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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Probing Interfacial Reaction Pathways in Atomic Layer Deposition on Sulfide Superionic Conductors

Sulfide superionic conductors (e.g., argyrodite Li 6 PS 5 Cl, LPSCl) are extremely promising for all solid-state batteries, but poor atmospheric stability and high interfacial reactivity limit widespread adoption. Coating LPSCl powders with ultrathin coatings using atomic layer deposition (ALD) mitigates these problems, protecting against atmospheric degradation and reducing reactivity with Li metal, yielding more stable cycling. Despite significant promise, the ALD mechanism is unknown, hampering the development of new coating chemistries. In this study, we elucidate the mechanism for Al 2 O 3 ALD on LPSCl using trimethyl aluminum (TMA) and H 2 O by combining in situ Fourier transform infrared spectroscopy, ex situ solid-state magic angle spinning nuclear magnetic resonance, UV Raman spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. We determine that ALD Al 2 O 3 nucleates promptly via TMA reaction with native —OH, —SH, and PS 3 -OH groups to form transient C–Al–O(S) species that are rapidly hydrolyzed during the subsequent H 2 O exposure. This reversible transformation maintains surface nucleophilicity and prevents sulfide decomposition. The resulting layer-by-layer growth leads to highly conformal Al 2 O 3 coatings on LPSCl that are readily scalable to ≥ 50 g quantities using a rotating drum fixture. This detailed understanding of ALD surface reactions provides critical insights guiding the selection of future ALD chemistries with improved performance.

atomic layer deposition↗
DOE OSTI2024

Construction of MoS 2 /NiS 2 heterostructure with fast interfacial reaction kinetics for ultrafast sodium storage

Constructing heterostructure is a valid method to reinforcing sodium storage performance of transition metal chalcogenides materials. Herein, a simple, safe and controllable one step hydrothermal method is proposed to synthesize MoS 2 /NiS 2 heterostructure. Due to the difference in band gaps and work functions of MoS 2 and NiS 2 , the charges are redistributed at the MoS 2 /NiS 2 heterointerfaces, thereby accelerating the migration of electrons and Na + . The heterointerfaces provide extra active sites for storing Na + , thus increasing the sodium storage capacity of the heterostructure. Furthermore, the distinct redox potentials of NiS 2 and MoS 2 promote the structural stability of MoS 2 /NiS 2 heterostructure during the electrochemical reaction processes. Consequently, the obtained MoS 2 /NiS 2 heterostructure exhibits superior rate properties (339.4 mAh g –1 at 10 A g –1 ) and ultra-stable cycling stability (480.5 mAh g –1 after 350 cycles at 1 A g –1 ). Finally, this paper presents a valid strategy for creating heterostructure anodes with excellent sodium storage properties.

25 ENERGY STORAGE↗
DOE OSTI2025

Approach to Evaluating Reorganization Energies of Interfacial Electrochemical Reactions

Reaction rate coefficients for electron-transfer processes at the electrode–electrolyte interface are commonly estimated by using the Butler–Volmer equation, but their values are inaccurate beyond a few tenths of volts of overpotential. The Marcus–Hush–Chidsey (MHC) formalism yields correct asymptotic behavior of the rate coefficients vs applied overpotential but has complex dependencies on the redox system’s intrinsic parameters, which can be difficult to model or measure. In this work, we bridge the two kinetics formalisms to estimate the reorganization energy, one of the important parameters for the MHC formalism, and investigate its dependence on other intrinsic parameters such as activation barriers, electronic coupling strength, and the density of states of the electrode surface. We examine the sensitivity of the reorganization energy to these parameters, establish some general relationships for accurately predicting rate coefficients using the MHC formalism over a wide range of applied overpotentials, and compare this approach to calculating MHC rate constants with other empirical approaches for the mechanisms of CO 2 reduction on different metal electrode surfaces.

