水热法制备锂离子二次电池用球形Li4Ti5O12负极材料及其电化学性能

doi:10.15541/jim20160121

无机材料学报 ›› 2016, Vol. 31 ›› Issue (11): 1242-1248.DOI: 10.15541/jim20160121

水热法制备锂离子二次电池用球形Li₄Ti₅O₁₂负极材料及其电化学性能

闫慧¹, 其鲁², 张鼎³, 王正德¹, 刘云颖¹, 王晓霞¹, 朱铁勇⁴

(1. 内蒙古科技大学化学与化工学院, 包头 014010; 2. 北京大学化学与分子工程学院, 应用化学系, 新能源材料与技术实验室, 北京100871; 3. 太原理工大学化学化工学院, 应用化学系, 太原 030024; 4. 内蒙古包头民航机场有限责任公司, 包头 014040)

收稿日期:2016-03-07 修回日期:2016-04-08 出版日期:2016-11-10 网络出版日期:2016-10-25
基金资助:
内蒙古自然科学基金(2014BS0203);内蒙古高等学校科学研究项目(NJZZ14160);内蒙古科技大学创新基金(2014QDL028)

Hydrothermal Synthesis and Electrochemical Performance of Spherical Li₄Ti₅O₁₂ as Anode Material for Lithium-ion Secondary Battery

YAN Hui¹, Qi Lu², ZHANG Ding³, WANG Zheng-De¹, LIU Yun-Ying¹, WANG Xiao-Xia¹, ZHU Tie-Yong⁴

(1. School of Chemistry and Chemical Engineering, Inner Mongolia University of Science and Technology, Baotou 014010, China; 2. New Energy Materials and Technology Laboratory, Department of Applied Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China; 3. Department of Applied Chemistry, College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China; 4. Inner Mongolia Baotou Civil Airport Co., Ltd., Baotou 014000, China)

Received:2016-03-07 Revised:2016-04-08 Published:2016-11-10 Online:2016-10-25
Supported by:
Natural Science Foundation of Inner Mongolia (2014BS0203);Items of Institution of Higher Education Scientific Research of Inner Mongolia (NJZZ14160);Inner Mongolia University of Science and Technology Innovation Fund (2014QDL028)

摘要/Abstract

摘要：

以LiOH溶液和不同粒径的自制球形TiO₂为反应物, 通过水热法快速地合成了尖晶石型结构的球形Li₄Ti₅O₁₂, 并考察了材料合成的水热反应机理和电化学性能。TiO₂在100℃、5 mol/L LiOH溶液中经水热反应20 h得到前驱体, 再经800℃热处理2 h便可得到粒径大小不同(0.5~1.5 µm)且分布均匀的球形尖晶石Li₄Ti₅O₁₂材料。LiOH在水热反应条件下扩散到球形TiO₂内部, 得到在分子水平混合均匀的Li-Ti-O中间体, 利于高温下生成纯相的尖晶石Li₄Ti₅O₁₂。所得粒径大小不同的Li₄Ti₅O₁₂材料均表现出稳定的电化学循环充放电性能, 其中, 粒径为0.5 µm 的Li₄Ti₅O₁₂材料的电化学性能最好: 室温下, 以0.2 C的倍率进行充放电, 其可逆容量达到158 mAh/g, 70周后容量保持率高于99%; 同时还表现出优异的高温循环稳定性, 55℃下以0.2 C的倍率进行充放电, 50次循环后其可逆放电比容量仍能达到125 mAh/g。

关键词: 锂离子二次电池, 水热法, 球形, Li4Ti5O12

Abstract:

Self-made TiO₂ with different particle sizes was adopted to react in LiOH solution via a fast hydrothermal process, from which spherical spinel lithium titanium oxide Li₄Ti₅O₁₂ was efficiently prepared. In detail, precursor was obtained from hydrothermal reaction between TiO₂ with 5 mol/L LiOH solution at 100℃ for 20 h, and Li₄Ti₅O₁₂ was synthesized by calcining the precursor at 800℃ for 2 h. The mechanism of the hydrothermal process discussed show that an even Li-Ti-O mixture is formed during Li cation diffusing into the TiO₂, resulting in the structure conversion to pure Li₄Ti₅O₁₂ fast at high temperature. While all the obtained Li₄Ti₅O₁₂ with different particle sizes show stable electrochemical cycling ability, the 0.5 µm Li₄Ti₅O₁₂ exhibits optimal electrochemical performance. Its initial discharge capacity reaches 158 mAh/g at 0.2 C and more than 99% of capacity is retained after 70 cycles, while the reversible capability readily exceeds 125 mAh/g after 50 cycles at 0.2 C at 50℃.

Key words: lithium-ion secondary battery, hydrothermal synthesis, spherical, Li4Ti5O12

中图分类号:

O646

闫慧, 其鲁, 张鼎, 王正德, 刘云颖, 王晓霞, 朱铁勇. 水热法制备锂离子二次电池用球形Li₄Ti₅O₁₂负极材料及其电化学性能[J]. 无机材料学报, 2016, 31(11): 1242-1248.

YAN Hui, Qi Lu, ZHANG Ding, WANG Zheng-De, LIU Yun-Ying, WANG Xiao-Xia, ZHU Tie-Yong. Hydrothermal Synthesis and Electrochemical Performance of Spherical Li₄Ti₅O₁₂ as Anode Material for Lithium-ion Secondary Battery[J]. Journal of Inorganic Materials, 2016, 31(11): 1242-1248.

图/表 7

图1 水热法所得前驱体(a)和固相法机械研磨所得混合物(b)的TG-DSC曲线

Fig. 1 TG-DSC curves of (a) precursor obtained by hydrothermal method and (b) mechanical mixture of TiO2 and LiOH·H2O obtained by solid-state method

图2 TiO2与不同浓度LiOH溶液(1 mol/L和5 mol/L)反应所得前驱体的XRD图谱

Fig. 2 XRD pattern of the precursors obtained from the hydrothermal reaction between TiO2 and LiOH solution with different concentrations (1 mol/L and 5 mol/L)

图3 水热反应所得前驱体(P1和P2)经800℃高温热处理2~ 10 h所得Li4Ti5O12样品的XRD图谱

Fig. 3 XRD patterns of the product by calcining precursor (P1 and P2) at 800℃ for 2 to 10 h

图4 水热法制备的不同粒径大小的Li4Ti5O12的XRD图谱

Fig. 4 XRD patterns of Li4Ti5O12 obtained by the hydrothermal method with different particle sizes

图5 水热反应所得前驱体(a′-c′)和高温处理后所得不同粒径大小的Li4Ti5O12 (a-c)的SEM图片

Fig. 5 SEM images of precursors (a′-c′) after hydrothermal reaction and the final spherical Li4Ti5O12 (a-c) samples with different particle sizes (a) 0.5 µm; (b) 1.0 µm; (c) 1.5 µm

图6 不同粒径大小Li4Ti5O12材料在不同充放电倍率下的放电比容量-循环图

Fig. 6 Cycle performance of Li4Ti5O12 with different particle sizes at various charge/discharge rates

图7 不同粒径Li4Ti5O12材料(0.5 ~1.5 μm)的高温循环容量图

Fig. 7 Cycle performance of as-obtained different particle sizes (0.5~1.5 μm) Li4Ti5O12 under high temperature

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水热法制备锂离子二次电池用球形Li₄Ti₅O₁₂负极材料及其电化学性能

Hydrothermal Synthesis and Electrochemical Performance of Spherical Li₄Ti₅O₁₂ as Anode Material for Lithium-ion Secondary Battery

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