A Dye-Sensitized Nanoporous TiO2 Photoelectrochemical Cell with Novel Gel Network Polymer Electrolyte

A novel gel network polymer electrolyte based on polysiloxane with internal plasticizing PEO chains was applied in fabricating solid-state dye-sensitized TiO₂ photoelectrochemical cells. Ethylene carbonate (EC)/propylene carbonate (PC) and LiI/I₂ were added as liquid plasticizer to improve the performance. The cells showed open circuit voltage of 0.69 V and short circuit current density of 1.7 mA cm^–2 under 28 mW cm^–2 white light illumination. The energy conversion efficiencies and fill factors of the cells were 2.9% and 0.72.     

Studies of solvent effect on the conductivity of 2‐mercaptopyridine‐doped solid polymer blend electrolytes and its application in dye‐sensitized solar cells

Solvents and electrolytes play an important role in the fabrication of dye‐sensitized solar cells (DSSCs). We have studied the poly(ethylene oxide)‐poly(methyl methacrylate)‐KI‐I₂ (PEO‐PMMA‐KI‐I₂) polymer blend electrolytes prepared with different wt % of the 2‐mercaptopyridine by solution casting method. The polymer electrolyte films were characterized by the FTIR, X‐ray diffraction, electrochemical impedance and dielectric studies. FTIR spectra revealed complex formation between the PEO‐PMMA‐KI‐I₂ and 2‐mercaptopyrindine. Ionic conductivity data revealed that 30% 2‐mercaptopyridine‐doped PEO‐PMMA‐KI‐I₂ electrolyte can show higher conductivity (1.55 × 10^?5 S cm^?1) than the other compositions (20, 40, and 50%). The effect of solvent on the conductivity and dielectric of solid polymer electrolytes was studied for the best composition (30% 2‐mercaptopyridine‐doped PEO‐PMMA‐KI‐I₂) electrolyte using various organic solvents such as acetonitrile, N,N‐dimethylformamide, 2‐butanone, chlorobenzene, dimethylsulfoxide, and isopropanol. We found that ac‐conductivity and dielectric constant are higher for the polymer electrolytes processed from N,N‐dimethylformamide. This observation revealed that the conductivity of the solid polymer electrolytes is dependent on the solvent used for processing and the dielectric constant of the film. The photo‐conversion efficiency of dye‐sensitized solar cells fabricated using the optimized polymer electrolytes was 3.0% under an illumination of 100 mW cm^?2. The study suggests that N,N‐dimethylformamide is a good solvent for the polymer electrolyte processing due to higher ac‐conductivity beneficial for the electrochemical device applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42489.     

Composite electrolyte of heteropolyacid (HPA) and polyethylene oxide (PEO) for solid-state dye-sensitized solar cell

A novel heteropolyacid (HPA) and polyethylene oxide (PEO) composite electrolyte was prepared and applied as the solid electrolyte for solid-state dye-sensitized solar cell. Advanced HPA-PEO composite electrolytes could be prepared by the optimized mixture solvent of chloroform and methanol (ChMe), which possessed the enhanced morphological properties, ionic conductivity and amorphicity. It is due to the presence of well-dispersed HPAs on the texture of PEO with the strong interaction between them. DSSCs fabricated with HPA-PEO/ChMe electrolyte showed significantly high photovoltaic (PV) performance with the overall conversion efficiency of 3.1%, open circuit voltage of 0.524 V and a short circuit current of 9.7 mA/cm². HPA in the composite electrolytes may act as an electron acceptor to prohibit the photo-reduction of I⁻, resulting in the advanced photocurrent density and stability without significant decline of the PV performance for 7 days.     

