Resolving Deactivation of Low-Spin Fe Sites by Redistributing Electron Density toward High-Energy Sodium Storage

Nano Lett. 2023 Nov 22;23(22):10423-10431. doi: 10.1021/acs.nanolett.3c03065. Epub 2023 Nov 13.

Abstract

Prussian blue (PB) has been an emerging class of cathode material for sodium-ion batteries due to its low cost and high theoretical capacity. However, their working voltage and capacity are substantially restricted due to the deactivation of low-spin Fe sites. Herein, we demonstrate a universal strategy to activate the low-spin Fe sites of PB by hybridizing them with the π-π conjugated electronic conductors. The redistribution of electron density between π-π conjugated conductors and PB effectively promotes the participation of low-spin Fe sites in sodium storage. Consequently, the low-spin Fe-induced plateau is greatly aroused, resulting in a high specific capacity of 148.4 mAh g-1 and remarkable energy density of 444.2 Wh kg-1. In addition, the excellent structural stability enables superior cycling stability over 2500 cycles and outstanding rate performance. The work will provide fundamental insight into activating the low-spin Fe sites of PB for advanced battery technologies.

Keywords: Prussian blue; activation; high energy density; low-spin Fe sites; sodium-ion batteries.