“Win-Win” Scenario of High Energy Density and Long Cycling Life in a Novel Na_3.9MnCr_0.9Zr_0.1(PO₄)₃ Cathode

Abstract

The development of high-energy and long-lifespan NASICON-type cathode materials for sodium-ion batteries has always been a research hotspot but a daunting challenge. Although Na₄MnCr(PO₄)₃ has emerged as one of the most promising high-energy-density cathode materials owing to its three-electron reactions, it still suffers from serious structural distortion upon repetitive charge/discharge processes caused by the Jahn-Teller active Mn³⁺. Herein, the selective substitution of Cr by Zr in Na₄MnCr(PO₄)₃ was explored to enhance the structural stability, due to the pinning effect of Zr ions and the ≈2.9-electron reactions, as-prepared Na_3.9MnCr_0.9Zr_0.1(PO₄)₃/C delivers a high capacity retention of 85.94% over 500 cycles at 5 C and an ultrahigh capacity of 156.4 mAh g^–1 at 0.1 C, enabling the stable energy output as high as 555.2 Wh kg^–1. Moreover, during the whole charge/discharge process, a small volume change of only 6.7% was verified by in situ X-ray diffraction, and the reversible reactions of Cr³⁺/Cr⁴⁺, Mn³⁺/Mn⁴⁺, and Mn²⁺/Mn³⁺ redox couples were identified via ex situ X-ray photoelectron spectroscopy analyses. Galvanostatic intermittent titration technique tests and density functional theory calculations further demonstrated the fast reaction kinetics of the Na_3.9MnCr_0.9Zr_0.1(PO₄)₃/C electrode. This work offers new opportunities for designing high-energy and high-stability NASICON cathodes by ion doping.

Keywords

high energy density / mechanism investigation / NASICON-type cathodes / sodium-ion batteries / structure modification

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