화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.138, No.35, 11211-11218, 2016
Anion Redox Chemistry in the Cobalt Free 3d Transition Metal Oxide Intercalation Electrode Li[Li0.2Ni0.2Mn0.6]O-2
Conventional intercalation cathodes for lithium batteries store charge in redox reactions associated with the transition metal cations, e.g., Mn3+/4+ in LiMn2O4, and this limits the energy storage of Li-ion batteries. Compounds such as Li[Li0.2Ni0.2Mn0.6]O-2 exhibit a capacity to store charge in excess of the transition metal redox reactions. The additional capacity occurs at and above 4.5 V versus Li+/Li. The capacity at 4.5 V is dominated by oxidation of the O-2(-) anions accounting for similar to 0.43 e(-)/formula unit, with an additional 0.06 e(-)/formula unit being associated with O loss from the lattice. In contrast, the capacity above 4.5 V is mainly O loss, similar to 0.08 e(-)/formula. The O redox reaction involves the formation of localized hole states on O during charge, which are located on O coordinated by (Mn4+/Li+). The results have been obtained by combining operando electrochemical mass spec on 180 labeled Li[Li0.2Ni0.2Mn0.6]O-2 with XANES, soft X-ray spectroscopy, resonant inelastic X-ray spectroscopy, and Raman spectroscopy. Finally the general features of O redox are described with discussion about the role of comparatively ionic (less covalent) 3d metal oxygen interaction on anion redox in lithium rich cathode materials.