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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Irradiation-induced amorphization of UO 2 films prepared by spraying-assisted combustion synthesis

Spraying-assisted combustion synthesis with uranyl nitrate – acetylacetone – 2-methoxyethanol solutions was used to prepare UO 2 films on an aluminum alloy substrate. The tuning of the spraying parameters and annealing temperatures allowed the preparation of UO 2 films with thicknesses varying from 10–300 nm and 5–10 nm UO 2 grain size. High-resolution electron microscopy and X-ray photoelectron spectroscopy showed that increasing the annealing temperature promotes Mg diffusion from the substrate into the films. The incorporation of Mg reduced the overall crystallinity of the films. The irradiation with Ar 2+ ions (1.7 MeV energy and a fluence of 2 × 10 16 ions/cm 2 ) did not degrade the quality of the films. However, the Mg content significantly influenced the irradiation-induced restructuring of the UO 2 films. Irradiated films with low or no Mg content exhibit high crystallinity, and the UO 2 /Al interfacial layer becomes highly porous. Films with higher Mg content are mostly amorphized after irradiation. The origin of irradiation-induced amorphization was related to the formation of Mg y U 1-y O 2±x solid solutions. Chemically complex, pore-free, and amorphous Mg-Al-O film/substrate interfacial layers enable continuous Mg diffusion during irradiation. As a result, the gradual increase in Mg amounts triggers irradiation-induced precipitation of a crystalline MgO-rich phase within the amorphous films.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRS2004

High Efficiency Thermoelectric Radioisotope Power Systems

The work performed and whose results presented in this report is a joint effort between the University of New Mexico s Institute for Space and Nuclear Power Studies (ISNPS) and the Jet Propulsion Laboratory (JPL), California Institute of Technology. In addition to the development, design, and fabrication of skutterudites and skutterudites-based segmented unicouples this effort included conducting performance tests of these unicouples for hundreds of hours to verify theoretical predictions of the conversion efficiency. The performance predictions of these unicouples are obtained using 1-D and 3-D models developed for that purpose and for estimating the actual performance and side heat losses in the tests conducted at ISNPS. In addition to the performance tests, the development of the 1-D and 3-D models and the development of Advanced Radioisotope Power systems for Beginning-Of-Life (BOM) power of 108 We are carried out at ISNPS. The materials synthesis and fabrication of the unicouples are carried out at JPL. The research conducted at ISNPS is documented in chapters 2-5 and that conducted at JP, in documented in chapter 5. An important consideration in the design and optimization of segmented thermoelectric unicouples (STUs) is determining the relative lengths, cross-section areas, and the interfacial temperatures of the segments of the different materials in the n- and p-legs. These variables are determined using a genetic algorithm (GA) in conjunction with one-dimensional analytical model of STUs that is developed in chapter 2. Results indicated that when optimized for maximum conversion efficiency, the interfacial temperatures between various segments in a STU are close to those at the intersections of the Figure-Of-Merit (FOM), ZT, curves of the thermoelectric materials of the adjacent segments. When optimizing the STUs for maximum electrical power density, however, the interfacial temperatures are different from those at the intersections of the ZT curves, but close to those at the intersections the characteristic power, CP, curves of the thermoelectric materials of the adjacent segments (CP = T(sup 2)Zk and has a unit of W/m). Results also showed that the number of the segments in the n- and p-legs of the STUs optimized for maximum power density are generally fewer than when the same unicouples are optimized for maximum efficiency. These results are obtained using the 1-D optimization model of STUs that is detailed in chapter 2. A three-dimensional model of STUs is developed and incorporated into the ANSYS commercial software (chapter 3). The governing equations are solved, subject to the prescribed

El-Genk, Mohamed↗
DOE OSTI2025

Dimolybdenum Paddlewheel Complexes with Cation Binding Sites as Electrolyte Additives to Manipulate the Solid-Electrolyte Interphase at Lithium Metal Anodes

