Thermal Stability of Materials for Thin-Film Electrochemical Cells Investigated by Thin-Film Calorimetry
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Thermal Stability of Materials for Thin-Film Electrochemical Cells Investigated by Thin-Film Calorimetry Hendrik Wulfmeier1, Alexander Omelcenko1, Daniel Albrecht1, Detlef Klimm2, Wassima El Mofid3, Marc Strafela4, Sven Ulrich4, Andreas Bund3, and Holger Fritze1 1
Institute of Energy Research and Physical Technologies, Clausthal University of Technology, Am Stollen 19 B, Goslar, 38640, Germany. 2 Leibniz Institute for Crystal Growth, Max-Born-Str. 2, Berlin, 12489, Germany. 3 Electrochemistry and Electroplating Group, Technische Universität Ilmenau, Gustav-KirchhoffStraße 6 (Arrheniusbau), Ilmenau, 97693, Germany. 4 Institute of Applied Materials (IAM-AWP), Karlsruhe Institute of Technology, Hermann-vonHelmholtz-Platz 1, Eggenstein-Leopoldshafen, 76344, Germany. ABSTRACT Phase transformation enthalpies are determined using the recently developed measurement technique Thin-Film Calorimetry (TFC), which is based on piezoelectric resonators vibrating in thickness shear mode. They are applicable up to at least 1000 °C. To the best of our knowledge, no comparable TFC systems for such high temperatures exist. The experimental part is divided into two subsections. The first is addressed to a thermodynamic investigation on piezoelectric langasite crystals (LGS, La3Ga5SiO14) which are the key component of the TFC system. The specific heat capacity is measured on LGS crystals of three different manufacturers. It ranges from about 0.45 J g-1 K-1 at 40 °C to about 0.60 J g-1 K-1 at 1000 °C. Thereby, deviations of up to 5 % between the different crystals are detected. Thermal diffusivity data for Y-cut LGS crystals are determined as well. Here, a constant decrease with temperature is detected ranging from 0.48 mm2 s-1 at room temperature to 0.38 mm2 s-1 at 700 °C. The second part presents thin-film calorimetric investigation on thin films of the family Li-Ni-Mn-Co-Al-Oxide (NMC/NMCA). These cathode materials are investigated and compared when annealed in ambient air or 0.5 % H2/Ar up to 860 °C. Three stoichiometries are chosen: Li(Ni1/3Mn1/3Co1/3)O2, Li(Ni0.6Mn0.2Co0.2)O2, and Li(Ni0.6Mn0.2Co0.15Al0.05)O2. The samples show three or four phase transformations. In air, the samples crystallize in the range of 250-350 °C. In 0.5 % H2/Ar, the transformations occur at higher temperatures. Especially in air, stoichiometric NMC crystallizes at lower temperatures compared to Ni-rich compositions. Additional doping with Al enhances the thermal stability which shifts all phase transformations to higher temperatures in both atmospheres. INTRODUCTION Thin-film batteries attract an increasing interest in e.g. medical and biotechnological applications. Here, miniaturized batteries are required. Furthermore, toxic or liquid electrolytes have to be avoided. Another focus lies on their use as model systems for larger applications. In any case, materials processing and battery operation requires reliable enthalpy data on phase transformations in a large temperature range. This work is based on the recently developed measurement technique Thin-Fil
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