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In the present work, the solvent‐deficient synthesis of the high‐entropy rare‐earth carbonate hydroxide RE(CO₃)(OH) (RE=La, Ce, Pr, Nd, Sm, and Gd) and its thermal conversion into bixbyite‐type sesquioxide RE₂O₃ are reported for the first time. The high‐entropy rare earth carbonate hydroxide was prepared via mechanochemical reaction of the corresponding metal nitrate hydrates with ammonium hydrogen carbonate followed by the removal of the NH₄NO₃ by‐product. Calcination of the carbonate hydroxide precursor in ambient atmosphere at temperatures in the range from 500 to 1000 °C led to the high‐entropy rare earth sesquioxide which exhibited a bixbyite‐type structure (Ia3) independent of the calcination temperature. Transmission electron microscopy (TEM) investigation revealed the homogeneous distribution of all six rare earth cations in the high‐entropy sesquioxide lattice, however, with some compositional variation between individual grains. The bixbyite‐type structure may be considered as the result of heavy doping of the fluorite‐type CeO₂ lattice with the other rare earth cations, which leads to a high concentration of oxygen vacancies, as revealed by electron diffraction and Raman spectroscopy data. The solvent‐deficient synthesis method used in the present study is considered as a valuable, straightforward and easily up‐scalable method to synthesize compositionally complex oxide ceramics.

Reversible field-induced phase transitions define antiferroelectric perovskite oxides and lay the foundation for high-energy storage density materials, required for future green technologies. However, promising new antiferroelectrics are hampered by transition´s irreversibility and low electrical resistivity. Here, we demonstrate an approach to overcome these problems by adjusting the local structure and defect chemistry, delivering NaNbO₃-based antiferroelectrics with well-defined double polarization loops. The attending reversible phase transition and structural changes at different length scales are probed by in situ high-energy X-ray diffraction, total scattering, transmission electron microcopy, and nuclear magnetic resonance spectroscopy. We show that the energy-storage density of the antiferroelectric compositions can be increased by an order of magnitude, while increasing the chemical disorder transforms the material to a relaxor state with a high energy efficiency of 90%. The results provide guidelines for efficient design of (anti-)ferroelectrics and open the way for the development of new material systems for a sustainable future.

The implementation of thermal barriers in thermoelectric materials improves their power conversion rates effectively. For this purpose, material boundaries are utilized and manipulated to affect phonon transmissivity. Specifically, interface intermixing and topography represents a useful but complex parameter for thermal transport modification. This study investigates epitaxial thin film multilayers, so called superlattices (SL), of TiNiSn/HfNiSn, both with pristine and purposefully deteriorated interfaces. High-resolution transmission electron microscopy and X-ray diffractometry are used to characterize their structural properties in detail. A differential 3w -method probes their thermal resistivity. The thermal resistivity reaches a maximum for an intermediate interface quality and decreases again for higher boundary layer intermixing. For boundaries with the lowest interface quality, the interface thermal resistance is reduced by 23% compared to a pristine SL. While an uptake of diffuse scattering likely explains the initial deterioration of thermal transport, we propose a phonon bridge interpretation for the lowered thermal resistivity of the interfaces beyond a critical intermixing. In this picture, the locally reduced acoustic contrast of the less defined boundary acts as a mediator that promotes phonon transition.

Dislocations in oxides can be described as charged line defects and means for one-dimensional doping, which can tune electrical and thermal properties. Furthermore, theoretically it was shown that dislocations can pin ferroelectric domain walls. Broader application of this concept hinges on the development of a methodology to avail this approach to polycrystalline ceramics. To this end, we use different creep mechanisms as a method to introduce multidimensional defects and quantify structural changes. A deformation map for fine-grained barium titanate is provided and the influences of the defects and creep regimes are correlated in this first study to modifications of electrical conductivity, dielectric, ferroelectric, and piezoelectric properties. A plastic deformation of 1.29% resulted in an increase in the Curie temperature by 5°C and a decrease in electromechanical strain by 30%, pointing toward electromechanical hardening by dislocations.

Lithium is in high demand: this is driven by current trends in e-mobility and results in increased global production and record prices for lithium ores and compounds. Pegmatite ores, in addition to brines, remain of particular interest because of their higher lithium content and lower geopolitical risks. In this work, we investigated lithium extraction via the mechanochemical treatment of the three most common lithium minerals: lepidolite, spodumene, and petalite. Indeed, we determine that the petalite crystal structure was much more suitable due to its less dense packing and the formation of cleavage planes along lithium sites, resulting in substantial lithium extraction of 84.9% and almost complete conversion to hydrosodalite after 120 min of ball milling in alkaline media. Further processing of the leach liquor includes desilication, the precipitation of lithium phosphate, and the conversion and crystallization of pure LiOH·H₂O. Special attention was paid to a holistic approach entailing the generation of by-products, each of which has a specific intended application. The leaching residues were investigated by powder X-ray diffraction, Fourier transform infrared spectroscopy, N₂ adsorption/desorption, and scanning electron microscopy. Moreover, hydrosodalite was found to have a high potential as an adsorbent for heavy metal ions which were studied separately using aqueous solutions containing Cu²⁺, Ni²⁺, Pb²⁺, and Zn²⁺.

