WO2017024896A1 - Preparation method for metal-doped composite lithium titanate negative electrode material - Google Patents

Preparation method for metal-doped composite lithium titanate negative electrode material Download PDF

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WO2017024896A1
WO2017024896A1 PCT/CN2016/086700 CN2016086700W WO2017024896A1 WO 2017024896 A1 WO2017024896 A1 WO 2017024896A1 CN 2016086700 W CN2016086700 W CN 2016086700W WO 2017024896 A1 WO2017024896 A1 WO 2017024896A1
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negative electrode
lithium titanate
electrode material
titanate negative
doped composite
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田东
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田东
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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
    • 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
    • H01M4/364—Composites as mixtures
    • 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
    • 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
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 a preparation method of a lithium ion battery anode material, in particular to a preparation method of a metal tin doped composite lithium titanate anode material.
  • Lithium-ion batteries which have been widely used in electronic products such as mobile phones and notebook computers, have large specific energy, high specific power, low self-discharge, good cycle characteristics, fast charging and high efficiency, wide operating temperature range, and no environmental pollution.
  • the lithium-ion batteries currently used in the market basically use carbon materials as the negative electrode, but the carbon material is the negative electrode in the practical application, there are some insurmountable weaknesses, for example, reacting with the electrolyte during the first discharge to form a surface.
  • the passivation film causes the electrolyte to be consumed and the first coulombic efficiency is low; the potential of the carbon electrode is very close to the potential of the metal lithium.
  • lithium titanate Compared with carbon negative electrode materials, lithium titanate has many advantages. Among them, the deintercalation of lithium ions in lithium titanate is reversible, and the crystal form of lithium ion in the process of inserting or extracting lithium titanate is not Changed, volume change is less than 1%, so it is called "zero strain material", which can avoid the structure damage caused by the back and forth expansion of the electrode material in the charge and discharge cycle, thereby improving the cycle performance and service life of the electrode, reducing the The number of cycles increases and the specific capacity is greatly attenuated, which has better cycle performance than the carbon negative electrode; however, since lithium titanate is an insulating material, its electrical conductivity is low, resulting in the rate performance in the application of lithium battery. The problem is poor.
  • the theoretical specific capacity of lithium titanate material is 175mAh/g
  • the actual specific capacity is more than 160mAh/g
  • it has the disadvantages of low gram capacity. Therefore, it is necessary to modify lithium titanate.
  • Metal tin has the advantages of high lithium storage capacity (994 mAh/g) and low lithium ion deintercalation platform voltage, and is a non-carbon negative electrode material with great development potential. In recent years, extensive research has been carried out on such materials and some progress has been made. However, in the process of reversible lithium storage, the volume expansion of metallic tin is remarkable, resulting in poor cycle performance and rapid decay of capacity, so it is difficult to meet the requirements of large-scale production.
  • the metal tin is stabilized by alloying or compounding, and the volume expansion of tin is slowed down.
  • Carbon can prevent direct contact between tin particles, inhibit the agglomeration and growth of tin particles, and act as a buffer layer.
  • the technical problem to be solved by the present invention is to provide a method for preparing a metal tin doped composite lithium titanate negative electrode material to solve the problems raised in the above background art.
  • a method for preparing a metal tin doped composite lithium titanate negative electrode material, the raw materials according to the proportion by weight, comprising the following process steps:
  • the precursor slurry prepared in the step (1) is subjected to atomization, drying and granulation, and then subjected to powder classification to obtain an average particle diameter of 5 to 15 ⁇ m.
  • the powder obtained in the step (2) is heated to a temperature of 800 to 1000 ° C at a rate of 1 to 5 ° C / min under the protection of an inert gas, and then kept for 1 to 5 hours, naturally cooled, and after cooling.
  • the composite lithium titanate negative electrode material of the present invention is obtained by pulverization and sieving.
  • the titanium oxide described in the step (1) is one of anatase type titanium dioxide or a gold stone type titanium dioxide.
  • the nano tin powder described in the step (1) has a particle diameter of not more than 100 nm.
  • the conductive agent in the step (1) is one or a mixture of one of acetylene black, Super-P, ketjen black, graphite conductive agent, carbon fiber, carbon nanotube, and graphene.
