Electrochemical and in-Situ Investigation of Quaternary Lithium Transition Metal Fluorides in Li-Ion Batteries

Wednesday, 8 October 2014
Expo Center, 1st Floor, Center and Right Foyers (Moon Palace Resort)
G. Lieser, C. Dräger, S. Glatthaar (Institute for Applied Materials (IAM)), H. Geßwein, L. de Biasi (Helmholtz Institute Ulm), S. Indris (Institute of Applied Materials – Energy Storage Systems, Karlsruhe Institute of Technology), H. Ehrenberg (Karlsruhe Institute of Technology), and J. R. Binder (Institute for Applied Materials (IAM))
During the last decade Lithium metal oxides or polyanionic compounds containing two or more different transition metal ions (e.g. LiNi0.5Mn1.5O4 or LiNi1-x-yCoxMnyO2) are in the focus of research and commercial interest as positive electrodes for Li-ion batteries. Lithium transition metal fluorides are very promising materials compared to common oxide materials with corresponding electrochemically active cations because the more electronegative fluorine atoms increase the redox potential leading to a higher specific energy. However, no reports are given about the electrochemical properties of quaternary lithium transition metal fluorides as positive electrode. In this study a novel sol-gel synthesis route was applied to synthesize several quaternary lithium transition metal fluorides LiMFeF6 (M2+ = 3d transition metal) without toxic chemicals like HF, LiF or F2(gas). After the structural and morphological characterization the fundamental electrochemical properties are characterized. It could be shown that up to 1 eq. Lithium can be inserted fully reversible into the LiMFeF6 host structure with a notable cycling stability and a remarkable rate performance. Furthermore an in-situ x-ray powder diffraction and x-ray absorption investigation reveals that the host structure is an insertion material. The electrochemical active redox couple Fe3+/2+ was confirmed by Mößbauer analysis.