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Results for “electronically conducting polymers”

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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Deformation Rate‐Adaptive Conducting Polymers and Composites

Abstract Materials are more easily damaged during accidents that involve rapid deformation. Here, a design strategy is described for electronic materials comprised of conducting polymers that defies this orthodox property, making their extensibility and toughness dynamically adaptive to deformation rates. This counterintuitive property is achieved through a morphology of interconnected nanoscopic core–shell micelles, where the chemical interactions are stronger within the shells than the cores. As a result, the interlinked shells retain material integrity under strain, while the rate of dissociation of the cores controls the extent of micelle elongation, which is a process that adapts to deformation rates. A prototype based on polyaniline shows a 7.5‐fold increase in ultimate elongation and a 163‐fold increase in toughness when deformed at increasing rates from 2.5 to 10 000% min −1 . This concept can be generalized to other conducting polymers and highly conductive composites to create “self‐protective” soft electronic materials with enhanced durability under dynamic movement or deformation.

Hernandez, Victor↗
DOE OSTI2021

Electronic, Ionic, and Mixed Conduction in Polymeric Systems

Polymers that simultaneously transport electrons and ions are paramount to drive the technological advances necessary for next-generation electrochemical devices, including energy storage devices and bioelectronics. However, efforts to describe the motion of ions or electrons separately within polymeric systems become inaccurate when both species are present. In this paper, we highlight the basic transport equations necessary to rationalize mixed transport and the multiscale materials properties that influence their transport coefficients. Potential figures of merit that enable a suitable performance benchmark in mixed conducting systems independent of end application are discussed. Practical design and implementation of mixed conducting polymers require an understanding of the evolving nature of structure and transport with ionic and electronic carrier density to capture the dynamic disorder inherent in polymeric materials.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
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↗
DOE OSTI2021

Microstructure and heteroatom dictate the doping mechanism and thermoelectric properties of poly(alkyl-chalcogenophenes)

Heteroatom substitution can favorably alter electronic transport in conductive polymers to improve their thermoelectric performance. Here we report the spectroscopic, structural, and thermoelectric properties of poly(3–(3',7'-dimethyloctyl) chalcogenophenes) or P3RX doped with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), where the heteroatom [X = thiophene (T), selenophene (Se), tellurophene (Te)], the doping methodology, and extent of doping are systematically varied. Spectroscopic measurements reveal that while all P3RX polymers are appreciably doped, the doping mechanism is inherently different. Poly(3-hexylthiophene) (P3HT, used as a control) and poly(3–(3',7'-dimethyloctyl)tellurophene) (P3RTe) are doped primarily via integer charge transfer (ICT), whereas poly(3–(3',7'-dimethyloctyl)selenophene) (P3RSe) and poly(3–(3',7'-dimethyloctyl)thiophene) (P3RT) are doped via charge transfer complex (CTC) mechanisms. Despite these differences, all polymers saturate with roughly the same number of F4TCNQ counterions (1 dopant per 4 to 6 heterocycles), reinforcing the idea that the extent of charge transfer varies with the doping mechanism. Grazing incidence wide-angle x-ray scattering measurements provide insight into the structural driving forces behind different doping mechanisms—P3RT and P3RSe have similar microstructures in which F4TCNQ intercalates between the π-stacked backbones resulting in CTC doping (localized carriers), while P3HT and P3RTe have microstructures in which F4TCNQ intercalates in the alkyl side chain region, giving rise to ICT doping (delocalized carriers). These structural and spectroscopic observations shed light on why P3HT and P3RTe obtain electrical conductivities ca. 3 S/cm, while P3RT and P3RSe have conductivities <10–3 S/cm under the same thin film processing conditions. Ultimately, this work quantifies the effects of heteroatom, microstructural ordering, extent of doping, and doping mechanism, thereby providing rational guidance for designing future thermoelectric polymer-dopant systems.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Side chain engineering control of mixed conduction in oligoethylene glycol-substituted polythiophenes

