Correlating Solid-Electrolyte Interface Composition to Charge Transfer Resistance for Improved Low-Temperature Performance of Lithium-Ion Batteries

Abstract

The adverse impact of low temperatures on Li-ion batteries (LIBs) is a well known challenge. Currently, at subfreezing temperatures, the efficiency of conventional LIBs greatly decreases compared to their room temperature performance, which of course severely limits the performance of applications using LIBs in the colder regions on the planet. From a fundamental perspective, the causes of such performance decreases are yet to be fully understood, but are believed to be related to the ability of ions to move through the various phases (as well as move across phase interfaces) that exist in the battery.Several studies have been conducted to improve the low-temperature performance of LIBs, most of them focusing on using solvents with lower viscosity and higher dielectric constant to promote transport through the electrolyte at the lower temperatures so as to achieve lower bulk resistance (Rbulk) of the cell. However, our Electrochemical Impedance Spectroscopy (EIS) studies at low temperatures have indicated that it is the charge transfer resistance (Rct) that grows exponentially as we go to sub-zero Celsius temperatures and is responsible for the increase in the total resistance of the cell. EIS on 3-electrode cells have shown that the anode side (Gr) is predominantly responsible for the poor cell performance, necessitating our focus on the charge transfer process in the Gr-electrolyte interface. We observe that the Rct is not only related to the Li-solvation shell but also to the composition of the Solid Electrolyte Interface (SEI). By modifying the electrolyte, such as by changing the salt concentration, adding additives, and changing the solvent, significant changes in the interface and hence in the RSEI and Rct of the cell have been observed. By combining EIS with various techniques like mass spectrometry, differential capacity analysis and SEM, we have been able to better understand the SEI composition and its impact on interfacial resistances. We specifically focus on the influence of SEI composition on the charge-transfer resistance of the cell, correlating the effect of amounts of LiF and carbonates in the SEI with the interfacial performance of the cell. Through these relations, we aim to facilitate the development of electrolytes by having a better understanding of the solvation shells and the SEI composition for low temperature performance.