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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 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Photoinduced charge transfer in transition metal dichalcogenide heterojunctions – towards next generation energy technologies

Increasing interest in using two-dimensional transition metal dichalcogenides (2D TMDCs) in optical energy conversion technologies creates a demand for improving the yields and lifetimes of photogenerated charge carriers. Despite inherently fast photocarrier decay in neat 2D TMDCs, the unique photophysics in these quantum-confined systems motivates continued effort to control the evolution of photoexcited states and create functional devices. Here, an intriguing strategy to accomplish this goal is to employ TMDCs in heterojunctions with appropriate semiconductors, where energy level offsets drive photoinduced charge transfer (PCT) across material interfaces. PCT in TMDC-based systems can be optimized for many different applications, such as driving free carriers to photocatalytic sites for redox reactions like water splitting, extracting charge to perform work in photovoltaics or photodetectors, and manipulating the spin and momentum valley electronic degrees of freedom for quantum computing systems. Here, we review recent strides in optimizing PCT for such applications through greater fundamental understanding of the photophysics that occurs at TMDC/semiconductor interfaces. After giving an overview of isolated TMDC properties, synthetic methods, and the basics of PCT, we discuss TMDCs in heterojunctions with several classes of materials, including other TMDCs, small molecule semiconductors, polymers, single-walled carbon nanotubes, quantum dots, perovskites, and electrolytes. In addition to highlighting the unique benefits of each materials category, we also identify parallels across common themes, such as the roles of charge-transfer states, spin, electronic coupling, delocalization, interfacial atomic morphology, and the precise design of energy landscapes to direct charge and energy motion. We hope to capture a broad range of the valuable work in this fast-paced field to inspire new research directions for employing PCT in targeted TMDC-based systems.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Interfacial engineering for stabilizing polymer electrolytes with 4V cathodes in lithium metal batteries at elevated temperature

Poly (ethylene oxide) (PEO) polymer electrolytes are promising candidates for next-generation rechargeable lithium batteries. However, the poor interfacial stability between 4 V cathodes and PEO electrolytes impedes their applications in 4 V lithium batteries with high energy density. Here, we demonstrate a facile and effective strategy to enhance the interfacial stability by the synergy of Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) coating on the cathode surface, and salt combination in the electrolyte, even with a cut-off voltage of 4.25–4.4 V vs. Li + /Li. Nano-LAGP coated Li|PEO|LiCoO 2 cell delivers stable cycling with a capacity retention of 81.9%/400 cycles and 84.7%/200 cycles at 60 °C when charged to 4.25 and 4.3 V in pure polyether electrolyte, respectively. Steady cycling is also demonstrated at room temperature and with LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM523) cathode. This work offers a viable and scalable approach to improve the stability between PEO electrolytes and 4 V cathodes and open up new possibilities for practical application of 4 V lithium metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

De Novo Design of Spiro-Type Hole-Transporting Material: Anisotropic Regulation Toward Efficient and Stable Perovskite Solar Cells

2,2',7,7'-Tetrakis(N,N-di-p-methoxyphenyl)-amine-9,9'-spirobifluorene (Spiro-OMeTAD) represents the state-of-the-art hole-transporting material (HTM) in n-i-p perovskite solar cells (PSCs). However, its susceptibility to stability issues has been a long-standing concern. In this study, we embark on a comprehensive exploration of the untapped potential within the family of spiro-type HTMs using an innovative anisotropic regulation strategy. Diverging from conventional approaches that can only modify spirobifluorene with single functional group, this approach allows us to independently tailor the two orthogonal components of the spiro-skeleton at the molecular level. The newly designed HTM, SF-MPA-MCz, features enhanced thermal stability, precise energy level alignment, superior film morphology, and optimized interfacial properties when compared to Spiro-OMeTAD, which contribute to a remarkable power conversion efficiency (PCE) of 24.53% for PSCs employing SF-MPA-MCz with substantially improved thermal stability and operational stability. Note that the optimal concentration for SF-MPA-MCz solution is only 30 mg/ml, significantly lower than Spiro-OMeTAD (>70 mg/ml), which could remarkably reduce the cost especially for large-area processing in future commercialization. This work presents a promising avenue for the versatile design of multifunctional HTMs, offering a blueprint for achieving efficient and stable PSCs.

