Cyanometallate coordination polymers, sometimes called Prussian blue analogues, have recently been proposed as electrode materials for low cost, long cycle life and high power batteries.[1-3] However, high capacity bimetallic examples show poor cycle stability due to instabilities of the reduced states. To enhance the surface stability, core@shell heterostructures were developed that combine high-capacity core particles with a compatible and highly stable shell material. For example, particle heterostructures composed of a high-capacity K0.1Cu[Fe(CN)6]0.7�3.8H2O (CuFe-PBA) core and lower capacity but highly stable shell of K0.1Ni[Fe(CN)6]0.7�4.1H2O lead to the coexistence of both high capacity and long cycle stability because the shell protects the otherwise reactive surface of the highly reduced state of the CuFe-PBA core. In addition, this heterostructure is shown to suppress a known structural phase transition upon reduction of the CuFe-PBA core, providing evidence of important role of mesoscale interfacial coupling in coordination polymer heterostructures.[1] M. Pasta et al., Nat. Commun. 2012  , 3, 1149[2] D. Asakura et al., J. Phys. Chem. C, 2012,  116  , 8364[3] D. Asakura et al., J. Am. Chem. Soc. 2013  , 135, 2739

Mesoscale effects in bimetallic cyanide-bridged coordination polymer heterostructures as Li-ion cathode materials

246th National Meeting (2013)

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