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Updated: Sep 5, 2025

Characterization of Electrode Materials for Lithium Ion and Sodium Ion Batteries Using Synchrotron Radiation Techniques
Published on: November 11, 2013
Stabilized Multi-Electron Reactions in a High-Energy Na4 Mn0.9 CrMg0.1 (PO4 )3 Sodium-Storage Cathode Enabled by the
Jie Li1, Xudong Zhao2, Pingge He3
1Beijing Advanced Innovation Center for Materials Genome Engineering, Institute for Advanced Materials and Technology, State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing, 100083, P. R. China.
Abstract:
Na superionic conductor (NASICON)-type Na4 MnCr(PO4 )3 has attracted extensive attention among the phosphate sodium-storage cathodes due to its ultra-high energy density originating from three-electron reactions but it suffers from severe structural degradation upon repeated sodiation/desodiation processes. Herein, Mg is used for partial substitution of Mn in Na4 MnCr(PO4 )3 to alleviate Jahn-Teller distortions and to prolong the cathode cycling life by virtue of the pinning effect induced by implanting inert MgO6 octahedra into the NASICON framework. The as-prepared Na4 Mn0.9 CrMg0.1 (PO4 )3 /C cathode delivers high capacity retention of 92.7% after 500 cycles at 5 C and fascinating rate capability of 154.6 and 70.4 mAh g-1 at 0.1 and 15 C, respectively. Meanwhile, it can provide an admirable energy density of ≈558.48 Wh kg-1 based on ≈2.8-electron reactions of Mn2+ /Mn3+ , Mn3+ /Mn4+ , and Cr3+ /Cr4+ redox couples. In situ X-ray diffraction reveals the highly reversible single-phase and bi-phase structural evolution of such cathode materials with a volume change of only 6.3% during the whole electrochemical reaction. The galvanostatic intermittent titration technique and density functional theory computations jointly demonstrate the superior electrode process kinetics and enhanced electronic conductivity after Mg doping. This work offers a new route to improve the cycling stability of the high-energy NASICON-cathodes for sodium-ion batteries.
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