title: Multiprobe Study of the Solid Electrolyte Interphase on Silicon-Based Electrodes in Full-Cell Configuration.
abstract: The failure mechanism of silicon-based electrodes has been studied only in a half-cell configuration so far. Here, a combination of7Li,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 LiNi1/3Mn1/3Co1/3O2as 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.
authors.affiliation: Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS , 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3, France.
authors.forename: N
authors.initials: N
authors.lastname: Dupré
authors.affiliation: Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS , 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3, France.
authors.forename: P
authors.initials: P
authors.lastname: Moreau
authors.affiliation: LITEN, CEA, Minatec Campus, 17 rue des Martyrs, F-38054 Grenoble, France; Université Grenoble Alpes, F-38000 Grenoble, France.
authors.forename: E
authors.initials: E
authors.lastname: De Vito
authors.affiliation: Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS , 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3, France.
authors.forename: L
authors.initials: L
authors.lastname: Quazuguel
authors.affiliation: INAC-SP2M, Université Grenoble Alpes, F-38000 Grenoble, France; INAC-SP2M, CEA, F-38054 Grenoble, France.
authors.forename: M
authors.initials: M
authors.lastname: Boniface
authors.affiliation: LITEN, CEA, Minatec Campus, 17 rue des Martyrs, F-38054 Grenoble, France; Université Grenoble Alpes, F-38000 Grenoble, France; Groupe de Physico-Chimie des Surfaces, Institut de Recherche de Chimie Paris, CNRS-Chimie ParisTech, 75005 Paris, France.
authors.forename: A
authors.initials: A
authors.lastname: Bordes
authors.affiliation: Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS , 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3, France.
authors.forename: C
authors.initials: C
authors.lastname: Rudisch
authors.affiliation: INAC-SP2M, Université Grenoble Alpes, F-38000 Grenoble, France; INAC-SP2M, CEA, F-38054 Grenoble, France.
authors.forename: P
authors.initials: P
authors.lastname: Bayle-Guillemaud
authors.affiliation: Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS , 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3, France.
authors.forename: D
authors.initials: D
authors.lastname: Guyomard