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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Plasma surface modification coupled with thermal and step-over distance effects on significant fracture improvement of adhesively-bonded metal-$\mathrm{CFRTP}$ dissimilar materials

Here, this work proposes an approach to improve the interfacial bonding between carbon-fiber-reinforced thermoplastic polymers (CFRTP) and thermoset adhesive by using the surface modification with the combination of air plasma, thermal, and step-over effects. Thanks to the proper heating which causes the exposure of carbon fibers on the CFRTP surface, both polymer matrix and these exposed carbon fibers can have improved bonding with adhesive due to air plasma treatment. By conducting the Double Cantilever Beam (DCB) tests performed on adhesively-bonded AA5052/CFRP-PA66 dissimilar joints, it was shown in this work that the average Mode I specific fracture energy can be improved up to about 180% compared to non-treated counterparts. The foregoing improvement can be further increased by considering the step-over distance of the surface treatment, which triggers the tortuous damage path in the failure process of adhesively-bonded structures. By manipulating this treatment parameter, often overlooked in the literature, and other parameters (i.e., treatment speed, nozzle tip-to-surface distance, etc.) investigated in this study, the average Mode I specific fracture energy of adhesively-bonded AA5052/CFRP-PA66 dissimilar joints can be improved reaching up to about 410% compared to non-treatment counterparts.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Engineering the Si Anode Interface via Particle Surface Modification: Embedded Organic Carbonates Lead to Enhanced Performance

Si nanoparticles (SiNPs) are recognized as a promising anode material for next-generation high-energy lithium-ion batteries. However, due to the more stringent requirements resulting from severe volume change, the solid-electrolyte interphase (SEI) on SiNPs plays a critical role in determining their cycling performance. Engineering the interface for higher stability has become an effective yet challenging approach to accommodate the deterioration of the silicon anode from the repeated lithiation/delithiation process. Herein, we report a novel approach of engineering a covalently bonded organic monolayer of ethylene carbonates onto the surface of the SiNPs that can help form a sturdy SEI. Finally, this molecule-level surface modification provides an effective approach to enable high-energy lithium-ion batteries with Si anodes.

25 ENERGY STORAGE↗
DOE OSTI2020

Surface Modification of Backsheets Using Coupling Agents for Roll-To-Roll Processed Thin-Film Solar Photovoltaic (PV) Module Packaging Application

For many flexible electronic and photonic devices, moisture stability is one of the most important factors that affects its short- and long-term performance. To maintain the performance, the device should be packaged in such a way that it hermetically blocks moisture from the device; however, in practice, it is rather difficult to achieve. The more practical solution is to impede the moisture ingress to the device. In optoelectronic devices that will be outdoors like solar cells, the interfacial adhesion strength between the encapsulant layer (adhesive) and a moisture barrier layer is also a critical parameter. This paper presents surface modifications of poly(ethylene terephthalate) (PET) carrier films, one of the layers in the trilayer barrier film that directly adheres to an encapsulant, using chemical, UV/ozone, and both treatments to improve adhesion with the thermoset encapsulant polymer material. Whereas previous studies also utilized treatment methods to increase the wettability characteristics, in this paper, we not only present the results of the adhesion strength upon various techniques to achieve good adhesion but also screen their behavior upon exposure to a damp–heat (60 °C, 90% RH) environment. Here, we found that the combined treatment method increases the adhesion by up to 12.1-fold and demonstrates up to a 200% increase in adhesion strength even upon our severe damp–heat environmental condition.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Surface modification of cathode material enhances electrochemical performance in dry-processed Li-ion battery electrodes

