Proceedings of MATSUS Spring 2025 Conference (MATSUSSpring25)
DOI: https://doi.org/10.29363/nanoge.matsusspring.2025.004
Publication date: 16th December 2024
Potassium-ion batteries (KIBs) are emerging as a promising option for large-scale energy storage. Compared to Li-ion batteries, KIBs offer advantages such as the abundance of potassium resources and the potential for cobalt-free cathode materials, leading to lower costs. The fast diffusion kinetics of K+ ions in liquid electrolytes may also enable faster charge and discharge processes. Key electrode materials for KIBs include Prussian blue analogues (PBAs), vanadium fluorophosphates such as KVPO4F, and transition metal oxides at the cathode, while graphite and hard carbon are the
most promising anode materials.
This study highlights the use of electrochemical characterization, along with a range of experimental techniques such as X-ray diffraction, Mössbauer spectroscopy, and Raman spectroscopy, supported by density functional theory (DFT) calculations, to analyze the electronic structure and electrochemical mechanisms of these materials for KIBs.
On the anode side, research shows that the mechanism of K+ intercalation into graphite in glyme-based electrolytes changes from co-intercalation to intercalation with increased electrolyte salt concentration, influenced primarily by K+ ion solvation rather than solid electrolyte interphase (SEI) formation. Graphite experiences a significant volume expansion (around 60%) during K+ intercalation, while hard carbon shows limited volume change, leading to superior performance in terms of initial coulombic efficiencies (ICEs) and specific capacities. This can be attributed to the uniform morphology and
higher interplanar distance of hard carbon structures.
On the cathode side, systems such as Mn-Fe PBAs and potassium manganese oxides like K3MnO4 were tested. While these materials are cost-effective and non-toxic, they suffer from Mn dissolution at extreme oxidation states, limiting stable cycling. Similarly, the instability at high potentials of KVPO4F restricts its electrochemical capacity.
These insights, enabled by advanced characterization techniques, especially under operando conditions, underscore the need for a detailed understanding of electrochemical properties and cycling mechanisms to develop new, effective materials for KIBs
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