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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 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Exploring filamentous fungi depolymerization of corn stover in the context bioenergy queuing operations

Recalcitrance of lignocellulosic feedstocks to depolymerization is a significant barrier for bioenergy production approaches that require conversion of monomeric carbohydrates to renewable energy sources. This study assesses how low-cost modifications in the feedstock supply chain can be transformed into targeted pretreatments in the context of the entire bioenergy supply chain. The aim of this research is to overcome the physiochemical barriers in corn stover that necessitate increased severity in conversion in terms of chemical loading, temperature, and residence time. Corn stover samples were inoculated with a selective (Ceriporiopsis subvermispora) and non-selective (Phaenarochaete chrysosporium) lignin degrading filamentous fungal strains, then stored aerobically to determine the working envelope for fungal pretreatment to achieve lignin degradation. Dry matter loss and gross chemical makeup of corn stover varied by the length of treatment (2 and 4 weeks) and by the moisture content of the treated corn stover samples (40 and 60%, wet basis). Dry matter loss in P. chrysosporium inoculated biomass was elevated compared to the C. subvermispora inoculated biomass; however, treatment also induced additional chemical composition changes suggestive of depolymerization. Scanning electron microscope images reveal hyphae attached within cell lumen and suggest structural changes within P. chrysosporium treated corn stover after 60% moisture storage. These results highlight that fungal treatment approaches must balance loss of convertible material with the potential for reduction in recalcitrance. Techno-economic assessment (TEA) of fungal pretreatment in a short-term queuing system indicated the viability of this approach compared to conventional queuing operations. The total queuing system cost was estimated at $\$$1.65/tonne of biomass stored. After applying the credit of $\$$1.48/tonne from energy savings in the conversion phase using fungal pretreated biomass, the total system cost was $0.80 lower than traditional biomass queueing approach. While the TEA results suggested that treating biomass with C. subvermispora is the most economically viable storage method in the designed fungal-assisted queuing system, future research should focus on additional fungal depolymerization such as those observed in the P. chrysosporium inoculated biomass.

09 BIOMASS FUELS↗
DOE OSTI2020

Real-time observations of TRIP-induced ultrahigh strain hardening in a dual-phase CrMnFeCoNi high-entropy alloy

Abstract Strategies involving metastable phases have been the basis of the design of numerous alloys, yet research on metastable high-entropy alloys is still in its infancy. In dual-phase high-entropy alloys, the combination of local chemical environments and loading-induced crystal structure changes suggests a relationship between deformation mechanisms and chemical atomic distribution, which we examine in here in a Cantor-like Cr 20 Mn 6 Fe 34 Co 34 Ni 6 alloy, comprising both face-centered cubic ( fcc ) and hexagonal closed packed ( hcp ) phases. We observe that partial dislocation activities result in stable three-dimensional stacking-fault networks. Additionally, the fraction of the stronger hcp phase progressively increases during plastic deformation by forming at the stacking-fault network boundaries in the fcc phase, serving as the major source of strain hardening. In this context, variations in local chemical composition promote a high density of Lomer-Cottrell locks, which facilitate the construction of the stacking-fault networks to provide nucleation sites for the hcp phase transformation.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Self-driving thin film laboratory: autonomous epitaxial atomic-layer synthesis via real-time computer vision analysis of electron diffraction

Emerging materials science platforms with the ability to make autonomous decisions on the fly are fundamentally changing the outlook and protocols for materials optimization and discovery. Because AI-driven self-navigating schemes can effectively reduce the total number of iterations needed to arrive at the "answer" (i.e. the best stochiometric composition for a desired physical property, optimum materials processing parameters, etc.) by significant margins, they have the potential to revolutionize materials and chemical manufacturing processes at large in research laboratory settings as well as in industrial plants. Here, we demonstrate a successful implementation of real-time closed-loop autonomous navigation of a multi-dimensional materials synthesis parameter space for fabricating phase-pure epitaxial films of a metastable phase of a functional oxide in a combinatorial pulsed laser deposition chamber. Sequential epitaxial growth iterations in search of the optimized recipe to stabilize the desired crystal phase were performed using frame-by-frame quantitative computer vision analysis of reflection high-energy electron diffraction (RHEED) images of the unit-cell level film being deposited. The autonomous scheme regularly resulted in > 30-fold reduction in the number of required experiments compared to a comprehensive mapping of the parameter space. The real-time workflow developed here can be readily extended to a variety of thin film synthesis platforms opening the door for self-driving atomic-level materials design as well as autonomous optimization of semiconductor manufacturing.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Probing the meta-stability of oxide core/shell nanoparticle systems at atomic resolution

