Anion–Cation Competition Chemistry for Comprehensive High‐Performance Prussian Blue Analogs Cathodes

The extensively studied Prussian blue analogs (PBAs) in various batteries are limited by their low discharge capacity, or subpar rate etc., which are solely reliant on the cation (de)intercalation mechanism. In contrast to the currently predominant focus on cations, we report the overlooked anion‐cation competition chemistry (Cl−, K+, Zn2+) stimulated by high‐voltage scanning. With our designed anion‐cation combinations, the KFeMnHCF cathode battery delivers comprehensively superior discharge performance, including voltage plateau >2.0 V (vs. Zn/Zn2+), capacity >150 mAh g−1, rate capability with capacity maintenance above 96 % from 0.6 to 5 A g−1, and cyclic stability exceeding 3000 cycles. We further verify that such comprehensive improvement of electrochemical performance utilizing anion‐cation competition chemistry is universal for different types of PBAs. Our work would pave a new and efficient road towards the next‐generation high‐performance PBAs cathode batteries. After high‐voltage CV scanning, the higher (de)intercalation voltage and lower diffusion activation energy for both Cl− and K+ boost the comprehensive improvement of the discharge voltage, capacity, rate and cyclic performance. The comprehensive improvement of electrochemical performance utilizing anion‐cation competition chemistry is universal for different types of PBAs.