新型锂盐Li[(CF3SO2)(n-C4F9SO2)N]电解液在高电压LiNi0.5Mn1.5O4电池中的性能

doi:10.7503/cjcu20170745

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (7): 1518.doi: 10.7503/cjcu20170745

新型锂盐Li[(CF₃SO₂)(n-C₄F₉SO₂)N]电解液在高电压LiNi_0.5Mn_1.5O₄电池中的性能

仝博^1,², 张仲祥^2,³, 刘圳杰^2,³, 彭章泉²(), 周志彬¹()

1. 能量转换与储存材料化学教育部重点实验室, 华中科技大学化学与化工学院, 武汉 430074
2. 电分析化学国家重点实验室, 中国科学院长春应用化学研究所, 长春 130022
3. 中国科学技术大学应用化学与工程学院, 合肥 230026

收稿日期:2017-11-17 出版日期:2018-07-10 发布日期:2018-06-09
作者简介:联系人简介: 周志彬, 男, 博士, 教授, 博士生导师, 主要从事有机氟化学和电解液材料研究. E-mail: zb-zhou@mail.hust.edu.cn; 彭章泉, 男, 博士, 研究员, 博士生导师, 主要从事现场电化学、光谱电化学和电极反应动力学研究. E-mail: zqpeng@ciac.ac.cn
基金资助:
国家自然科学基金(批准号: 51172083)和国防科技创新特区基金(批准号: 17-163-13-XJ-004-003-03)资助.

Novel Electrolyte Containing Li[(CF₃SO₂)(n-C₄F₉SO₂)N] for High Voltage LiNi_0.5Mn_1.5O₄-based Cell^†

TONG Bo^1,², ZHANG Zhongxiang^2,³, LIU Zhenjie^2,³, PENG Zhangquan^2,^*(), ZHOU Zhibin^1,^*()

1. Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education,School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology,Wuhan 430074, China
2. State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry,Chinese Academy of Sciences, Changchun 130022, China
3. School of Applied Chemistry and Engineering, University of Science and Technology of China,Hefei 230026, China

Received:2017-11-17 Online:2018-07-10 Published:2018-06-09
Contact: PENG Zhangquan,ZHOU Zhibin E-mail:zqpeng@ciac.ac.cn;zb-zhou@mail.hust.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.51172083) and the National Defense Science and Technology Innovation Special Zone Foundation of China(No.17-163-13-XJ-004-003-03).

摘要/Abstract

摘要：

探讨一种新型磺酰亚胺锂盐(三氟甲基磺酰)(全氟丁基磺酰)亚胺锂 {Li[(CF₃SO₂)(n-C₄F₉SO₂)N], LiTNFSI}的碳酸丙烯酯(PC)电解液的电导率、耐氧化性及基于该电解液的LiNi_0.5Mn_1.5O₄??Li电池循环性能和自放电行为. 结果表明, 1.0 mol/L LiTNFSI-PC电解液的室温电导率适中, 氧化电位较高, 并且基于该电解液的LiNi_0.5Mn_1.5O₄??Li电池表现出优异的循环性能, 综合性能明显优于1.0 mol/L LiPF₆-PC电解液体系. 这主要得益于1.0 mol/L LiTNFSI PC 电解液与LiNi_0.5Mn_1.5O₄良好的界面匹配性.

关键词: 锂离子电池, LiNi_0.5Mn_1.5O₄??Li电池, 电解液, (三氟甲基磺酰)(全氟丁基磺酰)亚胺锂, 界面匹配性, 碳酸丙烯酯

Abstract:

A novel electrolyte based on lithium(trifluoromethanesulfonyl)-(n-nonafluorobutanesulfonyl)imide {Li[(CF₃SO₂)(n-C₄F₉SO₂)N], LiTNFSI} and propylene carbonate(PC) for LiNi_0.5Mn_1.5O₄??Li cell was reported. The specific conductivity, anodic stability of the 1.0 mol/L LiTNFSI-PC(propylene carbonate) and the cycling performance of LiNi_0.5Mn_1.5O₄??Li cell were investigated. It is found that the 1.0 mol/L LiTNFSI-PC delivers decent specific conductivity(3.6 mS/cm) and high anodic stability[5.72 V(vs. Li/Li⁺)]. Furthermore, the LiNi_0.5Mn_1.5O₄??Li cell with 1.0 mol/L LiTNFSI-PC keeps capacity retention up to 99.7% after 100 cycles at 0.2C and the open circuit voltage stays up to 4.68 V after aging at 60 ℃ for 30 h, which is much better than that in LiPF₆-based electrolyte. This excellent electrochemical performance of LiNi_0.5Mn_1.5O₄??Li cell with 1.0 mol/L LiTNFSI-PC is mainly ascribed to the relatively high-quality cathode electrolyte interphase formed on LiNi_0.5Mn_1.5O₄.

Key words: Lithium-ion battery, LiNi_0.5Mn_1.5O₄??Li cell, Electrolyte, Lithium(trifluoromethanesulfonyl)-(n-nonafluorobutanesulfonyl)imide, Interface compatibility, Propylene carbonate

中图分类号:

O646

TrendMD:

仝博, 张仲祥, 刘圳杰, 彭章泉, 周志彬. 新型锂盐Li[(CF₃SO₂)(n-C₄F₉SO₂)N]电解液在高电压LiNi_0.5Mn_1.5O₄电池中的性能. 高等学校化学学报, 2018, 39(7): 1518.

TONG Bo, ZHANG Zhongxiang, LIU Zhenjie, PENG Zhangquan, ZHOU Zhibin. Novel Electrolyte Containing Li[(CF₃SO₂)(n-C₄F₉SO₂)N] for High Voltage LiNi_0.5Mn_1.5O₄-based Cell^†. Chem. J. Chinese Universities, 2018, 39(7): 1518.

图/表 7

Fig.1 Ionic conductivity of 1.0 mol/L LiTNFSI-PC(a) and 1.0 mol/L LiPF6-PC(b) electrolytes as a function of temperature

Fig.2 Linear sweep voltammetry curves obtained on planner Pt electrode of two [LiTNFSI-PC(a) and LiPF6-PC(b)] at 1 mV/s from the open circuit voltage to 6.0 V(vs. Li/Li+)

Fig.3 Charge/discharge curves of the LiNi0.5Mn1.5O4??Li cells with 1.0 mol/L LiTNFSI-PC(A) and LiPF6-PC(B) electrolytes, respectively

Fig.4 Cycling performance of the LiNi0.5Mn1.5O4??Li cells with 1.0 mol/L LiTNFSI-PC and LiPF6-PC electrolytes at room temperature

Fig.5 Self-discharge curves of LiNi0.5Mn1.5O4??Li cells storage at 60 ℃ with 1.0 mol/L LiPF6-PC(a) and LiTNFSI-PC(b) electrolytes at full-charged state

Fig.6 SEM images of the LiNi0.5Mn1.5O4 surfaces after cycling 10 cycles in the LiNi0.5Mn1.5O4??Li at 0.2C(A) pristine LiNi0.5Mn1.5O4 and the electrodes cycled in 1.0 mol/L LiPF6-PC(B) and 1.0 mol/L LiTNFSI-PC(C), respectively

Fig.7 XPS spectra of the LiNi0.5Mn1.5O4 in the LiNi0.5Mn1.5O4??Li cells after 10 cycles at 0.2C, as well as the fresh one for comparison^ (A) C1s; (B) F1s. a. Fresh; b. LiPF6; c. LiTNFSI.

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新型锂盐Li[(CF₃SO₂)(n-C₄F₉SO₂)N]电解液在高电压LiNi_0.5Mn_1.5O₄电池中的性能

Novel Electrolyte Containing Li[(CF₃SO₂)(n-C₄F₉SO₂)N] for High Voltage LiNi_0.5Mn_1.5O₄-based Cell^†

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