The use of electrolyte additives at millimolar loadings to control the surface chemistry of lithium metal anodes (LMAs) is a leading strategy to improve lithium metal batteries and promote electrosynthetic reactions. Whereas previous studies employed either inorganic or organic additives, in this study, we report the first organometallic additive, Mo 2 (mea) 4 [1, mea = 2-(2-methoxyethoxy)acetate], a dimolybdenum paddlewheel complex that is stable under Li plating conditions and features cation binding sites in the second coordination sphere that promote reversible Li + coordination. Binding of Li + ions to 1 induces immobilization of cationically charged aggregates (or products thereof) into the solid electrolyte interphase (SEI), imparting multiple beneficial functions. The modified SEI was found to protect the LMA against parasitic side reactions, produce modest but measurable improvements to Li plating properties (e.g., overpotential, surface structure, and Coulombic efficiency), and improve interfacial charge transport properties. Furthermore, the most notable benefit to battery cycling performance appears in calendar aging tests, which show that the presence of the additive protects the LMA from parasitic side reactions that would otherwise decrease overall cell cycling efficiency over time. Collectively, these data disclose a tactic for designing electrolyte additives using principles of organometallic synthesis.

Additives↗
DOE OSTI2020

Iron-Doped Sodium Vanadium Oxyflurophosphate Cathodes for Sodium-Ion Batteries—Electrochemical Characterization and In Situ Measurements of Heat Generation

Sodium-ion batteries (NaIBs) are increasingly being envisioned for grid-scale energy-storage systems because of cost advantages. However, implementation of this vision has been challenged by the low-energy densities delivered by most NaIB cathodes. Toward addressing this challenge, the authors report the synthesis and characterization of a new iron-doped Na 3 Fe 0.3 V 1.7 O(PO 4 ) 2 F 2 cathode using a novel facile hydrothermal route. The synthesized material was characterized using scanning electron microscopy, X-ray diffraction, and Mössbauer spectroscopy techniques. The obtained discharge capacity in the half-cell configuration lies from 119 to 125 to 130 mA h/g at C/10 while tested using three different electrolyte formulations, dimethyl carbonate–ethylene carbonate (EC)–propylene carbonate (PC), diethyl carbonate–EC, and EC–PC, respectively. The synthesized cathodes were also evaluated in full-cell configurations, which delivered an initial discharge capacity of 80 mA h/g with NaTi 2 (PO 4 ) 3 MWCNT as the anode. Ionic diffusivity and interfacial charge transfer kinetics were also evaluated as a function of temperature and sodium concentration, which revealed that electrochemical rate performances in this material were limited by charge-transfer kinetics. To understand the heat generation mechanism of the Na/Na 3 Fe 0.3 V 1.7 O(PO 4 ) 2 F 2 half-cell during charge and discharge processes, an electrochemical isothermal calorimetry measurement was carried out at different current rates for two different temperatures (25 and 45 °C). The results showed that the amount of heat generated was strongly affected by the operating charge/discharge state, C-rate, and temperature. Altogether, this work provides a new synthesis route for the development of iron-doped Na 3 Fe 0.3 V 1.7 O(PO 4 ) 2 F 2 -based high-performance sodium cathode materials aimed at providing a viable pathway for the development and deployment of large-scale energy-storage based on sodium battery systems.

25 ENERGY STORAGE↗
DOE OSTI2021

Self-Assembly of Flexible Linear–Semiflexible Bottlebrush–Flexible Linear Triblock Copolymers

