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    Dislocations in ceramic electrolytes for solid-state Li batteries
    ([London] : Macmillan Publishers Limited, part of Springer Nature, 2021) Porz, L.; Knez, D.; Scherer, M.; Ganschow, S.; Kothleitner, G.; Rettenwander, D.
    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.
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    AlF3-assisted flux growth of mullite whiskers and their application in fabrication of porous mullite-alumina monoliths
    (Amsterdam : Elsevier, 2021) Abdullayev, Amanmyrat; Klimm, Detlef; Kamutzki, Franz; Gurlo, Aleksander; Bekheet, Maged F.
    Mullite is a promising material with its competitive thermochemical and mechanical properties. Although mullite could be obtained by several synthesis methods, the flux method emerges with its advantages over other methods. However, obtaining mullite whiskers with a high aspect ratio and length for ceramic reinforcements is still challenging. In this work, mullite whiskers were grown from AlF3-assisted flux. The addition of AlF3 to flux salt not only decreases the formation temperature of mullite to as low as 700 ​°C and suppresses the formation of corundum side phase, but also increases the length and aspect ratio of the whiskers. The obtained mullite whiskers were used as reinforcement for porous alumina monoliths prepared by the freeze casting route and subsequent sintering at 1500 ​°C. The fabricated mullite-alumina monoliths show competitive compressive strength of 25.7 ​MPa while having as high as 70.6% porosity, which makes them a potential candidate for membrane applications.
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    Electronic Properties and Structure of Boron–Hydrogen Complexes in Crystalline Silicon
    (Weinheim : Wiley-VCH, 2021-9-17) De Guzman, Joyce Ann T.; Markevich, Vladimir P.; Coutinho, José; Abrosimov, Nikolay V.; Halsall, Matthew P.; Peaker, Anthony R.
    The subject of hydrogen–boron interactions in crystalline silicon is revisited with reference to light and elevated temperature-induced degradation (LeTID) in boron-doped solar silicon. Ab initio modeling of structure, binding energy, and electronic properties of complexes incorporating a substitutional boron and one or two hydrogen atoms is performed. From the calculations, it is confirmed that a BH pair is electrically inert. It is found that boron can bind two H atoms. The resulting BH2 complex is a donor with a transition level estimated at E c–0.24 eV. Experimentally, the electrically active defects in n-type Czochralski-grown Si crystals co-doped with phosphorus and boron, into which hydrogen is introduced by different methods, are investigated using junction capacitance techniques. In the deep-level transient spectroscopy (DLTS) spectra of hydrogenated Si:P + B crystals subjected to heat-treatments at 100 °C under reverse bias, an electron emission signal with an activation energy of ≈0.175 eV is detected. The trap is a donor with electronic properties close to those predicted for boron–dihydrogen. The donor character of BH2 suggests that it can be a very efficient recombination center of minority carriers in B-doped p-type Si crystals. A sequence of boron–hydrogen reactions, which can be related to the LeTID effect in Si:B is proposed.
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    Controlling palladium morphology in electrodeposition from nanoparticles to dendrites via the use of mixed solvents
    (Cambridge : RSC Publ., 2020) Hussein, Haytham E. M.; Amari, Houari; Breeze, Ben G.; Beanland, Richard; Macpherson, Julie V.
    By changing the mole fraction of water (χwater) in the solvent acetonitrile (MeCN), we report a simple procedure to control nanostructure morphology during electrodeposition. We focus on the electrodeposition of palladium (Pd) on electron beam transparent boron-doped diamond (BDD) electrodes. Three solutions are employed, MeCN rich (90% v/v MeCN, χwater = 0.246), equal volumes (50% v/v MeCN, χwater = 0.743) and water rich (10% v/v MeCN, χwater = 0.963), with electrodeposition carried out under a constant, and high overpotential (−1.0 V), for fixed time periods (50, 150 and 300 s). Scanning transmission electron microscopy (STEM) reveals that in MeCN rich solution, Pd atoms, amorphous atom clusters and (majority) nanoparticles (NPs) result. As water content is increased, NPs are again evident but also elongated and defected nanostructures which grow in prominence with time. In the water rich environment, NPs and branched, concave and star-like Pd nanostructures are now seen, which with time translate to aggregated porous structures and ultimately dendrites. We attribute these observations to the role MeCN adsorption on Pd surfaces plays in retarding metal nucleation and growth.