Redox Reactions in Li-ion Battery Cycling and in Cu Corrosion Studied by Soft X-ray Spectroscopy
Sammanfattning: The topic of this thesis is redox reactions in two technologically important contexts: firstly, in Li-ion battery electrodes during cycling, and secondly, in copper corrosion in oxygen-free ground water containing sulfide. In an attempt to expand the understanding of the charge uptake process in battery electrodes and the chemical reactions on copper surfaces upon sulfide exposure, soft X-ray spectroscopy has been used to study the electronic structure of these systems.To ascertain the changes in electron density at different atomic sites in a battery electrode material, both X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) have been applied to different electrode materials. This thesis explains in detail the assembling procedure, cycling, and situ sample preparation of the battery materials. Furthermore, two different designs used in in situ experiments for study of batteries during cycling are also discussed.The main result from the Li-ion battery materials is the justification to abandon the view of valences as integers. This is true for all battery electrodes examined in this thesis. Generally, oxygen plays a more important role in the charge uptake than commonly assumed, but also the transition metals and other species apart from expected behavior. In LiMnPO4, even the notion of Li as strictly Li+ must be questioned.Copper is intended to act as a corrosion barrier in a nuclear waste repository. In the corrosion experiments presented in this thesis, different copper oxides were exposed to the conditions present at the planned repository site, with exception for the concentration of sulfide, which was greatly increased.The conclusion from these experiments is that sulfide effectively reduces Cu(II) oxide to Cu(I) compounds and possibly forms a compound containing both oxygen and sulfur. Also, the thickness and inhomogeneity of the copper oxide surface layers are of great importance for the corrosion mechanisms, including passivation.
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