14 SOLAR ENERGY↗
DOE OSTI2021

Experimental observation of localized interfacial phonon modes

Interfaces impede heat flow in micro/nanostructured systems. Conventional theories for interfacial thermal transport were derived based on bulk phonon properties of the materials making up the interface without explicitly considering the atomistic interfacial details, which are found critical to correctly describing thermal boundary conductance. Recent theoretical studies predicted the existence of localized phonon modes at the interface which can play an important role in understanding interfacial thermal transport. However, experimental validation is still lacking. Through a combination of Raman spectroscopy and high-energy-resolution electron energy-loss spectroscopy in a scanning transmission electron microscope, we report the experimental observation of localized interfacial phonon modes at ~12 THz at a high-quality epitaxial Si-Ge interface. These modes are further confirmed using molecular dynamics simulations with a high-fidelity neural network interatomic potential, which also yield thermal boundary conductance agreeing well with that measured in time-domain thermoreflectance experiments. Simulations find that the interfacial phonon modes have an obvious contribution to the total thermal boundary conductance. Our findings significantly contribute to the understanding of interfacial thermal transport physics and have impact on engineering thermal boundary conductance at interfaces in applications such as electronics thermal management and thermoelectric energy conversion.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Exploring Cr and molten salt interfacial interactions for molten salt applications

Molten salts play an important role in various energy-related applications such as high-temperature heat transfer fluids and reaction media. However, the extreme molten salt environment causes the degradation of materials, raising safety and sustainability challenges. A fundamental understanding of material–molten salt interfacial evolution is needed. This work studies the transformation of metallic Cr in molten 50/50 mol% KCl–MgCl 2 via multi-modal in situ synchrotron X-ray nano-tomography, diffraction and spectroscopy combined with density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. Notably, in addition to the dissolution of Cr in the molten salt to form porous structures, a δ-A15 Cr phase was found to gradually form as a result of the metal–salt interaction. This phase change of Cr is associated with a change in the coordination environment of Cr at the interface. DFT and AIMD simulations provide a basis for understanding the enhanced stability of δ-A15 Cr vs. bcc Cr, by revealing their competitive phase thermodynamics at elevated temperatures and probing the interfacial behavior of the molten salt at relevant facets. This study provides critical insights into the morphological and chemical evolution of metal–molten salt interfaces. Finally, the combination of multimodal synchrotron analysis and atomic simulation also offers an opportunity to explore a broader range of systems critical to energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2007

Enhancing Spin Filters by Use of Bulk Inversion Asymmetry

Theoretical calculations have shown that the degrees of spin polarization in proposed nonmagnetic semiconductor resonant tunneling spin filters could be increased through exploitation of bulk inversion asymmetry (BIA). These enhancements would be effected through suitable orientation of spin collectors (or spin-polarization- inducing lateral electric fields), as described below. Spin filters -- more precisely, sources of spin-polarized electron currents -- have been sought for research on, and development of, the emerging technological discipline of spintronics (spin-transport electronics). The proposed spin filters were to be based on the Rashba effect, which is an energy splitting of what would otherwise be degenerate quantum states, caused by a spinorbit interaction in conjunction with a structural-inversion asymmetry (SIA) in the presence of interfacial electric fields in a semiconductor heterostructure. The magnitude of the energy split is proportional to the electron wave number. In a spin filter, the spin-polarized currents produced by the Rashba effect would be extracted by quantum-mechanical resonant tunneling.

Ting, David↗
NASA NTRS2007

Resonant Tunneling Spin Pump

The resonant tunneling spin pump is a proposed semiconductor device that would generate spin-polarized electron currents. The resonant tunneling spin pump would be a purely electrical device in the sense that it would not contain any magnetic material and would not rely on an applied magnetic field. Also, unlike prior sources of spin-polarized electron currents, the proposed device would not depend on a source of circularly polarized light. The proposed semiconductor electron-spin filters would exploit the Rashba effect, which can induce energy splitting in what would otherwise be degenerate quantum states, caused by a spin-orbit interaction in conjunction with a structural-inversion asymmetry in the presence of interfacial electric fields in a semiconductor heterostructure. The magnitude of the energy split is proportional to the electron wave number. Theoretical studies have suggested the possibility of devices in which electron energy states would be split by the Rashba effect and spin-polarized currents would be extracted by resonant quantum-mechanical tunneling.

