WO2016202162A1 - 一种锂离子负极材料Li4Ti5O12/C的合成方法 - Google Patents

一种锂离子负极材料Li4Ti5O12/C的合成方法 Download PDF

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WO2016202162A1
WO2016202162A1 PCT/CN2016/083771 CN2016083771W WO2016202162A1 WO 2016202162 A1 WO2016202162 A1 WO 2016202162A1 CN 2016083771 W CN2016083771 W CN 2016083771W WO 2016202162 A1 WO2016202162 A1 WO 2016202162A1
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titanium dioxide
lithium
electrode material
negative electrode
synthesizing
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/625—Carbon or graphite
    • 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 lithium ion battery anode material, in particular to a method for synthesizing a lithium ion anode material Li 4 Ti 5 O 12 /C prepared by a carbon coating titanium dioxide process.
  • Lithium-ion batteries have the advantages of high energy density, small self-discharge, no memory effect, wide operating voltage range, long service life and no environmental pollution. They are the main power source for new energy vehicles.
  • the key electrode material of lithium ion battery is the final determinant of battery performance, and the negative electrode material plays an important role in improving the performance of lithium ion battery. Therefore, the development of high-performance, low-cost anode materials is of great significance to promote the development of new energy vehicles and related emerging industries.
  • Li 4 Ti 5 O 12 is a new type of negative electrode material for lithium ion secondary batteries. Compared with other commercial materials, Li 4 Ti 5 O 12 has the advantages of good cycle performance, no reaction with electrolyte, high safety performance, and stable charge and discharge platform. It is one of the most excellent anode materials for lithium-ion batteries that has received much attention in recent years. Compared with carbon negative electrode materials, lithium titanate has many advantages.
  • 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.
  • the object of the present invention is to provide a method for synthesizing a lithium ion anode material Li 4 Ti 5 O 12 /C prepared by a carbon-coated titanium dioxide process, which is simple in process route and suitable for large-scale industrial production.
  • the invention comprises the following steps:
  • the dry powder obtained in the step 2) is treated in an inert atmosphere, and then subjected to a high-temperature heat treatment, and the lithium ion negative electrode material Li 4 Ti 5 O 12 /C is obtained by gas flow classification.
  • the titanium dioxide is one of anatase type titanium dioxide or a gold stone type titanium dioxide.
  • the organic carbon source may be one of water-soluble organic substances, and the water-soluble organic substance may be selected from the group consisting of glucose, sucrose, fructose, polyethylene glycol, polyacrylic acid, and shell polymerization.
  • the time of the ball milling treatment is 5 to 10 h; the temperature of the pretreatment is 400 to 500 ° C, and the pretreatment time is 5 to 8 h.
  • the lithium source may be one of a water-soluble lithium salt lithium acetate and lithium hydroxide; the ball milling treatment time is 2 to 3 hours.
  • the inert atmosphere may be nitrogen gas or argon gas or the like.
  • the treatment temperature is 500 to 600 ° C
  • the treatment time is 10 to 20 h
  • the high temperature heat treatment temperature is 750 to 850 ° C
  • the high temperature heat treatment time is 2 to 20 h.
  • the invention Compared with the conventional method for synthesizing lithium ion negative electrode material Li 4 Ti 5 O 12 , the invention has the advantages that carbon dioxide coating is first performed on the synthetic raw material titanium dioxide to avoid agglomeration of lithium titanate due to high temperature treatment in the later stage, and titanium is prevented.
  • the production of lithium acid crystallites is too large, which can effectively increase the diffusion rate of lithium ions in charge and discharge over-symmetry.
  • the organic carbon source soluble in water is used to make the carbon source more uniformly coated on the surface of the particle, and the nano-carbon coating layer with high conductivity after the organic substance is sintered and pyrolyzed greatly improves the conductivity of the material and ensures titanium.
  • the performance of lithium acid battery performance is used to make the carbon source more uniformly coated on the surface of the particle, and the nano-carbon coating layer with high conductivity after the organic substance is sintered and pyrolyzed greatly improves the conductivity of the material and ensures titanium.