A major limitation for polymeric mixed ionic/electronic conductors (MIECs) is the trade-off between ionic and electronic conductivity; changes made that improve one typically hinder the other. In order to address this fundamental problem, this work provides insight into ways that we could improve one type of conduction without hindering the other. Here, we investigated a common oligoethylene glycol side chain polymer by adjusting the oxygen atom content and position, providing structural insights for materials that better balanced the two conduction pathways. The investigated polymer series showed the prototypical conflict between ionic and electronic conduction for oxygen atom content, with increasing oxygen atom content increasing ionic conductivity, but decreasing electronic conductivity; however, by increasing the oxygen atom distance from the polymer backbone, both ionic and electronic conductivity could be improved. Following these rules, we show that poly(3-(methoxyethoxybutyl)thiophene), when blended with lithium bistrifluoromethanesulfonimide (LiTFSI), matches the ionic conductivity of a comparable MIEC [poly(3-(methoxyethoxyethoxymethyl)thiophene)], while simultaneously showing higher electronic conductivity, highlighting the potential of this design strategy. We also provide strategies for tuning the MIEC performance to fit a desired application, depending on if electronic, ionic, or balanced conduction is most important. These results have implications beyond just polythiophene-based MIECs, as these strategies for balancing backbone crystallization and coordinating group interconnectivity apply for all semicrystalline conjugated polymers.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Dimensionality-Dependent Electronic Properties of the Highly Conducting n-Type Polymer, Poly(benzodifurandione)

Poly(benzodifurandione) (n-PBDF) has garnered significant interest as it displays the highest reported n-type electrical conductivity among π-conjugated polymers. Earlier theoretical studies of n-PBDF could not rationalize this high conductivity. Here, we explore the geometric and electronic properties of two-dimensional (2D) and three-dimensional (3D) n-PBDF networks using first-principles calculations and tight-binding models. In 2D networks, a metallic electronic configuration occurs when considering a coplanar geometry with BDF moieties bounded to protons on the same side; however, backbone torsions disrupt the metallic behavior. In contrast, all 3D architectures consistently lead to a metallic nature, which is not impacted by variations in proton positions and stacking patterns. Tight-binding models allowed us to evaluate the respective strengths of intra- and interchain electronic couplings in n-PBDF. Altogether, our investigations provide a comprehensive picture into the electronic properties of n-PBDF and shed light on how they are affected by system dimensionality, proton positions, and stacking patterns.

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

Open-Shell Donor–Acceptor Conjugated Polymers with High Electrical Conductivity

Conductive polymers largely derive their electronic functionality from chemical doping, processes by which redox and charge-transfer reactions form mobile carriers. While decades of research have demonstrated fundamentally new technologies that merge the unique functionality of these materials with the chemical versatility of macromolecules, doping and the resultant material properties are not ideal for many applications. Here, it is demonstrated that open-shell conjugated polymers comprised of alternating cyclopentadithiophene and thiadiazoloquinoxaline units can achieve high electrical conductivities in their native “undoped” form. Spectroscopic, electrochemical, electron paramagnetic resonance, and magnetic susceptibility measurements demonstrate that this donor–acceptor architecture promotes very narrow bandgaps, strong electronic correlations, high-spin ground states, and long-range π-delocalization. A comparative study of structural variants and processing methodologies demonstrates that the conductivity can be tuned up to 8.18 S cm -1 . This exceeds other neutral narrow bandgap conjugated polymers, many doped polymers, radical conductors, and is comparable to commercial grades of poly(styrene-sulfonate)-doped poly(3,4-ethylenedioxythiophene). X-ray and morphological studies trace the high conductivity to rigid backbone conformations emanating from strong π-interactions and long-range ordered structures formed through self-organization that lead to a network of delocalized open-shell sites in electronic communication. The results offer a new platform for the transport of charge in molecular systems.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Controlled Dedoping and Redoping of N‐Doped Poly(benzodifurandione) (n‐PBDF)