Hybrid nanoparticles allow exploiting the interplay of confinement, proximity between different materials and interfacial effects. However, to harness their properties an in-depth understanding of their (meta)stability and interfacial characteristics is crucial. This is especially the case of nanosystems based on functional oxides working under reducing conditions, which may severely impact their properties. Here, the in-situ electron-induced selective reduction of Mn 3 O 4 to MnO is studied in magnetic Fe 3 O 4 /Mn 3 O 4 and Mn 3 O 4 /Fe 3 O 4 core/shell nanoparticles by means of high-resolution scanning transmission electron microscopy combined with electron energy-loss spectroscopy. Such in-situ transformation allows mimicking the actual processes in operando environments. A multi-stage image analysis using geometric phase analysis combined with particle image velocity enables direct monitoring of the relationship between structure, chemical composition and strain relaxation during the Mn 3 O 4 reduction. In the case of Fe 3 O 4 /Mn 3 O 4 core/shell the transformation occurs smoothly without the formation of defects. However, for the inverse Mn 3 O 4 /Fe 3 O 4 core/shell configuration the electron beam-induced transformation occurs in different stages that include redox reactions and void formation followed by strain field relaxation via formation of defects. This study highlights the relevance of understanding the local dynamics responsible for changes in the particle composition in order to control stability and, ultimately, macroscopic functionality.

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

Sodium diffusion in heterogeneous porous media: Connecting laboratory experiments and simulations

Sodium has been suggested as a tracer for brine in reservoir formations where a significant amount of sodium ion is found mainly in the aqueous phase. Fortunately, the most abundant sodium isotope, 23 Na, is Nuclear Magnetic Resonance (NMR) active, making it possible to study the structure and dynamical properties of both bulk and pore confined fluid systems. We investigated the diffusion of key dissolved sodium species in bulk solution and porous media as a function of composition, ionic strength, and permeability of the carbonate samples using NMR relaxometry and pulsed-field gradient (PFG) NMR techniques. We use Indiana limestone as an example of natural porous media and water as a freely diffusible tracer and carrier. We demonstrate apparent diffusion measurement of sodium based on changes in spin–spin relaxation time (T 2 ) signal in pore confinement. The diffusion rate of sodium decreases with increasing counter-ion size. This effect is greater at higher ionic strengths and lower chemical potentials in porous media. The reactive transport code, CrunchFlow, was used to complement the NMR experiments to simulate diffusion behavior in porous media. Combining these two methods provides a powerful approach to estimating effective diffusion coefficients in heterogeneous matrices. The modeling considers the influence of physical properties (porosity and tortuosity) and chemical properties (geochemical composition and chemical gradients). The results presented in this work highlight the advantage of measuring apparent diffusivity using NMR T 2 relaxometry in conjunction with numerical simulation to derive effective diffusivity and the corresponding matrix properties (i.e., tortuosity) of the system.

58 GEOSCIENCES↗
DOE OSTI2024

Solar Thermochemical Redox Cycling Using Ga- and Al-Doped LSM Perovskites for Renewable Hydrogen Production

Solar thermochemical hydrogen production using redox-active metal oxides is a promising pathway for the production of green hydrogen and synthetic fuel precursors. Herein, the perovskite material (La 0.6 Sr 0.4 ) 0.95 Mn 0.8 Ga 0.2 O 3–δ (LSMG6482) is identified as a promising metal oxide for thermochemical water splitting. LSMG6482, along with more-established water splitters ceria and (La 0.6 Sr 0.4 ) 0.95 Mn x Al 1–x O 3–δ (LSMA) perovskites, is experimentally characterized via thermogravimetric (TGA) analysis and high-temperature water splitting in a reactor simulating solar concentrating conditions. TGA analysis demonstrated that LSMG6482 has high and stable oxygen exchange capacity under controlled pO 2 redox cycling, demonstrated by large changes in oxygen nonstoichiometry (δ) relative to ceria. Water splitting experiments using laser heating (T red = 1400 °C, T ox = 1200 °C) resulted in H 2 yields of 165.1 μmol g –1 for the candidate LSMG6482 composition, exceeding that of all benchmark materials tested. Under high conversion oxidation conditions, where H 2 is cointroduced with H 2 O (150 ≤ nH 2 O/nH 2 ≤ 500), H 2 yields were greatest for LSMG6482 and LSMA6482, up to four times that of ceria at the highest nH 2 O/nH 2 conditions. Crystallographic analysis showed that over the course of experimentation, there is some secondary phase growth for all perovskite compositions, except for LSMA6482, but there was no observable degradation in H 2 yields.

