WO2022257311A1 - 一种高首效高倍率硅基负极材料及其制备方法 - Google Patents

一种高首效高倍率硅基负极材料及其制备方法 Download PDF

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WO2022257311A1
WO2022257311A1 PCT/CN2021/123440 CN2021123440W WO2022257311A1 WO 2022257311 A1 WO2022257311 A1 WO 2022257311A1 CN 2021123440 W CN2021123440 W CN 2021123440W WO 2022257311 A1 WO2022257311 A1 WO 2022257311A1
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silicon
negative electrode
efficiency
sio
electrode material
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French (fr)
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张小祝
苏敏
陈云
李凡群
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万向一二三股份公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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 invention relates to the technical field of lithium ion batteries, in particular to a silicon-based negative electrode material with high first efficiency and high rate and a preparation method thereof.
  • lithium-ion batteries have been extensively researched and developed due to their unique advantages. Development, in order to keep up with the pace of practical application, lithium-ion batteries are also constantly improving in terms of energy density, power density, cycle and safety; traditional graphite-based lithium battery anode materials, because of their low theoretical capacity, have become restrictions on the energy of lithium batteries. An important factor for density improvement. At the same time, silicon-based materials have become the most promising next-generation negative electrode materials to replace graphite because of their high capacity, wide range of sources, and low lithium intercalation potential.
  • Silicon-based materials are divided into nano-silicon and In the silicon-oxygen direction, compared with nano-silicon, silicon-oxygen materials are more favored by industry insiders because of their relatively smaller volume expansion and more stable cycles, and the theoretical capacity of silicon-oxygen materials is above 2000mAh/g, which can meet market demand, but silicon-oxygen materials Due to the formation of by-products such as Li 2 O and Li 4 SiO 4 during the first charging process, the first-time efficiency of the material is low, and the silicon-oxygen material itself has problems such as poor conductivity and large expansion, which also need to be further improved and improved.
  • patent CN111710848A mixes SiO x with doping element sources to obtain Doping the silicon source, and then mixing and calcining the doped silicon source and the lithium source to obtain a silicon-oxygen negative electrode material with good electrical conductivity and high first-efficiency, but the pre-lithium method is high-temperature sintering, and the uniformity is difficult to control.
  • the patent CN110010863A dissolves metal lithium in an organic solvent, and adds negative electrode powder to complete pre-lithium, which improves the first effect of the material and reduces the expansion of the battery during charging and discharging, and the liquid phase process can improve the accuracy of pre-lithium and consistency, but the lithium source used in this patent is a single metal lithium, which has limitations in application and is difficult to produce on a large scale;
  • the patent mixes hard carbon particles with silicon oxide, adds a water-based binder to adjust the viscosity of the slurry, and after spray drying The mixed particles are obtained, so that the small hard carbon particles are wrapped on the surface of the silicon oxide particles, and the prepared battery has the characteristics of good cycle performance, but this patent does not use hard carbon and does not pre-lithium the silicon material, and the first effect of the material is low.
  • the present invention aims to overcome the problems of low first effect, poor electrical conductivity and large expansion of silicon-oxygen materials in the prior art, and provide a high first-efficiency, high-magnification silicon-based negative electrode material and its preparation method.
  • the silicon material is subjected to liquid phase pre-lithiation treatment, and then the pre-lithiated silicon-oxygen material is mixed with graphite and hard carbon, and a carbon source is added for granulation, and the high-first-efficiency silicon-oxygen material is fixed between the graphite particles and the hard carbon particles , through the anchoring effect of carbon-based materials to relieve the volume expansion of silicon-based materials, the amorphous carbon that acts as an anchor also forms a carbon coating layer on the performance of high-first-efficiency silicon-oxygen materials, graphite and hard carbon to further improve
  • the cycle performance of the finished silicon-based material, and the presence of hard carbon particles can improve the rate performance of the composite material.
  • the final silicon-based composite material has the characteristics of high first efficiency, high rate and long cycle life
  • a silicon-based negative electrode material with high first-efficiency and high-magnification rate is a composite structure formed by distributing high-first-efficiency SiO/C material, graphite and hard carbon in amorphous carbon.
  • the mass ratio of high first-efficiency SiO/C material, graphite, hard carbon and amorphous carbon source (that is, the precursor material of amorphous carbon) in the silicon-based negative electrode material is 1:1 ⁇ 10:1 ⁇ 5: 0.1 ⁇ 0.3.
  • the pre-lithium of the silicon oxide negative electrode material is basically mixed with the silicon oxide and the lithium source powder and then solid-phase sintered.
  • the high-first-efficiency silicon-oxygen material prepared in this way grows large silicon particles, which is not conducive to long-term cycle, and the uniformity of pre-lithium is difficult to control, and there are some problems in the interface that will affect the overall performance; in addition, the existing technology lacks the design of the composite structure of high first-efficiency silicon-oxygen materials and graphite, hard carbon and other negative electrodes. The performance of the material is not improved through the structural control of the material end, resulting in poor performance of the silicon-oxygen material in terms of cycle stability and rate.
