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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Vapor-phase pillarization of MXenes for engineering hierarchical interlayer porosity

MXenes, a family of two-dimensional (2D) multilamellar materials, possess excellent thermal and electronic properties for a range of applications. Their use in heterogeneous catalysis, however, is limited by the low surface area resulting from stacked layers. Pillarization with inorganic oxides can create more open, mesoporous MXene structures, improving accessibility for guest species to diffuse, reside or react in the space between 2D layers. A previous liquid-phase pillarization method, however, involves excessive use of solvent-based precursors and multiple processing steps. Here, we report a vapor-phase pillarization (VPP) strategy to introduce pillars, exemplified by silica pillars, with high pillar precursor usage efficiency and a simplified processing workflow. The resulting silica-pillared mesoporous MXene exhibits significantly increased surface area and porosity. These textural properties can be easily tuned by the VPP synthesis conditions. When applied as a ruthenium (Ru) catalyst support for the hydrogenolysis of low-density polyethylene (LDPE), the silica-pillared MXene enabled high Ru dispersion and catalytic activity. This study highlights the potential of the VPP method for engineering mesoporous, 2D MXene materials and demonstrates the effectiveness of mesoporous MXene as a catalyst support in overcoming mass transport and active-site accessibility challenges in heterogeneous catalysis involving bulky substances, such as plastics upcycling.

Luo, Song [University of Delaware, Newark, DE (Uni↗
DOE OSTI2020

Engineering of Lead Selenide Quantum Dot Based Devices and Core/Shell Heterostructures

Near infrared (NIR) emitting colloidal quantum dots (QDs) such as PbSe are interesting materials for implementation in various optoelectronic devices such as solar cells, photodetectors, and radiation detectors. Material properties like size tunable emission wavelengths, facile solution processability, the possibility of carrier multiplication and Auger assisted up-conversion, and high Z number provide PbSe QDs with unique advantages over many currently available commercial materials used in these devices. In this dissertation, after an introduction to QDs in general, we first focus on synthesis of PbSe-based heterostructured QDs for study via optical spectroscopy. PbSe/CdSe QDs synthesized via cation exchange reaction were used as seeds to study the proper conditions for further CdSe or CdS shell growth. Optical spectroscopy studies show that growth of thicker CdSe shells leads to tunable visible emission, while growth of thick CdS shells can greatly increase the photoluminescence quantum yield (PLQY) observed from the intermediate CdSe shell. NIR PL lifetimes can be greatly enhanced by the growth of CdS shells, due to strong delocalization of the hole wavefunction within the PbSe core, while the electron is delocalized throughout the QD including in the CdS shell, resulting in radiative lifetimes in the tens of microseconds. Two pulse delay measurements show that Auger assisted up conversion is also taking place in these engineered QD dot heterostructures. In the sections that follow, we look at QD devices, first with a focus on novel devices fabricated from PbSe QDs, using an amine synthesis method that allows for facile in-solution ligand exchange. QD film mobilities are measured for PbSe QDs capped with various short ionic ligands. Carrier densities in PbSe QD films are calculated from C-V measurements, showing for the first time that carrier densities can be modulated by simply changing the capping ligand. vii Radiation detectors utilizing PbSe QDs capped with KI and NH4I ligands show tangible response to incident alpha radiation. Current output response to alpha radiation is dependent on strength of radiation source and amount of bias voltage applied. In the final section a critical review of hybrid layered 2D-QD photodetectors is presented. In a typical example, PbSe and PbS QDs act as the absorbing layer in phototransistor devices which utilize layered 2D materials such as graphene and transition metal dichalcogenides as transport layers. Resulting devices display high gains and improved directivities compared to QD only and 2D only devices.

