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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Selective ion transport through hydrated micropores in polymer membranes

Abstract Ion-conducting polymer membranes are essential in many separation processes and electrochemical devices, including electrodialysis 1 , redox flow batteries 2 , fuel cells 3 and electrolysers 4,5 . Controlling ion transport and selectivity in these membranes largely hinges on the manipulation of pore size. Although membrane pore structures can be designed in the dry state 6 , they are redefined upon hydration owing to swelling in electrolyte solutions. Strategies to control pore hydration and a deeper understanding of pore structure evolution are vital for accurate pore size tuning. Here we report polymer membranes containing pendant groups of varying hydrophobicity, strategically positioned near charged groups to regulate their hydration capacity and pore swelling. Modulation of the hydrated micropore size (less than two nanometres) enables direct control over water and ion transport across broad length scales, as quantified by spectroscopic and computational methods. Ion selectivity improves in hydration-restrained pores created by more hydrophobic pendant groups. These highly interconnected ion transport channels, with tuned pore gate sizes, show higher ionic conductivity and orders-of-magnitude lower permeation rates of redox-active species compared with conventional membranes, enabling stable cycling of energy-dense aqueous organic redox flow batteries. This pore size tailoring approach provides a promising avenue to membranes with precisely controlled ionic and molecular transport functions.

Science & Technology - Other Topics↗
NASA NTRS1988

Electrically Conducting Polymer-Copper Sulphide Composite Films, Preparation by Treatment of Polymer-Copper (2) Acetate Composites with Hydrogen Sulfide

Polymer copper sulfide composite films were prepared by treatment of polymer poly(vinyl chloride), poly(acrylonitrile), copolymer of vinyl chloride and vinyl acetate (90:10), and ABS resin copper (2) acetate composites with hydrogen sulfide. The films showed electrical conductivity higher than 0.015 S/cm when they contained more than 20 wt percent of copper sulfide. A poly(acrylonitrile)-copper sulfide composite film containing 40 to 50 wt percent of copper sulfide showed electrical conductivity of 10 to 150.0 S/cm and had relatively high mechanical strength to be used in practical purposes.

Yamamoto, Takakazu↗
NASA NTRS1987

A quantum theoretical study of polyimides

One of the most important contributions of theoretical chemistry is the correct prediction of properties of materials before any costly experimental work begins. This is especially true in the field of electrically conducting polymers. Development of the Valence Effective Hamiltonian (VEH) technique for the calculation of the band structure of polymers was initiated. The necessary VEH potentials were developed for the sulfur and oxygen atoms within the particular molecular environments and the explanation explored for the success of this approximate method in predicting the optical properties of conducting polymers.

Burke, Luke A.↗
NASA NTRS2012

Radiation Shielding System Using a Composite of Carbon Nanotubes Loaded with Electropolymers

Single-wall carbon nanotubes (SWCNTs) coated with a hydrogen-rich, electrically conducting polymer such as polyethylene, receive and dissipate a portion of incoming radiation pulse energy to electrical signals that are transmitted along the CNT axes, and are received at energy-dissipating terminals. In this innovation, an array of highly aligned nanowires is grown using a strong electric field or another suitable orientation procedure. Polyethylene (PE), polymethymlethacrylate (PMMA), or other electrically conducting polymer is spin-coated onto the SWCNTs with an average thickness of a few hundred nanometers to a few tenths of micrometers to form a PE/SWCNT composite. Alternatively, the polymer is spin-coated onto the nanowire array or an anodized alumina membrane (AAM) to form a PE/metal core shell structure, or PE can be electropolymerized using the SWCNTs or the metal nanowires as an electrode to form a PE/SWCNT core shell structure. The core shell structures can be extruded as anisotropic fibers. A monomer can be polymerized in the presence of SWCNTs to form highly cross-linked PE/SWCNT films. Alternatively, Pb colloid solution can be impregnated into a three-dimensional PE/SWCNT nanostructure to form a PW/SWCNT/Pb composite structure. A face-centered cubic (FCC) arrangement provides up to 12 interconnection channels connected to each core, with transverse channel dimensions up to 20 nm, with adequate mechanical compressive strength, and with an associated electrical conductivity of around 3 Seimens/cm for currents ranging from 0.01 to 10 mA. This threedimensional nanostructure is used as a host material to house appropriate radiation shielding material such as hydrogen- rich polymer/CNT structures, metal nanoparticles, and nanowires. Thicknesses of this material required to attenuate 10 percent, 50 percent, and 90 percent of an incident beam (gamma, X-ray, ultraviolet, neutron, proton, and electron) at energies in the range of 0 440 MeV are being determined, for example, by measuring fluence rate reduction. For example, a radiation field arrives first at an exposed surface of the innovation and produces an associated first electric field within the metal-like fingers of the three-dimensional nanostructure. This field is intensified near the exposed tips of the fingers, and this intensified field generates an intensified second electric field near the adjacent exposed tips of the coated CNSs. This generates an associated electrical current in the CNSs, and the associated electropolymer coating. The current is received by the second substrate transport component and is transported to the dissipation mechanism located contiguously to the second substrate.

