WO2021238600A1 - 一种锂离子电池用硅碳负极材料及其制备方法 - Google Patents

一种锂离子电池用硅碳负极材料及其制备方法 Download PDF

Info

Publication number
WO2021238600A1
WO2021238600A1 PCT/CN2021/091977 CN2021091977W WO2021238600A1 WO 2021238600 A1 WO2021238600 A1 WO 2021238600A1 CN 2021091977 W CN2021091977 W CN 2021091977W WO 2021238600 A1 WO2021238600 A1 WO 2021238600A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicon
negative electrode
electrode material
carbon negative
lithium ion
Prior art date
Application number
PCT/CN2021/091977
Other languages
English (en)
French (fr)
Inventor
宋宏芳
赵东辉
周鹏伟
Original Assignee
深圳市翔丰华科技股份有限公司
福建翔丰华新能源材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 深圳市翔丰华科技股份有限公司, 福建翔丰华新能源材料有限公司 filed Critical 深圳市翔丰华科技股份有限公司
Priority to KR1020227013148A priority Critical patent/KR20220104684A/ko
Publication of WO2021238600A1 publication Critical patent/WO2021238600A1/zh

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 present invention relates to the field of lithium ion battery technology, in particular to a silicon carbon negative electrode material for lithium ion batteries and a preparation method thereof.
  • Lithium-ion secondary batteries have excellent comprehensive performance such as high power characteristics. In the past ten years, it has been successfully and widely used in the field of mobile electronic terminal equipment.
  • lithium-ion battery performance mainly depends on the performance of lithium intercalation and deintercalation electrode materials.
  • commercial lithium-ion batteries widely use mesophase carbon microspheres and modified graphite as negative electrode materials, but there are disadvantages such as low theoretical lithium storage capacity (graphite is 372mAh/g) and organic solvent co-intercalation. Therefore, high-capacity lithium
  • graphite is 372mAh/g
  • organic solvent co-intercalation Therefore, high-capacity lithium
  • the research and application of anode materials for ion batteries has become the key to improving battery performance.
  • silicon has the highest theoretical capacity (when the mass of intercalated lithium is not included, it is approximately 4200mAh/g) and a relatively moderate lithium insertion/desorption potential (about 0.1-0.5V v s.Li/Li+), which is very suitable as a negative electrode material for lithium-ion batteries.
  • silicon-based materials have serious volume effects under high-level lithium insertion and release conditions, which can easily lead to structural collapse of the material and peeling of the electrode material, causing the electrode material to lose electrical contact, resulting in a sharp decline in the cycle performance of the electrode.
  • the main purpose of the present invention is to provide a silicon-carbon negative electrode material for lithium ion batteries and a preparation method thereof in view of the deficiencies in the prior art.
  • the prepared silicon-carbon negative electrode material has a large first-time reversible capacity and excellent cycle performance.
  • the preparation method is simple and is conducive to industrialization.
  • a preparation method of silicon carbon negative electrode material for lithium ion battery includes the following steps:
  • Block making Put the silicon-carbon negative electrode material precursor prepared in step (1) into a rubber mold, and place it in an isostatic press molding machine for molding at a pressure of 100-300 MPa to obtain an isostatically pressed block;
  • step (3) Carbonization: Place the block obtained in step (2) in a nitrogen atmosphere protection furnace for sintering, raise it to 400-1000°C at a heating rate of 2-25°C/min and keep it for 4-18 hours, crush and screen Then the silicon carbon anode material is obtained.
  • the graphite precursor is one or a mixture of artificial graphite or natural graphite, and the average particle size D50 is 5-10 ⁇ m.
  • the binder in the step (1) is a mixture of one or more of coal-based or oil-based asphalt, with a softening point of 200-300 °C.
  • the average particle size D50 of the nano-silicon in the step (1) is 10-100 nm.
  • the mechanical fusion treatment in the step (1) is: the rotation speed is 600-1000 rpm.