The transition to electric vehicles (EVs) is pivotal for achieving energy security and integrating grid stability, with lithium-ion batteries (LIBs) playing a central role in this transformation. However, the conventional wet electrode manufacturing relying on N-methyl-2-pyrrolidone (NMP) solvent is energy intensive and costly. Dry processing (DP) has emerged as a promising alternative, eliminating solvents and using polytetrafluoroethylene (PTFE) binder for electrode fabrications. Despite its advantages, DP faces a critical challenge: poor interfacial adhesion between the hydrophobic PTFE binder and the hydrophilic cathode active material (CAM), particularly LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811), which undermines electrode performance. Here, to address this, we introduced a novel vapor-phase trimethoxymethylsilane (TMMS) coating to hydrophobize the CAM surface, enhancing compatibility with PTFE. This surface modification significantly enhances binder – CAM interactions, enabling uniform mixing and robust electrode integrity without damaging the CAM particles. Our findings advance the feasibility of environmentally sustainable and cost-effective dry processing, representing a significant step toward sustainable battery manufacturing.

Choi, Junbin [Oak Ridge National Laboratory (ORNL)↗
DOE OSTI2021

Segregation resistant perovskite oxides with surface modification

A method and a composition to stabilize the surface cation chemistry of the perovskite or related oxides, and thus, to minimize or completely avoid the detrimental segregation and phase separation of dopant cations at the surface can include modifying the surface with more oxidizable metal cations and/or more oxidizable metal oxides, thereby reducing the oxygen vacancy concentration at the very surface.

Yildiz, Bilge↗
DOE OSTI2021

Nucleobase-Functionalized Poly(alkylthiophene)s: One-Pot, Sequential Direct Arylation Polymerization and Deprotection, and Surface Modification for Oil–Water Separations

Direct arylation polymerization (DArP) has emerged as an environmentally friendly, atom efficient method of synthesizing a variety of conjugated polymers. In this work, we report a one-pot approach consisting of DArP followed by Boc deprotection to synthesize a functional, surface-active adenine-containing poly(alkylthiophene). Careful control over the polymerization temperature enables the one-pot polymerization and deprotection strategy for synthesis, with quantitative (>99%) Boc deprotection achieved in 24 h. This temperature-controlled synthesis method reduces extra purification and isolation steps, which makes the total synthesis more efficient and practical, and allows higher molecular weight polymer to be made. We quantify the hydrogen bonding ability of the resulting adenine-containing polythiophene, T Ad -tT 4h , by 1 H NMR host–guest titration studies and analyze the results with the Benesi–Hildebrand model, yielding an association constant of 18.7 M –1 between alkylated thymine and T Ad -tT 4h . We demonstrate that T Ad -tT 4h robustly modifies the surface of cellulosic filter paper (CFP), and the modified cellulosic filter paper, CFP-T Ad -tT 4h , is an effective oil–water separatory filter with superhydrophobic properties (water contact angle (CA) ~151°). The utility of hydrogen bonding interactions between adenine and cellulose highlights the importance of side-chain engineering for creating functional materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

An improved oxygen reduction reaction activity and CO 2 -tolerance of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ achieved by a surface modification with barium cobaltite coatings

Solid oxide fuel cells (SOFCs) cathode often suffers from the poisoning effect of the contaminants commonly encountered in air such as CO 2 . Here we report an effective approach to enhancing the activity and CO 2 tolerance of the state-of-the-art La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) cathode enabled by a coating of BaCoO 3-δ (BCO), as verified by the electrochemical testings, Raman analyses, and density functional theory calculations. When surface modified with a thin-film BCO coating, LSCF displays a much enhanced ORR activity and an improved durability against CO 2 . For example, anode supported SOFCs with the LSCF cathode coated with BCO coatings show a remarkable peak power density (Pmax) of 0.41 Wcm -2 and a significantly reduced degradation rate in current density of ~0.08% h -1 at 0.8 V and 700 °C for a period of 300 hs when humidified H2 (with 3 vol%H2O) was used as fuel and air with 8 vol% CO 2 as oxidant. The demonstrated performance is improved when compared with those of the cells with a blank LSCF electrode (a Pmax of ~0.36 Wcm -2 and a degradation rate of ~0.15% h -1 ) under the same conditions. Furthermore, the adsorption energy calculations suggests that BCO coating makes CO 2 adsorption much weaker than LSCF (-0.54 eV versus -1.07 eV).

