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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Ethylene Carbonate–Free Electrolytes for Stable, Safer High–Nickel Lithium–Ion Batteries

Ethylene carbonate (EC) is an important component in state-of-the-art electrolytes for lithium-ion batteries (LIBs). However, EC is highly susceptible to oxidation on the surface of high-nickel layered oxide cathodes, making it undesirable for next-generation high-energy-density LIBs. In this study, a simple, yet effective, EC-free electrolyte (20F1.5M-1TDI) is presented by adding 20 wt% fluoroethylene carbonate (FEC) and 1 wt% lithium 4,5-dicyano-2-(trifluoromethyl)imidazole (LiTDI) into 1.5 M LiPF 6 in an ethyl methyl carbonate (EMC) electrolyte. The 20F1.5M-1TDI electrolyte is found to efficiently passivate the graphite anode and stabilize high-nickel cathodes by a synergistic decomposition of FEC and LiTDI. The LiNi 0.9 Mn 0.05 Al 0.05 O 2 (NMA90)/graphite full cell with the 20F1.5M-1TDI electrolyte, therefore, exhibits an enhanced cycling stability and a suppressed voltage hysteresis growth compared to that with an EC-containing baseline electrolyte (1 M LiPF 6 in EC:EMC, 3:7 in weight, with 2 wt% vinyl carbonate). Advanced analytical tools, such as time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy, are employed to understand the underlying working mechanism of the EC-free electrolyte. Furthermore, the present study clearly showcases the great potential of EC-free electrolytes as a straightforward, practical approach for LIBs with high-nickel cathodes.

electrode/electrolyte interface↗
DOE OSTI2022

Phenyl‐Free Polynorbornenes for Potential Anion Exchange Ionomers for Fuel Cells and Electrolyzers

Abstract Ionomers in the catalyst layer play a critical role in the performance of fuel cells and electrolyzers. Phenyl adsorption on hydrogen oxidation catalysts and electrochemical oxidation of phenyl moieties on oxygen evolution catalysts are detrimental to the alkaline devices’ performance. Here the adsorption energy of phenyl‐containing ionomers is compared to provide the rationale for implementing phenyl‐free ionomers. Density functional theory calculations indicated that the norbornane fragment has minimal adsorption energy on Pt(111) due to the absence of aromatic π electrons. A soluble quaternized polynorbornene ionomer is prepared by vinyl addition polymerization, and it exhibits high performance in both fuel cells and electrolyzers, proving the advantage of the phenyl‐free structure. This study establishes the phenyl adsorption energy‐electrode performance relationship, highlighting the importance of material interactions between the catalysts and ionomers.

25 ENERGY STORAGE↗
DOE OSTI2020

Polyethylene Terephthalate Deconstruction Catalyzed by a Carbon‐Supported Single‐Site Molybdenum‐Dioxo Complex

Abstract Polyethylene terephthalate (PET) is selectively depolymerized by a carbon‐supported single‐site molybdenum‐dioxo catalyst to terephthalic acid (PTA) and ethylene. The solventless reactions are most efficient under 1 atmosphere of H 2 . The catalyst exhibits high stability and can be recycled multiple times without loss of activity. Waste beverage bottle PET or a PET + polypropylene (PP) mixture (simulating the bottle + cap) proceeds at 260 °C with complete PET deconstruction and quantitative PTA isolation. Mechanistic studies with a model diester, 1,2‐ethanediol dibenzoate, suggest the reaction proceeds by initial retro‐hydroalkoxylation/β‐C−O scission and subsequent hydrogenolysis of the vinyl benzoate intermediate.

Kratish, Yosi↗
DOE OSTI2022

A Heterogeneous Palladium Catalyst for the Polymerization of Olefins Prepared by Halide Abstraction Using Surface R 3 Si + Species

Abstract The silylium‐like surface species [ i Pr 3 Si][(R F O) 3 Al−OSi≡)] activates (N^N)Pd(CH 3 )Cl (N^N=Ar−N=CMeMeC=N−Ar, Ar=2,6‐bis(diphenylmethyl)‐4‐methylbenzene) by chloride ion abstraction to form [(N^N)Pd−CH 3 ][(R F O) 3 Al−OSi≡)] ( 1 ). A combination of FTIR, solid‐state NMR spectroscopy, and reactions with CO or vinyl chloride establish that 1 shows similar reactivity patterns as (N^N)Pd(CH 3 )Cl activated with Na[B(Ar F ) 4 ]. Multinuclear 13 C{ 27 Al} RESPDOR and 1 H{ 19 F} S‐REDOR experiments are consistent with a weakly coordinated ion‐pair between (N^N)Pd−CH 3 + and [(R F O) 3 Al−OSi≡)]. 1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd−CH 3 ] + in solution and incorporates up to 0.4 % methyl acrylate in copolymerization reactions. 1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate.

