WO2017008614A1 - 一种无定形碳沉积改性钛酸锂负极材料的制备方法 - Google Patents

一种无定形碳沉积改性钛酸锂负极材料的制备方法 Download PDF

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WO2017008614A1
WO2017008614A1 PCT/CN2016/086277 CN2016086277W WO2017008614A1 WO 2017008614 A1 WO2017008614 A1 WO 2017008614A1 CN 2016086277 W CN2016086277 W CN 2016086277W WO 2017008614 A1 WO2017008614 A1 WO 2017008614A1
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lithium titanate
amorphous carbon
electrode material
transition metal
negative electrode
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PCT/CN2016/086277
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French (fr)
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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
    • H01M4/48—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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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 belongs to the field of lithium ion batteries, in particular to a negative electrode material, in particular to a method for modifying a lithium titanate negative electrode material by using amorphous carbon deposition.
  • Lithium-ion batteries are increasingly used in these fields due to their high open circuit voltage, high energy density, light weight and low self-discharge.
  • life and power performance of lithium-ion batteries is not satisfactory, especially in electric vehicles. This is because the structure of the conventional graphite anode material has a high degree of crystallization and orientation characteristics, so that during the charging process, solvent molecules enter the graphite layer and cause the graphite layer to peel off, thereby causing the battery cycle performance to be lowered and limited.
  • the application of graphite materials in power battery materials is because the structure of the conventional graphite anode material has a high degree of crystallization and orientation characteristics, so that during the charging process, solvent molecules enter the graphite layer and cause the graphite layer to peel off, thereby causing the battery cycle performance to be lowered and limited.
  • 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.
  • Amorphous carbon itself has good electrical conductivity and resistance to electrolyte corrosion, thereby improving the cycle stability and electrical conductivity of the material.
  • one of the objects of the present invention is to provide a method for modifying a lithium titanate negative electrode material by using amorphous carbon deposition, and the specific steps are as follows:
  • step D) removing the transition metal on the lithium titanate deposited with the amorphous carbon obtained in the step C) by using an acidic medium solution, washing to neutrality, and then drying to obtain a modified lithium titanate negative electrode material.
  • the mass ratio of the lithium titanate to the transition metal compound described in the step A) is 100: (5 to 20).
  • the transition metal compound described in the step A) includes one or more of a chloride of nickel, a chloride of iron, and a chloride of cobalt.
  • the molar concentration of the aqueous solution of the transition metal compound described in the step A) is preferably 0.05 to 0.3 mol/L.
  • the heating temperature described in the step A) is 30 to 85 °C.
  • step B) is hydrogen.
  • amorphous carbon-carbon source described in step C) includes gaseous hydrocarbons and/or liquid hydrocarbons.
  • the deposition temperature in the step C) is 600 to 800 ° C, and the deposition time is 0.5 to For 1.5 hours, the amount of amorphous carbon deposited was 5 to 20% by weight of lithium titanate.
  • the acidic medium solution described in the step D) is a hydrochloric acid solution having a molar concentration of 0.01 to 0.5 mol/L.
  • the invention provides a method for modifying a lithium titanate negative electrode material by using amorphous carbon deposition, and using a transition metal as a catalyst, the amorphous carbon and the lithium titanate are combined by a chemical bond to deposit amorphous carbon.
  • a composite anode material of lithium titanate and amorphous carbon is obtained, which avoids the direct contact between the lithium titanate and the lithium ion electrolyte, and solves the technical problem that the lithium titanate reacts with the electrolyte to generate flatulence, thereby Improve the cycle performance of lithium-ion batteries.
  • the anode material obtained by the preparation method provided by the present invention also has better rate performance.
  • the experimental data show that the lithium ion battery prepared by using the negative electrode material provided by the present invention has a capacity retention rate of 95% or more when the charge and discharge cycle is 2000 times, indicating the lithium ion capacity retention rate prepared by using the negative electrode material provided by the present invention. Higher, with better cycle performance.
  • lithium titanate:FeCl 3 100:15
  • a 0.3 mol/L aqueous solution of FeCl 3 was placed, then lithium titanate was added, and the mixture was uniformly dispersed and dried at a temperature of 65 ° C to obtain FeCl 3 supported on the surface.
  • Lithium titanate It is then reduced with hydrogen to obtain lithium titanate with metal Fe supported on the surface, and methane gas is introduced to deposit amorphous carbon on the surface of lithium titanate.
  • the control time is 2 h, and the amorphous carbon deposition accounts for the weight of lithium titanate. 14%
  • the metal Fe on the lithium titanate was removed with a 0.2 mol/L hydrochloric acid solution, washed to neutrality, and then dried to obtain a modified lithium titanate negative electrode material.
  • lithium titanate:CoCl 3 100:20
  • a 0.5 mol/L aqueous solution of CoCl 3 was added, then lithium titanate was added, and the mixture was uniformly dispersed and dried at a temperature of 85 ° C to obtain a surface-loaded CoCl 3 .
  • Lithium titanate It is then reduced with hydrogen to obtain lithium titanate with metal Co supported on the surface, and methane gas is introduced to deposit amorphous carbon on the surface of lithium titanate.
  • the control time is 1.5h, and the amorphous carbon deposition accounts for lithium titanate. 10% by weight, finally, the metal Co on the lithium titanate was removed with a 0.3 mol/L hydrochloric acid solution, washed to neutrality, and then dried to obtain a modified lithium titanate negative electrode material.
  • 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.

