CN108878831A - A method of improving silicon based anode material electric conductivity - Google Patents

A method of improving silicon based anode material electric conductivity Download PDF

Info

Publication number
CN108878831A
CN108878831A CN201810678006.2A CN201810678006A CN108878831A CN 108878831 A CN108878831 A CN 108878831A CN 201810678006 A CN201810678006 A CN 201810678006A CN 108878831 A CN108878831 A CN 108878831A
Authority
CN
China
Prior art keywords
silicon
negative electrode
based negative
improving
conductivity
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
CN201810678006.2A
Other languages
Chinese (zh)
Inventor
曾绍忠
何前军
郑先锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen University
Original Assignee
Shenzhen University
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 Shenzhen University filed Critical Shenzhen University
Priority to CN201810678006.2A priority Critical patent/CN108878831A/en
Publication of CN108878831A publication Critical patent/CN108878831A/en
Pending legal-status Critical Current

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
    • H01M4/362—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
    • H01M4/38—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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A method of improving silicon based anode material electric conductivity, the invention discloses a kind of methods for improving silicon based anode material electric conductivity, the present invention problem unstable for carbon coating layer, using Ti-O-Si chemical bond is formed between the oxygen and silicon particle in titanium oxide, a kind of method for improving silicon based anode material cyclical stability is provided：Titanium oxide is coated on silicon based anode material, the mass fraction of titanium oxide is about 2 ~ 50% after cladding.The beneficial effects of the present invention are：Since the combination of Ti-O key and Si-O key can be all very high, titanium oxide clad is firmly bonded in silicon particle surface, even if undergoing huge volume change, will not fall off from silicon particle surface.And since titanium oxide is semiconductor, conductivity is regulated and controled by defect, and titanium dioxide is converted to the titanium oxide of anoxic using the reproducibility of silicon, can effectively improve the electric conductivity of titanium oxide clad, the final electric conductivity for improving silicon based anode material.

Description

一种改善硅基负极材料导电性的方法A method for improving the conductivity of silicon-based negative electrode materials

技术领域technical field

本发明公开了一种改善硅基负极材料导电性的方法，属于电化学和新能源材料领域。The invention discloses a method for improving the conductivity of a silicon-based negative electrode material, belonging to the fields of electrochemistry and new energy materials.

背景技术Background technique

锂离子电池以其高电压、高能量密度和长循环寿命等优异性能而被广泛应用于手机和笔记本电池、动力电池及储能电池等。其中手机和笔记本电池已完全被锂离子电池占据，因为其他种类的电池根本无法达到这些便携式智能设备的严苛要求。随着锂离子电池技术发展，其在动力电池储能电池中所占的比例也越来越大，从目前的发展趋势而言，锂离子电池正处于一个飞速发展阶段，应用前景广阔。Lithium-ion batteries are widely used in mobile phone and notebook batteries, power batteries and energy storage batteries due to their excellent properties such as high voltage, high energy density and long cycle life. Among them, mobile phone and notebook batteries have been completely occupied by lithium-ion batteries, because other types of batteries cannot meet the stringent requirements of these portable smart devices. With the development of lithium-ion battery technology, its proportion in power battery energy storage batteries is also increasing. From the current development trend, lithium-ion batteries are in a stage of rapid development and have broad application prospects.

随着智能手机和笔记本电脑的轻薄化、多功能化和屏幕的加大，现有的锂离子电池同样难以满足消费类电子产品对电池日益苛刻的要求，迫切需要新型技术来有效提高锂离子电池的比能量。锂离子电池通常包括负极、隔膜、电解液、正极等四大关键材料及其他辅助材料，而四大关键材料中，负极和正极是其核心材料，负极和正极材料的比容量和嵌脱锂电压决定了锂离子电池的比能量。目前锂离子电池常用的正极材料有钴酸锂、锰酸锂、三元及磷酸铁锂，比容量在100~200mAh/g之间；常用的负极材料为碳类负极材料，比容量在250~360mAh/g之间。锂离子电池比能量的提高目前主要受限于正极材料的比容量，经过各国科学家二十多年的努力，尽管开发出比容量达到200~300mAh/g的固溶体正极材料，但由于尚未克服其固有缺陷，暂时无法商用，商用的正极材料的比容量仍然低于200 mAh/g。With the thinner and lighter, multi-functional and larger screens of smartphones and notebook computers, it is also difficult for existing lithium-ion batteries to meet the increasingly stringent requirements of consumer electronics for batteries. There is an urgent need for new technologies to effectively improve lithium-ion batteries. specific energy. Lithium-ion batteries usually include four key materials such as negative electrode, separator, electrolyte, positive electrode and other auxiliary materials. Among the four key materials, negative electrode and positive electrode are the core materials. Determines the specific energy of lithium-ion batteries. At present, the commonly used positive electrode materials for lithium-ion batteries include lithium cobaltate, lithium manganate, ternary and lithium iron phosphate, with a specific capacity between 100~200mAh/g; commonly used negative electrode materials are carbon negative electrode materials, with a specific capacity of 250~200mAh/g. Between 360mAh/g. The improvement of the specific energy of lithium-ion batteries is currently mainly limited by the specific capacity of the positive electrode material. After more than 20 years of efforts by scientists from various countries, although a solid solution positive electrode material with a specific capacity of 200~300mAh/g has been developed, it has not yet overcome its inherent Defects, it is temporarily unavailable for commercial use, and the specific capacity of commercial cathode materials is still lower than 200 mAh/g.

