钛酸锂/石墨烯复合负极材料的制备及电化学性能

doi:10.16085/j.issn.1000-6613.2018-0167

化工进展 ›› 2019, Vol. 38 ›› Issue (02): 949-955.DOI: 10.16085/j.issn.1000-6613.2018-0167

钛酸锂/石墨烯复合负极材料的制备及电化学性能

张利辉^1,^2,⁴(),徐宇兴^1,³(),刘振法²(),魏爱佳²,李文²

1. 中国科学院过程工程研究所，多相复杂系统国家重点实验室，北京 100190
2. 河北省科学院能源研究所，河北石家庄 050081
3. 中科廊坊过程工程研究院，河北廊坊 065001
4. 中国科学院大学，北京 100049

收稿日期:2018-01-19 修回日期:2018-08-30 出版日期:2019-02-05 发布日期:2019-02-05
通讯作者: 徐宇兴,刘振法
作者简介:<named-content content-type="corresp-name">张利辉</named-content>（1977—），男，硕士，副研究员，主要从事锂离子电池电极材料的制备与开发。E-mail：<email>zlhkxy@126.com</email>。|徐宇兴，博士，项目研究员，硕士生导师，主要从事锂离子电池和超级电容器电极材料关键技术研发及产业化应用研究。E-mail：<email>yxxu@ipe.ac.cn</email>|刘振法，博士，研究员，博士生导师，主要从事能源材料及资源化利用研究。E-mail：<email>lzf63@sohu.com</email>
基金资助:
河北省重点基础研究(17964407D);河北省科技计划(17394411D，16294403D)

Synthesis and electrochemical properties of Li₄Ti₅O₁₂/graphene composite as an anode material for Li-ion batteries

Lihui ZHANG^1,^2,⁴(),Yuxing XU^1,³(),Zhenfa LIU²(),Aijia WEI²,Wen LI²

1. State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
2. Institute of Energy Resources, Hebei Academy of Sciences, Shijiazhuang 050081, Hebei, China
3. Zhongke Langfang Institute of Process Engineering, Langfang 065001, Hebei, China
4. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2018-01-19 Revised:2018-08-30 Online:2019-02-05 Published:2019-02-05
Contact: Yuxing XU,Zhenfa LIU

摘要/Abstract

摘要：

以Li₂CO₃、锐钛矿TiO₂和石墨烯为原料，采用固相球磨及喷雾干燥相结合的方法制备钛酸锂和钛酸锂/石墨烯复合负极材料。用X射线衍射（XRD）、拉曼光谱、扫描电子显微镜（SEM）表征了样品的晶体结构及形貌。通过恒流充放电测试样品的电化学性能，考察不同石墨烯添加量对钛酸锂材料电化学性能的影响。当石墨烯添加量质量分数为1%时，钛酸锂/石墨烯复合负极材料（LTO-G-2）具有优异的倍率性能及循环稳定性。在0.2C、0.5C、1C、3C、5C和10C倍率下的充电比容量为172.9mA·h/g、165.7mA·h/g、163.5mA·h/g、157.4mA·h/g、154.0mA·h/g和143.5mA·h/g。5C倍率下经历200次循环，容量保持率为94.8%。循环伏安测试(CV)表明LTO-G-2样品的极化程度是最小的。交流阻抗测试（EIS）结果显示LTO-G-2的电荷转移阻抗（69.6Ω）小于纯的钛酸锂的电荷转移阻抗（140.5Ω）。

关键词: 固相球磨, 喷雾干燥, 钛酸锂, 石墨烯, 负极材料

Abstract:

Li₄Ti₅O₁₂ and Li₄Ti₅O₁₂/graphene composite have been successfully prepared by a solid-state ball milling and spray drying method using Li₂CO₃, TiO₂ and graphene as starting materials. X-ray diffraction (XRD), scanning electron microscopy (SEM) and Raman spectroscopy were used to confirm the structure and morphology of the materials. The effects of the amount of graphene on the electrochemical properties of Li₄Ti₅O₁₂ were investigated by the galvanostatic charge-discharge tests. When 1% graphene was added, the Li₄Ti₅O₁₂/graphene composite (LTO-G-2) exhibited excellent performance with the charge capacities of 172.9mA·h/g, 165.7mA·h/g, 163.5mA·h/g, 157.4mA·h/g, 154.0mA·h/g and 143.5mA·h/g at rates of 0.2C, 0.5C, 1C, 3C, 5C and 10C, respectively. Moreover, LTO-G-2 showed a charge capacity retention of 94.8% after 200 cycles at a rate of 5C. Cyclic voltammetry tests (CV) showed that LTO-G-2 had the smallest polarization. Electrochemical impedance (EIS) tests showed that the charge transfer resistance of LTO-G-2 (69.6Ω) was lower than that of neat LTO (140.5Ω).

Key words: solid-state ball milling method, spray drying, lithium titanate, graphene, anode material

中图分类号:

TM914

张利辉, 徐宇兴, 刘振法, 魏爱佳, 李文. 钛酸锂/石墨烯复合负极材料的制备及电化学性能[J]. 化工进展, 2019, 38(02): 949-955.

Lihui ZHANG, Yuxing XU, Zhenfa LIU, Aijia WEI, Wen LI. Synthesis and electrochemical properties of Li₄Ti₅O₁₂/graphene composite as an anode material for Li-ion batteries[J]. Chemical Industry and Engineering Progress, 2019, 38(02): 949-955.

图/表 9

图1 纯LTO、LTO-G-1、LTO-G-2和LTO-G-3的X射线衍射图

图2 纯LTO和LTO-G-2的拉曼图

图3 纯LTO和LTO-G-2的扫描电镜图

图4 电压范围1～3V，纯LTO、LTO-G-1、LTO-G-2和LTO-G-3在不同倍率下的比容量、倍率性能曲线和充放电曲线

图5 纯LTO、LTO-G-1、LTO-G-2和LTO-G-3在5C倍率的循环性能

图6 电压范围1～2.5V，纯LTO、LTO-G-1、LTO-G-2和LTO-G-3在0.2mV/s扫描速率下的循环伏安曲线

表1 电压范围1~2.5V，纯LTO、LTO-G-1、LTO-G-2和LTO-G-3的阳极（φ pa，V）峰和阴极（φ pc，V）峰的电位差

纯LTO				LTO-G-1				LTO-G-2				LTO-G-3
φ _pa	φ _pc	?V		φ _pa	φ _pc	?V		φ _pa	φ _pc	?V		φ _pa	φ _pc	?V
1.450	1.679	0.230		1.458	1.669	0.211		1.460	1.665	0.205		1.459	1.667	0.208

图7 纯LTO、LTO-G-1、LTO-G-2和LTO-G-3的交流阻抗谱图

表2 由图7得到的交流阻抗参数

样品	R _s/Ω	R _ct/Ω
纯LTO	1.5	140.5
LTO-G-1	1.4	96.3
LTO-G-2	1.3	69.6
LTO-G-3	1.5	82.8

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钛酸锂/石墨烯复合负极材料的制备及电化学性能

Synthesis and electrochemical properties of Li₄Ti₅O₁₂/graphene composite as an anode material for Li-ion batteries

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Synthesis and electrochemical properties of Li₄Ti₅O₁₂/graphene composite as an anode material for Li-ion batteries