Gao, Jiaxin↗
DOE OSTI2024

Ion‐Specific Interactions Engender Dynamic and Tailorable Properties in Biomimetic Cationic Polyelectrolytes

Abstract Biomaterials such as spider silk and mussel byssi are fabricated by the dynamic manipulation of intra‐ and intermolecular biopolymer interactions. Organisms modulate solution parameters, such as pH and ion co‐solute concentration, to effect these processes. These biofabrication schemes provide a conceptual framework to develop new dynamic and responsive abiotic soft material systems. Towards these ends, the chemical diversity of readily available ionic compounds offers a broad palette to manipulate the physicochemical properties of polyelectrolytes via ion‐specific interactions. In this study, we show for the first time that the ion‐specific interactions of biomimetic polyelectrolytes engenders a variety of phase separation behaviors, creating dynamic thermal‐ and ion‐responsive soft matter that exhibits a spectrum of physical properties, spanning viscous fluids to viscoelastic and viscoplastic solids. These ion‐dependent characteristics are further rendered general by the merger of lysine and phenylalanine into a single, amphiphilic vinyl monomer. The unprecedented breadth, precision, and dynamicity in the reported ion‐dependent phase behaviors thus introduce a broad array of opportunities for the future development of responsive soft matter; properties that are poised to drive developments in critical areas such as chemical sensing, soft robotics, and additive manufacturing.

Aubrecht, Filip J.↗
DOE OSTI2022

A Heterogeneous Palladium Catalyst for the Polymerization of Olefins Prepared by Halide Abstraction Using Surface R 3 Si + Species

The silylium-like surface species [ i Pr 3 Si][(R F O) 3 Al-OSi≡)] activates (N^N)Pd(CH 3 )Cl (N^N=Ar-N=CMeMeC=N-Ar, Ar=2,6-bis(diphenylmethyl)-4-methylbenzene) by chloride ion abstraction to form [(N^N)Pd-CH 3 ][(R F O) 3 Al-OSi≡)] ( 1 ). A combination of FTIR, solid-state NMR spectroscopy, and reactions with CO or vinyl chloride establish that 1 shows similar reactivity patterns as (N^N)Pd(CH 3 )Cl activated with Na[B(Ar F ) 4 ]. Multinuclear 13 C{ 27 Al} RESPDOR and 1 H{ 19 F} S-REDOR experiments are consistent with a weakly coordinated ion-pair between (N^N)Pd-CH 3 + and [(R F O) 3 Al-OSi≡)]. 1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd-CH 3 ] + in solution and incorporates up to 0.4% methyl acrylate in copolymerization reactions. 1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate.

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

A Diazo Linker Ligand Promotes Flexibility and Induced Fit Binding in a Microporous Copper Coordination Network

Abstract Flexible organic linkers represent an intuitive and effective strategy to design flexible metal–organic materials. We report herein a systematic study concerning the effect of varying the central bond of mixed pyridyl‐benzoate linkers, L, upon the flexibility of three isostructuralkddtopology microporous coordination networks (CNs) of formula ML 2 :X‐kdd‐1‐Cu,1= L = (E)‐4‐(pyridin‐4‐yldiazenyl)benzoate;X‐kdd‐2‐Cu,2= L = (E)‐4‐(2‐(pyridin‐4‐yl)vinyl)benzoate; the previously reportedX‐kdd‐3‐Cu,3= L = 4‐(pyridin‐4‐ylethynyl)benzoate. As revealed by single crystal x‐ray diffraction (SCXRD) and gas sorption studies,X‐kdd‐1‐Cu, exhibited gate‐opening during CO 2 and hydrocarbon (C2 and C8) sorption experiments whereas the other two CNs did not. Insight into these phase transformations was gained from in situ variable‐pressure and variable temperature powder X‐ray diffraction (PXRD), SCXRD, and modeling. Rotation of ligand1around the diazo bond, torsion angle changes between phenyl and carboxylate moieties, and deformation of the Cu‐based rod building blocks enabled activatedX‐kdd‐1‐Cuto form new phases with C8 isomers and CH 2 Cl 2 , CH 2 Cl 2 inducing contraction of the activated phase. Computational studies suggest that1enables flexibility thanks to its lower barrier of deformation versus2or3. This study teaches that diazo moieties could offer a general strategy to enhance the flexibility of CNs.

