WO2016192541A1 - 一种多相金属掺杂钛酸锂负极材料的制备方法 - Google Patents

一种多相金属掺杂钛酸锂负极材料的制备方法 Download PDF

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WO2016192541A1
WO2016192541A1 PCT/CN2016/082870 CN2016082870W WO2016192541A1 WO 2016192541 A1 WO2016192541 A1 WO 2016192541A1 CN 2016082870 W CN2016082870 W CN 2016082870W WO 2016192541 A1 WO2016192541 A1 WO 2016192541A1
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negative electrode
lithium titanate
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doped lithium
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田东
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/387—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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

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  • the invention relates to a preparation method of a multiphase metal-doped lithium titanate anode material, in particular to a preparation method of a lithium titanate anode material doped with metal nickel and metal tin.
  • 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.
  • the surface of the carbon electrode is liable to precipitate metallic lithium, which may cause a short circuit, thereby causing a short circuit.
  • the carbon material generally used as a negative electrode material has a low theoretical specific capacity of only 372 mAh/g, and the development space is very limited, it is necessary for the development of a novel negative electrode material.
  • the new negative electrode materials are alloy materials, tin-based oxide materials, and the like. Although the alloy material can provide a high reversible capacity, its cycle performance is not ideal. Although the tin-based oxide material has a high reversible capacity and good cycle performance, its disadvantage is that the irreversible capacity loss of the first cycle is large (usually greater than 50%). It is found that metal and its oxides have higher specific capacity when used as the anode material of lithium ion batteries. In addition, the ductility of metal nickel is good, which can greatly reduce the expansion rate of electrode materials during lithium insertion and removal. However, the conductivity of nickel oxide is low, which affects the charge and discharge performance of the battery.
  • spinel Li4Ti5O12 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.
  • 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 present invention provides a method for preparing a lithium titanate negative electrode material.
  • the negative electrode material prepared by the method has high conductivity and has good conductivity in the case of having a high capacity. Electrochemical cycle stability.
  • the present invention provides a method for preparing a multiphase metal-doped lithium titanate anode material, comprising the following steps:
  • the powder obtained in the step 2) is heated to a temperature of 5 to 20 ° C / min to 700 to 900 ° C under the protection of an inert gas, and then kept for 10 to 24 hours, naturally cooled, and pulverized after cooling.
  • the lithium titanate negative electrode material of the present invention is obtained by sieving.
  • the titanium oxide described in the step 1) is one of anatase type titanium dioxide or a gold stone type titanium dioxide.
  • the particle size of the tin powder and the nickel powder described in the step 1) is ⁇ 100 nm.
  • the grinding ball is one of a non-metallic zirconia, a ceramic ball, and a polyurethane ball.
  • step 1) the time of ball milling mixing in step 1) is 8 to 24 hours.
  • the slurry drying in the step 2) is carried out under a vacuum negative pressure, and the pressure is ⁇ -0.1 MPa.
  • the inert gas in the step (3) is one of nitrogen gas, argon gas and helium gas.
  • the invention adopts the nano powder to avoid the volume effect of the metal tin powder due to the large particle size during charging and discharging, ensuring the stability of the material during charging and discharging, and compounding with lithium titanate.
  • the treatment solves the defects of low capacity of the single lithium titanate anode material
  • the invention adopts vacuum low-temperature negative pressure to carry out slurry drying, which not only avoids the agglomeration of the powder in the high temperature state, but also can recycle the organic solvent, thereby playing the role of energy conservation and environmental protection.
  • the lithium titanate negative electrode material prepared by the invention has high specific capacity, and the material is modified to effectively improve the conductivity of the material and improve the cycle stability of the material. Therefore, the anode material has high energy density and good cycle stability when used for a lithium ion battery.
  • titanium dioxide: lithium carbonate: nickel powder: tin powder 100:38:3:1, 1000 g of titanium dioxide, 380 g of lithium carbonate, 30 g of nickel powder, and 10 g of tin powder were weighed and weighed according to a solid content of 30%.
  • zirconia grinding balls were used, ball milling for 12 h to obtain a uniform slurry; and the slurry was dried at -0.1 MPa, 30 ° C for 10 h to obtain a powder; and then the powder was in an inert gas. Under protection, the temperature is raised to 800 ° C at a rate of 5 ° C / min, and then kept for 10 h, and the temperature is naturally lowered. After cooling, the lithium titanate negative electrode material of the present invention is obtained by sieving.
  • Table 1 compares the performance of negative electrode materials in different examples and comparative examples.

