LiBOB对Li1.15Ni0.68Mn1.32O4电极电化学行为的影响

doi:10.7503/cjcu20140836

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (4): 739.doi: 10.7503/cjcu20140836

LiBOB对Li_1.15Ni_0.68Mn_1.32O₄电极电化学行为的影响

姜雪, 史楠楠, 张莹, 程魁, 叶克, 王贵领, 曹殿学()

超轻材料与表面技术教育部重点实验室, 哈尔滨工程大学材料科学与化学工程学院, 哈尔滨 150001

收稿日期:2014-09-15 出版日期:2015-04-10 发布日期:2015-03-27
作者简介:联系人简介: 曹殿学, 男, 博士, 教授, 博士生导师, 主要从事燃料电池、锂离子电池及超级电容器电极材料研究. E-mail: caodianxue@hrbeu.edu.cn
基金资助:
黑龙江省重大科技招标项目(批准号: GA14A101)和哈尔滨市应用技术研究与开发项目(批准号: 2014DB4AG016)资助

Influence of LiBOB on the Electrochemical Performance of Li_1.15Ni_0.68Mn_1.32O₄ Electrode^†

JIANG Xue, SHI Nannan, ZHANG Ying, CHENG Kui, YE Ke, WANG Guiling, CAO Dianxue^*()

Key Laboratory of Superlight Materials and Surface Technology of Ministry of Education,College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China

Received:2014-09-15 Online:2015-04-10 Published:2015-03-27
Contact: CAO Dianxue E-mail:caodianxue@hrbeu.edu.cn
Supported by:
† Supported by the Major Project of Science and Technology of Heilongjiang Province, China(No.GA14A101) and the Project of Research and Development of Applied Technology of Harbin, China(No.2014DB4AG016).

摘要/Abstract

摘要：

采用恒电流充放电技术研究了锂离子电池电解液添加剂双草酸硼酸锂(LiBOB)对Li_1.15Ni_0.68Mn_1.32O₄电极电化学性能的影响, 用X射线衍射(XRD)、衰减全反射傅里叶变换红外光谱(FTIR-ATR)、电感耦合等离子体发射光谱(ICP)、扫描电子显微镜(SEM)和电化学阻抗谱(EIS)分析了LiBOB对Li_1.15Ni_0.68Mn_1.32O₄电极性能的影响. 结果显示, LiBOB作为电解液添加剂能显著改善Li_1.15Ni_0.68Mn_1.32O₄电极的循环性能, 原因是LiBOB在充放电过程中会在Li_1.15Ni_0.68Mn_1.32O₄电极表面发生分解, 分解产物在电极表面沉积形成固体电解质界面(SEI)膜, SEI膜能够有效抑制Li_1.15Ni_0.68Mn_1.32O₄电极材料中Mn的溶解, 确保其晶体结构的稳定性, 从而提高Li_1.15Ni_0.68Mn_1.32O₄电极的循环性能.

关键词: 双草酸硼酸锂, 电解液添加剂, 固体电解质界面膜, 锰溶解

Abstract:

The influence of electrolyte additive lithium bis(oxalate)borate(LiBOB) on the electrochemistry performance of Li_1.15Ni_0.68Mn_1.32O₄ electrode was studied by means of galvanostatic charge-discharge. X-ray diffraction(XRD), Fourier transform infrared attenuated total reflectance(FTIR-ATR) spectroscopy, inductively coupled plasma-atomic emission spectrometry(ICP-AES), scanning electron microscopy(SEM) and electrochemical impedance spectroscopy(EIS) were used to investigate the influence. The results show that the cyclic performance of Li_1.15Ni_0.68Mn_1.32O₄ electrode is improved apparently by the addition of LiBOB, and the reason is that LiBOB may decompose during the charge-discharge process and the decomposition product further deposites on the surface of Li_1.15Ni_0.68Mn_1.32O₄ electrode, forming solid electrolyte interface(SEI) film, inhibiting the dissolution of Mn and keeping the crystal structure of Li_1.15Ni_0.68Mn_1.32O₄ stable, therefore, the cyclic performance of Li_1.15Ni_0.68Mn_1.32O₄ is improved.

Key words: Lithium bis(oxalate)borate(LiBOB), Electrolyte additive, Solid electrolyte interface(SEI) film, Mn dissolution

中图分类号:

O646

TrendMD:

姜雪, 史楠楠, 张莹, 程魁, 叶克, 王贵领, 曹殿学. LiBOB对Li_1.15Ni_0.68Mn_1.32O₄电极电化学行为的影响. 高等学校化学学报, 2015, 36(4): 739.

JIANG Xue, SHI Nannan, ZHANG Ying, CHENG Kui, YE Ke, WANG Guiling, CAO Dianxue. Influence of LiBOB on the Electrochemical Performance of Li_1.15Ni_0.68Mn_1.32O₄ Electrode^†. Chem. J. Chinese Universities, 2015, 36(4): 739.

图/表 5

Fig.1 Cyclic performance and coulombic efficiency of LNMO/Li cells(A), discharge curves of LNMO/Li cells before and after 100 cycles(B) and cyclic performance of LNMO/CLTO cells at room tem-perature(C) and 40 ℃(D) The inset of (C) shows the cyclic performance and coulombic efficiency of CLTO/Li cells.

Fig.2 XRD patterns(A), FTIR-ATR spectra(B) and ICP results(C) of LNMO electrodes before(a) and after(b, c) 100 cycles b. 0#; c. 1#.

Fig.3 SEM images of LNMO electrodes before(A, A') and after(B, B', C, C') 100 cycles (B), (B') 0#; (C), (C') 1#.

Fig.4 EIS of LNMO electrodes before(A) and after 100 cycles(B)

Fig.5 Schematics of the effect of LiBOB on the surface of LNMO electrode (A) Before cycles; (B) after cycles without LiBOB; (C) after cycles with LiBOB.

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LiBOB对Li_1.15Ni_0.68Mn_1.32O₄电极电化学行为的影响

Influence of LiBOB on the Electrochemical Performance of Li_1.15Ni_0.68Mn_1.32O₄ Electrode^†

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