Electrochemical Investigation of Calcium Substituted Monoclinic Li3V2(PO4)3 Negative Electrode Materials for Sodium- and Potassium-Ion Batteries

  • Qiang Fu
  • , Bingrui Guo
  • , Weibo Hua
  • , Angelina Sarapulova
  • , Lihua Zhu
  • , Peter G. Weidler
  • , Alexander Missyul
  • , Michael Knapp
  • , Helmut Ehrenberg
  • , Sonia Dsoke

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

Herein, the electrochemical properties and reaction mechanism of Li3‒2xCaxV2(PO4)3/C (x = 0, 0.5, 1, and 1.5) as negative electrode materials for sodium-ion/potassium-ion batteries (SIBs/PIBs) are investigated. All samples undergo a mixed contribution of diffusion-controlled and pseudocapacitive-type processes in SIBs and PIBs via Trasatti Differentiation Method, while the latter increases with Ca content increase. Among them, Li3V2(PO4)3/C exhibits the highest reversible capacity in SIBs and PIBs, while Ca1.5V2(PO4)3/C shows the best rate performance with a capacity retention of 46% at 20 C in SIBs and 47% at 10 C in PIBs. This study demonstrates that the specific capacity of this type of material in SIBs and PIBs does not increase with the Ca-content as previously observed in lithium-ion system, but the stability and performance at a high C-rate can be improved by replacing Li+ with Ca2+. This indicates that the insertion of different monovalent cations (Na+/K+) can strongly influence the redox reaction and structure evolution of the host materials, due to the larger ion size of Na+ and K+ and their different kinetic properties with respect to Li+. Furthermore, the working mechanism of both LVP/C and Ca1.5V2(PO4)3/C in SIBs are elucidated via in operando synchrotron diffraction and in operando X-ray absorption spectroscopy.

Original languageEnglish
Article number2304102
JournalSmall
Volume19
Issue number44
DOIs
StatePublished - 1 Nov 2023

Keywords

  • electrochemical performance
  • monoclinic LiV(PO)
  • negative electrode materials
  • potassium-ion batteries
  • sodium-ion batteries

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