Conductivities enhancement of poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) transparent electrodes with diol additives

High conductivity, good stability, and high transmittance in the visible region are the three essential requirements for the polymer electrodes used in the optoelectronic devices. It was found that with addition of diols, such as ethylene glycol, diethylene glycol, or poly(ethylene glycol) (PEG), to the poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT:PSS) emulsion before spin-coating could increase dramatically the conductivities of the resultant PEDOT:PSS thin films from 1 to 90 S cm^?1 while maintain the optical transparency of the modified thin films. With up to ?2.4 V potential applied, the PEDOT:PSS with PEG 200 additive does not show obvious color change, indicating its good electrochemical stability as polymer electrode. Detailed studies on the structures and morphologies of these modified PEDOT:PSS thin films, in comparison to that of PEDOT:PSS without additives were carried out using AFM, Raman, and FTIR to investigate the underlying mechanisms.     

NiO as an Efficient Counter Electrode Catalyst for Dye-Sensitized Solar Cells

NiO is an important heterogeneous catalyst employed in chemical processes. However, it is a new topic to explore NiO as a counter electrode catalyst for dye-sensitized solar cells (DSSCs). In this paper, NiO with poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) was demonstrated an efficient DSSC counter electrode with a maximum power conversion efficiency of 7.58 %. Furthermore, electrochemical impedance spectroscopy and cyclic voltammetry measurements revealed that the excellent photovoltaic performance is due to the combination between the high catalytic activity of NiO and the superior electrical conductivity of PEDOT:PSS. The optimum weight ratio of NiO to PEDOT:PSS is 48.     

A novel hierarchical Pt- and FTO-free counter electrode for dye-sensitized solar cell

A novel hierarchical Pt- and FTO-free counter electrode (CE) for the dye-sensitized solar cell (DSSC) was prepared by spin coating the mixture of TiO₂ nanoparticles and poly(3,4-ethylenedioxy-thiophene):poly(styrenesulfonate) (PEDOT:PSS) solution onto the glass substrate. Compared with traditional Pt/FTO CE, the cost of the new CE is dramatically reduced by the application of bilayer TiO₂-PEDOT:PSS/PEDOT:PSS film and the glass substrate. The sheet resistance of this composite film is 35 Ω sq⁻¹ and is low enough to be used as an electrode. The surface morphologies of TiO₂-PEDOT:PSS layer and modified PEDOT:PSS layer were characterized by scanning electron microscope, which shows that the former had larger surface areas than the latter. Electrochemical impedance spectra and Tafel polarization curves prove that the catalytic activity of TiO₂-PEDOT:PSS/PEDOT:PSS/glass CE is higher than that of PEDOT:PSS/FTO CE and is similar to Pt/FTO CE''s. This new fabricated device with TiO₂-PEDOT:PSS/PEDOT:PSS/glass CE achieves a high power conversion efficiency (PCE) of 4.67%, reaching 91.39% of DSSC with Pt/FTO CE (5.11%).     

A red-to-gray poly(3-methylthiophene) electrochromic device using a zinc hexacyanoferrate/PEDOT:PSS composite counter electrode

In this paper, we describe a novel red-to-gray poly(3-methylthiophene) (PMeT) electrochromic device (ECD) with the aid of a zinc hexacyanoferrate (ZnHCF)/PEDOT:PSS counter electrode. The application of ZnHCF to an ECD is first reported. ZnHCF has long suffered from poor deposition yield problem, but we demonstrate that a robust ZnHCF film can be prepared by spin coating of a liquid suspension composed of ZnHCF nanoparticles and PEDOT:PSS ink on ITO. It was found that the ZnHCF/PEDOT:PSS composite worked much better with PMeT than pure ZnHCF or pure PEDOT:PSS from both electrochemical and optical aspects. With a LiClO₄/PC electrolyte, the PMeT ECD having ZnHCF/PEDOT:PSS as its counter electrode could be reversibly switched between its red state (>0.8 V) and its gray state (<0 V). For a 2 cm × 2 cm prototype device, the response time for coloration was less than 1 s. The maximum transmittance modulation of the device could attain 45.3% at 750 nm, which resulted in a corresponding coloration efficiency of 336.8 cm²/C. The maximum contrast ratio was 5.45 at 720 nm. In addition, the charge capacity of the ECD could retain 95% of its original value after 10,000 cycles of cyclic voltammetry aging test, although an electrodeposited PMeT film alone could be cycled several hundred times only. To sum up, this work proposes a new, cost-effective transparent counter electrode and brings a stable, high visual-contrast PMeT ECD prototype for further development of a red-color bistable display.     