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Abstract

一种多相金属掺杂钛酸锂负极材料的制备方法，包括如下步骤：（1）前驱体浆料制备；（2）前驱体干燥；（3）热处理。制备的钛酸锂负极材料具备较高的比容量，通过对材料进行改性，有效提高了材料的导电性，改善了材料的循环稳定性。该负极材料在用于锂离子电池时，具有较高的能量密度和良好的循环稳定性。

Description

一种多相金属掺杂钛酸锂负极材料的制备方法 技术领域
本发明涉及一种多相金属掺杂钛酸锂负极材料的制备方法，具体涉及一种掺有金属镍和金属锡的钛酸锂负极材料的制备方法。
背景技术
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，进而导致电池爆炸。
由于一般采用的碳材料作为负极材料时理论比容量较低，仅为372mAh/g，发展空间非常有限，因此对新型负极材料的开发非常必要。新型的负极材料有合金材料、锡基氧化物材料等。合金材料虽然能提供较高的可逆容量，但其循环性能不够理想。锡基氧化物材料虽然具有较高的可逆容量和较好的循环性能，但它的缺点是首次循环不可逆容量损失较大(常大于50％)。研究发现，金属及其氧化物作为锂离子电池的负极材料时，具有较高的比容量，此外金属镍具的延展性好，可使电极材料在锂的嵌脱过程中膨胀率大大降低。但是氧化镍的导电率低，影响了电池的充放电性能。
同时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。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
为了克服现有技术的不足，本发明提供一种钛酸锂负极材料的制备方法，使用该方法制备的负极材料，在拥有高容量的情况下，材料自身具有高导电性，同时还具有良好的电化学循环稳定性。
为了实现上述目的，本发明提供一种多相金属掺杂钛酸锂负极材料的制备方法，包括如下步骤：
1)前驱体浆料制备：按照二氧化钛∶碳酸锂∶镍粉∶锡粉＝100∶38～40∶3～5∶1～5的重量比例，称取各组分分散于有机溶剂乙醇中，调节固含量至20％～40％，加入研磨球，进行球磨混合；
2)前驱体干燥：将球磨完毕后的浆料在30～40℃温度下进行干燥，得到粉体；
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5～20℃/min的速度升温至700～900℃，再保温10～24h，自然降温，冷却后经过粉碎、筛分即得到本发明所述的钛酸锂负极材料。
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。
进一步，步骤1)中所述的锡粉和镍粉的粒径≤100nm。
进一步，步骤1)中研磨球采用的是非金属材质的氧化锆求、陶瓷球、聚氨酯球中的一种。
进一步，步骤1)中球磨混合的时间为8～24h。
进一步，步骤2)中浆料干燥是在真空负压状态下进行的，其压力≤-0.1Mpa。
进一步，步骤(3)中惰性气体为氮气、氩气、氦气中的一种。
本发明的有益效果如下：
1、本发明通过选用纳米粉体，避免了金属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；
2、本发明采用真空低温负压进行浆料干燥，不仅可避免粉体在高温状态下干燥产生团聚，同时可对有机溶剂进行回收利用，起到节能环保的作用。
本发明制备的钛酸锂负极材料具备较高的比容量，通过对材料进行改性，有效提高了材料的导电性，改善了材料的循环稳定性。因此使得该负极材料在用于锂离子电池时，具有较高的能量密度和良好的循环稳定性。
具体实施方式
实施例一
按照二氧化钛∶碳酸锂∶镍粉∶锡粉＝100∶38∶3∶1的比例，称取1000g二氧化钛、380g碳酸锂、30g镍粉、10g锡粉，按照固含量为30％的比例，称取3313g的乙醇溶剂中，采用氧化锆研磨球，球磨12h，得到均匀浆料；再将浆料在-0.1Mpa、30℃的条件下，干燥10h，得到粉体；再将粉体在惰性气体的保护下，以5℃/min的速度升温至800℃，再保温10h，自然降温，冷却后过筛即得到本发明钛酸锂负极材料。
实施例二
按照二氧化钛∶碳酸锂∶镍粉∶锡粉＝100∶40∶5∶5的比例，称取1000g二氧化钛、400g碳酸锂、50g镍粉、50g锡粉，按照固含量为40％的比例，称取2250g的乙醇溶剂中，采用氧化锆研磨球，球磨12h，得到均匀浆料；再将浆料在-0.1Mpa、40℃的条件下，干燥80h，得到粉体；再将粉体在惰性气体的保护下，以20℃/min的速度升温至 900℃，再保温24h，自然降温，冷却后过筛即得到本发明钛酸锂负极材料。
实施例三
按照二氧化钛∶碳酸锂∶镍粉∶锡粉＝100∶39∶4∶3的比例，称取1000g二氧化钛、390g碳酸锂、40g镍粉、30g锡粉，按照固含量为30％的比例，称取3406g的乙醇溶剂中，采用氧化锆研磨球，球磨12h，得到均匀浆料；再将浆料在-0.1Mpa、35℃的条件下，干燥9h，得到粉体；再将粉体在惰性气体的保护下，以10℃/min的速度升温至850℃，再保温14h，自然降温，冷却后过筛即得到本发明钛酸锂负极材料。
对比例1
按照二氧化钛∶碳酸锂＝100∶38的比例，称取1000g二氧化钛、380g碳酸锂，按照固含量为30％的比例，称取3220g的乙醇溶剂中，采用氧化锆研磨球，球磨12h，得到均匀浆料；再将浆料在-0.1Mpa、30℃的条件下，干燥10h，得到粉体；再将粉体在惰性气体的保护下，以5℃/min的速度升温至800℃，再保温10h，自然降温，冷却后过筛即得到钛酸锂负极材料。
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 PCTCN2016082870-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。