McKay, Chris↗
DOE OSTI2022

Molecular Engineering of Biorefining Lignin Waste for Solid-State Electrolyte

Lignin is the second most abundant renewable biopolymer on Earth but also a waste in both the paper industry and lignocellulosic biorefineries. Recently, lignin valorization has been extensively sought after to return economics, enhance carbon efficiency, and improve the bioeconomy, but the commercial value and size compatibility still hinder its applications. In this study, we developed a facile strategy to apply lignin waste into a solid-state electrolyte (SSE), which represents a safe next generation energy storage. Here, lignin was grafted with polyethylene glycol (PEG), an efficient lithium-ion (Li + ) conductive polymer, to enable its ion conduction. The synthesized PEG-g-lignin was mixed with poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP) and PEG-g-lignin-based bis(trifluoromethanesulfonyl)imide (LiTFSI) to prepare a solid polymer electrolyte (SPE), which has an ionic conductivity of 2.5 × 10 –5 S/cm at 25 °C. This result was further enhanced to 6.5 × 10 –5 S/cm by adding an ion-conductive ceramic of Li 6.4 La 3 Ga 0.2 Zr 2 O 12 (LLGZO), which is referred to as composite polymer electrolyte (CPE). These data represent the highest ones among reported polymer-based SSE. A mechanistic study by using 2D HSQC NMR revealed that PEG-g-lignin has increased ether type β–O–4 linkages that can promote the interchain hopping of Li+ between lignin polymer chains, and 31 P NMR revealed that the lignin phenolic end can be associated by Li + . Moreover, the abundant aromatic moieties and methoxyl in PEG-g-lignin also enhanced Li + association and improved its ionic conductivity. The superior ionic conductivity of PEG-g-lignin-based SSE can enable massive applications of this biorefining waste in all-solid-state lithium batteries (ASSLBs), which has potential to promote the energy sector by promoting the bioeconomy and enhancing the renewability and sustainability of future energy storage.

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

Self-Assembly of a Triblock Copolymer in the Presence of a Rigid Conjugated Polyelectrolyte

The properties of conducting polymers are strongly influenced by structural changes induced by long-range order, which can be achieved by using block copolymers that self-assemble into crystalline structures. These blends result in unique mesophases distinct from the pure components with self-assembly behavior modulated by solution conditions and polymer architectures. High-throughput small-angle X-ray scattering data of aqueous Pluronic P123 (PEO 20 –PPO 70 –PEO 20 ) and conjugated polyelectrolyte poly[3-(potassium-4-butanoate) thiophene-2,5-diyl] (PPBT) blends at various concentrations and temperatures were automatically classified into phase maps by autophasemap, an unsupervised statistical analysis algorithm. The outlined phase boundaries revealed that adding PPBT to high P123 concentrations induced a transition from cubicly ordered spherical micelles to hexagonally packed cylindrical micelles. Shear alignment via rheological small-angle neutron scattering of the blends produced monolithic oriented cubic and hexagonal crystal gels. Furthermore, these insights into the self-assembly of conductive polymer blends will aid in the design of soft materials with tunable structural and electronic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Enabling ITO-free perovskite solar cells through n-doped poly(benzodifurandione) (n-PBDF) electrodes

The burgeoning commercialization of perovskite solar cells (PSCs) is propelled by their exceptional power conversion efficiency (PCE), enhanced stability, and ease of fabrication. However, the rigidity of mainstream transparent conductive oxides (TCOs) limits the adaptability of PSCs to various application scenarios. Although alternative materials such as silver nanowires, carbon nanotubes, graphene, and PEDOT:PSS have been evaluated, the p-type nature confines their device designs to inverted architecture and restricts broader applicability. Here, for the first time, a conducting polymer electrode based on n-doped poly(benzodifurandione) (n-PBDF) was used to replace TCOs in PSCs. The n-PBDF electrodes can be readily fabricated via low-temperature, solution-based processes, indicating substantial potential for reducing manufacturing costs. Furthermore, its integration into PSCs has negligible effect on the phase, morphology, or photophysical properties of the perovskite layer, which is comparable to the typical TCOs. After optimization, the n-PBDF-based device achieves a power conversion efficiency of 12.70 and 11.23%, for rigid and flexible devices, respectively. Our study provides a promising alternative to the widely used TCOs in PSCs, highlighting the advantages of using n-doped conducting polymers in terms of processability and flexibility.