  • the mass ratio of the graphite precursor, the binder, and the nano silicon in the step (1) is 1:0.01-0.1:0.01-0.1.
  • a silicon carbon negative electrode material for lithium ion batteries is prepared by using the aforementioned preparation method of a silicon carbon negative electrode material for lithium ion batteries.
  • the present invention adopts simple block asphalt pore-making technology and uses less than 10% of the asphalt dosage to realize the integrated preparation of coating and pore-making.
  • the asphalt not only coats the surface of graphite and nano silicon with a layer Uniform amorphous carbon.
  • the volatilization of the pitch will cause a certain inhibition.
  • the carbide produced during the carbonization of the pitch will become a pore former.
  • Inside the block is the surface of nano silicon and graphite. A variety of uniform network-like pores are formed, so that the nano-silicon is under a coating layer with many pores. These pores can better alleviate the volume expansion effect of nano-silicon in the prior art, thereby first charging and discharging efficiency and cycle stability.
  • the preparation method of the invention has simple process, convenient operation and few production equipment, thereby further reducing the cost, facilitating popularization and application, and being suitable for large-scale production.
  • Figure 1 is an SEM image of the present invention.
  • the invention discloses a preparation method of a silicon carbon negative electrode material for lithium ion batteries, which includes the following steps:
  • the graphite precursor is one or a mixture of artificial graphite or natural graphite
  • the average particle size D50 is 5-10 ⁇ m
  • the binder is one or a mixture of coal-based or oil-based pitch
  • the softening point is 200-300 °C
  • the average particle size D50 of nano-silicon is 10-100nm
  • the mechanical fusion treatment is: the rotation speed is 600-1000rpm.
  • the mass ratio of graphite precursor, binder, and nano-silicon is 1:0.01-0.1:0.01-0.1.
  • Block making Put the silicon-carbon negative electrode material precursor prepared in step (1) into a rubber mold, and place it in an isostatic pressing molding machine for molding at a pressure of 100-300 MPa to obtain an isostatic pressed block.
  • step (3) Carbonization: Place the block obtained in step (2) in a nitrogen atmosphere protection furnace for sintering, raise it to 400-1000°C at a heating rate of 2-25°C/min and keep it for 4-18 hours, crush and screen Then the silicon carbon anode material is obtained.
  • the invention also discloses a silicon carbon negative electrode material for lithium ion batteries, which is prepared by adopting the aforementioned preparation method of a silicon carbon negative electrode material for lithium ion batteries.
  • a preparation method of silicon carbon negative electrode material for lithium ion battery includes the following steps:
  • the graphite precursor is artificial graphite
  • the average particle size D50 is 8 ⁇ m
  • the binder is coal-based pitch
  • the softening point is 250°C
  • the average particle size D50 of nano-silicon is 60nm
  • the mechanical fusion treatment is: the rotation speed is 900rpm.
  • the mass ratio of graphite precursor, binder, and nano-silicon is 1: 0.1:0.05.
  • Block making Put the silicon-carbon negative electrode material precursor prepared in step (1) into a rubber mold, and place it in an isostatic pressing machine for molding at a pressure of 250 MPa to obtain an isostatic pressed block.
  • step (3) Carbonization: Place the block obtained in step (2) in a nitrogen atmosphere protection furnace for sintering, raise it to 800°C at a heating rate of 15°C/min and keep it for 10 hours. After crushing and sieving, the silicon carbon anode material is obtained .
  • the invention also discloses a silicon carbon negative electrode material for lithium ion batteries, which is prepared by adopting the aforementioned preparation method of a silicon carbon negative electrode material for lithium ion batteries.
  • a preparation method of silicon carbon negative electrode material for lithium ion battery includes the following steps:
  • the graphite precursor is natural graphite
  • the average particle size D50 is 10 ⁇ m
  • the binder is oil-based pitch
  • the softening point is 300°C
  • the average particle size D50 of nano-silicon is 100 nm
  • the mechanical fusion treatment is: the rotation speed is 1000 rpm.
  • the mass ratio of graphite precursor, binder, and nano-silicon is 1:0.05: 0.1.
  • Block making Put the silicon-carbon negative electrode material precursor prepared in step (1) into a rubber mold, and place it in an isostatic pressing molding machine for molding at a pressure of 300 MPa to obtain an isostatic pressed block.
  • step (3) Carbonization: Place the block obtained in step (2) in a nitrogen atmosphere protection furnace for sintering, raise it to 1000°C at a heating rate of 25°C/min and keep it for 18 hours, crush and screen to obtain silicon carbon anode material .
  • the invention also discloses a silicon carbon negative electrode material for lithium ion batteries, which is prepared by adopting the aforementioned preparation method of a silicon carbon negative electrode material for lithium ion batteries.
  • a preparation method of silicon carbon negative electrode material for lithium ion battery includes the following steps:
  • the graphite precursor is a mixture of artificial graphite and natural graphite.
  • the average particle size D50 is 5 ⁇ m.
  • the binder is a mixture of coal-based pitch and oil-based pitch.
  • the softening point is 200°C.
  • the average particle size D50 of nano-silicon is 10nm.
  • the fusion treatment is: the rotation speed is 600 rpm.
  • the mass ratio of graphite precursor, binder, and nano-silicon is 1:0.02:0.08.
  • Block making Put the silicon-carbon negative electrode material precursor prepared in step (1) into a rubber mold, and place it in an isostatic press molding machine for molding at a pressure of 100 MPa to obtain an isostatically pressed block.
  • step (3) Carbonization: Place the block obtained in step (2) in a nitrogen atmosphere protection furnace for sintering, raise it to 400°C at a heating rate of 2°C/min and keep it for 4 hours. After crushing and sieving, the silicon carbon anode material is obtained .
  • the invention also discloses a silicon carbon negative electrode material for lithium ion batteries, which is prepared by adopting the aforementioned preparation method of a silicon carbon negative electrode material for lithium ion batteries.
  • Comparative Example 1 The nano-silicon material directly coated with carbon on the silicon surface has only steps (1) and (3) and no step (2).
  • a computer-controlled charge and discharge cabinet is used for data collection and control.
  • the prepared silicon carbon anode material has excellent capacity performance, cycle performance, and first charge and discharge efficiency.
  • the porous carbon layer structure formed by the volatilization of pitch plays a very important role: the uniform pore structure can effectively alleviate the volume expansion effect of silicon during the deintercalation of lithium, and inhibit the powdering of active materials.
  • the design focus of the present invention is: the present invention adopts simple block asphalt pore-making technology, uses less than 10% of the asphalt dosage, and realizes the integrated preparation of coating and pore-making.
  • the asphalt is not only in graphite and nanometer
  • the surface of the silicon is coated with a uniform layer of amorphous carbon.
  • the carbide produced during the carbonization of the pitch will become a pore former, which is also in the interior of the block. It is the surface of nano-silicon and graphite that form various uniform network-like pores, so that the nano-silicon is under a coating layer with many pores.
  • the charging and discharging efficiency and cycle stability can be greatly improved.
  • the preparation method of the invention has simple process, convenient operation and few production equipment, thereby further reducing the cost, facilitating popularization and application, and being suitable for large-scale production.