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

Abstract

一种无定形碳沉积改性钛酸锂负极材料的制备方法，首先将钛酸锂与过渡金属化合物水溶液混合，进行加热至水分蒸发，再用还原剂将负载有过渡金属化合物的钛酸锂进行还原，然后用无定形碳碳源将得到的负载有过渡金属的钛酸锂进行沉积，最后利用酸性介质溶液将沉积有无定形碳的钛酸锂上的过渡金属去除。该制备方法中以过渡金属作为催化剂，使得无定形碳与钛酸锂之间通过化学键复合在一起，将无定形碳沉积在钛酸锂上，得到钛酸锂和无定形碳的复合负极材料，避免了钛酸锂和锂离子电解液的直接接触，解决了钛酸锂和电解液反应而产生胀气的技术问题，从而提高锂离子电池的循环性能。并且，使用该制备方法得到的负极材料还具有较好的倍率性能。

Description

一种无定形碳沉积改性钛酸锂负极材料的制备方法 技术领域
本发明属于锂离子电池领域，尤其涉及一种负极材料，具体涉及一种利用无定型碳沉积对钛酸锂负极材料进行改性的方法。
背景技术
随着汽车行业的发展，石油、天然气等不可再生石化燃料的耗竭日益受到关注，空气污染和室温效应也成为全球性的问题，以及国民经济的快速发展和人民生活水平的提高，我国对原油的依赖度与日俱增，已对我国能源安全构成直接威胁，另外，原油的价格波动也直接影响到我国国民经济的发展，随着国际原油价格的不断攀升，不仅增加了中国用高额外汇进口石油的经济压力，也使国内油品市场供求矛盾更加突出在我国石油消费结构中，交通工具消耗的石油占一半以上，且呈现连续性大幅度上升趋势，这些迫使人们不得不在寻找新能源、发展新的交通工具方面加快步伐动力电池和电动汽车的发展被放在越来越重要的位置。因此，以绿色二次电池为动力的二次能源越来越受到人们的重视，被视为是解决能源枯竭和环境污染的有效途径。
随着以绿色二次电池为动力的二次能源的迅速发展，各种新能源电动汽车及便携式电子设备、电动工具的广泛使用和高速发展，对化学电源的要求也相继提高。锂离子电池由于开路电压高、能量密度大、重量轻和自放电低等优点在这些领域得到日益广泛的应用。但是，锂离子电池的使用寿命和功率性能并不尽人意，尤其是在电动汽车上。这是由于传统的石墨负极材料的结构具有高度晶化和取向度特性，使之在充电过程中会发生溶剂分子进入石墨层间而引起石墨层剥落的现象，由此导致电池循环性能降低，限制了石墨类材料在动力电池材料方面的应用。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。
研究表明将无定形碳和钛酸锂复合制备所得到的复合材料能极大的改善钛酸锂的性能。无定形碳本身具有良好的导电性和抗电解液腐蚀性能，因此可提高材料的循环稳定性和导电性。
发明内容
针对现有技术存在的问题，本发明的目的之一在于提供一种利用无定型碳沉积对钛酸锂负极材料进行改性的方法，具体步骤如下：
A)将钛酸锂与过渡金属化合物水溶液混合，进行加热至水分蒸发，得到负载有过渡金属化合物的钛酸锂；
B)用还原剂将所述步骤A)得到的负载有过渡金属化合物的钛酸锂进行还原，得到负载有过渡金属的钛酸锂；
C)用无定形碳碳源将所述步骤B)得到的负载有过渡金属的钛酸锂进行沉积，得到沉积有无定形碳的钛酸锂；
D)利用酸性介质溶液将所述步骤C)中得到的沉积有无定形碳的钛酸锂上的过渡金属去除，并进行洗涤至中性，然后烘干，得到改性钛酸锂负极材料。
进一步，步骤A)中所述的钛酸锂与过渡金属化合物的质量比为100：(5～20)。
进一步，步骤A)中所述的过渡金属化合物包括镍的氯化物、铁的氯化物和钴的氯化物中的一种或几种。
进一步，步骤A)中所述的过渡金属化合物水溶液的摩尔浓度优选为0.05～0.3mol/L。
进一步，步骤A)中所述的加热温度为30～85℃。
进一步，步骤B)中所述的还原剂为氢气。
进一步，步骤C)中所述的无定形碳碳源包括气体碳氢化合物和/或液体碳氢化合物。
进一步，步骤C)中所述的沉积的温度为600～800℃，沉积的时间为0.5～ 1.5小时，无定形碳的沉积量占钛酸锂重量的5～20％。
进一步，步骤D)中所述的酸性介质溶液为盐酸溶液，摩尔浓度为0.01～0.5mol/L。
