The limited cyclability and inferior Coulombic efficiency of graphite negative electrodes have been major impediments to their practical utilization in potassium-ion batteries (PIBs). Herein, for the first time, potassium difluorophosphate (KDFP) electrolyte additive is demonstrated as a viable solution to these bottlenecks by facilitating the formation of a stable and K⁺-conducting solid–electrolyte interphase (SEI) on graphite. The addition of 0.2 wt % KDFP to the electrolyte results in significant improvements in the (de)potassiation kinetics, capacity retention (76.8% after 400 cycles with KDFP vs 27.4% after 100 cycles without KDFP), and average Coulombic efficiency (∼99.9% during 400 cycles) of the graphite electrode. Moreover, the KDFP-containing electrolyte also enables durable cycling of the K/K symmetric cell at higher efficiencies and lower interfacial resistance as opposed to the electrolyte without KDFP. X-ray diffraction and Raman spectroscopy analyses have confirmed the reversible formation of a phase-pure stage-1 potassium–graphite intercalation compound (KC₈) with the aid of KDFP. The enhanced electrochemical performance by the KDFP addition is discussed based on the analysis of the SEI layer on graphite and K metal electrodes by X-ray photoelectron spectroscopy
