Heteroatom-doped reduced graphene oxide/polyaniline nanocomposites with improved n-type thermoelectric performance

Polyaniline (PANI) is a potential candidate for n-type thermoelectric (TE) materials owing to its intrinsic electrical conductivity, low thermal conductivity, and facile synthesis techniques. However, its low Seebeck coefficient and power factor have limited its widespread usage. In this study, nitrogen-doped, and sulfur-nitrogen co-doped reduced graphene oxide (rGO) were used for tuning the TE properties of PANI. Doped rGO and PANI/doped-rGO nanocomposites were prepared via hydrothermal technique and chemical oxidative polymerization respectively and thereafter characterized. The TE properties of the nanocomposites were also studied and an optimized Seebeck coefficient, power factor and zT value of −1.75 mV K⁻¹, 95 μW m⁻¹ K⁻² and 0.06, respectively were reported for the PANI nanocomposite containing 1 wt% sulfur-nitrogen co-doped rGO. These results suggest that PANI/heteroatom-doped rGO can serve as promising candidates for n-type based TE applications.     

Enhanced thermoelectric performance of poly(3,4‐ethylenedioxythiophene):poly(4‐styrenesulfonate) (PEDOT:PSS) with long‐term humidity stability via sequential treatment with trifluoroacetic acid

This paper reports a range of effective sequential chemical processes to enhance the thermoelectric performance of conducting poly(3,4‐ethylenedioxythiophene) films doped with poly(styrene sulfonate) anions (PEDOT:PSS). The electrical conductivity of the PEDOT:PSS films was significantly increased from 0.33 to 3748 S cm^?1 after a series of sequential treatments with trifluoroacetic acid (TFA) while the Seebeck coefficient and thermal conductivity were slightly reduced from 17.5 ± 1.2 to 16.0 ± 1.1 μV K^?1 and 0.537 to 0.415 W m^–1 K^?1 for the pristine film and treated film, respectively, leading to a significant improvement in power factor up to 97.1 ± 5.4 μW m^–1 K^?2. More importantly, around 80% of the electrical conductivity and Seebeck coefficient was retained after 20 days for these TFA‐treated PEDOT:PSS films, revealing the potential for real thermoelectric applications. © 2019 Society of Chemical Industry     

Ternary system based on polyaniline,graphene, and acrylic matrix applied to thermoelectric systems

Thermoelectric (TE) materials have attracted attention for offering a green option for power generation, due to their ability to convert thermal energy into electricity. In recent years, a promising way to achieve efficiency in TE properties has been proposed based on composites of conjugated polymers, such as polyaniline (PANI), and carbon nanomaterials such as graphene (GR). Since polyaniline and GR composites are promising fillers for organic thermoelectric materials (OTE), we expanded their investigations for a ternary system (TS), providing materials with multiple functionalities, and high performance. In this research work, a TS based on an acrylic matrix (ACR), GR, and PANI was successfully prepared through the combination of in situ polymerization of aniline in contact with GR and mechanical mixture of the resulting hybrid with an ACR. Structural and morphological characterization confirmed that GR affected PANI morphology and crystallinity. The band gap determination by Tauc's relation indicated the occurrence of π-π interaction between the chains and an increase of the electrical conductivity of the composites allowed to infer a synergistic effect. The measured Seebeck coefficient reached a maximum value of −17.02 μVK⁻¹ and the highest power factor obtained was 4.94 μWm⁻¹ K⁻² for the ACR/PANI sample, indicating a material with promising thermoelectric properties.     

Incorporation of 4‐aminobenzene functionalized multi‐walled carbon nanotubes in polyaniline for application in formic acid electrooxidation

Incorporation of carbon nanotubes (CNTs) in conducting polymer can lead to new composites with enhanced electrical and mechanical properties. However, the development of such composites has been hampered by the inability to disperse CNTs in polymer matrix due to the lack of chemical compatibility between polymers and CNTs. Covalent sidewall functionalization of carbon nanotube provides a feasible route to incorporate carbon nanotube in polymer. In this work, 4‐aminobenzene groups were grafted onto the surface of multi‐walled carbon nanotube (MWNT) via C? C covalent bond. Polyaniline (PANI)/MWNT composites were fabricated by electrochemical polymerization of aniline containing well‐dissolved functionalized MWNTs. The obtained composites can be used as catalyst supports for electrooxidation of formic acid. Cyclic voltammogram results show that platinum particles deposited in PANI/MWNT composite films exhibit higher electrocatalytic activity and better long‐term stability towards formic acid oxidation than that deposited in pure PANI films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