本发明提供的一种利用无定型碳沉积对钛酸锂负极材料进行改性的方法，以过渡金属作为催化剂，使得无定形碳与钛酸锂之间通过化学键复合在一起，将无定形碳沉积在钛酸锂上，得到钛酸锂和无定形碳的复合负极材料，避免了钛酸锂和锂离子电解液的直接接触，解决了钛酸锂和电解液反应而产生胀气的技术问题，从而提高锂离子电池的循环性能。并且，使用本发明提供的制备方法得到的负极材料还具有较好的倍率性能。实验数据表明，使用本发明提供的负极材料制备得到的锂离子电池在充放电循环2000次的时候，容量保存率为95％以上，说明使用本发明提供的负极材料制备得到的锂离子容量保存率较高，具有较好的循环性能。
具体实施方式
为了进一步说明本发明，以下结合实施例对本发明的技术方案作一定的介绍，但不能将其理解为对本发明保护范围的限定。
实施例1
按照钛酸锂：NiCl2＝100：10的质量比，配置0.1mol/L的NiCl2水溶液，然后加入钛酸锂，在55℃的温度下搅拌分散均匀、烘干，得到表面负载有NiCl2的钛酸锂。再用氢气对其进行还原，得到表面负载有金属Ni的钛酸锂，通入甲烷气体，使无定型碳在钛酸锂表面沉积，控制时间为1h，无定型碳沉积量占钛酸锂重量的8％，最后用0.1mol/L的盐酸溶液对钛酸锂上的金属Ni进行去除，并洗涤至中性，然后烘干，得到改性钛酸锂负极材料。
实施例2
按照钛酸锂：FeCl3＝100：15的质量比，配置0.3mol/L的FeCl3水溶液，然后加入钛酸锂，在65℃的温度下搅拌分散均匀、烘干，得到表面负载有FeCl3的钛酸锂。再用氢气对其进行还原，得到表面负载有金属Fe的钛酸锂，通入甲烷气体，使无定型碳在钛酸锂表面沉积，控制时间为2h，无定型碳沉积量占钛酸锂重量的14％，最后用0.2mol/L的盐酸溶液对钛酸锂上的金属Fe进行去除，并洗涤至中性，然后烘干，得到改性钛酸锂负极材料。
实施例3
按照钛酸锂：CoCl3＝100：20的质量比，配置0.5mol/L的CoCl3水溶液，然后加入钛酸锂，在85℃的温度下搅拌分散均匀、烘干，得到表面负载有CoCl3的钛酸锂。再用氢气对其进行还原，得到表面负载有金属Co的钛酸锂，通入甲烷气体，使无定型碳在钛酸锂表面沉积，控制时间为1.5h，无定型碳沉积量占钛酸锂重量的10％，最后用0.3mol/L的盐酸溶液对钛酸锂上的金属Co进行去除，并洗涤至中性，然后烘干，得到改性钛酸锂负极材料。
实施例4
按照钛酸锂：NiCl2：FeCl3＝100：10：5的质量比，配置0.2mol/L的CoCl3和0.15mol/L的FeCl3水溶液，然后加入钛酸锂，在75℃的温度下搅拌分散均匀、烘干，得到表面负载有NiCl2和FeCl3的钛酸锂。再用氢气对其进行还原，得到表面负载有金属Ni和Fe的钛酸锂，通入甲烷气体，使无定型碳在钛酸锂表面沉积，控制时间为1h，无定型碳沉积量占钛酸锂重量的8％，最后用0.2mol/L的盐酸溶液对钛酸锂上的金属Ni和Fe进行去除，并洗涤至中性，然后烘干，得到改性钛酸锂负极材料。
对比例1
实施例1中未经处理的钛酸锂。
半电池检测
为检验本发明方法制备的负极材料的电性能，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/LLiPF6/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。
全电池测试
用上实施例和比较例的负极材料：SP：SBR(固含量50％)：CMC＝94：2.5：1.5：2(重量比)，加适量去离子水混合均匀调成浆状，涂于铜箔上，在90℃下抽真空干燥；将LiCoO2粉末：SP：KS-6：PVDF＝94：1.5：2：2.5(重量比)，以NMP做溶剂混合均匀进行调浆后，涂于铝箔上，在100℃下抽真空干燥；将干燥后的 正、负极极片经过辊压、裁片、卷绕、注液、封口、化成工序，制成18650圆柱电池，隔膜为Celgard2400，电解液为1M LiPF6/DMC：EC：DEC，使用电池检测装置进行倍率放电和循环性能的检测，测试结果见表1。
表1不同实施例和比较例中负极材料的性能比较
Figure PCTCN2016086277-appb-000001
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (8)