Block copolymer (BCP) self-assembly is a fundamental process in which incompatible blocks spontaneously form organized microstructures with broad practical applications. Classical understanding is that the domain spacing is limited by the contour length of the polymer backbone. Here, using a combination of molecular design, chemical synthesis, small-/wide-angle X-ray scattering, transmission electron microscopy, and electron tomography, we discover that this molecular picture does not hold for architecturally semiflexible BCPs. For strongly segregated linear–semiflexible bottlebrush–linear triblock copolymers, the size of the bottlebrush domain can be twice the bottlebrush backbone contour length. The mechanism of such anomalous self-assembly is likely that the interfacial repulsion between the incompatible blocks is large enough to pull a part of the linear end blocks into the bottlebrush domain. This effectively increases the bottlebrush domain size. Moreover, the semiflexible bottlebrush widens the regime for the cylinder morphology that is associated with the volume fraction of the end blocks fC SFB ∈ (0.10, >0.41). This window is much wider than that for flexible linear BCPs, fC F ∈ (0.14, 0.35), and that predicted by the recent self-consistent field theory for linear-bottlebrush BCPs of the same chemistry and molecular architecture. Finally, our experimental findings reveal previously unrecognized mechanisms for the self-assembly of architecturally complex BCPs.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Atomic Structural Origin of the High Methanol Selectivity over In 2 O 3 –Metal Interfaces: Metal–Support Interactions and the Formation of a InO x Overlayer in Ru/In 2 O 3 Catalysts during CO 2 Hydrogenation

CO 2 hydrogenation to methanol is of great environmental and economic interest due to its potential to reduce carbon emissions and produce valuable chemicals in one single reaction. Compared with the unmodified traditional Cu/ZnO/Al 2 O 3 catalyst, an indium oxide (In 2 O 3 )-based catalyst can double the methanol selectivity from 30–50 to 60–100%. It is worth noting that over catalysts involving various active metals dispersed on indium oxide (M/In 2 O 3 , M = Pd, Ni, Au, etc.), although the methanol yield is boosted, the selectivity remains similar to that of plain In 2 O 3 despite the distinct chemical properties of the added metals. Here, to investigate the phenomena behind this behavior, we used RuO 2 /In 2 O 3 as a test catalyst. The results of ambient pressure photoelectron spectroscopy, in situ X-ray absorption fine structure, and time-resolved X-ray diffraction indicate that the structure of the RuO 2 /In 2 O 3 catalyst is highly dynamic in the presence of a reactive environment. Specifically, under CO 2 hydrogenation conditions, Ru clusters facilitate the reduction of In 2 O 3 to generate In 2 O 3–x aggregates, which encapsulate the Ru systems in a migration driven by thermodynamics. In this way, the Ru O sites for CH 4 production are blocked while creating RuO x –In 2 O 3–x interfacial sites with tunable metal–oxide interactions for selective methanol production. In an inverse oxide/metal configuration, indium oxide has properties not seen in its bulk phase that are useful for the binding and conversion of CO 2 . This work reveals the dynamic nature of In 2 O 3 -based catalysts, providing insights for a rational design of materials for the selective synthesis of methanol.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Hierarchical assembly of ZnO nanowire trunks decorated with ZnO nanosheets for lithium ion battery anodes

Hierarchical architectures composed of nanomaterials in different forms are essential to improve the performance of lithium-ion battery (LIB) anodes. Here, we systematically studied the effects of hierarchical ZnO nanostructures on the electrochemical performance of LIBs. ZnO nanowire (NW) trunks were decorated with ZnO NWs or ZnO nanosheets (NSs) by successive hydrothermal synthesis to create hierarchical three-dimensional nanostructures. The branched ZnO NSs on the ZnO NW trunk exhibited a two-fold higher specific gravimetric capacity compared to ZnO NWs and branched ZnO NWs on ZnO NW trunks after 100 cycles of charging–discharging at 0.2C (197.4 mA g –1 ). The improvement in battery anode performance is attributable to the increased interfacial area between the electrodes and electrolyte, and the void space of the branched NSs that facilitates lithium ion transport and volume changes during cycling.

