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Microporous nickel phosphite [Ni11(HPO3)8(OH)6] nanocrystals were prepared using a hydrothermal method, and were successfully applied as a positive electrode in a flexible all solid-state asymmetric supercapacitor. Because of the specific micro/nanostructure, the flexible solid-state asymmetric supercapacitor can achieve a maximum energy density of 0.45 mW h cm(-3), which is higher than most reported supercapacitors. More importantly, the device performance remains efficient for 10,000 cycles.

Ni20[(OH)12(H2O)6][(HPO4)8(PO4)4]·12H2O nanorods are successfully synthesized via a one‐pot hydrothermal reaction. A high‐performance flexible asymmetric all‐solid‐state supercapacitor based on the obtained Ni20[(OH)12(H2O)6][(HPO4)8(PO4)4]·12H2O nanorods (positive electrode) and graphene nanosheets (negative electrode) is successfully assembled. It is the first report of this nanomaterial applied for all‐solid‐state supercapacitors. Interestingly, a maximum volumetric energy density of 0.446 mW h cm−3 at a current density of 0.5 mA cm−2 and a maximum power density of 44.1 mW cm−3 at a current density of 6.0 mA cm−2 are achieved by the as‐assembled device. What's more, the device also shows excellent mechanical flexibility and little capacitance change after over 5000 charge/discharge cycles at a current density of 0.5 mA cm−2.