Spinels of the general formula Li 2−δ M 2 O 4 are an essential class of cathode materials for Li-ion batteries, and their optimization in terms of electrode potential, accessible capacity, and charge/discharge kinetics relies on an accurate understanding of the underlying solid-state mass and charge transport processes. In this work, we report a comprehensive impedance study of sputter-deposited epitaxial Li 2−δ Mn 2 O 4 thin films as a function of state-ofcharge for almost the entire tetrahedral-site regime (1 ≤ δ ≤ 1.9) and provide a complete set of electrochemical properties, consisting of the charge-transfer resistance, ionic conductivity, volume-specific chemical capacitance, and chemical diffusivity. The obtained properties vary by up to three orders of magnitude and provide essential insights into the point defect concentration dependences of the overall electrode potential. We introduce a defect chemical model based on simple concentration dependences of the Li chemical potential, considering the tetrahedral and octahedral lattice site restrictions defined by the spinel crystal structure. The proposed model is in excellent qualitative and quantitative agreement with the experimental data, excluding the two-phase regime around 4.15 V. It can easily be adapted for other transition metal stoichiometries and doping states and is thus applicable to the defect chemical analysis of all spinel-type cathode materials.

Yttria-stabilized zirconia (YSZ) has become an indispensable solid electrolyte material in modern solid oxide fuel and electrolysis cells (SOFCs/SOECs) as well as oxygen sensors. The oxygen ionic conductivity of YSZ is among the highest known so far. For energy efficiency optimization of SOFCs and lowering the high-temperature degradation of electrodes, the oxygen ionic conductivity needs to be further enhanced. This would allow for a reduction in application temperature. Despite extensive regular point defect-doping strategies, this key issue remains unsolved. Here, we investigate the role of mechanically induced dislocations (line-defects) on electrical conductivity and oxygen transport in bulk YSZ. An advanced mechanical deformation approach is employed to generate distinctly aligned dislocation-rich and -deficient regions. The in-depth electrical characterization of these regions exhibited highly conducting effects of dislocation-induced strain inside the bulk material. Furthermore, targeted oxygen tracer diffusion experiments prove enriched oxygen incorporation within the dislocation bundles. Therefore, the potential of mechanically induced dislocations is elucidated as a design element to tune the bulk ionic transport in YSZ.