Vanadyl Phosphates AxVOPO4 (A = Li, Na, K) as Multielectron Cathodes for Alkali-Ion Batteries

Natasha A. Chernova, Marc Francis V. Hidalgo, Carol Kaplan, Krystal Lee, Isiksu Buyuker, Carrie Siu, Bohua Wen, Jia Ding, Mateusz Zuba, Kamila M. Wiaderek, Ieuan D. Seymour, Sylvia Britto, Louis F.J. Piper, Shyue Ping Ong, Karena W. Chapman, Clare P. Grey, M. Stanley Whittingham* (Corresponding Author)

*Corresponding author for this work

Research output: Contribution to journalReview articlepeer-review

21 Citations (Scopus)


Vanadyl phosphates comprise a class of multielectron cathode materials capable of cycling two Li+, about 1.66 Na+, and some K+ ions per redox center. In this review, structures, thermodynamic stabilities, and ion diffusion kinetics of various AxVOPO4 (A = Li, Na, K, NH4) polymorphs are discussed. Both the experimental data and first-principle calculations indicate kinetic limitations for alkali metal ions cycling, especially between for 0 ≤ x ≤ 1, and metastability of phases with x > 1. This creates challenges for multiple-ion cycling, as the slow kinetics call for nanosized particles, which being metastable and reactive with organic electrolytes are prone to side reactions. Thus, various synthesis approaches, surface coating, and transition metal ion substitution strategies are discussed here as possible ways to stabilize AxVOPO4 structures and improve alkali metal ion diffusion. The role of advanced characterization techniques, such as X-ray absorption spectroscopy, diffraction, pair distribution function analysis and 7Li and 31P NMR, in understanding the reaction mechanism from both structural and electronic points of view is emphasized.

Original languageEnglish
Article number2002638
JournalAdvanced Energy Materials
Issue number47
Early online date30 Oct 2020
Publication statusPublished - 15 Dec 2020

Bibliographical note

Funding Information:
This work was supported as part of NECCES, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award No. DE-SC0012583. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.


  • cathode materials
  • Li-ion batteries
  • vanadium compounds


Dive into the research topics of 'Vanadyl Phosphates AxVOPO4 (A = Li, Na, K) as Multielectron Cathodes for Alkali-Ion Batteries'. Together they form a unique fingerprint.

Cite this