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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 OSTI2024

In Situ Cyclized Polyacrylonitrile Coating: Key to Stabilizing Porous High-Entropy Oxide Anodes for High-Performance Lithium-Ion Batteries

High-entropy oxides (HEOs) composed of multiple metal elements have attracted great attention as anode materials for lithium-ion batteries (LIBs) due to the synergistic effects of various metal species. However, the practical applications of HEOs are still plagued by poor conductivity, unstable solid electrolyte interphase (SEI) and poor cycling stability. In this work, nanosized (FeCoNiCrMn) 3 O 4 HEO (NHEO) is prepared successfully by the NaCl-assisted mechanical ball-milling strategy. Novelly, polyacrylonitrile (PAN) is used as the binder and then in situ thermochemically cyclized to construct a cyclized PAN (cPAN) outer layer onto NHEO (NHEO-cPAN). The in situ formed cPAN coating not only improves the electrical conductivity, but also reinforces the structural and interfacial stability, and thereby, the resulted NHEO-cPAN electrode exhibits significantly enhanced rate and cyclic performance. Specifically, NHEO-PAN500 electrode delivers a high reversible capacity of 560 mAh g –1 at 5 A g –1 and a high-capacity retention of 83% over 800 cycles at 3 A g –1 . Furthermore, the structural evolution and electrochemical behavior of NHEO-PAN electrode during discharge/charge is systematically investigated by operando X-ray diffraction, in situ impedance spectroscopy and ex situ high-resolution transmission electron microscopy. Therefore, this work provides new insights into the engineering of electrode and interphase for high-performance HEO electrode materials, potentially enlightening the practical applications of HEO-based LIBs.

25 ENERGY STORAGE↗
DOE OSTI2024

Deep-Learning Interatomic Potential Connects Molecular Structural Ordering to the Macroscale Properties of Polyacrylonitrile

Polyacrylonitrile (PAN) is an important commercial polymer, bearing atactic stereochemistry resulting from nonselective radical polymerization. As such, an accurate, fundamental understanding of governing interactions among PAN molecular units is indispensable for advancing the design principles of final products at reduced processability costs. While ab initio molecular dynamics (AIMD) simulations can provide the necessary accuracy for treating key interactions in polar polymers, such as dipole–dipole interactions and hydrogen bonding, and analyzing their influence on the molecular orientation, their implementation is limited to small molecules only. Herein, we show that the neural network interatomic potentials (NNIPs) that are trained on the small-scale AIMD data (acquired for oligomers) can be efficiently employed to examine the structures and properties at large scales (polymers). NNIP provides critical insight into intra- and interchain hydrogen-bonding and dipolar correlations and accurately predicts the amorphous bulk PAN structure validated by modeling the experimental X-ray structure factor. Furthermore, the NNIP-predicted PAN properties, such as density and elastic modulus, are in good agreement with their experimental values. Overall, the trend in the elastic modulus is found to correlate strongly with the PAN structural orientations encoded in the Hermans orientation factor. In conclusion, this study enables the ability to predict the structure–property relations for PAN and analogues with sustainable ab initio accuracy across scales.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Characterization of thermally heat-treated polyacrylonitrile carbon fibers

This study investigates the graphitization process of polyacrylonitrile (PAN) carbon fibers by subjecting commercial fibers to thermal heat treatment at temperatures ranging from 1400 to 2100 °C in 100 °C increments, using either argon or nitrogen gas atmospheres. Changes in crystallinity, surface morphology, and lattice parameters were analyzed for two commercial carbon fibers using X-ray diffraction, scanning electron microscopy, and Raman spectroscopy. Results indicated minimal changes in surface morphology with increasing heat-treatment temperature; however, crystallinity significantly increased. Crystallinity changes were more strongly dependent on temperature rather than gas atmosphere or fiber type. At intermediate heat-treatment temperatures (1600–1800 °C), fibers treated in argon showed a slight preference for graphitization. The highest level of graphitization was measured at 2100 °C. Crystallite size increased as the intensity ratio of the D1 to G Raman peaks increased, reaching a peak around ~1800 °C, after which the ratio started to decrease. This behavior aligns with Ferrari's three-stage model of carbon crystallization and is consistent with both the Marie-Mering degree of graphitization and Brubaker's Integrated Absolute Differential models, all of which describe the transformation from an amorphous to a more graphitic structure. At the higher heat-treatment temperatures, the changes between atmospheres and fiber types were measured to converge to similar levels of graphitization. In conclusion, this study evaluates the progressive change in commercial grade carbon fibers when heat-treated.