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2024

Plasma-assisted surface modification of biopolymers

The interaction of non-thermal plasmas with surfaces is an important problem of interest in various applications. This work focuses on two main aspects of the problem - simulation and experiments. The development of a low-temperature plasma modeling is described along with experiments focusing on the interaction of a low-temperature plasma with liquid water. The simulation framework is capable of handling arbitrary geometries, chemistry and a fully-coupled boundary condition for plasma-dielectric interface. Representative examples for the verification and validation of the framework are provided. The experimental work deals with the study of low-temperature plasmas with water with the nitrate injection rate compared for three different configurations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Covalent surface modifications and superconductivity of two-dimensional metal carbide MXenes

Versatile chemical transformations of surface functional groups in two-dimensional transition-metal carbides (MXenes) open up a previously unexplored design space for this broad class of functional materials. We introduce a general strategy to install and remove surface groups by performing substitution and elimination reactions in molten inorganic salts. Successful synthesis of MXenes with oxygen, imido, sulfur, chlorine, selenium, bromine, and tellurium surface terminations, as well as bare MXenes (no surface termination), was demonstrated. These MXenes show distinctive structural and electronic properties. For example, the surface groups control interatomic distances in the MXene lattice, and Ti n +1 C n ( n = 1, 2) MXenes terminated with telluride (Te 2− ) ligands show a giant (>18%) in-plane lattice expansion compared with the unstrained titanium carbide lattice. The surface groups also control superconductivity of niobium carbide MXenes.

Kamysbayev, Vladislav↗
DOE OSTI2022

Noncovalent Surface Modification of Metal–Organic Frameworks: Unscrambling Adsorption Properties via Isothermal Titration Calorimetry

Despite the importance of noncovalent interactions in the utilization of metal–organic frameworks (MOFs), using these interactions to functionalize MOFs has rarely been explored. The ease of functionalization and potential for surface-selective functionalization makes modification via noncovalent interactions promising for the creation of porous photocatalytic assemblies. Here, using isothermal titration calorimetry, photoluminescence measurements, and desorption experiments, we have explored the nature and magnitude of the interactions of [Ru(bpy) 2 (bpy-R)] 2+ -functionalized dyes with the surface of MIL-96, where R = C 3 , C 8 , C 12 , and C 18 alkyl chains of either straight-chain or cyclic conformations. The orientation of the dyes appears to be flat against the surface with respect to the long alkyl chains, and the surface concentration approaches a monolayer at high initial concentrations of dye. Strangely, the dodecyl-functionalized dye, despite having a smaller interaction energy and larger footprint than either octyl-functionalized dye, achieves the highest maximum surface concentration. Based on photoluminescence spectra, desorption experiments, and ITC data, we believe this is due to the core of the dye being lifted from the surface as the chain length increases. Our understanding of these interactions is important for further utilization of this method for the functionalization of the internal and external surface areas of MOFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Boosting CO 2 Electrochemical Reduction with Atomically Precise Surface Modification on Gold Nanoclusters

Thiolate-protected gold nanoclusters (NCs) are promising catalytic materials for the electrochemical CO 2 reduction reaction (CO 2 RR). In this work an atomic level modification of a Au 23 NC is made by substituting two surface Au atoms with two Cd atoms, and it enhances the CO 2 RR selectivity to 90–95 % at the applied potential between -0.5 to -0.9 V, which is doubled compared to that of the undoped Au 23 . Additionally, the Cd-doped Au 19 Cd 2 exhibits the highest CO 2 RR activity (2200 mA mg -1 at -1.0 V vs. RHE) among the reported NCs. This synergetic effect between Au and Cd is remarkable. Density-functional theory calculations reveal that the exposure of a sulfur active site upon partial ligand removal provides an energetically feasible CO 2 RR pathway. The thermodynamic energy barrier for CO formation is 0.74 eV lower on Au 19 Cd 2 than on Au 23 . Here these results reveal that Cd doping can boost the CO 2 RR performance of Au NCs by modifying the surface geometry and electronic structure, which further changes the intermediate binding energy. This work offers insights into the surface doping mechanism of the CO 2 RR and bimetallic synergism.