在正极材料比容量提升受阻的情况下，提高负极材料的比容量是提高电池比能量的有效途径之一。目前商业化的锂离子电池主要采用石墨类负极材料，由于石墨的理论嵌锂容量仅为372mAh/g，且实际应用的材料已达到360mAh/g，因此该类材料在容量上几乎已无提升空间。为了提高锂离子电池的比能量，各种新型的高比容量和高倍率性能的负极材料被开发出来，包括硅基、锡基、纳米碳材料及金属氧化物，其中硅基材料由于具有最高的质量比容量和较低的电压平台（硅的理论比容量为4200 mAh/g，脱锂平台电压为0.4V）而成为研究热点，然而，硅基负极材料在嵌脱锂过程中伴随着严重的体积膨胀与收缩，导致电活性物质的粉化脱落和固体电解质膜（solid electrolyte interphase, SEI膜）的不断形成，直接导致比容量快速衰减且充放电效率低等问题，此外，单质硅为半导体，电导率较低，不利于充放电反应中的电子转移。In the case that the specific capacity of the positive electrode material is hindered, increasing the specific capacity of the negative electrode material is one of the effective ways to increase the specific energy of the battery. At present, commercial lithium-ion batteries mainly use graphite-based negative electrode materials. Since the theoretical lithium intercalation capacity of graphite is only 372mAh/g, and the actual application of materials has reached 360mAh/g, there is almost no room for improvement in the capacity of this type of material. . In order to improve the specific energy of lithium-ion batteries, various new negative electrode materials with high specific capacity and high rate performance have been developed, including silicon-based, tin-based, nano-carbon materials and metal oxides, among which silicon-based materials have the highest The mass specific capacity and lower voltage platform (the theoretical specific capacity of silicon is 4200 mAh/g, and the delithiation platform voltage is 0.4V) have become research hotspots. However, silicon-based negative electrode materials are accompanied by serious Volume expansion and contraction lead to the pulverization and shedding of electroactive materials and the continuous formation of solid electrolyte interphase (SEI film), which directly leads to the rapid decline of specific capacity and low charge and discharge efficiency. In addition, elemental silicon is a semiconductor. The low conductivity is not conducive to electron transfer in charge and discharge reactions.

针对硅基负极材料的上述问题，优化硅基负极材料本身的微观结构是一种根本性的解决方法。为了改善硅基负极材料的导电性，最常用的方法是碳包覆，这是由于碳材料导电性适中、稳定性好、原料成本低且包覆方法多，但是，碳包覆层与硅颗粒间的结合力较弱，在嵌脱锂的过程中由于硅颗粒巨大的体积变化，容易导致碳包覆层碎裂脱落，从而降低材料的导电性最终引起比容量的衰减。For the above-mentioned problems of silicon-based negative electrode materials, optimizing the microstructure of silicon-based negative electrode materials is a fundamental solution. In order to improve the conductivity of silicon-based negative electrode materials, the most commonly used method is carbon coating, which is due to the moderate conductivity of carbon materials, good stability, low raw material cost and many coating methods. However, carbon coating and silicon particles Due to the huge volume change of silicon particles in the process of inserting and removing lithium, it is easy to cause the carbon coating layer to break and fall off, thereby reducing the conductivity of the material and finally causing the specific capacity attenuation.

发明内容Contents of the invention

本发明针对上述碳包覆层不稳定的问题，利用氧化钛中的氧与硅颗粒间形成Ti-O-Si化学键，提供一种提高硅基负极材料循环稳定性的方法。本发明的技术方案如下：The present invention aims at the problem of instability of the above-mentioned carbon coating layer, utilizes the Ti-O-Si chemical bond formed between the oxygen in the titanium oxide and the silicon particles, and provides a method for improving the cycle stability of the silicon-based negative electrode material. Technical scheme of the present invention is as follows:

一种改善硅基负极材料导电性的方法，所述的方法为：在硅基负极材料上包覆氧化钛，包覆后氧化钛的质量分数约为2~50%，较佳的范围是5~20%。A method for improving the conductivity of a silicon-based negative electrode material, the method comprising: coating titanium oxide on the silicon-based negative electrode material, the mass fraction of titanium oxide after coating is about 2 to 50%, and the preferred range is 5% ~20%.

第一个改善硅基负极材料导电性的方法步骤如下（气相包覆法）：将所述的硅基负极材料置于四氯化钛的气氛中暴露一段时间，同时通入空气和水蒸气进行包覆，利用硅基负极材料表面吸附的水及硅材料表面的羟基吸附四氯化钛并水解成氧化钛，可以通过控制湿空气的通入量控制四氯化钛的水解程度进而实现二氧化钛包覆量的控制，充分搅拌使各种粉料分散均匀。包覆完成后在惰性气氛保护下均匀升温，于200~900℃保温0.5~12小时。优选的条件为300~600℃保温1-4小时。The first method for improving the conductivity of silicon-based negative electrode materials is as follows (gas-phase coating method): the silicon-based negative electrode material is exposed to an atmosphere of titanium tetrachloride for a period of time, and air and water vapor are introduced at the same time. Coating, using the water adsorbed on the surface of the silicon-based negative electrode material and the hydroxyl group on the surface of the silicon material to adsorb titanium tetrachloride and hydrolyze it into titanium oxide, the degree of hydrolysis of titanium tetrachloride can be controlled by controlling the amount of humid air to achieve titanium dioxide coating To control the amount of coating, fully stir to disperse all kinds of powder evenly. After the coating is completed, the temperature is raised evenly under the protection of an inert atmosphere, and the temperature is kept at 200~900°C for 0.5~12 hours. The preferred condition is 300~600°C for 1-4 hours.

第二个改善硅基负极材料导电性的方法步骤如下（液相包覆法）：将硅基负极材料分散在溶剂中，再加入钛源，搅拌使溶液吸收空气中的水分并水解，水解完成后过滤干燥，得到的产物在惰性气氛保护下均匀升温，于200~900℃保温0.5~12小时，优选的条件是在300~600℃下保温1~4小时。The second method to improve the conductivity of silicon-based negative electrode materials is as follows (liquid phase coating method): disperse silicon-based negative electrode materials in a solvent, then add titanium source, stir to make the solution absorb moisture in the air and hydrolyze, and the hydrolysis is completed After filtering and drying, the obtained product is evenly heated under the protection of an inert atmosphere, and kept at 200-900°C for 0.5-12 hours, preferably at 300-600°C for 1-4 hours.

优选的，所述的钛源为易水解的钛盐。Preferably, the titanium source is easily hydrolyzed titanium salt.

更优选的，所述的钛盐为四氯化钛、钛酸四丁酯和/或者氟钛酸铵。More preferably, the titanium salt is titanium tetrachloride, tetrabutyl titanate and/or ammonium fluorotitanate.