High Thermal Conductivity Nanocomposites Based on Conductive Polyaniline Nanowire Arrays on Boron Nitride

With the development of soft electronics, conductive composites are garnering an increasing amount of attention. The electrical conductivity, thermal conductivity, and electrical stability of conductive composites are all very important. In particular, the thermal conductivity of conductive composites is critical to the stability of their conductive properties. However, little is reported on thermal management in conductive systems. Herein, sufficiently hydroxylated boron nitride nanosheets (BN‐OH)@polyaniline (PANI) composite nanosheets with a high thermal conductivity and outstanding conductance stability are reported. PANI nanowire arrays are aligned vertically on BN‐OH. This well‐ordered nanostructure provides the means to form a good conductive and thermally conductive path. Notably, the composite through‐plane thermal conductivity is 2.1 W m^?1 K^?1(≈1000% that of pure PANI) and that the resistivity of the composite is 1.38 Ω cm. Importantly, the resistivity of the composite remains unchanged after 1 h of work. The results show that this composite has prospective applications for use in soft electronics.     

Transport Properties of the Binary Type I Clathrate K8Ge44□2

We report the synthesis and low-temperature electrical resistivity, Seebeck coefficient, and thermal conductivity of the binary type I clathrate K₈Ge₄₄□₂ (□=Ge framework vacancy). Electrical resistivity measurements indicated metallic or heavily doped semiconductor behavior, while the Seebeck was relatively high at −77 μV/K at room temperature. The thermal conductivity was very low, on the order of 1 W/m K at room temperature. This work is part of a continuing effort to investigate new compositions in open-structured and guest-framework materials for potential thermoelectric applications.     

Fabrication and properties of solution‐cast polyaniline/carboxymethylchitin blend films

Blend films consisting of polyaniline in emeraldine base form (PANI EB) dispersed in partially cross‐linked carboxymethylchitin (CM‐chitin) were prepared by solution casting, and characterized for their physical, thermal, and electrical properties. Homogeneous and mechanically robust blend films were obtained having PANI EB contents up to 50 wt % in the CM‐chitin matrix. FTIR spectra confirm intimate mixing of the two blend components. The thermal stability of the blend films increased with increase of PANI EB content, suggesting the formation of an intermolecular interaction, such as hydrogen bonding, between PANI EB and CM‐chitin chains. The addition of PANI EB into the pure CM‐chitin film resulted in a decrease in electrical conductivity of the films owing to disruption of ionic conduction of the CM‐chitin structure. After doping the blend films by immersion in HCl solution, the electrical conductivity of the HCl‐doped films increased with increase of the PANI EB content to a maximum value of the order of 10^?3 S/cm at 50 wt % PANI EB content. The electrical conductivity of the blend films was also dependent on the HCl concentration as well as on the type of acid dopant. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Enhancement of thermoelectric conversion efficiency of polymer/carbon nanotube nanocomposites through foaming‐induced microstructuring

Semiconducting‐based materials such as bismuth antimony are current thermoelectric (TE) materials of choice because of their superior TE efficiency, which can be characterized by the dimensionless figure of merit (ZT). However, factoring the cost, weight, and environmental concerns, polymeric TE material systems have become attractive alternatives despite their lower ZT values. The potential to tailor the flexibility of polymeric TE materials also represent another key advantage, especially for wearable electronics. One of the key challenges to enhance their ZT values is the need to simultaneously increase the electrical conductivity and the Seebeck coefficient, while supressing the thermal conductivity. In this research, physical foaming is suggested as an innovative and effective processing strategy to circumvent this challenge. Multi‐walled carbon nanotube (MWCNT)/high density polyethylene (HDPE) nanocomposite foams were fabricated as a case example. Experimental results showed that introducing cellular structures in MWCNT/HDPE nanocomposites, loaded with 15 wt % MWCNT, would result in a 600‐fold increase in their ZT values. This great improvement was achieved through significantly reducing their effective thermal conductivity, while simultaneously increasing their electrical conductivity and Seebeck coefficients. The findings have proven that foaming can serve as a novel strategy to enhance the efficiency of various polymeric TE materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45073.     

