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Prussian blue analogs (PBAs) formed with hexacyanide linkers have been studied for decades. The framework crystal structure of PBAs mainly benefits from the six-fold coordinated cyano functional groups. In this study, in-plane tetracyanonickelate was utilized to engineer an organic linker and design a family of four-fold coordinated PBAs (FF-PBAs; Fe2+Ni(CN)4, MnNi(CN)4, Fe3+Ni(CN)4, CuNi(CN)4, CoNi(CN)4, ZnNi(CN)4, and NiNi(CN)4), which showed an interesting two-dimensional (2D) crystal structure. It was found that these FF-PBAs could be utilized as cathode materials of Li-ion batteries, and the Ni/Fe2+ system exhibited superior electrochemical properties compared to the others with a capacity of 137.9 mA h g−1 at a current density of 100 mA g−1. Furthermore, after a 5000-cycle long-term repeated charge/discharge measurement, the Ni/Fe2+ system displayed a capacity of 60.3 mA h g−1 with a coulombic efficiency of 98.8% at a current density of 1000 mA g−1. In addition, the capacity of 86.1% was preserved at 1000 mA g−1 as compared with that at 100 mA g−1, implying a good rate capability. These potential capacities can be ascribed to an in situ reduction of Li+ in the interlayer of Ni/Fe2+ instead of the formation of other compounds with the host material according to ex situ XRD characterization. These specially designed FF-PBAs are expected to inspire new concepts in electrochemistry and other applications requiring 2D materials.

Prussian blue analogs (PBAs) are a type of metal–organic framework and have drawn significant attention recently. To date, most are constructed with divalent transition metal ions coordinated to the N end of a cyanide bridge. In this report, we studied a trivalent gallium ion-based Ga hexacyanocobaltate (GaHCCo), which depicted a face-centered cubic crystal structure. In addition, the synthesized GaHCCo was demonstrated as a cathode material of lithium-ion batteries (LIBs) and was found to exhibit long-term stability, having a capacity retention of 75% after 3000 cycles of repeated charge–discharge cycling and an extremely high coulombic efficiency of 98%, which was achieved because of a solid-state diffusion controlled Li-ion storage process. After ex situ XRD analysis on the different charge stages, the Li-ion storage in the GaHCCo was attributed to the Co species via the formation of a Li/Co compound. This work will pave the way toward the study of PBAs constructed with trivalent metal ions and provide more insights into the development of high-performance LIBs in the future.