上述提供的两个方法中，所述的硅基负极材料包括有单质硅颗粒、多孔硅、纳米硅、SiO和歧化后的SiO。包覆后TiO2的质量分数约为2~50%，较佳的范围是5~20%。In the two methods provided above, the silicon-based negative electrode material includes elemental silicon particles, porous silicon, nano-silicon, SiO and disproportionated SiO. The mass fraction of TiO 2 after coating is about 2-50%, and the preferred range is 5-20%.

原理是在硅基材料表面包覆一层二氧化钛，然后在一定温度下热处理，利用硅的还原性将二氧化钛包覆层转变成高导电性的缺氧氧化钛包覆层，并且由于氧化钛包覆层和硅颗粒间的强力化学键，该包覆层非常牢固，在嵌脱锂循环中不会脱落，从而有效提高硅基负极材料的循环稳定性。The principle is to coat a layer of titanium dioxide on the surface of the silicon-based material, and then heat-treat it at a certain temperature to transform the titanium dioxide coating layer into a highly conductive oxygen-deficient titanium oxide coating layer by using the reducibility of silicon. The strong chemical bond between the layer and the silicon particles, the coating layer is very strong and will not fall off during the lithium intercalation and desorption cycle, thereby effectively improving the cycle stability of the silicon-based negative electrode material.

本发明的有益效果在于：由于Ti-O键和Si-O键的结合能都很高，因此，氧化钛包覆层牢牢地键合在硅颗粒表面，即使经历巨大的体积变化，也不会从硅颗粒表面脱落。且由于氧化钛是半导体，其电导率受缺陷调控，利用硅的还原性将二氧化钛转化成缺氧的氧化钛，可有效地提高氧化钛包覆层的导电性，最终提高硅基负极材料的导电性。The beneficial effect of the present invention is: because the binding energy of Ti-O bond and Si-O bond is all very high, therefore, titanium oxide cladding layer is bonded firmly on the surface of silicon particle, even if undergoing huge volume change, it will not Will come off the surface of the silicon particles. And because titanium oxide is a semiconductor, its conductivity is regulated by defects. Using the reductivity of silicon to convert titanium dioxide into oxygen-deficient titanium oxide can effectively improve the conductivity of the titanium oxide coating layer, and ultimately improve the conductivity of the silicon-based negative electrode material. sex.

具体实施方式Detailed ways

实施例一Embodiment one

1、制作二氧化钛包覆层：将单质硅粉末（平均粒径1微米）放在旋转蒸发仪的玻璃管中，用氩气做载气将TiCl4蒸汽带入玻璃管中，同时通入湿空气 （湿度在10%-60%之间，气流速率在50-200 mL/min），玻璃管保持旋转，通气5小时后关闭，取出样品。1. Make the titanium dioxide coating layer: put the elemental silicon powder (average particle size 1 micron) in the glass tube of the rotary evaporator, use argon as the carrier gas to bring the TiCl 4 vapor into the glass tube, and at the same time, pass in the humid air (The humidity is between 10%-60%, the airflow rate is 50-200 mL/min), the glass tube keeps rotating, and it is closed after 5 hours of ventilation, and the sample is taken out.

2、热处理：将上述样品转入惰性气氛保护的炉子中，10℃每分钟升温到200℃保温12小时，取出得成品。2. Heat treatment: transfer the above sample into a furnace protected by an inert atmosphere, raise the temperature from 10°C per minute to 200°C for 12 hours, and take out the finished product.

3、电化学性能测试：将上述硅基负极材料、乙炔黑与LA133粘结剂按照80:10:10的复合制成均匀的浆料，涂覆到铜箔上，干燥，冲片，组装成扣式电池，其中对电极为金属锂片，电解液为通用锂离子电池电解液，充放电测试的电流为300 mA/g，测得其首次嵌锂容量为3127mAh/g，首次效率为57%，循环100次后比容量为359mAh/g；作为对比，原始单质硅粉料首次嵌锂容量为2433mAh/g，首次效率为34%，循环100次后比容量为132mAh/g。3. Electrochemical performance test: The above-mentioned silicon-based negative electrode material, acetylene black and LA133 binder were compounded according to the ratio of 80:10:10 to make a uniform slurry, coated on the copper foil, dried, punched, and assembled into a Button battery, in which the counter electrode is a metal lithium sheet, and the electrolyte is a general-purpose lithium-ion battery electrolyte. The current of the charge and discharge test is 300 mA/g. The measured lithium insertion capacity for the first time is 3127mAh/g, and the first-time efficiency is 57%. , the specific capacity after 100 cycles is 359mAh/g; as a comparison, the initial lithium intercalation capacity of the original elemental silicon powder is 2433mAh/g, the first efficiency is 34%, and the specific capacity after 100 cycles is 132mAh/g.

实施例二Embodiment two

1、制作二氧化钛包覆层：将多孔硅粉末（平均粒径3微米，比表面积120 m2/g）放在旋转蒸发仪的玻璃管中，用氩气做载气将TiCl4蒸汽带入玻璃管中，同时通入湿空气，玻璃管保持旋转，通气6小时后关闭，取出样品。1. To make a titanium dioxide coating: put porous silicon powder (average particle size 3 microns, specific surface area 120 m 2 /g) in a glass tube of a rotary evaporator, use argon as a carrier gas to bring TiCl 4 vapor into the glass At the same time, moist air was passed into the tube, the glass tube was kept rotating, and after 6 hours of ventilation, it was closed, and the sample was taken out.

2、热处理：将上述样品转入惰性气氛保护的炉子中，10℃每分钟升温到500℃保温2小时，取出得成品。2. Heat treatment: transfer the above sample into a furnace protected by an inert atmosphere, raise the temperature from 10°C per minute to 500°C and keep it warm for 2 hours, and take out the finished product.

