A first-principles investigation of the influence of polyanionic boron doping on the stability and electrochemical behavior of Na3V2(PO4)3

  • Qiang Wang
  • Quanyu Wang
  • Mingying Zhang
  • Bo Han
  • Chenggang ZhouEmail author
  • Yanling Chen
  • Guobin LvEmail author
Original Paper


Na3V2(PO4)3 (NVP) is one of the most promising candidates for use as cathodes in room-temperature sodium ion batteries owing to its high structural stability and rapid Na+ transportation kinetics. The cationic doping of foreign ions at Na or V sites in the NVP lattice has proven to be an effective approach for enhancing the electrochemical performance of NVP. In this work, we present a first-principles density functional theory investigation of the impact of polyanionic boron doping at P sites on the structural and electrochemical behavior of NVP. Our simulation results suggest that B doping considerably increases the structural stability of NVP while shrinking its lattice size to some extent. Since B donates far fewer electrons to connected O atoms, the surrounding V atoms become more positive, causing the operating voltage to increase with B content. However, the reduction in lattice size is not beneficial for the Na+ transportation kinetics. As demonstrated by a search for the transition state, a concerted ion-exchange mechanism is preferred for Na+ transportation, and increased B doping leads to a higher Na+ diffusion barrier. Improvements in electrochemical performance due to B doping see (Hu et al. Adv Sci 3(12):1600112, 2016) appear to originate mainly from the resulting increased electrical conductivity.


Na3V2(PO4)3 Boron doping at P sites Operating voltage Na+ transportation kinetics Density functional theory 



This work was supported by the National Natural Science Foundation of China (grant 21773217) and Wuhan Science & Technology Project 2018010401011276. Support from the High-Performance Computing Platform, China University of Geosciences, is also gratefully acknowledged.


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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Faculty of Materials Science and ChemistryChina University of Geosciences WuhanWuhanPeople’s Republic of China
  2. 2.Network & Education Technology CenterChina University of Geosciences WuhanWuhanPeople’s Republic of China

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