title: Electrolytes Ageing in Lithium-ion Batteries: A Mechanistic Study from Picosecond to Long Timescales.
abstract: 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.
authors.affiliation: Institut Rayonnement Matière de Saclay, Bât. 546, NIMBE UMR 3685 CNRS/CEA, LIONS, 91191, Gif-sur-Yvette Cedex, France.
authors.forename: Daniel
authors.initials: D
authors.lastname: Ortiz
authors.affiliation: CEA/LITEN/DEHT/SCGE, 38000, Grenoble, France.
authors.forename: Isabel
authors.initials: I
authors.lastname: Jiménez Gordon
authors.affiliation: Institut de Chimie Moléculaire et des Matériaux d'Orsay, CNRS UMR 8182, Bât. 410, 91405, Orsay, France.
authors.forename: Jean-Pierre
authors.initials: JP
authors.lastname: Baltaze
authors.affiliation: Laboratoire de Chimie-Physique/ELYSE, UMR 8000 CNRS/UPS, Université Paris Sud, Bât. 349, 91405, Orsay Cedex, France.
authors.forename: Oscar
authors.initials: O
authors.lastname: Hernandez-Alba
authors.affiliation: CEA/DEN/DANS/DPC/SECR/LRMO, Bât. 391, 91191, Gif-sur-Yvette Cedex, France.
authors.forename: Solène
authors.initials: S
authors.lastname: Legand
authors.affiliation: CEA/DEN/DANS/DPC/SECR/LRMO, Bât. 391, 91191, Gif-sur-Yvette Cedex, France.
authors.forename: Vincent
authors.initials: V
authors.lastname: Dauvois
authors.affiliation: CEA/LITEN/DEHT/SCGE, 38000, Grenoble, France.
authors.forename: Gregory
authors.initials: G
authors.lastname: Si Larbi
authors.affiliation: Laboratoire de Chimie-Physique/ELYSE, UMR 8000 CNRS/UPS, Université Paris Sud, Bât. 349, 91405, Orsay Cedex, France.
authors.forename: Uli
authors.initials: U
authors.lastname: Schmidhammer
authors.affiliation: Laboratoire de Chimie-Physique/ELYSE, UMR 8000 CNRS/UPS, Université Paris Sud, Bât. 349, 91405, Orsay Cedex, France.
authors.forename: Jean-Louis
authors.initials: JL
authors.lastname: Marignier
authors.affiliation: CEA/LITEN/DEHT/SCGE, 38000, Grenoble, France.
authors.forename: Jean-Frédéric
authors.initials: JF
authors.lastname: Martin
authors.affiliation: Laboratoire de Chimie-Physique/ELYSE, UMR 8000 CNRS/UPS, Université Paris Sud, Bât. 349, 91405, Orsay Cedex, France.
authors.forename: Jacqueline
authors.initials: J
authors.lastname: Belloni
authors.affiliation: Laboratoire de Chimie-Physique/ELYSE, UMR 8000 CNRS/UPS, Université Paris Sud, Bât. 349, 91405, Orsay Cedex, France.
authors.forename: Mehran
authors.initials: M
authors.lastname: Mostafavi
authors.affiliation: Institut Rayonnement Matière de Saclay, Bât. 546, NIMBE UMR 3685 CNRS/CEA, LIONS, 91191, Gif-sur-Yvette Cedex, France. sophie.le-caer@cea.fr.
authors.forename: Sophie
authors.initials: S
authors.lastname: Le Caër
mesh_terms: D011211:Electric Power Supplies; D004572:Electrolysis; D004573:Electrolytes / Q000737:chemistry*; D018020:Lithium Compounds / Q000737:chemistry*; D013058:Mass Spectrometry; D011675:Pulse Radiolysis; D012996:Solutions; D013997:Time Factors; D014783:Viscosity
chemical_list: D004573:Electrolytes; D018020:Lithium Compounds; D012996:Solutions
keywords: ageing; batteries; electrolysis; radiolysis; reaction mechanisms