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Synthesis of Ionic Liquid Based Electrolytes, Assembly of Li-ion Batteries, and Measurements of Performance at High Temperature
Published on: December 20, 2016
New State-Diagram of Aqueous Solutions Unveiling Ionic Hydration, Antiplasticization, and Structural Heterogeneities
Jinbing Zhang1,2, Fengping Wang1, Zexian Cao2,3
1School of Mathematics and Physics, University of Science and Technology Beijing, Beijing 100083, China.
Abstract:
Here, we report a new state-diagram for aqueous solutions based on concentration-dependent glass-transition temperatures of concentrated and ice freeze-concentrated solutions. Different from the equilibrium phase diagram, this new state-diagram can provide comprehensive information about the hydration numbers of solutes, nonequilibrium vitrification/cold-crystallization, and vitrification/devitrification processes of aqueous solutions in three distinct concentration zones separated by two critical water-content points of only functions of the hydration number. Based on this new state-diagram, we observe the comparable hydration ability of LiTFSI to LiCl and an atypical concentration-dependent cold-crystallization behavior of the LiTFSI-H2O system. These results unveil the negligible hydration ability of TFSI- in a water-rich solution, characterize the antiplasticizing effect of water induced by the strengthened Li+-TFSI--H2O interaction when only hydration water and confined water are present, and confirm the increasing fraction of water-rich domains with the decrease in water content when the cation and anion become incompletely hydrated on average. These results highlight the novel water-content-mediated interactions among the anion, cation, and H2O for LiTFSI-H2O.
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