Poly[dithio-2,5-(1,3,4-thiadiazole)] (PDMcT)–poly(3,4-ethylenedioxythiophene) (PEDOT) composite cathode for high-energy lithium/lithium-ion rechargeable batteries

We present a characterization of the redox behavior of organosulfur-based composite cathodes composed of poly[dithio-2,5-(1,3,4-thiadiazole)] (PDMcT), which is a polymer derived from 2,5-dimercapto-1,3,4-thiadiazole (DMcT), and poly(3,4-ethylenedioxythiophene) (PEDOT) in a carbonate-based mixed solvent containing 1.0 M LiBF₄. We have previously shown that PEDOT films, electrochemically generated at glassy carbon electrode surfaces, gave rise to a dramatic enhancement of the interfacial charge transfer kinetics of DMcT in solution. In a similar fashion, chemically prepared PEDOT films exhibited dramatic electrocatalytic activity towards the redox reactions of PDMcT in the composite cathodes. While the composite cathode exhibited a very high capacity of 205 mAh g⁻¹ (based on the electroactive mass) at the first discharge, in subsequent charge/discharge tests, the capacity of the PDMcT–PEDOT composite cathode (1:1 mole ratio) decreased significantly because of dissolution of the reduction products of PDMcT into the electrolyte solution. We also found that an ionic polymer, consisting of a mixture of PEDOT and polystyrene sulfonate (PEDOT–PSS) could electrostatically, but not physically, prevent, at least in part, leaching of the DMcT species into the electrolyte solution, thus improving the coulomb efficiency for the redox reactions of DMcT in a PDMcT–PEDOT composite film during charge/discharge cycles.     

Porous NiO/poly(3,4-ethylenedioxythiophene) films as anode materials for lithium ion batteries

NiO/poly(3,4-ethylenedioxythiophene) (PEDOT) films are prepared by chemical bath deposition and electrodeposition techniques using nickel foam as the substrate. These composite films are porous, and constructed by many interconnected nanoflakes. As anode materials for lithium ion batteries, the NiO/PEDOT films exhibit weaker polarization and better cycling performance as compared to the bare NiO film. Among these composite films, the NiO/PEDOT film deposited after 2 CV cycles has the best cycling performance, and its specific capacity after 50 cycles at the current density of 2 C is 520 mAh g⁻¹. The improvements of these electrochemical properties are attributed to the PEDOT, a highly conductive polymer, which covers on the surfaces of the NiO nanoflakes, forming a conductive network and thus enhances the electrical conduction of the electrode.     

Immobilization of Trametes hirsuta laccase into poly(3,4-ethylenedioxythiophene) and polyaniline polymer-matrices

The immobilization of Trametes hirsuta laccase (ThL) in the poly(3,4-ethylenedioxythiophene) (PEDOT) and polyaniline (PANI) matrices was carried out in order to study the catalytic effect of ThL in different biocathode structures in a biofuel cell application. By using 2,2′-azinobis (3-ethylbenzothiazoline-6-sulfonate) (ABTS) as a mediator compound, the immobilized ThL in both polymer matrices, exhibited catalytic activity for the reduction of oxygen into water. The amount of ThL was adjustable in the PEDOT matrix by controlling the working parameters, such as the charge density used in the electropolymerization of EDOT monomer and the ThL concentration used in the electropolymerization electrolyte. In the PEDOT biocathode structure, the utilization of porous material as the PEDOT supporting template was studied in order to improve the current density generated per unit area/volume. Reticulated vitreous carbon foam (RVC foam) was chosen as the PEDOT supporting template material and the biocathodes were manufactured by in situ entrapment of ThL into PEDOT films polymerized on the RVC foam. These biocathodes possessed a high cathodic open circuit potential and produced a large current density, reaching 1 mA cm⁻³ at 0.45 V when 19.5 μg ml⁻¹ of ThL was used in the electrolyte. The performance of these biocathodes was extremely sensitive to variations in pH and the optimal working pH was around 4.2. The biocathode reserved 80%, 50%, and 30% of the catalytic activity after storage in a +4 °C buffer solution for 1 day, 1 week, and 1 month, respectively. The PANI matrix was prepared in a form of printable ink where ThL was in situ entrapped in the PANI matrix during the laccase activated polymerization of aniline using a chemical batch reactor method. Different amounts of the ThL-containing printable PANI ink were then applied on carbon paper and the performance of the ink was subsequently electrochemically characterized. In this way, not only two different polymer matrices, but also two different matrix manufacturing procedures could be compared.     

