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

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

doi:10.1039/c8ta06469e

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

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

Research output: Contribution to journal › Article › peer-review

23 Scopus citations

Abstract

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. 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.

Original language	English
Pages (from-to)	20669-20677
Number of pages	9
Journal	Journal of Materials Chemistry A
Volume	6
Issue number	42
DOIs	https://doi.org/10.1039/c8ta06469e
State	Published - 2018
Externally published	Yes

Funding

This work was supported as part of the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award# DESC0012583. 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. The authors gratefully acknowledge Dr Qing Ma for his assistance during XAS experiments at beamline 5BM of Advanced Photon Source. The authors also acknowledge Diamond Light Source for access to beamline B18 (Proposal# SP18423) that contributed to the results presented here. M. J. Z. was supported as part of the Multidisciplinary GAANN in Smart Energy Materials, a Graduate Areas of National Need, funded by the U.S. Department of Education, under Award# P200A150135. The authors are grateful to Dr Matthew Wahila for inspiring Table of Contents graphics and cover page artworks.

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10.1039/c8ta06469e

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Rana, J., Shi, Y., Zuba, M. J., Wiaderek, K. M., Feng, J., Zhou, H., Ding, J., Wu, T., Cibin, G., Balasubramanian, M., Omenya, F., Chernova, N. A., Chapman, K. W., Whittingham, M. S., & Piper, L. F. J. (2018). Role of disorder in limiting the true multi-electron redox in ε-LiVOPO₄ Journal of Materials Chemistry A, 6(42), 20669-20677. https://doi.org/10.1039/c8ta06469e

@article{8c6f50d0ccc044968762a1cb7271e23c,

title = "Role of disorder in limiting the true multi-electron redox in ε-LiVOPO4 ",

abstract = "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. 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.",

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

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry.",

year = "2018",

doi = "10.1039/c8ta06469e",

language = "English",

volume = "6",

pages = "20669--20677",

journal = "Journal of Materials Chemistry A",

issn = "2050-7488",

publisher = "Royal Society of Chemistry",

number = "42",

}

Rana, J, Shi, Y, Zuba, MJ, Wiaderek, KM, Feng, J, Zhou, H, Ding, J, Wu, T, Cibin, G, Balasubramanian, M, Omenya, F, Chernova, NA, Chapman, KW, Whittingham, MS & Piper, LFJ 2018, 'Role of disorder in limiting the true multi-electron redox in ε-LiVOPO₄ ', Journal of Materials Chemistry A, vol. 6, no. 42, pp. 20669-20677. https://doi.org/10.1039/c8ta06469e

TY - JOUR

T1 - Role of disorder in limiting the true multi-electron redox in ε-LiVOPO4

AU - Rana, Jatinkumar

AU - Shi, Yong

AU - Zuba, Mateusz J.

AU - Wiaderek, Kamila M.

AU - Feng, Jun

AU - Zhou, Hui

AU - Ding, Jia

AU - Wu, Tianpin

AU - Cibin, Giannantonio

AU - Balasubramanian, Mahalingam

AU - Omenya, Fredrick

AU - Chernova, Natasha A.

AU - Chapman, Karena W.

AU - Whittingham, M. Stanley

AU - Piper, Louis F.J.

PY - 2018

Y1 - 2018

N2 - 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. 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.

AB - 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. 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.

UR - https://www.scopus.com/pages/publications/85056111577

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DO - 10.1039/c8ta06469e

M3 - Article

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SN - 2050-7488

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EP - 20677

JO - Journal of Materials Chemistry A

JF - Journal of Materials Chemistry A

IS - 42

ER -

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

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