The effect of vinylene carbonate additive on surface film formation on both electrodes in li-ion batteries

L. El Ouatani , Rémi Dedryvère (1) , C. Siret (2) , P. Biensan , Stephanie Reynaud (1) , P. Iraţabal , Danielle Gonbeau (3)

1 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux
2 Pathologies des récepteurs nucléaires (U 439)
3 LCTPCM - Laboratoire de Chimie théorique et Physico-chimie moléculaire

The effect of vinylene carbonate (VC) as electrolyte additive on the formation mechanisms of passivation films covering both electrodes in lithium-ion batteries was investigated by X-ray photoelectron spectroscopy (XPS). LiCo O2 /graphite coin cells using a LiP F6 /ethylene carbonate:diethyl carbonate:dimethyl carbonate liquid electrolyte with or without VC were charged at 20 and 60°C. The identification of VC-derived products formed at the surface of the electrodes was carried out by a dual experimental/theoretical approach. From a classical XPS core peak analysis completed by a detailed interpretation and simulation of valence spectra supported by ab initio calculations, and through direct synthesis of the VC polymer, we could evidence the formation of the radical poly(VC) at the electrode/electrolyte interfaces. We showed that the radical polymerization is the main reaction mechanism of VC contributing to the formation of the passivation layers at the surface of both electrodes. © 2008 The Electrochemical Society.

Mots clés: Passivation layers; Peak analyses; Radical polymerizations; Reaction mechanisms; Surface films; Vinylene carbonates; With or without; X-ray photoelectron spectroscopies; X ray photoelectron spectroscopy; Carbonation; Electrodes; Electrolytes; Ethylene; Free radical polymerization; Graphite; Graphite electrodes; Lithium alloys; Lithium batteries; Lithium compounds; Passivation; Photoelectron spectroscopy; Polymers; Ab initio calculations; Coin cells; Derived products; Diethyl carbonates; Dimethyl carbonates; Direct syntheses; Electrode/electrolyte interfaces; Electrolyte additives; Ethylene carbonates; Formation mechanisms; Ion batteries; Liquid electrolytes; Passivation films

Domaines: Matériaux; Chimie théorique et/ou physique

L. El Ouatani, Rémi Dedryvère, C. Siret, P. Biensan, Stephanie Reynaud, et al.. The effect of vinylene carbonate additive on surface film formation on both electrodes in li-ion batteries. Journal of The Electrochemical Society, 2009, 156 (2), pp.A103-A113. ⟨10.1149/1.3029674⟩. ⟨hal-01560427⟩