Solvation structure around the Li+ ion in succinonitrile–lithium salt plastic crystalline electrolytes
文献信息
Gang-Hua Deng, Chuanqi Ge, Yuhuan Tian, Guorong Wu, Xueming Yang, Junrong Zheng, Kaijun Yuan
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−1vs. 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 °C) and 2.5–3 in the liquid phase (80 °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 °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 °C, the salt dissociation ratio can be up to 90% ± 10%.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.












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