  • the innovation of the present invention lies in: 1) Pre-lithiation treatment of SiO/C materials is carried out in a liquid phase manner. Compared with traditional solid-state sintering, the accuracy and uniformity of pre-lithium can be improved, and the conditions of pre-lithium are mild. , will not generate a large amount of heat to cause the growth of Si grains, and will not have an adverse effect on the cycle performance of the material; 2) A composite structure with high first-efficiency SiO/C, graphite, and hard carbon is designed and synthesized, which will have a high first-efficiency Effective silicon oxide particles are fixed between graphite and graphite and between graphite and hard carbon particles.
  • the agglomeration of silicon oxide materials will not occur during the homogenization process, and the dispersion effect is better.
  • carbon-based materials can be used as a buffer matrix to inhibit silicon oxide materials during circulation.
  • the addition of hard carbon particles in the composite process improves the rate performance of the material by utilizing the characteristics of larger carbon layer spacing and isotropy of hard carbon.
  • the high first-efficiency SiO/C material is obtained by performing pre-lithiation treatment on the SiO/C negative electrode material by a liquid phase method, and the main component of the high-first-efficiency SiO/C material after pre-lithiation is Li 2 SiO 3 .
  • the preparation method of the silicon-based negative electrode material with high first efficiency and high rate comprises the following preparation steps:
  • the carbon source used in the carbon coating treatment of the raw material SiO is one or more of acetylene, methane, propyne, and ethylene, and the coating time is 1 to 10 h.
  • the raw material SiO The particle size D50 is 2-8 ⁇ m.
  • the lithium source is one or more of lithium metal, lithium hydroxide, lithium peroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium hydride, lithium fluoride, the The mass ratio of the lithium source to the SiO/C negative electrode material is 1:0.1-0.8; the organic solvent is one or more of ethanol, acetone, dimethyl carbonate, diethyl carbonate, benzene, and tetrahydrofuran.
  • described graphite is a kind of in spherical graphite, natural graphite, artificial graphite, mesophase carbon microsphere;
  • Described hard carbon is resin-based hard carbon or pitch-based hard carbon, and described hard The particle size of carbon is 7 to 15 ⁇ m.
  • the amorphous carbon source is one or more of low-temperature pitch, high-temperature pitch, coal tar, phenolic resin, coumarone resin;
  • the mixing and granulation equipment is a kneader, One of a VC heating coating machine, a vertical kettle, and a horizontal kettle; the reaction process in the granulation equipment is to raise the temperature to 200-500°C and keep it warm for 2-8 hours.
  • the inert atmosphere is one of nitrogen, argon, and helium; the high-temperature treatment temperature is 700-900° C., and the high-temperature treatment time is 2-15 hours.
  • the present invention provides a silicon-based negative electrode material with high first-efficiency and high-magnification and a preparation method thereof.
  • the volume expansion of the silicon-based material is alleviated through the anchoring effect of the carbon-based material, and the amorphous carbon that plays an anchoring role is simultaneously in high first-efficiency Silicon-oxygen material, graphite and hard carbon form a layer of carbon coating, and the final silicon-based composite material has the characteristics of high first efficiency, high rate and long cycle life, and excellent comprehensive performance;
  • the silicon-based material with a composite structure prepared by the present invention has uniform and controllable reaction steps, a simple preparation process, easy large-scale production, and excellent performance.
  • the first effect of the silicon-oxygen material is improved by pre-lithium, and the hard carbon particles are improved.
  • the multiplier of the material is increased by the addition of the compound structure, and the processing performance and cycle performance of the material are improved through the design of the composite structure.
  • the performance of the silicon-based negative electrode material is better in all aspects.
  • FIG. 1 is an SEM image of the silicon-based negative electrode material prepared in Example 1 of the present invention.
  • Fig. 2 is the XRD pattern of SiO/C before pre-lithium and SiO/C with high first effect after pre-lithium prepared in Example 1 of the present invention.
  • a silicon-based negative electrode material with high first-efficiency and high-magnification rate is a composite structure formed by distributing high-first-efficiency SiO/C material, graphite and hard carbon in amorphous carbon.
  • the high first-efficiency SiO/C material is obtained by performing pre-lithiation treatment on the SiO/C negative electrode material by a liquid phase method, and the main component of the high-first-efficiency SiO/C material after pre-lithiation is Li 2 SiO 3 .
  • the preparation method of the silicon-based negative electrode material with high first efficiency and high rate comprises the following preparation steps:
  • the lithium source one or more of lithium metal, lithium hydroxide, lithium peroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium hydride, lithium fluoride
  • an organic solvent ethanol, acetone, One or more of dimethyl carbonate, diethyl carbonate, benzene, and tetrahydrofuran
  • Add the SiO/C negative electrode material prepared in step (1) ultrasonically disperse and stir for a period of time, and then filter and dry to obtain high First-effect SiO/C material; the mass ratio of the lithium source to the SiO/C negative electrode material is 1:0.1-0.8;
  • a silicon-based negative electrode material with high first-efficiency and high-magnification rate is a composite structure formed by distributing high-first-efficiency SiO/C material, graphite and hard carbon in amorphous carbon.