Ionic conductivity of solid polymer electrolytes for dye‐sensitized solar cells

We developed an ionic conductivity model of solid polymer electrolytes for dye‐sensitized solar cells (DSSCs) based on the Nernst–Einstein equation in which the diffusion coefficient is derived from the molecular thermodynamic model. We introduced concentration‐dependence of the diffusion coefficient into the model, and the diffusion coefficient was expressed by differentiating the chemical potential by concentration. The ionic conductivities of polymer electrolytes (PEO/LiI/I₂ system) were investigated at various temperatures and compositions. We prepared a set of PEO in which an EO : LiI mole ratio of 10 : 1 was kept constant for PEO·LiI·(I₂)_n compositions with n = 0.02, 0.05, 0.1, 0.15, 0.2, and 0.3 (mole ratio of LiI : I₂). The ionic conductivities of the electrolytes were measured using a stainless steel/polymer‐electrolyte/stainless steel sandwich‐type electrode structure using alternating current impedance analysis. The values calculated using the proposed model agree well with experimental data. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Ionic liquid/polymer composite electrolytes by in situ photopolymerization and their application in dye-sensitized solar cells

A new kind of quasi-solid state electrolytes for dye-sensitized solar cells (DSCs) has been prepared by in situ photopolymerization from the precursor 1,6-hexanediol diacrylate (HDDA) in 1-hexyl-3-methyl imidazolium iodide (HMII). The optimal ratio of polymer/ionic liquid is determined by the conductivities of the electrolytes. In order to further increase the miscibility between ionic liquid and the polymer, oligomer polyethylene glycol dimethyl ether (PEGDME) is introduced. By optimization of the amount of PEGDME in the electrolyte, the DSCs using this kind of solid-state electrolytes can present 6.5% of light-to-electricity conversion efficiency under 41 mW cm⁻². In the meantime, the influence of PEGDME additive is detailedly investigated by electrochemical impedance spectrum (EIS) and intensity modulated photovoltage spectroscopy (IMVS) techniques. Preliminary long-term stability test revealed that this in situ photopolymerized electrolyte exhibits good stability after 1000 h thermal test.     

A new carbon nanotubes (CNTs)–poly acrylonitrile (PAN) composite electrolyte for solid state dye sensitized solar cells

A new carbon nanotube (CNTs)–poly acrylonitrile (PAN) composite electrolyte was prepared by the thermal polymerization of acrylonitrile (AN) with CNTs for solid-state dye sensitized solar cells (DSSCs). It was found that the uniform CNT–PAN composite was formed due to the thermal polymerization of AN on CNTs. The strong bonding between CNTs and PAN could be confirmed by the characterization of XPS and Raman spectroscopy, resulting in the lowering of crystallinity and the increasing the ionic conductivity of composite electrolytes. On comparison with bare CNTs and the other composite electrolytes, the formation of triiodide (I₃⁻) ions in CNT–PAN composite electrolytes was drastically increased which was expected from the high ionic conductivity of electrolyte via I₃⁻/I⁻ redox couple. DSSCs fabricated with CNT–PAN composite electrolytes achieved relatively high conversion efficiency of 3.9% with an open circuit voltage (V_OC) of 0.57 V, short circuit current density (J_SC) of 10.9 mA/cm² and fill factor of 63.6%, which attributed to supply the higher extent of I₃⁻ ions from CNT–PAN composite electrolyte during the charge transport process.     

Influence of 4-N,N-dimethylaminopyridine on the photovoltaic performance of dye-sensitized solar cells with poly(ethyleneoxide)/oligo(ethylene glycol) blend electrolytes

4-N,N-Dimethylaminopyridine (DMAP) was introduced into poly(ethyleneoxide)/oligo(ethylene glycol) (PEO/PEG) electrolytes for dye-sensitized solar cells (DSCs). The improved photovoltaic performance of DMAP-doped DSCs was attributed to the integrated effects of the upward displacement of the TiO₂ band edge and the decrease in the electron recombination rate. Remarkably, the presence of DMAP suppresses electron recombination via two combined pathways involving the dissociation of triiodide to iodide by a complexation reaction and a modification of the surface state distribution in the band gap of TiO₂. With the addition of DMAP, the open-circuit voltage enhances dramatically. The short-circuit photocurrent density has a small increase at low DMAP concentration and drops afterwards. The power conversion efficiency is 4.07%, which corresponds to a 63% increase over that of the DSC without DMAP.     

