LiODFB基电解液与高电压正极材料LiNi0.5Mn1.5O4的相容性*

doi:10.11901/1005.3093.2014.150

材料研究学报

2014, Vol. 28

Issue (10): 775-780 DOI: 10.11901/1005.3093.2014.150

本期目录 | 过刊浏览

LiODFB基电解液与高电压正极材料LiNi_0.5Mn_1.5O₄的相容性*

周宏明^1,²,耿文俊¹,李荐^1,²(

),杨杰²,姚书恒¹,孙文佼¹

1. 中南大学材料科学与工程学院长沙 410083
2. 湖南省正源储能材料与器件研究所长沙 410083

Compatibility of LiODFB Electrolyte with LiNi_0.5Mn_1.5O₄ as High-voltage Cathode Material

Hongming ZHOU^1,²,Wenjun GENG¹,Jian LI^1,^2,^**(

),Jie YANG²,Shuheng YAO¹,Wenjiao SUN¹

1. School of Materials Science and Engineering, Central South University, Changsha 410083
2. Hunan Province Zhengyuan Energy Storage Materials and Devices Research, Changsha 410083

引用本文:

周宏明,耿文俊,李荐,杨杰,姚书恒,孙文佼. LiODFB基电解液与高电压正极材料LiNi_0.5Mn_1.5O₄的相容性*[J]. 材料研究学报, 2014, 28(10): 775-780.
Hongming ZHOU, Wenjun GENG, Jian LI, Jie YANG, Shuheng YAO, Wenjiao SUN. Compatibility of LiODFB Electrolyte with LiNi_0.5Mn_1.5O₄ as High-voltage Cathode Material[J]. Chinese Journal of Materials Research, 2014, 28(10): 775-780.

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摘要:

研究了草酸二氟硼酸锂(LiODFB)基电解液与锂离子电池高电压正极材料锰酸镍锂(LiNi_0.5Mn_1.5O₄)的相容性, 结果表明: 在25℃和60℃, 以LiODFB 和六氟磷酸锂(LiPF₆)为电解液的LiNi_0.5Mn_1.5O₄/Li电池的CV曲线都具有单一的氧化还原峰, 电池的可逆性优良, 且LiODFB电池的循环性能优于LiPF₆电池。在25℃, LiODFB电池和LiPF₆电池以0.5C倍率首次充放电比容量分别为126.3 mAhg^-1、131.6 mAhg^-1, 经100次循环后容量保持率分别为97.1%、94.7%; 在60℃, LiODFB电池和LiPF₆电池以0.5C倍率首次充放电比容量分别为132.6 mAhg^-1、129.1 mAhg^-1, 经100次循环后容量保持率分别为94.1%、81.7%。电化学阻抗谱也表明: 在60℃, LiODFB电池的阻抗比LiPF₆电池的小, LiODFB电池具有更好的高温充放电性能。

关键词 ：材料科学基础学科, 草酸二氟硼酸锂, 锰酸镍锂, 电化学性能, 相容性

Abstract：

The compatibility of lithium di?uoro(oxalato)borate (LiODFB) electrolyte with LiNi_0.5Mn_1.5O₄ as high-voltage cathode material was investigated by cyclic voltammetry, charge-discharge test and AC impedance. The results show that the LiNi_0.5Mn_1.5O₄/Li half cells with LiODFB or LiPF₆ as electrolyte all have simple REDOX peak at 25℃ and 60℃, and the battery has an excellent reversibility. The battery with LiODFB has better cycle performance than that with LiPF6 at 25℃ and 60℃. Their 0.5C initial discharge specific capacities at 25℃ are 126.3 mAh?g^-1 and 131.6 mAh?g^-1, and the capacity retention ratios by the 100th cycle are 97.1 % and 94.7% respectively. The 0.5 C initial discharge specific capacities at 60℃are 132.6 mAhg^-1 and 129.1 mAhg^-1, and capacity retention ratios by the 100th cycle are 94.1% and 81.7% respectively. AC impedance plots also show that the battery with LiODFB has a lower charge-transfer resistance than that with LiPF6 at 60℃, indicating that the battery with LiODFB has excellent cyclic performance at high temperature.

Key words： foundational discipline in materials science lithium di?uoro(oxalato)borate LiNi_0.5Mn_1.5O₄ electrochemical performance compatibility

收稿日期: 2014-04-01

基金资助:* 湖南省科技计划2013GK3002和长沙市科技计划K1202039-11资助项目。

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https://www.cjmr.org/CN/10.11901/1005.3093.2014.150 或 https://www.cjmr.org/CN/Y2014/V28/I10/775

图1 LiNi0.5Mn1.5O4/Li电池在不同温度的循环伏安曲线

图2 LiNi0.5Mn1.5O4/Li电池在不同温度的首次充放电曲线

图3 LiNi0.5Mn1.5O4/Li电池在不同倍率下的循环性能曲线

图4 LiNi0.5Mn1.5O4/Li电池在不同温度的循环性能曲线

图5 LiNi0.5Mn1.5O4/Li电池在不同温度循环前后的EIS谱

图6 电解液体系的等效电路图

表1 不同温度下LiODFB与LiPF6在LiNi0.5Mn1.5O4/Li电池中的电阻值

图7 LiNi0.5Mn1.5O4/Li电池循环前后LiNi0.5Mn1.5O4极片的SEM像

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