Development of KPF6/KFSA Binary-Salt Solutions for Long-Life and High-Voltage K-Ion Batteries

A series of binary-salt electrolytes of KPF6/KN-(SO2F)(2) (KFSA) in carbonate ester solvents have been developed for high-voltage K-ion batteries by clarifying the effect of salt ratio and different solvents on the physical properties of the electrolyte solutions and electrochemical performance of K-ion batteries. The KPF6/KFSA carbonate ester solutions, such as KPF6/KFSA ethylene carbonate (EC)/diethyl carbonate (DEC), exhibit higher ionic conductivity than single-salt KPF6 one, and higher KFSA content results in higher ionic conductivity. The KPF6-rich binarysalt electrolytes with KPF6/KFSA ratios of >= 3 (mol/mol) provide enough oxidation stability and passivation against Al corrosion at 4.6 V over 100 h, ensuring reversible operation of a 4 V class positive electrode, K2Mn[Fe(CN)(6)] in half-cell. Graphite negative electrodes exhibit higher Coulombic efficiency and better rate performance in 0.75 mol kg(-1) K(PF6)(0.9) (FSA)(0.1)/EC/DEC and 1 mol kg(-1) K(PF6)(0.75)(FSA)(0.25)/EC/DEC electrolytes than those in the KPF6 one. Surface analysis by hard X-ray photoelectron spectroscopy reveals that the decomposition product of N(SO2F)(2)(-) anion contributes to stabilizing solid electrolyte interphase on a graphite electrode. From comparing different solvents of EC/DEC, EC/ethyl methyl carbonate, and EC/propylene carbonate (PC), the K2Mn[Fe(CN)(6)] electrode demonstrates the highest Coulombic efficiency in the EC/PC binary electrolyte, while graphite electrodes exhibit no significant difference. Based on the half-cell tests, we successfully achieve the 3.6 V class full cell of graphite vertical bar K(PF6)(0.75)(FSA)(0.23)/EC/PC vertical bar K2Mn[Fe(CN)(6)] showing excellent cyclability over 500 cycles, which is far superior to that of the conventional KPF6/EC/DEC electrolyte cell.