25 ENERGY STORAGE↗
DOE OSTI2022

Synthesis of Fluorine-Doped Lithium Argyrodite Solid Electrolytes for Solid-State Lithium Metal Batteries

Solid-state lithium metal batteries (SSLMBs) that utilize novel solid electrolytes (SEs) have garnered much attention because of their potential to yield safe and high-energy-density batteries. Sulfide-based argyrodite-class SEs are an attractive option because of their impressive ionic conductivity. Recent studies have shown that LiF at the interface between Li and SE enhances electrochemical stability. However, the synthesis of F-doped argyrodites has remained challenging because of the high temperatures used in the state-of-the-art solid-state synthesis methods. In this work, for the f irst time, we report F-doped Li 5+y PS 5 F y argyrodites with a tunable doping content and dual dopants (F-/Cl- and F-/Br-) that were synthesized through a solvent-based approach. Among all compositions, Li 6 PS 5 F 0.5 C l0.5 exhibits the highest Li-ion conductivity of 3.5 x 10 -4 S cm -1 at room temperature (RT). Furthermore, Li symmetric cells using Li 6 PS 5 F 0.5 Cl 0.5 show the best cycling performance among the tested cells. X-ray photoelectron spectroscopy and ab initio molecular dynamics simulations revealed that the enhanced interfacial stability of Li 6 PS 5 F 0.5 C l0.5 SE against Li metal can be attributed to the formation of a stable solid electrolyte interphase (SEI)-containing conductive species (Li 3 P), alongside LiCl and LiF. These findings open new opportunities to develop high-performance SSLMBs using a novel class of F-doped argyrodite electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2024

Supersoft Norbornene–Based Thermoplastic Elastomers with High Strength and Upper Service Temperature

With over 6 million tons produced annually, thermoplastic elastomers (TPEs) have become ubiquitous in modern society, due to their unique combination of elasticity, toughness, and reprocessability. Nevertheless, industrial TPEs display a tradeoff between softness and strength, along with low upper service temperatures, typically ≤100 °C. This limits their utility, such as in bio-interfacial applications where supersoft deformation is required in tandem with strength, in addition to applications that require thermal stability (e.g., encapsulation of electronics, seals/joints for aeronautics, protective clothing for firefighting, and biomedical devices that can be subjected to steam sterilization). Thus, combining softness, strength, and high thermal resistance into a single versatile TPE has remained an unmet opportunity. Through de novo design and synthesis of novel norbornene-based ABA triblock copolymers, this gap is filled. Ring-opening metathesis polymerization is employed to prepare TPEs with an unprecedented combination of properties, including skin-like moduli (<100 kPa), strength competitive with commercial TPEs (>5 MPa), and upper service temperatures akin to high-performance plastics (≈260 °C). Here, the materials are elastic, tough, reprocessable, and shelf stable (≥2 months) without incorporation of plasticizer. Structure–property relationships identified herein inform development of next-generation TPEs that are both biologically soft yet thermomechanically durable.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Facile Size-Selective Defect Sealing in Large-Area Atomically Thin Graphene Membranes for Sub-Nanometer Scale Separations

Atomically thin graphene with a high-density of precise subnanometer pores represents the ideal membrane for ionic and molecular separations. However, a single large-nanopore can severely compromise membrane performance and differential etching between pre-existing defects/grain boundaries in graphene and pristine regions presents fundamental limitations. Here, we show for the first time that size-selective interfacial polymerization after high-density nanopore formation in graphene not only seals larger defects (>0.5 nm) and macroscopic tears but also successfully preserves the smaller subnanometer pores. Low-temperature growth followed by mild UV/ozone oxidation allows for facile and scalable formation of high-density (4–5.5 $\times$ 10 12 cm –2 ) useful subnanometer pores in the graphene lattice. We demonstrate scalable synthesis of fully functional centimeter-scale nanoporous atomically thin membranes (NATMs) with water (~0.28 nm) permeance ~23$\times$ higher than commercially available membranes and excellent rejection to salt ions (~0.66 nm, >97% rejection) as well as small organic molecules (~0.7–1.5 nm, ~100% rejection) under forward osmosis. $\times$

