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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 55 records · Page 3

Mechanisms Controlling the Energy Barrier for Ion Hopping in Polymer Electrolytes

Here, the present work studies the mechanisms controlling the energy barrier for ion hopping in conducting polymers. Polymer electrolytes usually show Arrhenius-like temperature dependence of the conductivity relaxation time (characteristic time of local ion rearrangements) at temperatures below their glass transition T g . However, our analysis reveals that the Arrhenius fit of this regime leads to unphysically small prefactors, τ 0 $\ll$ 10 –13 s. Imposing a value of 10 –13 s for this parameter renders the fairly unexpected result that the energy barrier for charge transport in these polymers has strong temperature dependence even below T g . Our study also reveals significant temperature variations of the dielectric permittivity and the instantaneous shear modulus in the glassy state of these polymers. Using the Anderson and Stuart model, we demonstrate that these variations provide strong justifications for the temperature variation of energy barrier for ion hopping. Most importantly, the proposed approach reveals that the energy barrier controlling ion hopping in polymer electrolytes is significantly (~30–40%) lower than that estimated using traditional Arrhenius fit. These new insights call for revisions of many earlier results based on apparent Arrhenius fits, and the newly proposed approach can provide more accurate guidance for the design of solid-state electrolytes with enhanced ionic conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

2-Aminoanthracene Crystallization in Its Compatible Polystyrene Block: RAFT Synthesis and Enhanced Charge Retention in Pentacene Transistor Gate Dielectrics

We synthesized polystyrene-block-polyanthrylaminomethylstyrene (PS-b-PAAS) via RAFT reaction and side chain modification where the PAAS block is 50%. By blending 2-aminoanthracene (2AA) with PS-b-PAAS, the co-aggregation behavior of the PAAS block and 2AA within the thin film was observed by optical microscopy (OM) and x-ray diffraction. At 5 and 10 wt% of 2AA within the thin film, OM results showed a clear morphological difference between PS matrix and PS-b-PAAS matrix. Differences in the 2AA excited state lifetime in these matrices were also established using transient absorption spectroscopy (TAS). Blends were used as gate dielectrics in pentacene transistors. We compared characteristic voltage (Vc, an indicator of threshold voltage) before and after charging of PS-b-PAAS blended with unsubstituted PS and both polymers individually blended with 2AA. For blended PS-b-PAAS and PS, as the concentration of PS-b-PAAS increases, the decreased Vc especially with negative charging of the pentacene indicated a larger concentration of charge carriers induced by the dielectric film. The charging experiments also revealed that the unique structure formed by the 2AA/PS-b-PAAS blend significantly affected the charge storage capability of the organic field-effect transistors (OFET). Furthermore, this work demonstrates the novel co-aggregation structure in the dielectrics, and furthermore its impact on charge storage capability in pentacene OFETs.

36 MATERIALS SCIENCE↗

Thermal conductivity of multilayer polymer-nanocomposite thin films

The development of electrical insulators that are thermally conducting is critical for thermal management applications in many advanced electronics and electrical devices. Here, we synthesized polymer nanocomposite (PNC) films composed of polymers [polyethylenimine, poly(vinylamine), poly(acrylic acid), and poly(ethylene oxide)] and dielectric fillers (montmorillonite clay and hexagonal boron nitride) by layer-by-layer technique. The cross-plane thermal conductivity (k⊥) of the film was measured by the 3ω method. The effect of various factors such as film growth, filler type, filler volume fraction, polymer chemical structures, and temperature on the thermal conductivity is reported. The k⊥ of PNCs with thickness from 37 nm to 1.34 μm was found to be in the range of 0.11 to 0.21 ± 0.02 W m−1 K−1. The k⊥ values were found to be lower than the constituent polymer matrix. The experimental result is compared with existing theoretical models of nanocomposite systems to get insight into heat transfer behavior in such layered films composed of dielectrics and polymers.

