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Title: Evaluation of a Ag/Ag2S reference electrode with long-term stability for electrochemistry in ionic liquids

Abstract

We report on a reference electrode designed for use in ionic liquids, based on a silver wire coated with silver sulfide. The reference electrode potential is determined by the concentrations of Ag+ and S2-, which are established by the solubility of the Ag2S coating on the Ag wire. While potential shifts of >100 mV during an experiment have been reported when using silver or platinum wire quasi-reference electrodes, the reference electrode reported here provides a stable potential over several months of experimental use. Additionally, our reference electrode can be prepared and used in a normal air atmosphere, and does not need to be assembled and used in a glovebox, or protected from light. In conclusion, the reference electrode has been characterized by voltammetry measurements of ferrocene and cobaltocenium hexafluorophosphate, and was found to slowly drift to more positive potentials at a rate of <1 mV/day for five of the six ionic liquids investigated.

Authors:
ORCiD logo [1];  [1]
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  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1430991
Report Number(s):
LLNL-JRNL-742242
Journal ID: ISSN 1388-2481
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Electrochemistry Communications
Additional Journal Information:
Journal Volume: 88; Journal Issue: C; Journal ID: ISSN 1388-2481
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Horwood, Corie, and Stadermann, Michael. Evaluation of a Ag/Ag2S reference electrode with long-term stability for electrochemistry in ionic liquids. United States: N. p., 2018. Web. doi:10.1016/j.elecom.2018.02.005.
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Horwood, Corie, & Stadermann, Michael. Evaluation of a Ag/Ag2S reference electrode with long-term stability for electrochemistry in ionic liquids. United States. https://doi.org/10.1016/j.elecom.2018.02.005
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Horwood, Corie, and Stadermann, Michael. Thu . "Evaluation of a Ag/Ag2S reference electrode with long-term stability for electrochemistry in ionic liquids". United States. https://doi.org/10.1016/j.elecom.2018.02.005. https://www.osti.gov/servlets/purl/1430991.
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@article{osti_1430991,
title = {Evaluation of a Ag/Ag2S reference electrode with long-term stability for electrochemistry in ionic liquids},
author = {Horwood, Corie and Stadermann, Michael},
abstractNote = {We report on a reference electrode designed for use in ionic liquids, based on a silver wire coated with silver sulfide. The reference electrode potential is determined by the concentrations of Ag+ and S2-, which are established by the solubility of the Ag2S coating on the Ag wire. While potential shifts of >100 mV during an experiment have been reported when using silver or platinum wire quasi-reference electrodes, the reference electrode reported here provides a stable potential over several months of experimental use. Additionally, our reference electrode can be prepared and used in a normal air atmosphere, and does not need to be assembled and used in a glovebox, or protected from light. In conclusion, the reference electrode has been characterized by voltammetry measurements of ferrocene and cobaltocenium hexafluorophosphate, and was found to slowly drift to more positive potentials at a rate of <1 mV/day for five of the six ionic liquids investigated.},
doi = {10.1016/j.elecom.2018.02.005},
journal = {Electrochemistry Communications},
number = C,
volume = 88,
place = {United States},
year = {2018},
month = {2}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1016/j.elecom.2018.02.005
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Cited by: 9 works
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Figures / Tables:

Figure 1 Figure 1: Cyclic voltammograms of (a) Fe(cp)20/+ (10 mM) and Co(cp)2+/0 (10 mM) in EMIM NTf2 (purple solid trace) and BMP NTf2 (red dashed trace), (b) Fe(cp)20/+ (10 mM) and Co(cp)2+/0 (10 mM) in EMIM NTf2, first 20 cycles (green) and last 20 cycles (purple dashed) during 96 hour experiment,more » and (c) Fe(cp)2 0/+ (9 mM) and Co(cp)2 +/0 (12 mM) in EMIM OTf with a Ag2S coated Ag wire RE contained in a fritted tube containing 0.1 % water (red solid trace) and 0.5 % water (blue dashed trace). (d) half-wave potentials of Co(cp)2 +/0 (10 mM) in 6 different ionic liquids, measured from cyclic voltammograms over a 50-75 day period. Experimental temperature was 50°C for (a) and (c) and 80°C for (b) and (d). All experiments performed with scan rate 50 mV·s-1, using a Ag2S coated Ag wire RE, Au milli-electrode WE and Pt rod CE.« less
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Works referenced in this record:

Reference Potential Calibration and Voltammetry at Macrodisk Electrodes of Metallocene Derivatives in the Ionic Liquid [bmim][PF 6 ]
journal, July 2002

  • Hultgren, Victoria M.; Mariotti, Andrew W. A.; Bond, Alan M.
  • Analytical Chemistry, Vol. 74, Issue 13
  • DOI: 10.1021/ac015729k

