Solvation structure around the Li+ ion in succinonitrile-lithium salt plastic crystalline electrolytes

被引：34

作者：

Shen, Yuneng ^{[1
,2
]}

Deng, Gang-Hua ^{[1
]}

Ge, Chuanqi ^{[1
]}

Tian, Yuhuan ^{[1
]}

Wu, Guorong ^{[1
]}

Yang, Xueming ^{[1
]}

Zheng, Junrong ^{[3
]}

Yuan, Kaijun ^{[1
]}

机构：

[1] Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Liaoning, Peoples R China

[2] Univ Chinese Acad Sci, Beijing 100049, Peoples R China

[3] Peking Univ, Beijing Natl Lab Mol Sci, Coll Chem & Mol Engn, Beijing 100871, Peoples R China

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2016年 / 18卷 / 22期

基金：

中国国家自然科学基金;

关键词：

VIBRATIONAL-ENERGY; LIQUID; SPECTRA; PHASE;

D O I：

10.1039/c6cp02878k

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Herein, we discuss the study of solvation dynamics of lithium-succinonitrile (SN) plastic crystalline electrolytes by ultrafast vibrational spectroscopy. The infrared absorption spectra indicated that the CN stretch of the Li+ bound and unbound succinonitrile molecules in a same solution have distinct vibrational frequencies (2276 cm(-1) vs. 2253 cm(-1)). The frequency difference allowed us to measure the rotation decay times of solvent molecules bound and unbound to Li+ ion. The Li+ coordination number of the Li+-SN complex was found to be 2 in the plastic crystal phase (22 degrees C) and 2.5-3 in the liquid phase (80 degrees C), which is independent of the concentration (from 0.05 mol kg(-1) to 2 mol kg(-1)). The solvation structures along with DFT calculations of the Li+-SN complex have been discussed. In addition, the dissociation percentage of lithium salt was also determined. In 0.5 mol kg(-1) LiBF4-SN solutions at 80 degrees C, 60% +/- 10% of the salt dissociates into Li+, which is bound by 2 or 3 solvent molecules. In the 0.5 mol kg(-1) LiClO4-SN solutions at 80 degrees C, the salt dissociation ratio can be up to 90% +/- 10%.

引用

页码：14867 / 14873

页数：7

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