36 MATERIALS SCIENCE↗
DOE OSTI2022

In Situ Probing and Investigation of the Crystal Growth of Highly Correlated Intermetallics

The proposal seeks to investigate the synthetic process of a new class of highly correlated intermetallics Ce n+1 Co n Ge 3n+1 (n = 1 – 6). This family of compounds is attractive as members of the series consist of subunits found in quantum materials. With our efforts to grow single crystals, we will address the fundamental questions of 1) how do crystals that are built from subunits form during crystallization and 2) what determines how these subunits arrange. We hypothesize that the complex intergrowth structures of Ce n+1 Co n Ge 3n+1 form upon cooling by the assembly of subunit-like clusters that exist prior to crystallization in the melt. The second hypothesis is layer-by-layer growth. The third hypothesis is an alternative growth mechanism, such as the conversion of metastable structure into a different structure. By understanding the assembly of subunits, strategies to affect process could emerge, which will ultimately lead to controlled heterostructural stacking of various subunits in the growth of bulk materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Effects of graphene surface functionalities towards controlled reinforcement of a lignin based renewable thermoplastic rubber

In this report, we describe methods to enhance mechanical properties of a renewable thermoplastic rubber by incorporating functional graphene platelets into an equal-mass mixture of lignin, a feedstock from plant biomass, and a nitrile-butadiene rubber having 41 mol % acrylonitrile content (NBR41) that form a nanocomposite. Not all lignins yield mechanically strong material when they are combined with NBR41, and thus, limit its use for such rubbery products. Here, we evaluate different graphene oxides (GO) and reduced graphene oxides (rGO) dry-powders with different surface areas, functionality, and wettability in the synthesis of performance-enhanced nanocomposites of soft lignin/NBR41 matrix via a solvent-free, high shear reactive process. High surface area GO (HSGO) platelets with strong hydrophilicity exhibit good dispersion in the multiphase lignin/NBR41 composites with lignin dispersion varying from 200 to 2000 nm, resulting in superior reinforcement over other graphene derivatives. The addition of 1–4 wt % HSGO increased the tensile stress of the lignin/NBR41 thermoplastic rubber matrix by 60–160% (15–24 MPa) and the modulus by 200–700% (60–140 MPa). Scanning electron microscopy and small angle X-ray scattering results show that the well-dispersed HSGO platelets effectively disrupt the lignin-rich aggregates in NBR41 matrix, resulting in both strength and stiffness enhancements in the formed nanocomposites. This report on performance enhancement of lignin-based renewable polymers via the production of nanocomposite would increase potential for ‘finding the value of lignin’—a grand challenge associated with modern biorefineries.

36 MATERIALS SCIENCE↗
DOE OSTI2023

L1 0 Ordering in MnAl and FeNi Influenced by Magnetic Field and Strain

Due to various materials supply chain challenges, magnets free of constrained elements are attracting increasing interest. Magnetic materials such as rare-earth free FeNi and MnAl have been receiving considerable attention due to the high magnetocrystalline anisotropy and other associated magnetic properties derived from their unique chemically ordered tetragonal crystal structure, denoted as the L1 0 structure. However, synthesis of L1 0 FeNi has had limited success due to the extremely low atomic mobilities of Fe and Ni. In this work, isostructural MnAl was first studied as proxy to understand the L1 0 ordering process. Here, evidence of L1 0 ordering in FeNi derived from TEM studies is presented, where ordering was facilitated by the application of strain and magnetic field provided during thermal treatment of a severely plastically deformed FeNi alloy.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Direct Conversion of CO 2 to Olefins over a Cr 2 O 3 /ZSM-5@CaO Cooperative and Bifunctional Material Under Isothermal Conditions

