All-solid-state batteries promise significant safety and energy density advantages over liquid-electrolyte batteries. The interface between the cathode and the solid electrolyte is an important contributor to charge transfer resistance. Strong bonding of solid oxide electrolytes and cathodes requires sintering at elevated temperatures. Knowledge of the temperature dependence of the composition and charge transfer properties of this interface is important for determining the ideal sintering conditions. To understand the interfacial decomposition processes and their onset temperatures, model systems of LiCoO2 (LCO) thin films deposited on cubic Al-doped Li7La3Zr2O12 (LLZO) pellets were studied as a function of temperature using interface-sensitive techniques. X-ray photoelectron spectroscopy (XPS), secondary ion mass spectroscopy (SIMS), and energy-dispersive X-ray spectroscopy (EDS) data indicated significant cation interdiffusion and structural changes starting at temperatures as low as 300⁰C. La2Zr2O7 and Li2CO3 were identified as 2 decomposition products after annealing at 500°C by synchrotron X-ray diffraction (XRD). X-ray absorption spectroscopy (XAS) results indicate the presence of also LaCoO3, in addition to La2Zr2O7 and Li2CO3. Based on electrochemical impedance spectroscopy, and depth profiling of the Li distribution upon potentiostatic hold experiments on symmetric LCO|LLZO|LCO cells, the interfaces exhibited significantly increased impedance, up to 8 times that of the as-deposited samples after annealing at 500 o C. Our results indicate that lower-temperature processing conditions, shorter annealing time scales, and CO2-free environments are desirable for obtaining ceramic cathode-electrolyte interfaces that enable fast Li transfer and high capacity.
Exsolution generates stable and catalytically active metal nanoparticles via phase precipitation out of a host oxide. An ability to control the size and dispersion of the exsolution particles is desirable for design of nanostructured (electro)catalysts. Here, we demonstrate that tuning point defects by lattice strain affects both the thermodynamics and the kinetics of iron (Fe 0 ) exsolution on La 0.6 Sr 0.4 FeO 3 (LSF) thin film model. By combining in situ surface characterization and ab initio defect modeling, we show oxygen vacancy and Schottky defects to be the primary point defects formed upon Fe 0 exsolution. Lattice strain tunes the formation energy, and thus the abundance of these defects, and alters the amount and size of the resulting exsolution particles. In addition, we find that the density of exsolved nanoparticles matches the concentration of oxygen vacancy pairs, thus pointing to the surface oxygen vacancy pairs as preferential nucleation sites for exsolution. The tensile-strained LSF with a facile formation of these critical point defects results in a higher Fe 0 metal concentration, a larger density of nanoparticles, and a reduced particle size at its surfaces. These results provide important mechanistic insights and highlight the role of point-defect engineering in designing nanostructured catalysts in energy and fuel conversion technologies.
Ceramic Li7La3Zr2O12 garnet materials are promising candidates for the electrolytes in solid state batteries due to their high conductivity and structural stability. In this paper, the existence of “polyamorphism” leading to various glass‐type phases for Li‐garnet structure besides the known crystalline ceramic ones is demonstrated. A maximum in Li‐conductivity exists depending on a frozen thermodynamic glass state, as exemplified for thin film processing, for which the local near range order and bonding unit arrangement differ. Through processing temperature change, the crystallization and evolution through various amorphous and biphasic amorphous/crystalline phase states can be followed for constant Li‐total concentration up to fully crystalline nanostructures. These findings reveal that glass‐type thin film Li‐garnet conductors exist for which polyamorphism can be used to tune the Li‐conductivity being potential new solid state electrolyte phases to avoid Li‐dendrite formation (no grain boundaries) for future microbatteries and large‐scale solid state batteries.
The enhancement of oxygen ionic conductivity by over two orders of magnitude in an electroceramic oxide is explicitly shown to result from nanoscale enrichment of a grain boundary layer or complexion with high solute concentration. A series of CaCeO polycrystalline oxides with fluorite structure and varying nominal Ca solute concentration elucidates how local grain boundary composition, rather than structural grain boundary character, primarily regulates ionic conductivity. A correlation between high grain boundary solute concentration above ∼40 mol%, and four orders of magnitude increase in grain boundary conductivity is explicitly shown. A correlated experimental approach provides unique insights into fundamental grain boundary science, and highlights how novel aspects of nanoscale grain boundary design may be employed to control ion transport properties in electroceramics.
Stress and strain in thin films of Pr0.1Ce0.9O2-δ, supported on yttria stabilized zirconia (YSZ) and sapphire substrates, induced by large deviations from oxygen stoichiometry (δ = 0) were investigated by in situ high temperature X-ray diffraction and wafer curvature studies. The measured stresses and strains were correlated with change in δ, measured in situ using optical transmission spectroscopy of defect centers in the films and compared with prior chemical capacitance studies. The coefficient of chemical expansion and elastic modulus values for the films were found to be 18% less than, and 16% greater than in the bulk, respectively. Irreproducible stress and strain during cycling on YSZ substrates was observed and related to microstructural changes as observed by TEM. The enthalpy of defect formation was found to be similar for films supported on sapphire and YSZ, and appeared to decrease with tensile stress, and increase with compressive stress. Larger stresses observed for YSZ supported films as compared to sapphire supported films were found and accounted for by the difference in film orientations.
Exsolution synthesizes self-assembled metal nanoparticle catalysts via phase precipitation. An overlooked aspect in this method thus far is how exsolution affects the host oxide surface chemistry and structure. Such information is critical as the oxide itself can also contribute to the overall catalytic activity. Combining X-ray and electron probes, we investigated the surface transformation of thin-film SrTi0.65Fe0.35O3 during Fe0 exsolution. We found that exsolution generates a highly Fe-deficient near-surface layer of about 2 nm thick. Moreover, the originally single-crystalline oxide near-surface region became partially polycrystalline after exsolution. Such drastic transformations at the surface of the oxide are important because the exsolution-induced nonstoichiometry and grain boundaries can alter the oxide ion transport and oxygen exchange kinetics and, hence, the catalytic activity toward water splitting or hydrogen oxidation reactions. These findings highlight the need to consider the exsolved oxide surface, in addition to the metal nanoparticles, in designing the exsolved nanocatalysts.
Ionic heterostructures are used as a strain-modulated memristive device based on the model system Gd Ce O /Er O to set and tune the property of "memristance." The modulation of interfacial strain and the interface count is used to engineer the R /R ratio and the persistence of the system. A model describing the variation of mixed ionic-electronic mobilities and defect concentrations is presented.
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