Synthesis and thermoelectric performance of titanium diboride and its composites with lead selenide and carbon

The exploration of new thermoelectric material is the current area of research in energy conversion and storage technologies, in that nanocomposite approach is a promising root to get desirable thermoelectric properties. The present study demonstrates a composite containing highly conductive titanium diboride (TiB₂), polyvinyl alcohol (PVA) as binder and lead selenide (PbSe) as semiconductor. The synthesis and transport physics are studied with an intention to increase the power factor and figure of merit (ZT) of TiB₂ by reducing thermal conductivity through creating inhomogeneity in microstructures. Sol gel method and carbothermal reduction reaction have been used to synthesize TiB₂. More than 95% of thermal conductivity is reduced due to the phonon scattering, which is desirable to achieve a high power factor and ZT. TiB₂/PVA composite possesses a very low Seebeck coefficient and exhibits three order of magnitude reduction in electrical conductivity, which hinders in achieving a good power factor and ZT. Power factor of 25.3?µW/mK², Seebeck coefficient of 36.3 μV/K at 550?K and electrical conductivity of 2.5?×?10⁴ S/m at ~300?K and ZT of 0.064 at 550?K are worth to report in this study. Finally, the synthesized TiB₂ is incorporated into PbSe to evaluate thermoelectric properties. Maximum ZT of 0.12 at 495?K, Seebeck coefficient of ?342?µV/K at 550?K, electrical conductivity of 2.8?×?10³ S/m at 400?K, thermal conductivity of 1.03?W/mK at 550?K and highest power factor of 280.2?µW/mK² at 495?K have been achieved in this composite.     

Improved thermoelectric properties of SiC with TiC segregated network structure

A TiC segregated network structure (SNS) approach was utilised to improve the thermoelectric properties of SiC. Different amounts of TiC particles were dry coated on SiC granules to form electrically conductive SNS; then the powder mixtures were spark plasma sintered at 2200°C. The TiC-SNS simultaneously increased the electrical and decreased thermal conductivity of SiC but adversely affected the Seebeck coefficient. By adding 10 vol% TiC, an ≈ 800% increase in electrical conductivity and a ≈ 50% decrease in thermal conductivity were achieved, but the Seebeck coefficient deteriorated due to the metallic nature of the material. A maximum ZT of 5.04 × 10⁻³ was achieved at 923 K, by limiting the Seebeck coefficient's reduction by optimising TiC content to 1.5 vol% while simultaneously increasing the electrical conductivity by ≈ 100% and reducing thermal conductivity by ≈ 40%. This ZT value is almost 90% higher than any value recorded in the literature for SiC.     

The synthesis of covalent bonded single‐walled carbon nanotube/polyvinylimidazole composites by in situ polymerization and their physical characterization

Single‐walled carbon nanotube (SWCNT) polyvinylimidazole (PVI) composites have been prepared by in situ emulsion polymerization. Dispersion of raw SWCNTs in the PVI matrix was improved by surface modification of the SWCNTs using nitric acid treatment and air oxidation. The carbonyl‐terminated SWCNTs were covalently bonded to PVI by in situ polymerization and the SWCNT/PVI composite was thus obtained. The morphological and structural characterizations of the surface‐functionalized SWCNTs and SWCNT/PVI composites were carried out by Fourier transform infrared spectroscopy, X‐ray diffraction, conductivity measurements, scanning, and transmission electron microscopy. Thermograms of the materials were determined by the differential scanning calorimetry technique. The characterization results indicate that PVI was covalently bonded to SWCNTs and a new material was then obtained. The functionalized SWCNTs showed homogenous dispersion in the composites, whereas purified SWCNT resulted in poor dispersion and nanotube agglomeration. SWCNT/PVI composites exhibited chemical stability enhancement in many common solvents. I–V curves of the samples exhibit an ohmic character. Conductivity values for pure SWCNTs, pure PVI and SWCNT/PVI composite were measured to be 3.47, 2.11 × 10⁻⁹, and 2.3 × 10⁻³ S/m, respectively. Because of resonance, a large dielectric constant is obtained for SWCNT/PVI composite, which is not observed for ordinary materials. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Cellular structures of carbon nanotubes in a polymer matrix improve properties relative to composites with dispersed nanotubes

