An Investigation of the Impact of Protic Impurities, Different Housing Materials and Silicon on the Thermal Aging of Electrolytes Used in Lithium-Ion Batteries
LiPF6 (s) LiF (s) + PF5(g) 
PF5 (g) + H2O (l) → O=PF3(g) + 2 HF (l) 
Lux et al. (3) followed the HF formation in LiPF6 containing electrolytes by spectroscopic ellipsometry of SiO2 layers. As we reported recently (4), SiO2 probably promotes the degradation of LiPF6 in organic carbonate based electrolytes.
Herein, we report about the decomposition of 1M LiPF6 in a binary mixture of ethylene carbonate and diethylene carbonate in a ratio of 40:60 (w/w) at ambient and elevated temperature (cf. table 1). Degradation products are studied by nuclear magnetic resonance spectroscopy (NMR, cf. figure 1), gas chromatography mass spectrometry (GC-MS) and headspace GC-MS (HS-GC-MS). Acid-base and coulometric titration are used to determine the total amount of acid and water content upon aging, respectively. Ultraviolet-visible (UV-Vis) spectroscopy is used to follow the color change of the electrolyte (cf. figure 2). The influence of protic contamination, different housing materials and added active materials on the electrolyte aging is shown.
VOLKSWAGEN VARTA Microbattery Forschungsgesellschaft and Herbert Quandt Foundation are gratefully acknowledged for funding.
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3. S. F. Lux, I.T. Lucas, E. Pollak, S. Passerini, M. Winter, R. Kostecki, Electrochem. Commun., 14, 47 (2012)