884
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English (en)
French (fr)
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邓志强
屈丽娟
庞春雷
任建国
岳敏
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贝特瑞新材料集团股份有限公司
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Priority to EP19893220.4A priority Critical patent/EP3836260A4/en
Priority to JP2020572373A priority patent/JP7221996B2/ja
Priority to US17/286,016 priority patent/US20210384510A1/en
Priority to KR1020217005869A priority patent/KR20210034664A/ko
Publication of WO2020113982A1 publication Critical patent/WO2020113982A1/zh

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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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    • 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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    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • 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
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application belongs to the field of battery material preparation, for example, relates to a negative electrode material, and its preparation method and use.
  • lithium-ion batteries With the launch of commercial lithium-ion batteries by SONY in 1991, research on materials related to lithium-ion batteries is in full swing. Due to the diversification of the functional requirements of various products, the requirements for batteries are also increasing. In particular, energy-saving and low-emission electric vehicles (EV) have attracted great attention and become a focus of automotive research and development. The output power, energy density, safety and voltage put forward higher requirements. The performance of lithium-ion batteries depends on the performance of key materials, thus promoting the development and development of new lithium-ion battery electrode materials.
  • the anode material of the lithium ion battery generally uses industrial graphite, but the theoretical capacity of the graphite anode is only 372mAh/g, which is far from meeting the increasing market demand.
  • Silicon materials have attracted much attention because of their theoretical capacity up to 4200mAh/g, but due to their volume expansion of up to 300%, poor cycle performance, they are restricted in market promotion and application. Silicon oxide materials have high specific capacity and good cycle performance However, for the first time, silica-based materials have low coulombic efficiency.
  • CN104603993B discloses a non-aqueous electrolyte secondary negative electrode active material and a non-aqueous electrolyte secondary battery using the negative electrode active material, the negative electrode active material contains lithium silicate phase SiO x particles, the surface of the SiO x particles is covered with carbon 50% to 100%, the average particle diameter of the SiO x particles is 1 ⁇ m to 15 ⁇ m.
  • the negative electrode material has significantly improved coulombic efficiency for the first time, but the lithium silicate contained in the negative electrode active material is an electrochemically inert component, resulting in a decrease in the reversible capacity of the material.
  • One of the purposes of this application is to provide a negative electrode material, the negative electrode material comprising a composite matrix material and a carbon coating layer coated on the composite matrix material;
  • the composite matrix material includes lithium silicate, silicon oxide, an activator, and silicon embedded in the lithium silicate and the silicon oxide.
  • the negative electrode material provided in this application can reduce the consumption of lithium released from the positive electrode material when the silicon oxide material is charged for the first time, and can effectively improve the first coulomb of the negative electrode material. effectiveness.
  • silicon is embedded in lithium silicate, which can alleviate the volume expansion of silicon during charging and discharging.
  • the activator in the composite matrix material of the present application can enhance the conductivity of the material, thereby enhancing the electrochemical performance of the negative electrode material; on the other hand, the activator can act as a supporting framework, improve the crystal structure of lithium silicate, and make lithium ions There is sufficient space to be able to be detached and embedded from the structure, thereby showing a certain reversible capacity, and further improve the first coulombic efficiency of the anode material, the first coulombic efficiency ⁇ 83.6%.
  • the lithium silicate described in this application is different from the lithium silicate prepared in the prior art.
  • the lithium silicate produced in the silicon anode in the prior art is a chemically inert component.
  • the lithium silicate in this application is due to the activator, It has the ability to store lithium ions and remove lithium ions, has good electrochemical activity, and can further increase the capacity of the negative electrode material.
  • the specific capacity of the first discharge is ⁇ 1263mAh/g.
  • the carbon coating layer outside the composite matrix material of the present application can on the one hand further enhance the conductivity of the material and give full play to the capacity of the negative electrode material, on the other hand it can further alleviate the volume expansion problem of silicon and silicon oxide during charging and discharging.
  • the negative electrode material has good cycle stability. At a current density of 0.1 C, the 50-cycle cycle capacity retention rate is ⁇ 82%.
  • the activator includes any one or a combination of at least two of alkali metal, transition metal, alkali metal oxide and transition metal oxide, optionally potassium, magnesium, aluminum, potassium oxide, magnesium oxide and Any one of alumina or a combination of at least two.
  • the activator selected in this application is a metal element with an atomic radius greater than Li or an oxide of a metal element with an atomic radius greater than Li.
  • the lithium silicate content is 30wt%-70wt%, such as 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, etc.
  • the silicon oxide content is 1 wt% to 13 wt%, such as 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt% Wait.
  • the carbon content is 0.05 wt% to 25 wt%, such as 1 wt%, 3 wt%, 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, etc.