Chemistry↗
DOE OSTI2025

Chemically Recyclable and Tunable Polyolefin-Like Multiblock Copolymer Adhesives

Adhesives are important in creating multilayer products, such as in packaging and construction. Most current hot-melt adhesives such as poly(ethylene-co-vinyl acetate) (EVA) and polyurethanes lack chemical recyclability and do not easily de-bond, complicating recycling. Here, we achieved tunable adhesive properties of chemically recyclable polyolefin-like multiblock copolymers through regulating the incorporation of crystalline hard blocks, amorphous soft blocks, and ester content highlighted by adhesive strengths up to 6.80 MPa. We further demonstrated applications of these adhesives in multi-layer films and showed that the adhesives can be readily de-bonded, recovered, and chemically recycled. Overall, this study into structure-property relationships, including effects of crystallinity, soft-block incorporation, and ester content of the multiblock copolymers on adhesive properties, has resulted in a modular hot-melt adhesive platform that exhibits chemical recyclability for virgin-quality adhesive re-generation, reprocessability for repeated reuse of the recovered adhesive, and tunability for designing adhesives with a wide range of low to high (up to ~80% stronger than EVA) adhesion strengths.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Simultaneous Degradation‐Depolymerization of Bioderived Comb Copolymers

Poly(lactic acid) (PLA) is the most widely explored biodegradable alternative for polystyrene; however, its low toughness and glass transition temperature may limit its wider adoption as a sustainable replacement. To improve its material and thermal properties, PLA can be chemically or physically combined with other polymers, like poly(methyl methacrylate) (PMMA), though the incorporation of vinyl‐based polymer components complicates chemical recycling and reduces the sustainability of the material. Here, in this study, we synthesized polymethacrylate‐PLA comb copolymers designed to be thermally deconstructed. Our design strategically extends current polymer deconstruction methodologies to more complex macromolecular systems. Thermally labile units within the polymethacrylate backbone permitted depolymerization that was concurrent with PLA side chain degradation during heating. This dual degradation‐depolymerization process enhances the overall sustainability of lactide/vinyl‐based copolymers and demonstrates the synergistic potential of integrating multiple deconstruction pathways into a single system. This report elaborates on the design of advanced, degradable copolymers, contributing to the further development of sustainable polymer materials.

PLA↗
DOE OSTI2025

B‐Staging and Crosslinking of Polycarbosilane at Room Temperature: Cure Mechanism and Properties

The viscosity of polycarbosilane (PCS) polymers is not advantageous for free forming. Various fillers and heat are used to obtain a formable paste. Due to the low yield stress, structures and preforms tend to slump or resin will flow out, especially during the curing of the polymer. B-staging of PCS allows for a more stable structure from room temperature until the full cure of the allyl groups occurs with heat. Additionally, hydrosilation is an effective means of crosslinking at room temperature and controlling viscosity. A network structure was formed in SMP-10 using silane and a vinyl-based crosslinker to bridge each polymer chain. Pt addition catalysts were added to enhance the increase in viscosity to make a lightly crosslinked gel to aid in thickening and forming and to improve the ceramic yield at 1000°C. In conclusion, this enables several options for controlling rheology and improving the properties of preceramic polymers to avoid slumping during curing.