3、电化学性能测试：将上述硅基负极材料、乙炔黑与LA133粘结剂按照80:10:10的复合制成均匀的浆料，涂覆到铜箔上，干燥，冲片，组装成扣式电池，其中对电极为金属锂片，电解液为通用锂离子电池电解液，充放电测试的电流为300mA/g，测得其首次嵌锂容量为3347mAh/g，首次效率为77%，循环100次后比容量为1564mAh/g；作为对比，原始多孔硅粉料首次嵌锂容量为1974mAh/g，首次效率为64%，循环100次后比容量为1042mAh/g。3. Electrochemical performance test: The above-mentioned silicon-based negative electrode material, acetylene black and LA133 binder were compounded according to the ratio of 80:10:10 to make a uniform slurry, coated on the copper foil, dried, punched, and assembled into a Button battery, in which the counter electrode is a metal lithium sheet, the electrolyte is a general-purpose lithium-ion battery electrolyte, the current of the charge and discharge test is 300mA/g, and the measured lithium intercalation capacity for the first time is 3347mAh/g, and the first-time efficiency is 77%. The specific capacity after 100 cycles is 1564mAh/g; as a comparison, the initial lithium intercalation capacity of the original porous silicon powder is 1974mAh/g, the first efficiency is 64%, and the specific capacity after 100 cycles is 1042mAh/g.

实施例三Embodiment three

1、制作二氧化钛包覆层：将纳米硅粉末（平均粒径100nm）放在旋转蒸发仪的玻璃管中，用氩气做载气将TiCl4蒸汽带入玻璃管中，同时通入湿空气，玻璃管保持旋转，通气12小时后关闭，取出样品。1. To make the titanium dioxide coating layer: put the nano-silicon powder (average particle size 100nm) in the glass tube of the rotary evaporator, use argon as the carrier gas to bring the TiCl 4 vapor into the glass tube, and at the same time, pass in the humid air. The glass tube kept rotating, closed after 12 hours of ventilation, and the sample was taken out.

2、热处理：将上述样品转入惰性气氛保护的炉子中，10℃每分钟升温到300℃保温4小时，取出得成品。2. Heat treatment: transfer the above sample into a furnace protected by an inert atmosphere, raise the temperature from 10°C per minute to 300°C for 4 hours, and take out the finished product.

3、电化学性能测试：将上述硅基负极材料、乙炔黑与LA133粘结剂按照80:10:10的复合制成均匀的浆料，涂覆到铜箔上，干燥，冲片，组装成扣式电池，其中对电极为金属锂片，电解液为通用锂离子电池电解液，充放电测试的电流为300 mA/g，测得其首次嵌锂容量为3521mAh/g，首次效率为71%，循环100次后比容量为1232mAh/g；作为对比，原始纳米硅粉料首次嵌锂容量为3274mAh/g，首次效率为65%，循环100次后比容量为646mAh/g。3. Electrochemical performance test: The above-mentioned silicon-based negative electrode material, acetylene black and LA133 binder were compounded according to the ratio of 80:10:10 to make a uniform slurry, coated on the copper foil, dried, punched, and assembled into a Button battery, in which the counter electrode is a metal lithium sheet, and the electrolyte is a general-purpose lithium-ion battery electrolyte. The current of the charge and discharge test is 300 mA/g. The measured lithium intercalation capacity for the first time is 3521mAh/g, and the first-time efficiency is 71%. , the specific capacity after 100 cycles is 1232mAh/g; as a comparison, the original nano-silicon powder has a lithium intercalation capacity of 3274mAh/g for the first time, an initial efficiency of 65%, and a specific capacity of 646mAh/g after 100 cycles.

实施例四Embodiment Four

1、制作二氧化钛包覆层：将SiO粉末（平均粒径5微米）放在旋转蒸发仪的玻璃管中，用氩气做载气将TiCl4蒸汽带入玻璃管中，同时通入湿空气，玻璃管保持旋转，通气2小时后关闭，取出样品。1. To make a titanium dioxide coating: put SiO powder (average particle size 5 microns) in a glass tube of a rotary evaporator, use argon as a carrier gas to bring TiCl 4 vapor into the glass tube, and at the same time pass in humid air, The glass tube kept rotating, closed after 2 hours of ventilation, and the sample was taken out.

2、热处理：将上述样品转入惰性气氛保护的炉子中，10℃每分钟升温到900℃保温0.5小时，取出得成品。2. Heat treatment: transfer the above sample into a furnace protected by an inert atmosphere, raise the temperature from 10°C to 900°C per minute and keep it warm for 0.5 hours, and take out the finished product.

3、电化学性能测试：将上述硅基负极材料、乙炔黑与LA133粘结剂按照80:10:10的复合制成均匀的浆料，涂覆到铜箔上，干燥，冲片，组装成扣式电池，其中对电极为金属锂片，电解液为通用锂离子电池电解液，充放电测试的电流为300 mA/g，测得其首次嵌锂容量为1812mAh/g，首次效率为63%，循环100次后比容量为456mAh/g；作为对比，原始SiO料末首次嵌锂容量为1367mAh/g，首次效率为57%，循环100次后比容量为235mAh/g。3. Electrochemical performance test: The above-mentioned silicon-based negative electrode material, acetylene black and LA133 binder were compounded according to the ratio of 80:10:10 to make a uniform slurry, coated on the copper foil, dried, punched, and assembled into a Button battery, in which the counter electrode is a metal lithium sheet, and the electrolyte is a general-purpose lithium-ion battery electrolyte. The current of the charge and discharge test is 300 mA/g. The measured lithium intercalation capacity for the first time is 1812mAh/g, and the first-time efficiency is 63%. , the specific capacity after 100 cycles is 456mAh/g; as a comparison, the initial lithium intercalation capacity of the original SiO powder is 1367mAh/g, the first efficiency is 57%, and the specific capacity after 100 cycles is 235mAh/g.

实施例五Embodiment five

1、制作二氧化钛包覆层：将歧化后的SiO粉末（平均粒径2微米）放在旋转蒸发仪的玻璃管中，用氩气做载气将TiCl4蒸汽带入玻璃管中，同时通入湿空气，玻璃管保持旋转，通气3小时后关闭，取出样品。1. Make the titanium dioxide coating layer: put the disproportionated SiO powder (average particle size 2 microns) in the glass tube of the rotary evaporator, use argon as the carrier gas to bring the TiCl4 vapor into the glass tube, and at the same time pass it into the wet Air, the glass tube kept rotating, closed after 3 hours of ventilation, and the sample was taken out.

