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Lithium metal penetration induced by electrodeposition through solid electrolytes: Example in single-crystal Li6La3ZrTaO12 garnet
Solid electrolytes potentially enable rechargeable batteries with lithium metal anodes possessing higher energy densities than today’s lithium ion batteries. To do so the solid electrolyte must suppress instabilities that lead to poor coulombic efficiency and short circuits. In this work, lithium electrodeposition was performed on single-crystal Li6La3ZrTaO12 garnets to investigate factors governing lithium penetration through brittle electrolytes. In single crystals, grain boundaries are excluded as paths for lithium metal propagation. Vickers microindentation was used to introduce surface flaws of known size. However, operando optical microscopy revealed that lithium metal penetration propagates preferentially from a different, second class of flaws. At the perimeter of surface current collectors smaller in size than the lithium source electrode, an enhanced electrodeposition current density causes lithium filled cracks to initiate and grow to penetration, even when large Vickers defects are in proximity. Modeling the electric field distribution in the experimental cell revealed that a 5-fold enhancement in field occurs within 10 micrometers of the electrode edge and generates high local electrochemomechanical stress. This may determine the initiation sites for lithium propagation, overriding the presence of larger defects elsewhere.
Self-stabilization of the equilibrium state in ferroelectric thin films
(K,Na)NbO3 is a lead-free and sustainable ferroelectric material with electromechanical parameters comparable to Pb(Zr,Ti)O3 (PZT) and other lead-based solid solutions. It is therefore a promising candidate for caloric cooling and energy harvesting applications. Specifically, the structural transition from the low-temperature Mc- to the high-temperature c-phase displays a rich hierarchical order of domains and superdomains, that forms at specific strain conditions. The relevant length scales are few tens of nanometers for the domain and few micrometers for the superdomain size, respectively. Phase-field calculations show that this hierarchical order adds to the total free energy of the solid. Thus, domains and their formation has a strong impact on the functional properties relevant for electrocaloric cooling or energy harvesting applications. However, monitoring the formation of domains and superdomains is difficult and requires both, high spatial and high temporal resolution of the experiment. Synchrotron-based time-resolved X-ray diffraction methods in combination with scanning imaging X-ray microscopy is applied to resolve the local dynamics of the domain morphology with sub-micrometer spatial and nanosecond temporal resolution. In this regime, the material displays a novel self-stabilization mechanism of the domain morphology, which may be a general property of first-order phase transitions.
Atomic-Scale Mapping and Quantification of Local Ruddlesden-Popper Phase Variations
The Ruddlesden-Popper (An+1BnO3n+1) compounds are highly tunable materials whose functional properties can be dramatically impacted by their structural phase n. The negligible differences in formation energies for different n can produce local structural variations arising from small stoichiometric deviations. Here, we present a Python analysis platform to detect, measure, and quantify the presence of different n-phases based on atomic-resolution scanning transmission electron microscopy (STEM) images. We employ image phase analysis to identify horizontal Ruddlesden-Popper faults within the lattice images and quantify the local structure. Our semiautomated technique considers effects of finite projection thickness, limited fields of view, and lateral sampling rates. This method retains real-space distribution of layer variations allowing for spatial mapping of local n-phases to enable quantification of intergrowth occurrence and qualitative description of their distribution suitable for a wide range of layered materials.