A new processing method has been developed to combine a polymer and single wall carbon nanotubes (SWCNTs) to form electrically conductive composites with desirable rheological and mechanical properties. The process involves coating polystyrene (PS) pellets with SWCNTs and then hot pressing to make a contiguous, cellular SWCNT structure. By this method, the electrical percolation threshold decreases and the electrical conductivity increases significantly as compared to composites with well-dispersed SWCNTs. For example, a SWCNT/PS composite with 0.5 wt% nanotubes made by this coated particle process (CPP) has an electrical conductivity of ∼3 × 10⁻⁴ S/cm, while a well-dispersed composite made by a coagulation method with the same SWCNT amount has an electrical conductivity of only ∼10⁻⁸ S/cm. The rheological properties of the composite with a macroscopic cellular SWCNT structure are comparable to PS, while the well-dispersed composite exhibits a solid-like behavior, indicating that the composites made by this new CPP are more processable. In addition, the mechanical properties of the CPP-made composite decrease only slightly, as compared with PS. Relative to the common approach of seeking better dispersion, this new fabrication method provides an important alternative means to higher electrical conductivity in SWCNT/polymer composites. Our straightforward particle coating and pressing method avoids organic solvents and is suitable for large-scale, inexpensive processing using a wide variety of polymers and nanoparticles.     

Electrical conductivity and tensile properties of block‐copolymer‐wrapped single‐walled carbon nanotube/poly(methyl methacrylate) composites

Poly(methyl methacrylate) (PMMA) composites containing raw or purified single‐walled carbon nanotubes (SWCNTs) are prepared by in situ polymerization and solution processing. The SWCNTs are purified by centrifugation in a Pluronic surfactant, which consists of polyethyleneoxide and polypropyleneoxide blocks. Both the effects of SWCNT purity and non‐covalent functionalization with Pluronic are evaluated. Electrical conductivity of PMMA increases by 7 orders of magnitude upon the integration of raw or purified SWCNTs. The best electrical properties are measured for composites made of purified SWCNTs and prepared by in situ polymerization. Strains at fracture of the SWCNT/PMMA composites are nearly identical to those of the neat matrix. A certain decrease in the work to fracture is measured, particularly for composites containing purified SWCNTs (?31.6%). Fractography and Raman maps indicate that SWCNT dispersion in the PMMA matrix improves upon the direct addition of Pluronic, while dispersion becomes more difficult in the case of purified SWCNTs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41547.     

Effects of preparation method on thermoelectric properties of poly(aniline-co-3,4-ethylenedioxythiophene)/SWCNT composites

Composites of conducting polymer and single-walled carbon nanotubes (SWCNTs) are attracting great attentions in harvesting low-grade waste heat. Prefabricated SWCNTs film used as the working electrode was placed at the liquid interface between the inorganic phase (dilute sulfuric acid solution) and the organic phase consisting of dichloromethane (DCM), aniline (ANI), and 3,4-ethylenedioxythiophene (EDOT), together with a platinum wire (the counter electrode) and a silver chloride (AgCl/Ag) electrode (the reference electrode), to perform electrochemical polymerization of ANI and EDOT at the liquid interface. Thermoelectric (TE) composites of poly(ANI-co-EDOT) and SWCNTs were produced. Compared with composites from ultrasonic mixing and coating methods, the 10 wt% SWCNTs-composites in situ formed in electrochemical polymerization have the highest power factor (PF) of 41.56 ± 3.58 μW m⁻¹ K⁻², higher than the PF values of the composites formed by other two methods. The work indicates that the TE properties of ANI-EDOT copolymer/SWCNT (poly[ANI-co-EDOT]/SWCNT) composites prepared by electrochemical polymerization were better than those of the composites obtained by physical mixing the electrochemically synthesized poly(ANI-co-EDOT) with SWCNTs. Moreover, SWCNTs treated with sodium dodecylbenzene sulfonate (SDBS) could further improve the TE properties of the composites.     

Electrical conductivity of carbon black/single-wall carbon nanotube/low-density polyethylene ternary composite foam

In order to obtain high electrical conductive low-density polyethylene (LDPE) foam, carbon black (CB), single-wall carbon nanotube (SWCNT), and LDPE (CB/SWCNT/LDPE) ternary composite foams were successfully fabricated by chemical compression molding method. The electrical conductivity, mechanical properties, microstructure, density, and crystallinity of the foam were studied in detail. It can be found that CB and SWCNT have synergistic effect. For the CB/SWCNT/LDPE composite foam which containing 19 wt % CB and 0.05 wt % SWCNT, its density is only 0.082 g cm⁻¹ and the electrical conductivity can reach at 2.88 × 10⁻⁵ S cm⁻³, which is far more than 15 orders of magnitudes of pure polyethylene and 4 orders of magnitudes times higher than sample which CB content is 19 wt %. It is noteworthy that ultralow concentration of SWCNT could drastically improve the electrical conductivity and reduce the density of LDPE foams. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48382.     

