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Degradation of an Ethylene Carbonate/Diethyl Carbonate Mixture by Using Ionizing Radiation
Author(s) -
Wang Furong,
Varenne Fanny,
Ortiz Daniel,
Pinzio Valentin,
Mostafavi Mehran,
Le Caër Sophie
Publication year - 2017
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201700320
Subject(s) - radiolysis , chemistry , ethylene carbonate , reactivity (psychology) , solvated electron , diethyl carbonate , molecule , photochemistry , carbonate , radiation chemistry , reaction rate constant , propylene carbonate , inorganic chemistry , chemical reaction , radical , kinetics , organic chemistry , electrochemistry , electrolyte , medicine , alternative medicine , pathology , physics , quantum mechanics , electrode
Abstract The reactivity of ethylene carbonate (EC) and of a EC/diethyl carbonate (DEC) mixture was studied under ionizing radiation to mimic the aging phenomena that occur in lithium‐ion batteries. Picosecond‐pulse radiolysis experiments showed that the attachment of the electron to the EC molecule is ultrafast ( k (e − EC +EC)=1.3×10 9 L mol −1 s −1 at 46 °C). This reaction rate is accelerated by a factor of 5.7 compared with the electron attachment to propylene carbonate, which implies that the presence of the methyl group significantly slows the reaction. In a 50:50 EC/DEC mixture, just after the electron pulse the electron is solvated by a mixture of EC and DEC molecules, but its fast decay is attributed exclusively to electron attachment to the EC molecule. Stable products detected after steady‐state irradiation were mainly H 2 , CH 4 , CO, and CO 2 . The evolution of the radiolytic yields with the EC fraction shows that H 2 and CH 4 did not exhibit linear behavior, whereas CO and CO 2 did. Indeed, H 2 and CH 4 mainly arise from the excited state of DEC, the formation of which is significantly affected by the evolution of the dielectric constant of the mixture and by the electron attachment to EC. CO formation is mainly due to the reactivity of the EC molecule, which is not affected in the mixture, as proven by pulse‐radiolysis experiments.