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Simultaneous Mn and Cl doping on Na 3 V 2 (PO 4 ) 3 with high performance for full sodium-ion batteries.

Haodi DongChangcheng LiuQue HuangYanjun Chen
Published in: Dalton transactions (Cambridge, England : 2003) (2024)
Nowadays, the poor conductivity and unstable structure have become obstacles for the popularization of Na 3 V 2 (PO 4 ) 3 (NVP). In the current work, a dual-modified Mn 0.1 Cl 0.3 -NVP composite doped with Mn and Cl is prepared by a facile sol-gel method. When Mn 2+ with a large ionic radius replaces small V 3+ , it can improve the stability of the NVP crystal structure. In addition, the replacement of V 3+ by Mn 2+ in a low valence state can generate redundant hole carriers, which is conducive to the rapid transport of electrons. The substitution of PO 4 3- by Cl - , which is more electronegative, can reduce the impedance and facilitate the movement of Na + . Owing to the synergistic effect of Mn and Cl co-substitution, the structural stability of NVP was systematically enhanced, and the electron transfer and ion diffusion were effectively improved. Consequently, the optimized Mn 0.1 Cl 0.3 -NVP sample demonstrated superior electrochemical performance and kinetic properties. It exhibited a high reversible capacity of 109.2 mA h g -1 at 0.1C. Even at 15 and 30C, high discharge capacities of 70.3 mA h g -1 and 68.2 mA h g -1 were observed after 2000 cycles with capacity retention above 80%. Moreover, it delivered remarkable capacities of 77.1 and 73.4 mA h g -1 at 100 and 200C with retained capacity values of 50.3 and 47 mA h g -1 , respectively, after 2000 cycles. Furthermore, the assembled Mn 0.1 Cl 0.3 -NVP//HC full cell delivered a high value of 94.7 mA h g -1 and lit LED bulbs, indicating its excellent application potential.
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