Exploring the Role of Manganese on Structural, Transport, and Electrochemical Properties of NASICON-Na3Fe2-yMny(PO4)3-Cathode Materials for Na-Ion Batteries.

Given the extensive efforts focused on protecting the environment, eco-friendly cathode materials are a prerequisite for the development of Na-ion battery technology. Such materials should contain abundant and inexpensive elements. In the paper, we present NASICON-Na3Fe2-yMny(PO4)3 (y = 0, 0.1, 0.2, 0.3, and 0.4) cathode materials, which meet these requirements. Na3Fe2-yMny(PO4)3 compounds were prepared via a solid-state reaction at 600 °C, which allowed to obtain powders with submicron particles. The presence of manganese in the iron sub-lattice inhibits phase transitions, which occurs at ∼95 and ∼145 °C in Na3Fe2(PO4)3, changing the monoclinic structure to rhombohedral and affecting the structural and transport properties. The chemical stability of Na3Fe2-yMny(PO4)3 was thus higher than that of Na3Fe2(PO4)3, and it also exhibited enhanced structural, transport, and electrochemical properties. The observed correlation between the chemical composition and electrochemical properties proved the ability to precisely tune the crystal structure of NASICONs, allowing cathode materials with more desirable properties to be designed.