08 HYDROGEN↗
DOE OSTI2020

Probing Thermal Stability of Li-Ion Battery Ni-Rich Layered Oxide Cathodes by means of Operando Gas Analysis and Neutron Diffraction

Thermal stability is a crucial parameter that must be considered within the overall performance metrics of Ni-rich layered oxide cathodes. While the intrinsic structural stability of the cathode materials under thermal conditions is important, it is also critical to consider their reaction with electrolytes. In this study, operando gas analysis, ex situ neutron diffraction, and differential scanning calorimetry were combined to give a broader picture of the thermal stability of Ni-rich NMC cathodes. Li 1– x Ni 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) composite materials with four different states of charge were investigated with and without the presence of an electrolyte. It has been found that electrolyte can greatly accelerate both the structural and thermal decomposition of the cathode materials. A higher state of charge will also make cathode materials more susceptible to thermal shock. Without an electrolyte, O 2 release inducing a structural change from layered to rock salt was the major observation during thermal runaway. However, all samples retained some levels of layered structure after annealing up to 300 °C without the electrolyte. In comparison, almost all the O3-type layered phase transformed to the rock-salt phase for the cathode materials heated with the electrolyte at the same experimental conditions. Moreover, the amount of CO 2 increased by nearly two orders of magnitude when annealing cathode materials with electrolyte in operando gas analysis experiments. More delithiated NMC811 samples released larger amounts of CO 2 at earlier onset temperatures, resonating well with the differential scanning calorimetry (DSC) results showing that more delithiated samples release more heat during thermal shock.

25 ENERGY STORAGE↗
DOE OSTI2021

Composition Measurements of the LAW Phase 5 Glasses

This report provides the results from the chemical analyses of glass compositions for the Low-Activity Waste Phase 5 study glasses, a series of simulated nuclear waste glasses fabricated at Pacific Northwest National Laboratory. These data will be used in the development of enhanced property/composition models for waste glass vitrification at Hanford. Chemical analyses were performed on a representative sample of each of the quenched glasses to allow for comparisons with targeted compositions. The relative differences between the targeted and measured concentrations of CaO, Cl - , K 2 O, Li 2 O, and SO 3 for some of the glasses were greater than 10%. Several of these glass samples were rerun to verify original measurements; however, there were no significant changes in the measurements to indicate errors in preparation or analysis of the samples. These results can be used in further characterization of this series of glasses, including the normalization of Product Consistency Test results.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Dislocation dynamics in heterogeneous nanostructured materials

Crystalline materials can be strengthened by introducing dissimilar phases that impede dislocation glide. At the same time, the changes in microstructure and chemistry usually make the materials less ductile. One way to circumvent the strength–ductility dilemma is to take advantage of heterogeneous nanophases which simultaneously serve as dislocation barriers and sources. Owing to their superior mechanical properties, heterogeneous nanostructured materials (HNMs) have attracted a lot of attention worldwide. Nevertheless, it has been difficult to characterize dislocation dynamics in HNMs using classical continuum models, mainly due to the challenges in describing the elastic and plastic heterogeneity among the phases. Here, in this work, we advance a phase-field dislocation dynamics (PFDD) model to treat multi-phase materials, consisting of phases differing in composition, structural order, and size in the same system. We then apply the advanced PFDD model to exploring two important but divergent materials design problems in HNMs: dislocation/obstacle interactions and dislocation/interface interactions. Results show that the interactions between a dislocation and distribution of obstacles varying in structure and composition cannot be understood by simply interpolating from their individual interactions with a dislocation. It is also found that materials containing interfaces with nanoscale thicknesses and compositional gradients have a much higher dislocation bypass stress than those with sharp interfaces, providing an explanation for the simultaneous high strength and toughness of thick interface-containing nanolaminates as observed in recent experiments.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Prospects of Nanoscience with Nanocrystals: 2025 Edition

