Fluoride-Ion Batteries: On the Electrochemical Stability of Nanocrystalline La0.9Ba0.1F2.9 against Metal Electrodes.

Over the past years, ceramic fluorine ion conductors with high ionic conductivity have stepped into the limelight of materials research, as they may act as solid-state electrolytes in fluorine-ion batteries (FIBs). A factor of utmost importance, which has been left aside so far, is the electrochemical stability of these conductors with respect to both the voltage window and the active materials used. The compatibility with different current collector materials is important as well. In the course of this study, tysonite-type La 0.9 Ba 0.1 F 2.9 , which is one of the most important electrolyte in first-generation FIBs, was chosen as model substance to study its electrochemical stability against a series of metal electrodes viz. Pt, Au, Ni, Cu and Ag. To test anodic or cathodic degradation processes we carried out cyclic voltammetry (CV) measurements using a two-electrode set-up. We covered a voltage window ranging from -1 to 4 V, which is typical for FIBs, and investigated the change of the response of the CVs as a function of scan rate (2 mV/s to 0.1 V/s). It turned out that Cu is unstable in combination with La 0.9 Ba 0.1 F 2.9 , even before voltage was applied. The cells with Au and Pt electrodes show reactions during the CV scans; in the case of Au the irreversible changes seen in CV are accompanied by a change in color of the electrode as investigated by light microscopy. Ag and Ni electrodes seem to suffer from contact issues which, most likely, also originate from side reactions with the electrode material. The experiments show that the choice of current collectors in future FIBs will become an important topic if we are to develop long-lasting FIBs. Most likely, protecting layers between the composite electrode material and the metal current collector have to be developed to prevent any interdiffusion or electrochemical degradation processes.