Direct conversion of point-source CO 2 into fine chemicals over cooperative and bifunctional materials (BFMs) – composed of adsorbents and catalysts – has emerged as a promising approach to improve the energy efficiency of the carbon capture and conversion processes. In this study, a bifunctional material consisting of Cr 2 O 3 /ZSM-5 catalyst and CaO adsorbent was developed and tested in the CO 2 -oxidative dehydrogenation of propane (CO 2 –ODHP) for reactive capture of CO 2 in a fixed bed reactor. First, CaO was prepared using two distinct methods: solid-state and citrate sol–gel. The citrate sol–gel method resulted in small and finely-distributed CaO particles, allowing more accessible sites for CO 2 adsorption. Consequently, a high CO 2 adsorption capacity of ~14 mmol/g was achieved with fast adsorption kinetics compared to CaO prepared by the solid-state method. The CaO adsorbent was then combined with the Cr 2 O 3 /ZSM-5 catalyst for BFM synthesis and tested in the CO 2 –ODHP process, targeting propylene production. The BFM was extensively characterized to provide insights into the BFM’s surface chemistry, morphology, and reaction mechanism in the reactive capture process of CO 2 –ODHP. The results revealed that under isothermal adsorption–reaction conditions at 600 °C, a propane conversion of 22.5%, a propylene selectivity of 55.3%, and an olefin selectivity of 67.3% were achieved. The excellent propylene selectivity was attributed to the catalyst acidity and redox property of the Cr 2 O 3 /ZSM-5 catalyst, which facilitated the reaction pathway of propane dehydrogenation in the process of CO 2 –ODHP. Overall, this study renders Cr 2 O 3 /ZSM-5@CaO as promising BFMs with high CO 2 capture capacity and catalytic activity for integrated CO 2 capture and conversion in the ODHP reaction.

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

Mechanochemistry of Phosphorus and Arsenic Alloys for Visible and Infrared Photonics

Incorporating few‐layer 2D phosphorus–arsenic alloys (PAs) into optoelectronic devices requires a synthesis technique that allows control of the alloy composition while producing volumes of material suitable for application development such as photodetectors, solar cells, and lasers. With that goal in mind, high‐energy ball milling allows production of both orthorhombic (o‐PAs) and trigonal (t‐PAs) alloys by reacting red phosphorus and metallic arsenic powders. The synthesis follows a two‐step process in which arsenic rapidly reacts with red phosphorus to first produce t‐PAs followed by a slower phase transformation into o‐PAs; synthesis time and overall conversion rate are slightly enhanced by the presence of arsenic. Optical measurements on exfoliated alloys at the few‐layer atomic limit of the 2D PAs reveal emission spanning from the visible (≈1.9 eV) into the near‐infrared region, covering a broad application space. Rapid powder synthesis within a closed system for stochiometric control of the solid‐solution PAs alloys combined with solution‐based exfoliation opens up opportunities for a whole new class of optoelectronic devices based on PA nanomaterials.

Pedersen, Samuel V.↗
DOE OSTI2020

From smart homes to smart laboratories: connected instruments for materials science

The current focus on artificial intelligence and machine learning in the scientific community has the potential to greatly speed up discovery. In this article, we explore what a “smart facility” would mean for materials science. We propose to capture meta-data at every step of an experiment, including materials synthesis, sample production and characterization, simulation, and the analysis software used to extract information. Although most of this information is captured in various institutional systems and staff logbooks, more insight could be obtained by connecting this information through a system that allows automation. AI-enabled processes built on such a system would have the potential of making experiment planning easier and minimize the time between experiment and publication.

Doucet, Mathieu↗
DOE OSTI2023

High-entropy halide perovskite single crystals stabilized by mild chemistry

High entropy materials are excellent candidates for a range of functional materials but traditionally require high-temperature synthetic procedures over 1000°C and complex processing techniques such as hot rolling to form. One route to address the extreme synthetic requirements for high entropy materials should involve designing crystal structures with ionic bonding networks and low cohesive energies. Here, we develop room-temperature (20°C) and low temperature (80°C) solution synthesis procedures for a new class of metal-halide perovskite high entropy semiconductor (HES) single crystals. Due to the soft, ionic lattice nature of the class of metal-halide perovskites, these HES single crystals are designed on the cubic Cs 2 MCl 6 (M = Zr 4+ , Sn 4+ , Te 4+ , Hf 4+ , Re 4+ , Os 4+ , Ir 4+ , or Pt 4+ ) vacancy-ordered double perovskite structure from the self-assembly of stabilized complexes in multielement inks, namely free Cs + cations and five or six different isolated [MCl6] 2- anionic octahedral molecules well-mixed in strong hydrochloric acid. The resulting single-phase single crystals span two HES families of five- and six-elements occupying the M-site as a random alloy in near-equimolar ratios, with the overall Cs 2 MCl 6 crystal structure and stoichiometry maintained. In conclusion, the incorporation of various [MCl 6 ] 2- octahedral molecular orbitals disordered across the high entropy five- and six-element Cs 2 MCl 6 single crystals produces complex vibrational and electronic structures with energy transfer interactions between the confined exciton states of the five or six different isolated octahedral molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Novel Materials R&D for Next-Generation Accelerator Target Facilities

