The failure mechanism of silicon-based electrodes has been studied only in a half-cell configuration so far. Here, a combination of 7Li, 19F MAS NMR, XPS, TOF-SIMS, and STEM-EELS, provides an in-depth characterization of the solid electrolyte interphase (SEI) formation on the surface of silicon and its evolution upon aging and cycling with LiNi1/3Mn1/3Co1/3O2 as the positive electrode in a full Li-ion cell configuration. This multiprobe approach indicates that the electrolyte degradation process observed in the case of full Li-ion cells exhibits many similarities to what has been observed in the case of half-cells in previous works, in particular during the early stages of the cycling. Like in the case of Si/Li half-cells, the development of the inorganic part of the SEI mostly occurs during the early stage of cycling while an incessant degradation of the organic solvents of the electrolyte occurs upon cycling. However, for extended cycling, all the lithium available for cycling is consumed because of parasitic reactions and is either trapped in an intermediate part of the SEI or in the electrolyte. This nevertheless does not prevent the further degradation of the organic electrolyte solvents, leading to the formation of lithium-free organic degradation products at the extreme surface of the SEI. At this point, without any available lithium left, the cell cannot function properly anymore. Cycled positive and negative electrodes do not show any sign of particles disconnection or clogging of their porosity by electrolyte degradation products and can still function in half-cell configuration. The failure mechanism for full Li-ion cells appears then very different from that known for half-cells and is clearly due to a lack of cyclable lithium because of parasitic reactions occurring before the accumulation of electrolyte degradation products clogs the porosity of the composite electrode or disconnects the active material particles.

With a specific capacity of 3600 mA h g(-1), silicon is a promising anode active material for Li-ion batteries (LIBs). However, because of the huge volume changes undergone by Si particles upon (de)alloying with lithium, Si electrodes suffer from rapid capacity fading. A deep understanding of the associated failure mechanisms is necessary to improve these electrochemical performances. To reach this goal, we investigate here nano-Si based electrodes by several characterization techniques. Thanks to all these techniques, many aspects, such as the behaviour of the active material or the solid electrolyte interphase (SEI) and the lithiation mechanisms, are studied upon cycling. A clear picture of the failure mechanisms of nano-Si based electrodes is provided. In particular, by combining Hg analyses, SEM observations of electrode cross-sections, and EIS measurements, we follow the evolution of the porosity within the electrode. For the first time, our results clearly show a real dynamic of the pore size distribution: the first cycles lead to the formation of a micrometric porosity which is not present initially. During the following cycles, these large pores are progressively filled up with SEI products which form continuously at the Si particle surface. Thus, from the 50th cycle, Li(+) ion diffusion is dramatically hindered leading to a strongly heterogeneous lithiation of the electrode and a rapid capacity fading.