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Designing Particle Morphologies for Materials with Solid Transport Limitations: A Case Study of Lithium and Manganese Rich Cathode Oxides

A lithium and manganese rich nickel-manganese-cobalt oxide (LMR-NMC) cathode is a promising candidate for next-generation batteries due to its high specific capacity, low cost, and low cobalt content. However, the material suffers from poor rate capability due to the diffusion limitations of lithium in the cathode particles. Understanding the material performance requires careful control of the morphology of the cathode particles, taking into account the primary and agglomerated diffusion pathways and the presence of pores, some of which could be closed from electrolyte infiltration. Here, in this study, we use a microstructure-based mathematical model combined with experimental data to understand the role of the complex cathode particle morphology in the rate performance of the material. Scanning electron microscopy images of cathodes made under different synthesis conditions, which results in different agglomerate morphologies, serve as the input into the mathematical model. The model is then compared to rate data to understand the controlling parameters. The presence of intra-agglomerate closed pores results in a large agglomerate diffusion length in comparison to the ideal condition, where the primary particles are agglomerated in an open and dispersed manner such that the entire interfacial area is available for electrochemical reaction. Smaller primary and agglomerate diffusion lengths result in better electrochemical performance. This points us toward designing the morphology of the cathode particles to compensate for the diffusion limitation of LMR-NMC while maximizing the density.

Tewari, Deepti↗
DOE OSTI2024

Computational Insights into Phase Equilibria Between Wide-Gap Semiconductors and Contact Materials

Novel wide-band-gap semiconductors are needed for next-generation power electronics, but there is a gap between a promising material and a functional device. Finding stable (metal) contacts is one of the major challenges that is currently dealt with mainly via trial and error. Herein, we computationally investigate the thermochemistry and phase coexistence at the junction between three wide-gap semiconductors, ..beta..-Ga2O3, GeO2, and GaN, and possible contact materials. The pool of possible contacts includes 47 elemental metals and a set of 4 common, n-type transparent conducting oxides (ZnO, TiO2, SnO2, and In2O3). We use first-principles thermodynamics to model the Gibbs free energies of chemical reactions as a function of gas pressure (pO2/pN2) and equilibrium temperature. We deduce whether a semiconductor/contact interface will be stable at relevant conditions or a chemical reaction between them is to be expected, possibly influencing the long-term reliability and performance of devices. We generally find that most elemental metals tend to oxidize or nitridize and form various interface oxide/nitride layers. Exceptions include select late- and post-transition metals and, in the case of GaN, also the alkali metals, which are predicted to exhibit stable coexistence, although in many cases at relatively low gas partial pressures. Similar is true for the transparent conducting oxides, for which, in most cases, we predict a preference toward forming ternary oxides when in contact with ..beta..-Ga2O3 and GeO2. The only exception is SnO2, which we find to form stable contacts with both oxides. Finally, we show how the same approach can be used to predict gas partial pressure vs temperature phase diagrams to help direct synthesis of ternary compounds. We believe these results provide a valuable guidance in selecting contact materials to wide-gap semiconductors and suitable growth conditions.

contact materials↗
DOE OSTI2022

Wet chemical synthesis and properties of argyrodite sulfide solid electrolytes for solid state lithium batteries