Ting, David Z.↗
NASA NTRS2004

Electron-Spin Filters Based on the Rashba Effect

Semiconductor electron-spin filters of a proposed type would be based on the Rashba effect, which is described briefly below. Electron-spin filters more precisely, sources of spin-polarized electron currents have been sought for research on, and development of, the emerging technological discipline of spintronics (spin-based electronics). There have been a number of successful demonstrations of injection of spin-polarized electrons from diluted magnetic semiconductors and from ferromagnetic metals into nonmagnetic semiconductors. In contrast, a device according to the proposal would be made from nonmagnetic semiconductor materials and would function without an applied magnetic field. The Rashba effect, named after one of its discoverers, is an energy splitting, of what would otherwise be degenerate quantum states, caused by a spin-orbit interaction in conjunction with a structural-inversion asymmetry in the presence of interfacial electric fields in a semiconductor heterostructure. The magnitude of the energy split is proportional to the electron wave number. The present proposal evolved from recent theoretical studies that suggested the possibility of devices in which electron energy states would be split by the Rashba effect and spin-polarized currents would be extracted by resonant quantum-mechanical tunneling. Accordingly, a device according to the proposal would be denoted an asymmetric resonant interband tunneling diode [a-RITD]. An a-RITD could be implemented in a variety of forms, the form favored in the proposal being a double-barrier heterostructure containing an asymmetric quantum well. It is envisioned that a-RITDs would be designed and fabricated in the InAs/GaSb/AlSb material system for several reasons: Heterostructures in this material system are strong candidates for pronounced Rashba spin splitting because InAs and GaSb exhibit large spin-orbit interactions and because both InAs and GaSb would be available for the construction of highly asymmetric quantum wells. This mate-rial system affords a variety of energy-band alignments that can be exploited to obtain resonant tunneling and other desired effects. The no-common-atom InAs/GaSb and InAs/AlSb interfaces would present opportunities for engineering interface potentials for optimizing Rashba spin splitting.

Ting, David Z.-Y.↗
DOE OSTI2022

Tailored Solvation and Interface Structures by Tetrahydrofuran-Derived Electrolyte Facilitates Ultralow Temperature Lithium Metal Battery Operations

Ineffectiveness of Li-ion batteries (LIBs) in cold climates hinders electronics to work in various conditions including frigid environments, despite high demands. Given that intrinsic properties of LIB materials cause this problem, optimized cell chemistries ultimately are required for low-temperature usage. In this study, Li-metal batteries (LMBs) composed of a Li-metal anode (LMA) stabilized by a localized high-concentration electrolyte (LHCE) are found to significantly enhance low-temperature performance. The LHCE allows the LMA to have compact and regular deposition and excellent plating/stripping efficiency at sub-zero temperatures. The LHCE produces an inorganic-rich solid-electrolyte interphase with larger amounts of Li 2 O/LiF interfaces, dominance of ion aggregates in Li + solvation, and enhanced Li + transport, which can greatly improve the LMA stability. LMB full cells based on LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathodes with the tailored electrolyte show high retentions of 75 and 64 % at -20 and -40 °C, respectively. Furthermore, the LMB configuration retains its charge-discharge capability even at -60 °C.

25 ENERGY STORAGE↗
DOE OSTI2020

Ultrathin Free-Standing Oxide Membranes for Electron and Photon Spectroscopy Studies of Solid–Gas and Solid–Liquid Interfaces

Free-standing ultrathin (~2 nm) films of several oxides (Al 2 O 3 ,TiO 2 , and others) have been developed, which are mechanically robust and transparent to electrons with E kin ≥ 200 eV and to photons. We demonstrate their applicability in environmental X-ray photoelectron and infrared spectroscopy for molecular level studies of solid-gas (≥1 bar) and solid-liquid interfaces. These films act as membranes closing a reaction cell and as substrates and electrodes for electrochemical reactions. The remarkable properties of such ultrathin oxides membranes enable atomic/molecular level studies of interfacial phenomena, such as corrosion, catalysis, electrochemical reactions, energy storage, geochemistry, and biology, in a broad range of environmental conditions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Tin-based ionic chaperone phases to improve low temperature molten sodium–NaSICON interfaces

High temperature operation of molten sodium batteries impacts cost, reliability, and lifetime, and has limited the widespread adoption of these grid-scale energy storage technologies. Poor charge transfer and high interfacial resistance between molten sodium and solid-state electrolytes, however, prevents the operation of molten sodium batteries at low temperatures. In this study, in situ formation of tin-based chaperone phases on solid state NaSICON ion conductor surfaces is shown in this work to greatly improve charge transfer and lower interfacial resistance in sodium symmetric cells operated at 110 °C at current densities up to an aggressive 50 mA cm –2 . It is shown that static wetting testing, as measured by the contact angle of molten sodium on NaSICON, does not accurately predict battery performance due to the dynamic formation of a chaperone NaSn phase during cycling. This work demonstrates the promise of sodium intermetallic-forming coatings for the advancement of low temperature molten sodium batteries by improved mating of sodium–NaSICON surfaces and reduced interfacial resistance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Effects of surface charge and cluster size on the electrochemical dissolution of platinum nanoparticles using COMB3 and continuum electrolyte models