Blending thermoplastic polyurethanes and poly(ethylene oxide) for composite electrolytes via a mixture design approach

With the aim of obtaining proper composite electrolytes, a systematic modeling analysis for the percentage increase in weight due to swelling with respect to swollen weight, S_w, and the room temperature conductivity (σ₂₅) of the composite films of polyethylene glycol based thermoplastic polyurethane/polytetramethylene glycol based thermoplastic polyurethane/polyethylene oxide [denoted as TPU(PEG)/TPU(PTMG)/PEO] was performed. Using a mixture design approach, empirical models are fitted and plotted as contour diagrams which facilitate revealing the synergistic/antagonistic effects among the mixed polymers. The contour plot results show that both the maximum S_w (64.9%) and the maximum σ₂₅ (72.2 × 10⁻⁵ S cm⁻¹) appear at point X₃ (PEO 85%, TPU(PEG) 15%). The results are reasonably explained from the interactions among polymers on the basis of their molecular structures. The thermal analysis of the composite films is performed to demonstrate the speculations about the interactions among the mixed polymers by using differential scanning calorimeter. The crystallization of PEO spherulites at different compositions was examined by using a polarizing microscope. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 680–692, 2000     

Comparative study of composite membranes from nano‐metal‐oxide‐incorporated polymer electrolytes for direct methanol alkaline membrane fuel cells

A series of six composite membranes was prepared with two polymer electrolytes and three inorganic fillers, namely, silica, titania, and zirconia by a solution casting method. Two polymer electrolytes, that is, anion‐exchange membranes, were prepared from polystyrene‐block‐poly(ethylene‐ran‐butylene)‐block‐polystyrene (PSEBS) and polysulfone by chloromethylation and quaternization. A preliminary characterization of the ionic conductivity, methanol permeability, and selectivity ratio was done for all of the prepared composite membranes to check their suitability to work in direct methanol alkaline membrane fuel cells (DMAMFCs). The DMAMFC performance was analyzed with an in‐house fabricated single cell unit with a 25‐cm² area. Maximum performance was achieved for the composite membrane quaternized PSEBS/7.5% TiO₂ and was 74.5 mW/cm² at 60°C. For the comparison purposes, a commercially available anion‐exchange membrane (Anion Membrane International‐7001) was also investigated throughout the study. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Quasi-Solid Polymer Electrolyte Composed of poly(1-vinylpyrrolidone-co-vinyl acetate) Copolymer and the Influence of Its Composition on Electrochemical Properties and the Performances of Dye-Sensitized Solar Cells

Poly(1-vinylpyrrolidone-co-vinyl acetate)-based quasi-solid polymer electrolytes doped with potassium iodide are prepared. The highest room temperature ionic conductivity of 1.72 mS?cm^?1 is obtained. The dielectric studies are performed to understand the ion conduction mechanism. Fourier transform infrared study has been performed to understand complexation of the poly(1-vinylpyrrolidone-co-vinyl acetate)-based quasi-solid polymer electrolytes. The best power energy conversion efficiency (η) obtained is 2.94% with short circuit current density (J_sc) of 8.05?mA?cm^?2, open circuit voltage (V_oc) of 0.58?V, and fill factor of 63% under standard light intensity of 100?mW?cm^?2 irradiation.     