  • the content of the activator is 1wt% to 10wt%, for example, 2wt%, 4wt%, 5wt%, 6wt%, 8wt%, 9wt%, etc.
  • the content of the silicon is 20wt% to 40wt%, such as 22wt%, 24wt%, 25wt%, 26wt%, 28wt%, 30wt%, 32wt%, 35wt%, 38wt%, etc.
  • the lithium silicate in the anode material includes any one or a combination of at least two of lithium orthosilicate, lithium metasilicate, lithium disilicate, and lithium pentasilicate.
  • the molecular formula of the silicon oxide is SiO x , where x is a constant from 0.5 to 1.8, such as 0.8, 1, 1.2, 1.5, 1.7, and so on.
  • the second object of the present application is to provide a method for preparing a negative electrode material.
  • the method includes the following steps:
  • the activated precursor is subjected to secondary sintering under a protective atmosphere or vacuum conditions.
  • the mass ratio of the sintering mixture to the activator in step (3) of the present application is 5:1 to 30:1, for example, 8:1, 10:1, 12:1, 15:1, 18:1 20:1, 22:1, 25:1, 28:1, etc.
  • the temperature of the fusion is 100-300°C, for example, 150°C, 200°C, 250°C, 280°C, etc.
  • the fusion time is 1h to 4h, such as 1.5h, 2h, 2.5h, 3h, 3.5h, and so on.
  • the molar ratio of the carbon-containing silicon oxide to the lithium source in step (1) of the present application is 2.5:1 to 9:1, for example, 3:1, 4:1, 5:1, 6:1, 7 :1, 8:1, etc.
  • the molecular formula of the carbon-containing silicon oxide is SiO x C, where x is a constant of 0.5 to 1.8, and SiOC may be selected, such as 0.6, 0.8, 1, 1.2, 1.5, 1.7, and so on.
  • the lithium source includes any one or a combination of at least two of metal lithium, lithium carbonate, lithium hydroxide, and lithium acetate.
  • the temperature of the primary sintering in step (2) of the present application is 200-1000°C, optionally 500-900°C, for example 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, 900°C Wait.
  • the time for the first sintering is 2h-6h, for example, 3h, 3.5h, 4h, 4.5h, 5h, etc.
  • the temperature of the second sintering in step (4) is 150-1000°C, optionally 300-900°C, for example 200°C, 300°C, 400°C, 500°C, 600°C, 700°C, 800°C , 900°C, etc.
  • the second sintering time is 6h-10h, such as 6.5h, 7h, 7.5h, 8h, 9h, etc.
  • the protective atmosphere includes any one or a combination of at least two of nitrogen atmosphere, argon atmosphere, helium atmosphere, neon atmosphere, krypton atmosphere, and xenon atmosphere, for example, nitrogen atmosphere, argon atmosphere , Helium atmosphere, etc.
  • a method for preparing a negative electrode material described in this application includes the following steps:
  • the activated precursor is sintered at 300-900°C for 6-10 hours under a protective atmosphere to obtain a negative electrode material.
  • the third objective of the present application is to provide a use of the negative electrode material according to one of the objectives, the negative electrode material is used in the field of lithium ion batteries.
  • the negative electrode material is used as a negative electrode material for a lithium ion battery.
  • the fourth object of the present application is to provide a lithium ion battery including the negative electrode material described in one of the objects.
  • the anode material of the lithium ion battery is the anode material described in one of the purposes.
  • the negative electrode material provided in this application can reduce the consumption of lithium released from the positive electrode material during the initial charge of the silicon oxide material in the composite matrix material, which can effectively improve the negative electrode material The first Coulomb efficiency.
  • silicon is embedded in lithium silicate, which can alleviate the volume expansion of silicon during charging and discharging.
  • the lithium silicate described in this application is different from the lithium silicate prepared in the prior art.
  • the lithium silicate produced in the silicon anode in the prior art is a chemically inert component.
  • the lithium silicate in this application is due to an activator It has the ability of storing lithium ions and removing lithium ions, has good electrochemical activity, and can further increase the capacity of the negative electrode material.
  • the specific capacity of the first discharge is ⁇ 1263mAh/g.
  • the activator in the composite matrix material of the present application can improve the conductivity of the material, thereby enhancing the electrochemical performance of the negative electrode material; on the other hand, the activator can act as a supporting framework to improve the crystal structure of lithium silicate, Lithium ions have enough space to be extracted and inserted from the structure, and then show a certain reversible capacity, which can further improve the first coulombic efficiency of the anode material, the first coulombic efficiency ⁇ 83.6%.
