Search for: All records

Rare-earth-free permanent magnet materials based on Mn show great promise for applications in electric motors and devices. The metastable ferromagnetic τ phase of the Mn-Al system has magnetic properties between those of the high-performance Nd-Fe-B magnets and the lower-performance ferrite magnets. However, the hybrid displacive-diffusional pathway of τ formation, from the parent ε phase through the intermediary ε’ phase, is still not fully understood. This phase transformation progression was studied in-situ using diffractive, calorimetric, and magnetometric techniques to show that the progression from ε to τ in Mn54Al46 at <450 ◦C involves the ordering of ε into ε’. Density functional theory calculations were performed on each phase and confirmed the experimental observation that the ε to ε’ to τ pathway is energetically favorable. Isothermal annealing of quenched-in ε at 350 ◦C demonstrated that ε’ is ferromagnetic, also in agreement with theoretical results, with a moderate coercivity of at least 50 kA/m. The τ phase was observed to nucleate along the prior ε phase grain boundaries and grow into the ε’ phase regions. A boundary front of ε’ was observed between the τ and ε phases. Both Kissinger and Flynn-Wall-Ozawa methods were used to determine the activation energies for the ε’ and τ phase transformations with values of ~140 kJ/mol obtained for both phases. Therefore, the ordering transformation to ε’ and the hybrid displacive-diffusional transformation to τ were shown to overcome the same magnitude energy barrier. Both activation energies were less than previous τ phase activation energies measured on Mn55Al45 in the absence of a significant ε’ ordering exotherm, providing a kinetic benefit to the ε to ε’ to τ pathway at 350 ◦C. The results of this study give insight into the phase transformation of L10 binary materials as well as materials that undergo a disorder–order transformation followed by displacive shear. 

It has been suggested that Ba3In2O6 might be a high-Tcsuperconductor. Experimental investigation of the properties of Ba3In2O6 was long inhibited by its instability in air. Recently epitaxial Ba3In2O6 with a protective capping layer was demonstrated, which finally allows its electronic characterization. The optical bandgap of Ba3In2O6 is determined to be 2.99 eV in-the (001) plane and 2.83 eV along the c-axis direction by spectroscopic ellipsometry. First-principles calculations were carried out, yielding a result in good agreement with the experimental value. Various dopants were explored to induce (super-)conductivity in this otherwise insulating material. Neither A- nor B-site doping proved successful. The underlying reason is predominately the formation of oxygen interstitials as revealed by scanning transmission electron microscopy and first-principles calculations. Additional efforts to induce superconductivity were investigated, including surface alkali doping, optical pumping, and hydrogen reduction. To probe liquid-ion gating, Ba3In2O6 was successfully grown epitaxially on an epitaxial SrRuO3 bottom electrode. So far none of these efforts induced superconductivity in Ba3In2O6, leaving the answer to the initial question of whether Ba3In2O6 is a high-Tcsuperconductor to be “no” thus far.

 

Nonlinear optical (NLO) crystals with superior properties are significant for advancing laser technologies and applications. Introducing rare earth metals to borates is a promising and effective way to modify the electronic structure of a crystal to improve its optical properties in the visible and ultraviolet range. In this work, we computationally discover inversion symmetry breaking in EuBa₃(B₃O₆)₃, which was previously identified as centric, and demonstrate noncentrosymmetry via synthesizing single crystals for the first time by the floating zone method. We determine the correct space group to beP6¯. The material has a large direct bandgap of 5.56 eV and is transparent down to 250 nm. The complete anisotropic linear and nonlinear optical properties were also investigated with ad₁₁of ∼0.52 pm/V for optical second harmonic generation. Further, it is Type I and Type II phase matchable. This work suggests that rare earth metal borates are an excellent crystal family for exploring future deep ultraviolet (DUV) NLO crystals. It also highlights how first principles computations combined with experiments can be used to identify noncentrosymmetric materials that have been wrongly assigned to be centrosymmetric.

 

Abstract Nonaqueous sodium-based batteries are ideal candidates for the next generation of electrochemical energy storage devices. However, despite the promising performance at ambient temperature, their low-temperature (e.g., < 0 °C) operation is detrimentally affected by the increase in the electrolyte resistance and solid electrolyte interphase (SEI) instability. Here, to circumvent these issues, we propose specific electrolyte formulations comprising linear and cyclic ether-based solvents and sodium trifluoromethanesulfonate salt that are thermally stable down to −150 °C and enable the formation of a stable SEI at low temperatures. When tested in the Na||Na coin cell configuration, the low-temperature electrolytes enable long-term cycling down to −80 °C. Via ex situ physicochemical (e.g., X-ray photoelectron spectroscopy, cryogenic transmission electron microscopy and atomic force microscopy) electrode measurements and density functional theory calculations, we investigate the mechanisms responsible for efficient low-temperature electrochemical performance. We also report the assembly and testing between −20 °C and −60 °C of full Na||Na 3 V 2 (PO 4 ) 3 coin cells. The cell tested at −40 °C shows an initial discharge capacity of 68 mAh g −1 with a capacity retention of approximately 94% after 100 cycles at 22 mA g −1 . 

The interplay of synthesis, experiments, and theory in broadening the landscape of thermoelectric materials is reported. 

The Zintl phases, Yb 14 M Sb 11 ( M = Mn, Mg, Al, Zn), are now some of the highest thermoelectric efficiency p-type materials with stability above 873 K. Yb 14 MnSb 11 gained prominence as the first p-type thermoelectric material to double the efficiency of SiGe alloy, the heritage material in radioisotope thermoelectric generators used to power NASA’s deep space exploration. This study investigates the solid solution of Yb 14 Mg 1− x Al x Sb 11 (0 ≤ x ≤ 1), which enables a full mapping of the metal-to-semiconductor transition. Using a combined theoretical and experimental approach, we show that a second, high valley degeneracy ( N v = 8) band is responsible for the groundbreaking performance of Yb 14 M Sb 11 . This multiband understanding of the properties provides insight into other thermoelectric systems (La 3− x Te 4 , SnTe, Ag 9 AlSe 6 , and Eu 9 CdSb 9 ), and the model predicts that an increase in carrier concentration can lead to zT > 1.5 in Yb 14 M Sb 11 systems. 

The use of renewable electricity to prepare materials and fuels from abundant molecules offers a tantalizing opportunity to address concerns over energy and materials sustainability. The oxygen evolution reaction (OER) is integral to nearly all material and fuel electrosyntheses. However, very little is known about the structural evolution of the OER electrocatalyst, especially the amorphous layer that forms from the crystalline structure. Here, we investigate the interfacial transformation of the SrIrO 3 OER electrocatalyst. The SrIrO 3 amorphization is initiated by the lattice oxygen redox, a step that allows Sr 2+ to diffuse and O 2− to reorganize the SrIrO 3 structure. This activation turns SrIrO 3 into a highly disordered Ir octahedral network with Ir square-planar motif. The final Sr y IrO x exhibits a greater degree of disorder than IrO x made from other processing methods. Our results demonstrate that the structural reorganization facilitated by coupled ionic diffusions is essential to the disordered structure of the SrIrO 3 electrocatalyst.