Metallicity, Atomic Disorder, and Li-Ion Storage in Fast-Charging Anodes

Kira E. Wyckoff; Arava Zohar; Tianyu Li; Yucheng Zhou; Linus Kautzsch; Welton Wang; Ananya Kepper; Ashlea R. Patterson; H. Cein Mandujano; Krishna Prasad Koirala; Anna Kallistova; Wenqian Xu; Jue Liu; Laurent Pilon; Anthony K. Cheetham; Ram Seshadri

doi:10.1021/jacs.5c06578

Metallicity, Atomic Disorder, and Li-Ion Storage in Fast-Charging Anodes

Kira E. Wyckoff
, Arava Zohar
, Tianyu Li
, Yucheng Zhou
, Linus Kautzsch
, Welton Wang
, Ananya Kepper
, Ashlea R. Patterson
, H. Cein Mandujano
, Krishna Prasad Koirala
, Anna Kallistova
, Wenqian Xu
, Jue Liu
, Laurent Pilon
, Anthony K. Cheetham
, Ram Seshadri

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Abstract

Oxides of Nb with Wadsley-Roth shear structures comprise a family of stable, high-rate anode materials for Li-ion batteries. A particular pair of them offers the unusual opportunity to test how important metallic conduction of the starting electrode is for electrode performance. The selected pair of compounds with similar 4 × 3 Wadsley-Roth block structures are insulating Ti₂Nb₁₀O₂₉ and metallic Nb₁₂O₂₉. A combination of diffraction, electrochemistry, magnetic measurements, and entropic potential measurements is employed to establish key findings for these two anode materials. We find that starting with a metallic oxide is not especially advantageous over a comparable material that readily transitions into a metallic state upon lithiation. Second, the rate performance appears to be dictated by ion mobility, and atomic Ti/Nb disorder in Ti₂Nb₁₀O₂₉ contributes to improved capacity retention at high rates by suppressing Li-ion ordering. However, subtle details in the nature of redox processes make Nb₁₂O₂₉ a slightly better electrode material for long-term cycling at slower rates.

Original language	English
Pages (from-to)	33432-33441
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	147
Issue number	37
DOIs	https://doi.org/10.1021/jacs.5c06578
State	Published - Sep 17 2025

Funding

We gratefully acknowledge the help of Dr. Arda Genç in acquiring HAADF-STEM images. This work was supported as part of the Center for Synthetic Control Across Length scales for Advancing Rechargeables (SCALAR), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award DE-SC0019381. The research reported here made use of shared facilities of the UC Santa Barbara Materials Research Science and Engineering Center (MRSEC, NSF DMR 2308708), a member of the Materials Research Facilities Network ( www.mrfn.org ). 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. A portion of this research used resources at the High Flux Isotope Reactor and the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.

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10.1021/jacs.5c06578

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Wyckoff, K. E., Zohar, A., Li, T., Zhou, Y., Kautzsch, L., Wang, W., Kepper, A., Patterson, A. R., Mandujano, H. C., Koirala, K. P., Kallistova, A., Xu, W., Liu, J., Pilon, L., Cheetham, A. K., & Seshadri, R. (2025). Metallicity, Atomic Disorder, and Li-Ion Storage in Fast-Charging Anodes. Journal of the American Chemical Society, 147(37), 33432-33441. https://doi.org/10.1021/jacs.5c06578

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title = "Metallicity, Atomic Disorder, and Li-Ion Storage in Fast-Charging Anodes",

abstract = "Oxides of Nb with Wadsley-Roth shear structures comprise a family of stable, high-rate anode materials for Li-ion batteries. A particular pair of them offers the unusual opportunity to test how important metallic conduction of the starting electrode is for electrode performance. The selected pair of compounds with similar 4 × 3 Wadsley-Roth block structures are insulating Ti2Nb10O29 and metallic Nb12O29. A combination of diffraction, electrochemistry, magnetic measurements, and entropic potential measurements is employed to establish key findings for these two anode materials. We find that starting with a metallic oxide is not especially advantageous over a comparable material that readily transitions into a metallic state upon lithiation. Second, the rate performance appears to be dictated by ion mobility, and atomic Ti/Nb disorder in Ti2Nb10O29 contributes to improved capacity retention at high rates by suppressing Li-ion ordering. However, subtle details in the nature of redox processes make Nb12O29 a slightly better electrode material for long-term cycling at slower rates.",

