ABSTRACT As the development of sustainable, scalable post‐lithium‐ion batteries intensifies, Prussian blue analogues (PBAs) stand out for their unique open‐framework architecture. However, their translation into practical devices is hindered by intrinsic atomic‐scale challenges, including phase instability, Jahn‐Teller distortions, and ubiquitous vacancies. This review deciphers the fundamental mechanisms through which advanced engineering strategies, from precise elemental doping/substitution to disruptive high‐entropy design, reprogram PBAs’ electrochemical properties. We present a dedicated discourse on how these tactics selectively enhance intrinsic activity, engineer coordination environments, and dictate ion transport kinetics. By critically synthesizing these insights into actionable design principles, we provide a strategic blueprint for navigating the current challenges and accelerating the development of next‐generation PBA cathodes. This work is poised to serve as a foundational guide for researchers aiming to push the boundaries of energy storage materials.
Yang et al. (Wed,) studied this question.