Ca3Co4O9陶瓷的制备和热电性能

氧化物半导体陶瓷材料是新型的中、高温热电材料。采用传统固相合成法和溶胶－凝胶法成功地制备了Ca3Co4O9陶瓷。对它们的显微结构和热电性能（Seebeck系数、电导率和热导率）进行了研究。实验结果表明，由两种方法制备得到的Ca3Co4O9陶瓷具有类似的热电性能。Ca3Co4O9陶瓷为取向无规则片状结构，属于p型半导体热电材料，其热电品质因子随温度升高而增大。Ca3Co4O9陶瓷具有大的Seebeck系数和低的热导率，但它的电导率仍然偏低，导致了它的热电品质因子比传统热电合金的热电品质因子低。     

Formation and thermoelectric property of TiO2 nanotubes covered by Te–Bi–Pb nanoparticles

A variety of strategies have been attempted to improve the performance of thermoelectric materials. The primary approach is to employ low-dimensional materials to reduce the lattice thermal conductivity as described by the Wiedemann–Franz law. That is, to decrease the thermal conductivity, rattling structures, point defects, vacancies and nanocomposites have been used to efficiently scatter phonons within or between the unit cell crystals. Complex crystalline structures have been used to decouple the electrical conductivity and thermal conductivity to achieve this goal. Based on such considerations, we have prepared TiO₂ nanotubes from titanium foils. These nanotubes are low-dimensional, thus, preferable to achieve low lattice thermal conductivity to generate favorable thermoelectric properties. Moreover, scattered Te–Bi–Pb nanoparticles have been deposited on the surface of the TiO₂ nanotubes via electrochemical method. The purpose of the nanoparticles is to further enhance the performance of the thermoelectricity, specifically in our case, to increase the Seebeck coefficient. From the results obtained, the best Seebeck coefficient for pure TiO₂ nanotubes is about 90 μV/K; while the best Seebeck coefficient for TiO₂ nanotubes covered with scattered Te–Bi–Pb nanoparticles is about 155 μV/K. This significant improvement could be explained by the quantum confinement in such a peculiar nanostructure.     

Synthesis and characterization of conductive composite films of polyisoprene/PA12@ PANI

Polyamide@Polyaniline powders of core‐shell structure are known to have reduced conduction thresholds useful to maintain the mechanical and optical properties of the matrix. However, difficulties emerge at the synthesis stage, where dissolving the matrix without damaging the core‐shell particles becomes a challenge. The present solution avoids using solvents. Conductive polymer films containing solid Polyamide@Polyaniline particles are elaborated by UV photoreticulation of a liquid polyisoprene serving as a matrix. The conductive powders are obtained by in‐situ polymerization of aniline in presence of polyamide 12 (PA12) at room temperature using Dodecyl benzene sulfonic doping acid and Ammonium persulfate oxidant. Obtained films exhibit low percolation threshold compared to those containing pure solid polyaniline (PANI) particles even more conductive. This threshold is shown to be about 1.5 wt % of PANI. Films show good electrical conductivity and thermal stability up to 200°C allowing their use as antistatic polymer films for high temperatures. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39833.     

Enhanced thermoelectric performance by alcoholic solvents effects in highly conductive benzenesulfonate‐doped poly(3,4‐ethylenedioxythiophene)/graphene composites

Benzenesulfonate‐doped poly(3,4‐ethylenedioxythiophene) (PEDOT‐Bzs)/graphene thermoelectric (TE) composites with various graphene filler contents were synthesized in five different kinds of solvents. Dodecylbenzenesulfonic acid (DBSA) was used to achieve good dispersion of graphene into the PEDOT matrix. Among the synthesized PEDOT materials, the one synthesized in methanol (PEDOT‐MeOH) had the highest electrical conductivity. X‐ray photoelectron spectroscopy (XPS) analysis showed almost the same charge carrier concentration for all PEDOT materials. However, the X‐ray diffraction (XRD) analysis highlighted the enhancement of PEDOT chain stacking by shorter‐chain alcoholic solvents, as a result of which the carrier mobility and electrical conductivity were increased. The electrical conductivity and the Seebeck coefficient of the PEDOT/graphene composites were significantly improved with increasing the graphene content, which strongly depended on increased carrier mobility. The thermal conductivity of the composites exhibited relatively small changes, attributed to phonon scattering effects. The maximum TE efficiency of the PEDOT‐MeOH/graphene composite with 75 wt % graphene showed a substantially improved value of 1.9 × 10^?2, higher than that of the other PEDOT/graphene composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42107.     

