Influence of Vacancies in Manganese Hexacyanoferrate Cathode for Organic Na‐Ion Batteries: A Structural Perspective

Manganese hexacyanoferrates (MnHCF) are promising positive electrode materials for non-aqueous batteries, including Na-ion batteries, due to their large specific capacity (>130 mAh g${}^{–1}$), high discharge potential and sustainability. Typically, the electrochemical reaction of MnHCF associates with phase and structural changes, due to the Jahn-Teller (JT) distortion of Mn sites upon the charge process. To understand the effect of the MnHCF structure on its electrochemical performance, two MnHCF materials with different vacancies content are investigated herein. The electrochemical results show that the sample with lower vacancy content (4 %) exhibits relatively higher capacity retention of 99.1 % and 92.6 % at 2${}^{nd}$ and 10${}^{th}$ cycles, respectively, with respect to 97.4 % and 79.3 % in sample with higher vacancy content (11 %). Ex-situ X-ray absorption spectroscopy (XAS) and ex situ X-ray diffraction (XRD) characterization results show that a weaker cooperative JT-distortion effect and relatively smaller crystal structure modification occurred for the material with lower vacancies, which explains the better electrochemical performance in cycled electrodes.