Butler−Volmer↗
DOE OSTI2023

Atomic Dynamics of Multi‐Interfacial Migration and Transformations

Redox-induced interconversions of metal oxidation states typically result in multiple phase boundaries that separate chemically and structurally distinct oxides and suboxides. Directly probing such multi-interfacial reactions is challenging because of the difficulty in simultaneously resolving the multiple reaction fronts at the atomic scale. Using the example of CuO reduction in H 2 gas, a reaction pathway of CuO → monoclinic m-Cu 4 O 3 → Cu 2 O is demonstrated and identifies interfacial reaction fronts at the atomic scale, where the Cu 2 O/m-Cu 4 O 3 interface shows a diffuse-type interfacial transformation; while the lateral flow of interfacial ledges appears to control the m-Cu 4 O 3 /CuO transformation. Together with atomistic modeling, it is shown that such a multi-interface transformation results from the surface-reaction-induced formation of oxygen vacancies that diffuse into deeper atomic layers, thereby resulting in the formation of the lower oxides of Cu 2 O and m-Cu 4 O 3 , and activate the interfacial transformations. In conclusion, these results demonstrate the lively dynamics at the reaction fronts of the multiple interfaces and have substantial implications for controlling the microstructure and interphase boundaries by coupling the interplay between the surface reaction dynamics and the resulting mass transport and phase evolution in the subsurface and bulk.

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

Accelerated Zymonic Acid Formation from Pyruvic Acid at the Interface of Aqueous Nanodroplets

To explore the role of the liquid interface in mediating reactivity in small compartments, the formation kinetics of zymonic acid (ZA) is measured in submicron aerosols (average radius = 240 nm) using mass spectrometry. The formation of ZA, from a condensation reaction of two pyruvic acid (PA) molecules, proceeds over days in bulk solutions, while in submicron aerosols, it occurs in minutes. The experimental results are replicated in a kinetic model using an apparent interfacial reaction rate coefficient of krxn = (0.9 ± 0.2) × 10-3 M-1 s-1. The simulation reveals that surface activity of PA coupled with an enhanced interfacial reaction rate drives accelerated ZA formation in aerosols. Experimental and simulated results provide compelling evidence that the condensation reaction of PA occurs exclusively at the aerosol interface with a reaction rate coefficient that is enhanced by 4 orders of magnitude (∼104) relative to what is estimated for macroscale solutions.

Kim, Pyeongeun↗
DOE OSTI2026

Thermal cycling-driven microstructural changes of eutectic Al–Si phase change materials in SS304 containers revealed by multi-modal imaging

Aluminum-based Al–Si alloys are widely used as phase change materials (PCMs) in thermal energy storage (TES) systems owing to their high volumetric latent heat and superior thermal conductivity. However, their long-term reliability is limited by degradation processes that remain insufficiently understood. In this work, we employ a multimodal, correlative characterization framework to systematically resolve the degradation behavior of eutectic Al–Si PCMs in contact with SS304 containers under repeated thermal cycling. By integrating high-resolution electron microscopy, three-dimensional X-ray fluorescence (3D XRF) imaging, and differential scanning calorimetry (DSC), we directly link spatially resolved compositional and microstructural evolution to changes in thermophysical properties. The correlative analysis reveals that elemental leaching of Fe, Cr, and Ni from the stainless-steel container into the PCM drives the formation of intermetallic compounds (IMCs) both at the interface and within the bulk PCM, leading to pronounced compositional heterogeneity. These interfacial reactions and diffusion-induced transformations progressively destabilize the Al–Si eutectic, reducing the effective phase-transforming fraction. Consistent with these observations, DSC measurements show a decrease in melting temperature and latent heat of fusion with thermal cycling. These results underscore the critical influence of interfacial reactions and material compatibility on the stability, durability, and overall performance of Al–Si-based TES systems.

25 ENERGY STORAGE↗
DOE OSTI2025

Coupling Interfacial Redox‐Reactions with In Situ Proton Generation for the Photoelectrochemical Separation of Rare‐Earth Elements

