Constitution, microstructure, and battery performance of magnetron sputtered Li-Co-O thin film cathodes for lithium-ion batteries as a function of the working gas pressure

摘要

Li-Co-O thin film cathodes have been deposited onto Si and stainless steel substrates by RF magnetron sputtering from a ceramic LiCoO_2 target at various working gas pressures from 0.15 to 25Pa. Composition, crystal structure and thin film morphology were examined and properties such as intrinsic stress, conductivity and film density were determined. As-deposited films at 0.15Pa as well as in the range between 5Pa and 10Pa working gas pressure showed a nanocrystalline metastable rocksalt structure with disordered cation arrangement and were nearly stoichiometric. To induce a cation ordering the films were annealed in a furnace at temperatures between 100 and 600°C for 3h in argon/oxygen atmosphere (Ar:O_2=4.5:5) of 10Pa. This cation ordering process was observed by XRD and Raman spectroscopy. For the films deposited at 10Pa gas pressure an annealing temperature of 600°C leads to the formation of the high temperature phase HT-LiCoO_2 with a layered structure. The Raman spectrum of the films deposited at 0.15Pa and annealed at 400°C indicates the formation of the low temperature phase LT-LiCoO_2 with a cubic spinel-related structure, which is assumed to be stabilized due to high compressive stress in the film. The electrochemical characterisation of annealed thin film cathodes revealed that the discharge capacity strongly depends on the crystal structure. Thin Li-Co-O films with a perfect layered HT-LiCoO_2 structure showed the highest discharge capacities.