Uniform second Li ion intercalation in solid state Ïμ -LiVOPO4

Linda W. Wangoh; Shawn Sallis; Kamila M. Wiaderek; Yuh Chieh Lin; Bohua Wen; Nicholas F. Quackenbush; Natasha A. Chernova; Jinghua Guo; Lu Ma; Tianpin Wu; Tien Lin Lee; Christoph Schlueter; Shyue Ping Ong; Karena W. Chapman; M. Stanley Whittingham; Louis F.J. Piper

doi:10.1063/1.4960452

Uniform second Li ion intercalation in solid state Ïμ -LiVOPO₄

Linda W. Wangoh
, Shawn Sallis
, Kamila M. Wiaderek
, Yuh Chieh Lin
, Bohua Wen
, Nicholas F. Quackenbush
, Natasha A. Chernova
, Jinghua Guo
, Lu Ma
, Tianpin Wu
, Tien Lin Lee
, Christoph Schlueter
, Shyue Ping Ong
, Karena W. Chapman
, M. Stanley Whittingham
, Louis F.J. Piper

Chemistry

State University of New York Binghamton University
United States Department of Energy
University of California at San Diego
Lawrence Berkeley National Laboratory
Diamond Light Source

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

23 Scopus citations

Abstract

Full, reversible intercalation of two Li⁺ has not yet been achieved in promising VOPO₄ electrodes. A pronounced Li⁺ gradient has been reported in the low voltage window (i.e., second lithium reaction) that is thought to originate from disrupted kinetics in the high voltage regime (i.e., first lithium reaction). Here, we employ a combination of hard and soft x-ray photoelectron and absorption spectroscopy techniques to depth profile solid state synthesized LiVOPO₄ cycled within the low voltage window only. Analysis of the vanadium environment revealed no evidence of a Li⁺ gradient, which combined with almost full theoretical capacity confirms that disrupted kinetics in the high voltage window are responsible for hindering full two lithium insertion. Furthermore, we argue that the uniform Li⁺ intercalation is a prerequisite for the formation of intermediate phases Li_1.50VOPO₄ and Li_1.75VOPO₄. The evolution from LiVOPO₄ to Li₂VOPO₄ via the intermediate phases is confirmed by direct comparison between O K-edge absorption spectroscopy and density functional theory.

Original language	English
Article number	053904
Journal	Applied Physics Letters
Volume	109
Issue number	5
DOIs	https://doi.org/10.1063/1.4960452
State	Published - Aug 1 2016

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Wangoh, L. W., Sallis, S., Wiaderek, K. M., Lin, Y. C., Wen, B., Quackenbush, N. F., Chernova, N. A., Guo, J., Ma, L., Wu, T., Lee, T. L., Schlueter, C., Ong, S. P., Chapman, K. W., Whittingham, M. S., & Piper, L. F. J. (2016). Uniform second Li ion intercalation in solid state Ïμ -LiVOPO₄. Applied Physics Letters, 109(5), Article 053904. https://doi.org/10.1063/1.4960452

@article{782143c24f954644a8685818f0297881,

title = "Uniform second Li ion intercalation in solid state {\"I}μ -LiVOPO4",

abstract = "Full, reversible intercalation of two Li+ has not yet been achieved in promising VOPO4 electrodes. A pronounced Li+ gradient has been reported in the low voltage window (i.e., second lithium reaction) that is thought to originate from disrupted kinetics in the high voltage regime (i.e., first lithium reaction). Here, we employ a combination of hard and soft x-ray photoelectron and absorption spectroscopy techniques to depth profile solid state synthesized LiVOPO4 cycled within the low voltage window only. Analysis of the vanadium environment revealed no evidence of a Li+ gradient, which combined with almost full theoretical capacity confirms that disrupted kinetics in the high voltage window are responsible for hindering full two lithium insertion. Furthermore, we argue that the uniform Li+ intercalation is a prerequisite for the formation of intermediate phases Li1.50VOPO4 and Li1.75VOPO4. The evolution from LiVOPO4 to Li2VOPO4 via the intermediate phases is confirmed by direct comparison between O K-edge absorption spectroscopy and density functional theory.",