Physics↗

The effect of barrier films and exposure on the aging of vacuum insulation panels with fumed silica cores

Vacuum insulation panels have very low thermal conductivities compared to conventional insulation materials. The reduction of the core pressure significantly lowers gas phase conduction and overall thermal conductivity. As a consequence, increases in gas pressure can significantly increase thermal conductivity of the VIP. In addition, the thermal conductivity of the core is sensitive to moisture content. For vacuum insulation panels with fumed silica cores, work shows that the measured thermal conductivity increases by 0.5 x 10-3 W/mK per mass percent increase in water content [1]. This is significant since the thermal conductivity of vacuum insulation panels with fumed silica cores is in the range of 0.004 W/mK. This work investigates the long-term behavior of vacuum insulation panels comprised of fumed silica cores with polymer (ethylene vinyl alcohol) and metalized (aluminized) barrier films exposed to different exposure conditions: ambient conditions; exterior conditions in a mixed humid climate; and 24oC and 80 percent relative humidity. Results show that the increase in thermal conductivity is more pronounced for vacuum insulation panels made using polymer barrier films compared to the same panel protected by a metalized film. The increase is more pronounced when exposed to high relative humidity, 80 percent. After almost two years exposure, the decrease in thermal conductivity for vacuum insulation panels protected by a metalized barrier films are between 4 and 11 percent depending on exposure condition. The smallest decrease is for ambient conditions where the largest decrease is for exposure to 80 percent relative humidity. Similar behavior was observed for panels protected using polymer films, except the decrease in thermal conductivity was significantly higher, between approximately 20 and 60 percent, in the same order as for panels protected by metalized films. Measurements are ongoing with an attempt to develop a better relationship between these types of tests and vacuum insulation panel service life.

Aldykiewicz Jr, Antonio↗

Size Effects in the Thermal Conductivity of Amorphous Polymers

Manipulating thermal conductivity through nanoengineering is of critical importance to advance technologies, such as soft robotics, artificial skin, wearable electronics, batteries, thermal insulation, and thermoelectrics. Here, by examining amorphous polymers, including polystyrene, polypropylene, polyethylene, and ethylene vinyl alcohol, using molecular dynamics simulations, we find that the thermal conductivities of amorphous polymers can be reduced below their amorphous limit by size effects. Size-dependent thermal transport in amorphous materials is decomposed into crystalline, crystalline-to-amorphous, and amorphous regimes. In the amorphous regime, the mean free path of propagating heat carriers can range from tens of nanometers to more than 100 nm, contributing 16%–36% of the total thermal conductivity. A two-channel model that combines no size effect (i.e., difusons and locons) and size effect (i.e., propagons) is proposed to account for size-dependent thermal conductivity. We also find that the presence of charged molecules in polymers can significantly affect the thermal conductivity and its size effects due to electrostatic interactions. Overall, this work provides insights into the thermal conductivity of amorphous polymers that will have a broad impact on the nano- and chemical engineering of polymers for various energy-related applications.

36 MATERIALS SCIENCE↗

Application of Poly(ether sulfone)‐Based Membranes in Clean Energy Technology

Abstract Poly(ether sulfone) (PES) is a kind of polymer materials with excellent electrical insulation and acid/alkali stability. PES can be operated at high temperature continuously for a long time and still maintain excellent property stability in the environments with rapidly changed temperature, namely, great thermostability. Moreover, PES has low molding shrinkage, good dimensional stability and excellent film‐forming characteristics. Compared with inorganic membranes, PES‐based membranes have lower cost, which have received more attention and wide recognition in the field of clean energy technologies in recent years, such as flow batteries, fuel cells, water treatment, and gas separation. Therefore, this review summarizes the research status and prospect of the utilization of PES‐based membranes in clean energy fields, in order to further promote their development and application.

