Reversible Electrochemical Lithium Cycling in a Vanadium(IV)- and Niobium(V)-Based Wadsley–Roth Phase

Lawrence, Erick A.; Davenport, Matthew A.; Devi, Reshma; Cai, Zijian; Avdeev, Maxim; Belnap, Jonathan R.; Liu, Jue; Alnaser, Husain; Ho, Alice; Sparks, Taylor D.; Sai Gautam, Gopalakrishnan; Allred, Jared M.; Ji, Huiwen

doi:10.1021/acs.chemmater.2c03465

Reversible Electrochemical Lithium Cycling in a Vanadium(IV)- and Niobium(V)-Based Wadsley–Roth Phase

Journal Article · Tue Apr 18 00:00:00 EDT 2023 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.2c03465· OSTI ID:2349504

^[1]; Davenport, Matthew A. ^[2]; Devi, Reshma ^[3]; ^[4]; ^[5]; Belnap, Jonathan R. ^[6]; ^[7]; Alnaser, Husain ^[6]; Ho, Alice ^[8]; ^[6]; ^[3]; ^[2]; Ji, Huiwen ^[6]

Univ. of Utah, Salt Lake City, UT (United States); The University of Alabama
Univ. of Alabama, Tuscaloosa, AL (United States)
Indian Institute of Science, Karnataka (India)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Australian Nuclear Science and Technology Organisation (ANSTO), Sydney, NSW (Australia); Univ. of Sydney, NSW (Australia)
Univ. of Utah, Salt Lake City, UT (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Carnegie Mellon Univ., Pittsburgh, PA (United States)

Fast charging remains one of the greatest safety challenges in Li-ion batteries due to Li-dendrite growth occurring on graphite anodes if they are lithiated too quickly. The search for high-rate anodes has highlighted materials in the Wadsley–Roth (WR) shear phase family. The relative abundance of V compared with traditional WR compositions of Nb and W makes V-based phases attractive. However, the high voltage and poor reversibility typically associated with V redox have made V-rich WR phases less studied than Nb- and W-rich phases. Here, we show that a new V-rich Wadsley–Roth phase, V₇Nb₆O₂₉, achieves excellent rate capability and 80% capacity retention after 228 cycles with a relatively low average voltage of 1.76 V vs Li/Li⁺ compared with other V-rich WR phases. Single-crystal X-ray diffraction reveals a P4/m space group with repeating 2 × 2 × ∞ and 3 × 3 × ∞ blocks of V⁴⁺ and Nb⁵⁺ octahedra. Finally, combined neutron pair distribution function analysis, X-ray absorption spectroscopy, and density functional theory calculations show that V redox is the primary source of capacity and that cycling stability is provided by the stable octahedral coordination adopted by V⁴⁺ in the material.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Alabama, Tuscaloosa, AL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0018174

OSTI ID:: 2349504

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 9 Vol. 35; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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25 ENERGY STORAGE
36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Wadsley-Roth phase
battery
electrochemical cell
transition metal oxide
neutron pair distribution function
single crystal x-ray diffraction

Reversible Electrochemical Lithium Cycling in a Vanadium(IV)- and Niobium(V)-Based Wadsley–Roth Phase

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