Abstract Nanocrystals (NCs) of various compositions have made important contributions to science and technology, with their impact recognized by the 2023 Nobel Prize in Chemistry for the discovery and synthesis of semiconductor quantum dots (QDs). Over four decades of research into NCs has led to numerous advancements in diverse fields, such as optoelectronics, catalysis, energy, medicine, and recently, quantum information and computing. The last 10 years since the predecessor perspective “Prospect of Nanoscience with Nanocrystals” was published in ACS Nano have seen NC research continuously evolve, yielding critical advances in fundamental understanding and practical applications. Mechanistic insights into NC formation have translated into precision control over NC size, shape, and composition. Emerging synthesis techniques have broadened the landscape of compounds obtainable in colloidal NC form. Sophistication in surface chemistry, jointly bolstered by theoretical models and experimental findings, has facilitated refined control over NC properties and represents a trusted gateway to enhanced NC stability and processability. The assembly of NCs into superlattices, along with two-dimensional (2D) photolithography and three-dimensional (3D) printing, has expanded their utility in creating materials with tailored properties. Applications of NCs are also flourishing, consolidating progress in fields targeted early on, such as optoelectronics and catalysis, and extending into areas ranging from quantum technology to phase-change memories. In this perspective, we review the extensive progress in research on NCs over the past decade and highlight key areas where future research may bring further breakthroughs.

Chemistry↗
DOE OSTI2020

Complex Fluorine Chemical Potential Effects on the Shape and Compositional Heterogeneity of KTa 1– x Nb x O 3 Nanoparticles

When kinetic conditions dominate and dictate the growth in a nanoparticle synthesis, properties of the synthesis environment can have considerable effects on the properties of the products. Such effects were studied here, where the solution environment was changed via the addition of KF to the hydrothermal syntheses of KTa 1– x Nb x O 3 and KTaO 3 . One result demonstrated the straightforward cause-and-effect relationship between the solution and reaction kinetics: KF directly increased the solution stability of the Ta species and therefore decreased its reaction rate, resulting in a change in composition heterogeneity of Ta and Nb in the KTa 1– x Nb x O 3 particles. However, not all effects are so simple; changing the chemical potential of the solution with KF can also promote the formation of particles with anisotropic defect enhanced kinetic Wulff shapes instead of cuboidal shapes. The increased F chemical potential in the solution enabled the formation of planar defects in the bulk, which accelerated growth in-plane to form particles characterized by flat rectangular flake geometries. In this work, thermodynamic modeling with density functional theory calculations confirmed that sufficient KF concentrations can drive the formation of a defect phase K n +1 Ta n O 3 n F.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Cold-Sprayed NMC622 Composite as a Cathode for Lithium-Ion Batteries

The growing demand for high-energy, low-cost lithium-ion batteries (LIBs) to power electric vehicles (EVs) necessitates advances in both materials and manufacturing processes. Conventional cathode fabrication methods, such as slurry casting and drying, are energy-intensive and pose challenges for scalability and environmental compliance. In this study, we propose cold-spray (CS) deposition as a solvent-free approach for fabricating LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) composite cathodes. Powder blends of NMC622, poly(vinylidene fluoride) (PVDF), and carbon black (CB) are directly deposited onto stainless steel and Inconel substrates under varied gas temperatures, pressures (and thus velocities), and standoff distances. The effects of temperature on the deposit morphology, coating density, and volume are systematically investigated. Computational fluid dynamics simulations reveal that increasing the gas temperature enhances the particle velocity, narrows the spray angle, and reduces the mass concentration radially at the nozzle outlet. CS deposition results in a dense cathode microstructure, accompanied by fracture in polycrystalline NMC622 particles. X-ray diffraction analysis further verifies that there are no phase changes during the deposition process. The electrochemical performance of the cold-sprayed cathodes reveals an initial capacity of approximately 96 mAh g –1 for single-crystal NMC622 and 167 mAh g –1 for polycrystalline NMC622. While these values are modest compared to state-of-the-art slurry-cast cathodes, which typically exhibit 180–200 mAh g –1 under optimized conditions. The results demonstrate a competitive performance given the solvent-free nature of the CS process and compare favorably with tape-cast samples made from identical feedstock. In conclusion, he CS process enables the formation of dense, binder-integrated cathode coatings without the need for solvent processing, offering a promising pathway for scalable, energy-efficient dry electrode manufacturing of next-generation LIBs.

