Interfacial Reaction Mechanisms on Graphite Anodes for K-Ion Batteries

Potassium-ion (K-ion) batteries (KIBs) potentially offer numerous advantages over conventional lithium-ion batteries as a result of the high natural abundance of potassium and its lower positive charge density compared with lithium. This introduces the possibility of using K-ion in fast charging applications, in which cost effectiveness is also a major factor. Unlike in sodium-ion batteries, graphite can be used as an anode in K-ion cells, for which an extensive supply chain, electrode manufacturing infrastructure, and knowledge already exist. However, the performance of graphite anodes in K-ion cells does not meet expectations, with rapid capacity fading and poor first cycle irreversible capacities often reported. Here, we investigate the formation and composition of the solid electrolyte interphase (SEI) as well as K⁺ insertion in graphite anodes in KIBs. Through the use of energy-tuned synchrotron-based X-ray photoelectron spectroscopy, we make a detailed analysis at three probing depths up to ∼50 nm of graphite anodes cycled to various potentials on the first discharge-charge cycle. Extensive SEI formation from a KPF₆/DEC/EC electrolyte system is found to occur at low potentials during the insertion of potassium ions into graphite. During the subsequent removal of potassium ions from the structure, the thick SEI is partially stripped from the electrode, demonstrating that the SEI layer is unstable and contributes to a significant proportion of the capacity upon both discharge and charge. With this in mind, further work is required to develop an electrolyte system with stable SEI layer formation on graphite in order to advance the KIB technology.