Abstract A dual‐function photoelectrochemical (PEC) separation system is demonstrated for rare‐earth element (REE) recovery. The sustainable release of the captured REEs is promoted through the synergistic integration of a redox‐reaction for electrostatic repulsion, and in situ proton generation for ion‐exchange, all driven by photoelectrochemistry. The platform consists of a redox‐copolymer, poly(ferrocenylpropyl methacrylamide‐ co ‐methacrylic acid) (P(FPMAm‐ co ‐MAA)) (PFM), conjugated with carbon nanotubes (CNTs) and coated onto titanium dioxide nanorods (TNRs). The (PFM‐CNT)/TNR spontaneously adsorbs up to 214.2 mg of Yttrium/g PFM by ion‐exchange, and demonstrates broad applicability for other REEs. The adsorbed REEs are released through the PEC oxidation of ferrocene (Fc) to ferrocenium (Fc + ), and the simultaneous PEC water splitting reactions at the TNRs that protonate the carboxylate binding groups. This dual photoelectrochemically‐driven mechanism for REE release is investigated by in situ pH measurements, as well as vibrational and X‐ray photoelectron spectroscopy. Through PEC approaches, a 68.8% reduction in energy consumption during REE recovery has been achieved compared to purely electrochemical systems, with a regeneration efficiency close to 100%. For NdFeB magnets from waste hard disk drives, Nd and Dy recovery efficiencies of 59.2 and 61.1% are achieved. The dual‐functionality of these copolymer PEC systems offers a sustainable platform for modulating critical element recovery.

Cho, Ki‐Hyun [Department of Chemical and Biomolecu↗
DOE OSTI2026

A solid-state extrusion pathway extensible to upcycling aluminum scrap and end-of-life permanent magnets into ductile Al-6061/SmCo 5 structural magnetic composites

Permanent magnets offer strong potential for multifunctional structural components, but their inherent brittleness limits direct integration. Here, SolidStir® Extrusion (SSE) is used to embed SmCo5 powder into AA6061 in the solid state, and the resulting microstructure, interfacial chemistry, mechanical properties, and magnetic response are systematically characterized. SSE fragments the initial SmCo 5 powder into predominantly fine particles dispersed within an ultrafine Al matrix, with a volume fraction of ∼ 4–6 % in this proof-of-concept study. Interfacial reactions form a continuous Al–Co reaction layer, with local atomic-resolution indexing consistent with Al 13 Co 4 , together with Sm–Si-rich reaction products, while the matrix contains Sm–Co–Si-rich precipitates and Mg 2 Si, producing features from nanometers to micrometers. Compared with an Al extrudate, this architecture increases yield strength by ∼ 42 % and tensile strength by ∼ 31 %, while preserving uniform elongation, and it sustains work hardening in compression from 150 to 400 °C. The composite retained hard-magnetic behavior, with axial magnetization of 12.7 A·m 2 kg −1 at 6 T and intrinsic coercivity of 9.6 kOe. These findings demonstrate that SSE can produce Al-based load-bearing magnetic composites while preserving useful SmCo5 functionality.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Chemical and Structural Insights into Solid Electrolyte Interphase Evolution for Sodium Metal Electrodes

The solid electrolyte interphase (SEI) critically governs the reversibility of sodium metal batteries, through dynamically mediating ion transport and interfacial reactions. However, its kinetic evolution under operating conditions, and how it influences interfacial stability, remains poorly understood. Here, in this study, we reveal that the SEI undergoes coupled chemical and mechanical changes during sodium plating and stripping, leading to spatial and temporal heterogeneity that drives interfacial degradation. Synchrotron operando grazing-incidence wide-angle X-ray scattering and soft X-ray absorption spectroscopy capture the sequential formation and dissolution of inorganic SEI phases (NaF, NaH, NaOH, Na 2 PO 3 F), accompanied by depth-dependent alterations in organic SEI components. Mesoscale modeling connects this evolving SEI heterogeneity to localized current density fluctuations and stress accumulation at the Na interface, identifying pathways to electrically isolated sodium formation. These findings show that SEI instability fundamentally limits reversibility in sodium metal batteries, and that controlling SEI chemistry–mechanics coupling is essential to achieving its durability.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Mechanistic Insights into Oxygen Reduction Reaction on Metal Cathode Over BaZrO 3 -Based Electrolyte under Moist Atmosphere: Interfacial Interactions and Reaction Pathways

The oxygen reduction reaction (ORR) is a critical process that often governs the overall performance of electrochemical systems such as proton conducting solid oxide fuel cells. Despite its significance, the current understanding about the ORR, especially when it involves H 2 O is still limited. In this study, the proton involved ORR (PI-ORR) on metal cathode (e.g., Pt) over BaZrO 3 (BZO) electrolyte is investigated using density functional theory (DFT) under moist atmosphere. Two scenarios are considered: one at relatively high temperature (900 K) in the presence of oxygen vacancy in BZO substrate and one at relatively low temperature (700 K) without oxygen vacancy. We systematically explored oxygen vacancy effects on adsorption sites and proton transfer pathways, calculated energy profiles and Gibbs free energies for elementary steps along the O 2 dissociated and the O 2 concerted reaction pathways. We also evaluated H 2 O impacts on intermediate oxygen species (*O and *OH) through Ab Initio molecular dynamics. These analyses revealed pathway-dependent reaction mechanisms and hydration effects at triple-phase boundary, advancing fundamental understanding of PI-ORR in metal cathode/Ba-based electrolyte systems for energy applications.