An approach to laminated flexible Dye sensitized solar cells

We have built TiO₂ Dye sensitized solar cells (DSSCs) that combined flexible TiO₂ photoanodes coated on ITO/PET substrates with a gel electrolyte based on PVDF-HFP-SiO₂ films. Titanium isopropoxide (TiP₄) was used as additive to TiO₂ nanoparticles for increasing power conversion efficiency in Dye sensitized solar cell electrodes prepared at low-temperature (130 °C). An efficiency η_AM1.5G = 3.55% on ITO/PET substrates is obtained at 48 mW/cm² illumination with a standard liquid electrolyte based on methoxypropionitrile. Among several solvents forming gels with PVDF-HFP-SiO₂, N-methyl (pyrrolidone) (NMP) was found to enable the most stable devices. A power conversion efficiency η_AM1.5G = 2% was obtained under 10 mW/cm² with flexible TiO₂-ITO-PET photoanodes and the PVDF-HFP-SiO₂ + NMP gel electrolyte.     

Tertiary hierarchically structured TiO2 for CdS quantum-dot-sensitized solar cells

A tertiary hierarchically structured mesoporous spherical TiO₂ (with a diameter of 1190 ± 60 nm) was synthesized by combining the sol–gel and the subsequent solvothermal treatment, and applied to CdS quantum-dot-sensitized solar cells (QDSSCs). This mesoporous spherical (MS) TiO₂ offers a high surface area (76.02 m² g⁻¹), a high internal reflectance in the visible region and a pore accessibility. A conversion efficiency of 1.9% was achieved by CdS QDSSCs composed of the MS TiO₂ photoanode, which corresponds to ∼58% improvement as compared with the values obtained from the conventional devices made with 20-nm-sized nanocrystalline TiO₂ under AM 1.5 illumination of 100 mW cm⁻². Thus, the MS TiO₂ can be a promising candidate for the photoanode material of QDSSCs.     

Carbon nanotubes-polyethylene oxide composite electrolyte for solid-state dye-sensitized solar cells

Novel carbon nanotubes (CNTs)-polyethylene oxide (PEO) composite electrolyte for dye-sensitized solar cell (DSSC) was prepared and characterized for the first time. The strong bonding and interaction between CNTs and PEO in CNTs-PEO composites was observed by the characterization of X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and Raman spectra. The introduction of CNTs into PEO matrix significantly improved the electrolyte properties of DSSC such as roughness, amorphicity and ionic conductivity. The solid-state DSSC fabricated with the optimum composite electrolyte (added 1% CNTs in PEO matrix, 1%CNT-PEO) achieved maximum conversion efficiency of 3.5%, an open circuit voltage (V_OC) of 0.589 V, short circuit current density (J_SC) of 10.64 mA/cm² and fill factor (FF) of 56%. The highest IPCE in the DSSC fabricated with 1%CNT-PEO electrolyte is ascribed to the improved ionic conductivity of composite electrolytes and enhanced interfacial contact between electrode and electrolyte.     

Composite alkaline polymer electrolytes and its application to nickel-metal hydride batteries

In order to enhance the ionic conductivity of polyethylene oxide (PEO)-KOH based alkaline polymer electrolytes, three types of nano-powders, i.e., TiO₂, β-Al₂O₃ and SiO₂ were added to PEO-KOH complex, respectively, and the corresponding composite alkaline polymer electrolytes were prepared. The experimental results showed that the prepared polymer electrolytes exhibited higher ionic conductivities at room temperature, typically 10⁻³ S cm⁻¹ as measured by ac impedance method, and good electrochemical stability. The electrochemical stability window of ca. 1.6 V was determined by cyclic voltammetry with stainless steel blocking electrodes. The influence of the film composition such as KOH, H₂O and nano-additives on ion conductivity was investigated and explained. The temperature dependence of conductivity was also determined. In addition, polyvinyl alcohol (PVA)-sodium carboxymethyl cellulose (CMC)-KOH alkaline polymer electrolytes were obtained using solvent casting method. The properties of the polymer electrolytes were characterized by ac impedance, cyclic voltammetry and differential thermal analysis methods. The ionic conductivity of the prepared PVA-CMC-KOH-H₂O electrolytes can reach the order of 10⁻² S cm⁻¹. The effect of CMC addition on the alkaline polymer electrolytes was also explained. The experimental results demonstrated that the PVA-CMC-KOH-H₂O polymer electrolyte could be used in Ni/MH battery.     

