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Title: Early Stage Anodic Instability of Glassy Carbon Electrodes in Propylene Carbonate Solvent Containing Lithium Hexafluorophosphate

Abstract

In this paper, irreversible changes to the morphology of glassy carbon (GC) electrodes at potentials between 3.5 and 4.5 V vs Li/Li + in propylene carbonate (PC) solvent containing lithium hexafluorophosphate (LiPF 6) are reported. Analysis of cyclic voltammetry (CV) experiments in the range of 3.0 to 6.0 V shows that the capacitance of the electrochemical double -layer increased irreversibly beginning at potentials as low as 3.5 V. These changes resulted from nonfaradaic interactions, and were not due to oxidative electrochemical decomposition of the electrode and electrolyte, anion intercalation, nor caused by the presence of water, a common impurity in organic electrolyte solutions. Atomic force microscopy (AFM) images revealed that increasing the potential of a bare GC surface from 3.0 to 4.5 V resulted in a 6X increase in roughness, in good agreement with the changes in double -layer capacitance. Treating the GC surface via exposure to trichloromethylsilane vapors resulted in a stable double -layer capacitance between 3.0 and 4.5 V, and this treatment also correlated with less roughening. Lastly, these results inform future efforts aimed at controlling surface composition and morphology of carbon electrodes.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1];  [2]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research and Materials Science Division
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Department of Chemical Engineering
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1411150
Grant/Contract Number:
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 33; Journal Issue: 43; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Carino, Emily V., Newman, Daniel J., Connell, Justin G., Kim, Chaerin, and Brushett, Fikile R. Early Stage Anodic Instability of Glassy Carbon Electrodes in Propylene Carbonate Solvent Containing Lithium Hexafluorophosphate. United States: N. p., 2017. Web. doi:10.1021/acs.langmuir.7b02243.
Carino, Emily V., Newman, Daniel J., Connell, Justin G., Kim, Chaerin, & Brushett, Fikile R. Early Stage Anodic Instability of Glassy Carbon Electrodes in Propylene Carbonate Solvent Containing Lithium Hexafluorophosphate. United States. doi:10.1021/acs.langmuir.7b02243.
Carino, Emily V., Newman, Daniel J., Connell, Justin G., Kim, Chaerin, and Brushett, Fikile R. Tue . "Early Stage Anodic Instability of Glassy Carbon Electrodes in Propylene Carbonate Solvent Containing Lithium Hexafluorophosphate". United States. doi:10.1021/acs.langmuir.7b02243.
@article{osti_1411150,
title = {Early Stage Anodic Instability of Glassy Carbon Electrodes in Propylene Carbonate Solvent Containing Lithium Hexafluorophosphate},
author = {Carino, Emily V. and Newman, Daniel J. and Connell, Justin G. and Kim, Chaerin and Brushett, Fikile R.},
abstractNote = {In this paper, irreversible changes to the morphology of glassy carbon (GC) electrodes at potentials between 3.5 and 4.5 V vs Li/Li+ in propylene carbonate (PC) solvent containing lithium hexafluorophosphate (LiPF6) are reported. Analysis of cyclic voltammetry (CV) experiments in the range of 3.0 to 6.0 V shows that the capacitance of the electrochemical double -layer increased irreversibly beginning at potentials as low as 3.5 V. These changes resulted from nonfaradaic interactions, and were not due to oxidative electrochemical decomposition of the electrode and electrolyte, anion intercalation, nor caused by the presence of water, a common impurity in organic electrolyte solutions. Atomic force microscopy (AFM) images revealed that increasing the potential of a bare GC surface from 3.0 to 4.5 V resulted in a 6X increase in roughness, in good agreement with the changes in double -layer capacitance. Treating the GC surface via exposure to trichloromethylsilane vapors resulted in a stable double -layer capacitance between 3.0 and 4.5 V, and this treatment also correlated with less roughening. Lastly, these results inform future efforts aimed at controlling surface composition and morphology of carbon electrodes.},
doi = {10.1021/acs.langmuir.7b02243},
journal = {Langmuir},
number = 43,
volume = 33,
place = {United States},
year = {Tue Sep 19 00:00:00 EDT 2017},
month = {Tue Sep 19 00:00:00 EDT 2017}
}

Journal Article:
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  • Carbon and its related materials have been studied extensively as negative electrode materials for rechargeable lithium batteries since they can reversibly intercalate lithium ion. The electrolytic conductivities of lithium trifluoromethanesulfate (LiCF[sub 3]SO[sub 3]) and lithium hexafluorophosphate (LiPF[sub 6]) have been investigated as a function of the solvent composition. The organic solvent tested was ethylene carbonate (EC) or propylene carbonate mixed with 1,2-dimethoxyethane, diethyl carbonate, or dimethyl carbonate (DMC). For each solvent system, the electrolytes containing LiCF[sub 3]SO[sub 3] showed nearly half the values of the conductivity of the corresponding systems with LiPF[sub 6]. High discharge capacities (ca. 200 mAh/g) formore » charge-discharge cycling of the carbon fiber electrode with a graphite structure were obtained in LiCF[sub 3]SO[sub 3]/EC-based electrolytes. Especially, the highest coulombic efficiency (98%) was obtained in the LiCF[sub 3]SO[sub 3]/EC-DMC system. The EC-based electrolyte systems containing LiCF[sub 3]SO[sub 3] were found to be more compatible with the carbon fiber electrode than the systems containing LiPF[sub 6].« less
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