inorganic polymers↗
DOE OSTI2023

Transparent Conductive Encapsulants for Photoelectrochemical Applications

Utilizing sunlight to directly perform photoelectrochemical reactions is a promising route to renewable, net carbon-neutral fuels. However, a common problem with solar fuel production is semiconductor degradation in aqueous environments. An ideal protection layer should (1) prevent solution from reaching the semiconductor, (2) maintain charge transfer to and from solution, and (3) be transparent to light above the semiconductor band gap. While there have been substantial advances toward layers that meet these requirements, they are not easily adapted to new surfaces or new reactions, which can make protection difficult for newly developed photoabsorbers and (photo)electrochemical reaction pairings. In this work, we demonstrate the use of transparent conductive encapsulants (TCEs) to meet these requirements while also allowing for photoelectrode- and reaction-agnostic adaptability. TCEs are composed of an ethyl-vinyl acetate matrix with embedded conductive metal-coated microspheres that can be laminated to semiconductors. First, the electrochemical behavior of TCE-coated electrodes for the reduction of methyl viologen is characterized, demonstrating through-TCE electrical conduction. Then, photoelectrochemical measurements on TCE-protected semiconductors demonstrate the flexibility of this protection scheme. Finally, long-term photoelectrochemical measurements probe the efficacy of TCEs as protection layers. These findings demonstrate the potential of TCEs as adaptable protection layers in various photoelectrochemical applications.

14 SOLAR ENERGY↗
DOE OSTI2020

Gas–Phase Synthesis of 3–Vinylcyclopropene via the Crossed Beam Reaction of the Methylidyne Radical (CH; X 2 Π) with 1,3–Butadiene (CH 2 CHCHCH 2 ; X 1 Ag)

The crossed molecular beam reactions of the methylidyne radical (CH; X 2 Π) with 1,3-butadiene (CH 2 CHCHCH 2 ; X 1 Ag) along with their (partially) deuterated counterparts were performed at collision energies of 20.8 kJ mol -1 under single collision conditions. Combining our laboratory data with ab initio calculations, we reveal that the methylidyne radical may add barrierlessly to the terminal carbon atom and/or carbon-carbon double bond of 1,3-butadiene, leading to doublet C 5 H 7 intermediates with life times longer than the rotation periods. Furthermore, these collision complexes undergo non-statistical unimolecular decomposition through hydrogen atom emission yielding the cyclic cis- and trans-3-vinyl-cyclopropene products with reaction exoergicities of 119±42 kJ mol -1 . Since this reaction is barrierless, exoergic, and all transition states are located below the energy of the separated reactants, these cyclic C 5 H 6 products are predicted to be accessed even in low-temperature environments, such as in hydrocarbon-rich atmospheres of planets and cold molecular clouds such as TMC-1.

3-vinylcyclopropene↗
DOE OSTI2021

Reducing Antisolvent Use in the STRAP Process by Enabling a Temperature–Controlled Polymer Dissolution and Precipitation for the Recycling of Multilayer Plastic Films

The recently reported processing strategy called solvent-targeted recovery and precipitation (STRAP) enables deconstruction of multilayer plastic packaging films into their constituent resins by selective dissolution. It uses a series of solvent washes that are guided by thermodynamic calculations of polymer solubility. In this work, the use of antisolvents in the STRAP process was reduced and solvent mixtures were considered to enable the temperature-controlled dissolution and precipitation of the target polymers in multilayer films. This was considered as a means to further improve the STRAP process and its estimated costs. Two STRAP approaches were compared based on different polymer precipitation techniques: precipitation by the addition of an antisolvent (STRAP-A) and precipitation by decreasing the solvent temperature (STRAP-B). Both approaches were able to separate the constituent polymers in a post-industrial film composed primarily of polyethylene (PE), ethylene vinyl alcohol (EVOH), and polyethylene terephthalate (PET) with near 100 % material efficiency. Technoeconomic analysis indicates that the minimum selling price (MSP) of the recycled resins with STRAP-B is 21.0 % lower than that achieved with STRAP-A. This provides evidence that thermally driven polymer precipitation is an option to reduce the use of antisolvents, making the STRAP process more economically and environmentally attractive. A third process, STRAP-C, was demonstrated with another post-industrial multilayer film of a different composition. Here, the results demonstrate that this process can also recover polymers at similar costs to those of virgin resins, indicating that the STRAP technology is flexible and can remain economically competitive as the plastic feed complexity is increased.

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

Computational Approach for Rapidly Predicting Temperature–Dependent Polymer Solubilities Using Molecular–Scale Models

One promising approach to recycle multicomponent plastic waste (e. g., multilayer plastic films) is selective dissolution. Selective dissolution is a solvent-mediated process in which differences in polymer solubility in a carefully chosen solvent system are exploited to recover a target polymer. Here, a computational approach was developed that rapidly predicts temperature-dependent polymer solubilities to guide the design of solvent systems for solvent-mediated polymer recycling. Polymer conformations were obtained from molecular dynamics simulations by modeling the polymer as a short oligomer and then used as input to the conductor-like screening model for real solvents (COSMO-RS) for solubility predictions. Using polyethylene (PE) and ethylene vinyl alcohol (EVOH) as representative polymers, the effect of simulation parameters was systematically studied, and predicted solubilities were found to be in good agreement with experimental measurements. Furthermore, the applicability of the approach was demonstrated by identifying selective solvents for PE and EVOH dissolution from a library of 524 solvents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Selectively Depolymerizable Polyurethanes from Unsaturated Polyols Cleavable by Olefin Metathesis