  • the carbon coating layer outside the composite matrix material of this application can further improve the conductivity of the material and make the capacity of the negative electrode material fully play; on the other hand, it can further alleviate the volume expansion of silicon and silicon oxide during charging and discharging The problem makes the negative electrode material have good cycle stability. At a current density of 0.1C, the 50-cycle cycle capacity retention rate is ⁇ 82%.
  • a method for preparing a negative electrode material includes the following steps:
  • the activated precursor is sintered at 750°C for 8 hours under a protective atmosphere, and the morphological characteristics of the negative electrode material are shown in FIG. 1, and it can be seen from the figure that the particle size of the obtained negative electrode material is 5 to 10 ⁇ m.
  • the outermost layer has a carbon coating.
  • Example 1 The difference from Example 1 is that the molar ratio of the sintered mixture to Mg in step (3) is 5:1.
  • Example 1 The difference from Example 1 is that the molar ratio of the sintered mixture to Mg in step (3) is 30:1.
  • Example 1 The difference from Example 1 is that the molar ratio of the sintered mixture to Mg in step (3) is 4:1.
  • Example 1 The difference from Example 1 is that the molar ratio of the sintered mixture to Mg in step (3) is 31:1.
  • a method for preparing a negative electrode material includes the following steps:
  • the activated precursor is sintered at 150°C for 10 hours under a nitrogen atmosphere to obtain a negative electrode material.
  • a method for preparing a negative electrode material includes the following steps:
  • the activated precursor is sintered at 1000°C for 6 h under an argon atmosphere, and the morphological characteristics of the negative electrode material are shown in FIG. 2. From the figure, it can be seen that the particle size of the negative electrode material is 5-10 ⁇ m. The outermost layer has a carbon coating.
  • Example 1 The difference from Example 1 is that Mg is not added in step (3).
  • step (1) SiOC is replaced with SiO 2 .
  • the lithium silicate in the negative electrode materials prepared in Examples 1 to 7 of the present application is an electrochemically active component, and the negative electrode material has good electrochemical performance, and the first discharge specific capacity is ⁇ 1263mAh/g For the first time, the Coulomb efficiency is ⁇ 83.6%. At 0.1C current density, the 50-week cycle capacity retention rate is ⁇ 82%.
  • Example 4 It can be seen from Table 1 that the first Coulomb efficiency and the 50-week cycle capacity retention rate of Example 4 are lower than that of Example 1, possibly because the added amount of the activator Mg in Example 4 is too large, which damages the lithium silicate Therefore, the first discharge specific capacity, the first coulombic efficiency and the 50-cycle cycle capacity retention rate of the negative electrode material are lower.
  • Example 5 It can be seen from Table 1 that the first discharge specific capacity, the first coulombic efficiency, and the 50-cycle cycle capacity retention rate of Example 5 are lower than those of Example 1, which may be because the addition amount of the activator Mg in Example 5 is too small. Furthermore, the lithium silicate in the anode material is not activated, so the first discharge specific capacity, the first coulombic efficiency, and the 50-cycle cycle capacity retention rate of the produced anode material are low.
  • Comparative Example 1 has a lower first discharge specific capacity, first coulombic efficiency, and 50-week cycle capacity retention rate than Example 1, possibly because Comparative Example 1 does not add the activator Mg, and thus the anode material
  • the lithium silicate in is a chemically inert component, so the first discharge specific capacity, the first coulombic efficiency and the 50-cycle cycle capacity retention rate of the negative electrode material are low.
  • the comparative example 2 has a lower first coulombic efficiency and a 50-week cycle capacity retention rate than that of example 1, possibly because the silicon source in comparative example 2 is SiO 2 , and the prepared negative electrode material There is no carbon coating layer, so the first Coulomb efficiency and 50-cycle cycle capacity retention rate of the negative electrode material are low.

