Enhanced stability and rate performance of zinc-doped cobalt hexacyanoferrate (CoZnHCF) by the limited crystal growth and reduced distortion

Cobalt hexacyanoferrate (CoHCF) is a potential cathode for aqueous Na-ion batteries due to its high theoretical specific capacity (170 m Ah g^(-1));however,its lower rate capability and cyclability limit its applications.Structural distortion at a weak N-coordinated crystal field during cycling disintegrates Co,yielding an irreversible reaction.Different Zn amounts ranging 0–1 were added to the Co site to suppress the structural irreversibility of CoHCF,yielding Co_(1-x)Zn_(x)HCF powder;this Zn (x≤0.09) addition reduced the powder’s dimension because the lower four coordination of Zn–N,not the six coordination of Co–N,limits the powder growth.Simultaneously,a small lattice parameter and interaxial angle (~90°) are obtained,implying that a narrower Co_(1-x)Zn_(x)HCF inner structure is formed to accommodate Na ions.Moreover,the electronic conductivity of Co_(1-x)Zn_(x)HCF gradually increased within 0–0.09 range.A smaller particle size with a high surface area leads to a near-surface-limited redox process,similar to a capacitive reaction.Both the surface-limited reaction and electronic conductivity enhances the reversibility due to the smaller charge transfer resistance at the electrode/electrolyte interface caused by Zn addition.Replacing redox-active Co with non-active Zn amount of 0.07 (Co_(1-x)Zn_(x)HCF) slightly reduces the specific capacity from 127 to 119 mAh g^(-1)at 0.1 A g^(-1)due to the shrunken Co charging sites.Rate performance is enhanced by compromising the capacity and reduced distortion,resulting in 81%retention at a 20-times-faster charging rate.Notably,the Co_(1-x)Zn_(x)HCF sample exhibited the good stability while preserving 74%of the initial capacity at 0.5 A g^(-1)after 200 cycles.