ABSTRACT
The current sustained demand for "smart" and connected devices has created a need for more miniaturized power sources, hence for microbatteries. Lithium-ion or "lithium-free" all-solid-state thin-film batteries are adapted solutions to this issue. The capability to carry out spatially resolved chemical analysis is fundamental for the understanding of the operation in an all-solid-state microbattery. Classically cumbersome and not straightforward techniques as TEM/STEM/EELS and FIB preparation methods could be used to address this issue. The challenge in this work is to make the characterization of Li-based material possible by coupling ion-milling cross section preparation method and AES techniques to characterize the behavior of a LiCoO2 positive electrode in an all solid state microbattery. The surface chemistry of LiCoO2 has been studied before and after LiPON deposition. Modifications of the chemical environments characteristic of the positive electrode have been reported at different steps of the electrochemical process. An original qualitative and a semiquantitative analysis has been used in this work with the peak deconvolution method based on real, certified reference spectra to better understand the lithiation/delithiation process. This original coupling has demonstrated that a full study of the pristine, cycled, and post mortem positive electrode in a microbattery is also possible. The ion-milling preparation method allows access to a large area, and the resolution of Auger analysis is highly resolved in energy to separate the lithium and the cobalt signals in an accurate way.
ABSTRACT
Lithium nickel vanadate thin films were prepared by radio frequency magnetron sputtering at various substrate temperatures (Ts). These thin films have been investigated as anode electrode material in the use of microbatteries. Films were characterized by Rutherford backscattering spectroscopy, nuclear reaction analysis, Auger electron spectroscopy, glancing-incidence X-ray diffraction analysis, Raman spectroscopy, scanning electron microscopy, atomic force microscopy, and high-resolution transmission electron microscopy techniques. The anodic electrochemical performances of the films have been evaluated by cyclic voltammetry at a scan rate of 1 mV/s and by galvanostatic cycling, with lithium metal as the counter and the reference electrode, and cycled in the range of 0.02-3.0 V at a current density of 75 microA/cm2. Thin films prepared at a Ts of 650 degrees C show a discharge capacity at the 20th cycle of 1100 (+/-10) mAh/g, which exhibited excellent capacity retention with a small capacity fade.
