Reference Electrodes for Use in Nonaqueous Solutions

Izutsu, Kôsuke

doi:10.1007/978-3-642-36188-3_6

Cited by 17 publications

(16 citation statements)

References 198 publications

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“…There is an extensive literature on the choice of electrodes for measuring non-aqueous fluids [ 54 , 55 , 56 , 57 , 58 , 59 ]. Methods have been developed to use semiconductor pH sensors for non-aqueous fluids.…”

Section: Measurements Of Ph Of Calcium Hydroxide Preparations and mentioning

confidence: 99%

Aspects of Solvent Chemistry for Calcium Hydroxide Medicaments

Athanassiadis

Walsh

2017

Materials

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Calcium hydroxide pastes have been used in endodontics since 1947. Most current calcium hydroxide endodontic pastes use water as the vehicle, which limits the dissolution of calcium hydroxide that can be achieved and, thereby, the maximum pH that can be achieved within the root canal system. Using polyethylene glycol as a solvent, rather than water, can achieve an increase in hydroxyl ions release compared to water or saline. By adopting non-aqueous solvents such as the polyethylene glycols (PEG), greater dissolution and faster hydroxyl ion release can be achieved, leading to enhanced antimicrobial actions, and other improvements in performance and biocompatibility.

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Section: Measurements Of Ph Of Calcium Hydroxide Preparations and mentioning

confidence: 99%

Aspects of Solvent Chemistry for Calcium Hydroxide Medicaments

Athanassiadis

Walsh

2017

Materials

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“… [10] For miniature electrochemical cells, which are commonly used for measurements with costly and scarce ionic liquids (IL), usually, pseudo‐REs or quasi‐REs are employed. [11] A similar problem arises for in situ scanning tunneling microscopy (STM) and in situ atomic force microscopy (AFM) measurements with aqueous and non‐aqueous electrolytes, where geometrical constraints limit the application of commercial REs. Some pseudo‐REs, such as the often‐used Pt or Ag wires, can show quasi‐stable electrode potentials under certain conditions.…”

Section: Introductionmentioning

confidence: 99%

“…This can be caused, for example, by uncontrolled surface reactions, pH changes due to OH − or H + formation, or the evolution of oxygen or other electrochemical active compounds, e.g., electrolyte decomposition products. [ 11 , 12 , 13 ]…”

Section: Introductionmentioning

confidence: 99%

“…[ 14 , 15 , 16 , 17 ] For Pt wires, coatings consisting of poly (vinylferrocene) (PVFc) or poly ( N ‐ferrocenyl‐methyl‐ N ‐allylimidazolium bromide) have been reported which use the Fc/Fc + ‐couple as a reference. [ 11 , 18 , 19 ] However, all of these electrodes suffer from insufficient chemical stability, i.e., are prone to dissolution in certain electrolytes or decompose in light or in contact with oxygen, which among other aspects, significantly lowers their lifetime. [ 12 , 20 ] Another more recent approach is based on small REs made from an activated carbon/Teflon composite, explicitly designed for in situ STM studies.…”

Section: Introductionmentioning

confidence: 99%

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Versatile 3D‐Printed Micro‐Reference Electrodes for Aqueous and Non‐Aqueous Solutions

et al. 2021

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While numerous reference electrodes suitable for aqueous electrolytes exist, there is no well-defined standardfor non-aqueous electrolytes.F urthermore,r eference electrodes are often large and do not meet the sizerequirements for small cells.Inthis work, we present asimple method for fabricating stable 3D-printed micro-reference electrodes.T he prints are made from polyvinylidene fluoride,w hich is chemically inert in strong acids,b ases,a nd commonly used non-aqueous solvents.W ec hose six different reference systems based on Ag, Cu, Zn, and Na, including three aqueous and three nonaqueous systems to demonstrate the versatility of the approach. Subsequently,w ec onducted cyclic voltammetry experiments and measured the potential difference between the aqueous homemade reference electrodes and ac ommercial Ag/AgClelectrode.F or the non-aqueous reference electrodes,w ec hose the ferrocene redox couple as an internal standard. Fromthese measurements,w ed educed that this new class of microreference electrodes is leak-tight and shows as table electrode potential.

