Electrolytes Ageing in Lithium-ion Batteries: A Mechanistic Study from Picosecond to Long Timescales.

Autor: Ortiz D; Institut Rayonnement Matière de Saclay, Bât. 546, NIMBE UMR 3685 CNRS/CEA, LIONS, 91191, Gif-sur-Yvette Cedex, France., Jiménez Gordon I; CEA/LITEN/DEHT/SCGE, 38000, Grenoble, France., Baltaze JP; Institut de Chimie Moléculaire et des Matériaux d'Orsay, CNRS UMR 8182, Bât. 410, 91405, Orsay, France., Hernandez-Alba O; Laboratoire de Chimie-Physique/ELYSE, UMR 8000 CNRS/UPS, Université Paris Sud, Bât. 349, 91405, Orsay Cedex, France., Legand S; CEA/DEN/DANS/DPC/SECR/LRMO, Bât. 391, 91191, Gif-sur-Yvette Cedex, France., Dauvois V; CEA/DEN/DANS/DPC/SECR/LRMO, Bât. 391, 91191, Gif-sur-Yvette Cedex, France., Si Larbi G; CEA/LITEN/DEHT/SCGE, 38000, Grenoble, France., Schmidhammer U; Laboratoire de Chimie-Physique/ELYSE, UMR 8000 CNRS/UPS, Université Paris Sud, Bât. 349, 91405, Orsay Cedex, France., Marignier JL; Laboratoire de Chimie-Physique/ELYSE, UMR 8000 CNRS/UPS, Université Paris Sud, Bât. 349, 91405, Orsay Cedex, France., Martin JF; CEA/LITEN/DEHT/SCGE, 38000, Grenoble, France., Belloni J; Laboratoire de Chimie-Physique/ELYSE, UMR 8000 CNRS/UPS, Université Paris Sud, Bât. 349, 91405, Orsay Cedex, France., Mostafavi M; Laboratoire de Chimie-Physique/ELYSE, UMR 8000 CNRS/UPS, Université Paris Sud, Bât. 349, 91405, Orsay Cedex, France., Le Caër S; Institut Rayonnement Matière de Saclay, Bât. 546, NIMBE UMR 3685 CNRS/CEA, LIONS, 91191, Gif-sur-Yvette Cedex, France. sophie.le-caer@cea.fr.
Jazyk: angličtina
Zdroj: ChemSusChem [ChemSusChem] 2015 Nov; Vol. 8 (21), pp. 3605-16. Date of Electronic Publication: 2015 Jul 23.
DOI: 10.1002/cssc.201500641
Abstrakt: The ageing phenomena occurring in various diethyl carbonate/LiPF6 solutions are studied using gamma and pulse radiolysis as a tool to generate similar species as the ones occurring in electrolysis of Li-ion batteries (LIBs). According to picosecond pulse radiolysis experiments, the reaction of the electron with (Li(+), PF6(-)) is ultrafast, leading to the formation of fluoride anions that can then precipitate into LiF(s). Moreover, direct radiation-matter interaction with the salt produces reactive fluorine atoms forming HF(g) and C2H5F(g). The strong Lewis acid PF5 is also formed. This species then forms various R(1)R(2)R(3) P=O molecules, where R is mainly -F, -OH, and -OC2H5. Substitution reactions take place and oligomers are slowly formed. Similar results were obtained in the ageing of an electrochemical cell filled with the same model solution. This study demonstrates that radiolysis enables a description of the reactivity in LIBs from the picosecond timescale until a few days.
(© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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