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The reactivity of mixtures of high voltage spinel cathode materials Li2NiMn3O8, Li2FeMn3O8, and LiCoMnO4 cosintered with Li1.5Al0.5Ti1.5(PO4)3 and Li6.6La3Zr1.6Ta0.4O12 electrolytes is studied by thermal analysis using X-ray-diffraction and differential thermoanalysis and thermogravimetry coupled with mass spectrometry. The results are compared with predicted decomposition reactions from first-principles calculations. Decomposition of the mixtures begins at 600 °C, significantly lower than the decomposition temperature of any component, especially the electrolytes. For the cathode + Li6.6La3Zr1.6Ta0.4O12 mixtures, lithium and oxygen from the electrolyte react with the cathodes to form highly stable Li2MnO3 and then decompose to form stable and often insulating phases such as La2Zr2O7, La2O3, La3TaO7, TiO2, and LaMnO3 which are likely to increase the interfacial impedance of a cathode composite. The decomposition reactions are identified with high fidelity by first-principles calculations. For the cathode + Li1.5Al0.5Ti1.5(PO4)3 mixtures, the Mn tends to oxidize to MnO2 or Mn2O3, supplying lithium to the electrolyte for the formation of Li3PO4 and metal phosphates such as AlPO4 and LiMPO4 (M = Mn, Ni). The results indicate that high temperature cosintering to form dense cathode composites between spinel cathodes and oxide electrolytes will produce high impedance interfacial products, complicating solid state battery manufacturing.

Oxidation of the bond coat during turbine operation leads to additional stresses in the thermal barrier coating (TBC) system that promotes spalling of the thermal insulation. Therefore, the oxidation behavior of a TBC system plays an important role in the thermal cycling of a TBC system. To delay the loss of thermal insulation, research has typically focused for a long time on the composition and microstructure of the ceramic topcoats and metallic bond coats. More recently, heat treatment for the diffusion annealing of the bond coat has also become a focus of research. Several studies have shown that pre-oxidation of the bond coat prior to the application of the ceramic topcoat slows down the subsequent oxidation of the bond coat in service. The improved thermal cyclability has been demonstrated in studies for systems with atmospheric plasma-sprayed (APS), suspension plasma-sprayed (SPS) or electron beam physical vapor deposition (EB-PVD) top coatings. However, no study has directly compared the effects of pre-oxidation on different topcoats. Therefore, this study compared the effect of pre-oxidation on APS and SPS coatings with the same bond coat. For both topcoats, pre-oxidation slowed the subsequent TGO growth and thus increased the lifetime of the coatings. The improvement in lifetime was particularly pronounced for the systems with an SPS topcoat. Overall, the lifetime of the coatings with an APS topcoat was higher as the critical energy release rate within the coating was not exceeded in these coatings. [ABSTRACT FROM AUTHOR]

Garnet-type solid electrolytes stand out as promising Li-ion conductors for the next-generation batteries. It has been demonstrated that the inherent properties of garnets can be tailored by introducing various dopants into their crystal structures. Recently, there has been a growing interest in the concept of high entropy stabilization for materials design. In this study, we synthesized high-entropy garnets denoted as Li6La3Zro.7Tio.3Tao.5Sbo.5Oi2 (LLZTTSO), wherein Ti, Sb, and Ta occupy the Zr site. The formation of the cubic garnet phase in LLZTTSO was confirmed through X-ray diffraction (XRD), and the resulting lattice parameter agreed with predictions made using computational methods. Despite the substantial porosity (relative density 80.6%) attributed to the low sintering temperature, LLZTTSO exhibits a bulk ionic conductivity of 0.099 mS cm-1 at 25°C, and a total ionic conductivity of 0.088 mS cm-1, accompanied by an activation energy of 0.497 eV. Furthermore, LLZTTSO demonstrates a critical current density of 0.275mAcm-2 at 25°C, showcasing its potential even without any interfacial modification. [ABSTRACT FROM AUTHOR]

This study explores multi-component garnet-based materials as solid electrolytes for all-solid-state lithium batteries. Through a combination of computational and experimental approaches, we investigate the thermodynamic and structural properties of lithium lanthanum zirconium oxide garnets doped with various elements. Applying density functional theory, the influence of dopants on the thermodynamic stability of these garnets was studied. Probable atomic configurations and their impact on materials' properties were investigated with the focus on understanding the influence of these configurations on structural stability, phase preference, and ionic conductivity. In addition to the computational study, series of cubic-phase garnet compounds were synthesized and their electrochemical performance was evaluated experimentally. Our findings reveal that the stability of cubic phase in doped Li-garnets is primarily governed by enthalpy, with configurational entropy playing a secondary role. Moreover, we establish that the increased number of doping elements significantly enhances the cubic phase's stability. This in-depth understanding of materials' properties at atomic level establishes the basis for optimizing high-entropy ceramics, contributing significantly to the advancement of solid-state lithium batteries and other applications requiring innovative material solutions. [ABSTRACT FROM AUTHOR]