  • the powder was placed in a rotary kiln, sintered at 650 ° C for 8 h in a N 2 atmosphere, and further heated to 800 ° C for 5 h, cooled, sieved, and classified by gas flow to obtain a product.
  • the resulting product had a carbon content of 1.2%.
  • n (Li) 0.87
  • weigh 261 g of lithium hydroxide and 1000 g of titanium dioxide add 150 g of organic carbon source sucrose according to the weight of titanium dioxide 15%, add titanium dioxide and sucrose to add 3.5 L of brine-free mixture, ball mill
  • spray granulation the obtained powder was pretreated at 500 ° C for 8 h in an inert atmosphere to obtain a carbon-coated titanium dioxide powder.
  • Lithium hydroxide was dissolved in 3.5 L of anhydrous saline, and carbon-coated titanium dioxide powder was added thereto to be uniformly stirred, ball-milled for 3 hours, and spray-granulated to obtain a dry powder.
  • the powder was placed in a rotary kiln, sintered at 600 ° C for 8 h in a N 2 atmosphere, and further heated to 800 ° C for 4 h, cooled, sieved, and classified by gas flow to obtain a product.
  • the resulting product had a carbon content of 1.6%.
  • n (Li) 0.85
  • weigh 255g of lithium hydroxide and 1000g of titanium dioxide add 100g of organic carbon source polyethylene glycol according to 10% by weight of titanium dioxide, add titanium dioxide and polyethylene glycol to add 3.0L
  • the mixture was uniformly mixed without brine, ball milled for 3 hours, spray granulated, and the obtained powder was pretreated at 500 ° C for 8 hours in an inert atmosphere to obtain a carbon-coated titanium dioxide powder.
  • Lithium hydroxide was dissolved in 3.5 L of anhydrous saline, and carbon-coated titanium dioxide powder was added thereto to be uniformly stirred, ball-milled for 3 hours, and spray-granulated to obtain a dry powder.
  • the powder was placed in a rotary kiln, sintered at 650 ° C for 8 h in a N 2 atmosphere, and further heated to 820 ° C for 6 h, cooled, sieved, and classified by air flow to obtain a product.
  • the resulting product had a carbon content of 2.3%.
  • n (Li) 0.86
  • weigh 710g of lithium acetate and 1000g of titanium dioxide add 150g of organic carbon source polyacrylic acid according to the weight of titanium dioxide 15%, add titanium dioxide and polypropylene to add 3.6L of brine-free mixing
  • the obtained powder was pretreated at 500 ° C for 8 h in an inert atmosphere to obtain a carbon-coated titanium dioxide powder.
  • Lithium acetate was dissolved in 3.5 L of anhydrous saline, and carbon-coated titanium dioxide powder was added thereto to be uniformly stirred, ball-milled for 3 hours, and spray-granulated to obtain a dry powder.
  • the powder was placed in a rotary kiln, sintered at 650 ° C for 8 h in a N 2 atmosphere, heated to 880 ° C for 8 h, cooled, sieved, and classified by gas flow to obtain a product.
  • the resulting product had a carbon content of 2.6%.
  • n (Li) 0.87
  • weigh 261 g of lithium hydroxide and 1000 g of titanium dioxide add 100 g of organic carbon source glucose according to 10% by weight of titanium dioxide, add titanium dioxide and glucose to add 3.6 L of brine-free mixture, ball mill After 8 h of treatment, spray granulation, the obtained powder was pretreated at 500 ° C for 8 h in an inert atmosphere to obtain a carbon-coated titanium dioxide powder.
  • Lithium hydroxide was dissolved in 4.0 L of anhydrous saline, and carbon-coated titanium dioxide powder was added thereto to be uniformly stirred, ball-milled for 3 hours, and spray-granulated to obtain a dry powder.
  • the powder was placed in a rotary kiln, sintered at 650 ° C for 8 h in a N 2 atmosphere, and further heated to 880 ° C for 5 h, cooled, sieved, and classified by air flow to obtain a product.
  • the resulting product had a carbon content of 2.3%.