Batteries↗
DOE OSTI2025

Development of an interatomic potential for the Ta–Li system

A new interatomic potential for the Ta–Li system is introduced to facilitate the study of phase stability, mechanical properties and non-equilibrium dynamics after Li implantation in Ta. Here, this potential is based on a generalization of the embedded atom method (GEAM) and includes contributions from embedding energy, explicit two- and three-body interactions, and nonlocal many-body interaction terms. The parameters of the potential are optimized using energies and atomic forces for a wide range of configurations obtained from ab initio density functional theory (DFT) calculations. The potential is rigorously validated across a range of physical properties, including elastic constants, equations of state, phonon dispersion curves, point defect properties, and melting temperatures for different compositions. Although our potential is trained on a small dataset, its accuracy is comparable to that of available machine learning potentials for Li and Ta. Our simulations show that at temperatures below 500 K, Li atoms in Ta–Li alloys form clusters separated by Ta-rich domains, and we find no evidence of ordered phase formation. For Li concentrations below a few percent, Li atoms preferentially segregate to surfaces and grain boundaries. However, in alloys containing more than ~10% Li, the accumulation of Li in symmetric-tilt grain boundaries can lead to one of the following effects: formation of amorphous-like regions, changes in grain boundary structural units, or lateral movement of the grain boundary.

GEAM potential↗
DOE OSTI2022

Multi-stage heat release of multi-component fuels: Insights and implications for advanced engine operation

Multi-stage heat release (MSHR) is a unique phenomenon typically seen in lean/diluted and low- to intermediate-temperature combustion. Despite its relevance to advanced engine operation, the MSHR of multi-component fuels has barely been quantified. This study aims to characterize the MSHR of multi-component fuels in a rapid compression machine (RCM) at conditions representative of advanced combustion engines. New experimental data are first reported in the RCM at an equivalence ratio of 0.4, pressure of 60 bar and temperatures from 702 to 795 K for a research grade, multi-component gasoline surrogate, termed PACE-20. Here, experiments confirm the existence of MSHR for PACE-20 at all temperatures, and reveal the strong inhibiting effect of temperature on MSHR, where increasing temperature inhibits MSHR by suppressing first stage heat release and promoting second and third stage heat release. A detailed chemical kinetic model is also adopted to model the experiments, with good agreement observed. The response of MSHR characteristics to changes in different engine operating parameters (i.e., temperature, pressure, equivalence ratio and CO 2 dilution level) and fuel compositions (i.e., mole fraction of n-pentane, n-heptane, isooctane, cyclopentane, 1-hexene, ethanol and aromatics in PACE-20) is further evaluated via statistical analysis coupling quasi-random sampling, extensive computer experiments and high-dimensional model representation. The change in MSHR is characterized through 8 quantities of interest (QOIs), i.e., duration and extent of each heat release stage, and their standard deviations. The analysis highlights the dependence of the QOIs on the individual parameters as well as their interplays, with temperature exhibiting the strongest impact among all parameters. Furthermore, it is demonstrated that if MSHR is to be facilitated and combustion phasing is to be extended to enable engine operation at higher compression ratios, it is recommended to operate the engine at low intake temperatures, boosted intake pressures and high CO 2 dilutions (i.e., high EGR levels) with gasoline fuels containing more n-pentane and less aromatics.

42 ENGINEERING↗
DOE OSTI2026

Effects of PLA/PHB Blend Ratio and Wood Flour Loading on the Melt Rheology and Thermomechanical Properties of Biobased Polymer Composites

The development of sustainable, biobased polymer composites is crucial for reducing supply chain dependence on fossil fuels. A major challenge lies in understanding and predicting the processability of these sustainable material alternatives, which directly impacts large-scale manufacturing. Here, this study systematically investigates the effect of poly(lactic acid) (PLA)/polyhydroxybutyrate (PHB) blend ratios and wood flour (WF) loadings on the thermal, rheological, and mechanical properties of the composites. Composites were prepared via melt compounding and characterized by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), oscillatory shear melt rheology, tensile testing, and scanning electron microscopy. Results showed that increasing the PHB content lowered the glass transition temperature, while higher PHB and WF loadings decreased thermal stability. Complex viscosity decreased with increasing PHB in 0 and 10% WF, whereas it increased in 20% and 30% WF for PHB-rich blends (80/20 and 70/30 PLA/PHB) due to stronger filler interactions with flexible PHB chains. At 30% WF, PHB-containing composites also showed elastic dominance with G′ higher than G″. This behavior was confirmed by van Gurp–Palmen plots, where the phase angle decreased with increasing PHB and WF loadings. WF addition also shifted Cole–Cole plots away from semicircular terminal relaxation, while time–temperature superposition validity was maintained, confirming that polymer chain dynamics continue to dominate melt behavior. Young’s modulus increased with WF loading, while tensile strength and toughness decreased due to weaker interfacial adhesion between the matrix and the filler. Interestingly, 10% WF systems containing PHB exhibited the highest toughness among all of the filled systems, indicating synergistic reinforcement from WF fillers and PHB-induced ductility. Overall, melt rheology effectively captured the internal structure and stiffness of the composites as the formulation changed, reinforcing the concept that the PLA/PHB ratio and WF content can be tuned to adjust melt elasticity and balance mechanical property trade-offs for targeted applications.

