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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Solid-Phase Synthesis of Three-Armed Star-Shaped Peptoids and Their Hierarchical Self-Assembly

Due to the branched structure feature and unique properties, a variety of star-shaped polymers have been designed and synthesized. Despite those advances, solid-phase synthesis of star-shaped sequence-defined synthetic polymers that exhibit hierarchical self-assembly remains a significant challenge. Hence, we present an effective strategy for the solid-phase synthesis of three-armed star-shaped peptoids, in which ethylenediamine was used as the centric star pivot. Based on the sequence of monomer addition, a series of AA'A''-type and ABB'-type peptoids were synthesized and characterized by UPLC-MS (ultra-high performance liquid chromatography-mass spectrometry). By taking advantage of the easy-synthesis and large side-chain diversity, we synthesized star-shaped peptoids with tunable functions. We further demonstrated the aqueous self-assembly of some representative peptoids into biomimetic nanomaterials with well-defined hierarchical structures, such as nanofibers and nanotubes. These results indicate that star-shaped peptoids offer the potential in self-assembly of biomimetic nanomaterials with tunable chemistries and functions.

Solid-phase synthesis, star-shaped peptoids, aqueo↗
DOE OSTI2019

Fluid–Solid Reaction Kinetics for Solids of Nonbasic Geometries and Determination of the Appropriate Shape Factors

The rate analysis involving a solid of nonbasic geometry in general requires a complex numerical solution. A closed-form expression of the reaction rate for such a solid would be very convenient and greatly simplify the analysis. A method for this purpose was developed in this work for solids with shapes of finite cylinders and finite rectangular parallelepipeds reacting under the rate control by chemical reaction or mass transfer, which may be extended to other irregular shapes. In this method, an appropriate shape factor is first obtained under the conditions of a topochemical reaction, which is then applied to the unified rate expressions previously obtained for solids of three basic shapes. Good agreements between the rates predicted with the appropriate shape factors and the exact or numerical solutions were obtained for both reaction-controlled and pore-diffusion-controlled reactions.

36 MATERIALS SCIENCE↗
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 OSTI2023

Li 3– x Zr x (Ho/Lu) 1– x Cl 6 Solid Electrolytes Enable Ultrahigh-Loading Solid-State Batteries with a Prelithiated Si Anode

We report two new families of lithium metal chloride solid electrolytes Li 3–x Zr x (M) 1–x Cl 6 (0 ≤ x ≤ 0.8; M = Ho or Lu) with ionic conductivities of up to 1.8 mS cm –1 and a low activation energy of 0.34 eV. Structural elucidation via high-resolution neutron diffraction determines the Li ion distribution in trigonal Li 3 HoCl 6 , orthorhombic-I Li 3 LuCl 6 , and orthorhombic-II Li 2.4 Zr 0.6 (Ho/Lu) 0.4 Cl 6 . The last compound exhibits well-connected Li-ion pathways and abundant Li-ion carriers/vacancies to promote diffusion. All-solid-state batteries with Li 2.6 Zr 0.4 (Ho/Lu) 0.6 Cl 6 solid electrolytes and NCM85 cathodes exhibit stable cycling up to 4.6 V vs Li + /Li, which is even preserved up to 4.8 V. Stable cathode interphases are formed for both electrolytes upon cycling to 4.3, 4.6, and 4.8 V cutoff potentials, as identified by a ToF-SIMS analysis. Solid-state cells with a prelithiated Li 0.7 Si anode exhibit a significantly increased initial coulombic efficiency of 94.5% compared to Si and a high areal capacity of up to 16.3 mAh·cm –2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Imaging solid–electrolyte interphase dynamics using operando reflection interference microscopy

The quality of the solid–electrolyte interphase is crucial for the performance of most battery chemistries, but its formation dynamics during operation are not well understood due to a lack of reliable operando characterization techniques. Herein, we report a dynamic, non-invasive, operando reflection interference microscope to enable the real-time imaging of the solid–electrolyte interphase during its formation and evolution processes with high sensitivity. The stratified structure of the solid–electrolyte interphase formed during four distinct steps includes the emergence of a permanent inner inorganic layer enriched in LiF, a transient assembly of an interfacial electrified double layer and a consequent emergence of a temporary outer organic-rich layer whose presence is reversible with electrochemical cycling. Reflection interference microscope imaging reveals an inverse correlation between the thicknesses of two interphasial subcomponents, implying that the permanent inorganic-rich inner layer dictates the organic-rich outer layer formation and lithium nucleation. In conclusion, the real-time visualization of solid–electrolyte interphase dynamics provides a powerful tool for the rational design of battery interphases.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Solid–Liquid Phase Transition in the Octadecanoic Acid Film Adsorbed on the Toluene–Water Interface

