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

doi:10.1002/aenm.202002638

Vanadyl Phosphates A_xVOPO₄ (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

Chemistry

Research output: Contribution to journal › Review article › peer-review

21 Citations (Scopus)

Abstract

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 A_xVOPO₄ (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 A_xVOPO₄ 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 language	English
Article number	2002638
Journal	Advanced Energy Materials
Volume	10
Issue number	47
Early online date	30 Oct 2020
DOIs	https://doi.org/10.1002/aenm.202002638
Publication status	Published - 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.

Keywords

cathode materials
Li-ion batteries
vanadium compounds

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Cite this

Chernova, N. A., Hidalgo, M. F. V., Kaplan, C., Lee, K., Buyuker, I., Siu, C., Wen, B., Ding, J., Zuba, M., Wiaderek, K. M., Seymour, I. D., Britto, S., Piper, L. F. J., Ong, S. P., Chapman, K. W., Grey, C. P., & Whittingham, M. S. (2020). Vanadyl Phosphates A_xVOPO₄ (A = Li, Na, K) as Multielectron Cathodes for Alkali-Ion Batteries. Advanced Energy Materials, 10(47), Article 2002638. https://doi.org/10.1002/aenm.202002638

Chernova, NA, Hidalgo, MFV, Kaplan, C, Lee, K, Buyuker, I, Siu, C, Wen, B, Ding, J, Zuba, M, Wiaderek, KM, Seymour, ID, Britto, S, Piper, LFJ, Ong, SP, Chapman, KW, Grey, CP & Whittingham, MS 2020, 'Vanadyl Phosphates A_xVOPO₄ (A = Li, Na, K) as Multielectron Cathodes for Alkali-Ion Batteries', Advanced Energy Materials, vol. 10, no. 47, 2002638. https://doi.org/10.1002/aenm.202002638

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

abstract = "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.",

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AU - Chernova, Natasha A.

AU - Hidalgo, Marc Francis V.

AU - Kaplan, Carol

AU - Lee, Krystal

AU - Buyuker, Isiksu

AU - Siu, Carrie

AU - Wen, Bohua

AU - Ding, Jia

AU - Zuba, Mateusz

AU - Wiaderek, Kamila M.

AU - Seymour, Ieuan D.

AU - Britto, Sylvia

AU - Piper, Louis F.J.

AU - Ong, Shyue Ping

AU - Chapman, Karena W.

AU - Grey, Clare P.

AU - Whittingham, M. Stanley

N1 - 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.

PY - 2020/12/15

Y1 - 2020/12/15

N2 - 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.

AB - 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.

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