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Title: Role of disorder in limiting the true multi-electron redox in ε-LiVOPO 4

Abstract

Recent advances in materials syntheses have enabled ε-LiVOPO 4 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 V 5+/V 4+ redox more severely than the low-voltage V 4+/V 3+ 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.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [2];  [1];  [1];  [1];  [2]; ORCiD logo [3]; ORCiD logo [2];  [1]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [1]
  1. Binghamton Univ., Binghamton, NY (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Diamond Light Source Ltd., Oxfordshire (United Kingdom)
  4. Stony Brook Univ., Stony Brook, NY (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1493737
Alternate Identifier(s):
OSTI ID: 1475465
Grant/Contract Number:  
AC02-06CH11357; SC0012583
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 6; Journal Issue: 42; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; battery

Citation Formats

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, and Piper, Louis F. J. Role of disorder in limiting the true multi-electron redox in ε-LiVOPO4. United States: N. p., 2018. Web. doi:10.1039/C8TA06469E.
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. Role of disorder in limiting the true multi-electron redox in ε-LiVOPO4. United States. doi:10.1039/C8TA06469E.
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, and Piper, Louis F. J. Mon . "Role of disorder in limiting the true multi-electron redox in ε-LiVOPO4". United States. doi:10.1039/C8TA06469E. https://www.osti.gov/servlets/purl/1493737.
@article{osti_1493737,
title = {Role of disorder in limiting the true multi-electron redox in ε-LiVOPO4},
author = {Rana, Jatinkumar and Shi, Yong and Zuba, Mateusz J. and Wiaderek, Kamila M. and Feng, Jun and Zhou, Hui and Ding, Jia and Wu, Tianpin and Cibin, Giannantonio and Balasubramanian, Mahalingam and Omenya, Fredrick and Chernova, Natasha A. and Chapman, Karena W. and Whittingham, M. Stanley and Piper, Louis F. J.},
abstractNote = {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.},
doi = {10.1039/C8TA06469E},
journal = {Journal of Materials Chemistry. A},
number = 42,
volume = 6,
place = {United States},
year = {2018},
month = {9}
}

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Works referenced in this record:

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