Characterization↗
DOE OSTI2026

Concerted Electron-Ion Transport by Polyacrylonitrile Elucidated with Reactive Deep Learning Potentials

Charge transport in polymers, such as polyacrylonitrile (PAN), is crucial for electronics and energy storage. For instance, PAN can transport cations e.g., Li + , by facilitating dynamic cation-nitrile coordination in batteries. However, little is known regarding the underlying role of complex reactive polymer configurations. Herein, we develop a deep-learning potential, trained on ab initio energies and forces of nonequilibrium reactive PAN configurations, to unravel the kinetics of PAN cyclization initiated by a nucleophile (OH – dissociated from LiOH) attacking the terminal nitrile carbon. We find, based on the reaction free-energetics, rates, and charge analysis, that the nucleophile attack producing the first ring is the rate-limiting step, which subsequently triggers Li + -coupled electron transfer along the PAN backbone, causing ∼10 4 times faster sequential ring-formation of the remaining nitriles. PAN’s extended configurations, where dipolar and H-bonding interactions are minimal, enable such rapid kinetics. By validating our computational findings with IR and NMR experiments, we establish a pathway for designing reactive polymers with enhanced charge transport for energy applications.

Chahal-Crockett, Rajni [Oak Ridge National Laborat↗
DOE OSTI2024

Molecular structures of residual solvent in polyacrylonitrile based electrolytes: Implications for conductivity and stability

Lithium-ion batteries increasingly play significant roles in modern technologies; however, increased energy density also raises concerns about electrolyte safety. Traditional electrolytes that use volatile organic solvents face risks of thermal runaways and fires from electrode shorting. In response, polymer-based solid electrolytes have been developed for replacement. Polyacrylonitrile (PAN) is a promising fire-resistant component for electrolyte fabrication, but its limited solubility necessitates using low-volatility solvents, which are notoriously difficult to remove in subsequent drying processes. Here, we use femtosecond two-dimensional infrared spectroscopy to provide an in-depth understanding of how residual solvent from processing affects the molecular structures and dynamics within a polymer electrolyte. To this end, linear and nonlinear infrared spectroscopies are employed to interrogate the molecular interactions in PAN-based electrolytes containing various contents of N,N-dimethylformamide (DMF). We show that the amount of DMF within the PAN electrolyte affects the Li+ structure. Further, the coordination can proceed through the carbonyl group and/or the amide nitrogen to form antiparallel structures with the nitrile groups of PAN through dipole–dipole interactions. The free motion of DMF is drastically inhibited upon interaction with Li+ and PAN, which decreases the ionic conductivity and potentially affects the stability (resistance toward removal and chemical decomposition). These findings have implications for the design and processing of solid polymer electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Revealing key structures for reversible sulfur redox in amorphous polymeric sulfur

Amorphous polymeric sulfur cathodes, such as sulfurized polyacrylonitrile (SPAN), enable high-energy lithium-sulfur batteries without cobalt or nickel, leveraging abundant sulfur. However, the limited in situ understanding of their synthesis and electrochemistry has impeded targeted optimization. Here, in this study, we integrate operando high-energy total scattering with sulfur K-edge X-ray absorption spectroscopy to monitor SPAN's formation and cycling in real time. Our results show that S-C bond formation halts further fusion of cyclized polyacrylonitrile, fostering π-π stacking and a transition from long-chain to short-chain sulfur-critical for reversible sulfur redox. These features synergistically minimize polysulfide dissolution and charge-transfer resistance, enabling optimized SPAN to achieve high capacity retention over 1,000 cycles. Operando X-ray absorption spectroscopy reveals that residual protons drive thiol-thione tautomerism, with lithium replacement during the first discharge causing ~20% irreversible capacity loss. To enhance performance, minimizing -NH groups and expanding pyridine networks are key. These findings transform SPAN optimization from empirical tuning to mechanism‑guided engineering and point the way towards sulfur loadings and energy densities competitive with state‑of‑the‑art Li‑ion cathodes.