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Abstract

本申请涉及一种负极材料，所述负极材料包括复合基体材料和包覆在复合基体材料外的碳包覆层；所述复合基体材料包括硅酸锂、硅氧化物、活化剂和镶嵌在所述硅酸锂和所述硅氧化物中的硅。

Description

一种负极材料、及其制备方法和用途 技术领域
本申请属于电池材料制备领域，例如涉及一种负极材料、及其制备方法和用途。
背景技术
随着SONY公司在1991推出商品化的锂离子电池，对锂离子电池相关材料的研究如火如荼地进行。由于对各种产品功能需求的多样化，对电池的要求也日益提升，尤其是节能、低排放的电动汽车(EV)引起极大关注并成为汽车研究与开发的一个重点，对锂离子电池的输出功率、能量密度、安全性和电压等提出了更高的要求。锂离子电池的性能取决于关键材料的性能，从而推动了新型锂离子电池电极材料的开发和研制。
目前锂离子电池的负极材料一般采用工业化石墨，然而石墨负极理论容量只有372mAh/g，远远不能满足日益增长的市场需求。硅材料因其理论容量高达4200mAh/g而备受关注，但由于其高达300％的体积膨胀，循环性能差，在市场推广和应用中受到制约，硅氧材料拥有高的比容量并且循环性能好，但是硅氧材料首次库伦效率低。
CN104603993B公开了非水电解质二次负极活性物质以及使用该负极活性物质的非水电解质二次电池，所述负极活性物质内部含有硅酸锂相的SiO x颗粒，所述SiO x颗粒表面被碳覆盖50％～100％，所述SiO x颗粒平均粒径为1μm～15μm。所述负极材料和单纯的硅氧材料负极相比，首次库伦效率得到明显提高，但是所述负极活性物质内部所含的硅酸锂为电化学惰性成分，导致材料的可逆容量 降低。
因此，本领域需要开发一种负极材料，并使得制备的负极材料具有高的比容量、高的首次库伦效率以及良好的循环稳定性。
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。
本申请的目的之一在于提供一种负极材料，所述负极材料包括复合基体材料和包覆在复合基体材料外的碳包覆层；
所述复合基体材料包括硅酸锂、硅氧化物、活化剂和镶嵌在所述硅酸锂和所述硅氧化物中的硅。
本申请提供的负极材料，和单纯的硅氧材料相比，复合基体材料中的硅酸锂可减少硅氧材料初次充电时对正极材料脱出的锂的消耗，进而可以有效提升负极材料的首次库伦效率。同时，硅镶嵌在硅酸锂中，可缓解硅在充放电时的体积膨胀问题。
本申请复合基体材料中的活化剂，一方面可以提升材料的导电性，进而增强负极材料的电化学性能；另一方面，活化剂可以充当支撑骨架，改善硅酸锂的晶体结构，使锂离子具有充足的空间得以从结构中脱出和嵌入，进而表现出一定的可逆容量，进一步提升负极材料的首次库伦效率，首次库伦效率≥83.6％。
本申请所述硅酸锂与现有技术中制备的硅酸锂不同，现有技术中硅负极生成的硅酸锂均为化学惰性组分，本申请中的硅酸锂因活化剂的作用，而具有储藏锂离子和脱除锂离子的能力，具有良好的电化学活性，可以进一步提高负极材料的容量，首次放电比容量≥1263mAh/g。
本申请复合基体材料外的碳包覆层，一方面可以进一步提升材料的导电性，使负极材料容量充分发挥，另一方面可以进一步缓解硅和氧化硅在充放电过程中的体积膨胀问题，使负极材料具有良好的循环稳定性，0.1C电流密度下，50周循环容量保持率≥82％。
可选地，所述活化剂包括碱金属、过渡金属、碱金属氧化物和过渡金属氧化物中的任意一种或至少两种的组合，可选钾、镁、铝、氧化钾、氧化镁和氧化铝中的任意一种或至少两种的组合。
本申请选用的活化剂为原子半径比Li大的金属元素或原子半径比Li大的金属元素的氧化物。
可选地，所述硅酸锂含量为30wt％～70wt％，例如35wt％、40wt％、45wt％、50wt％、55wt％、60wt％、65wt％等。
可选地，所述硅氧化物含量为1wt％～13wt％，例如2wt％、3wt％、4wt％、5wt％、6wt％、7wt％、8wt％、9wt％、10wt％、11wt％、12wt％等。
可选地，所述碳含量0.05wt％～25wt％，例如1wt％、3wt％、5wt％、8wt％、10wt％、12wt％、15wt％、18wt％、20wt％、22wt％等。
可选地，所述活化剂的含量为1wt％～10wt％，例如2wt％、4wt％、5wt％、6wt％、8wt％、9wt％等。
可选地，所述硅的含量为20wt％～40wt％，例如22wt％、24wt％、25wt％、26wt％、28wt％、30wt％、32wt％、35wt％、38wt％等。
可选地，所述负极材料中硅酸锂包括正硅酸锂、偏硅酸锂、二硅酸锂和五硅酸锂中的任意一种或至少两种的组合。
可选地，所述硅氧化物的分子式为SiO x，其中x为0.5～1.8的常数，例如 0.8、1、1.2、1.5、1.7等。
本申请的目的之二是提供一种负极材料的制备方法，所述制备方法包括如下步骤：
