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皮秒脉冲辐解液体碳酸二乙酯。

Picosecond pulse radiolysis of the liquid diethyl carbonate.

机构信息

Laboratoire de Chimie Physique, ELYSE, UMR 8000 CNRS-UPS, Université Paris-Sud , Bât. 349, 91405 Orsay, France.

出版信息

J Phys Chem A. 2013 Oct 24;117(42):10801-10. doi: 10.1021/jp406856u. Epub 2013 Oct 16.

Abstract

The diethyl carbonate, DEC, is an ester that is used as a solvent in Li-ion batteries, but its behavior under ionizing radiation was unknown. The transient optical absorption spectra, the decay kinetics, and the influence of various scavengers have been studied by using the picosecond laser-triggered electron accelerator ELYSE. In neat DEC, the intense near-IR (NIR) absorption spectrum is assigned to the solvated electron. It is overlapped in the visible range by another transient but longer-lived and less intense band that is assigned to the oxidized radical DEC(-H). The solvated electron molar absorption coefficients and radiolytic yield evolution from 25 ps, the geminate recombination kinetics, and the rate constants of electron transfer reactions to scavengers are determined. The radiolytic mechanism, indicating a certain radioresistance of DEC, is compared with that for other solvents.

摘要

碳酸二乙酯(DEC)是一种酯类物质,被用作锂离子电池的溶剂,但它在电离辐射下的行为是未知的。使用皮秒激光触发电子加速器 ELYSE,研究了瞬态光吸收光谱、衰减动力学以及各种清除剂的影响。在纯 DEC 中,强烈的近红外(NIR)吸收光谱被分配给溶剂化电子。在可见范围内,另一个瞬态但寿命更长、强度更低的带与氧化自由基 DEC(-H)重叠。确定了从 25 ps 开始的溶剂化电子摩尔吸收系数和辐解产额演变、成对复合动力学以及向清除剂的电子转移反应速率常数。比较了辐解机制,表明 DEC 具有一定的抗辐射能力,与其他溶剂的辐解机制进行了比较。

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