Pressing demands for high power and high energy densities in novel electrical energy storage units have caused reconsiderations regarding both the choice of battery chemistry and design. Practical concerns originating in the conventional use of flammable liquid electrolytes have renewed the interests of using solvent-free polymer electrolytes (SPEs) as solid ionic conductors for safer batteries. In this thesis work, SPEs developed from two polymer host structures, polyethers and polycarbonates, have been investigated for all-solid-state Li- and Li-ion battery applications. In the first part, functional polyether-based polymer electrolytes, such as poly(propylene glycol) triamine based oligomer and poly(propylene oxide)-based acrylates, were investigated for 3D-microbattery applications. The amine end-groups were favorable for forming conformal electrolyte coatings onto 3D electrodes via self-assembly. In-situ polymerization methods such as UV-initiated and electro-initiated polymerization techniques also showed potential to deposit uniform and conformal polymer coatings with thicknesses down to nano-dimensions. Moreover, poly(trimethylene carbonate) (PTMC), an alternative to the commonly investigated polyether host materials, was synthesized for SPE applications and showed promising functionality as battery electrolyte. High-molecular-weight PTMC was first applied in LiFePO4-based batteries. By incorporating an oligomeric PTMC as an interfacial mediator, enhanced surface contacts at the electrode/SPE interfaces and obvious improvements in initial capacities were realized. In addition, room-temperature functionality of PTMC-based SPEs was explored through copolymerization of ε-caprolactone (CL) with TMC. Stable cycling performance at ambient temperatures was confirmed in P(TMC/CL)-based LiFePO4 half cells (e.g., around 80 and 150 mAh g-1 at 22 °C and 40 °C under C/20 rate, respectively). Through functionalization, hydroxyl-capped PTMC demonstrated good surface adhesion to metal oxides and was applied on non-planar electrodes. Ionic transport behavior in polycarbonate-SPEs was examined by both experimental and computational approaches. A coupling of Li ion transport with the polymer chain motions was demonstrated. The final part of this work has been focused on exploring the key characteristics of the electrode/SPE interfacial chemistry using PEO and PTMC host materials, respectively. X-ray photoelectron spectroscopy (XPS) was used to get insights on the compositions of the interphase layers in both graphite and LiFePO4 half cells.

We will introduce our approach to prepare and investigate thin film materials for application in all solid state batteries by using integrated UHV preparation facilities.

<p>This thesis addresses the electronic structure of vanadium and copper oxides using soft X-ray absorption (SXA) spectroscopy and resonant inelastic X-ray scattering (RIXS) at high brightness synchrotron radiation sources. In RIXS incident photons, tuned to the energy of specific absorption resonances, are inelastically scattered leaving behind a low energy valence excitation in the system studied. Effects of electron localization are reflected by the occurrence of low-energy excitations in form of dd- and charge-transfer excitations that are modelled by cluster calculations. Band-like states are dominating when the intermediate core excited state is delocalized.</p><p>RIXS at V 2p and O 1s resonances has been used to study the electronic structure of the monovalent vanadium oxides VO₂ and V₂O₃, and of the mixed valence compounds, NaV₂O₅ and V₆O₁₃. For NaV₂O₅ and V₆O₁₃ significant contributions from localized low-energy excitations reflect the partly localized character of their valence band electronic structure, whereas VO₂ and V₂O₃ appear mostly as band-like. Effects of carrier doping are addressed for the case of Mo doping into VO₂ and reveal a quasi-rigid band behavior. In the cases of VO₂ and V₆O₁₃ the temperature dependent metal-insulator transition could be monitored by following the spectral evolution of bands originating from V 3d and V 3d - O2p hybridized states. For Na₂V₃O₇ nanotubes it was possible to selectively probe states from the apical and the basal oxygen sites of VO₅ pyramids that constitute these nanotubes. Furthermore, the RIXS technique has been demonstrated to be highly valuable in characterizing the charge transfer processes that accompany lithium insertion into vanadium oxide battery cathodes. Finally, for insulating cuprates RIXS at O 1s, Cu 3p and Cu 3s resonances has been recorded at high-resolution for the detailed investigation of crystal field excitations.</p>

This thesis addresses the electronic structure of vanadium and copper oxides using soft X-ray absorption (SXA) spectroscopy and resonant inelastic X-ray scattering (RIXS) at high brightness synchrotron radiation sources. In RIXS incident photons, tuned to the energy of specific absorption resonances, are inelastically scattered leaving behind a low energy valence excitation in the system studied. Effects of electron localization are reflected by the occurrence of low-energy excitations in form of dd- and charge-transfer excitations that are modelled by cluster calculations. Band-like states are dominating when the intermediate core excited state is delocalized. RIXS at V 2p and O 1s resonances has been used to study the electronic structure of the monovalent vanadium oxides VO2 and V2O3, and of the mixed valence compounds, NaV2O5 and V6O13. For NaV2O5 and V6O13 significant contributions from localized low-energy excitations reflect the partly localized character of their valence band electronic structure, whereas VO2 and V2O3 appear mostly as band-like. Effects of carrier doping are addressed for the case of Mo doping into VO2 and reveal a quasi-rigid band behavior. In the cases of VO2 and V6O13 the temperature dependent metal-insulator transition could be monitored by following the spectral evolution of bands originating from V 3d and V 3d - O2p hybridized states. For Na2V3O7 nanotubes it was possible to selectively probe states from the apical and the basal oxygen sites of VO5 pyramids that constitute these nanotubes. Furthermore, the RIXS technique has been demonstrated to be highly valuable in characterizing the charge transfer processes that accompany lithium insertion into vanadium oxide battery cathodes. Finally, for insulating cuprates RIXS at O 1s, Cu 3p and Cu 3s resonances has been recorded at high-resolution for the detailed investigation of crystal field excitations.