Aqueous processing based novel composite electrode for Li-ion batteries using an environmentally benign binder

Along with the high energy density and safer battery materials, easy and environment benign electrode processing is also one of the major concerns for the battery manufacturing industries. Therefore, herein, water-based electrode processing is used which reduces manufacturing cost and makes easy and cost-effective recycling of discarded batteries. In addition, the increasing use of Li-ion batteries from portable electronics to electric vehicles has imposed a threat to the environment due to hazardous materials used. The present study also focuses on the replacement of polyvinylidene difluoride (PVDF) non-conducting binder dissolves in toxic solvent N-methyl 2-pyrrolidone with water-soluble poly (3,4-ethylene dioxythiophene): poly (styrene sulfonate) (PEDOT:PSS) conducting binder. The entire study is performed on the synergistic effect of PEDOT:PSS with multi-walled carbon nanotubes (MWCNTs or MC) and carbon black (CB) on Li-ion battery performance using LiFePO₄ cathode active material. The discharge capacities were found 144 mAh g⁻¹ and 160 mAh g⁻¹ at 0.1C for composite electrodes LFP/CB-9P and LFP/MC-9P, respectively having 9 wt% PEDOT:PSS. Whereas the composite electrodes LFP/CB-10PV and LFP/MC-10PV having 10 wt% PVDF binder show only capacities 117 mAh g⁻¹ and 134 mAh g⁻¹, respectively. The composite electrode LFP/MC-9P shows the highest capacities up to 20C rate and maximum retention capacity of 84% at 5C after 500 cycles among all samples studied. Whereas electrodes prepared with PVDF binder could not perform well at more than 5C current rate, capacity retention is also found nearly 0% after 500 cycles. Therefore, superior results of PEDOT:PSS and MWCNTs with LiFePO₄ propose an environmentally benign composite electrode of next generation Li-ion batteries for electric vehicles.     

Ultrafast-laser-treated poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) electrodes with enhanced conductivity and transparency for semitransparent perovskite solar cells

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is an important organic electrode for solution-processed low-cost electronic devices. However, it requires doping and post-solvent treatment to improve its conductivity, and the chemicals used for such treatments may affect the device fabrication process. In this study, we developed a novel route for exploiting ultrafast lasers (femtosecond and picosecond laser) to simultaneously enhance the conductivity and transparency of PEDOT:PSS films and fabricate patterned solution-processed electrodes for electronic devices. The conductivity of the PEDOT:PSS film was improved by three orders of magnitude (from 3.1 to 1024 S·cm^–1), and high transparency of up to 88.5% (average visible transmittance, AVT) was achieved. Raman and depth-profiling X-ray photoelectron spectroscopy revealed that the oxidation level of PEDOT was enhanced, thereby increasing the carrier concentration. The surface PSS content also decreased, which is beneficial to the carrier mobility, resulting in significantly enhanced electrical conductivity. Further, we fabricated semitransparent perovskite solar cells using the as-made PEDOT:PSS as the transparent top electrodes, and a power conversion efficiency of 7.39% was achieved with 22.63% AVT. Thus, the proposed route for synthesizing conductive and transparent electrodes is promising for vacuum and doping-free electronics.     

