Size‐, Water‐, and Defect‐Regulated Potassium Manganese Hexacyanoferrate with Superior Cycling Stability and Rate Capability for Low‐Cost Sodium‐Ion Batteries

Potassium manganese hexacyanoferrate (KMHCF) is a low‐cost Prussian blue analogue (PBA) having a rigid and open framework that can accommodate large alkali ions. Herein, the synthesis of KMHCF and its application as a high‐performance cathode in sodium‐ion batteries (NIBs) is reported. High‐quality...

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Bibliographic Details
Published in:Small (Weinheim an der Bergstrasse, Germany) Germany), 2019-10, Vol.15 (42), p.e1902420-n/a
Main Authors: Zhou, Aijun, Xu, Zemin, Gao, Hongcai, Xue, Leigang, Li, Jingze, Goodenough, John B.
Format: Article
Language:English
Subjects:
cathode
Cathodes
Chemical precipitation
Chemical synthesis
cointercalation
Crystal defects
Cycles
Grain growth
Manganese
Metal ions
Nanotechnology
Nucleation
Pigments
Potassium
potassium manganese hexacyanoferrate
Prussian blue
Rechargeable batteries
Sodium-ion batteries
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Summary:Potassium manganese hexacyanoferrate (KMHCF) is a low‐cost Prussian blue analogue (PBA) having a rigid and open framework that can accommodate large alkali ions. Herein, the synthesis of KMHCF and its application as a high‐performance cathode in sodium‐ion batteries (NIBs) is reported. High‐quality KMHCF with low amounts of crystal water and defects and with homogeneous microstructure is obtained by controlling the nucleation and grain growth by using a high‐concentration citrate solution as a precipitation medium. The obtained KMHCF exhibits superior cycling and rate performance as a NIB cathode, showing 80% capacity retention after 1000 cycles at 1 C and a high capacity of 95 mA h g−1 at 20 C. Unlike conventional single‐cation batteries, the hybrid NIB with KMHCF as cathode and Na as anode in Na‐ion electrolyte displays three reversible plateaus that involve stepwise insertion/extraction of both K+ and Na+ in the PBA framework. In later cycling, the K+–Na+ cointercalated phase is partially converted into a cubic sodium manganese hexacyanoferrate (NaMHCF) phase due to the increasing replacement of Na+ for K+. A K2MnFe(CN)6 Prussian blue analogue with low amount of crystal water and defects, and uniform size distribution can be obtained by precipitation in a citrate medium. This material shows high stability and rate capability as a hybrid sodium‐ion battery cathode, with both Na+ and K+ being reversible cations in the monoclinic framework.
ISSN:1613-6810
1613-6829
DOI:10.1002/smll.201902420