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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]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (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.
Horwood, Corie, & Stadermann, Michael. Evaluation of a Ag/Ag2S reference electrode with long-term stability for electrochemistry in ionic liquids. United States. doi:10.1016/j.elecom.2018.02.005.
Horwood, Corie, and Stadermann, Michael. Thu . "Evaluation of a Ag/Ag2S reference electrode with long-term stability for electrochemistry in ionic liquids". United States. doi:10.1016/j.elecom.2018.02.005. https://www.osti.gov/servlets/purl/1430991.
@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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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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