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“…Therefore, the choice of REs is often of critical concern in experiment design. While in aqueous media, there are many reliable, well-established reference electrodes such as Ag/AgCl and calomel electrodes, − nonaqueous electroanalytical measurements commonly utilize Ag/Ag + RE ,, or quasi-reference electrodes (QREs) such as Ag wire. , In particular, electrochemical measurements in the domain of energy storage technologies such as Li-ion batteries (LiBs) often rely on Li metal strips or Li transition metal oxides as QREs. ,, Issues associated with the use of QREs include (i) unknown poising reaction (i.e., undefined terms in the Nernst equation) and (ii) drift in reference potential when the solution composition is changed (for instance, upon adding an internal standard such as ferrocene for calibration) among others. ,, While the Ag/Ag + RE avoids these issues, its use in nonaqueous media can lead to the development of junction potentials due to dissimilar solution compositions across the RE frit. − , Furthermore, the use of high reactivity REs and QREs such as Li metal limits their use in nonaqueous solvents such as acetonitrile, , wherein byproducts such as methane gas are generated . Additionally, in our own experience of using the Ag/Ag + RE, we have observed dark precipitates forming on the frit upon extended use, possibly due to photoreactivity of Ag + .…”

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confidence: 99%

Pt/Polypyrrole Quasi-References Revisited: Robustness and Application in Electrochemical Energy Storage Research

2021

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Choosing reference electrodes for nonaqueous electrochemical measurements, especially in energy storage research, is challenging due to lengthy experiments (>1 day), the lack of alternatives to the commonly used Ag/Ag + reference electrode (RE), the introduction of junction potentials, and the possibility of sample contamination. Often, quasi-reference electrodes (QREs) such as Ag wires and Li metal strips are used. However, small changes in electrolyte composition can cause large potential drifts, and their surfaces may be reactive to the solution. Here, we propose an alternative QRE based on polypyrrole electrodeposited on Pt wire (PPyQRE) encased in a glass tube with the open end sealed with commercial frits. While freestanding PPyQRE wires have been reported in the literature, simple encasing of the PPyQRE overcomes the above-mentioned drawbacks of QREs while providing a reliable reference potential that is closer to the performance of an RE. During cyclic voltammetric and bulk electrolysis testing of a redox mediator in solution, the encased PPyQRE exhibited stable reference potentials over multiple charge/discharge cycles with minimal drift (∼5 mV) after ∼2.25 days of operation. We also tested the reliability of our reference during the testing of multilayer graphene Li-ion anodes, which often involve cycling samples at highly reducing potentials (<−3 V vs Fc/Fc + ) over long durations (>1 day). In the same testing conditions, the Ag/Ag + electrode led to observable Ag deposits on the graphene and large potential drifts (∼50 mV), while the PPyQRE exhibited no measurable drift and revealed changes in voltammetric features that were obscured by reference drift when using Ag/Ag + . Minor reference drifts of ∼30 mV over long usage of the PPyQRE (∼2 months) can be addressed by calibration with a ferrocene couple at the end of experiments. These results highlight the advantages of using an encased PPyQRE as a simple and practical reference electrode for electrochemical measurements in the field of nonaqueous energy storage research.

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Reference Electrodes for Use in Nonaqueous Solutions

Cited by 17 publications

References 198 publications

Aspects of Solvent Chemistry for Calcium Hydroxide Medicaments

Aspects of Solvent Chemistry for Calcium Hydroxide Medicaments

Versatile 3D‐Printed Micro‐Reference Electrodes for Aqueous and Non‐Aqueous Solutions

Pt/Polypyrrole Quasi-References Revisited: Robustness and Application in Electrochemical Energy Storage Research

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