We study the site-dependent dissolution of platinum nanoparticles under electrochemical conditions to assess their thermodynamic stability as a function of shape and size using empirical molecular dynamics and electronic-structure models. The third-generation charge optimized many-body potential is employed to determine the validity of uniform spherical representations of the nanoparticles in predicting dissolution potentials (the Kelvin model). To understand the early stages of catalyst dissolution, implicit solvation techniques based on the self-consistent continuum solvation method are applied. It is demonstrated that interfacial charge and polarization can shift the dissolution energies by amounts on the order of 0.74 eV depending on the surface site and nanoparticle shape, leading to the unexpected preferential removal of platinum cations from highly coordinated sites in some cases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Irradiation-induced reactions at the CeO 2 /SiO 2 /Si interface

The influence of high-energy (1.6 MeV) Ar 2+ irradiation on the interfacial interaction between cerium oxide thin films (~15 nm) with a SiO 2 /Si substrate is investigated using transmission electron microscopy, ultrahigh vacuum x-ray photoelectron spectroscopy (XPS), and a carbon monoxide (CO) oxidation catalytic reaction using ambient pressure XPS. The combination of these methods allows probing the dynamics of vacancy generation and its relation to chemical interactions at the CeO 2 /SiO 2 /Si interface. The results suggest that irradiation causes amorphization of some portion of CeO 2 at the CeO 2 /SiO 2 /Si interface and creates oxygen vacancies due to the formation of Ce 2 O 3 at room temperature. The subsequent ultra-high-vacuum annealing of irradiated films increases the concentration of Ce 2 O 3 with the simultaneous growth of the SiO 2 layer. Interactions with CO molecules result in an additional reduction of cerium and promote the transition of Ce 2 O 3 to a silicate compound. Furthermore, thermal annealing of thin films exposed to oxygen or carbon monoxide shows that the silicate phase is highly stabile even at 450 °C.

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

Mapping hidden space-charge distributions across crystalline metal oxide/group IV semiconductor interfaces

The electronic structures of semiconducting heterojunctions are critically dependent on composition including the presence and concentrations of dopants, both intended and unintended. Dopant profiles in the interfacial region can have major effects on band energies which in turn drive transport properties. Here, in this study, we use core-level photoelectron line shapes excited with hard x rays to extract information about electric fields resulting from internal charge transfer in epitaxial La 0.03 Sr 0.97 Zr x Ti 1–x O 3 /Ge(001) (0.1≤x≤0.7) heterostructures. Experiments were carried out for heterojunctions involving both n- and p-type Ge substrates. These heterojunctions were not amenable to electronic characterization of all regions by transport measurements because the doped substrates act as electrical shunts, precluding probing the more resistive films and masking interface conductivity. However, the core-level line shapes were found to be a rich source of information on built-in potentials that exist throughout the heterostructure, and yielded valuable insight into the impact of band bending on band alignment at the buried interfaces. The electronic effects expected for Ge with uniform n- and p-type doping are eclipsed by those of unintended oxygen dopants in the Ge near the interface. This study illustrates the power of hard x-ray photoemission spectroscopy and related modeling to determine electronic structure in material systems for which insight from traditional transport measurements is limited.

36 MATERIALS SCIENCE↗
DOE OSTI2024

De novo Materials Design of Catalytic Surface Motifs for Water-Gas-Shift (Final Progress Report DOE Grant DE-SC0019281)

This project was aimed at developing innovative theoretical methods and models to understand essential catalysis-relevant issues such as CO 2 conversion, fuel cells, and lithium batteries. Through collaborations with experimentalists, we strive to develop new quantum and machine learning methods for the understanding of surface and interfacial chemistry that can empower the design of energy and sustainability systems. Overall, our work under this grant brings cross-disciplinary insights into catalytic materials, microenvironments, and other conditions, which can serve to provide design rules for the next generation of catalysts.