2、热处理：将上述样品转入惰性气氛保护的炉子中，10℃每分钟升温到500℃保温4小时，取出得成品。2. Heat treatment: transfer the above sample into a furnace protected by an inert atmosphere, raise the temperature from 10°C per minute to 500°C for 4 hours, and take out the finished product.

3、电化学性能测试：将上述硅基负极材料、乙炔黑与LA133粘结剂按照80:10:10的复合制成均匀的浆料，涂覆到铜箔上，干燥，冲片，组装成扣式电池，其中对电极为金属锂片，电解液为通用锂离子电池电解液，充放电测试的电流为300mA/g，测得其首次嵌锂容量为1541mAh/g，首次效率为75%，循环100次后比容量为923mAh/g；作为对比，原始歧化SiO粉料首次嵌锂容量为1348mAh/g，首次效率为62%，循环100次后比容量为595mAh/g。3. Electrochemical performance test: The above-mentioned silicon-based negative electrode material, acetylene black and LA133 binder were compounded according to the ratio of 80:10:10 to make a uniform slurry, coated on the copper foil, dried, punched, and assembled into a Button battery, in which the counter electrode is a metal lithium sheet, the electrolyte is a general-purpose lithium-ion battery electrolyte, the current of the charge and discharge test is 300mA/g, the measured lithium intercalation capacity for the first time is 1541mAh/g, and the first-time efficiency is 75%. The specific capacity after 100 cycles is 923mAh/g; as a comparison, the initial lithium intercalation capacity of the original disproportionated SiO powder is 1348mAh/g, the first efficiency is 62%, and the specific capacity after 100 cycles is 595mAh/g.

实施例六Embodiment six

1、制作二氧化钛包覆层：在烧杯将纳米硅粉末（平均粒径100nm）分散在正己烷中，滴入TiCl4，搅拌一天后关闭，取出样品，由于TiCl4几乎全部水解，因此可以控制纳米硅和TiCl4的加入量来控制二氧化钛含量 ，其中TiCl4的所加质量比范围在4.6%-70%，本例中TiCl4加入量为46%，所制备得到的二氧化钛含量为20%。1. Make titanium dioxide coating layer: disperse nano-silicon powder (average particle size 100nm) in n-hexane in a beaker, drop TiCl4, stir for one day and then close it, take out the sample, since TiCl4 is almost completely hydrolyzed, it can control the nano-silicon and The content of titanium dioxide is controlled by the addition of TiCl4 , wherein the mass ratio of TiCl4 is in the range of 4.6%-70%. In this example, the addition of TiCl4 is 46%, and the prepared titanium dioxide content is 20%.

2、热处理：将上述样品转入惰性气氛保护的炉子中，10℃每分钟升温到600℃保温4小时，取出得成品。2. Heat treatment: transfer the above sample into a furnace protected by an inert atmosphere, raise the temperature from 10°C per minute to 600°C for 4 hours, and take out the finished product.

3、电化学性能测试：将上述硅基负极材料、乙炔黑与LA133粘结剂按照80:10:10的复合制成均匀的浆料，涂覆到铜箔上，干燥，冲片，组装成扣式电池，其中对电极为金属锂片，电解液为通用锂离子电池电解液，充放电测试的电流为300mA/g，测得其首次嵌锂容量为2640mAh/g，首次效率为78%，循环100次后比容量为1232mAh/g；作为对比，原始纳米硅粉料首次嵌锂容量为3274mAh/g，首次效率为65%，循环100次后比容量为646mAh/g。3. Electrochemical performance test: The above-mentioned silicon-based negative electrode material, acetylene black and LA133 binder were compounded according to the ratio of 80:10:10 to make a uniform slurry, coated on the copper foil, dried, punched, and assembled into a Button battery, in which the counter electrode is a metal lithium sheet, and the electrolyte is a general-purpose lithium-ion battery electrolyte. The current of the charge and discharge test is 300mA/g. The measured lithium intercalation capacity for the first time is 2640mAh/g, and the first-time efficiency is 78%. The specific capacity after 100 cycles is 1232mAh/g; as a comparison, the original nano-silicon powder has a lithium intercalation capacity of 3274mAh/g for the first time, an initial efficiency of 65%, and a specific capacity of 646mAh/g after 100 cycles.

实施例七Embodiment seven

1、制作二氧化钛包覆层：在烧杯将歧化后的SiO粉末（平均粒径2微米）分散水中，滴入氟钛酸铵，搅拌一天后关闭，取出样品，由于氟钛酸铵几乎全部水解，因此可以控制纳米硅和氟钛酸铵的加入量来控制二氧化钛含量 ，本例中二氧化钛含量为5%。1. Make the titanium dioxide coating layer: disperse the disproportionated SiO powder (average particle size 2 microns) in water in a beaker, drop in ammonium fluorotitanate, stir for one day and then close it, take out the sample, because the ammonium fluorotitanate is almost completely hydrolyzed, Therefore, the addition amount of nanometer silicon and ammonium fluorotitanate can be controlled to control the content of titanium dioxide. In this example, the content of titanium dioxide is 5%.

2、热处理：将上述样品转入惰性气氛保护的炉子中，10℃每分钟升温到450℃保温4小时，取出得成品。2. Heat treatment: transfer the above sample into a furnace protected by an inert atmosphere, raise the temperature from 10°C per minute to 450°C for 4 hours, and take out the finished product.

3、电化学性能测试：将上述硅基负极材料、乙炔黑与LA133粘结剂按照80:10:10的复合制成均匀的浆料，涂覆到铜箔上，干燥，冲片，组装成扣式电池，其中对电极为金属锂片，电解液为通用锂离子电池电解液，充放电测试的电流为300mA/g，测得其首次嵌锂容量为1655mAh/g，首次效率为76%，循环100次后比容量为821mAh/g；作为对比，原始歧化SiO粉料首次嵌锂容量为1348mAh/g，首次效率为62%，循环100次后比容量为595mAh/g。3. Electrochemical performance test: The above-mentioned silicon-based negative electrode material, acetylene black and LA133 binder were compounded according to the ratio of 80:10:10 to make a uniform slurry, coated on the copper foil, dried, punched, and assembled into a Button battery, in which the counter electrode is a metal lithium sheet, and the electrolyte is a general-purpose lithium-ion battery electrolyte. The current of the charge and discharge test is 300mA/g. The measured lithium intercalation capacity for the first time is 1655mAh/g, and the first-time efficiency is 76%. The specific capacity after 100 cycles is 821mAh/g; as a comparison, the initial lithium intercalation capacity of the original disproportionated SiO powder is 1348mAh/g, the first efficiency is 62%, and the specific capacity after 100 cycles is 595mAh/g.