A complementary electrochromic device based on polyaniline and poly(3,4-ethylenedioxythiophene)

In this study, two conducting polymers, polyaniline (PANI) and poly(3,4-ethylenedioxythiophene) (PEDOT), were used to construct an electrochromic device (ECD). PANI was employed as the anodic coloring polymer while PEDOT was used as the cathodic coloring polymer. The electrochemical and optical properties of PANI, which has a coloration efficiency of 25 cm²/C at 570 nm, were coupled with the complementary coloring material, PEDOT, which has a coloration efficiency of 206 cm²/C at 570 nm. A suitable operating potential window was switched between −0.6 and 1.0 V to explore the cycle life of the ECD. We tested the PANI–PEDOT ECD, which consisted of PANI, PEDOT, and an organic electrolyte containing 0.1 M LiClO₄ in propylene carbonate and 1 mM HClO₄. The transmittance of the ECD at 570 nm changed from 58% (−0.6 V) to 14% (1.0 V) with a coloration efficiency of 285 cm²/C. Within the selected operating voltage range, the PANI–PEDOT ECD could be cycled for up to 2×10⁴ cycles.     

Improvement of the electrochemical properties via poly(3,4-ethylenedioxythiophene) oriented micro/nanorods

Arrays of oriented poly(3,4-ethylenedioxythiophene) (PEDOT) micro/nanorods are synthesized by electrochemical galvanostatic method at the current density of 1 mA cm⁻² in the cetyltrimethylammonium bromide (CTAB) aqueous solution whose pH value is 1. The CTAB is used both as the surfactant and the supporting salt in the electrolyte solution. The electrochemical properties of PEDOT films are characterized by cyclic voltammetry and galvanostatic charge/discharge techniques, which indicate that the arrays of oriented PEDOT micro/nanorods can be applied as the electrode materials of supercapacitors. In addition, the cycling performance of PEDOT micro/nanorods is much better than that of traditional PEDOT particles. The effects of the concentration of CTAB, the current density, and pH value of electrolyte solutions on the morphologies and electrochemical properties of PEDOT films are investigated. The mechanism of different morphologies formation is discussed in this study as well.     

A cross-linked sheet structured poly(3,4-ethylenedioxythiophene) grown on Ni foam: Morphology control and application for long-life cyclic asymmetric supercapacitor

In this work, a cross-linked sheet structured conducting polymer ploy(3,4-ethylenedioxythiophene) (PEDOT) decorated on Ni foam is synthesized via one-step electrodeposition using the sodium p-toluenesulfonate (STSA) as surfactant and applied for supercapacitor electrode. The surfactants play a vital role in controlling the morphologies of PEDOT leading to the electrochemical performance difference. The optimized PEDOT electrode exhibits the highest capacitance of 711.6 mF cm⁻² at 3.0 mA cm⁻² in the three-electrode system. An asymmetric device (PEDOT/STSA//AC) is constructed by PEDOT/STSA (the positive electrode), activated carbon (AC) (the negative electrode) as well as 1 M Na₂SO₄ (the electrolyte). The device has been worked in a high-voltage range of 0–1.5 V, which displays the satisfied energy density of 14.0 Wh·kg⁻¹ at 535.5 W kg⁻¹. Furthermore, the PEDOT/STSA//AC device presents excellent rate capability and long-time cyclic stability.     

Cycling and at-rest stabilities of a complementary electrochromic device containing poly(3,4-ethylenedioxythiophene) and Prussian blue

PEDOT-based electrochromic devices (ECDs) have been investigated intensively in recent years. In order to obtain an ECD having long cycle life, the counter electrode and electrolyte used should be compatible in the electrochemical environment. Prussian blue (PB) is proven to be electrochemically stable when cycling in non-aqueous solutions. Thus a new organic-inorganic complementary ECD was assembled in combination with a PMMA-based gel polymer electrolyte. This ECD exhibited deep blue-violet when applying −2.1 V and became light blue when applying 0.6 V. Under these conditions, the transmittance of the ECD at 590 nm changed from 13.8% (−2.1 V) to 60.5% (+0.6 V) with a coloration efficiency of 338 cm²/C. The cell retained 55% of its maximum transmittance window (ΔT_max) after 50,640 repeated cycles. Moreover, the at-rest stability test revealed a transmittance window (ΔT) decay of 9.6% over a period of 107 days. Therefore, the proposed PEDOT-PB ECD may have potential for practical applications.     