  • the high first-efficiency SiO/C material is obtained by performing pre-lithiation treatment on the SiO/C negative electrode material by a liquid phase method, and the main component of the high-first-efficiency SiO/C material after pre-lithiation is Li 2 SiO 3 .
  • the preparation method of the silicon-based negative electrode material with high first efficiency and high rate comprises the following preparation steps:
  • a silicon-based negative electrode material with high first-efficiency and high-magnification rate is a composite structure formed by distributing high-first-efficiency SiO/C material, graphite and hard carbon in amorphous carbon.
  • the high first-efficiency SiO/C material is obtained by performing pre-lithiation treatment on the SiO/C negative electrode material by a liquid phase method, and the main component of the high-first-efficiency SiO/C material after pre-lithiation is Li 2 SiO 3 .
  • the preparation method of the silicon-based negative electrode material with high first efficiency and high rate comprises the following preparation steps:
  • step (2) Dissolve the lithium source lithium peroxide in the organic solvent dimethyl carbonate, add the SiO/C negative electrode material prepared in step (1), ultrasonically disperse and stir for a period of time, and then filter and dry to obtain a high first-efficiency SiO/C C material; the mass ratio of the lithium source to the SiO/C negative electrode material is 1:0.1;
  • a silicon-based negative electrode material with high first-efficiency and high-magnification rate is a composite structure formed by distributing high-first-efficiency SiO/C material, graphite and hard carbon in amorphous carbon.
  • the high first-efficiency SiO/C material is obtained by performing pre-lithiation treatment on the SiO/C negative electrode material by a liquid phase method, and the main component of the high-first-efficiency SiO/C material after pre-lithiation is Li 2 SiO 3 .
  • the preparation method of the silicon-based negative electrode material with high first efficiency and high rate comprises the following preparation steps:
  • step (2) Dissolve the lithium source metal lithium in the organic solvent diethyl carbonate, add the SiO/C negative electrode material prepared in step (1), ultrasonically disperse and stir for a period of time, and then filter and dry to obtain high first-efficiency SiO/C Material; the mass ratio of the lithium source to the SiO/C negative electrode material is 1:0.8;
  • Comparative Example 1 (the difference from Example 1 is that the step (2) is not pre-lithiated, that is, the coated SiO/C negative electrode material is directly granulated and sintered with graphite and hard carbon to obtain the finished material)
  • a silicon-based negative electrode material with high initial efficiency and high rate is a composite structure formed by distributing SiO/C negative electrode material, graphite and hard carbon in amorphous carbon.
  • the preparation method of the silicon-based negative electrode material with high first efficiency and high rate comprises the following preparation steps:
  • Comparative Example 2 (the difference from Example 1 is that no hard carbon particles are added in the step (3) granulation process.)
  • a silicon-based negative electrode material with high first-efficiency and high-magnification rate is a composite structure formed by distributing high-first-efficiency SiO/C material, graphite and hard carbon in amorphous carbon.
  • the high first-efficiency SiO/C material is obtained by performing pre-lithiation treatment on the SiO/C negative electrode material by a liquid phase method, and the main component of the high-first-efficiency SiO/C material after pre-lithiation is Li 2 SiO 3 .
  • the preparation method of the silicon-based negative electrode material with high first efficiency and high rate comprises the following preparation steps:
  • the finished materials prepared in Examples 1-3 and Comparative Examples 1 and 2 were prepared into model 2032 button batteries for evaluation.
  • the specific plan was to prepare the materials, conductive agent SP, conductive agent VGCF, and binder LA136 according to the ratio of 75:5 : 10:10 ratio mixing, using water as solvent, coating slurry on copper foil, counter electrode is lithium sheet, diaphragm is Celgard 2400 microporous polypropylene film, charge and discharge cut-off voltage is 0.005 ⁇ 1.5V, discharge The rate is firstly discharged at 0.1C to 0.005V, then at 0.02C to 0.005V, the charge rate is 0.1C to 1.5V; the second cycle is 1C to 0.005V, and 0.1C to 1.5V; The three-turn cycle is 2C discharge to 0.005V, and 0.1C charge to 1.5V.
  • Table 1 is the deduction test result of embodiment 1-3 and comparative example 1,2:
  • the prepared composite material has high efficiency for the first time, which can reach more than 90%, and has excellent rate performance.
  • Materials without adding hard carbon composites show obvious advantages. Liquid-phase pre-lithiation treatment of SiO/C can improve the accuracy and uniformity of pre-lithium, and the conditions of pre-lithium are mild, and will not generate a lot of heat to cause the growth of Si grains, and will not affect the material cycle. The performance is adversely affected; the addition of hard carbon particles in the composite process takes advantage of the larger and isotropic characteristics of the hard carbon carbon layer to improve the rate performance of the material.
