Role of disorder in limiting the true multi-electron redox in ε-LiVOPO4

Rana, Jatinkumar; Shi, Yong; Zuba, Mateusz J.; Wiaderek, Kamila M.; Feng, Jun; Zhou, Hui; Ding, Jia; Wu, Tianpin; Cibin, Giannantonio; Balasubramanian, Mahalingam; Omenya, Fredrick; Chernova, Natasha A.; Chapman, Karena W.; Whittingham, M. Stanley; Piper, Louis F. J.

doi:10.1039/C8TA06469E

Title: Role of disorder in limiting the true multi-electron redox in ε-LiVOPO₄

Journal Article · Mon Sep 17 00:00:00 EDT 2018 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/C8TA06469E· OSTI ID:1493737

^[1];

^[1]; Zuba, Mateusz J. ^[1];

^[2]; Feng, Jun ^[1]; Zhou, Hui ^[1]; Ding, Jia ^[1]; Wu, Tianpin ^[2];

^[3];

^[2]; Omenya, Fredrick ^[1];

^[1];

^[4];

^[1];

^[1]

Binghamton Univ., Binghamton, NY (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Diamond Light Source Ltd., Oxfordshire (United Kingdom)
Stony Brook Univ., Stony Brook, NY (United States)

Recent advances in materials syntheses have enabled ε-LiVOPO₄ to deliver capacities approaching, and in some cases exceeding the theoretical value of 305 mA h g^–1 for 2Li intercalation, despite its poor electronic and ionic conductivity. However, not all of the capacity corresponds to the true electrochemical intercalation/deintercalation reactions as evidenced upon systematic tracking of V valence through combined operando and rate-dependent ex situ X-ray absorption study presented herein. Structural disorder and defects introduced in the material by high-energy ball milling impede kinetics of the high-voltage V⁵⁺/V⁴⁺ redox more severely than the low-voltage V⁴⁺/V³⁺ redox, promoting significant side reaction contributions in the high-voltage region, irrespective of cycling conditions. In conclusion, the present work emphasizes the need for nanoengineering of active materials without compromising their bulk structural integrity in order to fully utilize high-energy density of multi-electron cathode materials.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); Argonne National Laboratory (ANL), Argonne, IL (United States)

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

Grant/Contract Number:: AC02-06CH11357; SC0012583

OSTI ID:: 1493737

Alternate ID(s):: OSTI ID: 1475465

Journal Information:: Journal of Materials Chemistry. A, Vol. 6, Issue 42; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 22 works

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