RESUMEN
All-solid-state batteries with a Li anode and ceramic electrolyte have the potential to deliver a step change in performance compared with today's Li-ion batteries1,2. However, Li dendrites (filaments) form on charging at practical rates and penetrate the ceramic electrolyte, leading to short circuit and cell failure3,4. Previous models of dendrite penetration have generally focused on a single process for dendrite initiation and propagation, with Li driving the crack at its tip5-9. Here we show that initiation and propagation are separate processes. Initiation arises from Li deposition into subsurface pores, by means of microcracks that connect the pores to the surface. Once filled, further charging builds pressure in the pores owing to the slow extrusion of Li (viscoplastic flow) back to the surface, leading to cracking. By contrast, dendrite propagation occurs by wedge opening, with Li driving the dry crack from the rear, not the tip. Whereas initiation is determined by the local (microscopic) fracture strength at the grain boundaries, the pore size, pore population density and current density, propagation depends on the (macroscopic) fracture toughness of the ceramic, the length of the Li dendrite (filament) that partially occupies the dry crack, current density, stack pressure and the charge capacity accessed during each cycle. Lower stack pressures suppress propagation, markedly extending the number of cycles before short circuit in cells in which dendrites have initiated.
RESUMEN
For high (angular) resolution electron backscatter diffraction (HR-EBSD), the selection of a reference diffraction pattern (EBSP0) significantly affects the precision of the calculated strain and rotation maps. This effect was demonstrated in plastically deformed body-centred cubic and face-centred cubic ductile metals (ferrite and austenite grains in duplex stainless steel) and brittle single-crystal silicon, which showed that the effect is not only limited to measurement magnitude but also spatial distribution. An empirical relationship was then identified between the cross-correlation parameter and angular error, which was used in an iterative algorithm to identify the optimal reference pattern that maximises the precision of HR-EBSD.
RESUMEN
Despite being one of the most promising candidates for grid-level energy storage, practical aqueous zinc batteries are limited by dendrite formation, which leads to significantly compromised safety and cycling performance. In this study, by using single-crystal Zn-metal anodes, reversible electrodeposition of planar Zn with a high capacity of 8 mAh cm-2 can be achieved at an unprecedentedly high current density of 200 mA cm-2 . This dendrite-free electrode is well maintained even after prolonged cycling (>1200 cycles at 50 mA cm- 2 ). Such excellent electrochemical performance is due to single-crystal Zn suppressing the major sources of defect generation during electroplating and heavily favoring planar deposition morphologies. As so few defect sites form, including those that would normally be found along grain boundaries or to accommodate lattice mismatch, there is little opportunity for dendritic structures to nucleate, even under extreme plating rates. This scarcity of defects is in part due to perfect atomic-stitching between merging Zn islands, ensuring no defective shallow-angle grain boundaries are formed and thus removing a significant source of non-planar Zn nucleation. It is demonstrated that an ideal high-rate Zn anode should offer perfect lattice matching as this facilitates planar epitaxial Zn growth and minimizes the formation of any defective regions.
RESUMEN
Porous silicon carbide is a promising material for ceramic receivers in next-generation concentrated solar power receivers. To investigate its tolerance to thermal shock, accelerated ageing of large coupons (50 × 50 × 5 mm) was conducted in a solar furnace to investigate the effects of thermal cycling up to 1000 °C, with gradients of up to 22 °C/mm. Non-destructive characterization by computed X-ray tomography and ultrasonic inspection could detect cracking from thermal stresses, and this informed the preparation of valid specimens for thermophysical characterization. The effect of thermal ageing on transient thermal properties, as a function of temperature, was investigated by using the light-flash method. The thermophysical properties were affected by increasing the severity of the ageing conditions; thermal diffusivity decreased by up to 10% and specific heat by up to 5%.
RESUMEN
Lithium dendrite (filament) propagation through ceramic electrolytes, leading to short circuits at high rates of charge, is one of the greatest barriers to realizing high-energy-density all-solid-state lithium-anode batteries. Utilizing in situ X-ray computed tomography coupled with spatially mapped X-ray diffraction, the propagation of cracks and the propagation of lithium dendrites through the solid electrolyte have been tracked in a Li/Li6PS5Cl/Li cell as a function of the charge passed. On plating, cracking initiates with spallation, conical 'pothole'-like cracks that form in the ceramic electrolyte near the surface with the plated electrode. The spallations form predominantly at the lithium electrode edges where local fields are high. Transverse cracks then propagate from the spallations across the electrolyte from the plated to the stripped electrode. Lithium ingress drives the propagation of the spallation and transverse cracks by widening the crack from the rear; that is, the crack front propagates ahead of the Li. As a result, cracks traverse the entire electrolyte before the Li arrives at the other electrode, and therefore before a short circuit occurs.
RESUMEN
Two-dimensional, Knight-shifted, T2 -contrasted 23 Na magnetic resonance imaging (MRI) of an all-solid-state cell with a Na electrode and a ceramic electrolyte is employed to directly observe Na microstructural growth. A spalling dendritic morphology is observed and confirmed by more conventional post-mortem analysis; X-ray tomography and scanning electron microscopy. A significantly larger 23 Na T2 for the dendritic growth, compared with the bulk metal electrode, is attributed to increased sodium ion mobility in the dendrite. 23 Na T2 -contrast MRI of metallic sodium offers a clear, routine method for observing and isolating microstructural growths and can supplement the current suite of techniques utilised to analyse dendritic growth in all-solid-state cells.
RESUMEN
Two-dimensional, Knight-shifted, T 2-contrasted 23Na magnetic resonance imaging (MRI) of an all-solid-state cell with a Na electrode and a ceramic electrolyte is employed to directly observe Na microstructural growth. A spalling dendritic morphology is observed and confirmed by more conventional post-mortem analysis; X-ray tomography and scanning electron microscopy. A significantly larger 23Na T 2 for the dendritic growth, compared with the bulk metal electrode, is attributed to increased sodium ion mobility in the dendrite. 23Na T 2-contrast MRI of metallic sodium offers a clear, routine method for observing and isolating microstructural growths and can supplement the current suite of techniques utilised to analyse dendritic growth in all-solid-state cells.