The cycling performance of silicon thin film electrodes was investigated in the presence of anode solid electrolyte interphase (SEI) forming additives. Incorporation of vinylene carbonate (VC), flouroethylene carbonate (FEC), and lithium difluorooxalatoborate (LiFOB) improve the cycling efficiency and capacity retention of cells. Ex-situ surface analysis of the silicon anodes after cycling indicates that incorporation of the additives changes the structure of the SEI. Additives decrease the concentration of LiF on the anode surface consistent with inhibition of LiPF6 decomposition. The changes in surface structure correlate with improved cycling performance. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.076205jes] All rights reserved.