实施例八Embodiment Eight

1、制作二氧化钛包覆层：在烧杯将SiO粉末（平均粒径5微米）分散在乙醇中，滴入钛酸四丁酯，搅拌一天后关闭，取出样品，由于钛酸四丁酯几乎全部水解，因此可以控制纳米硅和钛酸四丁酯的加入量来控制二氧化钛含量，本例中二氧化钛含量为2%。1. Make the titanium dioxide coating layer: disperse SiO powder (average particle size 5 microns) in ethanol in a beaker, drop tetrabutyl titanate into it, stir for one day and then close it, take out the sample, because tetrabutyl titanate is almost completely hydrolyzed , so the addition of nano-silicon and tetrabutyl titanate can be controlled to control the content of titanium dioxide. In this example, the content of titanium dioxide is 2%.

2、热处理：将上述样品转入惰性气氛保护的炉子中，10℃每分钟升温到450℃保温4小时，取出得成品。2. Heat treatment: transfer the above sample into a furnace protected by an inert atmosphere, raise the temperature from 10°C per minute to 450°C for 4 hours, and take out the finished product.

3、电化学性能测试：将上述硅基负极材料、乙炔黑与LA133粘结剂按照80:10:10的复合制成均匀的浆料，涂覆到铜箔上，干燥，冲片，组装成扣式电池，其中对电极为金属锂片，电解液为通用锂离子电池电解液，充放电测试的电流为300 mA/g，测得其首次嵌锂容量为1912mAh/g，首次效率为66%，循环100次后比容量为657mAh/g；作为对比，原始SiO料末首次嵌锂容量为1367mAh/g，首次效率为57%，循环100次后比容量为235mAh/g。3. Electrochemical performance test: The above-mentioned silicon-based negative electrode material, acetylene black and LA133 binder were compounded according to the ratio of 80:10:10 to make a uniform slurry, coated on the copper foil, dried, punched, and assembled into a Button battery, in which the counter electrode is a metal lithium sheet, and the electrolyte is a general-purpose lithium-ion battery electrolyte. The current of the charge and discharge test is 300 mA/g. The measured lithium intercalation capacity for the first time is 1912mAh/g, and the first-time efficiency is 66%. , the specific capacity after 100 cycles is 657mAh/g; as a comparison, the initial lithium intercalation capacity of the original SiO powder is 1367mAh/g, the first efficiency is 57%, and the specific capacity after 100 cycles is 235mAh/g.

实施例九Embodiment nine

1、制作二氧化钛包覆层：在烧杯将多孔硅粉末（平均粒径3微米，比表面积120 m2/g）分散在乙醇中，滴入钛酸四丁酯，搅拌一天后关闭，取出样品，由于钛酸四丁酯几乎全部水解，因此可以控制纳米硅和钛酸四丁酯的加入量来控制二氧化钛含量，本例中二氧化钛含量为50%。1. To make the titanium dioxide coating layer: disperse porous silicon powder (average particle size: 3 microns, specific surface area: 120 m2/g) in ethanol in a beaker, drop tetrabutyl titanate into it, and close it after stirring for one day, take out the sample, because Tetrabutyl titanate is almost completely hydrolyzed, so the addition of nano-silicon and tetrabutyl titanate can be controlled to control the content of titanium dioxide. In this example, the content of titanium dioxide is 50%.

2、热处理：将上述样品转入惰性气氛保护的炉子中，10℃每分钟升温到450℃保温4小时，取出得成品。2. Heat treatment: transfer the above sample into a furnace protected by an inert atmosphere, raise the temperature from 10°C per minute to 450°C for 4 hours, and take out the finished product.

3、电化学性能测试：将上述硅基负极材料、乙炔黑与LA133粘结剂按照80:10:10的复合制成均匀的浆料，涂覆到铜箔上，干燥，冲片，组装成扣式电池，其中对电极为金属锂片，电解液为通用锂离子电池电解液，充放电测试的电流为300mA/g，测得其首次嵌锂容量为1569mAh/g，首次效率为69%，循环100次后比容量为1023mAh/g；作为对比，原始多孔硅粉料首次嵌锂容量为1974mAh/g，首次效率为64%，循环100次后比容量为1042mAh/g。3. Electrochemical performance test: The above-mentioned silicon-based negative electrode material, acetylene black and LA133 binder were compounded according to the ratio of 80:10:10 to make a uniform slurry, coated on the copper foil, dried, punched, and assembled into a Button battery, in which the counter electrode is a metal lithium sheet, and the electrolyte is a general-purpose lithium-ion battery electrolyte. The current of the charge and discharge test is 300mA/g. The measured lithium intercalation capacity for the first time is 1569mAh/g, and the first-time efficiency is 69%. The specific capacity after 100 cycles is 1023mAh/g; as a comparison, the initial lithium intercalation capacity of the original porous silicon powder is 1974mAh/g, the first efficiency is 64%, and the specific capacity after 100 cycles is 1042mAh/g.