The effects of hyperbranched poly(siloxysilane)s on conductive polymer aluminum solid electrolytic capacitors

An aluminum solid electrolytic capacitor, using poly-(3,4-ethylenedioxythiophene) (PEDOT) as a counter electrode, was prepared with hyperbranched poly(siloxysilane)s (HBPSi) that has a large number of vinyl groups to improve the interfacial properties between aluminum oxide and PEDOT. Capacitance and equivalent series resistance (Rs) were significantly improved compared to untreated oxide film and vinyl terminated polydimethylsiloxane coated interfaces. From electrochemical measurement of the withstand voltage, damage to the oxide film from chemical polymerization of PEDOT was less with the HBPSi treatment. Frequency characteristics and electrical conductivity measurements of the polymer indicated that the resistance inside the etched porous layer was greatly reduced. These results show that the HBPSi pre-coating layer inhibited degradation of the oxide film by chemical polymerization of PEDOT and the conductivity of PEDOT in the etched porous oxide layer, and also enlarges the contact area by improving interfacial adhesion.     

Boosting the performance of poly(ethylene oxide)-based solid polymer electrolytes by blending with poly(vinylidene fluoride-co-hexafluoropropylene) for solid-state lithium-ion batteries

To seek a solid polymer electrolyte (SPE) with excellent performance, a novel poly(ethylene oxide) (PEO) based SPE is prepared by blending an appropriate amount of microcrystalline poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) with PEO using a universal solution casting method. Field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and differential scanning calorimetry (DSC) are utilized to analyse the samples. The crystallinity of the blend solid polymer electrolyte is significantly lower than that of the neat PEO-based SPE. The addition of the PVDF-HFP disrupts the segment structure of the PEO crystal region and increases the proportion of the amorphous region, thus boosting the migration of lithium ions. The results show that the electrochemical stability window of the blend solid polymer electrolyte reaches as high as 4.8 V. The initial discharge specific capacity of the solid-state LiFePO₄/SPE/Li battery is 131 mAh g⁻¹ at 0.5 C and 60°C, and the discharge specific capacity is still 110.5 mAh g⁻¹ after 100 cycles. On the basis of the results, the novel SPE has a widespread application prospects in solid-state lithium-ion batteries.     

Polypropylene-supported and nano-Al2O3 doped poly(ethylene oxide)-poly(vinylidene fluoride-hexafluoropropylene)-based gel electrolyte for lithium ion batteries

A new gel polymer electrolyte (GPE) is reported in this paper. In this GPE, blending polymer of poly(ethylene oxide) (PEO) with poly(vinylidene fluoride-hexafluoropropylene) (P(VdF-HFP)), doped with nano-Al₂O₃ and supported by polypropylene (PP), is used as polymer matrix, namely PEO-P(VdF-HFP)-Al₂O₃/PP. The performances of the PEO-P(VdF-HFP)-Al₂O₃/PP membrane and the corresponding GPE are characterized with mechanical test, CA, EIS, TGA and charge-discharge test. It is found that the performances of the membrane and the GPE depend to a great extent on the content of doped nano-Al₂O₃. With doping 10 wt.% nano-Al₂O₃ in PEO-P(VdF-HFP), the mechanical strength from 9.3 MPa to 14.3 MPa, the porosity of the membrane increases from 42% to 49%, the electrolyte uptake from 176% to 273%, the thermal decomposition temperature from 225 °C to 355 °C, and the ionic conductivity of corresponding GPE is improved from 2.7 × 10⁻³ S cm⁻¹ to 3.8 × 10⁻³ S cm⁻¹. The lithium ion battery using this GPE exhibits good rate and cycle performances.     

Enhanced conductivity and stability of composite membranes based on poly (2,5-benzimidazole) and zirconium oxide nanoparticles for fuel cells

Poly (2,5-benzimidazole) (ABPBI) and zirconium oxide (ZrO₂) nanoparticles composite membranes were synthesized. These membranes can be fabricated into tough, dense membranes by blending Poly (2,5-benzimidazole) (ABPBI) with zirconium oxide (ZrO₂) nanoparticles, which were characterized by using FTIR, XRD, SEM, TGA, DSC and tensile test. These composite membranes showed increased conductivity compared with original ABPBI membrane. Maximum proton conductivity at 100 °C was found to be 0.069 S cm⁻¹ on 10% ZrO₂ incorporated ABPBI composite membrane, almost four times as high as the 0.018 S cm⁻¹ obtained in the case of the ABPBI membrane. The conductivity was 0.0325 S cm⁻¹ at 180 °C in dry condition for ABPBI with 10% ZrO₂ nanoparticles composite membrane, higher than the conductivity 0.011 S cm⁻¹ of the ABPBI membrane at same condition. Furthermore, the composite membranes were shown to have high thermal and mechanical stability. These results suggest that ABPBI/ZrO₂ composite membranes may be a promising polymer electrolyte for fuel cells at medium or high temperature, due to their strong physical properties.     