Nanocomposites of CuO/SWCNT: Promising thermoelectric materials for mid-temperature thermoelectric generators

Nanocomposites of ultra-thin copper oxide nanosheets (CuO NSs) and single-wall carbon nanotubes (SWCNTs) were produced and studied for their thermoelectric (TE) properties. Incorporating a small amount of SWCNTs into the matrix of CuO NSs enhanced the TE properties. This might be due to good band alignment between the two phases with large contact areas. The nanocomposite [CuO]_99.9[SWCNT]_0.1 showed a rapid increase with the increasing temperature in both the Seebeck coefficient and power factor. At 673 K, they reached 882 μV/K and 2500 μW/mK², respectively. The phonon and charge transport properties were attributed to the CuO NS/SWCNT interfaces. A small module of 2 p-n pairs based on CuO/SWCNT nanocomposites (p-type) and SnO₂ nanoparticles (n-type) was constructed and worked in a temperature range of 573–673 K with good stability and reusability. The measured output power was ˜1200 μW, which can power small electronic devices.     

Stability of electrical properties of carbon black‐filled rubbers

Conducting composites were prepared by melt mixing of ethylene–propylene–diene terpolymer (EPDM) or styrene‐butadiene rubber (SBR) and 35 wt % of carbon black (CB). Stability of electrical properties of rubber/CB composites during cyclic thermal treatment was examined and electrical conductivity was measured in situ. Significant increase of the conductivity was observed already after the first heating–cooling cycle to 85°C for both composites. The increase of conductivity of EPDM/35% CB and SBR/35% CB composites continued when cyclic heating‐cooling was extended to 105°C and 125°C. This effect can be explained by reorganization of conducting paths during the thermal treatment to the more conducting network. EPDM/35% CB and SBR/35% CB composites exhibited very good stability of electrical conductivity during storage at ambient conditions. The electrical conductivity of fresh prepared EPDM/35% CB composite was 1.7 × 10⁻² S cm⁻¹, and slightly lower conductivity value 1.1 × 10⁻² S cm⁻¹ was measured for SBR/35% CB. The values did not significantly change after three years storage. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of a novel biphenyl epoxy resin and its hybrid composite with high thermal conductivity

A novel biphenyl epoxy monomer of p-methyl phenylhydroquinone epoxy resin (p-MEP) was synthesized and characterized. We researched its potential in the area of thermal conduction application and prepared a series of hybrid composites based on it with different mass ratios of sphere Al₂O₃ filler. From the good mobility and low viscosity of p-MEP, it allowed mixing with more Al₂O₃ fillers. The hybrid epoxy resins owned the advantages of traditional epoxy resins as well as quite considerable thermal conductivity. Therefore, the hybrid composite at the maximum mass fraction of 70% possess the highest thermal conductivity of 5.6 W mK⁻¹, which is 5.6 times higher than that of pristine p-MEP (0.1 W mK⁻¹). © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47078.     

Enhancement in thermoelectric properties using a P‐type and N‐type thin‐film device structure

In this study, we have fabricated thermoelectric devices with p‐type and n‐type conducting polymers and research the effect of device structure with the thermoelectric properties. It was found that the p‐type and n‐type structure greatly enhances the device's electrical conductivity due to separated charge carrier channels, but the Seebeck coefficient was reduced due to the increase of charge density by doping. Photoexcitation can improve the device's thermoelectric properties and can increase the Seebeck coefficient and electrical conductivity with increasing doping concentration simultaneously. The increases in both properties are due to the phonon–electron coupling effect: the concentration of electrons and holes are increased under illumination, and the phonon component of the heat flux can be reduced by phonon scattering. Consequently, the thermoelectric device structure can improve the efficiency of thermoelectric conversion. The P3HT:PCBM devices demonstrate a significant enhancement in the power factor (PF = S²σ), with a maximum value of ZT = 0.5 at 147°C, in which the PF value (34.8 μV/cm K²) is bigger than Bi₂Te₃/Sb₂Te₃ superlattice devices at room temperature. POLYM. COMPOS., 34:1728–1734, 2013. © 2013 Society of Plastics Engineers     

Effect of moisture on the thermoelectric properties in expanded graphite/carbon fiber cement composites

A kind of dry mixing and pressing process was introduced to prepare expanded graphite/carbon fiber cement composites (EG-CFRC). Significant effect of moisture on the thermoelectric properties of EG-CFRC was observed. The higher the moisture content is, the greater the absolute Seebeck coefficient. The maximum of absolute Seebeck coefficient 11.59 μV/°C was obtained with moisture of 14.98% at 33 °C. Simultaneously, the maximum of electrical conductivity 0.78 S cm⁻¹ was got with moisture of 11.44%. Furthermore, the largest power factor 7.85×10⁻⁴ µW m⁻¹ K⁻² was calculated at 33 °C with moisture of 11.44%. The carrier scattering, polarization effects and high density defects interface of EG-CFRC are attributed to the enhancement of thermoelectric properties in the case of higher moisture content.     