  • the powder was placed in a rotary kiln, sintered at 650 ° C for 8 h in a N 2 atmosphere, and further heated to 800 ° C for 5 h, cooled, sieved, and classified by gas flow to obtain a product.
  • the resulting product has a carbon content of zero.
  • 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

一种锂离子负极材料Li 4Ti 5O 12/C的合成方法，其特征在于包括以下步骤：1）将二氧化钛和有机碳源加水混合，球磨处理后喷雾造粒，得到的粉体在惰性气氛中预处理，得到碳包覆二氧化钛粉体；2）将锂源溶于水中，加入步骤1）得到的二氧化钛粉体，然后球磨处理后喷雾造粒，得到干燥粉体；3）将步骤2）得到的干燥粉体在惰性气氛中处理，再进行高温热处理，经过气流分级即得到锂离子负极材料Li 4Ti 5O 12/C。通过对二氧化钛首先进行碳包覆，避免后期因高温处理导致钛酸锂的团聚，防止钛酸锂晶粒生产过大，能有效地提高锂离子在充放电过程中的扩散速率，提高材料的导电性能，保证钛酸锂电性能的发挥。

Description

一种锂离子负极材料Li4Ti5O12/C的合成方法 技术领域
本发明涉及锂离子电池负极材料，尤其是涉及采用碳包覆二氧化钛工艺所制备的一种锂离子负极材料Li4Ti5O12/C的合成方法。
背景技术
目前随着全球性石油资源紧缺与气候环境的不断恶化，人类社会发展面临着严峻的挑战。发展清洁节能的新能源汽车受到世界各国的高度重视。新能源汽车的发展，关键在其动力电源。锂离子电池具有能量密度大、自放电小、无记忆效应、工作电压范围宽、使用寿命长、无环境污染等优点，是目前新能源汽车主要的动力电源。而锂离子电池关键电极材料是电池性能的最终决定性因素，其中负极材料对锂离子电池性能的提高起着至关重要的作用。因此，开发高性能、廉价的负极材料对促进新能源汽车及相关新兴产业的发展具有重要的意义。
目前的负极材料主要为石墨，其比容量已经接近372mAh/g的理论值，很难再有提升的空间，因此寻找替代碳的高比容量负极材料成为一个重要的发展方向。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。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。
发明内容
本发明的目的是提供工艺路线简单，适用于大规模工业生产，采用碳包覆二氧化钛工艺所制备的一种锂离子负极材料Li4Ti5O12/C的合成方法。
本发明包括以下步骤：
1)将二氧化钛和有机碳源加水混合，球磨处理后喷雾造粒，得到的粉体在惰性气氛中预处理，得到碳包覆二氧化钛粉体；
2)将锂源溶于水中，加入步骤1)得到的二氧化钛粉体，然后球磨处理后喷雾造粒，得到干燥粉体；
3)将步骤2)得到的干燥粉体在惰性气氛中处理，再进行高温热处理，经过气流分级即得到锂离子负极材料Li4Ti5O12/C。
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。
步骤1)中，所述有机碳源可采用可溶于水的有机物中的一种，所述可溶于水的有机物可选自葡萄糖、蔗糖、果糖、聚乙二醇、聚丙烯酸、壳聚糖等中的一种；所述球磨处理的时间为5～10h；所述预处理的温度为400～500℃，预处理的时间为5～8h。
在步骤2)中，所述锂源可采用水溶性锂盐醋酸锂、氢氧化锂中的一种；所述球磨处理的时间为2～3h。
