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Na4Mn0.9Ce0.1V(PO4)3@CeO2/C
Journal of Materials Chemistry A · 2022 ·Vol. 10 ·期 19 ·10625-10637 · IF 14.511

3D porous spheroidal Na4Mn0.9Ce0.1V(PO4)3@CeO2/C cathode for high-energy Na ion batteries

Kun Wang,Xiaobing Huang,Tao Zhou,Dan Sun,Haiyan Wang,Zhi Zhang

The NASICON-type Na4MnV(PO4)3 (NMVP) possesses potential as a cathode material in SIBs, and is known for its stable 3D Na+ superconductive framework, high voltage platform, and relatively low cost and toxicity. Nevertheless, the intrinsic poor electronic conductivity and Jahn–Teller effect from Mn3+ during cycling limit its further application. Herein, to address such issues, a well-designed 3D porous spheroidal Ce3+-doped NMVP@CeO2/C cathode was constructed via a simple spraying drying-assisted route. As proved, the synergistic effect of Ce3+ doping in the crystal framework and CeO2 surface coating was achieved simultaneously, which greatly improved the electronic conductivity, facilitated the ion diffusion transfer and stabilized the crystalline structure. As a result, the as-prepared sample delivered superior discharge performance (50.3 mA h g−1 at 50C) and long circular life (91.0 mA h g−1 after 2000 cycles at 5C with 86.7% capacity retention). Furthermore, the reversible biphasic reaction for cathodes was confirmed by Galvanostatic intermittent titration technique (GITT) and ex situ XRD. The DFT calculation revealed the influence of Ce3+-doping on the crystalline framework and electrochemical properties. Finally, the optimized NMVP cathode also showed great potential for practical utilization through the successful assembly of full cells.

研究领域: 材料科学 · 电化学 · 能源存储
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