(1)将含碳硅氧化物与锂源混合，得到原料混合物；
(2)在保护性气氛或真空条件下将所述原料混合物进行一次烧结，得到烧结混合物；
(3)将所述烧结混合物与活化剂融合，得到活化前驱体；
(4)在保护性气氛或真空条件下将所述活化前驱体进行二次烧结。
可选地，本申请步骤(3)所述烧结混合物与活化剂的质量比为5:1～30:1，例如8:1、10:1、12:1、15:1、18:1、20:1、22:1、25:1、28:1等。
可选地，所述融合的温度为100～300℃，例如150℃、200℃、250℃、280℃等。
可选地，所述融合的时间为1h～4h，例如1.5h、2h、2.5h、3h、3.5h等。
可选地，本申请步骤(1)所述含碳硅氧化物与锂源的摩尔比为2.5:1～9:1，例如3:1、4:1、5:1、6:1、7:1、8:1等。
可选地，所述含碳硅氧化物的分子式为SiO xC，其中x为0.5～1.8的常数，可选SiOC，例如0.6、0.8、1、1.2、1.5、1.7等。
可选地，所述锂源包括金属锂、碳酸锂、氢氧化锂和醋酸锂中的任意一种或至少两种的组合。
可选地，本申请步骤(2)所述一次烧结的温度为200～1000℃，可选500～900℃，例如300℃、400℃、500℃、600℃、700℃、800℃、900℃等。
可选地，所述一次烧结的时间为2h～6h，例如3h、3.5h、4h、4.5h、5h等。
可选地，步骤(4)所述二次烧结的温度为150～1000℃，可选为300～900℃，例如200℃、300℃、400℃、500℃、600℃、700℃、800℃、900℃等。
可选地，所述二次烧结的时间为6h～10h，例如6.5h、7h、7.5h、8h、9h等。
可选地，所述保护性气氛包括氮气气氛、氩气气氛、氦气气氛、氖气气氛、氪气气氛和氙气气氛中的任意一种或至少两种的组合，例如氮气气氛、氩气气氛、氦气气氛等。
作为可选技术方案，本申请所述一种负极材料的制备方法，所述制备方法包括如下步骤：
(1)将SiOC与氢氧化锂按摩尔比为2.5:1～9:1进行混合，得到原料混合物；
(2)在保护性气氛下将所述原料混合物在500～900℃下烧结2h～6h，得到烧结混合物；
(3)将所述烧结混合物与Mg按质量比为5:1～30:1，在100～300℃温度下融合1h～4h，得到活化前驱体；
(4)在保护性气氛下将所述活化前驱体在300～900℃下烧结6h～10h，得到负极材料。
本申请目的之三是提供一种如目的之一所述负极材料的用途，所述负极材料用于锂离子电池领域。
可选地，所述负极材料用作锂离子电池的负极材料。
本申请目的之四是提供一种锂离子电池，所述锂离子电池包括目的之一所述的负极材料。
可选地，所述锂离子电池的负极材料为目的之一所述的负极材料。
与现有技术相比，本申请具有如下有益效果：
(1)本申请提供的负极材料，和单纯的硅氧材料相比，复合基体材料中的硅酸锂可减少硅氧材料初次充电时对正极材料脱出的锂的消耗，进而可以有效提升负极材料的首次库伦效率。同时，硅镶嵌在硅酸锂中，可缓解硅在充放电时的体积膨胀问题。
(2)本申请所述硅酸锂与现有技术中制备的硅酸锂不同，现有技术中硅负极生成的硅酸锂均为化学惰性组分，本申请中的硅酸锂因活化剂的作用，而具有储藏锂离子和脱除锂离子的能力，具有良好的电化学活性，可以进一步提高负极材料的容量，首次放电比容量≥1263mAh/g。
(3)本申请复合基体材料中的活化剂，一方面可以提升材料的导电性，进而增强负极材料的电化学性能；另一方面，活化剂可以充当支撑骨架，改善硅酸锂的晶体结构，使锂离子具有充足的空间得以从结构中脱出和嵌入，进而表现出一定的可逆容量，可进一步提升负极材料的首次库伦效率，首次库伦效率≥83.6％。
(4)本申请复合基体材料外的碳包覆层，一方面可以进一步提升材料的导电性，使负极材料容量充分发挥，另一方面可以进一步缓解硅和氧化硅在充放电过程中的体积膨胀问题，使负极材料具有良好的循环稳定性，0.1C电流密度下，50周循环容量保持率≥82％。
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是本申请具体实施方式1得到样品的SEM图；
图2是本申请具体实施方式7得到样品的SEM图。
具体实施方式
为便于理解本申请，本申请列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
实施例1
一种负极材料的制备方法包括如下步骤：
(1)将SiOC与金属锂按摩尔比为3:1进行混合，得到原料混合物；
(2)在保护性气氛下将所述原料混合物在700℃烧结4h，得到烧结混合物；
(3)将所述烧结混合物与Mg按质量比为10:1，在180℃温度下融合2h，得到活化前驱体；
(4)在保护性气氛下将所述活化前驱体在750℃烧结8h，得到负极材料的形貌特征如图1所示，由图中可以看出得到的负极材料粒径为5～10μm，最外层有碳包覆层。
实施例2
与实施例1的区别在于，步骤(3)中烧结混合物与Mg的摩尔比为5:1。
实施例3