Abstract The doping levels of conjugated polymers significantly influence their conductivity, energetics, and optical properties. Recently, a highly conductive n‐doped polymer called poly (3,7‐dihydrobenzo[1,2‐b:4,5‐b′]difuran‐2,6‐dione) (poly(benzodifurandione), n‐PBDF) is discovered, opening new possibilities for n‐type conducting polymers in printed electronics and other fields. Controlling the doping level of n‐PBDF is of great interest due to its wide range of potential applications. Here controlled dedoping and redoping of n‐PBDF is reported and a mechanistic understating of such a process is provided. Dedoping occurs through electron transfer and proton capture, wherein the ionic dopants, tris(4‐bromophenyl)ammoniumyl hexachloroantimonate (Magic Blue), exhibit efficient proton capture ability and stronger interaction with n‐PBDF, resulting in high dedoping efficiency. Moreover, chemically dedoped PBDF can be redoped using various proton‐coupled electron transfer agents. By manipulating the doping levels of n‐PBDF thin films, ranging from highly doped to dedoped states, the system demonstrates controllable conductivity in five orders of magnitude, adjustable optical properties, and energetics. As a result, these characteristics demonstrate the potential applications of n‐PBDF in organic electrochemical transistors and thermoelectrics.

Chemistry↗
DOE OSTI2022

Lithium-sulfur battery with high sulfur loading

A lithium-sulfur battery cathode including conductive porous carbon particles vacuum infused with sulfur and a conductive collector substrate to which the sulfur infused porous carbon particles are deposited. The sulfur infused carbon particles are encapsulated by an encapsulation polymer, the encapsulation polymer having ionic conductivity, electronic conductivity, polysulfide affinity, or combinations thereof. A lithium-sulfur battery including the lithium-sulfur battery cathode, a lithium anode and an electrolyte disposed between the sulfur cathode and the lithium anode is also provided. Methods of producing the sulfur cathode for use in a lithium-sulfur battery by a hybrid vacuum-and-melt method are also provided.

Henslee, Brian E.↗
DOE OSTI2020

Dichlorinated Dithienylethene-Based Copolymers for Air-Stable n-Type Conductivity and Thermoelectricity

Here, two donor-acceptor polymers were obtained by coupling difluoro- and dichloro-substituted forms of the electron-deficient unit BDOPV and the relatively weak donor moiety dichlorodithienylethene (ClTVT). The conductivity and power factors of doped devices are different for the chlorinated and fluorinated BDOPV polymers. High electron conductivity of 38.3 and 16.1 S cm -1 were obtained from the chlorinated and fluorinated polymers with N-DMBI, respectively, and 12.4 and 2.4 S cm -1 were obtained from the chlorinated and fluorinated polymers with CoCp 2 , respectively, from drop-cast devices. The corresponding power factors are 22.7, 7.6, 39.5 and 8.0 μW m -1 K -2 , respectively. Doping of PClClTVT with N-DMBI results in excellent air-stability; the electron conductivity of devices with 50 mol% N-DMBI as dopant remained up to 4.9 S m -1 after 222 days in the air, the longest for an n-doped polymer stored in air, with a thermoelectric power factor of 9.3 μW m -1 K -2 . However, the conductivity of PFClTVT-based devices can hardly be measured after 103 days. These observations are consistent with morphologies determined by grazing incidence wide angle X-ray scattering (GIWAXS) and atomic force microscopy (AFM). The results demonstrate that chemical structures leading to dense and ordered packing can enhance electron conductivity and air stability of n-type donor-acceptor polymers.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2024

