Solid-solution reaction suppresses the Jahn–Teller effect of potassium manganese hexacyanoferrate in potassium-ion batteries

Abstract

Potassium manganese hexacyanoferrate (KMnHCF) suffers from poor cycling stability in potassium-ion batteries due to the Jahn–Teller effect, and experiences destabilizing asymmetric expansions and contractions during cycling. Herein, hollow nanospheres consisting of ultrasmall KMnHCF nanocube subunits (KMnHCF-S) are developed by a facile strategy. In situ XRD analysis demonstrates that the traditional phase transition for KMnHCF is replaced by a single-phase solid-solution reaction for KMnHCF-S, which effectively suppresses the Jahn–Teller effect. From DFT calculations, it was found that the calculated reaction energy for K⁺ extraction in the solid-solution reaction is much lower than that in the phase transition, indicating easier K⁺ extraction during the solid-solution reaction. KMnHCF-S delivers high capacity, outstanding rate capability, and superior cycling performance. Impressively, the K-ion full cell composed of the KMnHCF-S cathode and graphite anode also displays excellent cycling stability. The solid-solution reaction not only suppresses the Jahn–Teller effect of KMnHCF-S but also provides a strategy to enhance the electrochemical performance of other electrodes which undergo phase transitions.