Role of the LiPF6 Salt for the Long-Term Stability of Silicon Electrodes in Li-Ion Batteries: A Photoelectron Spectroscopy Study
2013 (English)In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 25, no 3, 394-404 p.Article in journal (Refereed) Published
Silicon presents a very high theoretical capacity (3578 mAh/g) and appears as a promising candidate for the next generation of negativeelectrodes for Li-ion batteries. An important issue for the implementation ofsilicon is the understanding of the interfacial chemistry taking place duringcharge/discharge since it partly explains the capacity fading usually observedupon cycling. In this work, the mechanism for the evolution of the interfacialchemistry (reaction of surface oxide, Li−Si alloying process, and passivationlayer formation) upon long-term cycling has been investigated byphotoelectron spectroscopy (XPS or PES). A nondestructive depth resolved analysis was carried out by using both soft Xrays(100−800 eV) and hard X-rays (2000−7000 eV) from two different synchrotron facilities. The results are compared withthose obtained with an in-house spectrometer (1486.6 eV). The important role played by the LiPF6 salt on the stability of thesilicon electrode during cycling has been demonstrated in this study. A partially fluorinated species is formed upon cycling at theoutermost surface of the silicon nanoparticles as a result of the reaction of the materials toward the electrolyte. We have shownthat a similar species is also formed by simple contact between the electrolyte and the pristine electrode. The reactivity betweenthe electrode and the electrolyte is investigated in this work. Finally, we also report in this work the evolution of the compositionand covering of the SEI upon cycling as well as proof of the protective role of the SEI when the cell is at rest.
Place, publisher, year, edition, pages
American Chemical Society (ACS), 2013. Vol. 25, no 3, 394-404 p.
lithium-ion batteries, silicon, alloy, SEI, XPS, PES, synchrotron
Research subject Chemistry with specialization in Inorganic Chemistry
IdentifiersURN: urn:nbn:se:uu:diva-196593DOI: 10.1021/cm303399vISI: 000315018500016OAI: oai:DiVA.org:uu-196593DiVA: diva2:610408