Analysis of Transport Properties of Polycarbonate-Based Polymer Electrolytes Containing Lithium (perfluoroalkylsulfonyl)Imides for Possible Application in Lithium-Ion Batteries

Abstract

The search for safe electrolytes for the use in lithium metal batteries and high energy density batteries has driven the interest in alternative polymer electrolytes with enhanced performance. The central interest focuses on transport properties as good ionic conductivities and on high electrochemical stability towards lithium metal anodes and cathodes for high voltage batteries. To gain insight in the Li-ion movement in polycarbonates, as dry or gel electrolyte, is necessary for understanding how to improve these systems and achieve better performances. In this context, we present a critical study on polycarbonates as alternative to polyethylene oxide (PEO) in salt-in-polymer electrolytes. [1] Polymer electrolytes based on PEO as well as some related with grafted PEO side chains along polymer backbones such as polyphosphazenes, polysiloxanes and others are known to reach ionic conductivities in the range of 10-3 - 10-4 S·cm-1 in a favourable temperature range and typical Li+ transference numbers around 0.2.[2,3] In contrast to that, polycarbonates were reported to exhibit transference numbers up to about 0.5 as well as higher ionic conductivities and electrochemical stability.[4] In this work, the commercially available polycarbonates polyethylene carbonate (PEC) and polypropylene carbonate (PPC) were prepared as flexible self-standing membranes with dissolved fluorinated lithium salts such as LiTFSI and others. With the use of propylene carbonate (PC) novel gel-polymer electrolytes have been fabricated. The ion conducting polymer membranes were examined regarding their electrochemical and transport characteristics with respect to possible battery applications. We studied ionic conductivity and Li-ion transference number as well as the coordination of lithium with different dissolved lithium salts on carefully purified polycarbonate samples. We obtained ionic conductivities in dry state around 10-6 S·cm-1 at room temperature and up to 10-3 in gelled systems. The novel gel systems based on PEC and PPC perform significantly better than the dry alternatives. Acknowledgements The authors acknowledge the funding within the project BenchBatt (03XP0047A) by the German Ministry of education and research. We are also grateful for the support by the Helmholtz Association within the Helmholtz Institute Münster (HI MS). [1] P. Knauth, Solid State Ionics, 180 (2009) 911-916.[2] M. Grünebaum, M.M. Hiller et al., Prog. Solid State Chem. 42 (2014) 85–105.[3] M. Hiller, M. Joost et al., Electrochim. Acta 114 (2013) 21-29.[4] Y. Tominaga, K. Yamazaki, Chem. Commun. 50 (2014) 4448-4450.