Chemistry↗

Coupling and Decoupling between Stickers and Backbones in Associating Polymers with Terminally Functionalized Side Chains

Associating polymers have recently attracted tremendous attention as self-healing polymers due to the dynamic reversibility of sticker association–dissociation processes. These sticker dynamics inevitably slow significantly as segmental dynamics decelerate below the glass transition temperature that limits the operational temperatures of associating polymers. Using broadband dielectric spectroscopy on a new set of associating polymers composed side chains of various lengths and terminal carboxylic-acid sticker functionality, we discovered an unexpected decoupling near the glass transition (T g ) between the slower backbone and fast sticker motions. These two motions have distinct activation energies for the motion of the sulfur linkage adjacent to the backbone (~22 to 26 kJ/mol) and the carboxylic acid groups (~5 to 8 kJ/mol). A second decoupling appears in the polymer with the longest side chain length at T g – 20 K, reflecting the dynamics of various carboxylic acid binding configurations. Furthermore, our findings open the door to design associating polymers with the capability of sticker association/dissociation at low temperatures.

36 MATERIALS SCIENCE↗

Localized and Collective Dynamics in Liquid-like Polyethylenimine-Based Nanoparticle Organic Hybrid Materials

In this work, broadband dielectric spectroscopy, rheology, and nuclear magnetic resonance spectroscopy are employed to study molecular dynamics in a nanoparticle organic hybrid materials(NOHMs)system comprising 20 wt% silica nanoparticles ionically-bonded to a polyethylenimine canopy. By comparing the neat polymer (used as a canopy) to the derivative NOHMs, we find that timescales characterizing segmental dynamics in the NOHM are identical to those for the neat polymer. Detailed analysis of the carbon-spin lattice relaxation times yields mechanistic insights into localized and collective dynamics, in quantitative agreement with dielectric results. Interestingly, the NOHMs retain liquid-like characteristics unlike conventional polymer nanocomposites but exhibit higher viscosity due to additional contributions from tethered polymer chains, and mesoscopic structuring. These findings demonstrate the potential of achieving unique and desired material properties via NOHMs by an informed choice of the canopy material.

36 MATERIALS SCIENCE↗

Critical Role of the Interfacial Layer in Associating Polymers with Microphase Separation

Polymers with dynamic (transient) bonds, often called associating polymers, have been attracting significant attention in recent years due to their unique viscoelastic properties, self-healing ability, and recyclability. Nevertheless, understanding the mechanisms and the factors controlling their macroscopic properties remains limited due to the higher complexity introduced by the dynamic bonds. Here in this study, small-angle X-ray scattering (SAXS), broadband dielectric spectroscopy (BDS), and rheology were applied to unravel the structure and dynamics of telechelic associating polymers with different molecular weights. SAXS measurements revealed phase separation of the functional end groups with an average cluster size of ~2–3 nm and the distance between clusters controlled by the chain length. Borrowing the interfacial layer model analysis of BDS data from the polymer nanocomposite field, we demonstrated the presence of an interfacial polymer layer with a thickness of ~0.7–0.9 nm surrounding these clusters. Rheological measurements showed quantitatively that the presence of the interfacial layer significantly alters the viscoelastic behavior of these materials, indicating the crucial role of the interfacial layer in defining the macroscopic mechanical properties of the studied telechelic materials. The presented results emphasize that phase separation of the functional groups in associating polymers leads to very significant changes of the viscoelastic properties, opening a promising avenue in the design of novel functional materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Role of Functionalized Conducting Polymer Binders in Improving Power Density and Cycle Life of Lithium-Sulfur Batteries