melt rheology↗
DOE OSTI2024

Resolving local ordering and structure in Mn x Ge 1- x Te alloys through thermodynamic ensembles of pair distribution functions

Characterizing local bonding environments in complex materials is essential for understanding and optimizing their properties. Equally as important is the ability to predict local motifs as a function of synthesis conditions, enhancing chemists’ ability to design properties into materials. In this study, we present an approach to leverage statistical mechanics to generate temperature- and energy-informed ensemble averaged pair distribution functions (PDFs). This method, which we have named Thermodynamic Ensemble Averages of PDFs for Ordering and Transformations (TEAPOT), utilizes density functional theory (DFT) to relax supercells while incorporating energetic penalties for local order, enabling accurate and computationally efficient analysis of local structure. We apply this method to the neutron PDF measurements of the pseudobinary MnTe–GeTe (MGT) alloy, demonstrating its capability to resolve complex local distortions and chemical ordering. Our results reveal detailed insights into phase transformations and local distortions driven by Mn substitution. For compositions that globally present as rock salt, our analysis reveals that Ge coordination geometry is heavily impacted by synthesis temperature. We propose that high temperature synthesis conditions promote a lowered Ge polyhedra distortion, promoting high charge carrier mobility due to the alignment of local and global structure. Incorporating statistical mechanics and computation into experimental analysis thus guides synthesis of tailored local structure.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Thermodynamic modeling of the Pd–Zn system with uncertainty quantification and its implication to tailor catalysts

Pd–Zn intermetallic catalysts show encouraging combinations of activity and selectivity on well-defined active site ensembles. Thermodynamic description of the Pd–Zn system, delineating phase boundaries and enumerating site occupancies within intermediate alloy phases, is essential to determining the ensembles of Pd–Zn atoms as a function of composition and temperature. Combining the present extensive first-principles calculations based on density functional theory (DFT) and available experimental data, the Pd–Zn system was remodeled using the CALculation of PHAse Diagrams (CALPHAD) approach. High throughput modeling tools with uncertainty quantification, i.e., ESPEI and PyCalphad, were incorporated in the phase analysis. Here, the site occupancies across the γ phase composition region were given special attention. A four-sublattice model was used for the γ phase owing to its four Wyckoff positions, i.e., the outer tetrahedral (OT) site 8c, the inner tetrahedral (IT) site 8c, the octahedral (OH) site 12e, and the cuboctahedral (CO) site 24g. The site fractions of Pd and Zn calculated from the present thermodynamic model show the occupancy preference of Pd in the OT and OH sublattices in agreement with experimental observations. The force constants obtained from DFT-based phonon calculations further supports the tendency of Pd occupying the OH sublattice compared with the IT and CO sublattice. The catalytic ensembles changing from Pd monomers (Pd 1 ) to trimers (Pd 3 ) on the surface of γ phase are attributed to the increase of Pd occupancy in the OH sublattice.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Compositions and Formation Mechanisms of Solid-Electrolyte Interphase on Microporous Carbon/Sulfur Cathodes

We report the formation mechanism and compositions of a solid-electrolyte interphase (SEI) on a microporous carbon/sulfur (MC/S) cathode in Li–S batteries using a carbonate-based electrolyte (1 M LiPF 6 in ethylene carbonate (EC)/dimethyl carbonate, v:v = 1:1). Through characterizations using 1D and 2D solution-phase nuclear magnetic resonance spectroscopy, coupled with model chemical reactions and DFT calculations, we have identified two critical roles of Li + in steering the SEI formation. First, the preferential solvation of Li + by EC in the mixed carbonate electrolyte renders EC as the dominant participant in the SEI formation, and second, Li + coordination to the EC carbonyl alters activation barriers and changes the reaction pathways relative to Na + . The main organic components in the SEI are identified as lithium ethylene monocarbonate and lithium methyl carbonate, which are virtually identical to those formed on Li and graphite anodes of lithium-ion batteries but via a different pathway.

25 ENERGY STORAGE↗