High‐performing dye‐sensitized solar cells based on reduced graphene oxide/PEDOT‐PSS counter electrodes with sulfuric acid post‐treatment

Four kinds of counter electrodes are prepared with polystyrene‐sulfonate doped poly(3,4‐ethylenedioxythiophene) (PEDOT‐PSS) as basic material, reduced graphene oxide (rGO) sheets as additives and H₂SO₄ as treating agent. The cyclic voltammetry and Tafel polarization are measured to evaluate catalytic activity of these counter electrodes for /I^? redox couple. It is found that H₂SO₄ treated rGO and PEDOT‐PSS hybrid counter electrode (S/rGO/PEDOT‐PSS counter electrode) has the highest catalytic activity among these counter electrodes. Power conversion efficiency of the dye‐sensitized solar cell with S/rGO/PEDOT‐PSS counter electrode can attain to 7.065%, distinctly higher than that of the cells with the other three ones, owing to the great enhanced fill factor and short‐circuit current density. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42648.     

Capacitance properties of graphite oxide/poly(3,4‐ethylene dioxythiophene) composites

Poly(3,4‐ethylene dioxythiophene) (PEDOT) and graphite oxide (GO)/PEDOT composites (GPTs) doped with poly(sodium styrene sulfate) (PSS) were synthesized by in situ polymerization in aqueous media. The electrochemical capacitance performances of GO, PEDOT–PSS, and GPTs as electrode materials were investigated. The GPTs had a higher specific capacitance of 108 F/g than either composite constituent (11 F/g for GO and 87 F/g for PEDOT–PSS); this was attributable to its high electrical conductivity and the layer‐within/on‐layer composite structure. Such an increase demonstrated that the synergistic combination of GO and PEDOT–PSS had advantages over the sum of the individual components. On the basis of cycle‐life tests, the capacitance retention of about 78% for the GPTs compared with that of 66% for PEDOT–PSS after 1200 cycles suggested a high cycle stability of the GPTs and its potential as an electrode material for supercapacitor applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electropolymerization of a poly(3,4-ethylenedioxythiophene) and functionalized, multi-walled, carbon nanotubes counter electrode for dye-sensitized solar cells and characterization of its performance

Composite films of poly(3,4-ethylenedioxythiophene) and functionalized, multi-walled, carbon nanotubes (PEDOT–MWCNT) were fabricated by a simple oxidative electropolymerization method. These films were formed on fluorine-doped, tin oxide, glass substrates as counter electrodes (CEs) of platinum-free, dye-sensitized solar cells (DSSCs). The surface morphology, formation mechanism and electrochemical nature of PEDOT–MWCNT films were investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM), cyclic voltammetry (CV) and alternating current (AC) impedance spectroscopy. The SEM and AFM images showed that PEDOT–MWCNT films were more porous than PEDOT films. CV and AC impedance spectroscopy revealed that the PEDOT–MWCNT electrode had higher electrocatalytic activity for the I₃⁻/I⁻ redox reaction and a smaller charge transfer resistance than the PEDOT electrodes. The energy conversion efficiency of the DSSC with a PEDOT–MWCNT CE was 13.0% higher than with a PEDOT CE using the same conditions with a ruthenium sensitizer.     

Enhanced thermoelectric properties of poly(3,4-ethylenedioxythiophene): Poly(styrenesulfonate)/copper phthalocyanine disulfonic acid composite films

A series of poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate)/copper phthalocyanine disulfonic acid (PEDOT: PSS/CuPc-[SO₃H]₂) composite films were prepared by using CuPc-(SO₃H)₂ as the dopant. EG treatment was applied to further improve the thermoelectric properties of PEDOT: PSS/CuPc-(SO₃H)₂ composites. Structural analyses indicated the strong π − π interactions existed between PEDOT: PSS and CuPc-(SO₃H)₂, and led to more ordered regions in the composite films, and benefit the conductivity. CuPc-(SO₃H)₂ can greatly improve the thermoelectric properties of PEDOT: PSS/CuPc-(SO₃H)₂ composite films, which have a Seebeck coefficient of 13.2 μV K⁻¹ and a conductivity of 2.8 × 10⁵ S/m with 20 wt% CuPc-(SO₃H)₂ at room temperature, and the corresponding power factor is 48.8 μW m⁻¹ K⁻², which is almost 6.83 times higher than the PEDOT: PSS films without CuPc-(SO₃H)₂.     