  • Fig. 1 is the SEM picture of the silicon-based negative electrode material prepared in Example 1 of the present invention, it can be seen that the overall particle is a granulated structure of silicon-based material and graphite, the components are evenly distributed, and the particle size uniformity of each added component is good, the obtained The stability of silicon-based negative electrode materials and good material cycle performance;
  • Fig. 2 is the XRD spectrum of the SiO/C before pre-lithium and the high first-effect SiO/C material after pre-lithium prepared in Example 1 of the present invention; it can be seen from the figure that the silicate composition formed after the pre-lithiation treatment is mainly It is Li 2 SiO 3 .
  • Components and equipment used in the present invention are commonly used components and equipment in the field; methods used in the present invention, if not specified, are conventional methods in the field.

Abstract

本发明涉及锂离子电池技术领域，针对现有技术中硅氧材料首效低、电导率不佳及膨胀较大的问题，公开了一种高首效高倍率硅基负极材料及其制备方法，硅基负极材料为高首效SiO/C材料、石墨及硬碳分布于无定型碳中形成的复合结构；硅基负极材料中高首效SiO/C材料、石墨、硬碳和无定型碳源的质量比为1：1～10：1～5：0.1～0.3。对氧化亚硅材料进行液相预锂化处理，将高首效硅氧材料固定在石墨颗粒和硬碳颗粒之间，通过碳基材料的锚定作用缓解硅基材料的体积膨胀，起锚定作用的无定型碳同时在高首效硅氧材料、石墨及硬碳表现形成了一层碳包覆层，最终制得的硅基复合材料具有高首效高倍率长循环寿命的特点，综合性能优异。

Description

一种高首效高倍率硅基负极材料及其制备方法 技术领域
本发明涉及锂离子电池技术领域，尤其是涉及一种高首效高倍率硅基负极材料及其制备方法。
背景技术
随着消费类电子行业及电动汽车等领域的蓬勃发展，人们对储能设备的要求越来越严格，在众多的储能器件中，锂离子电池因其独特的优势而得到了广泛的研究与发展，为了跟进实际应用的步伐，锂离子电池在能量密度、功率密度、循环及安全方面也在不断提升；传统的石墨类锂电池负极材料，因为其理论容量低，已经成为制约锂电池能量密度提升的一项重要因素，与此同时，硅基材料因为其高容量、来源广泛、嵌锂电位低等有点成为最有希望取代石墨的下一代负极材料，硅基材料又分为纳米硅与硅氧方向，与纳米硅相比，硅氧材料因为体积膨胀相对较小、循环更稳定而更被业内人士看好，而且硅氧材料理论容量在2000mAh/g以上，能够满足市场需求，但硅氧材料因为首次充电过程形成Li 2O、Li 4SiO 4等副产物，导致其首次效率低，而且硅氧材料本身电导率不佳、膨胀依然较大等问题，也需要进一步改善与提升。
针对硅基材料目前存在的问题，科研人员已经展开了大量的研究，改善的手段主要集中在预锂化、包覆、掺杂以及结构设计；专利CN111710848A将SiO x与掺杂元素源混合，得到掺杂硅源，再将掺杂硅源与锂源混合煅烧，得到导电性能好、首效高的硅氧负极材料，但是其预锂方式是高温烧结，均匀性难以控制且在规模化应用时会存在加工性的问题；专利CN110010863A将金属锂溶解在有机溶剂，加入负极粉末完成预锂，提升材料首效同时减小了电池在充放电过程的膨胀，且液相过程可以提高预锂的精度及一致性，但本专利使用的锂源为单一的金属锂，应用有局限性难以规模化生产；专利将硬碳颗粒与氧化亚硅混合，加入水性粘结剂调节浆料粘度，喷雾干燥后得到混合颗粒，使硬碳小颗粒包裹在氧化亚硅颗粒表面，制备出的电池具有循环性能好的特性，但此专利未使用硬碳且没有对硅材料进行预锂，材料首效偏低。
