Optimizing Mn in Prussian blue analogs with double redox active sites to induce boosted Zn2+ storage

Abstract

Prussian Blue analogs (PBAs) are a suitable aqueous zinc-ion batteries (AZIBs) cathode material, but they face issues related to low specific capacity and cycling lifespan due to insufficient active sites and poor ion de-intercalation structural stability. In this study, Mn-Prussian Blue Analog (Mn-PBA) is fabricated using a simple co-precipitation method and the morphology of Mn-PBA is further optimized through artificially manipulating concentration gradients strategy, effectively enhancing the structural stability of Zn2+ de-intercalation. Furthermore, the introduction of Mn established dual Zn2+ active centers in Mn-PBA (Mn-O and Fe(CN)6]4−/[Fe(CN)6]3−), leading to an increased specific capacity. As a proof of concept for AZIBs, the optimized Mn-PBA-3 cathode exhibits a high reversible specific capacity of 143.5 mAh/g and maintains a capacity retention of 88.5 % after 250 cycles at 1 A/g, surpassing commercial MnO2 (30.5 mAh/g after 100 cycles). Mn-PBA-3 also delivers a high capacity of 79.0 mA h g−1 after 2000 cycles of 10 A/g. The mechanism of the Zn2+ double redox reaction of Mn-PBA-3 has been revealed in detail by in situ Raman and a series of ex situ techniques. Under a high operating voltage window of 0–1.9 V, Zn//Mn-PBA-3 demonstrates a capacity of 99.3 mAh/g after 800 cycles (5 A/g) by assembling zinc ion button battery. This work has reference significance for structurally modulated PBAs used in high performance AZIBs.