A focus on polystyrene tacticity in synthesized conductive PEDOT:PSS thin films

Poly(3,4-ethylenedioxythiophene):poly (styrenesulfonate) (PEDOT:PSS) is a transparent conductive material and a good candidate for being employed as substitute for indium tin oxide (ITO) in reducing the production costs of organic solar cells. To enhance the performance of organic devices, an improving in the conductivity of PEDOT:PSS is crucial and using the solvent additive rises the electrical conductivity by the optimization of the film morphology. The studies have only focused on the relationship between the electrical conductivity of thin films and the crystallinity of PEDOT, and it is also found that the high conductivity is observed in the highly crystalline samples. This study focused on the effect of tacticity of PS on the conductivity of PEDOT:PSS films. First, atactic and isotactic polystyrenes were sulfonated and the complexes of PEDOT:PSS were synthesized. The N-methylpyrrolidone (NMP), as a secondary dopant, was then added to the complexes and conductivity enhancement was investigated in various annealing times. The obtained films were characterized by atomic force microscopy, X-ray diffraction, four point probe resistivity measurement system, UV–visible spectroscopy, FT-IR, and cyclic voltammetry. The electrical conductivity of PEDOT:iPSS films synthesized by the isotactic polystyrene was ~ 0.68 S/cm and by adding 5 wt% NMP into PEDOT:PSS solution, the conductivity of the annealed thin layers increased more than 10-folds (~ 7.73 S/cm) at an appropriate temperature.     

Enhanced performance of a dye-sensitized solar cell with an electrodeposited-platinum counter electrode

A counter electrode was prepared for a dye-sensitized solar cell (DSSC) through electrochemical deposition of mesoporous platinum on fluorine-doped tin oxide glass in the presence of a structure-directing nonionic surfactant, octaethylene glycol monohexadecyl ether (C₁₆EO₈). The DSSC fabricated with the electrochemically deposited Pt (ED-Pt) counter electrode rendered a higher solar-to-electricity conversion efficiency of 7.6%, compared with approximately 6.4% of the cells fabricated with the sputter-deposited or most commonly-employed thermal deposited Pt counter electrodes. This enhanced efficiency is attributed to the higher short-circuit photocurrent arising from the increases in the active surface area and light reflection as well as the decrease in the sheet resistance of the ED-Pt film, relative to those of the Pt films prepared by the other two deposition methods. The sputter-deposited Pt film yielded almost the same photovoltaic characteristics as the thermal deposited Pt film. The Pt films were characterized by FE-SEM, AFM, cyclic voltammetry, chronoamperometry, electrochemical impedance spectroscopy, sheet resistance measurements, adhesion tests, and light reflection tests.     

Electro‐synthesized PEDOT/glutamate chemically modified electrode: a combination of electrical and biocompatible features

BACKGROUND: Neural prosthetic devices have been developed that can facilitate the stimulation and recording of electrical activity when implanted in the central nervous system. The key parts of the devices are metal (gold) electrodes; however, surface modification of the gold electrode is desired. Conducting polymers are promising candidates for this purpose. RESULTS: A conducting polymer, poly(3,4‐ethylenedioxythiophene) (PEDOT), was electro‐polymerized onto gold electrodes with a neural transmitter of glutamate (Glu) as dopant. A protocol of ion exchange was employed due to the difficulty of direct incorporation of Glu into PEDOT. Sodium p‐toluenesulfonate (TSNa) was chosen as the first dopant and subsequent incorporation of Glu was accomplished via ion exchange. The electrochemical properties of the resultant PEDOT/Glu were studied using electrochemical impedance spectroscopy and cyclic voltammetry. The purpose of incorporating Glu was to improve the biocompatibility of the coated electrode. The PEDOT/Glu‐coated electrode showed better cell attachment compared with a PEDOT/TSNa‐coated electrode in in vitro cell culture of PC12. The stability of PEDOT was studied by immersing the coated electrode in a biologically relevant reducing agent of glutathione. CONCLUSION: The charge capacity of the coated electrode had an initial slight decrease and then remained unchanged. Good electro‐activity was conserved, indicating the superior stability of PEDOT in the biological environment. Copyright © 2007 Society of Chemical Industry     