发明内容
本发明是为了克服现有技术中硅氧材料首效低、电导率不佳及膨胀较大的问题，提供一种高首效高倍率硅基负极材料及其制备方法，本发明首先对氧化亚硅材料进行液相预锂化处理，再将预锂后的硅氧材料与石墨、硬碳混合并添加碳源进行造粒，将高首效硅氧材料固定在石墨颗粒和硬碳颗粒之间，通过碳基材料的锚定作用缓解硅基材料的体积膨胀，起锚定 作用的无定型碳同时在高首效硅氧材料、石墨及硬碳表现形成了一层碳包覆层，以进一步提升成品硅基材料的循环性能，且硬碳颗粒的存在可以提升复合材料的倍率性能，最终制得的硅基复合材料具有高首效高倍率长循环寿命的特点，综合性能优异。
为了实现上述目的，本发明采用以下技术方案：
一种高首效高倍率硅基负极材料，所述硅基负极材料为高首效SiO/C材料、石墨及硬碳分布于无定型碳中形成的复合结构。
作为优选，所述硅基负极材料中高首效SiO/C材料、石墨、硬碳和无定型碳源(即无定型碳的前驱体材料)的质量比为1：1～10：1～5：0.1～0.3。
现有的技术中，对氧化亚硅负极材料的预锂基本都是将氧化亚硅与锂源粉末混合后固相烧结，这样制备的高首效硅氧材料硅颗粒生长较大，不利于长期循环，且预锂均匀性难以控制，界面存在一些问题会影响整体性能的发挥；除此之外，现有的技术缺乏对高首效硅氧材料与石墨、硬碳等负极复合结构的设计，没有通过材料端的结构控制来提升材料性能，导致硅氧材料在循环稳定性和倍率方面的性能表现不佳。
本发明的创新的在于：1)采用液相的方式对SiO/C材料进行预锂化处理，与传统的固相烧结相比，可以提高预锂的精度与均匀性，且预锂的条件温和，不会产生大量的热而导致Si晶粒的生长，不会对材料的循环性能产生不利的影响；2)设计合成了高首效SiO/C、石墨、硬碳的复合结构，将高首效硅氧颗粒固定在石墨与石墨及石墨与硬碳颗粒之间，匀浆过程不会发生硅氧材料的团聚，分散效果更好，且循环过程中碳基材料可以作为缓冲基质抑制硅氧材料的膨胀，循环性能更佳；3)复合过程中硬碳颗粒的添加，利用硬碳碳层间距更大、各向同性的特点，提升材料的倍率性能。作为优选，所述高首效SiO/C材料通过液相法对SiO/C负极材料进行预锂化处理得到，预锂后的高首效SiO/C材料主要组分为Li 2SiO 3。
所述高首效高倍率硅基负极材料的制备方法，包括以下制备步骤：
(1)对原料SiO进行CVD碳包覆处理，得到SiO/C负极材料；
(2)将锂源溶解在有机溶剂中，加入步骤(1)中制备好的SiO/C负极材料，超声分散并搅拌一段时间后过滤干燥，得到高首效SiO/C材料；
(3)将(2)中制得的高首效SiO/C材料、石墨、硬碳及无定型碳源加入混合造粒设备，得到复合材料前驱体；
(4)将(3)中制得的复合材料前驱体置于惰性氛围气氛炉，高温处理一段时间，得到最终的成品负极材料。
作为优选，步骤(1)中，所述原料SiO的碳包覆处理所用碳源为乙炔、甲烷、丙炔、 乙烯中的一种或多种，包覆时间为1～10h，所述原料SiO的粒度D50为2～8μm。
作为优选，步骤(2)中，所述锂源为金属锂、氢氧化锂、过氧化锂、碳酸锂、醋酸锂、草酸锂、氢化锂、氟化锂中的一种或多种，所述锂源与SiO/C负极材料的质量比为1：0.1～0.8；所述有机溶剂为乙醇、丙酮、碳酸二甲酯、碳酸二乙酯、苯、四氢呋喃中的一种或多种。
作为优选，步骤(3)中，所述石墨为球形石墨、天然石墨、人造石墨、中间相碳微球中的一种；所述硬碳为树脂基硬碳或沥青基硬碳，所述硬碳的粒径为7～15μm。
作为优选，步骤(3)中，所述无定型碳源为低温沥青、高温沥青、煤焦油、酚醛树脂、古马隆树脂中的一种或多种；所述混合造粒设备为捏合机、VC加热包覆机、立式釜、卧式釜中的一种；所述造粒设备中的反应工艺为升温到200～500℃，保温2～8h。
作为优选，步骤(4)中，所述惰性氛围为氮气、氩气、氦气中的一种；所述高温处理温度为700～900℃，所述高温处理时间为2～15h。
所述的高首效高倍率硅基负极材料在锂离子电池中的应用。
因此，本发明具有如下有益效果：
(1)本发明提供一种高首效高倍率硅基负极材料及其制备方法，通过碳基材料的锚定作用缓解硅基材料的体积膨胀，起锚定作用的无定型碳同时在高首效硅氧材料、石墨及硬碳表现形成了一层碳包覆层，最终制得的硅基复合材料具有高首效高倍率长循环寿命的特点，综合性能优异；
