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.
For millennia, ceramics have been densified via sintering in a furnace, a time-consuming and energy-intensive process. The need to minimize environmental impact calls for new physical concepts beyond large kilns...
High power solid-state Li batteries (SSLB) are hindered by the formation of dendrite-like structures at high current rates. Hence, new design principles are needed to overcome this limitation. By introducing dislocations, we aim to tailor mechanical properties in order to withstand the mechanical stress leading to Li penetration and resulting in a short circuit by a crack-opening mechanism. Such defect engineering, furthermore, appears to enable whisker-like Li metal electrodes for high-rate Li plating. To reach these goals, the challenge of introducing dislocations into ceramic electrolytes needs to be addressed which requires to establish fundamental understanding of the mechanics of dislocations in the particular ceramics. Here we evaluate uniaxial deformation at elevated temperatures as one possible approach to introduce dislocations. By using hot-pressed pellets and single crystals grown by Czochralski method of Li6.4La3Zr1.4Ta0.6O12 garnets as a model system the plastic deformation by more than 10% is demonstrated. While conclusions on the predominating deformation mechanism remain challenging, analysis of activation energy, activation volume, diffusion creep, and the defect structure potentially point to a deformation mechanism involving dislocations. These parameters allow identification of a process window and are a key step on the road of making dislocations available as a design element for SSLB.
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.
Dislocation networks have been demonstrated to substantially enhance functional properties. As-sintered samples are virtually devoid of dislocations, new innovative techniques for introducing sufficiently high dislocation densities into polycrystalline ceramics are needed. While dislocation-based plasticity at high temperatures has been demonstrated for a large range of ceramic single crystals, plasticity in polycrystals is much less understood. Here, we demonstrate plastic strains in excess of several % based on dislocation motion in polycrystalline SrTiO3 at ≈ 1100 °C with 3.9 µm grain size. Ultra-high voltage electron microscopy reveals an associated increase in dislocation density by three orders of magnitude. Achievable strain rates are comparable to creep-based mechanisms and much less sensitive to applied stress than observed for metals. A specialized testing protocol allows quantification of the deformability via stress exponent, activation volume and activation enthalpy giving additional quantification. In conjunction with TEM images, the mechanical data gives insight into the underlying mechanisms.
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