Claims (8)

1.一种改善硅基负极材料导电性的方法，其特征在于，所述的方法为：采用气相包覆法或液相包覆法在硅基负极材料上包覆氧化钛，包覆的氧化钛所占质量分数约为2~50%。1. A method for improving the electrical conductivity of a silicon-based negative electrode material, characterized in that, the method is: adopting a vapor phase coating method or a liquid phase coating method to coat titanium oxide on a silicon-based negative electrode material, and the coated oxide The mass fraction of titanium is about 2-50%. 2.如权利要求1所述的改善硅基负极材料导电性的方法，其特征在于，所述的气相包覆法包括如下的步骤：将所述的硅基负极材料置于四氯化钛的气氛中，同时通入湿空气进行包覆，包覆完成后在惰性气氛保护下均匀升温，在200~900℃下保温0.5~12小时。2. The method for improving the electrical conductivity of silicon-based negative electrode materials as claimed in claim 1, characterized in that, said gas-phase coating method comprises the steps of: placing said silicon-based negative electrode materials in titanium tetrachloride In the atmosphere, humid air is introduced at the same time for coating. After the coating is completed, the temperature is evenly raised under the protection of an inert atmosphere, and the temperature is kept at 200-900 ° C for 0.5-12 hours. 3.如权利要求2所述的改善硅基负极材料导电性的方法，其特征在于，所通入湿空气的湿度范围为10%-60%,气流速率在50-200 mL/min之间，包覆完成后处理方法是在300~600℃保温1-4小时。3. the method for improving the conductivity of silicon-based negative electrode materials as claimed in claim 2, is characterized in that, the humidity scope of passing into moist air is 10%-60%, and air velocity is between 50-200 mL/min, After the coating is completed, the treatment method is to keep the temperature at 300~600°C for 1-4 hours. 4.如权利要求1所述的改善硅基负极材料导电性的方法，其特征在于，所述的液相包覆法包括如下的步骤：将硅基负极材料分散在溶剂中，再加入钛源，搅拌使其水解，水解完成后过滤干燥，得到的产物在惰性气氛保护下均匀升温，于200~900℃保温0.5~12小时。4. The method for improving the conductivity of silicon-based negative electrode materials as claimed in claim 1, wherein the liquid-phase coating method comprises the steps of: dispersing silicon-based negative electrode materials in a solvent, and then adding titanium source , stir to make it hydrolyze, filter and dry after the hydrolysis is completed, the obtained product is evenly heated under the protection of an inert atmosphere, and kept at 200~900°C for 0.5~12 hours. 5.如权利要求4所述的改善硅基负极材料导电性的方法，其特征在于，所述的，得到的产物在惰性气氛保护下均匀升温，于300~600℃下保温1-4小时。5. The method for improving the conductivity of a silicon-based negative electrode material as claimed in claim 4, characterized in that, the obtained product is evenly heated under the protection of an inert atmosphere, and kept at 300-600° C. for 1-4 hours. 6.如权利要求4所述的改善硅基负极材料导电性的方法，其特征在于，所述的钛源为易水解的钛盐。6. The method for improving the conductivity of silicon-based negative electrode materials according to claim 4, wherein the titanium source is an easily hydrolyzed titanium salt. 7.如权利要求5所述的改善硅基负极材料导电性的方法，其特征在于，所述的钛盐为TiCl4、钛酸四丁酯和/或者氟钛酸铵。7 . The method for improving the conductivity of silicon-based negative electrode materials according to claim 5 , wherein the titanium salt is TiCl 4 , tetrabutyl titanate and/or ammonium fluorotitanate. 8.如权利要求1-7任一权利要求所述的改善硅基负极材料导电性的方法，其特征在于，所述的硅基负极材料包括有单质硅、多孔硅、纳米硅、SiO和歧化后的SiO。8. The method for improving the conductivity of silicon-based negative electrode materials according to any one of claims 1-7, wherein said silicon-based negative electrode materials include simple silicon, porous silicon, nano-silicon, SiO and disproportionated After SiO.
CN201810678006.2A 2018-06-27 2018-06-27 A method of improving silicon based anode material electric conductivity Pending CN108878831A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810678006.2A CN108878831A (en) 2018-06-27 2018-06-27 A method of improving silicon based anode material electric conductivity

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810678006.2A CN108878831A (en) 2018-06-27 2018-06-27 A method of improving silicon based anode material electric conductivity

Publications (1)

Publication Number Publication Date
CN108878831A true CN108878831A (en) 2018-11-23

Family

ID=64294965

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810678006.2A Pending CN108878831A (en) 2018-06-27 2018-06-27 A method of improving silicon based anode material electric conductivity

Country Status (1)

Country Link
CN (1) CN108878831A (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109817949A (en) * 2019-03-11 2019-05-28 清华大学 Silicon or its oxide@titania@carbon core-shell composite particles and their preparation
CN111326714A (en) * 2018-12-13 2020-06-23 宝山钢铁股份有限公司 Method for manufacturing composite electrode used as high-specific-capacity negative electrode
CN112108137A (en) * 2020-10-19 2020-12-22 中国科学院兰州化学物理研究所 Method for uniformly preparing attapulgite-titanium dioxide composite material
CN112226264A (en) * 2020-10-19 2021-01-15 中国科学院兰州化学物理研究所 Attapulgite-titanium dioxide modified ultra-high molecular weight polyethylene composite material and preparation method and application thereof
CN113036137A (en) * 2021-03-05 2021-06-25 昆山宝创新能源科技有限公司 Lithium ion battery cathode material and preparation method and application thereof
CN113299868A (en) * 2021-03-02 2021-08-24 南京理工大学 Vanadium oxide surface modification method based on humidity regulation and control anaerobic heat treatment technology
CN113471442A (en) * 2019-01-02 2021-10-01 宁德新能源科技有限公司 Negative active material, and negative electrode sheet, electrochemical device, and electronic device using same
CN113728467A (en) * 2020-12-28 2021-11-30 宁德新能源科技有限公司 Negative electrode material, electrochemical device, and electronic device
CN114068901A (en) * 2021-11-15 2022-02-18 陕西煤业化工技术研究院有限责任公司 Silicon-carbon composite negative electrode material, preparation method and application
CN116779769A (en) * 2022-03-10 2023-09-19 比亚迪股份有限公司 Composite negative electrode material, preparation method thereof, negative electrode plate and battery
CN117239105A (en) * 2023-11-14 2023-12-15 比亚迪股份有限公司 Silicon anode material and preparation method thereof, anode piece, battery and electric equipment

