SummaryNon-lithium energy storage devices, especially sodium ion batteries, are drawing attention due to insufficient and uneven distribution of lithium resources. Prussian blue and its analogs (Prussian blue analogs [PBAs]), or hexacyanoferrates, are well-known since the 18th century and have been used for hydrogen storage, cancer therapy, biosensing, seawater desalination, and sewage treatment. Owing to their unique features, PBAs are receiving increasing interest in the field of energy storage, such as their high theoretical specific capacity, ease of synthesis, as well as low cost. In this review, a general summary and evaluation of the applications of PBAs for rechargeable batteries are given. After a brief review of the history of PBAs, their crystal structure, nomenclature, synthesis, and working principle in rechargeable batteries are discussed. Then, previous works classified based on the combination of insertion cations and transition metals are analyzed comprehensively. The review includes an outlook toward the further development of PBAs in electrochemical energy storage.

Rechargeable sodium ion batteries (SIBs) are surfacing as promising candidates for applications in large-scale energy-storage systems. Prussian blue (PB) and its analogues (PBAs) have been considered as potential cathodes because of their rigid open framework and low-cost synthesis. Nevertheless, PBAs suffer from inferior rate capability and poor cycling stability resulting from the low electronic conductivity and defi ciencies in the PBAs framework. Herein, to understand the vacancy-impacted sodium storage and Na-insertion reaction kinetics, we report on an in-situ synthesized PB@C composite as a high-performance SIB cathode. Perfectly shaped, nanosized PB cubes were grown directly on carbon chains, assuring fast charge transfer and Na-ion diffusion. The existence of [Fe(CN) 6 ] vacancies in the PB crystal is found to greatly degrade the electrochemical activity of the Fe LS (C) redox couple via fi rst-principles computation. Superior reaction kinetics are demonstrated for the redox reactions of the Fe HS (N) couple, which rely on the partial insertion of Na ions to enhance the electron conduction. The synergistic effects of the structure and morphology results in the PB@C composite achieving an unprecedented rate capability and outstanding cycling stability (77.5 mAh g −1 at 90 C, 90 mAh g − 1 after 2000 cycles at 20 C with 90% % capacity retention).

In situ polymerization is used to obtain PEDOT tightly coated MnHCF, inhibiting phase transition and Mn dissolution during cycling.