Novel methods based on hyphenated analytical techniques for the analysis of LiPF6 commercially available battery electrolytes are presented. PF6- and the formed main decomposition products F-, PO2F2- and HPO3F- were separated by ion chromatography (IC) and detected by electrospray ionization mass spectrometry (ESI-MS). Inductively coupled plasma optical emission spectroscopy (ICP-OES) on the phosphorous trace supported the results obtained by ESI-MS. Samples, which were stored at room temperature and at 5 degrees C, were analyzed several times over a period of two weeks to demonstrate the progress of the hydrolysis of LiPF6 in aqueous solution and commercially available electrolyte (EC/DEC (3:7 w/w) 1 M LiPF6). Subsequently, the same commercially available electrolyte system was analyzed to prove the usefulness of the proposed method to investigate the influence of the thermal aging in lithium-ion batteries. (C) 2013 Elsevier B.V. All rights reserved.