与实施例1的区别在于，步骤(3)中烧结混合物与Mg的摩尔比为30:1。
实施例4
与实施例1的区别在于，步骤(3)中烧结混合物与Mg的摩尔比为4:1。
实施例5
与实施例1的区别在于，步骤(3)中烧结混合物与Mg的摩尔比为31:1。
实施例6
一种负极材料的制备方法包括如下步骤：
(1)将SiO xC(x＝0.5)与氢氧化锂按摩尔比为9:1进行混合，得到原料混 合物；
(2)在氮气气氛下将所述原料混合物在200℃烧结6h，得到烧结混合物；
(3)将所述烧结混合物与K 2O按摩尔比为5:1，在100℃温度下融合4h，得到活化前驱体；
(4)在氮气气氛下将所述活化前驱体在150℃烧结10h，得到负极材料。
实施例7
一种负极材料的制备方法包括如下步骤：
(1)将SiO xC(x＝1.8)与金属锂按摩尔比为2.5:1进行混合，得到原料混合物；
(2)在氩气气氛下将所述原料混合物在1000℃烧结2h，得到烧结混合物；
(3)将所述烧结混合物与Al按摩尔比为30:1，在300℃温度下融合1h，得到活化前驱体；
(4)在氩气气氛下将所述活化前驱体在1000℃烧结6h，得到负极材料的形貌特征如图2所示，由图中可以看出得到的负极材料粒径为5～10μm，最外层有碳包覆层。
对比例1
与实施例1的区别在于，步骤(3)中不添加Mg。
对比例2
与实施例1的区别在于，步骤(1)中将SiOC替换为SiO 2。
性能测试：
将制备得到的负极材料进行如下性能测试：
(1)锂离子电池的制备：将制备得到的负极材料：导电炭黑： CMC/SBR＝75:15:10的比例涂覆在铜箔上，制备成负极片，金属锂片作为对电极，PP/PE作为隔膜，制成纽扣电池。
(2)首次库伦效率测试：采用蓝电5V/10mA型电池测试仪测试电池的电化学性能，充放电电压为1.5V，充放电速率为0.1C，首次库伦效率＝首次充电比容量/首次放电比容量。
(3)50周循环容量保持率测试：采用蓝电5V/10mA型电池测试仪测试电池的电化学性能，充放电电压为1.5V，充放电速率为0.1C，50周循环容量保持率＝第50次充电比容量/首次充电比容量。
表1
Figure PCTCN2019098884-appb-000001
通过表1可以看出，本申请实施例1～7中制备得到的负极材料中硅酸锂为电化学活性成分，进而所述负极材料具有良好的电化学性能，首次放电比容量 ≥1263mAh/g，首次库伦效率≥83.6％，0.1C电流密度下，50周循环容量保持率≥82％。
通过表1可以看出，实施例4相对于实施例1的首次库伦效率和50周循环容量保持率较低，可能是因为实施例4中活化剂Mg的添加量过大，破坏了硅酸锂的结构所以制得负极材料的首次放电比容量、首次库伦效率和50周循环容量保持率较低。
通过表1可以看出，实施例5相对于实施例1的首次放电比容量、首次库伦效率和50周循环容量保持率较低，可能是因为实施例5中活化剂Mg的添加量过小，进而负极材料中硅酸锂未被活化，所以制得负极材料的首次放电比容量、首次库伦效率和50周循环容量保持率较低。
通过表1可以看出，对比例1相对于实施例1的首次放电比容量、首次库伦效率和50周循环容量保持率较低，可能是因为对比例1中不添加活化剂Mg，进而负极材料中的硅酸锂为化学惰性成分，所以制得负极材料的首次放电比容量、首次库伦效率和50周循环容量保持率较低。
通过表1可以看出，对比例2相对于实施例1的首次库伦效率和50周循环容量保持率较低，可能是因为对比例2中的硅源为SiO 2，并且制得的负极材料中无碳包覆层，所以制得负极材料的首次库伦效率和50周循环容量保持率较低。
申请人声明，本申请通过上述实施例来说明本申请的详细工艺设备和工艺流程，但本申请并不局限于上述详细工艺设备和工艺流程，即不意味着本申请必须依赖上述详细工艺设备和工艺流程才能实施。

Claims (13)

  1. 一种负极材料，其中，所述负极材料包括复合基体材料和包覆在复合基体材料外的碳包覆层；
    所述复合基体材料包括硅酸锂、硅氧化物、活化剂和镶嵌在所述硅酸锂和所述硅氧化物中的硅。
  2. 如权利要求1所述的负极材料，其中，所述活化剂包括碱金属、过渡金属、碱金属氧化物和过渡金属氧化物中的任意一种或至少两种的组合，可选钾、镁、铝、氧化钾、氧化镁和氧化铝中的任意一种或至少两种的组合。
  3. 如权利要求1或2所述的负极材料，其中，所述硅酸锂含量为30wt％～70wt％；
    可选地，所述硅氧化物含量为1wt％～13wt％；
    可选地，所述碳含量0.05wt％～25wt％；
    可选地，所述活化剂的含量为1wt％～10wt％；
    可选地，所述硅的含量为20wt％～40wt％；
    可选地，所述硅酸锂包括正硅酸锂、偏硅酸锂、二硅酸锂和五硅酸锂中的任意一种或至少两种的组合；
    可选地，所述硅氧化物的分子式为SiO x，其中x为0.5～1.8的常数。
  4. 一种如权利要求1-3之一所述负极材料的制备方法，其中，所述制备方法包括如下步骤：
