STRUCTURAL AND ELECTROCHEMICAL STUDIES OF SILICON- AND CARBON-BASED MATERIALS FOR LI-ION BATTERY APPLICATIONS

Abstract

Four topics are presented in this thesis. Firstly, a new design for a combinatorial electrochemical cell plate based on circuit board technology is described. The new combinatorial cell plate was tested using sputtered silicon and capacity as a function of mass was determined. The measured specific capacity was 3580 mAh/g, which corresponds to Li15Si4 stoichiometry. The irreversible capacity was measured to be less than 2% of the reversible capacity. This design reduced the spurious capacity that came from the lead pattern of the old plate. Second, the role of oxygen content on the electrochemical properties of sputtered Si1-xOx was investigated. All the prepared thin film samples had an amorphous or nanostructured nature. The measured specific capacity (first charge) suggests that Si1-xOx is made up of amorphous silicon that reacts reversibly with lithium, and SiO2 that forms inactive Li4SiO4 after the first lithiation. The current study shows that the irreversible capacity is directly proportional to the oxygen content. This study indicates clearly that in order to produce material with high capacity, oxygen should be minimized to reduce Li consumption during Li4SiO4 formation. However, the Si:O ratio should be optimized to get a reasonable active: inactive ratio. Third, a systematic study to investigate the effect of the addition of carbon on the electrochemical performance of the Sn-Si binary is reported. This study involved the preparation and investigation of three pseudobinary libraries. The addition of carbon was found to inhibit the aggregation of tin and reduce the two-phase coexistence regions as evidenced by smooth differential capacity plots. This was reflected in the improved electrochemical performance such as reversible capacity and cycleability. Fourth, an investigation of carbon-rich alloys of Fe1-xCx is reported. Both x-ray diffraction and 57Fe Mössbauer spectroscopy were employed to get insight into the structural properties of this system. X-ray diffraction revealed the amorphous or nanostructured nature of all samples with different Fe:C ratios. The distribution of hyperfine parameters extracted from the Mössbauer analysis shows the existence of two components suggesting that Fe exists in two distinct sites: (1) Fe surrounded with Fe neighbors and (2) Fe surrounded with C neighbors. The asymmetric environment was found more pronounced as carbon content increases in the films. This was reflected by high quadrupole splitting in excess of 1.0 mm/s.