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

Improved interfacial li-ion transport in composite polymer electrolytes via surface modification of LLZO

Composite polymer electrolytes that incorporate ceramic fillers in a polymer matrix offer mechanical strength and flexibility as solid electrolytes for lithium metal batteries. However, fast Li + transport between polymer and Li + -conductive filler phases is not a simple achievement due to high barriers for Li + exchange across the interphase. This study demonstrates how modification of Li 7 La 3 Zr 2 O 12 (LLZO) nanofiller surfaces with silane chemistries influences Li + transport at local and global electrolyte scales. Anhydrous reactions covalently link amine-functionalized silanes [(3-aminopropyl)triethoxysilane (APTES)] to LLZO nanoparticles, which protects LLZO in air. APTES functionalization lowers the poly (ethylene oxide) (PEO)-LLZO interphase resistance to half that of unmodified LLZO and increases effective Li + transference number, while insulating Al 2 O 3 completely blocks ion exchange and lowers transference number and conductivity in PEO-lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-LLZO composites. Modeling an inner resistive interphase between LLZO and PEO surrounded by an outer conductive interphase explains non-linear conductivity trends. Solid-state 7 Li & 6 Li nuclear magnetic resonance shows Li + only exchanges between PEO-LiTFSI and some LLZO interphase, with no appreciable Li + transport through bulk LLZO. Surface functionalization is a promising path toward lowering the polymer-ceramic interphase resistance. This work demonstrates that local changes in Li + transport affect macroscopic performance, highlighting the intricate relationships between all interfaces in inherently heterogeneous composite polymer electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2025

Hybrid Doping Strategy with High‐Entropy Cu/Fe Surface Modification and Zr Bulk Incorporation for Ni‐Rich Cathodes

A hybrid doping strategy combining Zr 4+ bulk doping with high-entropy Cu 2+ /Fe 3+ surface doping is developed to enhance the structural and interfacial stability of Ni-rich layered oxide cathodes. Cu and Fe are selectively introduced at the particle surface via a surface-selective ion-exchange process, forming a ≈15 nm Fe-rich layer while preserving the layered framework. Compared to the pristine cathode, the hybrid sample exhibits significantly improved electrochemical performance in both half-cell and full-cell configurations. In half-cells, the hybrid retains 88.5% and 90.2% after 100 cycles at 1C under 4.6 and 4.5 V, respectively. During high-voltage full-cell cycling, the hybrid cathode maintains over 80% capacity retention, whereas the pristine counterpart retains less than 10% under identical conditions over the same cycling period. XPS, EELS, and DEMS analyses confirm improved oxygen retention, suppressed gas evolution, and stable surface chemistry, while DFT calculations indicate enhanced Me–O bonding in the selected Fe 0.75 Cu 0.25 (Mn 1/16 Co 2/16 Ni 13/16 )O 2 surface composition, which is identified through DFT-calculated mixing energy reaching a minimum at this ratio, indicating the most thermodynamically favorable configuration. In conclusion, these results demonstrate the effectiveness of this hybrid doping strategy in mitigating coupled degradation pathways in Ni-rich cathodes.