  • the inlet temperature of the spray-dried hot air described in the step (2) is from 150 ° C to 200 ° C, and the outlet temperature is from 40 ° C to 70 ° C.
  • the inert gas in the step (3) is one of nitrogen gas, argon gas and helium gas.
  • the invention adopts the nano tin powder, avoids the volume effect of the tin powder due to the large particle size, and ensures the stability of the material during the charging and discharging process, and simultaneously performs the composite treatment with the lithium titanate to solve the problem.
  • the short capacity of the single lithium titanate anode material is low; and by adding a conductive agent to the composite system, a conductive network is formed inside the material system to increase the electrical conductivity of the composite material.
  • the ratio of titanium dioxide: lithium carbonate: nano tin: conductive agent 100:38:3:10, weigh 1000g of dioxide, 380g of lithium carbonate, 30g of nano tin, 50g of acetylene black, according to the ratio of solid content of 30%, weigh 3406 g of ethanol solvent, stirring constantly, mixing into a uniform slurry; then spraying, drying, and classifying the slurry to obtain a powder having an average particle diameter of 10 ⁇ m, and then the powder is protected by an inert gas to 5
  • the temperature of °C/min is raised to 1000 °C, and then kept for 3 hours, and the temperature is naturally lowered. After cooling, the composite lithium titanate anode material is obtained by sieving.
  • the ratio of titanium dioxide: lithium carbonate: nano tin: conductive agent 100:40:3:10, weigh 1000g of dioxide, 400g of lithium carbonate, 30g of nano tin, 50g of Super-P, according to the ratio of solid content of 30%, weigh Take 3453g of ethanol solvent, stir constantly, mix into a uniform slurry; then spray, dry and classify the slurry to obtain a powder with an average particle size of 10 ⁇ m, and then the powder under the protection of inert gas, 3 The temperature of °C/min is raised to 900 °C, and then kept for 2 hours, and the temperature is naturally lowered. After cooling, the composite lithium titanate negative electrode material is obtained.
  • the ratio is weighed into 3500g of ethanol solvent, continuously stirred and mixed into a uniform slurry; then the slurry is sprayed, dried and classified to obtain a powder with an average particle diameter of 10 ⁇ m, and then the powder is protected by an inert gas.
  • the temperature is raised to 950 ° C at a rate of 4 ° C / min, and then kept for 3.5 h, and the temperature is naturally lowered. After cooling, the composite lithium titanate negative electrode material is obtained by sieving.
  • the ratio of titanium dioxide: lithium carbonate 100:40, weigh 1000g of dioxide, 400g of lithium carbonate, weigh 3366g of ethanol solvent according to the ratio of solid content of 30%, stir constantly, mix into a uniform slurry; The slurry is sprayed, dried, and classified to obtain a powder having an average particle diameter of 6 ⁇ m, and then the powder is in an inert state. Under the protection of the gas, the temperature is raised to 1000 ° C at a rate of 5 ° C / min, and then kept for 3 h, and the temperature is naturally lowered. After cooling, the lithium titanate negative electrode material is obtained by sieving.
  • the charge-discharge voltage is 1.0-2.5V, and the charge-discharge rate is 0.5C.
  • the battery performance can be tested. The test results are shown in Table 1.
  • Table 1 compares the performance of negative electrode materials in different examples and comparative examples.

Abstract

A preparation method for a metal-doped composite lithium titanate negative electrode material, with raw material being in parts by weight, comprising the following process steps: (1) preparation of a precursor slurry; (2) atomization, drying, granulation, and classification; and (3) heat treatment. The method, by selecting the tin nanopowder, prevents a volume effect produced by tin powder due to large particle size when charging/discharging, ensures the stability of the material in charging and discharging processes, at the same time, by means of composite treatment with lithium titanate, solves the shortcoming of low capacity of a solely lithium titanate negative electrode material, and then, by adding an electrically-conductive agent into a composite material system, allows an electrically-conductive network to be formed within the material system, thus increasing the electrical conductivity of the composite material.

Description

一种金属锡掺杂复合钛酸锂负极材料的制备方法Method for preparing metal tin doped composite lithium titanate anode material 技术领域Technical field
本发明涉及一种锂离子电池负极材料的制备方法，具体来说是一种金属锡掺杂复合钛酸锂负极材料的制备方法。The invention relates to a preparation method of a lithium ion battery anode material, in particular to a preparation method of a metal tin doped composite lithium titanate anode material.