(2)本发明制备的复合结构的硅基材料，各反应步骤均匀可控，制备工艺简单，易规模化生产，且性能优异，通过预锂来提升硅氧材料的首效，提过硬碳颗粒的添加提升材料的倍率，通过复合结构的设计提升材料的加工性能和循环性能，制得的硅基负极材料各个方面的性能表现都较佳。
附图说明
图1为本发明实施例1制备的硅基负极材料的SEM图。
图2为本发明实施例1制备的预锂前SiO/C及预锂后后高首效SiO/C材料的XRD图谱。
具体实施方式
下面结合具体实施方式对本发明做进一步的描述。
总实施例
一种高首效高倍率硅基负极材料，所述硅基负极材料为高首效SiO/C材料、石墨及硬碳分布于无定型碳中形成的复合结构。所述高首效SiO/C材料通过液相法对SiO/C负极材料进行预 锂化处理得到，预锂后的高首效SiO/C材料主要组分为Li 2SiO 3。
所述高首效高倍率硅基负极材料的制备方法，包括以下制备步骤：
(1)对粒度D50为2～8μm的原料SiO进行CVD碳包覆处理1～10h，得到SiO/C负极材料，所述原料SiO的碳包覆处理所用碳源为乙炔、甲烷、丙炔、乙烯中的一种或多种；
(2)将锂源(金属锂、氢氧化锂、过氧化锂、碳酸锂、醋酸锂、草酸锂、氢化锂、氟化锂中的一种或多种)溶解在有机溶剂(乙醇、丙酮、碳酸二甲酯、碳酸二乙酯、苯、四氢呋喃中的一种或多种)中，加入步骤(1)中制备好的SiO/C负极材料，超声分散并搅拌一段时间后过滤干燥，得到高首效SiO/C材料；所述锂源与SiO/C负极材料的质量比为1：0.1～0.8；
(3)将(2)中制得的高首效SiO/C材料、石墨(球形石墨、天然石墨、人造石墨、中间相碳微球中的一种)、粒径为7～15μm的硬碳(树脂基硬碳或沥青基硬碳)及无定型碳源(低温沥青、高温沥青、煤焦油、酚醛树脂、古马隆树脂中的一种或多种)按质量比1：1～10：1～5：0.1～0.3加入混合造粒设备(捏合机、VC加热包覆机、立式釜、卧式釜中的一种)，得到复合材料前驱体；所述造粒设备中的反应工艺为升温到200～500℃，保温2～8h；
(4)将(3)中制得的复合材料前驱体置于惰性氛围(氮气、氩气、氦气中的一种)气氛炉，700～900℃处理2～15h，得到最终的成品负极材料。
所述的高首效高倍率硅基负极材料在锂离子电池中的应用。
实施例1
一种高首效高倍率硅基负极材料，所述硅基负极材料为高首效SiO/C材料、石墨及硬碳分布于无定型碳中形成的复合结构。所述高首效SiO/C材料通过液相法对SiO/C负极材料进行预锂化处理得到，预锂后的高首效SiO/C材料主要组分为Li 2SiO 3。
所述高首效高倍率硅基负极材料的制备方法，包括以下制备步骤：
(1)对粒度D50为5μm的原料SiO进行CVD碳包覆处理5h，得到SiO/C负极材料，所述原料SiO的碳包覆处理所用碳源为乙炔；
(2)将锂源氢氧化锂溶解在有机溶剂乙醇中，加入步骤(1)中制备好的SiO/C负极材料，超声分散并搅拌一段时间后过滤干燥，得到高首效SiO/C材料；所述锂源与SiO/C负极材料的质量比为1：0.5；
(3)将(2)中制得的高首效SiO/C材料、球形石墨、粒径为11μm的树脂基硬碳及煤焦油按质量比1：5：3.5：0.2加入混合造粒设备立式釜，得到复合材料前驱体；所述造粒设备中的反应工艺为升温到350℃，保温5h；
(4)将(3)中制得的复合材料前驱体置于氮气惰性氛围气氛炉，800℃处理9h，得到最终 的成品负极材料。
所述的高首效高倍率硅基负极材料在锂离子电池中的应用。
实施例2
一种高首效高倍率硅基负极材料，所述硅基负极材料为高首效SiO/C材料、石墨及硬碳分布于无定型碳中形成的复合结构。所述高首效SiO/C材料通过液相法对SiO/C负极材料进行预锂化处理得到，预锂后的高首效SiO/C材料主要组分为Li 2SiO 3。
所述高首效高倍率硅基负极材料的制备方法，包括以下制备步骤：
(1)对粒度D50为2μm的原料SiO进行CVD碳包覆处理1h，得到SiO/C负极材料，所述原料SiO的碳包覆处理所用碳源为甲烷；
(2)将锂源过氧化锂溶解在有机溶剂碳酸二甲酯中，加入步骤(1)中制备好的SiO/C负极材料，超声分散并搅拌一段时间后过滤干燥，得到高首效SiO/C材料；所述锂源与SiO/C负极材料的质量比为1：0.1；
(3)将(2)中制得的高首效SiO/C材料、天然石墨、粒径为7μm的树脂基硬碳及无定型碳源高温沥青按质量比1：1：1：0.1加入混合造粒设备捏合机，得到复合材料前驱体；所述造粒设备中的反应工艺为升温到200℃，保温2h；