The commercialization of the lithium-ion battery (LIB) in 1991 was responsible for the explosion in portable electronic technologies that has been seen over the past 30 years. With the advent of electric vehicles and other high-powered technologies, there is tremendous demand for LIBs with higher energy density and high safety. To achieve this, new electrode materials must be explored. The obvious choice of anode material would be pure metal lithium, which has a theoretical specific capacity of 3860 mAh g-1 . Unfortunately, metal lithium anodes have not been widely commercialized due to their tendency to react violently with the flammable liquid electrolytes used in today’s batteries. Battery safety can best be achieved by adopting solid electrolytes in place of liquid electrolytes. Solid electrolytes are nonvolatile and nonflammable, safely allowing for the combination of high-capacity cathode materials with a Li metal anode. Argyrodite sulfide solid electrolytes such as halogen-doped Li6PS5X (X = Cl, Br, I) are noted for their high ionic conductivity. But before sulfides can be commercially adopted, they possess several disadvantages which must be addressed, including time- and energy-consuming synthesis processes, poor electrochemical stability, and intrinsically poor air stability. This dissertation seeks to address each of these challenges through materials design an synthesis strategies. In this work, we pioneer a solvent-based approach for the synthesis of argyrodite solid electrolytes Li7PS6 and Li6PS5Xinstead of a stringent solid-state synthesis. Nontoxic ethanol is employed as the solvent, enabling a rapid synthetic approach to produce argyrodite solid electrolytes with high phase purity and compositional flexibility. Compared with Li7PS6, halogen doping (i.e. X = F, Cl, Br, I) not only increases the ionic conductivity, but also enhances the electrochemical stability at the interface towards Li metal. Specifically, F-doped argyrodites produce a robust SEI layer containing LiF, contributing to enhanced interfacial stability. Finally, to address the air instability challenge, argyrodite-incorporated composite solid electrolytes (CSEs) are designed and prepared to produce stable and flexible membranes that are demonstrated in solid-state Li metal batteries. These advances push argyrodite sulfide solid electrolyte research further and pave the way for the proliferation of next generation lithium metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2023

Highly Selective Photoelectroreduction of Carbon Dioxide to Ethanol over Graphene/Silicon Carbide Composites

Using sunlight to produce valuable chemicals and fuels from carbon dioxide (CO 2 ), i.e., artificial photosynthesis (AP) is a promising strategy to achieve solar energy storage and a negative carbon cycle. However, selective synthesis of C 2 compounds with a high CO 2 conversion rate remains challenging for current AP technologies. Here, we performed CO 2 photoelectroreduction over a graphene/silicon carbide (SiC) catalyst under simulated solar irradiation with ethanol (C 2 H 5 OH) selectivity of>99 % and a CO 2 conversion rate of up to 17.1 mmol g cat -1 h -1 with sustained performance. Experimental and theoretical investigations indicated an optimal interfacial layer to facilitate the transfer of photogenerated electrons from the SiC substrate to the few-layer graphene overlayer, which also favored an efficient CO 2 to C 2 H 5 OH conversion pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Interactions of clathrate hydrate promoters sodium dodecyl sulfate and tetrahydrofuran investigated using 1H diffusion nuclear magnetic resonance at hydrate-forming conditions

Thermodynamic hydrate promoters and kinetic hydrate promoters can be used to reduce the P–T conditions for clathrate hydrate synthesis to decrease the nucleation induction time while increasing growth rates. Two commonly used promoters for hydrate research are tetrahydrofuran (THF) and sodium dodecyl sulfate (SDS), which can increase the overall hydrate promotion when used in tandem as compared to individually. There are several molecular theories regarding how SDS promotes hydrate growth. This study explores the micellular theory, for which hydrate formation depends on surfactant aggregates (micelles) at a critical micelle concentration (CMC) to increase the interfacial surface area. The micellular theory is the most investigated and criticized surfactant hydrate promotion theory. To address questions related to micellar behavior, this study investigates the intermolecular behavior between SDS and THF for the identification of micelles at hydrate-forming conditions. The systems explored contained THF at 3 and 5 wt. % with varying concentrations of SDS below and above the CMC. Several methods including a qualitative visual method, conductivity, interfacial tensiometry, 13C Liquid-state Nuclear Magnetic Resonance (NMR) spectroscopy, and 1H diffusion NMR spectroscopy were evaluated at temperatures below the Krafft point of SDS and above 0 °C. The presence of THF at low concentrations decreased the critical temperature for the formation of SDS micelles, where SDS is solubilized in THF/water solution at hydrate-forming temperatures without precipitation. The CMC of SDS was decreased significantly even at hydrate-forming conditions. Mixed surfactant–cosolvent micellular behavior of SDS in the presence of low concentrations of THF was confirmed at hydrate-forming conditions above 0 °C.