Lithium-Sulfur batteries are promising as the next-generation of low-cost, high-energy rechargeable batteries. However, the commercialization of this battery has been limited by poor rate capability and cycle life. To improve the performance of Li-S cells, we have investigated the role of two n-dopable conducting polymers, N2200 and N2200-OE, as binders for the sulfur cathode. The electron and ion transport properties of these polymer binders, along with their strong affinity for polysulfides, results in significantly enhanced performance compared to cells with the traditional insulating PVDF binder. The role of these conducting polymer binders in enhancing the performance of the cells is analyzed using impedance spectroscopy, shuttle current measurements, conductivity measurements, UV–vis spectroscopy, GIWAXS studies and post-cycling analysis of the anodes. The conducting polymer binders reduce the cell impedance by a factor of four leading to a marked improvement in rate capability. The shuttling of the polysulfides and the formation of insoluble sulfides at the anode is curtailed by the interaction of the polysulfides with the backbone of the polymer binders, leading to an impressive capacity retention of 82% after 500 cycles. These studies demonstrate the benefit of tailored polymer binders at the sulfur electrode in addressing the limitations of lithium-sulfur batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamics of PDMS- g -PDMS Bottlebrush Polymers by Broadband Dielectric Spectroscopy

Poly(dimethylsiloxane) (PDMS)-based bottlebrush polymers, PDMS-g-PDMS, have been synthesized by anionic polymerization in combination with a condensation-based grafting reaction. Bottlebrush polymers show intriguing features, e.g., extremely low viscosities. Hereby, studies of their dynamics are rare. Therefore, we focus on the segmental relaxation by broadband dielectric spectroscopy. An increasing cross-sectional radius proportional to the increasing side chain length has been observed by small-angle neutron scattering over three samples. Here, a comparison of the segmental relaxation times of the bottlebrushes with the respective linear chains reveals slower dynamics in the former. For longer chains, this effect vanishes.

36 MATERIALS SCIENCE↗

Enhanced Surface Interactions Enable Fast Li + Conduction in Oxide/Polymer Composite Electrolyte

Abstract Li + ‐conducting oxides are considered better ceramic fillers than Li + ‐insulating oxides for improving Li + conductivity in composite polymer electrolytes owing to their ability to conduct Li + through the ceramic oxide as well as across the oxide/polymer interface. Here we use two Li + ‐insulating oxides (fluorite Gd 0.1 Ce 0.9 O 1.95 and perovskite La 0.8 Sr 0.2 Ga 0.8 Mg 0.2 O 2.55 ) with a high concentration of oxygen vacancies to demonstrate two oxide/poly(ethylene oxide) (PEO)‐based polymer composite electrolytes, each with a Li + conductivity above 10 −4 S cm −1 at 30 °C. Li solid‐state NMR results show an increase in Li + ions (>10 %) occupying the more mobile A2 environment in the composite electrolytes. This increase in A2‐site occupancy originates from the strong interaction between the O 2− of Li‐salt anion and the surface oxygen vacancies of each oxide and contributes to the more facile Li + transport. All‐solid‐state Li‐metal cells with these composite electrolytes demonstrate a small interfacial resistance with good cycling performance at 35 °C.

Wu, Nan↗

Investigation of Inverse Temperature Effects During Thermal-Radiation Aging of Semicrystalline Cable Insulation

Inverse temperature effects were observed for semi-crystalline polymers subjected to combined thermal and irradiation aging. The mechanical durability of materials aged at low temperatures degrades with dose faster than at high temperatures. In this paper, two crosslinked polyethylene (XLPE) and two ethylene propylene rubber (EPR) type nuclear cable insulations were exposed to thermal-radiation aging at 100Gy/h up to 30Mrad and three temperatures (26°C, 50°C, 90°C). Their mass change and color change after aging were analyzed.

Ni, Yelin↗

Role of Complexation Strength on the Photophysical and Transport Properties of Semiconducting Charged Polymer Complexes

The high polymer fraction in complexes of conjugated and insulating polyelectrolytes offers unique opportunities for the fabrication of conductive thick films and bulk structures. The electrostatic interactions in these systems further provide a handle for controlling their structure and properties. The impact of charge-mediated complexation strength on the photophysical and electronic transport properties in blends of conjugated polyelectrolytes (CPEs) with oppositely charged polymeric ionic liquids (PILs) was examined. Complexes were formed with varying frequency of charged repeat units, from 50 to 100%, on an anionic polythiophene-based CPE and a complimentary cationic PIL. In highly charged complexes, the intimate mixing between the CPE and the PIL reduced the structural disorder along the CPE backbone, enhancing its intrachain conjugation and interchain stacking. In weakly charged complexes (<90%), these chain planarization effects were absent and microphase separation occurred. At all charge fractions examined, the electrical conductivity of an acid-doped complex was higher than that of the unblended constituent CPE. Further, the highest electrical conductivity, near 1 S cm –1 , was found for a charge fraction of 100%. These results demonstrate the potential for designing effective polymeric conductors using electrostatic complexation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of fabrication methods on binder distribution and charge transport in composite cathodes of all-solid-state batteries