(4)将(3)中制得的复合材料前驱体置于惰性氛围氩气气氛炉，700℃处理2h，得到最终的成品负极材料。
所述的高首效高倍率硅基负极材料在锂离子电池中的应用。
实施例3
一种高首效高倍率硅基负极材料，所述硅基负极材料为高首效SiO/C材料、石墨及硬碳分布于无定型碳中形成的复合结构。所述高首效SiO/C材料通过液相法对SiO/C负极材料进行预锂化处理得到，预锂后的高首效SiO/C材料主要组分为Li 2SiO 3。
所述高首效高倍率硅基负极材料的制备方法，包括以下制备步骤：
(1)对粒度D50为8μm的原料SiO进行CVD碳包覆处理10h，得到SiO/C负极材料，所述原料SiO的碳包覆处理所用碳源为丙炔；
(2)将锂源金属锂溶解在有机溶剂碳酸二乙酯中，加入步骤(1)中制备好的SiO/C负极材料，超声分散并搅拌一段时间后过滤干燥，得到高首效SiO/C材料；所述锂源与SiO/C负极材料的质量比为1：0.8；
(3)将(2)中制得的高首效SiO/C材料、石墨中间相碳微球、粒径为15μm的硬碳沥青基硬碳及无定型碳源酚醛树脂按质量比1：10：5：0.3加入混合造粒设备VC加热包覆机，得 到复合材料前驱体；所述造粒设备中的反应工艺为升温到500℃，保温8h；
(4)将(3)中制得的复合材料前驱体置于惰性氛围氦气气氛炉，900℃处理15h，得到最终的成品负极材料。
所述的高首效高倍率硅基负极材料在锂离子电池中的应用。
对比例1(与实施例1的区别在于，未对步骤(2)进行预锂化处理，即直接将包覆后的SiO/C负极材料与石墨、硬碳造粒烧结后得到成品材料)
一种高首效高倍率硅基负极材料，所述硅基负极材料为SiO/C负极材料、石墨及硬碳分布于无定型碳中形成的复合结构。
所述高首效高倍率硅基负极材料的制备方法，包括以下制备步骤：
(1)对粒度D50为5μm的原料SiO进行CVD碳包覆处理5h，得到SiO/C负极材料，所述原料SiO的碳包覆处理所用碳源为乙炔；
(2)将(1)中制得的SiO/C负极材料、球形石墨、粒径为11μm的树脂基硬碳及煤焦油按质量比1：5：3.5：0.2加入混合造粒设备立式釜，得到复合材料前驱体；所述造粒设备中的反应工艺为升温到350℃，保温5h；
(3)将(2)中制得的复合材料前驱体置于氮气惰性氛围气氛炉，800℃处理9h，得到最终的成品负极材料。
所述的高首效高倍率硅基负极材料在锂离子电池中的应用。
对比例2(与实施例1的区别在于，在步骤(3)造粒过程中未加入硬碳颗粒。)
一种高首效高倍率硅基负极材料，所述硅基负极材料为高首效SiO/C材料、石墨及硬碳分布于无定型碳中形成的复合结构。所述高首效SiO/C材料通过液相法对SiO/C负极材料进行预锂化处理得到，预锂后的高首效SiO/C材料主要组分为Li 2SiO 3。
所述高首效高倍率硅基负极材料的制备方法，包括以下制备步骤：
(1)对粒度D50为5μm的原料SiO进行CVD碳包覆处理5h，得到SiO/C负极材料，所述原料SiO的碳包覆处理所用碳源为乙炔；
(2)将锂源氢氧化锂溶解在有机溶剂乙醇中，加入步骤(1)中制备好的SiO/C负极材料，超声分散并搅拌一段时间后过滤干燥，得到高首效SiO/C材料；所述锂源与SiO/C负极材料的质量比为1：0.5；
(3)将(2)中制得的高首效SiO/C材料、球形石墨及煤焦油按质量比1：5：3.7加入混合造粒设备立式釜，得到复合材料前驱体；所述造粒设备中的反应工艺为升温到350℃，保温5h；
(4)将(3)中制得的复合材料前驱体置于氮气惰性氛围气氛炉，800℃处理9h，得到最终的成品负极材料。
所述的高首效高倍率硅基负极材料在锂离子电池中的应用。
将实施例1-3及对比例1、2制得的成品材料制备成型号2032纽扣电池进行评测，具体方案为，将制备材料、导电剂SP、导电剂VGCF、粘结剂LA136按照75:5:10:10的比例混合，以水为溶剂，将浆料涂布在铜箔上，对电极为锂片，隔膜为Celgard 2400微孔聚丙烯膜，充放电截止电压为0.005～1.5V，放电倍率为先以0.1C放至0.005V，再以0.02C放至0.005V，充电倍率为0.1C充电至1.5V；第二圈循环为1C放电至0.005V，以0.1C充电至1.5V；第三圈循环为2C放电至0.005V，以0.1C充电至1.5V。
表1 为实施例1-3及对比例1、2的扣电测试结果：
材料 可逆容量(mAh/g) 首次效率(％) 2C容量保持率(％)
实施例1 467.8 92.1 83.7
实施例2 458.9 92.5 84.5