Abstract

本发明公开一种锂离子电池用硅碳负极材料的制备方法，包括有以下步骤：（1）混料：将石墨前驱体、粘结剂、纳米硅按照比例加入机械融合机中处理5-20min，得到硅碳负极材料前驱体；（2）制块：将步骤（1）制备的硅碳负极材料前驱体装入橡胶模具中，放入等静压成型机中进行成型，压力为100-300MPa，得到等静压的块体；（3）碳化。本发明进行了创新性的改进，通过混料、制块、碳化三步法制备出硅碳负极材料，制备出的硅碳负极材料首次可逆容量大和循环性能优良，制备方法简单，利于工业化。

Description

一种锂离子电池用硅碳负极材料及其制备方法 技术领域
本发明涉及锂离子电池领域技术，尤其是指一种锂离子电池用硅碳负极材料及其制备方法。
 背景技术
随着各种便携式电子设备及电动汽车的广泛应用和快速发展，人们对各类电产品电源的需求和性能要求也越来越高，锂离子二次电池以其高功率特性等优越的综合性能在近十年来成功并广泛应用于移动电子终端设备领域。
锂离子电池性能的改善主要取决于嵌脱锂电极材料的性能。目前，商用锂离子电池广泛采用中间相碳微球和改性石墨作为负极材料，但存在理论储锂容量较低(石墨为372mAh/g)，易发生有机溶剂共嵌入等缺点，因此高容量锂离子电池负极材料的研究与应用已成为提高电池性能的关键。在已知的储锂材料中，硅具有最高的理论容量（不包括嵌入锂的质量时，约为 4200mAh/g）和较为适中的嵌脱锂电位（约0.1-0.5V v s.Li/Li+），非常适用于作锂离子电池的负极材料。但是硅基材料在高程度嵌脱锂条件下，存在严重的体积效应，容易导致材料的结构崩塌和电极材料的剥落而使电极材料失去电接触，从而造成电极循环性能急剧下降。
 技术解决方案
有鉴于此，本发明针对现有技术存在之缺失，其主要目的是提供一种锂离子电池用硅碳负极材料及其制备方法，其制备出的硅碳负极材料首次可逆容量大和循环性能优良，制备方法简单，利于工业化。
为实现上述目的，本发明采用如下之技术方案：
一种锂离子电池用硅碳负极材料的制备方法，包括有以下步骤：
（1）混料：将石墨前驱体、粘结剂、纳米硅按照比例加入机械融合机中处理5-20min，得到硅碳负极材料前驱体；
（2）制块：将步骤（1）制备的硅碳负极材料前驱体装入橡胶模具中，放入等静压成型机中进行成型，压力为100-300MPa，得到等静压的块体；
（3）碳化：将步骤（2）得到的块体置于氮气气氛保护炉中进行烧结，以 2～ 25℃/min 的升温速率升至400～1000℃并保温 4～18小时，粉碎筛分后得到硅碳负极材料。
作为一种优选方案，所述步骤（1）中石墨前驱体为人造石墨或者天然石墨的一种或几种混合，平均粒径D50为5 -10μm。
作为一种优选方案，所述步骤（1）中的粘结剂为煤系或者油系沥青的一种或几种混合，软化点为200-300 ℃。
作为一种优选方案，所述步骤（1）中的纳米硅平均粒径D50为10-100 nm。
作为一种优选方案，所述步骤（1）中机械融合处理为：转速为600-1000rpm。
作为一种优选方案，所述步骤（1）中所述的石墨前驱体、粘结剂、纳米硅的质量比为1:0.01-0.1:0.01-0.1。
一种锂离子电池用硅碳负极材料，采用前述一种锂离子电池用硅碳负极材料的制备方法制得。
本发明与现有技术相比具有明显的优点和有益效果，具体而言，由上述技术方案可知：