Effect of oligomer on dye-sensitized solar cells employing polymer electrolytes

The effect of oligomer (M _n =400–500 g/mol) on dye-sensitized solar cells (DSSC) employing polymer electrolytes consisting of poly(epichlorohydrin-co-ethylene oxide) (Epichlomer), LiI, 1-methyl-3-propylimidazolium iodide (MPII) and I₂ is investigated. Five kinds of oligomer, poly(ethylene glycol) (PEG, M _n =400 and 1,000 g/mol), poly(ethylene glycol) dimethyl ether (PEGDME), poly(propylene glycol) (PPG) and poly(ethylene glycol) diglycidyl ether (PEGDGE), were introduced to elucidate the role of terminal groups and chain length. The coordinative interactions and structures of polymer electrolytes were characterized by FT-IR spectroscopy and X-ray diffraction (XRD). The improved interfacial contact between the electrolytes and the electrodes by the oligomer addition was confirmed using a field-emission scanning electron microscope (FE-SEM). The electrolytes exhibited ionic conductivities on the order of 10^?4 S/cm, but PEGDGE electrolyte showed much lower value (～10^?8 S/cm). As a result, the energy conversion efficiency of DSSC was significantly affected by the oligomer. For example, the DSSC employing PEGDME with methyl terminal groups exhibited 3.95% at 100 mW/cm², which is 200-fold higher than that employing PEGDGE.     

Environmental Friendly, Low Cost Quasi Solid State Dye Sensitized Solar Cell: Polymer Electrolyte Introduction

The most efficient DSSCs reported till date contains liquid electrolytes with I^?/I^3? redox couple. However, the disadvantages of liquid electrolytes lead to reduce the impact of DSSCs. In the present work, the I^?/I^3? liquid electrolyte was replaced by quasi-solid gel polymer electrolytes (GPEs) using polyethylene glycol (M_wt = 20,000), which are incorporated in small fractions (0, 1, 5, 10, 15 and 20 % w/v) into the liquid iodine/iodide electrolyte matrix. The roughness and homogeneity of the GPEs on the surface of the TiO₂ electrodes was monitored by atomic force microscope which indicates the physical cross linking of polymer chains in a gel network. The conductivity (σ) and the thermal stability (TGA) of the GPEs compared with the liquid electrolyte were studied in details. The photovoltaic characteristics [V_oc, I_sc, fill factor and efficiency (η)] of the DSSCs based GPEs were recorded, The results revealed the DSSCs assembled with the gel polymer electrolyte reports a higher short circuit density (J_SC) and lower or similar open circuit voltage (V_OC) than the cells with liquid electrolyte. The overall light-to-electrical-energy conversion efficiencies (η) of the cells based GPEs showed a relatively higher stability over a period of time compared with those based liquid electrolyte, indicating that the quasi-solid nature of the GPEs may impart flexibility to DSSCs so that some large-scale productions such as roll-to-roll process can be realized.     

Low temperature preparation of a high performance Pt/SWCNT counter electrode for flexible dye-sensitized solar cells

A platinum/single-wall carbon nanotube (Pt/SWCNT) film was sprayed onto a flexible indium-doped tin oxide coated polyethylene naphthalate (ITO/PEN) substrate to form a counter electrode for use in a flexible dye-sensitized solar cell using a vacuum thermal decomposition method at low temperature (120 °C). The obtained Pt/SWCNT electrode showed good chemical stability and light transmittance and had lower charge transfer resistance and higher electrocatalytic activity for the I₃⁻/I⁻ redox reaction compared to the flexible Pt electrode or a commercial Pt/Ti electrode. The light-to-electric energy conversion efficiency of the flexible DSSC based on the Pt/SWCNT/ITO/PEN counter electrode and the TiO₂/Ti photoanode reached 5.96% under irradiation with a simulated solar light intensity of 100 mW cm⁻². The efficiency was increased by 25.74% compared to the flexible DSSC with an unmodified Pt counter electrode.     