Aluminum nitride‐single walled carbon nanotube nanocomposite with superior electrical and thermal conductivities

Development of aluminum nitride (AlN)‐single walled carbon nanotube (SWCNT) ceramic‐matrix composite containing 1‐6 vol% SWCNT by hot pressing has been reported in this article. The composites containing 6 vol% SWCNT are dense (~99% relative density) and show high dc electrical conductivity (200 Sm^?1) and thermal conductivity (62 Wm^?1K^?1) at room temperature. SWCNTs contain mostly metallic variety tubes obtained by controlled processing of the pristine tubes before incorporation into the ceramic matrix. Raman spectroscopy and field emission scanning electron microscopy (FESEM) of the fracture surface of the samples show the excellent survivability of the SWCNTs even after high‐temperature hot pressing. The results indicate the possibility of preparation of AlN nanocomposite for use in plasma devices and electromagnetic shielding.     

Differential scanning calorimetry analysis of an enhanced LiNi0.8Co0.2O2 cathode with single wall carbon nanotube conductive additives

The replacement of traditional conductive carbon additives with single wall carbon nanotubes (SWCNTs) in lithium metal oxide cathode composites has been shown to enhance thermal stability as well as power capability and electrode energy density. The dispersion of 1 wt% high purity laser-produced SWCNTs in a LiNi_0.8Co_0.2O₂ electrode created an improved percolation network over an equivalent composite electrode using 4 wt% Super C65 carbon black; evidenced by additive connectivity in SEM images and an order of magnitude increase in electrode electrical conductivity. The cathode with 1 wt% SWCNT additives showed comparable active material capacity (185–188 mAh g⁻¹), at a low rate, and Coulombic efficiency to the cathode composite with 4 wt% Super C65. At increased cycling rates, the cathode with SWCNT additives had higher capacity retention with more than three times the capacity at 10C (16.4 mA cm⁻²). The thermal stability of the electrodes was evaluated by differential scanning calorimetry after charging to 4.3 V and float charging for 12 h. A 40% reduction of the cathode exothermic energy released was measured when using 1 wt% SWCNTs as the additive. Thus, the results demonstrate that replacing traditional conductive carbon additives with a lower weight loading of SWCNTs is a simple way to improve the thermal transport, safety, power, and energy characteristics of cathode composites for lithium ion batteries.     

Improving tribological properties of phenolic resin/carbon fiber composites using m-Si3N4@PANI core–shell particles

Phenolic resin/carbon fiber (PF/CF) composites have good tribological properties; however, their extensive applications are limited because of the poor thermal conductivity of the phenolic resins. In this work, core‑shell particles of polyaniline-coated (3-aminopropyl) triethoxysilane-modified β-Si₃N₄ (m-SiN@PANI) were used to enhance the tribological, electrical, and thermal conductivity properties of a PF/CF composite. A core‑shell particle, consisting of m-SiN@PANI, was characterized by Fourier Transform Infrared Spectrometry, X-Ray Diffraction, Scanning Electron Microscope, and Transmission Electron Microscope. The friction, thermal, and electrical properties of the composites were characterized by multifunctional vertical friction testing, wear measurement testing, thermogravimetric analysis, thermal constant analysis, and electrical conductivity testing. Remarkably, the test results showed that compared with the wear surface of the PF/CF composite, that of the phenolic resin/(2.0 wt % m-SiN@PANI)/carbon fiber composite exhibited a smoother morphology. The results indicated that the addition of m-SiN@PANI effectively improved the thermal conductivity, electrical conductivity, friction coefficient, and wear rate of the composites, which were 3.164 Wm⁻¹ K⁻¹, 5.33 × 10⁻⁶ S/m, 0.1681 and 1.13 × 10⁻⁸ mm³/Nm, respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47785.     

