New Investigations on the Surface Reactivity of Layered Lithium Oxides

作者：Andreu Nathalie; Baraille Isabelle^*; Martinez Herve; Dedryvere Remi; Loudet Michel; Gonbeau Danielle

来源：Journal of Physical Chemistry C, 2012, 116(38): 20332-20341.

DOI：10.1021/jp304293u

Density Functional Theory is applied to understand the large difference in surface reactivity of LiCoO2 due to Al/Co substitution which is experimentally observed. In this way, we explore the SO2 and CO2 adsorption modes on the (110) surface of LiCoO2 and alpha-LiAlO2. For SO2 adsorption, chemisorption produces sulfite species (for LiCoO2 and alpha-LiAlO2) and sulfate species (in the case of LiCoO2). We demonstrate that the modification of the surface reactivity when Co3+. ions are substituted by Al3+ ions is due to a change from an adsorption mode controlled by redox properties for LiCoO2 to a less energetically favorable adsorption mode controlled by acid base properties for alpha-LiAlO2. For CO2 adsorption, the formation of carbonate species is observed for both compounds, illustrating the fundamental difference in the factors controlling SO2 adsorption compared to CO2 adsorption.

• 出版日期2012-9-27