author = "Wyckoff, \{Kira E.\} and Arava Zohar and Tianyu Li and Yucheng Zhou and Linus Kautzsch and Welton Wang and Ananya Kepper and Patterson, \{Ashlea R.\} and Mandujano, \{H. Cein\} and Koirala, \{Krishna Prasad\} and Anna Kallistova and Wenqian Xu and Jue Liu and Laurent Pilon and Cheetham, \{Anthony K.\} and Ram Seshadri",

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Wyckoff, KE, Zohar, A, Li, T, Zhou, Y, Kautzsch, L, Wang, W, Kepper, A, Patterson, AR, Mandujano, HC, Koirala, KP, Kallistova, A, Xu, W, Liu, J, Pilon, L, Cheetham, AK & Seshadri, R 2025, 'Metallicity, Atomic Disorder, and Li-Ion Storage in Fast-Charging Anodes', Journal of the American Chemical Society, vol. 147, no. 37, pp. 33432-33441. https://doi.org/10.1021/jacs.5c06578

TY - JOUR

T1 - Metallicity, Atomic Disorder, and Li-Ion Storage in Fast-Charging Anodes

AU - Wyckoff, Kira E.

AU - Zohar, Arava

AU - Li, Tianyu

AU - Zhou, Yucheng

AU - Kautzsch, Linus

AU - Wang, Welton

AU - Kepper, Ananya

AU - Patterson, Ashlea R.

AU - Mandujano, H. Cein

AU - Koirala, Krishna Prasad

AU - Kallistova, Anna

AU - Xu, Wenqian

AU - Liu, Jue

AU - Pilon, Laurent

AU - Cheetham, Anthony K.

AU - Seshadri, Ram

PY - 2025/9/17

Y1 - 2025/9/17

N2 - Oxides of Nb with Wadsley-Roth shear structures comprise a family of stable, high-rate anode materials for Li-ion batteries. A particular pair of them offers the unusual opportunity to test how important metallic conduction of the starting electrode is for electrode performance. The selected pair of compounds with similar 4 × 3 Wadsley-Roth block structures are insulating Ti2Nb10O29 and metallic Nb12O29. A combination of diffraction, electrochemistry, magnetic measurements, and entropic potential measurements is employed to establish key findings for these two anode materials. We find that starting with a metallic oxide is not especially advantageous over a comparable material that readily transitions into a metallic state upon lithiation. Second, the rate performance appears to be dictated by ion mobility, and atomic Ti/Nb disorder in Ti2Nb10O29 contributes to improved capacity retention at high rates by suppressing Li-ion ordering. However, subtle details in the nature of redox processes make Nb12O29 a slightly better electrode material for long-term cycling at slower rates.

AB - Oxides of Nb with Wadsley-Roth shear structures comprise a family of stable, high-rate anode materials for Li-ion batteries. A particular pair of them offers the unusual opportunity to test how important metallic conduction of the starting electrode is for electrode performance. The selected pair of compounds with similar 4 × 3 Wadsley-Roth block structures are insulating Ti2Nb10O29 and metallic Nb12O29. A combination of diffraction, electrochemistry, magnetic measurements, and entropic potential measurements is employed to establish key findings for these two anode materials. We find that starting with a metallic oxide is not especially advantageous over a comparable material that readily transitions into a metallic state upon lithiation. Second, the rate performance appears to be dictated by ion mobility, and atomic Ti/Nb disorder in Ti2Nb10O29 contributes to improved capacity retention at high rates by suppressing Li-ion ordering. However, subtle details in the nature of redox processes make Nb12O29 a slightly better electrode material for long-term cycling at slower rates.

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SN - 0002-7863

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EP - 33441

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 37

ER -

Metallicity, Atomic Disorder, and Li-Ion Storage in Fast-Charging Anodes

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