背景技术Background technique
目前已广泛应用于移动电话、笔记本电脑等电子产品中的锂离子电池具有比能量大、比功率高、自放电小、循环特性好以及可快速充电且效率高、工作温度范围宽、无环境污染等优点，目前市场上所用锂离子电池，基本都是以碳材料为负极，但是碳材料为负极在实际应用中还有一些难以克服的弱点，例如，首次放电过程中与电解液发生反应形成表面钝化膜，导致电解液的消耗和首次库伦效率较低；碳电极的电位与金属锂的电位很接近，当电池过充电时，碳电极表面易析出金属锂，从而可能会引起短路，进而导致电池***。为了解决锂电池的安全问题，人们做了大量的研究。尖晶石Li4Ti5O12作为一种新型的锂离子二次电池负极材料，与其它商业化的材料相比，具有循环性能好、不与电解液反应、安全性能高、充放电平台平稳等优点，是近几年来备受关注的最优异的锂离子电池负极材料之一。Lithium-ion batteries, which have been widely used in electronic products such as mobile phones and notebook computers, have large specific energy, high specific power, low self-discharge, good cycle characteristics, fast charging and high efficiency, wide operating temperature range, and no environmental pollution. Advantages, the lithium-ion batteries currently used in the market basically use carbon materials as the negative electrode, but the carbon material is the negative electrode in the practical application, there are some insurmountable weaknesses, for example, reacting with the electrolyte during the first discharge to form a surface. The passivation film causes the electrolyte to be consumed and the first coulombic efficiency is low; the potential of the carbon electrode is very close to the potential of the metal lithium. When the battery is overcharged, the surface of the carbon electrode is liable to precipitate metallic lithium, which may cause a short circuit, thereby causing a short circuit. The battery exploded. In order to solve the safety problem of lithium batteries, a lot of research has been done. As a new type of lithium ion secondary battery anode material, spinel Li4Ti5O12 has the advantages of good cycle performance, no reaction with electrolyte, high safety performance, stable charge and discharge platform, etc., compared with other commercial materials. One of the most excellent lithium ion battery anode materials that has received much attention in recent years.
与碳负电极材料相比，钛酸锂有很多的优势，其中，锂离子在钛酸锂中的脱嵌是可逆的，而且锂离子在嵌入或脱出钛酸锂的过程中，其晶型不发生变化，体积变化小于1％，因此被称为“零应变材料”，能够避免充放电循环中由于电极材料的来回伸缩而导致结构的破坏，从而提高电极的循环性能和使用寿命，减少了随循环次数增加而带来比容量大幅度的衰减，具有比碳负极更优良的循环性能；但是，由于钛酸锂是一种绝缘材料，其电导率低，从而导致在锂电中的应用存在倍率性能较差的问题，同时钛酸锂材料理论比容量为175mAh/g，实际比容量大于160mAh/g，具有克容量较低等缺点，因此，对于钛酸锂进行改性是十分必要的。而金属锡具有高的储锂容量(994mAh/g)和低的锂离子脱嵌平台电压等优点，是一种极具发展潜力的非碳负极材料。近年来人们对这类材料开展了广泛的研究，并取得了一定的进展。但在可逆储锂过程中，金属锡体积膨胀显著，导致循环性能变差，容量迅速衰减，因此难以满足大规模生产的要求。为此，通过引入碳等非金属元素，以合金化或复合的方式来稳定金属锡，减缓锡的体积膨胀。碳能够阻止锡颗粒间的直接接触，抑制锡颗粒的团聚和长大，起到缓冲层的作用。Compared with carbon negative electrode materials, lithium titanate has many advantages. Among them, the deintercalation of lithium ions in lithium titanate is reversible, and the crystal form of lithium ion in the process of inserting or extracting lithium titanate is not Changed, volume change is less than 1%, so it is called "zero strain material", which can avoid the structure damage caused by the back and forth expansion of the electrode material in the charge and discharge cycle, thereby improving the cycle performance and service life of the electrode, reducing the The number of cycles increases and the specific capacity is greatly attenuated, which has better cycle performance than the carbon negative electrode; however, since lithium titanate is an insulating material, its electrical conductivity is low, resulting in the rate performance in the application of lithium battery. The problem is poor. At the same time, the theoretical specific capacity of lithium titanate material is 175mAh/g, the actual specific capacity is more than 160mAh/g, and it has the disadvantages of low gram capacity. Therefore, it is necessary to modify lithium titanate. Metal tin has the advantages of high lithium storage capacity (994 mAh/g) and low lithium ion deintercalation platform voltage, and is a non-carbon negative electrode material with great development potential. In recent years, extensive research has been carried out on such materials and some progress has been made. However, in the process of reversible lithium storage, the volume expansion of metallic tin is remarkable, resulting in poor cycle performance and rapid decay of capacity, so it is difficult to meet the requirements of large-scale production. For this reason, by introducing a non-metallic element such as carbon, the metal tin is stabilized by alloying or compounding, and the volume expansion of tin is slowed down. Carbon can prevent direct contact between tin particles, inhibit the agglomeration and growth of tin particles, and act as a buffer layer.