Thermoelectric Properties of Pb‐Doped BiCuSeO Ceramics

A high‐performance thermoelectric BiCuSeO oxyselenides has been prepared by a simple fabrication approach. Phase composition and microstructure analysis indicate that the obtained ceramic samples are almost BiCuSeO phase with plate structure. Our results show that Pb‐doped BiCuSeO bulks have good electrical conductivity, large Seebeck coefficient, and low thermal conductivity. A large power factor ~672 μ/Wm/K² at 573 K can be observed in the BiCuSeO ceramic by the 10% Pb doping, and the dimensionless figure of merit (ZT) can reach 0.95 at 873 K, which makes them promising candidates for thermoelectric applications.     

Polyaniline‐coated PET conductive yarns: Study of electrical,mechanical, and electro‐mechanical properties

Intelligent and multifunctional yarns (textiles) have attracted interest because of their high potential in applications such as flexible displays, batteries, or sensors. The main objective of our research was to obtain the flexible and electrically conducting yarn based on the conductive polymer and polyethylene terephtalate (PET) yarns. Among the conductive polymers, polyaniline (PANI) is considered as a promising material and is well adapted for modifications of textile structure because of its excellent environmental, thermal, and chemical stability. Chemical PANI coating on PET yarns was performed by absorption of yarns through PANI solution. The electrical, mechanical, and electro‐mechanical properties of PET conductive yarns prepared were investigated. The environmental effects on the electrical and mechanical properties of the obtained conductive yarns were also studied. These conductive yarns are expected to be used as fibrous sensors, connection devices in smart clothing, and for electromagnetic shielding applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1252–1256, 2006     

Conductive IPN based on polyaniline and silicon‐crosslinked styrene‐isoprene‐styrene triblock copolymer

A series of new conducting interpenetrating polymer networks (IPNs) are prepared by sequential crosslinking reactions of tetraethyl orthosilicate with silicon‐grafted functional styrene‐isoprene‐styrene triblock copolymer (SIS) and polyaniline (PANI) doped with dodecylbenzenesulfonic acid (DBSA). The various factors affecting the properties of conductive IPNs are investigated. The conductivity is found to increase only slightly after the IPN films are treated at 140 ° C . The thermal stability of the IPNs is much better than that of the pure polymer under nitrogen atmosphere, as shown by the results from thermal gravimetry analysis (TGA). © 1999 Society of Chemical Industry     

Increasing the thermoelectric power factor of polymer composites using a semiconducting stabilizer for carbon nanotubes

Poly(vinyl acetate) (PVAc) copolymer latex-based composites were prepared with multi-walled carbon nanotubes (MWCNT), stabilized with sodium deoxycholate (DOC) or meso-tetra(4-carboxyphenyl) porphine (TCPP). SEM images show that a segregated MWCNT network developed during drying, which resulted in relatively low percolation thresholds (1.62 and 2.17 wt.% MWCNT for DOC and TCPP, respectively). The electrical conductivity (σ) of TCPP-stabilized composites is very similar to that of DOC-stabilized, while the thermopower (or Seebeck coefficient (S)) is five times as large. This enhanced thermopower suggests the MWCNT:TCPP/PVAc composite will have an order of magnitude greater power factor (S²σ), which is an important measure of efficiency for thermoelectric materials (i.e., materials capable of converting a thermal gradient to a voltage). The thermal conductivity of these composites remains comparable to typical polymeric materials due to numerous tube–tube connections that act as phonon scattering centers. The universality of this approach was confirmed using much more electrically conductive double-walled carbon nanotube-filled composites that showed similar improvement with TCPP stabilization. It is possible that other porphyrin derivatives, or semiconducting molecules capable of stabilizing nanotubes in water, could be used to further enhance the Seebeck coefficient and improve the ability of these composites to convert waste heat into electricity.     

Assessment of mechanical performance,thermal stability and water resistance of novel conductive poly(lactic acid)/modified natural rubber blends with low loading of polyaniline