Claims (7)

  1. 一种多相金属掺杂钛酸锂负极材料的制备方法，包括如下步骤：
    1)前驱体浆料制备：按照二氧化钛∶碳酸锂∶镍粉∶锡粉＝100∶38～40∶3～5∶1～5的重量比例，称取各组分分散于有机溶剂乙醇中，调节固含量至20％～40％，加入研磨球，进行球磨混合；
    2)前驱体干燥：将球磨完毕后的浆料在30～40℃温度下进行干燥，得到粉体；
    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5～20℃/min的速度升温至700～900℃。
  2. 根据权利要求1所述的一种多相金属掺杂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。
  3. 根据权利要求1所述的一种多相金属掺杂钛酸锂负极材料的制备方法，其特征在于，步骤1)中所述的锡粉和镍粉的粒径≤100nm。
  4. 根据权利要求1所述的一种多相金属掺杂钛酸锂负极材料的制备方法，其特征在于，步骤1)中研磨球采用的是非金属材质的氧化锆求、陶瓷球、聚氨酯球中的一种。
  5. 根据权利要求1所述的一种多相金属掺杂钛酸锂负极材料的制备方法，其特征在于，步骤1)中球磨混合的时间为8～24h。
  6. 根据权利要求1所述的一种多相金属掺杂钛酸锂负极材料的制备方法，其特征在于，步骤2)中浆料干燥是在真空负压状态下进行的，其压力≤-0.1Mpa。
  7. 根据权利要求1所述的一种多相金属掺杂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。
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