发明内容Summary of the invention
本发明所解决的技术问题在于提供一种金属锡掺杂复合钛酸锂负极材料的制备方法，以解决上述背景技术中提出的问题。The technical problem to be solved by the present invention is to provide a method for preparing a metal tin doped composite lithium titanate negative electrode material to solve the problems raised in the above background art.
为了达到上述目的，本发明采用以下技术方案来实现：In order to achieve the above object, the present invention is implemented by the following technical solutions:
一种金属锡掺杂复合钛酸锂负极材料的制备方法，原料按照重量份比例，包括以下工艺步骤：A method for preparing a metal tin doped composite lithium titanate negative electrode material, the raw materials according to the proportion by weight, comprising the following process steps:
(1)制备前驱体浆料：按照二氧化钛：碳酸锂：纳米锡：导电剂＝100:38～40:3～5:5～10的比例，称取各组分分散于有机溶剂乙醇中，调节固含量至20％～40％，然后不断搅拌，得到前驱体浆料；(1) Preparation of precursor slurry: According to the ratio of titanium dioxide: lithium carbonate: nano tin: conductive agent = 100: 38 to 40: 3 to 5: 5 to 10, each component is weighed and dispersed in an organic solvent ethanol, and adjusted. a solid content of 20% to 40%, and then continuously stirred to obtain a precursor slurry;
(2)雾化、干燥、造粒以及分级：将步骤(1)中制备的前驱体浆料通过雾化、干燥和造粒，再经过粉体分级得到平均粒径介于5～15μm之间的粉体； (2) atomization, drying, granulation and classification: the precursor slurry prepared in the step (1) is subjected to atomization, drying and granulation, and then subjected to powder classification to obtain an average particle diameter of 5 to 15 μm. Powder
(3)热处理：将步骤(2)中所得到的粉体在惰性气体的保护下，以1～5℃/min的速度升温至800～1000℃，再保温1～5h，自然降温，冷却后经过粉碎、筛分即得到本发明所述的复合钛酸锂负极材料。(3) Heat treatment: the powder obtained in the step (2) is heated to a temperature of 800 to 1000 ° C at a rate of 1 to 5 ° C / min under the protection of an inert gas, and then kept for 1 to 5 hours, naturally cooled, and after cooling. The composite lithium titanate negative electrode material of the present invention is obtained by pulverization and sieving.
进一步，步骤(1)中所述的二氧化钛为锐钛型二氧化钛或金石型二氧化钛中的一种。Further, the titanium oxide described in the step (1) is one of anatase type titanium dioxide or a gold stone type titanium dioxide.
进一步，步骤(1)中所述的纳米锡粉的粒径不大于100纳米。Further, the nano tin powder described in the step (1) has a particle diameter of not more than 100 nm.
进一步，步骤(1)中所述导电剂为乙炔黑、Super-P、科琴黑、石墨导电剂、碳纤维、碳纳米管、石墨烯中的一种或一种以上的混合物。Further, the conductive agent in the step (1) is one or a mixture of one of acetylene black, Super-P, ketjen black, graphite conductive agent, carbon fiber, carbon nanotube, and graphene.
