Effect of the alkali insertion ion on the electrochemical properties of nickel hexacyanoferrate electrodes.

Nickel hexacyanoferrate (NiHCFe) is an attractive cathode material in both aqueous and organic electrolytes due to a low-cost synthesis using earth-abundant precursors and also due to its open framework, Prussian blue-like crystal structure that enables ultra-long cycle life, high energy efficiency, and high power capability. Herein, we explored the effect of different alkali ions on the insertion electrochemistry of NiHCFe in aqueous and propylene carbonate-based electrolytes. The large channel diameter of the structure offers fast solid-state diffusion of Li(+), Na(+), and K(+) ions in aqueous electrolytes. However, all alkali ions in organic electrolytes and Rb(+) and Cs(+) in aqueous electrolytes show a quasi-reversible electrochemical behavior that results in poor galvanostatic cycling performance. Kinetic regimes in aqueous electrolyte were also determined, highlighting the effect of the size of the alkali ion on the electrochemical properties.