Kumar, Prashant [Purdue University, West Lafayette↗
DOE OSTI2022

Synthesis of poly(3,4-ethylenedioxythuophene) derivatives using three-armed conjugated cross-linker and its thermoelectric properties

Conducting polymer based thermoelectric systems are very effective at harvesting electricity from waste heat with low-temperature gradients relative to environmental temperature. However, although various studies concerning the doping effect exist, there are insufficient reports on the effect of the change in polymer chain structure on the thermoelectric properties. Here we demonstrate different poly(3,4-ethylenedioxythiophene) (PEDOT)-derivative chain structures (such as linear, two-dimensional, co-polymer), by varying the amount of three-armed conjugated cross-linker (1,3,5-tri(2-thienyl)-benzene (TTB)). Further, at a small amount of TTB addition (until 0.5 mM), the electrochemical charge transport of the PEDOT films increased without shift of the UV–Vis absorbing property. However, from higher than 0.5 mM TTB, electrochemical charge transport decreased with blue shift of the UV–Vis absorbing curve. Moreover, the power factor of the PEDOT-derivative films without TTB to a small amount of TTB (0.5 mM) was improved from (27.03 to 49.43) µWm -1 K -2 , and at higher than 0.5 mM TTB concentration, was diminished, respectively, because a small amount of TTB enhanced the π–π interaction of the polymer chains without disrupting the conjugation, while excess TTB molecules blocked conjugation of the polymer.

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

Controlling solvation in conducting redox polymers for selective electrochemical separation of nitrate from wastewater

Selective capture of nitrate from wastewater is crucial for ensuring safe drinking water and promoting resource circularity. This study investigated alkylated polyaniline redox polymers as highly-selective electrosorbents to address this challenge. By controlling polymer solvation properties through synthetic functionalization, poly(N-methylaniline) (PNMA) achieves a nitrate uptake of up to 1.38 mmol g −1 -polymer and a separation factor of 7 over chloride. Poly(N-butylaniline) (PNBA) further enhances selectivity, achieving a separation factor beyond 14 due to increased hydrophobicity. The mechanisms underlying this selectivity are investigated using ab initio molecular dynamics (AIMD) and in-situ electrochemical quartz crystal microbalance (EQCM) studies, which reveal that hydrophobicity reduces chloride binding. A technoeconomic analysis indicates that methylation on PANI reduces nitrate removal costs by 50% compared to non-functionalized PANI, due to enhanced selectivity and uptake, and decreased energy consumption. PNMA electrodes demonstrate practical nitrate selectivity over 20 versus chloride in real wastewater, while avoiding sulfate binding. This study highlights the potential of controlling solvation at electroactive polymers to enhance nitrate selectivity, offering a promising design path for redox-mediated electrochemical separations.

chemical engineering↗
NASA NTRS1992

The effects of molecular structure on the electrical conductivity of polymers

The role of Quantum Theoretical Methods is both predictive and supportive of experimental results in Chemistry. Present day methods are able to calculate vibrational spectra and stereochemical interactions for molecules of moderate size (up to 20 atoms). As for the predictive side, the electronic structure of molecules and polymers can be calculated in order to narrow down the field of many potential candidates, which would have the novel properties looked for. The following has been accomplished at the Rutgers Camden Chemistry Department as results of calculations on molecular and polymeric systems of interest to the Polymers Branch of the NASA Lewis Research Center, under Grant NAG3-956.

Burke, Luke A.↗
DOE OSTI2020

Review—Polymer/Ceramic Interface Barriers: The Fundamental Challenge for Advancing Composite Solid Electrolytes for Li-Ion Batteries

Composite-solid electrolytes, in which ion-conducting polymers are combined with superionic ceramics, could revolutionize electrochemical-energy-storage devices enabling higher energy density, providing greater stability during operation and enhanced safety. However, the interfacial resistance between the ceramic and polymer phases strongly suppresses the ionic conductivity and presents the main obstacle to the use of these materials. Here, we emphasize the need for a distinct focus on reducing energy barriers to interfacial ion transport and improving the cation transference number. To achieve this goal, it is essential to develop a fundamental understanding of the parameters that influence the interfacial barriers to ion transport in composite electrolytes, and to understand the effect of the type of ceramic ("active" and "inert") and its content on ion-transport phenomena. We suggest that adapting the polymer chemistry, mainly directed on polymerized ionic liquids, (PolyILs), and combined with functionalization of the surface of ceramic nanoparticles is a promising route for overcoming the high-energy-barrier challenge. Owing to high content of ion-conducting ceramics and high t+ of PolyILs, the fractional contribution of the migrating cationic species to the total ionic conductivity of polymer-in-ceramic electrolytes via an interfacial percolation path, will be close to unity, thus eliminating complications that might arise from emerging concentration gradients during the operation of solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2023

