Preparation of Low-Defect Manganese-Based Prussian Blue Cathode Materials with Cubic Structure for Sodium-Ion Batteries via Coprecipitation Method.

Abstract

Sodium-ion batteries have important application prospects in large-scale energy storage due to their advantages, such as safety, affordability, and abundant resources. Prussian blue analogs (PBAs) have a stable and open framework structure, making them a very promising cathode material. However, high-performance manganese-based Prussian blue cathode materials for sodium-ion batteries still suffer from significant challenges due to several key issues, such as a high number of vacancy defects and a high crystal water content. This article investigates the effects of the Fe-Mn molar ratio, Mn ion concentration, and reaction time on the electrochemical performance of MnHCF during the coprecipitation process. When Fe:Mn = 1:2, c(Mn2+) = 0.02 mol/L, and the reaction time is 12 h, the content of interstitial water molecules in the sample is low, and the Fe(CN)6 defects are few. At 0.1 C, the prepared electrode has a high initial discharge specific capacity (121.9 mAh g-1), and after 100 cycles at 0.2 C, the capacity retention rate is 65% (~76.2 mAh g-1). Meanwhile, the sample electrode exhibits excellent reversibility. The discharge capacity can still be maintained at around 75% when the magnification is restored from 5 C to 0.1 C. The improvement in performance is mainly attributed to two aspects: On the one hand, reducing the Fe(CN)6 defects and crystal water content is conducive to the diffusion and stable structure of N. On the other hand, reducing the reaction rate can significantly delay the crystallization of materials and optimize the nucleation process.