Abstract The manufacturing process of all-solid-state batteries necessitates the use of polymer binders. However, these binders, being ionic insulators by nature, can adversely affect charge transport within composite cathodes, thereby impacting the rate performance of the batteries. In this work, we aim to investigate the impact of fabrication methods, specifically the solvent-free dry process versus the slurry-cast wet process, on binder distribution and charge transport in composite cathodes of solid-state batteries. In the dry process, the binder forms a fibrous network, while the wet process results in binder coverage on the surface of cathode active materials. The difference in microstructure leads to a notable 20-fold increase in ionic conductivity in the dry-processed cathode. Consequently, the cells processed via the dry method exhibit higher capacity retention of 89% and 83% at C/3 and C/2 rates, respectively, in comparison to 68% and 58% for the wet-processed cells at the same rate. These findings provide valuable insights into the influence of fabrication methods on binder distribution and charge transport, contributing to a better understanding of the binder’s role in manufacturing of all-solid-state batteries.

Emley, Benjamin↗

Recent trends in all-organic polymer dielectrics for high-temperature electrostatic energy storage capacitors

Electrostatic energy storage (EES) capacitors are critical for renewable energy and high-power systems, driving the search for dielectric materials that combine superior electrical insulation, mechanical flexibility, low density, cost-effectiveness, and processability. Polymer-based dielectrics have emerged as leading candidates, particularly for high electric field applications. However, conventional polymers often fail to meet the demands of high-temperature environments due to increased electrical conductivity and reduced discharged energy density at elevated temperatures, resulting in energy loss and reduced performance. High glass transition temperature (T g) polymers show promise but require further optimization to enhance their energy storage capabilities under thermal and electrical stress. This review provides a comprehensive update on recent advancements in high-T g polymer-based dielectrics for EES capacitors, focusing on both intrinsic polymers and all-organic composites. It outlines key design principles, critical performance parameters, and innovative strategies—such as nanofiller doping, layered architectures, physical blending, and chemical crosslinking—to improve electrical, thermal, and mechanical properties. The review also highlights emerging trends, including the integration of machine learning algorithms to explore novel polymer structures and expand the chemical design space. By bridging the gap between academic research and industrial application, this review aims to accelerate the development of next-generation dielectric materials capable of balancing multiple performance metrics for high-temperature EES capacitors.

Xie, Zongliang↗

Metal-like Charge Transport in PEDOT(OH) Films by Post-processing Side Chain Removal from a Soluble Precursor Polymer

Herein, a route to produce highly electrically conductive doped hydroxymethyl functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) films, termed PEDOT(OH) with metal-like charge transport properties using a fully solution processable precursor polymer is reported. Further, this is achieved via an ester-functionalized PEDOT derivative [PEDOT(EHE)] that is soluble in a range of solvents with excellent film-forming ability. PEDOT(EHE) demonstrates moderate electrical conductivities of 20–60 S cm -1 and hopping-like (i.e., thermally activated) transport when doped with ferric tosylate (FeTos 3 ). Upon basic hydrolysis of PEDOT(EHE) films, the electrically insulative side chains are cleaved and washed from the polymer film, leaving a densified film of PEDOT(OH). These films, when optimally doped, reach electrical conductivities of ≈1200 S cm -1 and demonstrate metal-like (i.e., thermally deactivated and band-like) transport properties and high stability at comparable doping levels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