Multilayer photoactive nanocolloidal PPy:PSS as a novel substitute for Pt free counter electrode in DSSC

Water dispersible and highly processable, Polypyrrole (PPy) nanocolloidal particles were synthesized by chemical oxidation polymerization with 15 wt % of anionic polyelectrolyte poly(styrene sulfonate) (PSS) at 5°C has been reported in this work. This polymer composite (PPy:PSS) was competent with conventional Pt counter electrode (CE) when compared for dye sensitized solar cells (DSSCs). Morphological analysis revealed smooth and spherical shaped nanoparticles of PPy. Interaction between the SO₃H groups and Py units in PPy improved the thermal stability of PPy with higher doping levels of PSS. The nanocolloidal solution was spin coated at 4000 rpm. The layer by layer, self‐assembled multilayer thin films were used as CE in DSSCs. There was a linear dependence of DSSCs performance with film roughness for the self‐assembled multilayer PPy:PSS films. Single layer films showed better electrocatalytic behavior than multilayer films. All the PPy:PSS films had good electrochemical stability. The DSSC efficiency of 3.40% was observed for chemically oxidized PPy with 15 wt % PSS for single layer film, with a highest FF of 0.7154. The low cost, good performance, rapid and simple fabrication method of PPy:PSS composite modified CE could be a potential alternative for Pt in the DSSCs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43114.     

In situ electrochemical synthesis of a poly(o‐anisidine) counter electrode for a dye‐sensitized solar cell

Poly(o‐anisidine) (POA) counter electrodes (CEs) were fabricated by potentiodynamic deposition and incorporated into platinum (Pt)‐free dye‐sensitized solar cells (DSSCs). A different sweep number had great impact on the morphology and electrocatalytic activity of the POA films. The POA film fabricated by 25 sweep cycles was observed to have a highly porous morphology, and this resulted in a lower charge‐transfer resistance of 57 cm² in comparison with the Pt CE. The DSSC assembled with the POA CE showed a higher photovoltaic conversion efficiency of 1.67% compared to 1.2% for the DSSC with the Pt CE under full sunlight illumination. Therefore, the high active surface area of the 25‐sweep‐segmented POA film could be considered a promising alternative CE for use in DSSCs because of its high electrocatalytic performance and electrochemical stability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42041.     

染料敏化太阳能电池非铂对电极研究进展

对电极作为染料敏化太阳能电池（dye-sensitized solar cell,DSSC）的重要组成部分,对电极材料性能的好坏直接影响着染料敏化太阳能电池的光电转化效率。最常使用的对电极电催化材料是贵金属铂,而铂十分稀少而且价格昂贵,并且铂很容易被碘电解液腐蚀,不利于染料敏化太阳能电池的产业化发展。本文重点综述了2010年以来染料敏化太阳能电池非铂对电极的研究成果,简要说明了对电极在染料敏化太阳能电池中的作用,详细介绍了非铂金属、碳材料、导电聚合物和无机化合物等对电极材料,分析了各类非铂对电极材料的特点、制备工艺、发展前景、优缺点和改进措施。最后提出,继续开发各种成本低、原料易得以及稳定高效的新型非金属对电极材料仍是今后染料敏化太阳能电池研究的一个重要方向。     

On the mechanism of conductivity enhancement in poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) film through solvent treatment