    (1)将含碳硅氧化物与锂源混合，得到原料混合物；
    (2)在保护性气氛或真空条件下将所述原料混合物进行一次烧结，得到烧结混合物；
    (3)将所述烧结混合物与活化剂融合，得到活化前驱体；
    (4)在保护性气氛或真空条件下将所述活化前驱体进行二次烧结。
  5. 如权利要求4所述的制备方法，其中，步骤(3)所述烧结混合物与活化剂的质量比为5:1～30:1；
    可选地，所述融合的温度为100～300℃；
    可选地，所述融合的时间为1h～4h。
  6. 如权利要求4或5所述的制备方法，其中，步骤(1)所述含碳硅氧化物与锂源的摩尔比为2.5:1～9:1。
  7. 如权利要求4或5所述的制备方法，其中，所述含碳硅氧化物的分子式为SiO xC，其中x为0.5～1.8的常数，可选SiOC；
    可选地，所述锂源包括金属锂、碳酸锂、氢氧化锂和醋酸锂中的任意一种或至少两种的组合。
  8. 如权利要求4-7之一所述的制备方法，其中，步骤(2)所述一次烧结的温度为200～1000℃，可选500～900℃；
    可选地，所述一次烧结的时间为2h～6h；
    可选地，步骤(4)所述二次烧结的温度为150～1000℃，可选为300～900℃；
    可选地，所述二次烧结的时间为6h～10h；
    可选地，所述保护性气氛包括氮气气氛、氩气气氛、氦气气氛、氖气气氛、氪气气氛和氙气气氛中的任意一种或至少两种的组合。
  9. 如权利要求4-8之一所述的负极材料的制备方法，其中，所述制备方法包括如下步骤：
    (1)将SiOC与金属锂按摩尔比为2.5:1～9:1进行混合，得到原料混合物；
    (2)在保护性气氛下将所述原料混合物在500～900℃下烧结2h～6h，得到 烧结混合物；
    (3)将所述烧结混合物与Mg按摩尔比为5:1～30:1，在100～300℃温度下融合1h～4h，得到活化前驱体；
    (4)在保护性气氛下将所述活化前驱体在300～900℃下烧结6h～10h，得到负极材料。
  10. 一种如权利要求1-3之一所述负极材料的用途，其中，所述负极材料用于锂离子电池领域。
  11. 如权利要求10所述的负极材料的用途，其中，所述负极材料用作锂离子电池的负极材料。
  12. 一种锂离子电池，其中，所述锂离子电池包括权利要求1-3之一所述的负极材料。
  13. 如权利要求12所述的锂离子电池，其中，所述锂离子电池的负极材料为权利要求1-3之一所述的负极材料。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114212766A (zh) * 2021-11-04 2022-03-22 湖南金硅科技有限公司 一种补锂改性硅材料及其制备方法和应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111710845A (zh) * 2020-06-28 2020-09-25 贝特瑞新材料集团股份有限公司 硅氧复合负极材料及其制备方法和锂离子电池
CN111710848A (zh) * 2020-06-30 2020-09-25 贝特瑞新材料集团股份有限公司 硅氧复合负极材料及其制备方法和锂离子电池
CN112467108B (zh) * 2020-11-26 2022-04-12 东莞理工学院 一种多孔硅氧复合材料及其制备方法和应用
CN118213521A (zh) * 2022-12-16 2024-06-18 贝特瑞新材料集团股份有限公司 负极材料及其制备方法、锂离子电池

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104603993A (zh) 2012-09-27 2015-05-06 三洋电机株式会社 非水电解质二次电池用负极活性物质以及使用该负极活性物质的非水电解质二次电池
CN107210442A (zh) * 2015-01-28 2017-09-26 三洋电机株式会社 非水电解质二次电池用负极活性物质和非水电解质二次电池
US20170301915A1 (en) * 2015-03-02 2017-10-19 Eocell Ltd. Silicon-silicon oxide-lithium composite material having nano silicon particles embedded in a silicon:silicon lithium silicate composite matrix, and a process for manufacture thereof
CN107408682A (zh) * 2015-02-23 2017-11-28 三洋电机株式会社 非水电解质二次电池用负极活性物质、非水电解质二次电池用负极、和非水电解质二次电池