Novel silica/poly(2,6-dimethyl-1,4-phenylene oxide) hybrid anion-exchange membranes for alkaline fuel cells: Effect of silica content and the single cell performance

Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)-based organic-inorganic hybrid alkaline membranes with enhanced hydroxyl (OH⁻) conductivity are prepared in response to the relatively low conductivity of previously reported PPO-based systems. The membranes also exhibit higher swelling-resistant properties and the hydroxyl (OH⁻) conductivity values are comparable to previously reported fluoropolymer-containing membranes: 0.012-0.035 S cm⁻¹ in the temperature range 30-90 °C. Other favorable properties for fuel cell application include high tensile strengths up to 25 MPa and large ion-exchange capacities in the range 2.01-2.27 mmol g⁻¹. Beginning-of-life fuel cell testing of a membrane with a thickness of 140 μm yielded an acceptable H₂/O₂ peak power density of 32 mW cm⁻² when incorporated into an alkaline membrane electrode assembly. Therefore, this class of hybrid membrane is suitable for application in alkaline membrane fuel cells.     

Graphene‐wrapped poly(2,5‐dihydroxy‐1,4‐benzoquinone‐3,6‐methylene) nanoflowers as low‐cost and high‐performance cathode materials for sodium‐ion batteries

Graphene‐wrapped poly 2,5‐dihydroxy‐1,4‐benzoquinone‐3,6‐methylene (PDBM) nanocomposites with three‐dimensional nanoflower structures have been successfully prepared through the ultrasonic exfoliation and reassembly process in methanol. Compact distribution of graphene into the nanocomposite has established a three‐dimensional conductive network, which contributes to improved properties on discharge capacity and cycle performance. Composite with 20 wt% graphene was proved the best ratio when used in sodium‐ion batteries. Its initial discharge capacity can achieve 210 at 30 mA g^?1. After 100 cycles, the capacity is stable at 121 mAh g^?1. The composite featuring highly conductive channels and multidimensional electron transport pathway is synthesized by an easy ultrasonic way, which may be applied in large scales for sodium‐ion batteries.     

Investigation on sulphonated zinc oxide nanorod incorporated sulphonated poly (1,4-phenylene ether ether sulfone) nanocomposite membranes for improved performance of microbial fuel cell

Hydrothermally prepared zinc oxide nanorods are sulphonated (S–ZnO NR) and incorporated into 15% Sulphonated Poly (1,4-Phenylene Ether Ether Sulfone) (SPEES) to improve the hydrophilicity, water uptake and ion transfer capacity. Water uptake and ion transfer capacity increased to 34.6 ± 0.6% and 2.0 ± 0.05 meq g^?1 from 29.8 ± 0.3% and 1.4 ± 0.04 meq g^?1 by adding 7.5 wt% S–ZnO NR to SPEES. Morphological studies show the prepared S–ZnO NR is well dispersed in the polymer matrix. SPEES +7.5 wt% S–ZnO NR membrane exhibits optimum performance after three-weeks of continual operation in a fabricated microbial fuel cell (MFC) to produce a maximum power density of 142 ± 1.2 mW m^?2 with a reduced biofilm compared to plain SPEES (59 ± 0.8 mW m^?2), unsulphonated filler incorporated SPEES (SPEES + 7.5 wt% ZnO, 68 ± 1.1 mW m^?2) and Nafion (130 ± 1.5 mW m^?2) thereby suggesting its suitability as a sustainable and improved cation exchange membrane (CEM) for MFCs.     

Effect of Cr doping on the structural,electrochemical properties of Li[Li0.2Ni0.2−x/2Mn0.6−x/2Crx]O2 (x = 0, 0.02, 0.04, 0.06, 0.08) as cathode materials for lithium secondary batteries

Prospective positive-electrode (cathode) materials for a lithium secondary battery, viz., Li[Li_0.2Ni_0.2−x/2Mn_0.6−x/2Cr_x]O₂ (x = 0, 0.02, 0.04, 0.06, 0.08), were synthesized using a solid-state pyrolysis method. The structural and electrochemical properties were examined by means of X-ray diffraction, cyclic voltammetry, SEM and charge–discharge tests. The results demonstrated that the powders maintain the α-NaFeO₂-type layered structure regardless of the chromium content in the range x ≤ 0.08. The Cr doping of x = 0.04 showed improved capacity and rate capability comparing to undoped Li[Li_0.2Ni_0.2Mn_0.6]O₂. ac impedance measurement showed that Cr-doped electrode has the lower impedance value during cycling. It is considered that the higher capacity and superior rate capability of Cr-doping samples would be ascribed to the reduced resistance of the electrode during cycling.