The conductivity of a poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) film is enhanced by more than 100-folds on adding some organic compounds into PEDOT:PSS aqueous solutions or by treating the PEDOT:PSS film with organic solvents, such as ethylene glycol (EG), 2-nitroethanol, methyl sulfoxide or 1-methyl-2-pyrrolidinone. The mechanism for this conductivity enhancement was studied through various chemical and physical characterizations. The PEDOT:PSS film which is soluble in water becomes insoluble after treatment with EG. This strongly suggests an increased interchain interaction among the PEDOT chains. Raman spectroscopy indicates that this increased interchain interaction results from conformational changes of the PEDOT chains, which change from a coil to linear or expanded-coil structure. The increased interchain interaction and conformation changes are further confirmed by the temperature dependence of conductivity and the electron spin resonance (ESR). It is found that EG treatment lowers the energy barrier for charge hopping among the PEDOT chains, lowers the polaron concentration in the PEDOT:PSS film by ∼50%, and increases the electrochemical activity of the PEDOT:PSS film in NaCl aqueous solution by ∼100%. Atomic force microscopy (AFM) and contact angle measurements show that the surface morphology of the PEDOT:PSS film changes as well after the EG treatment. Conductivity enhancement was also observed when other organic compounds were used, but it was strongly dependent on the chemical structure of the organic compounds, and observed only with organic compound with two or more polar groups. These experimental results support our proposal that the conductivity enhancement is due to the conformational change of the PEDOT chains and the driving force is the interaction between the dipoles of the organic compound and dipoles or charges on the PEDOT chains.     

Improved photocurrent of a poly (3,4-ethylenedioxythiophene)-ClO₄⁻/TiO₂ thin film-modified counter electrode for dye-sensitized solar cells

We prepared a poly(3,4-ethylenedioxythiophene) (PEDOT)-ClO??-supported TiO? thin-film electrode as a counter electrode on a transparent conductive oxide glass electrode for a dye-sensitized solar cell (DSSC) using a combination of sol-gel and electropolymerization methods. The photocurrent-voltage characteristics indicate that DSSCs with PEDOT-ClO??/TiO? thin-film counter electrodes had a high photovoltaic conversion efficiency similar to that of PEDOT-ClO??/TiO? particle composite-film electrodes. Furthermore, it was found that the photocurrent was increased by attaching a reflector to the opposite side of the transparent counter electrode.     

Graphene aerogels as a highly efficient counter electrode material for dye-sensitized solar cells

Graphene aerogels (GAs) prepared with an organic sol–gel process, possessing a high specific surface area of 814 m²/g and a high electric conductivity of 850 S/m, are applied as a counter electrode material for dye-sensitized solar cells (DSSCs). The performance of the GA as the counter electrode material is found to be dependent on its film thickness, with thicker films offering more surface areas for the involved catalytic reduction reaction but at the same time increasing the charge and mass transport resistances. At an optimum GA film thickness of 4.9 μm, a power conversion efficiency of 96% of that achieved with a Pt counter electrode based DSSC is obtained. In addition, a thinner GA film of 1.7 μm, when loaded with Pt of 1 mol% through a photo-reduction process, achieves a power conversion efficiency of 98% of that obtained with a Pt counter electrode based DSSC. The excellent performances of the GA-based counter electrodes are manifested with electrochemical impedance analyses and cyclic voltammetry based catalytic activity analyses.     

Chemical cross-linking of conducting poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) using poly(ethylene oxide) (PEO)

Hybrid films of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) were prepared with different molecular weights of poly(ethylene oxide) (PEO). The cross-linking reaction between PEO and PEDOT:PSS was performed at high temperature and confirmed by using differential scanning calorimeter (DSC), contact angle measurement, and solid-state ¹H NMR. The effect of chemical reaction on the conductivity and morphology of these hybrid films was studied by using 4-point probe and atomic force microscope (AFM), respectively. As-spun PEO/PEDOT:PSS films have lower electric conductivity due to the addition of nonconductive PEO, and exhibits no molecular weight dependence on conductivity. After chemical cross-linking reaction at high temperature, only PEDOT:PSS films with lowest molecular weight PEO additives show enhanced conductivity with increasing reaction time. AFM result indicates that the heat-treated PEO/PEDOT:PSS hybrid films show grain-like morphology compared to ethylene glycol treated PEDOT:PSS films which shows continuous PEDOT domain. In the present work we demonstrate that the cross-linking reaction can be used to improve the wet stability of PEDOT:PSS nanofiber, showing good water resistance and excellent dimensional stability.