author = "Wangoh, \{Linda W.\} and Shawn Sallis and Wiaderek, \{Kamila M.\} and Lin, \{Yuh Chieh\} and Bohua Wen and Quackenbush, \{Nicholas F.\} and Chernova, \{Natasha A.\} and Jinghua Guo and Lu Ma and Tianpin Wu and Lee, \{Tien Lin\} and Christoph Schlueter and Ong, \{Shyue Ping\} and Chapman, \{Karena W.\} and Whittingham, \{M. Stanley\} and Piper, \{Louis F.J.\}",

note = "Publisher Copyright: {\textcopyright} 2016 Author(s).",

year = "2016",

month = aug,

day = "1",

doi = "10.1063/1.4960452",

language = "English",

volume = "109",

journal = "Applied Physics Letters",

issn = "0003-6951",

number = "5",

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TY - JOUR

T1 - Uniform second Li ion intercalation in solid state Ïμ -LiVOPO4

AU - Wangoh, Linda W.

AU - Sallis, Shawn

AU - Wiaderek, Kamila M.

AU - Lin, Yuh Chieh

AU - Wen, Bohua

AU - Quackenbush, Nicholas F.

AU - Chernova, Natasha A.

AU - Guo, Jinghua

AU - Ma, Lu

AU - Wu, Tianpin

AU - Lee, Tien Lin

AU - Schlueter, Christoph

AU - Ong, Shyue Ping

AU - Chapman, Karena W.

AU - Whittingham, M. Stanley

AU - Piper, Louis F.J.

PY - 2016/8/1

Y1 - 2016/8/1

N2 - Full, reversible intercalation of two Li+ has not yet been achieved in promising VOPO4 electrodes. A pronounced Li+ gradient has been reported in the low voltage window (i.e., second lithium reaction) that is thought to originate from disrupted kinetics in the high voltage regime (i.e., first lithium reaction). Here, we employ a combination of hard and soft x-ray photoelectron and absorption spectroscopy techniques to depth profile solid state synthesized LiVOPO4 cycled within the low voltage window only. Analysis of the vanadium environment revealed no evidence of a Li+ gradient, which combined with almost full theoretical capacity confirms that disrupted kinetics in the high voltage window are responsible for hindering full two lithium insertion. Furthermore, we argue that the uniform Li+ intercalation is a prerequisite for the formation of intermediate phases Li1.50VOPO4 and Li1.75VOPO4. The evolution from LiVOPO4 to Li2VOPO4 via the intermediate phases is confirmed by direct comparison between O K-edge absorption spectroscopy and density functional theory.

AB - Full, reversible intercalation of two Li+ has not yet been achieved in promising VOPO4 electrodes. A pronounced Li+ gradient has been reported in the low voltage window (i.e., second lithium reaction) that is thought to originate from disrupted kinetics in the high voltage regime (i.e., first lithium reaction). Here, we employ a combination of hard and soft x-ray photoelectron and absorption spectroscopy techniques to depth profile solid state synthesized LiVOPO4 cycled within the low voltage window only. Analysis of the vanadium environment revealed no evidence of a Li+ gradient, which combined with almost full theoretical capacity confirms that disrupted kinetics in the high voltage window are responsible for hindering full two lithium insertion. Furthermore, we argue that the uniform Li+ intercalation is a prerequisite for the formation of intermediate phases Li1.50VOPO4 and Li1.75VOPO4. The evolution from LiVOPO4 to Li2VOPO4 via the intermediate phases is confirmed by direct comparison between O K-edge absorption spectroscopy and density functional theory.

UR - https://www.scopus.com/pages/publications/84981332668

U2 - 10.1063/1.4960452

DO - 10.1063/1.4960452

M3 - Article

AN - SCOPUS:84981332668

SN - 0003-6951

VL - 109

JO - Applied Physics Letters

JF - Applied Physics Letters

IS - 5

M1 - 053904

ER -

Uniform second Li ion intercalation in solid state Ïμ -LiVOPO₄

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