Effect of Electrolyte Anion on Electrochemical Behavior of Nickel Hexacyanoferrate Electrode in Aqueous Sodium-Ion Batteries

Abstract

Nickel hexacyanoferrate (NiHCF) has a three-dimensional open framework structure, excellent long-cycling stability and rate performance as a cathode for aqueous sodium-ion batteries. However, the specific capacity of NiHCF is lower than that of present cathodes for aqueous batteries. A sodium-ion electrolyte was explored to achieve optimum capacity with NiHCF. Powder-type NiHCF was fabricated by coprecipitation with the atomic composition K0.065Ni1.44Fe(CN)6·4.4H2O. The presence of Fe vacancies in the atomic composition is attributable to the inclusion of coordinating and zeolitic water during coprecipitation. Two sodium-ion electrolytes, 1 M Na2SO4 and 1 M NaNO3, were employed to analyze the electrochemical behavior of the NiHCF electrode. Identical redox potentials to 0.58 V (vs. NHE) were measured in both electrolytes. However, a lower overpotential was observed in NaNO3 compared to Na2SO4 as a result of the smaller interfacial charge transfer resistance. The lower charge transfer resistance in the NaNO3 solution produced a higher specific capacity of 57 mAh g<sup>-1</sup> (1 C-rate) and the superior capacity retention of 46.6% at 20 C-rate. The anion in the aqueous electrolyte changed the charge transfer resistance at the electrode/electrolyte interface, confirming the electrolyte anion has a crucial effect on the charge capacity and rate performance of NiHCF.