Domain wall motion in ferroics, similar to dislocation motion in metals, can be tuned by well‐concepted microstructural elements. In demanding high‐power applications of piezoelectric materials, the domain wall motion is considered as a lossy hysteretic mechanism that should be restricted. Current applications for so‐called hard piezoelectrics are abundant and hinge on the use of an acceptor‐doping scheme. However, this mechanism features severe limitations due to enhanced mobility of oxygen vacancies at moderate temperatures. By analogy with metal technology, the authors present here a new solution for electroceramics, where precipitates are utilized to pin domain walls and improve piezoelectric properties. Through a sequence of sintering, nucleation, and precipitate growth, intragranular precipitates leading to a fine domain structure are developed as shown by transmission electron microscopy, piezoresponse force microscopy, and phase‐field simulation. This structure impedes the domain wall motion as elucidated by electromechanical characterization. As a result, the mechanical quality factor is increased by ≈50% and the hysteresis in electrostrain is suppressed considerably. This is even achieved with slightly increased piezoelectric coefficient and electromechanical coupling factor. This novel process can be smoothly implemented in industrial production processes and is accessible to simple laboratory experimentation for microstructure optimization and implementation in various ferroelectric systems.

Dense diamond-like BCN compounds are of interest due to their extreme hardness and predicted excellent thermal and chemical stability, which are superior to those of diamond and c-BN. Here, we report on the high-pressure high-temperature (HP-HT) behavior of amorphous BC₂N and BC₄N -as potential precursors for HP-HT synthesis of diamond-like BCN. Prepared via hydroboration reaction of piperazine borane and pyridine borane, respectively, amorphous BC₂N and BC₄N are characterized by well-mixed B-N, C-C and C-N bonds, confirmed by XPS analysis. These BCN compositions were subjected to pressures between 5-12 GPa and temperatures up to 1700 °C using multi-anvil apparatus and toroid-type press. In- and ex-situ X-ray diffraction reveals the decomposition of BC₄N to graphite and h-BN between 5 and 12 GPa above 500 °C, in contrast to BC₂N which remains amorphous up to 1600 °C.

Reversible antiferroelectric‐ferroelectric phase transitions were recently observed in a series of SrSnO₃‐modified NaNbO₃ lead‐free antiferroelectric materials, exhibiting well‐defined double polarization hysteresis loops at ambient conditions. Here, transmission electron microscopy was employed to investigate the crystallography and domain configuration of this newly designed system via electron diffraction and centered dark‐field imaging. It was confirmed that antiferroelectricity is maintained in all compositions, manifested by the characteristic ¼ superlattice reflections in the electron‐diffraction patterns. By investigating the antiferroelectric domains and domain boundaries in NaNbO₃, we demonstrate that antiphase boundaries are present and their irregular periodicity is responsible for the streaking features along the ¼ superlattice reflections in the electron‐diffraction patterns. The signature domain blocks observed in pure NaNbO₃ are maintained in the SrSnO₃‐modified ceramics, but disappear when the amount of SrSnO₃ reaches 7 mol.%. In particular, a well‐defined and distinct domain configuration is observed in the NaNbO₃ sample modified with 5 mol.% SrSnO₃, which presents a parallelogram domain morphology.

We report an intrinsic strain engineering, akin to thin filmlike approaches, via irreversible high-temperature plastic deformation of a tetragonal ferroelectric single-crystal BaTiO3. Dislocations well-aligned along the [001] axis and associated strain fields in plane defined by the [110]/[1¯10] plane are introduced into the volume, thus nucleating only in-plane domain variants. By combining direct experimental observations and theoretical analyses, we reveal that domain instability and extrinsic degradation processes can both be mitigated during the aging and fatigue processes, and demonstrate that this requires careful strain tuning of the ratio of in-plane and out-of-plane domain variants. Our findings advance the understanding of structural defects that drive domain nucleation and instabilities in ferroic materials and are essential for mitigating device degradation., RST/Storage of Electrochemical Energy

Reversible field-induced phase transitions define antiferroelectric perovskite oxides and lay the foundation for high-energy storage density materials, required for future green technologies. However, promising new antiferroelectrics are hampered by transition´s irreversibility and low electrical resistivity. Here, we demonstrate an approach to overcome these problems by adjusting the local structure and defect chemistry, delivering NaNbO3-based antiferroelectrics with well-defined double polarization loops. The attending reversible phase transition and structural changes at different length scales are probed by in situ high-energy X-ray diffraction, total scattering, transmission electron microcopy, and nuclear magnetic resonance spectroscopy. We show that the energy-storage density of the antiferroelectric compositions can be increased by an order of magnitude, while increasing the chemical disorder transforms the material to a relaxor state with a high energy efficiency of 90%. The results provide guidelines for efficient design of (anti-)ferroelectrics and open the way for the development of new material systems for a sustainable future., RST/Storage of Electrochemical Energy