08 - HYDROGEN↗
DOE OSTI2026

Lattice-Oxygen-Driven Selective Oxidation Strategy for Stable Argyrodite Solid-State Lithium Metal Batteries

All-solid-state lithium metal batteries (ASSLMBs) with Li6PS5Cl argyrodite electrolytes and high-voltage LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes offer high energy density but suffer from rapid capacity fading due to the layered-to-rock-salt transition of NMC811 and structural degradation of Li6PS5Cl from parasitic interfacial reactions. Here, we demonstrate a catholyte engineering strategy using a Li2S scavenging additive to suppress interfacial reactivity and preserve the structural and electrochemical stability of both NMC811 and Li6PS5Cl. Incorporating 0.10 wt.% Li2S enables exceptional cycling stability, achieving 76% capacity retention after 550 cycles at C/10 and 88% retention after 800 cycles at C/3 at 60 degrees C, compared with rapid failure in pristine cells. Spectroscopic, electrochemical, and morphological analyses confirm that Li2S maintains electrode integrity by sustaining particle contact and suppressing phase decomposition. This work elucidates interfacial degradation pathways in NMC811/argyrodite systems and introduces a low-cost, scalable strategy to stabilize nickel-rich oxide cathodes in ASSLMBs, advancing their practical viability.

25 ENERGY STORAGE↗
DOE OSTI2026

Mitigating electrochemical degradation in CsPbBr{sub 3} gamma detectors by organic and inorganic encapsulation.

CsPbBr3 perovskite semiconductors have emerged as a leading candidate for nextgeneration radiation detectors because of their exceptional charge transport properties, defect tolerance, and record-breaking sensitivity and energy resolution. Their long-term stability, however, is hindered by electrode-driven electrochemical decomposition, which is accelerated by moisture- and oxygen-assisted ion migration during operation. Here, we investigated organic and inorganic encapsulation strategies as both environmental barriers and means to suppress interfacial degradation pathways. Atomic layer deposition (ALD) of Al2O3 provided a conformal passivation layer that blocked environmental ingress, suppressed ionic diffusion, reduced leakage current, enhanced energy resolution and expanded the operational electric-field window beyond 5 kV∙cm1 . By contrast, organic encapsulants such as paraffin wax and polystyrene slowed moisture diffusion but did not suppress interfacial reactions, with wax extending stability to over 90 days. These results show that ALD-Al2O3 suppresses dominant interfacial degradation pathways, enabling stable, high-field operation and advancing the practical deployment of CsPbBr3 γ-ray detectors.

Unal, Mustafa↗
DOE OSTI2025

Challenges in the study of chemistry and photochemistry at air–water interfaces: Toward in situ monitoring of reaction kinetics with spectroscopic techniques

Air–water interfaces, including those on droplet surfaces, have been the subject of many recent experiments due to their propensity for unique chemistry. Here, in this study, an overview of some recent advancements in understanding interfacial reaction kinetics is provided, highlighting non-surface-specific methods—such as mass spectrometry—compared with the advantages of surface-specific techniques—such as reflection–absorption spectroscopy, sum frequency generation, and photoelectron spectroscopy. This Perspective discusses the information depth and time constraints of common surface-specific spectroscopic methods that need to be addressed to monitor interfacial chemistry in situ and uses a few key examples from the literature as case studies. It concludes by advocating for the continued development of advanced spectroscopic methods to further investigate interfacial chemistry, underscoring the need for interdisciplinary collaboration to bridge the gap between molecular-level insights and macroscopic observations in future research.