25 ENERGY STORAGE↗
DOE OSTI2026

Uranium Sorbent Development

This report describes the synthesis of amidoxime-based sorbents for uranium extraction from natural waters. Two sorbents were tested, a commercial polyacrylonitrile-based commercial yarn and a nonwoven polypropylene fabric that was grafted with polyacrylonitrile and itaconic acid. The commercial yarn was chosen due to the ease of access and anticipated reproducibility. The polypropylene fabric was produced exclusively during the previous DOE funded Uranium from Seawater campaign and is no longer available. The polypropylene fabric represented a comparison against material developed to extract uranium from seawater, not freshwater.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Facile synthesis of co-doped Carbon nanofibers for supercapacitor applications

Here, in this study, the synthesis and electrochemical performance of carbon nanofibers (CNFs) co-doped with aluminum (Al) and nitrogen (N) and decorated with zinc oxide (ZnO) nanoparticles are investigated. After electrospinning polyacrylonitrile (PAN) nanofibers, the nanofiber mats are coated with Al and ZnO precursors by the dip coating method and converted into carbon nanofibers by thermal treatments at 850 °C. Co-doping and nanoparticle decoration affect the efficacy of carbon nanofibers as supercapacitors. With a maximal specific capacitance of 206.28 Fg -1 , it is believed that our produced carbon nanofibers, which can effectively store the renewable energy resources required to meet the rising energy demand, offer superior electrochemical properties compared to traditional supercapacitor materials. The effective incorporation of Al, N, and ZnO into the CNF structure, in conjunction with enhanced electrochemical performance, represents a significant advancement in the development of functional carbon nanofibers.

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

Designing Physicochemically‐Ordered Interphases for High‐Performance Composites

To enhance the mechanical properties of carbon fiber‐reinforced polymer composites, a physicochemical scaffold is designed incorporating microscopically architected chemically reactive nanofibers that act as a multiscale bridge between the carbon fibers and the matrix. Thermally activated nanofibers leverage their morphologically driven mechanochemical properties to form covalent bonds with adjacent polymer molecules, creating a co‐continuous network that dramatically enhances fiber‐matrix load transfer. By meticulously controlling the nanofiber architecture through variable surface area, functional group availability, and polymer chain alignment effects, the extent of covalent bonding between nanofibers and the matrix is manipulated ultimately resulting in improved carbon fiber‐matrix adhesion. Further, the concept was validated using polyacrylonitrile nanofibers within an acrylonitrile butadiene styrene matrix in a discontinuous carbon fiber‐reinforced composite system. Nanomechanical studies using atomic force microscopy and low‐field nuclear magnetic resonance spectroscopy confirmed immobilized, chemically transferred, and ordered nanostructures at the interphase. The resulting composites demonstrated ≈56% and ≈175% improvements in tensile strength and toughness, respectively, compared to composites without nanofiber. Comprehensive thermal, rheological, and X‐ray scattering analyses, along side all‐atomic molecular dynamics simulations, revealed the fundamental mechanisms behind these improvements in mechanical behavior. The versatility and efficacy of the approach have the potential to address longstanding interphase challenges in the composite industry.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Composite Lithium Metal Structure to Mitigate Pulverization and Enable Long‐Life Batteries

