Key role of paracrystalline motifs on iridium oxide surfaces for acidic water oxidation
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Engineering topics
Publications and source records attributed to Edgington, Jane.
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Achieving energy densities exceeding 350 Wh kg -1 while operating at elevated voltages (>4.5 V vs Li/Li + ) is attainable through judicious selection of electrochemical pairs at the cathode and anode. However, current state-of-the-art electrolytes exhibit limited stability when exposed to systems operating at or above 4.3 V. This limitation contributes to the degradation of electrode materials and raises critical safety concerns, impeding the commercialization of such systems. Consequently, there has been a notable surge in research efforts aimed at developing innovative electrolyte compositions capable of supporting high-voltage lithium-ion batteries (LIBs). A substantial portion of this research has focused on the family of organosulfur molecules, which possess high oxidative stability. Organosulfur salts also facilitate the formation of dense, ionically conductive solid electrolyte interfaces (SEI) and demonstrate excellent solubility. This article provides a comprehensive overview of the field of organosulfur electrolyte components for their applications in energy storage, encompassing solvents, alternative conducting salts, and additives. It emphasizes the idea that the deliberate design of electrolyte compositions is instrumental in controlling electrode passivation, with organosulfur-based structures historically proving advantageous in every aspect of the electrolyte. Crucially, it should be noted that many of these components are commercially available, holding significant implications for industrial applications.
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Employing benchmarking metrics to capture the activity and stability of electrocatalysts for the oxygen evolution reaction (OER) in acid is a critical practice that enables meaningful comparison of catalyst material candidates reported throughout the literature. In this work, we find that ubiquitously used glassy carbon electrode substrates oxidize under typical OER operating conditions, forming a pacified, electrically insulating, and oxygen-rich surface layer that causes drastic loss of current density over the course of extended chronoamperometric stability tests at an anodic potential of 1.7 VRHE. We show that the experimentally observed stability of glassy carbon-based electrodes is approximately two orders of magnitude lower than that expected solely from dissolution-based catalyst intrinsic stability of Ir-based catalysts. We additionally find that glassy carbon-based electrode stability measured by chronoamperometric holds is greatly impacted by catalyst loading, with high catalyst loadings improving the stability of the overall electrode via a protective effect on the glassy carbon substrate. Altogether, our investigation highlights that glassy carbon is not electrochemically inert under OER conditions on the timescale of common stability tests, which can cause electrodes to exhibit performance losses that do not reflect the intrinsic stability of the actual catalyst material being investigated. In light of our findings, we underscore the usefulness of metrics, such as the S-number, to reflect intrinsic catalyst material stability.
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