本发明采用简单的块体沥青造孔技术，使用不到10%的沥青用量，实现了包覆和造孔的一体化制备，通过此方法，沥青不仅在石墨和纳米硅的表面包覆一层均匀的无定形碳，同时，因为压成块体，沥青的挥发会造成一定的抑制，沥青碳化过程中产生的碳化物会变成造孔剂，在块体内部也就是纳米硅和石墨的表面形成各种均匀的网络状孔隙，这样纳米硅处于一个有很多孔隙的包覆层下，这些孔隙可以更好的缓解现有技术中纳米硅的体积膨胀效应，从而首次充放电效率和循环稳定性能大幅提升。本发明制备方法工艺简单，操作方便，生产设备少，从而进一步降低成本，便于推广应用，适于大规模生产。
 附图说明
图1是本发明的SEM图。
 本发明的实施方式
本发明揭示了一种锂离子电池用硅碳负极材料的制备方法，包括有以下步骤：
（1）混料：将石墨前驱体、粘结剂、纳米硅按照比例加入机械融合机中处理5-20min，得到硅碳负极材料前驱体。石墨前驱体为人造石墨或者天然石墨的一种或几种混合，平均粒径D50为5-10μm，粘结剂为煤系或者油系沥青的一种或几种混合，软化点为200-300℃，纳米硅的平均粒径D50为10-100nm，机械融合处理为：转速为600-1000rpm。并且，石墨前驱体、粘结剂、纳米硅的质量比为1:0.01-0.1:0.01-0.1。
（2）制块：将步骤（1）制备的硅碳负极材料前驱体装入橡胶模具中，放入等静压成型机中进行成型，压力为100-300MPa，得到等静压的块体。
（3）碳化：将步骤（2）得到的块体置于氮气气氛保护炉中进行烧结，以 2～ 25℃/min 的升温速率升至400～1000℃并保温 4～18小时，粉碎筛分后得到硅碳负极材料。
本发明还公开了一种锂离子电池用硅碳负极材料，采用前述一种锂离子电池用硅碳负极材料的制备方法制得。
下面以多个实施例对本发明作进一步详细说明：
实施例1：
一种锂离子电池用硅碳负极材料的制备方法，包括有以下步骤：
（1）混料：将石墨前驱体、粘结剂、纳米硅按照比例加入机械融合机中处理5-20min，得到硅碳负极材料前驱体。石墨前驱体为人造石墨，平均粒径D50为8μm，粘结剂为煤系沥青，软化点为250℃，纳米硅的平均粒径D50为60nm，机械融合处理为：转速为900rpm。并且，石墨前驱体、粘结剂、纳米硅的质量比为1: 0.1:0.05。
（2）制块：将步骤（1）制备的硅碳负极材料前驱体装入橡胶模具中，放入等静压成型机中进行成型，压力为250MPa，得到等静压的块体。
（3）碳化：将步骤（2）得到的块体置于氮气气氛保护炉中进行烧结，以 15℃/min 的升温速率升至800℃并保温 10小时，粉碎筛分后得到硅碳负极材料。
本发明还公开了一种锂离子电池用硅碳负极材料，采用前述一种锂离子电池用硅碳负极材料的制备方法制得。
实施例2：
一种锂离子电池用硅碳负极材料的制备方法，包括有以下步骤：
（1）混料：将石墨前驱体、粘结剂、纳米硅按照比例加入机械融合机中处理5-20min，得到硅碳负极材料前驱体。石墨前驱体为天然石墨，平均粒径D50为10μm，粘结剂为油系沥青，软化点为300℃，纳米硅的平均粒径D50为100nm，机械融合处理为：转速为1000rpm。并且，石墨前驱体、粘结剂、纳米硅的质量比为1:0.05: 0.1。
（2）制块：将步骤（1）制备的硅碳负极材料前驱体装入橡胶模具中，放入等静压成型机中进行成型，压力为300MPa，得到等静压的块体。
（3）碳化：将步骤（2）得到的块体置于氮气气氛保护炉中进行烧结，以 25℃/min 的升温速率升至1000℃并保温 18小时，粉碎筛分后得到硅碳负极材料。
