Ge4+、Sn4+掺杂尖晶石LiMn2O4的合成与电化学表征

doi:10.3866/PKU.WHXB201302211

物理化学学报 >> 2013, Vol. 29 >> Issue (04): 763-769.doi: 10.3866/PKU.WHXB201302211

Ge⁴⁺、Sn⁴⁺掺杂尖晶石LiMn₂O₄的合成与电化学表征

熊礼龙, 徐友龙, 陶韬

西安交通大学, 电子陶瓷与器件教育部重点实验室和国际电介质研究中心, 西安710049

收稿日期:2012-12-03 修回日期:2013-02-19 发布日期:2013-03-25
通讯作者: 徐友龙 E-mail:ylxuxjtu@mail.xjtu.edu.cn
基金资助:
国家自然科学基金(21203145)资助项目

Synthesis and Electrochemical Characterization of Ge⁴⁺, Sn⁴⁺ Doped Spinel LiMn₂O₄

XIONG Li-Long, XU You-Long, TAO Tao

Electronic Materials Research Laboratory, Key Laboratory of the Ministry of Education, Xi’an Jiaotong University, Xi’an 710049, P. R. China;International Center for Dielectric Research, Xi’an Jiaotong University, Xi’an 710049, P. R. China

Received:2012-12-03 Revised:2013-02-19 Published:2013-03-25
Supported by:
The project was supported by the National Natural Science Foundation of China (21203145).

摘要/Abstract

摘要：

使用Ge⁴⁺、Sn⁴⁺作为掺杂离子, 通过高温固相法制备四价阳离子掺杂改性的尖晶石LiMn₂O₄材料. X射线衍射(XRD)和扫描电子显微镜(SEM)分析表明, Ge⁴⁺离子取代尖晶石中Mn⁴⁺离子形成了LiMn_2-xGe_xO₄ (x=0.02,0.04, 0.06)固溶体; 而Sn⁴⁺离子则以SnO₂的形式存在于尖晶石LiMn₂O₄的颗粒表面. Ge⁴⁺离子掺入到尖晶石LiMn₂O₄材料中, 抑制了锂离子在尖晶石中的有序化排列, 提高了尖晶石LiMn₂O₄的结构稳定性; 而在尖晶石颗粒表面的SnO₂可以减少电解液中酸的含量, 抑制酸对LiMn₂O₄活性材料的侵蚀. 恒电流充放电测试表明, 两种离子改性后材料的容量保持率均有较大幅度的提升, 有利于促进尖晶石型LiMn₂O₄锂离子电池正极材料的商业化生产.

关键词: 尖晶石LiMn₂O₄, 锗掺杂, 锡掺杂, 固相反应, 循环性能

Abstract:

Spinel LiMn₂O₄ materials doped with tetravalent cations Ge⁴⁺ and Sn⁴⁺ were synthesized through solid-state reaction. Analysis of the materials by X-ray diffraction (XRD) and scanning electron microscopy (SEM) suggested that Ge⁴⁺ ions occupied octahedral sites by substituting Mn⁴⁺ ions in the spinel structure to form the solid solution LiMn_2-xGe_xO₄ (x=0.02, 0.04, 0.06), while Sn⁴⁺ ions were present at the surface of the spinel LiMn₂O₄ as SnO₂. The substitution of Mn⁴⁺ with Ge⁴⁺ could suppress the long-range ordering of the Li⁺ ions in the spinel LiMn₂O₄, enhancing its stability. SnO₂ on the surface of LiMn₂O₄ could reduce the acidity of the liquid electrolyte, suppressing acid etching of the LiMn₂O₄ active material. Galvanostatic charge/ discharge tests showed that both Ge⁴⁺ and Sn⁴⁺-modified spinel LiMn₂O₄ materials exhibited significantly higher capacity retention than LiMn₂O₄. The increased capacity retention should benefit the application of spinel LiMn₂O₄ as a cathode material for lithium-ion batteries.

Key words: Spinel LiMn₂O₄, Ge⁴⁺ doping, Sn⁴⁺ doping, Solid-state reaction, Cycleability

熊礼龙, 徐友龙, 陶韬. Ge⁴⁺、Sn⁴⁺掺杂尖晶石LiMn₂O₄的合成与电化学表征[J]. 物理化学学报, 2013, 29(04), 763-769. doi: 10.3866/PKU.WHXB201302211

XIONG Li-Long, XU You-Long, TAO Tao. Synthesis and Electrochemical Characterization of Ge⁴⁺, Sn⁴⁺ Doped Spinel LiMn₂O₄[J]. Acta Phys. -Chim. Sin. 2013, 29(04), 763-769. doi: 10.3866/PKU.WHXB201302211

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201302211

https://www.whxb.pku.edu.cn/CN/Y2013/V29/I04/763

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Ge⁴⁺、Sn⁴⁺掺杂尖晶石LiMn₂O₄的合成与电化学表征

Synthesis and Electrochemical Characterization of Ge⁴⁺, Sn⁴⁺ Doped Spinel LiMn₂O₄

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