Search for: All records

A series of perovskite oxides (Ln = La, Pr, Nd, Gd; A = Ba, Sr) was investigated to understand the effects of A-site cation size on oxygen vacancy formation. Quasirandom mixed structures were generated using Alloy Theoretic Automated Toolkit (ATAT), followed by density functional theory (DFT) calculations. While mixing the orthorhombic structures with the hexagonal AMnO3 structures leads to lattices and global symmetries closer to cubic, the average volume generally increases with the average ionic size, and the local bond and angles exhibit more variations due to A-site mixing. DFT calculations and a statistical model were combined to predict oxygen reduction abilities. Thermogravimetric analysis (TGA) provided experimental validation of these predictions by measuring changes in oxygen non-stoichiometry under controlled conditions. Both indicated that larger A-site ionic size differences lead to greater, consistent with the larger variation in local structures, and enhanced redox capabilities. This combined computational-experimental approach highlights the importance of local structure variation, instead of average properties, in A-site cation engineering to optimize perovskite oxides for different devices relying on oxygen vacancy redox activity. 

Abstract Sulfide solid-state electrolytes (SSEs) are promising candidates to realize all solid-state batteries (ASSBs) due to their superior ionic conductivity and excellent ductility. However, their hypersensitivity to moisture requires processing environments that are not compatible with today’s lithium-ion battery manufacturing infrastructure. Herein, we present a reversible surface modification strategy that enables the processability of sulfide SSEs (e. g., Li₆PS₅Cl) under humid ambient air. We demonstrate that a long chain alkyl thiol, 1-undecanethiol, is chemically compatible with the electrolyte with negligible impact on its ion conductivity. Importantly, the thiol modification extends the amount of time that the sulfide SSE can be exposed to air with 33% relative humidity (33% RH) with limited degradation of its structure while retaining a conductivity of above 1 mS cm^-1for up to 2 days, a more than 100-fold improvement in protection time over competing approaches. Experimental and computational results reveal that the thiol group anchors to the SSE surface, while the hydrophobic hydrocarbon tail provides protection by repelling water. The modified Li₆PS₅Cl SSE maintains its function after exposure to ambient humidity when implemented in a Li_0.5In | |LiNi_0.8Co_0.1Mn_0.1O₂ASSB. The proposed protection strategy based on surface molecular interactions represents a major step forward towards cost-competitive and energy-efficient sulfide SSE manufacturing for ASSB applications. 

Adsorption transitions at grain boundaries in a polycrystal result in structures that are forbidden in bulk crystals 

Abstract Recent work in ultra-high temperature in situ electron microscopy has presented the need for accurate, contact-free temperature determination at the microscale. Optical measurement based on thermal radiation (pyrometry) is an attractive solution but can be difficult to perform correctly due to effects, such as emissivity and optical transmission, that must be accounted for. Here, we present a practical guide to calibrating and using a spectral pyrometry system, including example code, using a Czerny-Turner spectrometer attached to a transmission electron microscope. Calibration can be accomplished using a thermocouple or commercial heated sample holder, after which arbitrary samples can be reliably measured for temperatures above ∼600∘C. An accuracy of 2% can be expected with the possibility of sub-second temporal resolution and sub-Kelvin temperature resolution. We then demonstrate this capability in conjunction with traditional microscopic techniques, such as diffraction-based strain measurement for thermal expansion coefficient, or live-video sintering evolution. 

A new series of 20-component fluorite-based compositionally complex oxides (20CCFBOxNb/Ta) with the general chemical formula (15RE1/15)2x+1(Ce1/3Zr1/3Hf1/3)3-3x(Nb1/2Ta1/2)xO8-delta (0 <= x <= 1, where 15RE1/15 = La1/15Pr1/15Nd1/15Sm1/15Eu1/15Gd1/15Tb1/15Dy1/15Y1/15Ho1/15Er1/15Tm1/15Yb1/15Lu1/15Sc1/15) are synthesized. Despite that the Gibbs phase rule allows for the existence of up to 20 phases at the thermodynamic equilibrium, 17 of the 20CCFBOxNb/Ta compositions synthesized in this study all possess single ultrahigh-entropy phases in fluorite, pyrochlore, or weberite structure, as shown by X-ray diffraction (XRD). Only < 1 vol.% of secondary phases are observed in two compositions near the phase-transition points. With changing compositional variable x, this series of 20CCFBOxNb/Ta undergoes an abrupt fluorite-pyrochlore transition at x = ~0.27 and an abrupt pyrochlore-weberite transition at x = ~0.87. Careful characterization reveals abrupt changes of order parameters at both phase transitions. In addition, weberite short-range ordering can persist into the long-range pyrochlore phase, which leads to the lowest thermal conductivities.