Structural Distortion in the Wadsley-Roth Niobium Molybdenum Oxide Phase Triggering Extraordinarily Stable Battery Performance

Zhibin Wu; Gemeng Liang; Wei Kong Pang; Jinshuo Zou; Wenchao Zhang; Libao Chen; Xiaobo Ji; Christophe Didier; Vanessa K Peterson; Carlo U Segre; Bernt Johannessen; Zaiping Guo

doi:10.1002/anie.202317941

Structural Distortion in the Wadsley-Roth Niobium Molybdenum Oxide Phase Triggering Extraordinarily Stable Battery Performance

Angew Chem Int Ed Engl. 2024 Feb 26;63(9):e202317941. doi: 10.1002/anie.202317941. Epub 2024 Jan 22.

Authors

Zhibin Wu^{1

2}, Gemeng Liang³, Wei Kong Pang², Jinshuo Zou³, Wenchao Zhang², Libao Chen¹, Xiaobo Ji^{1

4}, Christophe Didier^{2

5}, Vanessa K Peterson^{2

5}, Carlo U Segre⁶, Bernt Johannessen⁷, Zaiping Guo^{3

2}

Affiliations

¹ State Key Laboratory for Powder Metallurgy, Central South University, Changsha, 410083, China.
² Institute for Superconducting & Electronic Materials, School of Mechanical, Materials, Mechatronic and Biomedical Engineering, University of Wollongong, Wollongong, NSW 2522, Australia.
³ School of Chemical Engineering, The University of Adelaide, Adelaide, SA 5005, Australia.
⁴ College of Chemistry and Chemical Engineering, Central South University, Changsha, 410083, China.
⁵ Australian Centre for Neutron Scattering, Australian Nuclear Science and Technology Organisation, Sydney, NSW 2234, Australia.
⁶ Department of Physics and Center for Synchrotron Radiation Research and Instrumentation, Illinois Institute of Technology, Chicago, IL, 60616, USA.
⁷ Australian Synchrotron, 800 Blackburn Rd, Clayton, VIC 3168, Australia.

PMID: 38197798
DOI: 10.1002/anie.202317941

Abstract

Wadsley-Roth niobium oxide phases have attracted extensive research interest recently as promising battery anodes. We have synthesized the niobium-molybdenum oxide shear phase (Nb, Mo)₁₃ O₃₃ with superior electrochemical Li-ion storage performance, including an ultralong cycling lifespan of at least 15000 cycles. During electrochemical cycling, a reversible single-phase solid-solution reaction with lithiated intermediate solid solutions is demonstrated using in situ X-ray diffraction, with the valence and short-range structural changes of the electrode probed by in situ Nb and Mo K-edge X-ray absorption spectroscopy. This work reveals that the superior stability of niobium molybdenum oxides is underpinned by changes in octahedral distortion during electrochemical reactions, and we report an in-depth understanding of how this stabilizes the oxide structure during cycling with implications for future long-life battery material design.

Keywords: In Situ X-Ray Absorption Spectroscopy; In Situ X-Ray Diffraction; Niobium Molybdenum Oxide; Ultralong Battery Life; Wadsley-Roth Phases.

Abstract

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