Surface reactivity of Li2MnO3: first-principles and experimental study

Ambroise Quesne-Turin (1, 2) , Delphine Flahaut (1, 2) , Laurence Croguennec (3, 2) , Germain Vallverdu (1, 2) , Joachim Allouche (1, 2) , Youn Charles-Blin (1, 2) , Jean-Noel Chotard (4, 2) , Michel Ménétrier (3, 2) , Isabelle Baraille (1, 2)

1 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux
2 RS2E - Réseau sur le stockage électrochimique de l'énergie
3 ICMCB - Institut de Chimie de la Matière Condensée de Bordeaux
4 LRCS - Laboratoire réactivité et chimie des solides - UMR CNRS 7314

The present paper deals with the surface reactivity of (001) oriented Li2MnO3 crystals investigated from a multi-techniques approach combining, material synthesis, X-ray photoemission spectroscopy (XPS), Scanning Electron Microscopy (SEM), Auger Electron Spectroscopy (AES) and first-principle calculations. Li2MnO3 is considered as a model compound suitable to go further in the understanding of the role of tetravalent manganese atoms in the surface reactivity of layered lithium oxides. The knowledge of the surface properties of such materials is essential in order to understand the mechanisms involved in parasitic phenomena responsible for early aging or poor storage performances of lithium-ion batteries. The surface reactivity was probed through the adsorption of SO2 gas molecules on large Li2MnO3 crystals in order to be able to focus the XPS beam on the top of the (001) surface. A chemical mapping and XPS characterization of the material before and after the SO2 adsorption show in particular that the adsorption is homogeneous at the micro and nanoscale and involves Mn reduction, while first-principle calculations on a slab model of the surface allow us to conclude that the most energetically favorable species formed is a sulfate with charge transfer implying reduction of Mn.

Mots clés: Surface reactivity; XPS; single crystal; AES; first-principle calculations

Domaines: Matériaux

Ambroise Quesne-Turin, Delphine Flahaut, Laurence Croguennec, Germain Vallverdu, Joachim Allouche, et al.. Surface reactivity of Li2MnO3: first-principles and experimental study. ACS Applied Materials & Interfaces, 2017, 9 (50), pp.44222-44230. ⟨10.1021/acsami.7b14826⟩. ⟨hal-01670660⟩