本发明还公开了一种锂离子电池用硅碳负极材料，采用前述一种锂离子电池用硅碳负极材料的制备方法制得。
实施例3：
一种锂离子电池用硅碳负极材料的制备方法，包括有以下步骤：
（1）混料：将石墨前驱体、粘结剂、纳米硅按照比例加入机械融合机中处理5-20min，得到硅碳负极材料前驱体。石墨前驱体为人造石墨和天然石墨的混合，平均粒径D50为5μm，粘结剂为煤系沥青和油系沥青的混合，软化点为200℃，纳米硅的平均粒径D50为10nm，机械融合处理为：转速为600rpm。并且，石墨前驱体、粘结剂、纳米硅的质量比为1:0.02:0.08。
（2）制块：将步骤（1）制备的硅碳负极材料前驱体装入橡胶模具中，放入等静压成型机中进行成型，压力为100MPa，得到等静压的块体。
（3）碳化：将步骤（2）得到的块体置于氮气气氛保护炉中进行烧结，以 2℃/min 的升温速率升至400℃并保温 4小时，粉碎筛分后得到硅碳负极材料。
本发明还公开了一种锂离子电池用硅碳负极材料，采用前述一种锂离子电池用硅碳负极材料的制备方法制得。
对比例1：在硅表面直接包覆碳的纳米硅材料，只有步骤（1）和（3），没有步骤（2）。
为检测本发明负极材料的锂离子电池负极材料的性能，用半电池测试方法测试，用以上实施例和比较例的负极材料∶SBR(固含量50％)∶CMC∶Super-p＝95.5∶2∶1.5∶1(重量比 )，加适量去离子水调和成浆状，涂布于铜箔上并于真空干燥箱内干燥 12 小时制成负极片，电解液为1M LiPF6/EC+DEC+DMC ＝1∶1∶1，聚丙烯微孔膜为隔膜，对电极为锂片，组装成电池。在LAND电池测试***进行恒流充放电实验，充放电电压限制在 0.01-3.0 V，用计算机控制的充放电柜进行数据的采集及控制。
上述各实施例和比较例中负极材料性能比较如下表1所示：
表1
实施例/对比例 0.1C首次比容量（mAh/g） 0.1C首次效率 （%） 0.1 C 300次循环容量保持率（%）
实施例1 690 91.5 89.9
实施例2 600 89.1 87.7
实施例3 570 90.2 88.3
对比例1 478 84 76
从表1可以看出，所制备出的硅碳负极材料，拥有优良的容量性能、循环性能性能、首次充放电效率。沥青挥发形成的多孔的碳层结构起到了非常关键的作用：均匀的孔隙结构可以非常有效缓解脱嵌锂过程中硅的体积膨胀效应，抑制活性物质的粉化 。
并且从图1可以看出，纳米硅和石墨均被沥青挥发形成的多孔状的无定形碳所包裹住，分布均匀，孔隙多。
本发明的设计重点在于：本发明采用简单的块体沥青造孔技术，使用不到10%的沥青用量，实现了包覆和造孔的一体化制备，通过此方法，沥青不仅在石墨和纳米硅的表面包覆一层均匀的无定形碳，同时，因为压成块体，沥青的挥发会造成一定的抑制，沥青碳化过程中产生的碳化物会变成造孔剂，在块体内部也就是纳米硅和石墨的表面形成各种均匀的网络状孔隙，这样纳米硅处于一个有很多孔隙的包覆层下，这些孔隙可以更好的缓解现有技术中纳米硅的体积膨胀效应，从而首次充放电效率和循环稳定性能大幅提升。本发明制备方法工艺简单，操作方便，生产设备少，从而进一步降低成本，便于推广应用，适于大规模生产。
以上所述，仅是本发明的较佳实施例而已，并非对本发明的技术范围作任何限制，故凡是依据本发明的技术实质对以上实施例所作的任何细微修改、等同变化与修饰，均仍属于本发明技术方案的范围内。

