Extending and Automating Quantitative Microelectrode Voltammetry through an Oblate Spheroidal Coordinate Framework

2023

Preprint

Voltammetry is a powerful analytical technique for evaluating electrochemical reactions and holds particular promise for interrogating electrolyte solutions suitable for energy storage technologies, including examining features such as state-of-charge and state-of-health. However, individual voltammetry techniques are likely to be subcomponents of broader analytical workflows that incorporate complementary methods to diagnose evolving electrolyte solutions of uncertain composition. As such, we demonstrate that jointly evaluating electrolyte solutions with distinct voltammetric modes can enhance the capabilities and sensitivities of characterization protocols. Specifically, by considering both macroelectrode cyclic square wave and microelectrode cyclic voltammograms in sequential ("one after another") and simultaneous ("all at once") manners, the composition of an electrolyte solution may be estimated with greater accuracy, and analytes that exhibit near identical electrode potentials may be more readily differentiated. We additionally explore means of further improving this method, finding that protocol accuracy increases when multiple voltammetry techniques are included in the training dataset. We also observe that the algorithm typically becomes more confident--but not necessarily more accurate--when the number of data points increases. Overall, these studies show that the sequential and simultaneous methods may hold utility when evaluating multiple voltammetry datasets that, in turn, may be leveraged to streamline diagnostic workflows used to examine electrolyte solutions within electrochemical technologies.

show abstract

Section: Modified Library Construction From Both Cyclic Square Wave A...mentioning

confidence: 99%

Leveraging graphical models to enhance in situ analyte identification via multiple voltammetric techniques

2023

Preprint

show abstract

“…In Equations ( 1 Once the experimental voltammograms were acquired, the diffusion coefficient of the reduced species was determined by using the estimated microelectrode radius, microelectrode voltammograms acquired almost immediately after assembling the three-electrode configuration, and steady-state microelectrode models. [55][56][57] For this regression process, the redox potential was also estimated, and, for simplicity, the ratio of diffusion coefficients was assumed to be 1 (i.e.,…”

Section: Modified Library Construction From Both Cyclic Square Wave A...mentioning

confidence: 99%

Leveraging graphical models to enhance in situ analyte identification via multiple voltammetric techniques

2022

Preprint

Voltammetry is a powerful analytical technique for evaluating electrochemical reactions and holds particular promise for interrogating electrolyte solutions suitable for energy storage technologies, including examining features such as state-of-charge and state-of-health. However, individual voltammetry techniques are likely to be subcomponents of broader analytical workflows that incorporate complementary methods to diagnose evolving electrolyte solutions of uncertain composition. As such, we demonstrate that jointly evaluating electrolyte solutions with distinct voltammetric modes can enhance the capabilities and sensitivities of characterization protocols. Specifically, by considering macroelectrode cyclic square wave and microelectrode cyclic voltammograms in sequential (“one after another”) and simultaneous (“all at once”) manners, the composition of an electrolyte solution may be estimated with greater accuracy, and analytes that exhibit near identical electrode potentials may be more readily differentiated. We explore means of further improving this method, finding that protocol accuracy increases when multiple voltammetry techniques are included in the training dataset. We also observe that the algorithm typically becomes more confident—but not necessarily more accurate—when the potential mesh granularity becomes finer. Overall, these studies show that the sequential and simultaneous methods may hold utility when evaluating multiple voltammetry datasets that, in turn, may be leveraged to streamline diagnostic workflows used to examine electrolyte solutions within electrochemical technologies.

show abstract

Leveraging graphical models to enhance in situ analyte identification via multiple voltammetric techniques

Journal of Electroanalytical Chemistry

2023