High-Entropy Alloys and Electrospun Nanofiber materials are two classes of novel materials that can offer improved resistance to beam-induced radiation damage and thermal shock. Research to develop these new materials specifically for multi-megawatt accelerator target applications, such as beam windows and particle-production targets, are ongoing at Fermilab within the scope of a DOE Early Career Research Program. The research program combines in-beam experiments with complementary simulations to tailor the microstructures of these novel materials for use in next-generation accelerator target facilities. Iterative simulations to optimize the material composition, physics performance, and beam-induced thermomechanical response will guide the material design and fabrication processes based on established figures of merit. This will be followed by material irradiation experiments using low-energy ions and prototypic high-energy protons with extensive post-irradiation material characterization to assess and qualify the selected novel materials. This talk will describe the alloy design and synthesis, microstructural pre-characterization of the alloys, and plans for the eventual down selection following low-energy ion irradiation studies.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2020

Experimental Performance Evaluation of a Hyper-Branched Polymer Electrolyte for Rechargeable Li-Air Batteries

A hyper-branched polymer (HBP) electrolyte is synthesized for rechargeable lithium-air (Li-air) battery cell and experimentally evaluated its performance in actual battery cell environment. Several real-world battery cells were fabricated with synthesized HBP electrolyte, pure lithium metal as anode and an oxygen permeable air cathode to evaluate reproducibility of the rechargeable Li-air battery cell. The effect of various conditions such as various HBP based electrolytes, discharge current -0.1~0.5 mA, cathode preparation processes and carbon contents on the battery cell performance were experimentally evaluated using the fabricated battery cells under dry air condition. Detailed HBP electrolyte synthesis procedures and experimental performance evaluation of Li-air battery cell for various conditions are presented. The experimental results showed that different conditions and processes significantly affect the Li-air battery performance. Upon taking into account the effect of different conditions and processes, optimized HBP electrolyte materials, cathode process and conditions were determined. Several Li-air battery cells were fabricated with optimized conditions and optimized battery cell materials to determine the reproducibility and performance consistency. Experimental results showed that over 55–65 h of discharge occurred over 2.5 V terminal cell voltage with all three optimized Li-air battery cells. It implied that the optimized Li-air battery cells were reproducible and were able to hold charge over 2.5 V for more than 2 days. Experimental results of the Li-air battery cell with further refined optimized materials revealed that the battery cell can discharge more than 10 days (i.e., more than 250 h) at or above 2.0 V. The experimental results also showed that the Li-air battery discharge time got shorter as the discharge-charge cycle increases due to increase in internal resistances of battery cell materials. The experimental results confirmed that the lithium-air battery cell can be reproduced without loss of performance and can hold charge more than 10 days at or over 2.0 V. The investigation results obtained may usher a pathway to manufacture a long-life rechargeable Li-air battery cell in the near future.