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106099062A (en) * 2016-07-21 2016-11-09 中国科学院山西煤炭化学研究所 Double-coated silicon-based composite material Si@C@TiO2 and its preparation method
CN107623104A (en) * 2017-09-25 2018-01-23 常州市宇科不绣钢有限公司 A kind of structure silicon-based negative material of multi-buffer and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106099062A (en) * 2016-07-21 2016-11-09 中国科学院山西煤炭化学研究所 Double-coated silicon-based composite material Si@C@TiO2 and its preparation method
CN107623104A (en) * 2017-09-25 2018-01-23 常州市宇科不绣钢有限公司 A kind of structure silicon-based negative material of multi-buffer and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Y. WANG等: ""Amorphous TiO2 Shells: A Vital Elastic Buffering Layer on Silicon Nanoparticles for High- Performance and Safe Lithium Storage"", 《ADVANCED MATERIALS》 *
YING BAI等: ""Core-shell Si@TiO2 nanosphere anode by atomic layer deposition for Li-ion batteries"", 《JOURNAL OF POWER SOURCES 》 *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111326714A (en) * 2018-12-13 2020-06-23 宝山钢铁股份有限公司 Method for manufacturing composite electrode used as high-specific-capacity negative electrode
CN113471442B (en) * 2019-01-02 2022-08-02 宁德新能源科技有限公司 Negative active material, and negative electrode sheet, electrochemical device, and electronic device using same
CN113471442A (en) * 2019-01-02 2021-10-01 宁德新能源科技有限公司 Negative active material, and negative electrode sheet, electrochemical device, and electronic device using same
CN109817949B (en) * 2019-03-11 2021-05-14 清华大学 Silicon or oxide @ titanium dioxide @ carbon core-shell structure composite particle thereof and preparation
CN109817949A (en) * 2019-03-11 2019-05-28 清华大学 Silicon or its oxide@titania@carbon core-shell composite particles and their preparation
CN112226264A (en) * 2020-10-19 2021-01-15 中国科学院兰州化学物理研究所 Attapulgite-titanium dioxide modified ultra-high molecular weight polyethylene composite material and preparation method and application thereof
CN112226264B (en) * 2020-10-19 2021-07-23 中国科学院兰州化学物理研究所 A kind of attapulgite-titanium dioxide modified ultra-high molecular weight polyethylene composite material and its preparation method and application
CN112108137A (en) * 2020-10-19 2020-12-22 中国科学院兰州化学物理研究所 Method for uniformly preparing attapulgite-titanium dioxide composite material
WO2022140962A1 (en) * 2020-12-28 2022-07-07 宁德新能源科技有限公司 Negative electrode material, electrochemical device, and electronic apparatus
CN113728467A (en) * 2020-12-28 2021-11-30 宁德新能源科技有限公司 Negative electrode material, electrochemical device, and electronic device
CN113299868A (en) * 2021-03-02 2021-08-24 南京理工大学 Vanadium oxide surface modification method based on humidity regulation and control anaerobic heat treatment technology
CN113036137A (en) * 2021-03-05 2021-06-25 昆山宝创新能源科技有限公司 Lithium ion battery cathode material and preparation method and application thereof
CN114068901A (en) * 2021-11-15 2022-02-18 陕西煤业化工技术研究院有限责任公司 Silicon-carbon composite negative electrode material, preparation method and application
CN116779769A (en) * 2022-03-10 2023-09-19 比亚迪股份有限公司 Composite negative electrode material, preparation method thereof, negative electrode plate and battery
CN116779769B (en) * 2022-03-10 2024-11-15 比亚迪股份有限公司 Composite negative electrode material, preparation method thereof, negative electrode plate and battery
CN117239105A (en) * 2023-11-14 2023-12-15 比亚迪股份有限公司 Silicon anode material and preparation method thereof, anode piece, battery and electric equipment
CN117239105B (en) * 2023-11-14 2024-02-27 比亚迪股份有限公司 Silicon anode material and preparation method thereof, anode piece, battery and electric equipment

Similar Documents

Publication Publication Date Title
CN108878831A (en) A method of improving silicon based anode material electric conductivity
CN103730645B (en) Coated carbon fiber nanometer composite material of a kind of silicon and its preparation method and application
CN106025221B (en) A kind of preparation method of silicon/carbon graphite composite negative pole material
CN102394305B (en) Foamy copper oxide/copper lithium ion battery anode and preparation method thereof
CN110212183A (en) Powder pre-lithiation silicon-based negative electrode material and preparation method and application thereof
CN105428611B (en) A kind of Porous hollow composite negative pole material and its preparation method and application
CN103367719A (en) Yolk-shell structure tin dioxide-nitrogen-doped carbon material and preparation method thereof
CN102646810A (en) Preparation method of a three-dimensional porous graphene doped and coated lithium titanate composite negative electrode material
CN108899550B (en) Composite coated positive electrode active material, preparation method thereof, lithium ion battery positive electrode material and solid-state lithium ion battery
CN107742702A (en) Three-dimensional "face-line-face" structure of carbon nanotubes and tin dioxide modified titanium carbide lithium ion battery negative electrode material and preparation method
CN104319366B (en) Silicon/graphite/lithium titanate composite anode material and preparation method thereof
CN112110448A (en) A kind of nitrogen-doped carbon and nano-silicon composite negative electrode material and preparation method thereof
CN105355892A (en) Preparation method of lithium ion battery cathode
CN110048114A (en) A kind of bivalve silicon carbon material and preparation method thereof
WO2023124025A1 (en) Graphite composite negative electrode material, preparation method therefor and application thereof
CN103378355B (en) Alkali metal secondary battery and the preparation method of negative electrode active material, negative material, negative pole and negative electrode active material
CN110048099A (en) Electrode material of sodium-ion battery and its preparation method and application
CN112928246B (en) Composite material, preparation method and application thereof
WO2021102847A1 (en) Negative electrode material, electrochemical device comprising same, and electronic device
CN107706383A (en) In-situ titanium-doped carbon-coated silicon oxide/graphite material and preparation method thereof
CN112125304B (en) Metal oxide modified micro-nano silicon-graphite composite negative electrode material and preparation method thereof
CN103956497B (en) Class Graphene doped lithium ion battery ferric metasilicate lithium composite positive pole preparation method
CN117352685A (en) Silicon-carbon composite materials and preparation methods thereof, negative electrode materials, lithium-ion batteries
CN107195897B (en) Nano FeNbO4Graphene composite material and preparation and application thereof
CN108428879A (en) A kind of preparation method and application of New Type of Carbon silicon based composite material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20181123

RJ01 Rejection of invention patent application after publication