进一步，步骤(2)中所述的喷雾干燥的热空气的进口温度为150℃～200℃，出口温度为40℃～70℃。Further, the inlet temperature of the spray-dried hot air described in the step (2) is from 150 ° C to 200 ° C, and the outlet temperature is from 40 ° C to 70 ° C.
进一步，步骤(3)中惰性气体为氮气、氩气、氦气中的一种。Further, the inert gas in the step (3) is one of nitrogen gas, argon gas and helium gas.
有益效果：Beneficial effects:
本发明通过选用纳米锡粉，避免了锡粉因粒径较大而在充放电时产生的体积效应，保证了材料的在充放电过程中的稳定性，同时和钛酸锂进行复合处理，解决了单一钛酸锂负极材料容量偏低等缺点；再通过在复合材料体系里添加导电剂，是使材料体系内部形成导电网络，增加复合材料的导电性能。The invention adopts the nano tin powder, avoids the volume effect of the tin powder due to the large particle size, and ensures the stability of the material during the charging and discharging process, and simultaneously performs the composite treatment with the lithium titanate to solve the problem. The short capacity of the single lithium titanate anode material is low; and by adding a conductive agent to the composite system, a conductive network is formed inside the material system to increase the electrical conductivity of the composite material.
具体实施方式detailed description
为了使本发明的技术手段、创作特征、工作流程、使用方法达成目的与功效易于明白了解，下面结合具体实施例，进一步阐述本发明。In order to make the technical means, the creative features, the workflow, and the method of use of the present invention easy to understand and understand, the present invention will be further described below in conjunction with specific embodiments.
实施例1Example 1
按照二氧化钛：碳酸锂：纳米锡：导电剂＝100:38:3:10的比例，称取1000g二氧化、380g碳酸锂、30g纳米锡、50g乙炔黑，按照固含量为30％的比例，称取3406g的乙醇溶剂中，不断搅拌，混合成均匀浆体；再将浆体进行喷雾、干燥、分级，得到平均粒径为10μm的粉体，再将粉体在惰性气体的保护下，以5℃/min的速度升温至1000℃，再保温3h，自然降温，冷却后过筛即得到复合钛酸锂负极材料。According to the ratio of titanium dioxide: lithium carbonate: nano tin: conductive agent = 100:38:3:10, weigh 1000g of dioxide, 380g of lithium carbonate, 30g of nano tin, 50g of acetylene black, according to the ratio of solid content of 30%, weigh 3406 g of ethanol solvent, stirring constantly, mixing into a uniform slurry; then spraying, drying, and classifying the slurry to obtain a powder having an average particle diameter of 10 μm, and then the powder is protected by an inert gas to 5 The temperature of °C/min is raised to 1000 °C, and then kept for 3 hours, and the temperature is naturally lowered. After cooling, the composite lithium titanate anode material is obtained by sieving.
实施例2Example 2
按照二氧化钛：碳酸锂：纳米锡：导电剂＝100:40:3:10的比例，称取1000g二氧化、400g碳酸锂、30g纳米锡、50gSuper-P，按照固含量为30％的比例，称取3453g的乙醇溶剂中，不断搅拌，混合成均匀浆体；再将浆体进行喷雾、干燥、分级，得到平均粒径为10μm的粉体，再将粉体在惰性气体的保护下，以3℃/min的速度升温至900℃，再保温2h，自然降温，冷却后过筛即得到复合钛酸锂负极材料。According to the ratio of titanium dioxide: lithium carbonate: nano tin: conductive agent = 100:40:3:10, weigh 1000g of dioxide, 400g of lithium carbonate, 30g of nano tin, 50g of Super-P, according to the ratio of solid content of 30%, weigh Take 3453g of ethanol solvent, stir constantly, mix into a uniform slurry; then spray, dry and classify the slurry to obtain a powder with an average particle size of 10μm, and then the powder under the protection of inert gas, 3 The temperature of °C/min is raised to 900 °C, and then kept for 2 hours, and the temperature is naturally lowered. After cooling, the composite lithium titanate negative electrode material is obtained.