25 ENERGY STORAGE↗
DOE OSTI2023

Intercalation And High-Pressure Effects On Structural Phase Transitions In Layered As x P 1-x Alloys

This project was aimed at understanding the role of composition, intercalation, and high pressure on the structural evolution of black phosphorous (BP) and layered arsenic phosphorous alloys, As y P 1-y . Under normal conditions, BP is the most stable phase of phosphorous, known as the α-phase, characterized by an orthorhombic honeycomb puckered crystal structure with the Cmca space group. On the other hand, the most stable phase of arsenic is its β-phase, known as gray arsenic (g-As), which has a rhombohedral buckled layered crystal structure with the R3m space group. In a wide range of compositions (y < 0.83), the arsenic phosphorous alloys form the α-phase, known as black arsenic phosphorous (b-As y P 1-y ) with a similar structure to BP. The project was aimed at the synthesis of BP and b-As y P 1-y with different compositions and at studying the structural evolution of these materials during intercalation with alkali metal (especially Li), and under high-pressure conditions. The main goals were to gain a better understanding of these processes and structural changes taking place under these conditions. In particular, the project was aimed at addressing whether such conditions could induce a structural transition between the α- and β-phases. For this, a series of systematic in-situ studies were conducted, including electrochemical lithium intercalation in an in-situ electrochemical cell, and high-pressure experiments in a diamond anvil cell (DAC). Overall, both types of experiments have shown that above a certain composition-dependent threshold level of intercalation or high pressure, the system undergoes phase segregation rather than phase transition. Specifically, the segregation of the excess arsenic was observed, and a single-phase system of b-As y P 1-y transformed into a two-phase system consisting of b-As y P 1-y and g-As, through the following process: 1∗(b-As y P 1-y ) → 1∗(b As y-δ P 1-y ) + δ∗(g-As). Also, the study showed that intercalation and high-pressure are two competing rather than synergistic processes causing at least a partial cancelation of these two factors

36 MATERIALS SCIENCE↗
DOE OSTI2020

Microclusters of Kinked Silicon Nanowires Synthesized by a Recyclable Iodide Process for High-Performance Lithium-Ion Battery Anodes

Silicon shows great promise as a high-capacity anode material for lithium-ion batteries. Nanostructuring silicon minimizes the impact of fracturing during charging and discharging. However, synthesizing nanostructured silicon typically requires complicated procedures with high manufacturing costs. Additionally, these complicated procedures typically have poor secondary particle formation, a requirement to achieve a high tap density. Here, a cost-effective synthesis procedure which generates nearly ideal secondary particle clusters of nanostructured silicon is developed. The cost-effectiveness is a result of the in operando generation of silicon iodide from iodine gas and low-grade silicon microparticle. Decomposition of silicon iodide into crystalline silicon and iodine gas enables recycling of the iodine gas, allowing for near full reutilization of iodine in the following cycles. Additionally, the optimal nanostructures and microstructures of silicon synthesized by the recyclable iodide decomposition reaction enables 83.6% capacity retention over 1000 cycles. The good performance is a result of well-maintained morphology during cycling, enabling reutilization of the solid electrolyte interphase.

25 ENERGY STORAGE↗
DOE OSTI2021

Blending Polyurethane Thermosets Using Dynamic Urethane Exchange

Recycling crosslinked polyurethanes (PUs) is accomplished through mechanical or chemical processes that are energy-intensive or produce plastics of lesser value. Polymer recycling processes are notably intolerant of polymer mixtures, yet the ability to reprocess and compatibilize two or more crosslinked PUs together will make this process more amenable to mixed waste streams while offering an opportunity to tune the properties of the recycled polymer products. Here, we blend a rigid polyester PU and a soft polyether PU using twin-screw extrusion to yield materials with tunable mechanical properties based on the feed composition. Their material properties were compared to those of compression-molded reprocessed blends and blends where the monomers were mixed prior to synthesis. The extruded materials showed similar mechanical and thermal properties to newly prepared blends and had higher-value mechanical properties compared to the samples reprocessed via compression molding. The morphologies of the blends were observed using phase imaging via atomic force microscopy to show that there is less phase separation in the extruded materials compared to compression-molded blends. The mechanical properties of these materials were tunable from soft to elastomeric to rigid based on the feed composition, and this tunability was demonstrated through four consecutive reprocessing cycles, through which the mechanical properties were steadily varied from rigid to soft by incorporating increasing amounts of soft polyether PU material. Here, this blending method for reprocessing mixed waste compatibilizes different PUs and provides a means to tune the mechanical properties of a PU product, even if starting from waste streams of varying compositions. As such, this process represents an intriguing new approach for polymer reprocessing.