In lithium metal batteries, non‐uniform stripping of lithium results in pit formation, which promotes subsequent non‐uniform, dendritic deposition. This viscous cycle leads to pulverization of lithium which promotes cell shorting or capacity degradation, symptoms further exaggerated by high electrode areal loading and lean electrolytes. Here, to address this challenge, a composite lithium metal anode is engineered that contains uniformly distributed, nanometer‐sized carbon particles. This composite lithium is shown to strip more uniformly since the growth of non‐uniform pits is intercepted by the carbon particles. This mechanism is corroborated by a continuum electrochemical model. Subsequent lithium deposition on carbon particles is also found to be more uniform than on the surface with irregular pits. Notably, the pulverization rate of composite lithium is 26 times slower than that of commercial lithium. Moreover, in a Li‐S battery with sulfurized polyacrylonitrile cathode, the use of the composite anode extends the cycle life by three times when the areal capacity is 8 mAh cm −2 . The approach of using an engineered lithium composite structure to address challenges during both stripping and plating can inform future designs of lithium metal anodes for high areal capacity operations.

high areal capacity↗
DOE OSTI2026

Carbon fiber design improvements based on economic models

Circular fiber geometries are predominant in commercial carbon fiber material systems, but the use of this fiber shape has numerous limitations. Circular geometries have continuous symmetry, which is helpful for various processing considerations, but also have the largest possible maximum diffusion thickness for a given fiber area. This characteristic means that circular carbon fibers always have the highest material processing cost and lowest production throughput compared to any other fiber shape with the same area and tow count. To quantify material cost and other benefits for non-circular carbon fiber geometries, process models for polyacrylonitrile based carbon fiber production are developed in relationship to the carbon fiber shape, size, and tow count. For a given fiber shape, precursor production costs are shown to favor maximizing fiber size while conversion costs are minimized by the smallest fiber size. These competing cost trends result in a numerically optimal fiber size for a given shape and tow count, while both cost components are decreased by increasing tow count. Cost–performance tradeoffs for three lobe fiber geometries are studied by supplementing the cost trends with a numerical failure model to predict compressive strength for discrete shape variants. The shape selection is shown to be more sensitive to variations in cost than compressive strength while suboptimal shape designs can improve manufacturing robustness and achievable fiber volume fractions. Finally, an optimal three lobe carbon fiber is identified that balances the set of considerations while reducing costs and embodied energy and increasing production throughput compared to a commercial carbon fiber.

Carbon fiber↗
DOE OSTI2024

A Coordinated-Anion-Enriched Electrolyte for Lean-Electrolyte Li–S Batteries

The solid electrolyte interphase (SEI) on Li and cathode electrolyte interphase (CEI) at sulfurized polyacrylonitrile (SPAN) formed in the commonly used liquid electrolytes cannot accommodate the large volume change of both Li anode and SPAN cathode, resulting in severe electrolyte and Li consumption and fast capacity decay under high mass loading and lean electrolyte condition. Herein, a LiF-rich SEI and a LiF-Li x N y O z co-enriched CEI are simultaneously formed by adding ionic liquid (Py 13 TFSI) in the localized high-concentration electrolyte (LHCE), which forms a coordinated-anion-enriched solvation structure. In this study, the LiF-rich interphase results in less stress/strain during large volume changes of Li and SPAN and therefore achieving obviously improved stability even at a high areal capacity. Consequently, Li (50 μm)||SPAN (6 mg cm -2 ) pouch cells under the lean electrolyte condition (E/S ratio of 5 mL g SPAN -1 ) delivers a stable cycle life of 120 cycles with 79.2% capacity retention, demonstrating great promise for high-energy-density lithium-sulfur batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Advanced All-Fluorinated Electrolytes for Extended Cycle Life and Stability of Li||SPAN Batteries