实施例3Example 3
按照二氧化钛：碳酸锂：纳米锡：导电剂＝100:40:5:10的比例，称取1000g二氧化、400g碳酸锂、50g纳米锡、50g导电石墨KS-6，按照固含量为30％的比例，称取3500g的乙醇溶剂中，不断搅拌，混合成均匀浆体；再将浆体进行喷雾、干燥、分级，得到平均粒径为10μm的粉体，再将粉体在惰性气体的保护下，以4℃/min的速度升温至950℃，再保温3.5h，自然降温，冷却后过筛即得到复合钛酸锂负极材料。According to the ratio of titanium dioxide: lithium carbonate: nano tin: conductive agent=100:40:5:10, weigh 1000g of dioxide, 400g of lithium carbonate, 50g of nano tin, 50g of conductive graphite KS-6, according to the solid content of 30% The ratio is weighed into 3500g of ethanol solvent, continuously stirred and mixed into a uniform slurry; then the slurry is sprayed, dried and classified to obtain a powder with an average particle diameter of 10 μm, and then the powder is protected by an inert gas. The temperature is raised to 950 ° C at a rate of 4 ° C / min, and then kept for 3.5 h, and the temperature is naturally lowered. After cooling, the composite lithium titanate negative electrode material is obtained by sieving.
对比例1Comparative example 1
按照二氧化钛：碳酸锂＝100:40的比例，称取1000g二氧化、400g碳酸锂，按照固含量为30％的比例，称取3366g的乙醇溶剂中，不断搅拌，混合成均匀浆体；再将浆体进行喷雾、干燥、分级，得到平均粒径为6μm的粉体，再将粉体在惰 性气体的保护下，以5℃/min的速度升温至1000℃，再保温3h，自然降温，冷却后过筛即得到钛酸锂负极材料。According to the ratio of titanium dioxide: lithium carbonate = 100:40, weigh 1000g of dioxide, 400g of lithium carbonate, weigh 3366g of ethanol solvent according to the ratio of solid content of 30%, stir constantly, mix into a uniform slurry; The slurry is sprayed, dried, and classified to obtain a powder having an average particle diameter of 6 μm, and then the powder is in an inert state. Under the protection of the gas, the temperature is raised to 1000 ° C at a rate of 5 ° C / min, and then kept for 3 h, and the temperature is naturally lowered. After cooling, the lithium titanate negative electrode material is obtained by sieving.
电化学性能测试Electrochemical performance test
为检验本发明方法制备的复合钛酸锂负极材料的性能，用半电池测试方法进行测试，用以上实施例和比较例的负极材料：乙炔黑：PVDF(聚偏氟乙烯)＝93：3：4(重量比)，加适量NMP(N-甲基吡咯烷酮)调成浆状，涂布于铜箔上，经真空110℃干燥8小时制成负极片；以金属锂片为对电极，电解液为1mol/L LiPF6/EC+DEC+DMC＝1：1：1，聚丙烯微孔膜为隔膜，组装成电池。充放电电压为1.0～2.5V，充放电速率为0.5C，对电池性能进行能测试，测试结果见表1。To test the properties of the composite lithium titanate negative electrode material prepared by the method of the present invention, the test was carried out by a half-cell test method using the negative electrode materials of the above examples and comparative examples: acetylene black: PVDF (polyvinylidene fluoride) = 93:3: 4 (weight ratio), add appropriate amount of NMP (N-methylpyrrolidone) to make a slurry, apply on copper foil, dry at 110 ° C for 8 hours to make a negative electrode sheet; use lithium metal sheet as the counter electrode, electrolyte The polypropylene microporous membrane was a separator of 1 mol/L LiPF6/EC+DEC+DMC=1:1:1, and assembled into a battery. The charge-discharge voltage is 1.0-2.5V, and the charge-discharge rate is 0.5C. The battery performance can be tested. The test results are shown in Table 1.
表1为不同实施例和比较例中负极材料的性能比较Table 1 compares the performance of negative electrode materials in different examples and comparative examples.
Figure PCTCN2016086700-appb-000001
Figure PCTCN2016086700-appb-000001
以上显示和描述了本发明的基本原理、主要特征及本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明的要求保护范围由所附的权利要求书及其等效物界定。 The basic principles, main features, and advantages of the present invention are shown and described above. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, and that the present invention is only described in the foregoing description and the description of the present invention, without departing from the spirit and scope of the invention. Various changes and modifications are intended to be included within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and their equivalents.