在步骤1)和2)中，所述二氧化钛、锂源按元素摩尔数为n(Li)∶n(Ti)＝0.84～0.87；在步骤1)中，所述有机碳源的质量为二氧化钛质量的10％～15％；在步骤1)和2)中，所述水采用无盐水，其中步骤1)中水的加入量按质量比可为二氧化钛的3～4倍，步骤2)中水的加入量按质量比为碳包覆二氧化钛粉体质量的3～4倍。
在步骤1)和3)中，所述惰性气氛可采用氮气或氩气等。
在步骤3)中，所述处理的温度为500～600℃，处理的时间为10～20h；所述高温热处理的温度为750～850℃，高温热处理的时间为2～20h。
与现有的锂离子负极材料Li4Ti5O12的合成方法相比，本发明的优点在于：对合成原料二氧化钛首先进行碳包覆，避免后期因高温处理导致钛酸锂的团聚，防止钛酸锂晶粒生产过大，能有效地提高锂离子在充放电过称中的扩散速率。采用了可溶于水的有机碳源，使碳源更均匀包覆在粒子表面，有机物经过烧结热解后形成的电导率高纳米碳包覆层，极大提高了材料的导电性能，保证钛酸锂电性能的发挥。
具体实施方式
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。
实施例1
按照n(Li)∶n(Ti)＝0.84，称取694g醋酸锂和1000g二氧化钛，按照二氧化钛10％的重量加入有机碳源葡萄糖100g，将二氧化钛和葡萄糖加入加3L无盐水混合均匀，球磨处理8h，喷雾造粒，得到的粉体在惰性气氛中于500℃预处理7h，得到碳包覆二氧化钛粉体。将醋酸锂溶于3.5L无盐水中，加入碳包覆二氧化钛粉体搅拌均匀，球磨处理3h，喷雾造粒得到干燥粉体。将该粉体加入到回转炉中，在N2气氛中650℃烧结8h，再升温至800℃烧结5h后，冷却，过筛，气流分级及得到产品。
所得产品碳含量为1.2％。
实施例2
按照n(Li)∶n(Ti)＝0.87，称取261g氢氧化锂和1000g二氧化钛，按照二氧化钛15％的重量加入有机碳源蔗糖150g，将二氧化钛和蔗糖加入加3.5L无盐水混合均匀，球磨处理8h，喷雾造粒，得到的粉体在惰性气氛中于500℃预处理8h，得到碳包覆二氧化钛粉体。将氢氧化锂溶于3.5L无盐水中，加入碳包覆二氧化钛粉体搅拌均匀，球磨处理3h，喷雾造粒得到干燥粉体。将该粉体加入到回转炉中，在N2气氛中600℃烧结8h，再升温至800℃烧结4h后，冷却，过筛，气流分级及得到产品。
所得产品碳含量为1.6％。
实施例3
按照n(Li)∶n(Ti)＝0.85，称取255g氢氧化锂和1000g二氧化钛，按照二氧化钛10％的重量加入有机碳源聚乙二醇100g，将二氧化钛和聚乙二醇加入加3.0L无盐水混合均匀，球磨处理3h，喷雾造粒， 得到的粉体在惰性气氛中于500℃预处理8h，得到碳包覆二氧化钛粉体。将氢氧化锂溶于3.5L无盐水中，加入碳包覆二氧化钛粉体搅拌均匀，球磨处理3h，喷雾造粒得到干燥粉体。将该粉体加入到回转炉中，在N2气氛中650℃烧结8h，再升温至820℃烧结6h后，冷却，过筛，气流分级及得到产品。
所得产品碳含量为2.3％。
实施例4
按照n(Li)∶n(Ti)＝0.86，称取710g醋酸锂和1000g二氧化钛，按照二氧化钛15％的重量加入有机碳源聚丙烯酸150g，将二氧化钛和聚丙烯加入加3.6L无盐水混合均匀，球磨处理8h，喷雾造粒，得到的粉体在惰性气氛中于500℃预处理8h，得到碳包覆二氧化钛粉体。将醋酸锂溶于3.5L无盐水中，加入碳包覆二氧化钛粉体搅拌均匀，球磨处理3h，喷雾造粒得到干燥粉体。将该粉体加入到回转炉中，在N2气氛中650℃烧结8h，再升温至880℃烧结8h后，冷却，过筛，气流分级及得到产品。
所得产品碳含量为2.6％。
实施例5
按照n(Li)∶n(Ti)＝0.87，称取261g氢氧化锂和1000g二氧化钛，按照二氧化钛10％的重量加入有机碳源葡萄糖100g，将二氧化钛和葡萄糖加入加3.6L无盐水混合均匀，球磨处理8h，喷雾造粒，得到的粉体在惰性气氛中于500℃预处理8h，得到碳包覆二氧化钛粉体。将氢氧化锂溶于4.0L无盐水中，加入碳包覆二氧化钛粉体搅拌均匀，球磨处理3h，喷雾造粒得到干燥粉体。将该粉体加入到回转炉中， 在N2气氛中650℃烧结8h，再升温至880℃烧结5h后，冷却，过筛，气流分级及得到产品。