Biodegradable conductive polymer blends made from poly(lactic acid) (PLA), liquid natural rubber (LNR) and polyaniline (PANI) were prepared via a melt‐blending technique assisted by ultrasonic treatment. The effects of PANI at low loading (0.03 to 0.11 wt%) on the electrical conductivity and mechanical, thermal and physical properties of PLA/LNR/PANI blends were investigated. It was found that the mechanical properties of samples improved when PANI was introduced into PLA/LNR. Tensile results showed that the optimum loading of PANI was achieved at 0.07 wt% with an improvement of 8% in tensile strength compared to neat PLA/LNR. Although it was at low loading, the incorporation of PANI promoted an outstanding electrical conductivity to PLA/LNR blends. Thermal analysis of the PLA/LNR/PANI blends was conducted using differential scanning calorimetry and thermogravimetry. The thermal stabilities of the blends were improved markedly with the presence of PANI. Comparing to PLA/LNR, the incorporation of PANI component improved the resistance towards water absorption. Variable‐pressure scanning electron microscopy micrographs of PLA/LNR/PANI confirmed the good mixing of PANI with PLA/LNR and strong interaction networks among the PANI, PLA and LNR components. © 2018 Society of Chemical Industry     

The effect of graphite oxide on the thermoelectric properties of polyaniline

Graphite oxide (GO)/ordered polyaniline (PANI) composites have been prepared through an in situ polymerization. TEM, XRD, FTIR and XPS analyses show that the PANI grew along the surface of exfoliated GO as a template to form a more ordered structure with high crystallinity during polymerization. Compared with pure PANI, both higher electrical conductivity and higher Seebeck coefficient of GO/PANI composites result from the increased carrier mobility, which is confirmed by Hall measurement. Strong interactions exist between graphene oxide and PANI, including electrostatic forces, hydrogen bonding and π–π stacking. There is no significant difference in thermal conductivity between GO/PANI composites and PANI. The maximum electrical conductivity and Seebeck coefficient of the composites reach 751 S m^?1 and 28.31 μV K^?1, respectively. The maximum thermoelectric figure of merit is up to 4.86 × 10^?4, 2 orders of magnitude higher than that of pure PANI.     

The Cross‐Linking Effect on the Thermoelectric Properties of Conjugated Polymer/Carbon Nanotube Composite Films

Composite insulating organic material with conducting inorganic nanomaterial is a promising way to compensate the electrical conductivity, which is a prerequisite for the practical realization of the organic thermoelectrics. It is demonstrated that organic–inorganic interfacial interactions play critical rules for composites' thermoelectric performance. Here, an alternative interfacial engineering approach is proposed; that is, post‐blending cross‐linking of conjugated polymers (CPs). CPs substituted by exo‐olefin side chains that can form covalent cross‐linking via ruthenium‐catalyzed olefin metathesis are newly designed and synthesized. Pre‐cross‐link CP/single‐walled carbon nanotube (SWCNT) composites exhibit relatively high power factor that reach up to 70.3 µW m^?1 K^?2. It is found that the cross‐linking process, using second generation Grubbs reagent, is detrimental to the thermoelectric performance. Cross‐linked composites exhibit much lower power factor (0.77–19.7 µW m^?1 K^?2) mainly due to the low electric conductivity of the samples, while there is no significant change in Seebeck coefficient. It may be because the formation of tightly cross‐linked network hinders the transport of carriers in CP/SWCNT, resulting in a significant decrease in the electric conductivity. These structure–property relationship studies provide useful guidelines for designing organic thermoelectric materials with performance improvement and applied green processing.     

Micro‐contact reconstruction of adjacent carbon nanotubes in polymer matrix through annealing‐Induced relaxation of interfacial residual stress and strain

Thermoplastic polyurethane (TPU)/multi‐walled carbon nanotubes (CNT) nanocomposites were prepared by twin‐screw extrusion and micro injection molding. The electrical conductivity of micro injection molded polymer nanocomposites exhibits a low value and uneven distribution in the micromolded samples. Real‐time tracing of electrical conductivity was conducted to investigate the post thermal treatment on the electrical conductivity of microinjection molded composites. The results show that postmolding thermal treatment leads to a significant increase in the electrical conductivity by over three orders of magnitude for 5 wt % CNT‐filled TPU composites. In‐situ Transmission electron microscopy confirms the conductive CNT network does not change at the micron/sub‐micron scale during thermal treatment. TEM image analysis by a statistical method was used to determine the spatial distribution of CNT in the sample and showed that the average distance between adjacent CNT reduced slightly at the nanometer scale after postmolding thermal treatment. A new conductive mechanism is proposed to explain the enhancement of electrical conductivity after thermal treatment, i.e. micro‐contact reconstruction of adjacent CNT in the polymer matrix through annealing‐induced relaxation of interfacial residual stress and strain. Raman spectra and small angle X‐ray scattering curve of annealed samples provide supporting evidence for the proposed new conductive mechanism. The electron tunneling model was used to understand the effect of inter‐particle distance on the conductivity of polymer composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42416.