  1. 一种无定形碳沉积改性钛酸锂负极材料的制备方法，其制备步骤步骤如下：
    A)将钛酸锂与过渡金属化合物水溶液混合，进行加热至水分蒸发，得到负载有过渡金属化合物的钛酸锂；
    B)用还原剂将所述步骤A)得到的负载有过渡金属化合物的钛酸锂进行还原，得到负载有过渡金属的钛酸锂；
    C)用无定形碳碳源将所述步骤B)得到的负载有过渡金属的钛酸锂进行沉积，得到沉积有无定形碳的钛酸锂；
    D)利用酸性介质溶液将所述步骤C)中得到的沉积有无定形碳的钛酸锂上的过渡金属去除，并进行洗涤至中性，然后烘干，得到改性钛酸锂负极材料。
  2. 根据权利要求1所述的一种无定形碳沉积改性钛酸锂负极材料的制备方法，其特征在于步骤A)中钛酸锂与过渡金属化合物的质量比为100：(5～20)。
  3. 根据权利要求1所述的一种无定形碳沉积改性钛酸锂负极材料的制备方法，其特征在于步骤A)中过渡金属化合物包括镍的氯化物、铁的氯化物和钴的氯化物中的一种或几种。
  4. 根据权利要求1所述的一种无定形碳沉积改性钛酸锂负极材料的制备方法，其特征在于步骤A)中加热温度为30～85℃。
  5. 根据权利要求1所述的一种无定形碳沉积改性钛酸锂负极材料的制备方法，其特征在于步骤A)中还原剂为氢气。
  6. 根据权利要求1所述的一种无定形碳沉积改性钛酸锂负极材料的制备方法，其特征在于步骤C)中无定形碳碳源包括气体碳氢化合物和/或液体碳氢化合物。
  7. 根据权利要求1所述的一种无定形碳沉积改性钛酸锂负极材料的制备方法，其特征在于步骤C)中沉积的温度为600～800℃，沉积的时间为0.5～1.5小时，无定形碳的沉积量占钛酸锂重量的5～20％。
  8. 根据权利要求1所述的一种无定形碳沉积改性钛酸锂负极材料的制备方法，其特征在于步骤D)中酸性介质溶液为盐酸溶液，摩尔浓度为0.01～0.5mol/L。
PCT/CN2016/086277 2015-07-15 2016-06-17 一种无定形碳沉积改性钛酸锂负极材料的制备方法 WO2017008614A1 (zh)

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