实施例3 468.6 91.9 83.8
对比例1 470.1 85.5 80.1
对比例2 450.2 92.2 75.5
结论：从扣电数据可以看出，制备出的复合材料首次效率高，能达到90％以上，且倍率性能优异，2C下容量保持率＞80％，相比于未对SiO/C预锂及未添加硬碳复合的材料，均表现出明显的优势。对SiO/C进行液相法预锂化处理，可以提高预锂的精度与均匀性，且预锂的条件温和，不会产生大量的热而导致Si晶粒的生长，不会对材料的循环性能产生不利的影响；复合过程中硬碳颗粒的添加，利用硬碳碳层间距更大、各向同性的特点，提升材料的倍率性能。
图1为本发明实施例1制备的硅基负极材料的SEM图，可以看到整体颗粒是硅基材料和石墨的造粒结构，组分分布均匀，各添加组分粒径均匀性好，所得硅基负极材料的稳定，材料循环性能好；
图2为本发明实施例1制备的预锂前SiO/C及预锂后后高首效SiO/C材料的XRD图谱；由图中可看出预锂化处理后形成的硅酸盐成分主要为Li 2SiO 3。
本发明中所用元件、设备，若无特别说明，均为本领域的常用元件、设备；本发明中所用方法，若无特别说明，均为本领域的常规方法。
以上所述，仅是本发明的较佳实施例，并非对本发明作任何限制，凡是根据本发明技术实质对以上实施例所作的任何简单修改、变更以及等效变换，均仍属于本发明技术方案的保护范围。

Claims (10)

  1. 一种高首效高倍率硅基负极材料，其特征是，所述硅基负极材料为高首效SiO/C材料、石墨及硬碳分布于无定型碳中形成的复合结构。
  2. 根据权利要求1所述一种高首效高倍率硅基负极材料，其特征在于，所述高首效SiO/C材料通过液相法对SiO/C负极材料进行预锂化处理得到，预锂后的高首效SiO/C材料主要组分为Li 2SiO 3。
  3. 一种如权利要求2所述高首效高倍率硅基负极材料的制备方法，其特征在于，包括以下制备步骤：
    (1)对原料SiO进行CVD碳包覆处理，得到SiO/C负极材料；
    (2)将锂源溶解在有机溶剂中，加入步骤(1)中制备好的SiO/C负极材料，超声分散并搅拌后过滤干燥，得到高首效SiO/C材料；
    (3)将(2)中制得的高首效SiO/C材料、石墨、硬碳及无定型碳源混合造粒，得到复合材料前驱体；
    (4)将(3)中制得的复合材料前驱体置于惰性氛围气氛炉，高温处理，得到高首效高倍率硅基负极材料。
  4. 根据权利要求3所述高首效高倍率硅基负极材料的制备方法，其特征在于，步骤(1)中，所述原料SiO的碳包覆处理所用碳源为乙炔、甲烷、丙炔和乙烯中的一种或多种，包覆时间为1～10h，所述原料SiO的粒度D50为2～8μm。
  5. 根据权利要求3所述高首效高倍率硅基负极材料的制备方法，其特征在于，步骤(2)中，所述锂源为金属锂、氢氧化锂、过氧化锂、碳酸锂、醋酸锂、草酸锂、氢化锂和氟化锂中的一种或多种，所述锂源与SiO/C负极材料的质量比为1：0.1～0.8；所述有机溶剂为乙醇、丙酮、碳酸二甲酯、碳酸二乙酯、苯、四氢呋喃中的一种或多种。
  6. 根据权利要求3所述一种高首效高倍率硅基负极材料的制备方法，其特征在于，步骤(3)中，所述高首效SiO/C材料、石墨、硬碳和无定型碳源的质量比为1：1～10：1～5：0.1～0.3。
  7. 根据权利要求3所述高首效高倍率硅基负极材料的制备方法，其特征在于，步骤(3)中，所述石墨为球形石墨、天然石墨、人造石墨和中间相碳微球中的一种；所述硬碳为树脂基硬碳或沥青基硬碳，所述硬碳的粒径为7～15μm。
  8. 根据权利要求3所述高首效高倍率硅基负极材料的制备方法，其特征在于，步骤(3)中，所述无定型碳源为低温沥青、高温沥青、煤焦油、酚醛树脂和古马隆树脂中的一种或多种；所述混合造粒的设备为捏合机、VC加热包覆机、立式釜和卧式釜中的一种；所述造粒设备中的反应工艺为升温到200～500℃，保温2～8h。
  9. 根据权利要求3所述高首效高倍率硅基负极材料的制备方法，其特征在于，步骤(4)中，所述惰性氛围为氮气、氩气和氦气中的一种；所述高温处理温度为700～900℃，所述高温处理时间为2～15h。
  10. 如权利要求1或2所述的高首效高倍率硅基负极材料在锂离子电池中的应用。
PCT/CN2021/123440 2021-06-11 2021-10-13 一种高首效高倍率硅基负极材料及其制备方法 WO2022257311A1 (zh)

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