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100578870B1 (ko) * 2004-03-08 2006-05-11 삼성에스디아이 주식회사 리튬 이차 전지용 음극 활물질, 그의 제조 방법 및 그를포함하는 리튬 이차 전지
KR100578871B1 (ko) * 2004-03-08 2006-05-11 삼성에스디아이 주식회사 리튬 이차 전지용 음극 활물질, 그의 제조 방법 및 그를포함하는 리튬 이차 전지
CN100547830C (zh) * 2004-03-08 2009-10-07 三星Sdi株式会社 可充电锂电池的负极活性物质及其制法以及包含它的可充电锂电池
JP5411780B2 (ja) * 2010-04-05 2014-02-12 信越化学工業株式会社 非水電解質二次電池用負極材及び非水電解質二次電池用負極材の製造方法並びにリチウムイオン二次電池
JP6123430B2 (ja) * 2013-03-29 2017-05-10 日本電気株式会社 二次電池および負極活物質
KR101586816B1 (ko) * 2015-06-15 2016-01-20 대주전자재료 주식회사 비수전해질 이차전지용 음극재, 이의 제조방법, 및 이를 포함하는 비수전해질 이차전지
JP6389159B2 (ja) * 2015-10-08 2018-09-12 信越化学工業株式会社 非水電解質二次電池用負極活物質、非水電解質二次電池、非水電解質二次電池用負極材の製造方法、及び非水電解質二次電池の製造方法
JP6688673B2 (ja) * 2016-05-11 2020-04-28 株式会社大阪チタニウムテクノロジーズ 酸化珪素系粉末負極材
JP6876946B2 (ja) * 2016-11-30 2021-05-26 パナソニックＩｐマネジメント株式会社 負極材料および非水電解質二次電池
JP6765997B2 (ja) * 2017-03-13 2020-10-07 信越化学工業株式会社 負極材及びその負極材の製造方法、並びに混合負極材
JP6994690B2 (ja) * 2017-03-29 2022-01-14 パナソニックＩｐマネジメント株式会社 非水電解質二次電池用負極材料および非水電解質二次電池
US10804530B2 (en) * 2017-08-03 2020-10-13 Nanograf Corporation Composite anode material including surface-stabilized active material particles and methods of making same
WO2019080346A1 (zh) * 2017-10-23 2019-05-02 中航锂电（洛阳）有限公司 一种空间缓冲、掺杂锂的硅氧化物复合材料及其制备方法、锂离子电池
CN108269979A (zh) * 2017-12-28 2018-07-10 合肥国轩高科动力能源有限公司 一种氧化亚硅/硅/偏硅酸锂复合负极材料及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104603993A (zh) 2012-09-27 2015-05-06 三洋电机株式会社 非水电解质二次电池用负极活性物质以及使用该负极活性物质的非水电解质二次电池
CN107210442A (zh) * 2015-01-28 2017-09-26 三洋电机株式会社 非水电解质二次电池用负极活性物质和非水电解质二次电池
CN107408682A (zh) * 2015-02-23 2017-11-28 三洋电机株式会社 非水电解质二次电池用负极活性物质、非水电解质二次电池用负极、和非水电解质二次电池
US20170301915A1 (en) * 2015-03-02 2017-10-19 Eocell Ltd. Silicon-silicon oxide-lithium composite material having nano silicon particles embedded in a silicon:silicon lithium silicate composite matrix, and a process for manufacture thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114212766A (zh) * 2021-11-04 2022-03-22 湖南金硅科技有限公司 一种补锂改性硅材料及其制备方法和应用
CN114212766B (zh) * 2021-11-04 2024-02-13 湖南金硅科技有限公司 一种补锂改性硅材料及其制备方法和应用

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