Enhancing structural and cycle stability of Prussian blue cathode materials for calcium-ion batteries by introducing divalent Fe

Abstract

Calcium-ion batteries (CIBs) have been of interest for rechargeable batteries due to their high energy density and fast ion diffusion in liquid electrolyte originated from the divalence and low charge/radius ratio of Ca ion. However, exploring high performance cathode materials for CIBs is very challenging. In this work, divalent Fe ions are introduced into copper hexacyanoferrate (CuHCF) to construct a new Prussian blue cathode material rich of Fe²⁺ by using K₄Fe(CN)₆ as the precursor instead of K₃Fe(CN)₆. The Fe²⁺ ions at low-spin state can improve the structural stability of CuHCF during Ca ions extraction and insertion processes effectively. It is found that the lattice parameter change of CuHCF is only 0.13 % during charge and discharge, much less than the CuHCF with Fe³⁺. X-ray absorption spectroscopy indicates that the charge compensation of CuHCF(Fe²⁺) is mainly contributed by Fe²⁺/Fe³⁺ redox couple. The octahedral distortion in CuHCF is also suppressed effectively. As a result, the CuHCF(Fe²⁺) cathode can deliver a reversible capacity of 54.5 mAh/g at 20 mA g⁻¹ with a high capacity retention of 90.43 % after 1000 cycles.