新型导电盐(三氟甲基磺酰)(三氟乙氧基磺酰)亚胺锂及其非水电解液的制备与性能

doi:10.7503/cjcu20131260

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (8): 1771.doi: 10.7503/cjcu20131260

新型导电盐(三氟甲基磺酰)(三氟乙氧基磺酰)亚胺锂及其非水电解液的制备与性能

刘成勇¹, 张恒¹, 郑丽萍¹, 徐飞¹, 冯文芳¹, 聂进¹(), 黄学杰², 周志彬¹()

1. 大型电池关键材料与系统教育部重点实验室, 华中科技大学化学与化工学院, 武汉 430074
2. 中国科学院物理研究所, 北京 100190

收稿日期:2013-12-23 出版日期:2014-08-10 发布日期:2014-04-29
作者简介:联系人简介: 聂进, 男, 博士, 教授, 博士生导师, 主要从事有机氟化学和含氟有机功能材料研究.E-mail:niejin@mail.hust.edu.cn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质材料研究. E-mail: zb-zhou@mail.hust.edu.cn
基金资助:
国家自然科学基金(批准号: 51172083)资助

Preparation and Properties of Lithium(trifluoromethanesulfonyl)-(trifluoroethoxysulfonyl)imide as Conducting Salt for Nonaqueous Electrolyte Solutions^†

LIU Chengyong¹, ZHANG Heng¹, ZHENG Liping¹, XU Fei¹, FENG Wenfang¹, NIE Jin^1,^*(), HUANG Xuejie², ZHOU Zhibin^1,^*()

1. Key Laboratory for Large-Format Battery Materials and System, Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
2. Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China

Received:2013-12-23 Online:2014-08-10 Published:2014-04-29
Contact: NIE Jin,ZHOU Zhibin E-mail:niejin@mail.hust.edu.cn;zb-zhou@mail.hust.edu.cn
Supported by:
Supported by the National Natural Science Foundation of China(No.51172083)

摘要/Abstract

摘要：

制备了一种新型含氟磺酰亚胺锂盐(三氟甲基磺酰)(三氟乙氧基磺酰)亚胺锂{Li[(CF₃SO₂)·(CF₃CH₂OSO₂)N], Li[TFO-TFSI]}及其与碳酸乙烯酯(EC)/碳酸甲乙酯(EMC)混合溶剂(3∶7, 体积比)组成的非水电解液. 采用核磁共振波谱(NMR)、红外光谱(IR)、质谱(MS)、元素分析(EA)和离子色谱(IC)等手段对合成锂盐Li[TFO-TFSI]进行了结构表征及纯度分析. 通过差示量热扫描(DSC)和热重分析(TG)对Li[TFO-TFSI]及其电解液1.0 mol/L Li[TFO-TFSI]-EC/EMC(3∶ 7)的热学性质进行了表征. 采用交流阻抗(EIS)、循环伏安(CV)、计时安培法及扫描电子显微镜(SEM)等对Li[TFO-TFSI]/碳酸酯电解液的基础物化和电化学性质进行了表征. 结果表明, Li[TFO-TFSI]/碳酸酯电解液具有较好的电化学稳定性; 在4.2 V(vs. Li/Li⁺)以下Al箔不发生腐蚀; 室温下基于Li[TFO-TFSI]/碳酸酯电解液的Li/人造石墨和人造石墨/LiCoO₂电池均保持较好的循环性能, 特别是人造石墨/LiCoO₂锂离子电池循环100周后, 其比容量保持率明显高于相应的基于LiPF₆/碳酸酯电解液体系的电池.

关键词: 锂离子电池, 非水电解液, (三氟甲基磺酰)(三氟乙氧基磺酰)亚胺锂, Al箔腐蚀

Abstract:

A novel lithium salt, lithium(trifluoromethanesulfonyl)(trifluoroethoxysulfonyl)imide{Li[(CF₃SO₂)(CF₃CH₂OSO₂)N], Li[TFO-TFSI]}, and the corresponding nonaqueous electrolytes of 1.0 mol/L Li[TFO-TFSI] in a mixture of ethylene carbonate/ethyl methyl carbonate(EC/EMC, 3∶7, volume ratio) were prepared. The structure, composition and purity of the as-prepared Li[TFO-TFSI] were confirmed by nuclear magnetic resonance spectroscopy(NMR), infrared spectroscopy(IR), mass spectrometry(MS), elemental analysis(EA), and ion chromatography(IC). The thermal properties of Li[TFO-TFSI] and its nonaqueous electrolytes, 1.0 mol/L Li[TFO-TFSI]-EC/EMC(3∶7), were characterized by differential scanning calorimetry(DSC) and thermogravimetric analysis(TGA). The fundamental properties of nonaqueous electrolyte solution of Li[TFO-TFSI] were characterized by electrochemical impedance spectroscopy(EIS), cyclic voltammetry(CV), chronoamperometry and scanning electron microscope(SEM). The nonaqueous electrolytes of Li[TFO-TFSI] shows excellent electrochemical stability, and does not corrode Al below 4.2 V. Both Li/synthetic graphite and synthetic graphite/LiCoO₂ cells using Li[TFO-TFSI] show good cycling performances at room temperature, and the graphite/LiCoO₂ cells using Li[TFO-TFSI] shows much better capacity retention after 100 cycles than those using LiPF₆.

Key words: Lithium-ion battery, Nonaqueous electrolyte, Lithium(trifluoromethanesulfonyl)(trifluoroethoxysulfonyl)imide{Li[TFO-TFSI]}, Al foil corrosion

中图分类号:

O646

TrendMD:

刘成勇, 张恒, 郑丽萍, 徐飞, 冯文芳, 聂进, 黄学杰, 周志彬. 新型导电盐(三氟甲基磺酰)(三氟乙氧基磺酰)亚胺锂及其非水电解液的制备与性能. 高等学校化学学报, 2014, 35(8): 1771.

LIU Chengyong, ZHANG Heng, ZHENG Liping, XU Fei, FENG Wenfang, NIE Jin, HUANG Xuejie, ZHOU Zhibin. Preparation and Properties of Lithium(trifluoromethanesulfonyl)-(trifluoroethoxysulfonyl)imide as Conducting Salt for Nonaqueous Electrolyte Solutions^†. Chem. J. Chinese Universities, 2014, 35(8): 1771.

图/表 15

Fig.1 1H NMR(A), 19F NMR(B), MS(C) and IR(D) spectra of Li[TFO-TFSI] salt

Fig.2 DSC(A) and TG(B) curves for Li[TFO-TFSI] salt

Table 1 Density(ρ), viscosity(η), ionic conductivity(κ) and lithium-ion transference number(tLi+) at 25 ℃, van der Waals volume(Va) of anion[10], glass transition temperature(Tg) and the parameters of VTF equation for various electrolytes

Electrolyte	ρ/(g·mL^-1)	η/(mPa·s^-1)	κ/(mS·cm^-1)	$t L i +$	V_a/nm³	T_g/K	k(T)=AT^-1/2exp[-B/(T-T₀)]
Electrolyte	ρ/(g·mL^-1)	η/(mPa·s^-1)	κ/(mS·cm^-1)	$t L i +$	V_a/nm³	T_g/K	T₀/K	A/(S·m^-1·K^-1/2)	B/K	R²
Li[TFO-TFSI]	1.26	3.78	4.60	0.37	0.176	171	130	2.32	565	0.9999
LiBF₄	1.16	2.23	3.72	0.31	0.049	154	127	1.55	543	0.9999
LiClO₄	1.18	2.77	6.26	0.40	0.055	152	137	2.54	509	0.9999
LiPF₆	1.21	3.00	9.33	0.48	0.069	193	153	2.86	418	0.9999
LiTFSI	1.23	3.40	7.57	0.55	0.147	156	151	2.10	408	0.9999

Electrolyte	ρ/(g·mL^-1)	η/(mPa·s^-1)	κ/(mS·cm^-1)	$t L i +$	V_a/nm³	T_g/K	k(T)=AT^-1/2exp[-B/(T-T₀)]
Electrolyte	ρ/(g·mL^-1)	η/(mPa·s^-1)	κ/(mS·cm^-1)	$t L i +$	V_a/nm³	T_g/K	T₀/K	A/(S·m^-1·K^-1/2)	B/K	R²
Li[TFO-TFSI]	1.26	3.78	4.60	0.37	0.176	171	130	2.32	565	0.9999
LiBF₄	1.16	2.23	3.72	0.31	0.049	154	127	1.55	543	0.9999
LiClO₄	1.18	2.77	6.26	0.40	0.055	152	137	2.54	509	0.9999
LiPF₆	1.21	3.00	9.33	0.48	0.069	193	153	2.86	418	0.9999
LiTFSI	1.23	3.40	7.57	0.55	0.147	156	151	2.10	408	0.9999

