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Integrating transducer/sensing materials into microfluidic platforms has enhanced gas sensors′ sensitivity, selectivity, and response time while facilitating miniaturization. In this manuscript, microfluidics has been integrated with non-planar microelectrode array and functionalized ionic liquids (ILs) to develop a novel miniaturized electrochemical gas sensor architecture. The sensor employs the IL 1-ethyl-3-methylimidazolium 2-cyanopyrolide ([EMIM][2-CNpyr]) as the electrolyte and capture molecule for detecting carbon dioxide (CO 2 ). The three-layer architecture of the sensor consists of a microchannel with the IL sandwiched between glass slides containing microelectrode arrays, forming a non-planar structure. This design facilitates electric field penetration through the IL, capturing CO 2 binding perturbations throughout the channel volume to enhance sensitivity. CO 2 binding with [EMIM][2-CNpyr] generates carboxylate ([EMIM] + -CO2 − ]), carbamate ([2-CNpyr]-CO2 − ]), and pyrrole-2-carbonitrile (2-CNpyrH) species, significantly decreasing the conductivity. The viscosity is also increased, leading to a further decrease in conductivity. These cumulative effects increase charge transfer resistance in the impedance spectrum, allowing a linear calibration curve obtained using Langmuir Isotherm. The sensitivity and reproducibility in CO 2 detection are demonstrated by two electrode configurations using the calibration curve. The developed sensor offers a versatile platform for future applications.more » « less
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Gardas, Ramesh L. (Ed.)The solvation structure and transport properties of Li+ in ionic liquid (IL) electrolytes based on n-methyl-n-butylpyrrolidinium cyano(trifluoromethanesulfonyl)imide [PYR14][CTFSI] and [Li][CTFSI] (0 ≤ xLi ≤ 0.7) were studied by Raman and Nuclear Magnetic Resonance (NMR) diffusometry, and molecular dynamics (MD) simulations. At xLi < 0.3, Li+ coordination is dominated by the cyano group. As xLi is increased, free cyano-sites become limited, resulting in increased coordination via the sulfonyl group. The 1:1 mixture of the symmetric anions bis(trifluoromethanesulfonyl)imide ([TFSI]) and dicyanamide ([DCA]) results in similar physical properties as the IL with [CTFSI]. However, anion asymmetry is shown to increase Li-salt solubility and promote Li+ transference. The lifetimes of Li+-cyano coordination for [CTFSI] are calculated to be shorter than those for [DCA], indicating that the competition from the sulfonyl group weakens its solvation with Li+. This resulted in higher Li+ transference for the electrolyte with [CTFSI]. In relation to the utility of these electrolytes in energy storage, the Li–LiFePO4 half cells assembled with IL electrolyte (xLi = 0.3, 0.5, and 0.7) demonstrated a nominal capacity of 140 mAh/g at 0.1C rate and 90 °C where the cell with xLi = 0.7 IL electrolyte demonstrated 61% capacity retention after 100 cycles and superior rate capability owing to increased electrochemical stability.more » « less
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