Multiscale Scrutinizing Ion Storage Kinetics in Hollow Ni‐Mn Prussian Blue Analogues for Enhanced Capacitive Deionization

Prussian blue analogues (PBAs) are a class of promising materials for capacitive deionization. However, the kinetic mismatch between their slow ion storage rate and the demand from short‐time desalination severely limits their desalination performance. Here, a group of structure‐tuneable Ni‐Mn PBAs have been developed by a combination strategy of surface‐protected chemical etching and Ostwald ripening to study their ion storage kinetics. Treating them as demos, the characterizations and investigations, e.g., in situ XRD in a three‐electrode system, dynamic impedance, finite element simulation, and DFT calculations etc., reveal that the slow ion diffusion caused by the severe agglomeration of the nanoparticles and the unsuitable lattice parameter controls the final desalination behavior. Therefore, the correspondingly optimized sample (HC‐t) possessing a microscale hollow structure, nanoscale shell thickness, and expanded lattice, displays a fast ion storage kinetics with the ratio of surface‐controlled current as high as 82% at a scan rate of 20 mV s−1. Consequently, it delivers an impressive desalination capacity of 120.8 mg g−1 (2.06 mmol g−1 Na+) with a fast average desalination rate of 0.25 mg g−1 s−1 (0.004 mmol g−1 s−1) at 1.2 V, competitive with those reported in the literature. Moreover, the elucidation of the structure‐performance correlation provides valuable insights for the development and design of next‐generation PBAs for capacitive deionization (CDI). This work systematically studies the kinetic issue of PBAs during their capacitive deionization process, and proves the ion diffusion is the rate determining step for their desalination. To achieve a faster desalination rate, the ion diffusion process must be accelerated by simultaneously optimizing the structure of PBAs including: morphology, lattice parameter, and composition.