Achieving long-term stability and consistent capacity in lithium (Li) metal batteries with sulfurized polyacrylonitrile (SPAN) cathodes requires precisely engineered electrolytes to optimize interphase formation and redox reversibility. Here, this study presents 1,1-difluoro-2-(2-methoxyethoxy)ethane (DFE)-based localized high-concentration electrolytes (LHCEs), incorporating fluorinated components such as salt, solvating solvent, and diluent for improved electrode stability. Molecular dynamics simulations and surface analyses reveal that the DFE-LHCE with 1,2-bis(1,1,2,2-tetrafluoroethoxy)ethane (BTFEE) diluent produces uniform and robust interphase layers on both cathode and anode, enriched with inorganic species like LiF and Li 2 O. These properties lead to prolonged redox reversibility of the SPAN cathode, suppressed side reactions, and extended cycle life for Li||SPAN cells. Remarkably, DFE-BTFEE-LHCE enables Li||SPAN coin cells with an areal capacity of ∼7 mAh cm -2 for SPAN to retain 81.3% capacity after 200 cycles and pouch cells of 0.12 Ah with 8 mAh cm -2 of SPAN and lean electrolyte to maintain 96.4% capacity over 80 cycles. These findings pave the way for advancing Li||SPAN battery technologies.

25 ENERGY STORAGE↗
DOE OSTI2026

Lithium–Sulfur Batteries Enabled by Fluorine-Free Electrolytes with a Compressed Solvation Structure

In this paper, a fluorine-free aromatic cosolvent strategy is presented to regulate electrolyte solvation chemistry in Li-S batteries with sulfurized polyacrylonitrile (SPAN) cathodes. Assisted by the Uni-ELF AI tool and experimental validation, toluene is identified as an optimal weakly solvating cosolvent. Its incorporation compresses the Li⁺ solvation sheath and induces an anion-dominated solvation structure, thereby enhancing interfacial ion transport and sulfur redox kinetics through controlled π-π interactions with polysulfides. Consequently, Li || Li symmetric cells exhibit stable cycling for over 1,000 cycles at a current density of 1 mA cm⁻². Meanwhile, Li-S cells employing high-loading SPAN cathodes retain more than 75% of their initial capacity after 250 cycles at -10 °C. Additionally, a practical pouch cell with high SPAN loading and a low electrolyte-to-SPAN ratio of 3 µL mg⁻¹ delivers an initial capacity of around 600 mAh gSPAN⁻¹, underscoring the potential of fluorine-free electrolytes for practical metal-sulfur batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Quantitative insights for diagnosing performance bottlenecks in lithium–sulfur batteries

Lithium–sulfur (Li–S) batteries hold significant promise for electric vehicles and aviation due to their high energy density and cost-effectiveness. However, understanding the root causes of performance degradation remains a formidable challenge, as the interplay of multiple factors obscures key failure mechanisms. A major limitation has been the inability to quantify soluble sulfur species within practical detection limits accurately and to correlate electrochemical processes with associated physical inventory changes. Here, we introduce the high-performance liquid chromatography-ultraviolet spectroscopy and gas chromatography sequential characterization (HUGS) toolkit, capable of precisely quantifying seven distinct sulfur and polysulfide species at concentrations as low as 40 ppb. HUGS has been successfully applied to practical coin and pouch cells without requiring cell modification. Furthermore, our self-developed software, Dr HUGS, enhanced the data analysis speed by over 30 times, enabling multi-source data integration and delivering comprehensive analysis results within minutes. Using HUGS, we identify significant capacity losses from inactive lithium and sulfur during initial cycles and sulfide-rich solid–electrolyte interphase (SEI) formation on the anode during later cycles. Notably, our findings reveal that soluble polysulfides have minimal contributions to capacity loss, challenging long-standing assumptions. Moreover, HUGS demonstrates that constant-pressure setups in Li–S pouch cells improve compositional uniformity compared to constant-gap configurations. For sulfurized polyacrylonitrile (SPAN) cathodes, unique issues such as non-sulfide SEI formation and lithium pulverization are observed, which can be mitigated through localized high-concentration electrolytes to enhance lithium inventory retention. By enabling precise quantification of critical inventory components, HUGS provides transformative insights into failure mechanisms across various electrolytes and cathode chemistries, guiding rational design strategies for next-generation energy storage systems.

