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Title: Uniform second Li ion intercalation in solid state ϵ -LiVOPO 4

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.

Authors:
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Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science - Energy Frontier Research Center - NorthEast Center for Chemical Energy Storage (NECCES)
OSTI Identifier:
1392348
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Applied Physics Letters; Journal Volume: 109; Journal Issue: 5
Country of Publication:
United States
Language:
English

Citation Formats

Wangoh, Linda W., Sallis, Shawn, Wiaderek, Kamila M., Lin, Yuh-Chieh, Wen, Bohua, Quackenbush, Nicholas F., Chernova, Natasha A., Guo, Jinghua, Ma, Lu, Wu, Tianpin, Lee, Tien-Lin, Schlueter, Christoph, Ong, Shyue Ping, Chapman, Karena W., Whittingham, M. Stanley, and Piper, Louis F. J.. Uniform second Li ion intercalation in solid state ϵ -LiVOPO 4. United States: N. p., 2016. Web. doi:10.1063/1.4960452.
Wangoh, Linda W., Sallis, Shawn, Wiaderek, Kamila M., Lin, Yuh-Chieh, Wen, Bohua, Quackenbush, Nicholas F., Chernova, Natasha A., Guo, Jinghua, Ma, Lu, Wu, Tianpin, Lee, Tien-Lin, Schlueter, Christoph, Ong, Shyue Ping, Chapman, Karena W., Whittingham, M. Stanley, & Piper, Louis F. J.. Uniform second Li ion intercalation in solid state ϵ -LiVOPO 4. United States. doi:10.1063/1.4960452.
Wangoh, Linda W., Sallis, Shawn, Wiaderek, Kamila M., Lin, Yuh-Chieh, Wen, Bohua, Quackenbush, Nicholas F., Chernova, Natasha A., Guo, Jinghua, Ma, Lu, Wu, Tianpin, Lee, Tien-Lin, Schlueter, Christoph, Ong, Shyue Ping, Chapman, Karena W., Whittingham, M. Stanley, and Piper, Louis F. J.. Mon . "Uniform second Li ion intercalation in solid state ϵ -LiVOPO 4". United States. doi:10.1063/1.4960452.
@article{osti_1392348,
title = {Uniform second Li ion intercalation in solid state ϵ -LiVOPO 4},
author = {Wangoh, Linda W. and Sallis, Shawn and Wiaderek, Kamila M. and Lin, Yuh-Chieh and Wen, Bohua and Quackenbush, Nicholas F. and Chernova, Natasha A. and Guo, Jinghua and Ma, Lu and Wu, Tianpin and Lee, Tien-Lin and Schlueter, Christoph and Ong, Shyue Ping and Chapman, Karena W. and Whittingham, M. Stanley and Piper, Louis F. J.},
abstractNote = {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.},
doi = {10.1063/1.4960452},
journal = {Applied Physics Letters},
number = 5,
volume = 109,
place = {United States},
year = {Mon Aug 01 00:00:00 EDT 2016},
month = {Mon Aug 01 00:00:00 EDT 2016}
}