Claims (7)

  1. 一种锂离子电池用硅碳负极材料的制备方法，其特征在于：包括有以下步骤：
    （1）混料：将石墨前驱体、粘结剂、纳米硅按照比例加入机械融合机中处理5-20min，得到硅碳负极材料前驱体；
    （2）制块：将步骤（1）制备的硅碳负极材料前驱体装入橡胶模具中，放入等静压成型机中进行成型，压力为100-300MPa，得到等静压的块体；
    （3）碳化：将步骤（2）得到的块体置于氮气气氛保护炉中进行烧结，以 2～ 25℃/min 的升温速率升至400～1000℃并保温 4～18小时，粉碎筛分后得到硅碳负极材料。
  2. 根据权利要求1所述的一种锂离子电池用硅碳负极材料的制备方法，其特征在于：所述步骤（1）中石墨前驱体为人造石墨或者天然石墨的一种或几种混合，平均粒径D50为5 -10μm。
  3. 根据权利要求1所述的一种锂离子电池用硅碳负极材料的制备方法，其特征在于：所述步骤（1）中的粘结剂为煤系或者油系沥青的一种或几种混合，软化点为200-300 ℃。
  4. 根据权利要求1所述的一种锂离子电池用硅碳负极材料的制备方法，其特征在于：所述步骤（1）中的纳米硅平均粒径D50为10-100 nm。
  5. 根据权利要求1所述的一种锂离子电池用硅碳负极材料的制备方法，其特征在于：所述步骤（1）中机械融合处理为：转速为600-1000rpm。
  6. 根据权利要求1所述的一种锂离子电池用硅碳负极材料的制备方法，其特征在于：所述步骤（1）中所述的石墨前驱体、粘结剂、纳米硅的质量比为1:0.01-0.1:0.01-0.1。
  7. 一种锂离子电池用硅碳负极材料，其特征在于：采用如权利要求1-6任一项所述一种锂离子电池用硅碳负极材料的制备方法制得。
PCT/CN2021/091977 2020-05-26 2021-05-07 一种锂离子电池用硅碳负极材料及其制备方法 WO2021238600A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020227013148A KR20220104684A (ko) 2020-05-26 2021-05-07 리튬 이온 전지용 실리콘-탄소 음극재 및 그 제조 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010456796.7 2020-05-26
CN202010456796.7A CN111725504B (zh) 2020-05-26 2020-05-26 一种锂离子电池用硅碳负极材料及其制备方法

Publications (1)

Publication Number Publication Date
WO2021238600A1 true WO2021238600A1 (zh) 2021-12-02

Family

ID=72565175

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/091977 WO2021238600A1 (zh) 2020-05-26 2021-05-07 一种锂离子电池用硅碳负极材料及其制备方法

Country Status (3)

Country Link
KR (1) KR20220104684A (zh)
CN (1) CN111725504B (zh)
WO (1) WO2021238600A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114744166A (zh) * 2022-02-25 2022-07-12 深圳市翔丰华科技股份有限公司 预锂化硅氧复合材料的制备方法
CN117174836A (zh) * 2023-11-03 2023-12-05 陕西晶泰新能源科技有限公司 一种锂离子电池氧化亚硅负极的预镁化中间缓冲层

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111725504B (zh) * 2020-05-26 2021-10-29 深圳市翔丰华科技股份有限公司 一种锂离子电池用硅碳负极材料及其制备方法
CN112290006A (zh) * 2020-11-23 2021-01-29 山东硅纳新材料科技有限公司 一种简单高效的硅碳负极材料制备方法
CN114436238B (zh) * 2021-12-28 2023-07-18 深圳市翔丰华科技股份有限公司 锂离子电池用低膨胀硅碳负极材料的制备方法
CN114538432B (zh) * 2022-02-09 2024-01-09 上海杉杉新材料有限公司 石墨负极材料、其前驱体、其生料前驱体及其制备方法和应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103855369A (zh) * 2012-12-05 2014-06-11 上海杉杉科技有限公司 一种锂电池负极材料及其制备方法
US20170342578A1 (en) * 2014-11-11 2017-11-30 William Marsh Rice University A new class of electrocatalysts
CN107785560A (zh) * 2017-11-15 2018-03-09 国联汽车动力电池研究院有限责任公司 一种高性能硅碳负极材料及其制备方法
CN108682830A (zh) * 2018-06-11 2018-10-19 清华大学深圳研究生院 一种锂离子电池硅碳复合负极材料及其制备方法
CN108963208A (zh) * 2018-06-22 2018-12-07 清华大学深圳研究生院 一种硅碳负极材料的制备方法及锂离子电池
CN111725504A (zh) * 2020-05-26 2020-09-29 深圳市翔丰华科技股份有限公司 一种锂离子电池用硅碳负极材料及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103633307B (zh) * 2013-12-20 2015-06-17 大连宏光锂业股份有限公司 一种锂离子电池硅碳复合负极材料生产方法
CN106257716B (zh) * 2016-08-30 2019-01-11 浙江超威创元实业有限公司 一种硅碳复合负极材料的制备方法及锂离子电池
CN106784833A (zh) * 2016-12-26 2017-05-31 国联汽车动力电池研究院有限责任公司 硅碳负极材料及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103855369A (zh) * 2012-12-05 2014-06-11 上海杉杉科技有限公司 一种锂电池负极材料及其制备方法
US20170342578A1 (en) * 2014-11-11 2017-11-30 William Marsh Rice University A new class of electrocatalysts
CN107785560A (zh) * 2017-11-15 2018-03-09 国联汽车动力电池研究院有限责任公司 一种高性能硅碳负极材料及其制备方法
CN108682830A (zh) * 2018-06-11 2018-10-19 清华大学深圳研究生院 一种锂离子电池硅碳复合负极材料及其制备方法
CN108963208A (zh) * 2018-06-22 2018-12-07 清华大学深圳研究生院 一种硅碳负极材料的制备方法及锂离子电池
CN111725504A (zh) * 2020-05-26 2020-09-29 深圳市翔丰华科技股份有限公司 一种锂离子电池用硅碳负极材料及其制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114744166A (zh) * 2022-02-25 2022-07-12 深圳市翔丰华科技股份有限公司 预锂化硅氧复合材料的制备方法
CN117174836A (zh) * 2023-11-03 2023-12-05 陕西晶泰新能源科技有限公司 一种锂离子电池氧化亚硅负极的预镁化中间缓冲层

