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Prussian blue (PB) and its analogues (PBA), especially with hollow structures, have attracted growing attention from the researchers of energy storage field. Herein, we have developed a facile self-templating method to synthesize hollow-structured cobalt hexacyanoferrate (CoHCF) with controllable morphologies by using water-soluble precursors as templates. The method is versatile and can be extended to synthesize various PB/PBA hollow structures with tunable composition and morphology. Profiting from the unique hollow structure, the CoHCF hollow prisms manifest exceptional electrochemical performance in the NaSO aqueous electrolyte, including a high specific capacitance (284 F g at 1 A g), a high rate capability, and an excellent cycling stability (92% retention after 5000 cycles). A hybrid supercapacitor device assembled with the CoHCF hollow prisms and activated carbon shows a high specific density of 47 W h kg at a specific power of 1000 W kg and stable cycling performance.

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