The structure of the soluble protonated (pH = 2) octadecanoic acid film adsorbed on the saturated hydrocarbon (n-hexane)–water and aromatic hydrocarbon (toluene)–water interfaces is studied by X-ray reflectometry using synchrotron radiation. The experimental data demonstrate that a solid phase of a Gibbs monolayer 26 ± 1 Å thick, in which aliphatic tails are perpendicular to the surface and the area per molecule is A = 18 ± 2 Å{sup 2}, is formed in the film at the n-hexane–water interface. The solid monolayer on the toluene–water interface in the adsorbed film melts when temperature increases, and this transition is caused by disordering of the hydrocarbon tails of the acid. During the solid–liquid transition, the Gibbs monolayer thickness remains almost the same, 22 ± 1 Å. In the solid phase, we have A = 20 ± 2 Å{sup 2}, and the angle of deviation of the molecular tails from the normal to the surface is about 30°. The density of the liquid monolayer phase with A = 24 ± 2 Å{sup 2} corresponds to liquid n-octadecane.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Control of Two Solid Electrolyte Interphases at the Negative Electrode of an Anode‐Free All Solid‐State Battery based on Argyrodite Electrolyte

Abstract Anode‐free all solid‐state batteries (AF‐ASSBs) employ “empty” current collector with three active interfaces that determine electrochemical stability; lithium metal – Solid electrolyte (SE) interphase (SEI‐1), lithium – current collector interface, and collector – SE interphase (SEI‐2). Argyrodite Li 6 PS 5 Cl (LPSCl) solid electrolyte (SE) displays SEI‐2 containing copper sulfides, formed even at open circuit. Bilayer of 140 nm magnesium/30 nm tungsten (Mg/W‐Cu) controls the three interfaces and allows for state‐of‐the‐art electrochemical performance in half‐cells and fullcells. AF‐ASSB with NMC811 cathode achieves 150 cycles with Coulombic efficiency (CE) above 99.8%. With high mass‐loading cathode (8.6 mAh cm −2 ), AF‐ASSB retains 86.5% capacity after 45 cycles at 0.2C. During electrodeposition of Li, gradient Li‐Mg solid solution is formed, which reverses upon electrodissolution. This promotes conformal wetting/dewetting by Li and stabilizes SEI‐1 by lowering thermodynamic driving force for SE reduction. Inert refractory W underlayer is required to prevent ongoing formation of SEI‐2 that also drives electrochemical degradation. Inert Mo and Nb layers likewise protect Cu from corroding, while Li‐alloying layers (Mg, Sn) are less effective due to ongoing volume changes and associated pulverization. Mechanistic explanation for observed Li segregation within alloying Li x Mg layer is provided through mesoscale modelling, considering opposing roles of diffusivity differences and interfacial stresses.

Wang, Yixian [Materials Science and Engineering Pr↗
DOE OSTI2019

Incorporating Solvate and Solid Electrolytes for All‐Solid‐State Li 2 S Batteries with High Capacity and Long Cycle Life

Abstract The development of all‐solid‐state lithium–sulfur batteries is hindered by the poor interfacial properties at solid electrolyte (SE)/electrode interfaces. The interface is modified by employing the highly concentrated solvate electrolyte, (MeCN) 2 −LiTFSI:TTE, as an interlayer material at the electrolyte/electrode interfaces. The incorporation of an interlayer significantly improves the cycling performance of solid‐state Li 2 S batteries compared to the bare counterpart, exhibiting a specific capacity of 760 mAh g −1 at cycle 100 (330 mAh g −1 for the bare cell). Electrochemical impedance spectroscopy shows that the interfacial resistance of the interlayer‐modified cell gradually decreases as a function of cycle number, while the impedance of the bare cell remains almost constant. Cross‐section scanning electron microscopy (SEM)/ energy dispersive X‐ray spectroscopy (EDS) measurements on the interlayer‐modified cell confirm the permeation of solvate into the cathode and the SE with electrochemical cycling, which is related to the decrease in cell impedance. In order to mimic the full permeation of the solvate across the entire cell, the solvate is directly mixed with the SE to form a “solvSEM” electrolyte. The hybrid Li 2 S cell using a solvSEM electrolyte exhibits superior cycling performance compared to the solid‐state cells, in terms of Li 2 S loading, Li 2 S utilization, and cycling stability. The improved performance is due to the favorable ionic contact at the battery interfaces.