Effects of hybrid fillers on the electrical conductivity,EMI shielding effectiveness,and flame retardancy of PBT and PolyASA composites with carbon fiber and MWCNT

The effects of hybrid fillers of carbon fiber (CF) and multiwall carbon nanotube (MWCNT) on the electrical conductivity, electromagnetic interference shielding effectiveness (EMI SE), flame retardancy, and mechanical properties of poly(butylene terephthalate) (PBT)/poly(acrylonitrile-co-styrene-co-acrylate) (PolyASA) (70/30, wt %) with conductive filler composites were investigated. The CF was used as the main filler, and MWCNT was used as the secondary filler to investigate the hybrid filler effect. For the PBT/PolyASA/CF (8 vol %)/MWCNT (2 vol %) composite, a higher electrical conductivity (1.4 × 10⁰ S cm⁻¹) and EMI SE (33.7 dB) were observed than that of the composite prepared with the single filler of CF (10 vol %), which were 9.0 × 10⁻² S cm⁻¹ and 23.7 dB, respectively. This increase in the electrical properties might be due to the longer CF length and hybrid filler effect in the composites. From the results of aging test at 85 °C, 120 h, the electrical conductivity and EMI SE of the composites decreased slightly compared to that of the composite without aging. The results of electrical conductivity, EMI SE, and flame retardancy suggested that the composite with the hybrid fillers of CF and MWCNT showed a synergetic effect in the PBT/PolyASA/CF (8 vol %)/MWCNT (2 vol %) composite. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48162.     

The influence of single-walled carbon nanotube functionalization on the electronic properties of their polyaniline composites

The “in situ” preparation and characterization of composites of polyaniline (PANI) and single-walled carbon nanotubes (SWCNTs) are reported. To improve the dispersion and compatibility with the polymer matrix the raw SWCNTs were modified following different routes. SWCNTs oxidized by chemical or thermal treatments (nitric acid and air oxidation, respectively) were subjected to covalent functionalization with octadecylamine (ODA). SWCNT/PANI composites were prepared either from just oxidized SWCNTs, or from ODA functionalized SWCNTs. Temperature-programmed desorption, elemental analyses, ultraviolet-visible (UV-vis), UV-vis with near infrared and Raman spectroscopy, X-ray diffraction, scanning and transmission electron microscopy and conductivity measurements were used to characterize the functionalized SWCNT materials, dispersions and composites. The PANI composite prepared from air oxidized SWCNTs showed the best electrical conductivity indicating a better interaction with polyaniline than ODA functionalised SWCNTs. The improvement of conductivity is attributed to the doping effect or charge transfer of quinoide rings from PANI to SWCNTs.     

Single-walled carbon nanotube/silicone rubber composites for compliant electrodes

Single-walled carbon nanotube (SWCNT)/silicone rubber composites that can be used in fabricating compliant electrodes are prepared by spraying a mixed solution of ionic-liquid-based SWCNT gel and silicone rubber onto an elastic substrate. Subsequently, the composites are exposed to nitric acid vapor. Scanning electron microscopy and atomic force microscopy images of the composites show that the SWCNTs are finely dispersed in the polymer matrix due to the addition of the ionic liquid. Doping of the SWCNTs by nitric acid can significantly lower the sheet resistance (R_s) of the composites; samples with 4 wt% of SWCNT content exhibit the lowest R_s value (50 Ω sq^?1). This sheet resistance corresponds to a conductivity value of 63 S cm^?1. In addition, the composites retain a high conductivity after several tensile strains are applied. Stretching the composite sample to 300% of the original length increased the R_s value to 320 Ω sq^?1 (19 S cm^?1). Even after 20th stretch/release/stretch cycle, the conductivity remains constant at a value of 18 S cm^?1. These results provide a scalable route for preparing highly stretchable and conductive SWCNT composites with relatively low SWCNT concentrations.     

Studies of thermoelectric transport properties of atomic layer deposited gallium-doped ZnO

The thermoelectric transport properties of atomic layer deposited (ALD) gallium doped zinc oxide (GZO) thin films were investigated to identify their potential as a thermoelectric material. The overall thermoelectric properties, such as the Seebeck coefficient and electrical conductivity, were probed as a function of Ga concentration in ZnO. The doping concentration was tuned by varying the ALD cycle ratio of zinc oxide and gallium oxide. The GZO was deposited at 250 °C and the doping concentration was modified from 1% to 10%. Sufficient thermoelectric properties appeared at a doping concentration of 1%. The crystallinity and electronic state, such as the effective mass, were investigated to determine the enhancement of the thermoelectric properties. The efficient Ga doping of GZO showed a Seebeck coefficient of 60 μV/K and an electrical conductivity of 1808.32 S/cm, with a maximum power factor of 0.66 mW/mK².     

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.