Structure, texture and reactivity versus lithium of chromium-based oxides films as revealed by TEM investigations

Analytical high resolution transmission electron microscopy has been used to clearly evidence the electrochemical reactivity of Cr2O3 thin films versus lithium. We showed that during the reduction process, chromium sesquioxide (+III) transforms first into chromium monoxide (+II) and then into metallic chromium nanoparticles embedded into a Li2O matrix at 0 V. On the subsequent recharge up to 3 V, we did not convert back to Cr2O3, but only to a chromium monoxide implying a partial re-oxidation process, thus explaining the irreversibility measured during the first cycle. We extended this study to the comprehension of the electrochemical performances of Cr2O3-based electrodes obtained by thermal treatment, under different atmospheres, of chromium rich stainless steel disks. In addition to the characterization of the particles forming the so-obtained electro-active layers, we showed, using nano-probe EDS, that a mixed "Fe-Cr-O" oxide could react versus lithium, through a conversion reaction mechanism, leading to alloyed metallic nanoparticles upon reduction and nanograins of mixed oxide during the following oxidation. (c) 2006 Elsevier B.V. All rights reserved.