Shin, Minjeong↗
DOE OSTI2024

Uncovering the Size-dependent Thermal Solid Transformation of Akaganéite

Investigating the structural evolution and phase transformation of iron oxides is crucial for gaining a deeper understanding of geological changes on diverse planets and preparing oxide materials suitable for industrial applications. In this study, we employed in-situ heating techniques in conjunction with transmission electron microscopy (TEM) observations and ex-situ characterization to thoroughly analyze the thermal solid-phase transformation of akaganéite one-dimensional (1D) nanostructures with varying diameters. Our findings offer compelling evidence for a size-dependent morphology evolution in akaganéite 1D nanostructures, which can be attributed to the transformation from akaganéite to maghemite (?-Fe2O3) and subsequent crystal growth. Specifically, we observed that akaganéite nanorods with a diameter of around 50 nm transformed into hollow polycrystalline maghemite nanorods, which demonstrated remarkable stability without arresting crystal growth under continuous heating. In contrast, smaller akaganéite nanoneedles or nanowires with a diameter ranging from 20 to 8 nm displayed a propensity for forming single-crystal nanoneedles or nanowires through phase transformation and densification. By manipulating the size of the precursors, we have developed a straightforward method for the synthesis of single-crystal and polycrystalline maghemite nanowires through solid-phase transformation. These significant findings provide new insights into the size-dependent structural evolution and phase transformation of iron oxides at the nanoscale.

Wang, Xiang↗
DOE OSTI2024

Self‐Templated 3D Sulfide‐Based Solid Composite Electrolyte for Solid‐State Sodium Metal Batteries

Abstract Rechargeable solid‐state sodium metal batteries (SSMBs) experience growing attention owing to the increased energy density (vs Na‐ion batteries) and cost‐effective materials. Inorganic sulfide‐based Na‐ion conductors also possess significant potential as promising solid electrolytes (SEs) in SSMBs. Nevertheless, due to the highly reactive Na metal, poor interface compatibility is the biggest obstacle for inorganic sulfide solid electrolytes such as Na 3 SbS 4 to achieve high performance in SSMBs. To address such electrochemical instability at the interface, new design of sulfide SE nanostructures and interface engineering are highly essential. In this work, a facile and straightforward approach is reported to prepare 3D sulfide‐based solid composite electrolytes (SCEs), which utilize porous Na 3 SbS 4 (NSS) as a self‐templated framework and fill with a phase transition polymer. The 3D structured SCEs display obviously improved interface stability toward Na metal than pristine sulfide. The assembled SSMBs (with TiS 2 or FeS 2 as cathodes) deliver outstanding electrochemical cycling performance. Moreover, the cycling of high‐voltage oxide cathode Na 0.67 Ni 0.33 Mn 0.67 O 2 (NNMO) is also demonstrated in SSMBs using 3D sulfide‐based SCEs. This study presents a novel design on the self‐templated nanostructure of SCEs, paving the way for the advancement of high‐energy sodium metal batteries.

Guo, Xiaolin↗
DOE OSTI2020

Solidity without inhomogeneity: perfectly homogeneous, weakly coupled, UV-complete solids

Solid-like behavior at low energies and long distances is usually associated with the spontaneous breaking of spatial translations at microscopic scales, as in the case of a lattice of atoms. We exhibit three quantum field theories that are renormalizable, Poincaré invariant, and weakly coupled, and that admit states that on the one hand are perfectly homogeneous down to arbitrarily short scales, and on the other hand have the same infrared dynamics as isotropic solids. All three examples presented here lead to the same peculiar solid at low energies, featuring very constrained interactions and transverse phonons that always propagate at the speed of light. In particular, they violate the well known c$^2_L$>$\frac{4}{3}$c$^2_T$ bound, thus showing that it is possible to have a healthy renormalizable theory that at low energies exhibits a negative bulk modulus (we discuss how the associated instabilities are absent in the presence of suitable boundary conditions). We do not know whether such peculiarities are unavoidable features of large scale solid-like behavior in the absence of short scale inhomogeneities, or whether they simply reflect the limits of our imagination.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Parametric study of solid-solid translucent phase change materials in building windows

Thermal energy storage and solar radiation management are crucial to improve the sustainability and energy efficiency of buildings. Compared with the implementation of phase change materials (PCMs) in opaque components, the energy saving potential of incorporating PCMs in transparent glazing windows is much less studied and not well understood. Here we present a comprehensive parametric study of novel PCM windows for building energy saving with a focus on optimizing and quantitatively distinguishing the contributions from the optical and thermal properties of the PCM, which is particularly useful for the design of solid-solid PCM windows. We investigate a reference commercial office building using EnergyPlus by developing an equivalent model of our PCM window that is compatible with EnergyPlus's modeling capabilities. Compared with a clear-clear double-pane window, the integration of 3 mm solid-solid PCMs with optimal properties in warm, mixed, and cold climates can respectively save up to 17.2%, 14.0%, and 5.8% energy for the HVAC (heating, ventilation, and air conditioning) system, and 9.4%, 6.7%, and 3.2% energy for the whole building. We also demonstrate that these energy savings are most sensitive to the solar absorptance of PCMs for all three climates. The optimal transition temperature varies with climate and is related to the climate and solar radiation heat gain. Other issues are also briefly discussed, such as hysteresis, window orientations, and the effect of interior lighting. Finally, although the optimal PCM windows show energy saving performance comparable with low-emissivity windows, the PCM windows provide a unique advantage in terms of shifting HVAC loads which can provide benefits to the electrical grid.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