Also Published As

Publication number Publication date
CN111725504A (zh) 2020-09-29
KR20220104684A (ko) 2022-07-26
CN111725504B (zh) 2021-10-29

Similar Documents

Publication Publication Date Title
CN107785560B (zh) 一种高性能硅碳负极材料及其制备方法
WO2021056981A1 (zh) 一种锂电池硅基复合负极材料的制备方法
WO2021238600A1 (zh) 一种锂离子电池用硅碳负极材料及其制备方法
WO2022121136A1 (zh) 一种高倍率锂离子电池人造石墨负极材料及其制备方法
CN106711461A (zh) 一种球形多孔硅碳复合材料及其制备方法与用途
CN107845797B (zh) 一种锂离子电池用纳米硅碳复合负极材料及其制备方法
CN110620224A (zh) 用于锂电池的负极材料及其制备方法和锂电池
CN106784741B (zh) 一种碳硅复合材料、其制备方法及包含该复合材料的锂离子电池
CN114447325B (zh) 多孔碳材料、其制备方法、负极和锂金属电池
CN108448080A (zh) 一种石墨烯包覆硅/金属复合负极材料及其制备方法
WO2022021933A1 (zh) 非水电解质二次电池用负极材料及其制备方法
CN108682787B (zh) 一种锂离子电池极片及其制备方法
CN113193183B (zh) 一种高振实密度双碳层硅碳复合材料及其制备方法
CN108682830B (zh) 一种锂离子电池硅碳复合负极材料及其制备方法
KR20220083974A (ko) 자가충진 코팅 실리콘 기반 복합 재료 및 그 제조 방법 및 응용
CN115332523B (zh) 以高分子凝胶为基体衍生的硅碳负极材料及其制备方法
CN111430691B (zh) 一种锂离子电池硅基负极材料及其制备方法
WO2023173772A1 (zh) 硬碳负极材料的制备方法和应用
CN108807903B (zh) 一种锂电池用复合修饰锂电池负极材料的制备方法
CN113644243A (zh) 氮掺杂中空结构石墨微球、复合负极材料及其制备方法
CN113471405A (zh) 预锂化负极、其制备方法和含预锂化负极的锂离子电池和超级电容器
CN110895999A (zh) 一种多孔石墨烯增强的超级电容器及其制备方法
CN108878823B (zh) 一种金属橄榄石包覆纳米硅的制备方法
CN111725507B (zh) 一种锂离子电池用高压实硅碳负极材料及其制备方法
CN116230895A (zh) 一种锂电池负极材料、锂电池及制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21813706

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT 1205A DATED 17/04/2023)

122 Ep: pct application non-entry in european phase

Ref document number: 21813706

Country of ref document: EP

Kind code of ref document: A1