25 ENERGY STORAGE↗
DOE OSTI2024

Iodine Capture Studies of Silver Mordenite and Novel Alternative Metal Sorbents

Radioiodine is one of the radionuclides of concern when considering reprocessing of used nuclear fuel (UNF). It is expected to be released primarily in the dissolver off-gas (DOG) stream. Sorbents that target I 2 removal from a UNF processing off gas must perform efficiently under elevated temperatures in the presence of water vapor and nitrogen oxide gasses (NOx). Many studies have been conducted that examine the adsorption of iodine species in the presence of NOx gases through reduced silver-exchanged mordenite (Ag 0 Z), a zeolite mineral. This study characterizes the effects of iodine, water vapor, and nitrogen dioxide on the adsorption of I 2 by Ag 0 Z at lower temperatures suitable for comparison with novel Cu- and Bi- bearing sorbents which offer a non-RCRA alternative. When exposed to ‘harsh’ conditions such as I 2 , H 2 O, and NO 2 vapors carried by air, Cu 2 S-polyacrylonitrile (PAN) is more efficient than Ag 0 Z and all other novel sorbents, providing with 11% I capture efficiency. However, under ‘ideal’ conditions in which I 2 is carried by dry air), Ag 0 Z is more efficient than Cu 2 S-PAN and other novel sorbents, providing 74% I capture efficiency. To investigate this result and the overall performance of all sorbents tested, several characterization techniques were employed, including thermal gravimetric analysis, scanning electron microscopy – electron dispersion X-Ray spectroscopy, powder X-ray diffraction, and X-ray photoelectron spectroscopy. These techniques are discussed within this report. This document also includes a design and test plan update from Idaho National Laboratory as the next step in testing the high performing sorbents from thin-bed tests carried out by Oak Ridge National Laboratory.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Low-Cost, High-Performance Carbon Fiber for Compressed Natural Gas Storage Tanks (Final Technical Report – Down Select Report)

The aim of this project is to reduce the cost of Type IV, carbon fiber (CF) composite overwrap compressed gas storage tanks by reducing the cost of CF and CF composites. The project team worked to reduce the cost of CF by exploring and testing opportunities for a low-cost alternative precursor material for CF production to supplant market-dominant and costly polyacrylonitrile (PAN). Concurrently, the team aimed to reduce the cost of the tanks at the composite level by improving the interfacial adhesion between the fibers and the matrix resin through the incorporation of low-cost nanoparticles recycled from waste materials, which would reduce the volume of costly CF required to achieve the same tank performance. At the end of the first year, the project team selected mesophase pitch as the primary precursor candidate from a field of materials based on the superior mechanical performance and cost-saving potential. During the second year, the team produced CFs derived from mesophase pitch achieving an average tensile strength of 365.6 ksi and average tensile modulus of 40.74 Msi. Facility availability for spinning and converting these fibers at greater scale has hindered scale-up demonstration, but the team has identified opportunities to conduct this work in the near term. Cost modeling shows that these mesophase pitch-derived CFs can be up to 40% less expensive than PAN-derived CFs due to the lower cost of the feedstock material, higher throughput, greater conversion yield, and lower cost spinning method and compared to PAN. Additionally, the team has demonstrated at lab-scale that nanoparticle coating CFs can significantly increase the interfacial shear strength and load transfer efficiency of CFs in a matrix. Single filament pull-out testing showed a 27% average increase in max interfacial shear strength due to this coating. A continuous method of applying these coatings to a tow of CF has been developed for scale-up. 26 m tows of coated CFs were produced using this system and formed into composite ring samples for ASTM ring burst testing. Issues with the testing protocol have limited assessment of these results. A prototype Type IV tank was designed to meet ANSI HGV2 standards, and the design criteria set out by DOE, using the CF properties developed by the team paired with a proprietary resin matrix, a polyamide liner, and aluminum end bosses. The tank weighs 153.1 kg and with a total capacity of 5.8 kg H2 (5.6 kg usable), which yields a gravimetric capacity of 1.17 kWh/kg. Cost modeling predicts that the tank will have a projected cost of $15.73/kWh. Tank performance modeling does not include considerations for fiber-matrix load transfer efficiency improvements offered by nanoparticle coating method.

08 HYDROGEN↗