This communication describes a novel series of linear and crosslinked polyurethanes (PUs) and their selective depolymerization under mild conditions. Two unique polyols are synthesized bearing unsaturated units in a configuration designed to favor ring-closing metathesis (RCM) to five- and six-membered cycloalkenes. These polyols are co-polymerized with toluene diisocyanate to generate linear PUs and trifunctional hexamethylene- and diphenylmethane-based isocyanates to generate crosslinked PUs. The polyol design is such that the RCM reaction cleaves the backbone of the polymer chain. Upon exposure to dilute solutions of Grubbs’ catalyst under ambient conditions, the PUs are rapidly depolymerized to low molecular weight, soluble products bearing vinyl and cycloalkene functionalities. These functionalities enable further re-polymerization by traditional strategies for polymerization of double bonds. We anticipate that this general approach can be expanded to develop a range of chemically recyclable condensation polymers that are readily depolymerized by orthogonal metathesis chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Degradation in photovoltaic encapsulation strength of attachment: Results of the first PVQAT TG5 artificial weathering study

Delamination of the encapsulant in photovoltaic (PV) module technology results in immediate optical loss and may enable subsequent corrosion or mechanical damage. The effects of artificial weathering were not previously known; therefore, an empirical study was performed to survey the factors most affecting adhesion, including the ultraviolet (UV) source (ie, Xe or fluorescent lamp[s]), the optical filters for the lamp, the chamber temperature, and the relative humidity. Natural weathering was also performed at locations, including the following: Golden, Colorado; Miami, Florida; Phoenix, Arizona; QiongHai, China; Riyadh, Saudi Arabia; and Turpan, China. Specimens were constructed using a laminated glass/poly (ethylene-co-vinyl acetate)/glass geometry. The compressive shear test (CST) was used to quantify the mechanical strength of attachment, taken as a proxy for adhesion. The fractography of select specimens (including cross-sectional optical microscopy) was used to verify the failure mode (delamination or decohesion). Additional analysis of the local solar spectrum as well as the specimen temperature was performed to interpret the results of natural weathering. The goals of this study include to identify the most significant stressors, clarify where strong coupling may occur between stressors, and validate accelerated test results relative to natural weathering. The importance of specimen conditioning (for moisture) and hygrometric degradation as well as the effects of UV degradation are identified in this paper.

14 SOLAR ENERGY↗
DOE OSTI2020

Drivers for the cracking of multilayer polyamide‐based backsheets in field photovoltaic modules: In‐depth degradation mapping analysis

Abstract There is a lack of understanding on the root cause of cracking of photovoltaic (PV) backsheets due to the challenge of multilayer characterization and the complicated failure modes at the submodule level. In this work, the in‐depth degradation mapping of field‐exposed polyamide‐based (PA‐based) PV module backsheets was studied, with the major focus on the identification of underlying drivers for the through cracking (in between the solar cells). PV modules were retrieved from five different locations, comprising a variety of climates, including humid subtropical, hot‐summer Mediterranean, tropical savanna climate, and hot arid. A suite of microscale cross‐sectional characterizations, including chemical changes, fluorescence intensity, and modulus as a function of distance from the air surface of the backsheet, was performed. Results showed more advanced signs of degradation of the inner layer than the outer layer in the cracking region. Increases in the modulus were identified as the major indicator for the cracking. Moreover, a rudimentary test by immersion in acetic acid, which forms during photodegradation of the ethylene‐vinyl acetate copolymer (EVA) encapsulant, showed the first‐time direct evidence that acetic acid can largely accelerate the chemical degradation and facilitate the cracking of PA inner layer. This study suggests that the field cracking of PA‐based backsheet can be attributed to the combined effects of chemical degradation and physical reorganization (chemi‐crystallization) under cyclic thermomechanical stresses. Therefore, it is important to consider effects of local microclimates and interlayer infection to understand the heterogeneous nature of backsheet failures.

Lyu, Yadong↗