15 GEOTHERMAL ENERGY↗
DOE OSTI2021

Near-surface modification of defective KTaO 3 by ionizing ion irradiation

The synergistic effect of nuclear (S n ) and electronic (S e ) energy loss observed in some ABO 3 perovskites has attracted considerable attention due to the real possibility to modify various near-surface properties, such as the electronic and optical properties, by patterning ion tracks in the defective near-surface regions. In this study, we show that low-energy ion-induced disordering in conjunction with ionizing ion irradiation (18 MeV Si, 21 MeV Ni and 91.6 MeV Xe) is a promising approach for tailoring ion tracks in the near-surface of defective KTaO 3 . Experimental characterization and computer simulations reveal that the size of these latent ion tracks increases with S e and level of pre-existing damage. These results further reveal that the threshold S e value (S e th ) for track creation increases with decreasing pre-damage level. The values of S e th increase from 5.02 keV nm -1 , for a pre-existing fractional disorder of 0.53 in KTaO 3 , to 10.81 keV nm -1 for pristine KTaO 3 . Above these thresholds, amorphous latent tracks are produced due local melting and rapid quenching. Below a disorder fraction of 0.08 and S e ≤ 6.68 keV nm -1 , the synergistic effect is not active, and damage accumulation is suppressed due to a competing ionization-induced damage annealing process. These results indicate that, depending on S e and the amount of pre-existing damage, highly ionizing ions can either enhance or suppress damage accumulation in KTaO 3 , thus providing a pathway to tailoring defects states. Comprehending the conflicting roles of highly ionizing ions in defective ABO 3 oxides is vital for understanding and predictive modeling of ion-solid interactions in complex oxides, as well as for achieving control over ion track size in the near-surface of defective KTaO 3 .

36 MATERIALS SCIENCE↗
DOE OSTI2024

Gas-phase surface modification to control catalyst structure and yields in methane dehydroaromatization

Methane dehydroaromatization (MDA) is a promising approach for direct methane transformation to aromatics and hydrogen. The benchmark catalyst Mo/H-ZSM-5 struggles to find commercial adoption because of thermodynamically-limited yields and rapid coking on Brønsted acid and molybdenum carbide species, especially on zeolite external surfaces. Here, gas-phase atomic layer deposition (ALD) overcoats H-ZSM-5 external surfaces with SiO 2 or Al 2 O 3 . NH 3 -TPD, HRTEM, and textural properties show that these overcoats exclusively passivate zeolite external surfaces. Under MDA conditions, SiO 2 gives softer coke and increases cumulative benzene yields by 25%, while Al 2 O 3 strongly decreases yields. H 2 -TPR and UV-visible and Raman spectroscopy show how the overcoats redisperse the MoO x precatalysts, especially over multiple deactivation and isothermal oxidative regeneration cycles. Combined with 27 Al-MAS NMR, MoO x redistribution and dealumination are seen as the causes of long-term deactivation over multiple regeneration cycles, and this process continues to occur regardless of the overcoat. Altogether, the deposition of a small amount of silica on the outer surface of Mo/H-ZSM-5 reduces the formation of hard coke, which could be regenerated by milder methods such as hydrogen treatment.

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

Graphene coating on silicon anodes enabled by thermal surface modification for high-energy lithium-ion batteries

Silicon is a high-energy density anode material for lithium-ion batteries, but it possesses shortcomings such as poor electronic conductivity, interfacial instability and mechanical fracturing that hinder its battery cycling. Carbon coating has been an important strategy for stabilizing silicon anodes, but the effects of the silicon surface properties on carbon coating morphology and the consequent silicon cycling stability have not been clearly elucidated. Herein, we find that thermal oxidation of the silicon anodes followed by chemical vapor deposition of carbonaceous precursors leads to a well-ordered graphene coating, whereas disordered graphite coating is formed on the native silicon surface. Graphene-coated silicon exhibits superior cycling performance, retaining a discharge capacity of ~1300 mAh g -1 after 300 cycles, whereas the disordered graphite-coated silicon suffers continuous degradation, retaining only~600 mAh g -1 after 300 cycles. Cryogenic electron microscopy reveals the mechanism behind the difference in cycling stabilities; graphene coated silicon is able to withstand the large mechanical strains induced during extended cycling, whereas disordered graphite coating is ruptured, exposing silicon surfaces to the electrolyte, leading to extensive buildup of SEI and poor cycling performance. Characterization of the silicon surface reveals that thermal treatment yields an oxygen-rich surface layer, which is hypothesized to play a decisive role in dictating the carbon coating. This work highlights the effect of silicon surface properties on carbon coating microstructure, and presents thermal treatment as a facile avenue to attain graphene coating on silicon anodes.

25 ENERGY STORAGE↗