Evaluation of a Ag∣Ag+ reference electrode for use in room temperature ionic liquids
journal, September 2006

Morphological dependence of silver electrodeposits investigated by changing the ionic liquid solvent and the deposition parameters
journal, January 2016

  • Figueredo-Sobrinho, Francisco A. A.; Santos, Luis P. M.; Leite, Davi S.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 10
  • DOI: 10.1039/C5CP06665D

Practical considerations associated with voltammetric studies in room temperature ionic liquids
journal, January 2005

  • Zhang, Jie; Bond, Alan M.
  • The Analyst, Vol. 130, Issue 8
  • DOI: 10.1039/b504721h

1-Butyl-3-methylimidazolium cobalt tetracarbonyl [bmim][Co(CO)4]: a catalytically active organometallic ionic liquid
journal, January 2001

  • Brown, Richard J. C.; Welton, Thomas; Dyson, Paul J.
  • Chemical Communications, Issue 18
  • DOI: 10.1039/b104601m

Electroformation of Microlayers of Ionic Liquids in Undiluted Nitromethane and Its Homologues. Unusual Oscillations behind the Range of Limiting Steady-State Current
journal, December 2003

  • Caban, Karolina; Donten, Mikolaj; Stojek, Zbigniew
  • The Journal of Physical Chemistry B, Vol. 108, Issue 3
  • DOI: 10.1021/jp036637x

Enlarged electrochemical window in dialkyl-imidazolium cation based room-temperature air and water-stable molten salts
journal, January 1997

Critical evaluation of reference systems for voltammetric measurements in ionic liquids
journal, November 2012

Recommendations on reporting electrode potentials in nonaqueous solvents (Recommendations 1983)
journal, January 1984

Reference Electrode for Ionic Liquids
journal, February 2006

Trialkyl-Substituted Imidazolium-Based Ionic Liquids for Electrochemical Applications: Basic Physicochemical Properties
journal, January 2009

  • Andriyko, Yuriy O.; Reischl, Wolfgang; Nauer, Gerhard E.
  • Journal of Chemical & Engineering Data, Vol. 54, Issue 3
  • DOI: 10.1021/je800636k

New Class of Ag/AgCl Electrodes Based on Hydrophobic Ionic Liquid Saturated with AgCl
journal, September 2007

  • Kakiuchi, Takashi; Yoshimatsu, Takahiro; Nishi, Naoya
  • Analytical Chemistry, Vol. 79, Issue 18
  • DOI: 10.1021/ac070820v

Development of a Ag/Ag+ micro-reference electrode for electrochemical measurements in ionic liquids
journal, July 2011

Thermodynamic Properties of Silver Sulfide 1
journal, February 1951

  • Goates, J. Rex; Cole, Arthur G.; Gray, Earl L.
  • Journal of the American Chemical Society, Vol. 73, Issue 2
  • DOI: 10.1021/ja01146a063

Miniaturized Reference Electrodes. II. Use in Corrosive, Biological, and Organic Media
journal, August 2004

  • Ciobanu, Madalina; Wilburn, Jeremy P.; Lowy, Daniel A.
  • Electroanalysis, Vol. 16, Issue 16
  • DOI: 10.1002/elan.200302960

Volatilisation of ferrocene from ionic liquids: kinetics and mechanism
journal, January 2011

  • Fu, Chaopeng; Aldous, Leigh; Dickinson, Edmund J. F.
  • Chemical Communications, Vol. 47, Issue 25
  • DOI: 10.1039/c1cc12336j

Ionic liquid effects on the redox potential of ferrocene
journal, March 2012

Voltammetric Characterization of the Ferrocene|Ferrocenium and Cobaltocenium|Cobaltocene Redox Couples in RTILs
journal, February 2008

  • Rogers, Emma I.; Silvester, Debbie S.; Poole, Darren L.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 7
  • DOI: 10.1021/jp710134e

Nonadditivity of Faradaic Currents and Modification of Double Layer Capacitance in the Voltammetry of Mixtures of Ferrocene and Ferrocenium Salts in Ionic Liquids
journal, January 2010

  • Shiddiky, Muhammad J. A.; Torriero, Angel. A. J.; Reyna-González, Juan M.
  • Analytical Chemistry, Vol. 82, Issue 5
  • DOI: 10.1021/ac9020159

Effect of Water on the Electrochemical Window and Potential Limits of Room-Temperature Ionic Liquids
journal, December 2008

  • O’Mahony, Aoife M.; Silvester, Debbie S.; Aldous, Leigh
  • Journal of Chemical & Engineering Data, Vol. 53, Issue 12
  • DOI: 10.1021/je800678e
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    Methods and Protocols for Reliable Electrochemical Testing in Post-Li Batteries (Na, K, Mg, and Ca)
    journal, October 2019

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