Solid-electrolyte interphase nucleation and growth on carbonaceous negative electrodes for Li-ion batteries visualized with in situ atomic force microscopy

Li-ion battery performance and life cycle strongly depend on a passivation layer called solid-electrolyte interphase (SEI). Its structure and composition are studied in great details, while its formation process remains elusive due to difficulty of in situ measurements of battery electrodes. Here we provide a facile methodology for in situ atomic force microscopy (AFM) measurements of SEI formation on cross-sectioned composite battery electrodes allowing for direct observations of SEI formation on various types of carbonaceous negative electrode materials for Li-ion batteries. Using this approach, we observed SEI nucleation and growth on highly oriented pyrolytic graphite (HOPG), MesoCarbon MicroBeads (MCMB) graphite, and non-graphitizable amorphous carbon (hard carbon). Besides the details of the formation mechanism, the electrical and mechanical properties of the SEI layers were assessed. The comparative observations revealed that the electrode potentials for SEI formation differ depending on the nature of the electrode material, whereas the adhesion of SEI to the electrode surface clearly correlates with the surface roughness of the electrode. Finally, the same approach applied to a positive LiNi(1/3)Mn(1/3)Co(1/3)O(2) electrode did not reveal any signature of cathodic SEI thus demonstrating fundamental differences in the stabilization mechanisms of the negative and positive electrodes in Li-ion batteries.