Chemistry↗
DOE OSTI2020

Epitaxial Er-doped Y 2 O 3 on silicon for quantum coherent devices

Rare-earth ions have incomplete 4f shells and possess narrow optical intra-4f transitions due to shielding from electrons in the 5s and 5p orbitals, making them good candidates for solid-state optical quantum memory. The emission of Er 3+ in the telecom C-band (1530 nm – 1565 nm) makes it especially attractive for this application. In order to build practical, scalable devices, the REI needs to be embedded in a non-interacting host material, preferably one that can be integrated with silicon. In this paper, we show that Er 3+ can be isovalently incorporated into epitaxial Y 2 O 3 thin films on Si (111). We report on the synthesis of epitaxial, single-crystalline Er:Y 2 O 3 on Si with a narrow inhomogeneous linewidth in the photoluminescence spectra, 5.1 GHz (<100 mK) and an optical excited state lifetime of 8.1 ms. The choice of Y 2 O 3 was driven by its low nuclear spin and small lattice mismatch with Si. Using photoluminescence (PL) and electron paramagnetic resonance, we show that Er 3+ substitutes for Y in the crystal lattice. The role of interfacial SiO x , diffusion of silicon into the film, and the effect of buffer layers on inhomogeneous PL linewidth are examined. We also find that the linewidth decreased monotonically with film thickness but surprisingly exhibits no correlation with the film crystalline quality as measured by the x-ray rocking curve scans suggesting other factors at play that limit the inhomogeneous broadening in Y 2 O 3 films.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Spontaneous Lithiation of Binary Oxides during Epitaxial Growth on LiCoO 2

Epitaxial growth is a powerful tool for synthesizing heterostructures and integrating multiple functionalities. Interfacial mixing can readily occur at temperatures required for complete film crystallization and can significantly modify the properties of layered structures, particularly for those containing energy storage materials with smaller cations. Here we show a two-step sequence involving the growth of an epitaxial LiCoO 2 cathode layer followed by the deposition of a binary transition metal oxide (WO 3 , TiO 2 , and others) in which controlled lithiation of the binary oxide occurs. Orientation-controlled epitaxial synthesis of the model solid-state-electrolyte Li 2 WO 4 and model anode material Li 4 Ti 5 O 12 occurs as WO 3 and TiO 2 nucleate their respective host lattices and attract Li ions from the underlying cathode. The cathode layer readily provides a tunable amount of Li ions for the controlled lithiation of the subsequent layer. We demonstrate that this approach can be used for energy materials discovery and exploring different combinations of epitaxial interfaces that can serve as well-defined model systems for mechanistic studies of energy storage and conversion processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Dislocation-induced stop-and-go kinetics of interfacial transformations

Most engineering materials are based on multiphase microstructures produced either through the control of phase equilibria or by the fabrication of different materials as in thin-film processing. In both processes, the microstructure relaxes towards equilibrium by mismatch dislocations (or geometric misfit dislocations) across the heterophase interfaces (1-5) . Despite their ubiquitous presence, directly probing the dynamic action of mismatch dislocations has been unachievable owing to their buried nature. In this work, using the interfacial transformation of copper oxide to copper as an example, we demonstrate the role of mismatch dislocations in modulating oxide-to-metal interfacial transformations in an intermittent manner, by which the lateral flow of interfacial ledges is pinned at the core of mismatch dislocations until the dislocation climbs to the new oxide/metal interface location. Together with atomistic calculations, we identify that the pinning effect is associated with the non-local transport of metal atoms to fill vacancies at the dislocation core. These results provide mechanistic insight into solid-solid interfacial transformations and have substantial implications for utilizing structural defects at buried interfaces to modulate mass transport and transformation kinetics.

25 ENERGY STORAGE↗