Air-water interface↗
DOE OSTI2026

Time-Evolved Hetero-Alkali Interphases Enable Long-Life Sulfide-Based Anode-Free Solid-State Batteries

Sulfide-based anode-free solid-state batteries (AFSSBs) offer compelling advantages in terms of energy density and safety, yet their practical implementation is severely hindered by undesirable interfacial reactions between sulfide solid electrolytes (SEs) and freshly plated lithium (Li), as well as non-uniform Li plating/stripping behavior. Herein, an effective interfacial stabilization strategy by incorporating sodium bis(fluorosulfonyl)imide (NaFSI) additive into the Li5.4PS4.4Cl1.6 (LPSC) is investigated. Unlike conventional Li-based additives that form static passivation layers, NaFSI introduces a transient hetero-alkali chemistry that kinetically governs interphase evolution during fresh Li plating. NaFSI induces a timesequenced interphase evolution: an initial NaF/LiF-rich layer that suppresses early sulfide reduction, followed by a LiF/Li3N-rich layer that optimizes Li⁺ transport during repeated anode-free cycling. This evolved robust and fast ion conducting layer mitigates interfacial impedance growth, enhances Li + transport kinetics, and suppresses localized Li growth and filamentary shorting. As a result, the anode-free full cell with NaFSI modified LPSC as the interlayer exhibits an excellent cycling stability over 500 cycles at 0.2 C with a capacity retention of 77.6%, whereas the cell with bare LPSC suffers from rapid capacity decay after 100 cycles, retaining only 32.1% of its initial capacity. This work establishes dynamic heteroalkali additive chemistry as a general strategy to kinetically program solid-solid interphases, guiding the interface design in anode-free solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Effect of Propagating Dopant Reactivity on Lattice Oxygen Loss in LLZO Solid Electrolyte Contacted with Lithium Metal

Lithium lanthanum zirconium oxide (LLZO) is widely known as the most stable solid electrolyte against lithium metal electrodes. This thermodynamic stability can be lost by the presence of dopants which are required to stabilize the cubic phase of LLZO and can be reduced by lithium metal. However, the role of oxygen in such reactions is taken for granted. In this work, the reduction of Nb-substituted LLZO (Nb-LLZO) is explored by Li metal and shows that interfacial reactions propagate and lead to the decomposition with substantial Nb 5+ reduction deep into the bulk electrolyte. Scanning Transmission Electron Microscopy with Energy Dispersive X-ray Spectroscopy and thermogravimetric analyses show much of the reduction is due to oxygen vacancies formed, leading to increased electronic conductivity mapped with conductive Atomic Force Microscopy. Density functional theory calculations indicate oxygen release is favored by increased excess lithiation of Nb-LLZO. Electrochemical impedance of polycrystalline Nb-LLZO shows the continuous evolution of ionically resistive interphases near the lithium metal interface with Nb-LLZO while single crystals show little reactivity at room temperature and self-limiting reduction at 60°C. This work underlines the role of grain boundaries in propagating destructive solid electrolyte reactions and highlights previously unseen mechanisms involving lattice oxygen in LLZO.

Li metal, solid-state electrolytes↗
DOE OSTI2024

Variation in Cation Adsorption Mechanism Controlled by Chemical and Structural Heterogeneities at the Quartz (101)–Water Interface

Mineral–water interfacial reactions are central to chemical processes that control the fate of nutrients and contaminants in natural environments. Mineral surfaces commonly have complex structures and compositions whose impact on interfacial reactivity is poorly understood. Here, in this work, we investigated the effects of surface heterogeneities on Rb + sorption at the quartz (101)–10 mM RbCl solution interface at pH 9.8 using in situ high-resolution X-ray reflectivity. Two surface locales (i.e., Spots A and B) having distinct interfacial structures were chosen: Spot A was characterized by its low defect density (≤20% topmost Si vacancies) and Rb + adsorption occurred predominantly as an inner-sphere complex. In comparison, Spot B had a higher defect density (~50% vacancies) and was covered with poorly crystalline SiO 2 . A substantially larger Rb + uptake (i.e., 7-times higher coverage) was observed on this defective surface where Rb + incorporated in the vacancy sites (confirmed by density functional tight binding-based molecular dynamics simulations) or adsorbed directly on the disordered film. These results provide a direct quantification of how surface heterogeneity influences the geochemical behavior of mineral–water interfaces, in particular highlighting the important role of chemical and structural defects on the sorbate speciation and coverage at silicate mineral surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