Fig.3 DSC curves for electrolyte solutions and various lithium salts[1.0 mol/L lithium salts in EC/EMC(3∶7, volume ratio)] a. EC/EMC(3∶7); b. Li[TFO-TFSI]; c. LiBF4; d. LiClO4; e. LiPF6; f. LiTFSI.

Fig.4 1H NMR(A) and 19F NMR(B) spectra of fresh solution of 1.0 mol/L Li[TFO-TFSI]-EC/EMC(3∶7)

Fig.5 1H NMR(A) and 19F NMR(B) spectra of electrolyte solutions of 1.0 mol/L Li[TFO-TFSI]-EC/EMC(3∶7) after aging at 85 ℃ for 14 d

Fig.6 Vogel-Tammann-Fulcher plots of electrolyte solutions of 1.0 mol/L Li[TFO-TFSI], LiBF4, LiClO4, LiPF6 and LiTFSI in EC/EMC(3∶7)

Fig.7 Impedance spectra of electrolyte solutions of 1.0 mol/L Li[TFO-TFSI]-EC/EMC(3∶7) before polarization(A) and time-dependence response of dc polarization of 1.0 mol/L Li[TFO-TFSI]-EC/EMC(3∶7) with an applied voltage of 10 mV(B)

Fig.8 Cyclic voltammogram of electrolyte solutions of 1.0 mol/L Li[TFO-TFSI]-EC/EMC(3∶7) Working electrode: Pt; reference and counter electrode: Li; scan rate: 0.5 mV/s.

Fig.9 Cyclic voltammograms of electrolyte solutions of 1.0 mol/L Li[TFO-TFSI]-(A) and LiTFSI(B) in EC/EMC(3∶7) Working electrode: Al; reference and counter electrode: Li; scan rate: 1.0 mV/s.

Fig.10 SEM images of Al foil after testing of cyclic voltammograms in electrolyte solutions of 1.0 mol/L Li[TFO-TFSI](A) and LiTFSI(B) in EC/EMC(3∶7)

Fig.11 Chronoamperometric profiles of 1.0 mol/L lithium salts in a mixture of EC/EMC(3∶7) (A) Li[TFO-TFSI] recorded at 4.2 V(a) and 4.5 V(b); (B) LiTFSI recorded at 4.2 V.

Fig.12 Cyclic voltammograms of electrolyte solutions of 1.0 mol/L Li[TFO-TFSI]-EC/EMC(3∶7) Working electrode: synthetic graphite; reference and counter electrode: Li; scan rate: 0.01 mV/s.

Fig.13 Specific capacity and columbic efficiency as a function of cycle number for Li/graphite half cells using 1.0 mol/L Li[TFO-TFSI] and LiPF6 in EC/EMC(3∶7) as electrolyte solutions

Fig.14 Specific capacity(A) and columbic efficiency(B) as a function of cycle number for graphite/LiCoO2 using 1.0 mol/L Li[TFO-TFSI] and LiPF6 in EC/EMC(3∶7) as electrolyte solutions

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新型导电盐(三氟甲基磺酰)(三氟乙氧基磺酰)亚胺锂及其非水电解液的制备与性能

Preparation and Properties of Lithium(trifluoromethanesulfonyl)-(trifluoroethoxysulfonyl)imide as Conducting Salt for Nonaqueous Electrolyte Solutions^†

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新型导电盐(三氟甲基磺酰)(三氟乙氧基磺酰)亚胺锂及其非水电解液的制备与性能

Preparation and Properties of Lithium(trifluoromethanesulfonyl)-(trifluoroethoxysulfonyl)imide as Conducting Salt for Nonaqueous Electrolyte Solutions†

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Preparation and Properties of Lithium(trifluoromethanesulfonyl)-(trifluoroethoxysulfonyl)imide as Conducting Salt for Nonaqueous Electrolyte Solutions^†