Tuning Transport via Interaction Strength in Cationic Conjugated Polyelectrolytes

Tuning polymer-ion interaction strength is critical for balancing ion solvation and transport in solid polymer electrolytes for battery applications. In mixed Li + /electron conducting systems for improved battery binders, the design space is further complicated by seemingly opposing design rules for electron and ion conducting polymers. Conjugated polymers functionalized with cationic side chains have demonstrated high ionic conductivity, lithium transport, and electronic conductivity by combining long-range polymer ordering with diffuse ion interactions. Herein, we demonstrate a family of mixed conducting polythiophenes functionalized with a range of cationic side chains, namely imidazolium, trimethylammonium, and ammonium groups. The strength of ionic interactions and structure of the side chains govern lithium-selective transport, resulting in high Li + conductivity (~10 –4 S/cm at 80 °C) and electronic conductivity. The more diffuse imidazolium ion affords labile ionic interactions, resulting in higher lithium transference than the other cations studied. Electronic conductivity is also higher in the imidazolium system, stemming from the ability of the planar side chains to stack while also accommodating the bulky TFSI – counterions. Finally, these results demonstrate the importance of interaction strength in ion transport while also indicating that the physical structure of the side chain has an impact on electronic conduction. The imidazolium group strikes a balance, achieving superior properties across all metrics.

36 MATERIALS SCIENCE↗
NASA NTRS1982

Some characteristics of polymers in composite materials and as electrical conductors

The characteristics of carbon fibers (CF) made from polyacrylonitrile (PAN) materials are discussed, together with research on conducting polymers. CF materials have better mechanical properties, chemical inertness, and higher stiffness than metallic materials but are subject to environmental instability, flammability, and delamination fatigue. Polymerization procedures for the monopolymer PAN are described, noting the use of SEM and X-ray diffraction techniques for studying the fiber structure. High modulus and strength of CF are caused by covalent sp(2) bonds in hexagonal carbon rings, which are stronger than the same links in diamonds. Details of the molecular chain structures and macroformations, stress-strain as a function of temperature, and thermosetting and glass transition temperatures of polymers are provided. Computational quantum chemistry techniques are being applied to studying electrical conductance in polymers, mainly to discover ways to stabilize the materials. Doped CH(x) has exhibited photovoltaic properties and other polymers have become superconductors at cryogenic temperatures.

Hansen, C. F.↗
NASA NTRS1990

Symposium on Rechargeable Lithium Batteries, Hollywood, FL, Oct. 19-24, 1989, Proceedings

Recent advances in the technology and applications of rechargeable Li cells are discussed in reviews and reports. A general overview of the field is provided, and sections are devoted to organic electrolyte systems, polymeric electrolyte systems, inorganic electrolytes systems, and molten-salt electrolytes. Particular attention is given to electrolyte stabilization, the effects of organic additives on electrolyte performance, a cycle-life sensor, consumer-product applications, in situ measurements of gas evolution in Li secondary cells, ultrathin polymer cathodes, electrochemical growth of conducting polymers, and sealing Li/FeS(x) cells for a bipolar battery.

Subbarao, S.↗
DOE OSTI2023

Advancing ionomer design to boost interfacial and thin-film proton conductivity via styrene-calix[4]arene-based ionomers

Sub-micrometer-thick ion-conducting polymer (ionomer) layers often suffer from poor ionic conductivity at the substrate/catalyst interface. The weak proton conductivity makes the electrochemical reaction at the cathode of proton-exchange-membrane fuel cells sluggish. To address this, here we report on a class of polystyrene-based ionomers having sub-nanometer-sized, sulfonated macrocyclic calix[4]arene-based pendants (PS-calix). In films with thickness comparable to that of ionomer-based binder layers, the conductivity of PS-calix film (~41 mS/cm) is ~13 times higher than that of the current state-of-the-art ionomer, Nafion. We observe a similar improvement in proton conductivity when PS-calix interfaces with Pt nanoparticles, demonstrating the potential of PS-calix in catalyst ink. Leveraging a favorable interfacial chemical composition, PS-calix enhances proton conduction at the film-substrate interface, a shortcoming of Nafion. Moreover, the water in PS-calix films diffuses faster than bulk water and the water confined in Nafion films, suggesting an important role played by sub-nanometer-sized calix[4]arene cavities in creating unique water/ion transport pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