所得产品碳含量为2.3％。
对比例1
按照n(Li)∶n(Ti)＝0.84，称取694g醋酸锂和1000g二氧化钛，加入加3L无盐水混合均匀，球磨处理8h，喷雾造粒得到干燥粉体。将该粉体加入到回转炉中，在N2气氛中650℃烧结8h，再升温至800℃烧结5h后，冷却，过筛，气流分级及得到产品。
所得产品碳含量为0。
电化学性能测试
为检验本发明方法制备的改性锂离子电池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。
表1为不同实施例和比较例中负极材料的性能比较
Figure PCTCN2016083771-appb-000001
以上显示和描述了本发明的基本原理和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，本发明要求保护范围由所附的权利要求书及其等效物界定。

Claims (10)

  1. 一种锂离子负极材料Li4Ti5O12/C的合成方法，其特征在于包括以下步骤：
    1)将二氧化钛和有机碳源加水混合，球磨处理后喷雾造粒，得到的粉体在惰性气氛中预处理，得到碳包覆二氧化钛粉体；
    2)将锂源溶于水中，加入步骤1)得到的二氧化钛粉体，然后球磨处理后喷雾造粒，得到干燥粉体；
    3)将步骤2)得到的干燥粉体在惰性气氛中处理，再进行高温热处理，经过气流分级即得到锂离子负极材料Li4Ti5O12/C。
  2. 如权利要求1所述一种锂离子负极材料Li4Ti5O12/C的合成方法，其特征在于在步骤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。
  3. 如权利要求1所述一种锂离子负极材料Li4Ti5O12/C的合成方法，其特征在于在步骤1)中，所述有机碳源采用可溶于水的有机物中的一种，所述可溶于水的有机物选自葡萄糖、蔗糖、果糖、聚乙二醇、聚丙烯酸、壳聚糖中的一种。
  4. 如权利要求1所述一种锂离子负极材料Li4Ti5O12/C的合成方法，其特征在于在步骤1)中，所述球磨处理的时间为5～10h；所述预处理的温度为400～500℃，预处理的时间为5～8h。
  5. 如权利要求1所述一种锂离子负极材料Li4Ti5O12/C的合成方法，其特征在于在步骤2)中，所述锂源可采用水溶性锂盐醋酸锂、氢氧化锂中的一种；所述球磨处理的时间为2～3h。
  6. 如权利要求1所述一种锂离子负极材料Li4Ti5O12/C的合成方法，其特征在于在步骤1)和2)中，所述二氧化钛、锂源按元素摩尔数为n(Li)∶n(Ti)＝0.84～0.87。
  7. 如权利要求1所述一种锂离子负极材料Li4Ti5O12/C的合成方法，其特征在于在步骤1)中，在步骤1)中，所述有机碳源的质量为二氧化钛质量的10％～15％。
  8. 如权利要求1所述一种锂离子负极材料Li4Ti5O12/C的合成方法，其特征在于在步骤1)和2)中，在步骤1)和2)中，所述水采用无盐水，其中步骤1)中水的加入量按质量比为二氧化钛的3～4倍，步骤2)中水的加入量按质量比为碳包覆二氧化钛粉体质量的3～4倍。
  9. 如权利要求1所述一种锂离子负极材料Li4Ti5O12/C的合成方法，其特征在于在步骤1)和3)中，所述惰性气氛采用氮气或氩气。
  10. 如权利要求1所述一种锂离子负极材料Li4Ti5O12/C的合成方法，其特征在于在步骤3)中，所述处理的温度为500～600℃，处理的时间为10～20h；所述高温热处理的温度为750～850℃，高温热处理的时间为2～20h。
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