纳米级Li4Ti5O12负极材料的制备及其输运特性

doi:10.11868/j.issn.1001-4381.2019.000955

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摘要

以酞酸丁酯和乙酸锂为前驱体，通过溶胶凝胶法成功制备了纳米钛酸锂Li₄Ti₅O₁₂(LTO)负极材料。采用X射线衍射分析、扫描电镜(SEM)和透射电镜(TEM)分别对材料的物相与形貌进行了表征分析，并研究了煅烧条件和包覆改性对LTO输运特性的影响。研究表明，煅烧温度为800℃，时间为10 h条件下制备的样品的输运特性最佳，离子电导率为8.8×10^-8 S/cm，电子电导率为8.53×10^-10 S/cm。均匀的碳包覆层可以有效地改善样品的输运特性，LTO/C复合活性材料的离子与电子电导率分别达到4.35×10^-7 S/cm和9.63×10^-8 S/cm。电化学性能测试表明，碳包覆后的活性材料在0.1 C倍率下首次放电容量可达172.4 mAh/g；在5 C高倍率下循环充放电50次后，容量保持率可达94.4%，表现出较好的电化学性能。

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	廉恬柔
	卢玉晓
	吴冰
	石光跃
	马蕾
	刘磊
	娄建忠

关键词 ：溶胶凝胶法, 负极材料, 钛酸锂, 电导率

Abstract：

Li₄Ti₅O₁₂ (LTO) anode materials are successfully prepared by sol-gel method using butyl phthalate and lithium acetate as precursors.The phase and morphology of the material were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The effects of calcination conditions and coating modification on transport properties of LTO were also studied.The results show that the ionic conductivity and electronic conductivity of the sample prepared at 800 ℃ and 10 h are 8.8×10^-8 S/cm and 8.53×10^-10 S/cm, respectively. The ionic and electronic conductivities of LTO/C are 4.35×10^-7 S/cm and 9.63×10^-8 S/cm, respectively.The electrochemical performance tests show that the first discharge capacity of carbon-coated active materials can reach 172.4 mAh/g at the ratio of 0.1 C.After 50 cycles at 5 C, the capacity retention rate can reach 94.4%, indicating a good electrochemical performance of the samples.

Key words： sol-gel method anode material lithium titanate conductivity

收稿日期: 2020-10-17 出版日期: 2021-03-20

中图分类号:	TM912
	O484.3

基金资助:天津市重点研究开发项目(19YFHBQY00030);河北省自然科学基金(F2017201130)

作者简介: 娄建忠(1966-), 男, 教授, 博士, 研究方向为半导体材料、锂离子电池, 联系地址: 河北省保定市七一东路2666号河北大学电子信息工程学院(071002), E-mail: jzhlou@163.com

引用本文:

廉恬柔, 卢玉晓, 吴冰, 石光跃, 马蕾, 刘磊, 娄建忠. 纳米级Li₄Ti₅O₁₂负极材料的制备及其输运特性[J]. 材料工程, 2021, 49(3): 59-66.
Tian-rou LIAN, Yu-xiao LU, Bing WU, Guang-yue SHI, Lei MA, Lei LIU, Jian-zhong LOU. Preparation and transport property of nano-Li₄Ti₅O₁₂ anode materials. Journal of Materials Engineering, 2021, 49(3): 59-66.

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http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2019.000955 或 http://jme.biam.ac.cn/CN/Y2021/V49/I3/59

Fig.1 不同煅烧条件下合成LTO的XRD谱图
(a)不同温度下煅烧10 h后产物的XRD谱图；(b) 在800 ℃下不同煅烧时间后产物的XRD谱图

Fig.2 不同煅烧温度下合成LTO的SEM图
(a)600 ℃；(b)700 ℃；(c)800 ℃；(d)900 ℃

Fig.3 LTO/C样品物相与形貌分析
(a)SEM图；(b)TEM图；(c) 高分辨图像与选区电子衍射斑点

Fig.4 不同煅烧条件下的LTO本征电导率
(1)煅烧温度和时间对LTO交流阻抗的影响；(2)煅烧温度和时间对LTO电子电导率的影响；(a)煅烧温度; (b)煅烧时间；(c)LTO离子电导率在不同煅烧条件下的变化趋势；(d)LTO电子电导率在不同煅烧条件下的变化趋势

Fig.5 不同煅烧条件下LTO/C的电导率
(1)煅烧温度和时间对LTO/C交流阻抗的影响；(2)煅烧温度和时间对LTO/C电子电导率的影响；(a)煅烧温度; (b)煅烧时间; (c)LTO/C离子电导率在不同煅烧条件下的变化趋势；(d)LTO/C电子电导率在不同煅烧条件下的变化趋势

Fig.6 以LTO与LTO/C为负极材料制成的半电池的化学性能
(a)0.1 C倍率下首次充放电测试图；(b)倍率性能；(c)5 C倍率下的循环性能分析

Table 1 Li₄Ti₅O₁₂负极材料的电化学性能

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