Extrusion↗
DOE OSTI2025

Advancing the Performance of Lithium-Rich Oxides in Cooperation with Inherent Complexities: Engineering Domain Structure

The nanodomain structure of lithium- and manganese-rich, composite cathode materials has been systematically altered through synthesis conditions while keeping larger-scale morphological differences to a minimum. Clear changes in electrochemical performance across the samples studied are observed, especially with respect to the anomalous impedance at low states-of-charge. Atomic-scale modeling, coupled to electrochemical measurements and physical characterization, reveals the local consequences of the high-voltage activation charge process as a function of specific domain structures. Furthermore, the results explain the influence of different postactivation structures on the insertion of Li-ions and the associated impedance during discharge. This work adds to our series of studies on lithium- and manganese-rich oxides, demonstrating that the inherent performance of LMRs can be greatly enhanced through rational, highly controlled synthetic strategies based on an understanding of synthesis–structure–property relationships across length scales.

25 ENERGY STORAGE↗
DOE OSTI2024

Insight of Synthesis of Single Crystal Ni-Rich LiNi 1-x-y Co x Mn y O 2 Cathodes

Single-crystal Ni-rich LiNi 1-x-y Co x Mn y O 2 (NCM) cathodes have garnered widespread attention in the lithium-ion battery community due to their unique advantages in mechanical performance and their ability to minimize interfacial electrochemical side reactions. The synthesis of single-crystal materials with monodisperse and appropriate size, minimal lattice defects, and highly ordered structures is the key for high-performance batteries. However, achieving this goal poses challenges due to the lack of in-depth understanding regarding specific experimental parameters and the solid reaction mechanism during the synthesis process. Further, in this review, the aim is to provide an in-depth analysis of the critical process parameters involved in the synthesis and their impact on crystal morphology, structure, and electrochemical performance. Consequently, the first section focuses on the effect of the precursor morphology, lithium salt, atmosphere, and sintering procedure. In the second section, the study delves into an in-depth discussion of the solid reaction and crystal growth mechanism. Lastly, it is concluded by highlighting the prospects and challenges associated with the synthesis and application of single-crystal Ni-rich NCM cathodes.

25 ENERGY STORAGE↗
DOE OSTI2020

Thermodynamics and kinetics of solution combustion synthesis: Ni(NO 3 ) 2 + fuels systems

Solution combustion synthesis (SCS) utilizes exothermic self-propagating reactions to prepare nanoscale materials that can be used widely in energy, electronics, and biomedical technologies and other applications. SCS is a specific variety of a more general combustion synthesis (CS) method. Investigations of the thermodynamics, kinetics, and the mechanisms of SCS reactions, are not as well studied as the other CS processes. This work reports on a systematic study of the thermodynamics and kinetics of SCS reactions involving Ni(NO 3 ) 2 , an oxidizer, and either glycine (C 2 H 5 NO 2 ) or hexamethylenetetramine (HMT, C 6 H 12 N 4 ) as fuels. A thermodynamic modeling approach, based on the Gibbs free energy minimization principle, is applied to the simultaneous calculations of the adiabatic temperatures and compositions of the equilibrium products. Our calculations reveal the influence of fuel-to-oxidizer ratio, amount of water, and the oxygen in air on the combustion temperature under adiabatic conditions and the composition of the resulting products. We have, in turn, measured the combustion temperature and phase composition of products and compared them with the calculations. Variations of drying times for the solutions yield precursor gels with varying water contents. This approach enables the manipulation of combustion parameters and confirms the use of calculated activation energies for reactions using the Merzhanov-Khaikin method. Here, the results show that SCS reactions in fuel-lean solutions producing NiO have higher activation energy in contrast to reactions with fuel-rich solutions that form Ni. Reduction of activation energies due to the increase in the fuel-to-oxidizer ratio could be related to the observed change of the rate-limiting stages of the endothermic decomposition of the individual reactants to the exothermic decomposition of coordinate compounds formed between the reactants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