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Electrolytes Ageing in Lithium‐ion Batteries: A Mechanistic Study from Picosecond to Long Timescales
Author(s) -
Ortiz Daniel,
Jiménez Gordon Isabel,
Baltaze JeanPierre,
HernandezAlba Oscar,
Legand Solène,
Dauvois Vincent,
Si Larbi Gregory,
Schmidhammer Uli,
Marignier JeanLouis,
Martin JeanFrédéric,
Belloni Jacqueline,
Mostafavi Mehran,
Le Caër Sophie
Publication year - 2015
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201500641
Subject(s) - radiolysis , chemistry , picosecond , electrochemistry , reactivity (psychology) , lithium (medication) , solvated electron , ion , electrolyte , inorganic chemistry , lithium fluoride , fluoride , photochemistry , radical , organic chemistry , electrode , medicine , laser , physics , alternative medicine , pathology , endocrinology , optics
The ageing phenomena occurring in various diethyl carbonate/LiPF 6 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 + , PF 6 − ) 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 C 2 H 5 F(g). The strong Lewis acid PF 5 is also formed. This species then forms various R 1 R 2 R 3 P=O molecules, where R is mainly −F, −OH, and −OC 2 H 5 . 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.