25 ENERGY STORAGE↗
DOE OSTI2026

Influence of Nanoconfinement and Elevated Temperatures on Geocolloid-Facilitated Transport of Energy-related Contaminants

The main objective of this project is to obtain a better understanding of the transport behavior and interactions of geocolloids in the presence of energy- related contaminants under bulk and nanoconfined conditions. In that, we first established solid protocols to synthesize and fabricate numerous types of geocolloids with a. various sizes ranging from 40 – 800 nm and b. different hydrophile-lipophile balance (HLB) ratios in the range of 25:75 to 75:25. Direct force measurements with geocolloids having different degrees of surface coverages (i.e. HLB to realistically mimic adsorption of energy related contaminants) were conducted using the Surface Forces Apparatus (SFA) over a distance regime starting from 8μm all the way down to molecular contact. Repulsive forces were observed on approach starting from > 3μm, followed by an exponential increase of which magnitude appears to be larger than a decay length obtained from Derjaguin–Landau–Verwey–Overbeek (DLVO) theory in pure water. When the geocolloids were confined in salted water, the magnitude of onset of repulsion was varied as a function of salinity in solution, which can significantly alter a purely repulsive screened electrostatic (coulombic) interaction arising from, among geocolloids as well as between geocolloids and geosurfaces. The viscosity and flow characteristics of geocolloidal suspensions at different degrees of confinement were also investigated where we identified highly discontinuous rheological behaviors below a critical nanoconfinement level. We anticipate that the knowledge gained through this study will enable the scientists and researchers to better assess transport and fate behaviors of geocolloidal dispersions that can carry energy-related contaminants under realistically emulated geosystem.

03 NATURAL GAS↗
DOE OSTI2020

Expression of interfacial Seebeck coefficient through grain boundary engineering with multi-layer graphene nanoplatelets

Energy filtering has been a long-sought strategy to enhance a thermoelectric material's figure of merit zT through improving its power factor. Here we show a composite of multi-layer graphene nanoplatelets (GNP) and n-type Mg 3 Sb 2 leads to the expression of an energy filtering like effect demonstrated by an increase in the material's Seebeck coefficient and maximum power factor, without impact on the material's carrier concentration. We analyse these findings from the perspective of a heterogeneous material consisting of grain and grain boundary phases, instead of a more traditional and common analysis that assumes a homogeneously transporting medium. An important implication of this treatment is that it leads to the development of an interfacial Seebeck coefficient term, which can explain the observed increase in the material's Seebeck coefficient. The contribution of this interfacial Seebeck coefficient to the overall Seebeck coefficient is determined by the relative temperature drop across the grain boundary region compared to that of the bulk material. In Te doped Mg 3 Sb 2 we show the introduction of GNP increases the interfacial thermal resistance of grain boundaries, enhancing the contribution of the interfacial Seebeck coefficient arising from grain boundaries to the overall Seebeck coefficient. Without significant detriment to the electrical conductivity this effect results in a net increase in maximum power factor. This increased interfacial thermal resistance also leads to the synergistic reduction of the total thermal conductivity. As a result, we enhance zT of the Mg 3 Sb 2 to a peak value of 1.7 near 750 K. Considering the two-dimensional nature of the grain boundary interface, this grain boundary engineering strategy could be applied to a few thermoelectric systems utilizing various two-dimensional nanomaterials.

42 ENGINEERING↗
DOE OSTI2021

Continuous Liquid–Liquid Extraction and in-Situ Membrane Separation of Miscible Liquid Mixtures

Separation operations are critical across a wide variety of manufacturing industries and account for about one quarter of all in-plant energy consumption in the United States. Conventional liquid-liquid separation operations require either thermal or chemical treatment, both of which have a large environmental impact and carbon footprint. Consequently, there is a great need to develop sustainable, clean methodologies for separation of miscible liquid mixtures. The greatest opportunities to achieve this lie in replacing high-energy separation operations (e.g., distillation) with low-energy alternatives such as liquid-liquid extraction. One of the primary design challenges in liquid-liquid extraction is to maximize the interfacial area between two immiscible (e.g., polar and non-polar) liquids for efficient mass transfer. However, this often involves energy-intensive methods including ultrasonication, pumping the feed and the extractant through packed columns with high tortuosity, or using a supercritical fluid as an extractant. Emulsifying the feed and the extractant, especially with a surfactant, offers a large interfacial area, but subsequent separation of emulsions can be energy-intensive and expensive. Thus, emulsions are typically avoided in conventional extraction operations. Herein, we discuss a novel, easily scalable, platform separation methodology termed CLEANS (Continuous Liquid-liquid Extraction And iN-situ membrane Separation). CLEANS integrates emulsion-enhanced extraction with continuous, gravity-driven, membrane-based separation of emulsions into a single unit operation. Furthermore, our results demonstrate that the addition of a surfactant and emulsification significantly enhance extraction (by > 250% in certain cases), even for systems where the best extractants for miscible liquid mixtures are known. Utilizing the CLEANS methodology, we demonstrate continuous separation of a wide range of miscible liquid mixtures, including soluble organic molecules from oils, alcohols from esters, and even azeotropes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