Direct electron beam patterning of electro-optically active PEDOT:PSS

The optical and electronic tunability of the conductive polymer poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) has enabled emerging applications as diverse as bioelectronics, flexible electronics, and micro- and nano-photonics. High-resolution spatial patterning of PEDOT:PSS opens up opportunities for novel active devices in a range of fields. However, typical lithographic processes require tedious indirect patterning and dry etch processes, while solution-processing methods such as ink-jet printing have limited spatial resolution. Here, we report a method for direct write nano-patterning of commercially available PEDOT:PSS through electron-beam induced solubility modulation. The written structures are water stable and maintain the conductivity as well as electrochemical and optical properties of PEDOT:PSS, highlighting the broad utility of our method. We demonstrate the potential of our strategy by preparing prototypical nano-wire structures with feature sizes down to 250 nm, an order of magnitude finer than previously reported direct write methods, opening the possibility of writing chip-scale microelectronic and optical devices. We finally use the high-resolution writing capabilities to fabricate electrically-switchable optical diffraction gratings. We show active switching in this archetypal system with >95 % contrast at CMOS-compatible voltages of +2 V and -3 V, offering a route towards highly-miniaturized dynamic optoelectronic devices.

42 ENGINEERING↗
DOE OSTI2023

Synthesis and exceptional operational durability of polyaniline-inspired conductive ladder polymers

Ladder-type structures can impart exceptional stability to polymeric electronic materials. This article introduces a new class of conductive polymers featuring a fully ladder-type backbone. A judicious molecular design strategy enables the synthesis of a low-defect ladder polymer, which can be efficiently oxidized and acid-doped to achieve its conductive state. The structural elucidation of this polymer and the characterization of its open-shell nature are facilitated with the assistance of studies on small molecular models. An autonomous robotic system is used to optimize the conductivity of the polymer thin film, achieving over 7 mS cm −1 . Impressively, this polymer demonstrates unparalleled stability in strong acid and under harsh UV-irradiation, significantly surpassing commercial benchmarks like PEDOT:PSS and polyaniline. Moreover, it displays superior durability across numerous redox cycles as the active material in an electrochromic device and as the pseudocapacitive material in a supercapacitor device. This work provides structural design guidance for durable conductive polymers for long-term device operation.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Redox active polymer devices and methods of using and manufacturing the same

The disclosed technology relates generally to apparatus comprising conductive polymers and more particularly to tag and tag devices comprising a redox-active polymer film, and method of using and manufacturing the same. In one aspect, an apparatus includes a substrate and a conductive structure formed on the substrate which includes a layer of redox-active polymer film having mobile ions and electrons. The conductive structure further includes a first terminal and a second terminal configured to receive an electrical signal therebetween, where the layer of redox-active polymer is configured to conduct an electrical current generated by the mobile ions and the electrons in response to the electrical signal. The apparatus additionally includes a detection circuit operatively coupled to the conductive structure and configured to detect the electrical current flowing through the conductive structure.

Johnson, Paul B.↗
DOE OSTI2021

Redox active polymer devices and methods of using and manufacturing the same

The disclosed technology relates generally to apparatuses comprising conductive polymers and more particularly to tags and tag devices comprising a redox-active polymer film, and methods of using and manufacturing the same. In one aspect, an apparatus includes a substrate and a conductive structure formed on the substrate which includes a layer of redox-active polymer film having mobile ions and electrons. The conductive structure further includes a first terminal and a second terminal configured to receive an electrical signal therebetween, where the layer of redox-active polymer is configured to conduct an electrical current generated by the mobile ions and the electrons in response to the electrical signal. The apparatus additionally includes a detection circuit operatively coupled to the conductive structure and configured to detect the electrical current flowing through the conductive structure.

Friesen, Cody A.↗
DOE OSTI2022

Redox active polymer devices and methods of using and manufacturing the same

The disclosed technology relates generally to apparatus comprising conductive polymers and more particularly to tag and tag devices comprising a redox-active polymer film, and method of using and manufacturing the same. In one aspect, an apparatus includes a substrate and a conductive structure formed on the substrate which includes a layer of redox-active polymer film having mobile ions and electrons. The conductive structure further includes a first terminal and a second terminal configured to receive an electrical signal therebetween, where the layer of redox-active polymer is configured to conduct an electrical current generated by the mobile ions and the electrons in response to the electrical signal. The apparatus additionally includes a detection circuit operatively coupled to the conductive structure and configured to detect the electrical current flowing through the conductive structure.

Johnson, Paul B.↗