Claims (6)

  1. 一种金属锡掺杂复合钛酸锂负极材料的制备方法，原料按照重量份比例，包括以下工艺步骤：A method for preparing a metal tin doped composite lithium titanate negative electrode material, the raw materials according to the proportion by weight, comprising the following process steps:
    (1)制备前驱体浆料：按照二氧化钛：碳酸锂：纳米锡：导电剂＝100:38～40:3～5:5～10的比例，称取各组分分散于有机溶剂乙醇中，调节固含量至20％～40％，然后不断搅拌，得到前驱体浆料；(1) Preparation of precursor slurry: According to the ratio of titanium dioxide: lithium carbonate: nano tin: conductive agent = 100: 38 to 40: 3 to 5: 5 to 10, each component is weighed and dispersed in an organic solvent ethanol, and adjusted. a solid content of 20% to 40%, and then continuously stirred to obtain a precursor slurry;
    (2)雾化、干燥、造粒以及分级：将步骤(1)中制备的前驱体浆料通过雾化、干燥和造粒，再经过粉体分级得到平均粒径介于5～15μm之间的粉体；(2) atomization, drying, granulation and classification: the precursor slurry prepared in the step (1) is subjected to atomization, drying and granulation, and then subjected to powder classification to obtain an average particle diameter of 5 to 15 μm. Powder
    (3)热处理：将步骤(2)中所得到的粉体在惰性气体的保护下，以1～5℃/min的速度升温至800～1000℃，再保温1～5h，自然降温，冷却后经过粉碎、筛分即得到本发明所述的高容量钛酸锂负极材料。(3) Heat treatment: the powder obtained in the step (2) is heated to a temperature of 800 to 1000 ° C at a rate of 1 to 5 ° C / min under the protection of an inert gas, and then kept for 1 to 5 hours, naturally cooled, and after cooling. After pulverization and sieving, the high-capacity lithium titanate negative electrode material of the present invention is obtained.
  2. 根据权利要求1所述的一种金属锡掺杂复合钛酸锂负极材料的制备方法，其特征在于，步骤(1)中所述的二氧化钛为锐钛型二氧化钛或金石型二氧化钛中的一种。The method for preparing a metal tin-doped composite lithium titanate negative electrode material according to claim 1, wherein the titanium dioxide in the step (1) is one of an anatase type titanium dioxide or a gold stone type titanium dioxide.
  3. 根据权利要求1所述的一种金属锡掺杂复合钛酸锂负极材料的制备方法，其特征在于，步骤(1)中所述的纳米锡粉的粒径不大于100纳米。The method for preparing a metal tin-doped composite lithium titanate negative electrode material according to claim 1, wherein the nano tin powder in the step (1) has a particle diameter of not more than 100 nm.
  4. 根据权利要求1所述的一种金属锡掺杂复合钛酸锂负极材料的制备方法，其特征在于，步骤(1)中所述导电剂为乙炔黑、Super-P、科琴黑、石墨导电剂、碳纤维、碳纳米管、石墨烯中的一种或一种以上的混合物。The method for preparing a metal tin-doped composite lithium titanate negative electrode material according to claim 1, wherein the conductive agent in the step (1) is acetylene black, Super-P, Ketjen black, and graphite conductive One or a mixture of one or more of a carbon fiber, a carbon nanotube, and a graphene.
  5. 根据权利要求1所述的一种金属锡掺杂复合钛酸锂负极材料的制备方法，其特征在于，步骤(2)中所述的喷雾干燥的热空气的进口温度为150℃～200℃，出口温度为40℃～70℃。The method for preparing a metal tin-doped composite lithium titanate negative electrode material according to claim 1, wherein the inlet temperature of the spray-dried hot air in the step (2) is 150 ° C to 200 ° C, The outlet temperature is 40 ° C to 70 ° C.
  6. 根据权利要求1所述的一种金属锡掺杂复合钛酸锂负极材料的制备方法，其特征在于，步骤(3)中惰性气体为氮气、氩气、氦气中的一种。 The method for preparing a metal tin-doped composite lithium titanate negative electrode material according to claim 1, wherein the inert gas in the step (3) is one of nitrogen gas, argon gas and helium gas.
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