Solid-state storage batteries

Investigations were conducted to study the feasibility of a solid-state battery system for storage applications. During the development of various high energy density solid-state batteries we noted that the solid electrolyte material, LiI dispersed in large surface area Al₂O₃, has a high ionic conductivity at elevated temperatures, (for example 0.1^–1 cm^–1 at 300° C) and is suitable for high-rate storage battery applications. In solid-state battery systems both the electrodes and electrolytes are in the solid state under the operating conditions of the battery. The absence of any liquid phase makes the individual cell containers unnecessary in a multicell battery resulting in a simplified battery structure and increased package efficiency. Furthermore, no material compatibility problem is encountered in the system. As a result, the solid-state battery system has excellent charge retention characteristics and a long projected operating life. Solid-state test cells, Li-Si/LiI(Al₂O₃)/TaS₂/Ta, Li-Si/LiI(Al₂O₃/TiS₂/Ti and Li-Si/LiI(Al₂O₃)/TiS₂, Sb₂S₃, Bi were constructed and subjected to discharge-charge cycle tests at 300±10° C, at 13·7 mA cm^–2. Preliminary test results demonstrated that these solid-state battery systems are rechargeable and may be suitable for both load levelling and/or vehicle propulsion. From the considerations of material availability and cost and operational efficiencies it was concluded that the Li-Si/LiI(Al₂O₃)/TiS₂, Sb₂S₃, Bi system is most suitable among the three systems studied for the development of practical storage batteries. Preliminary design studies showed that practical energy densities of 200W h kg^–1 and 520 W h l^–1 can be realized with the Li-Si/TiS₂, Sb₂S₃, Bi storage batteries.     

Intermediate temperature electrical properties in 4 mol% ZnO-doped Zr0.92Y0.08O2-α/NaCl-KCl composite electrolyte

In this paper, 4?mol% ZnO-doped Zr_0.92Y_0.08O_2-α (8YSZ) and its 8YSZ+4ZnO/NaCl-KCl composite electrolyte were synthesized by a solid-state reaction. The X–ray diffraction (XRD) analysis indicates that 8YSZ+4ZnO and inorganic chlorides phases can coexist. The inorganic chlorides decrease the synthesis temperature of 8YSZ+4ZnO. The highest conductivities of 8YSZ+4ZnO and 8YSZ+4ZnO-NK are 7.0?×?10^?3 S?cm^?1 and 7.7?×?10^?2 S?cm^?1 at 700?°C, respectively. The oxygen concentration discharge cell shows that 8YSZ+4ZnO and 8YSZ+4ZnO-NK are good oxide ionic conductors under an oxygen-containing atmosphere. Finally, an H₂/O₂ fuel cell based on the 8YSZ+4ZnO-NK electrolyte reached the maximum power density (P_max) of 315.5?mW?cm^?2 at 700?°C.     

Novel PEO-based solid composite polymer electrolytes with inorganic–organic hybrid polyphosphazene microspheres as fillers

Novel solid-state composite polymer electrolytes based on poly (ethylene oxide) (PEO) by using LiClO₄ as doping salts and inorganic–organic hybrid poly (cyclotriphosphazene-co-4,4′-sulfonyldiphenol) (PZS) microspheres as fillers were prepared. Electrochemical and thermal properties of PEO-based polymer electrolytes incorporated with PZS microspheres were studied. Differential scanning calorimetry (DSC) results showed there was a decrease in the glass transition temperature of the electrolytes and the crystallinity of the samples in the presence of the fillers. Maximum ionic conductivity values of 1.2 × 10⁻⁵ S cm⁻¹ at ambient temperature and 7.5 × 10⁻⁴ S cm⁻¹ at 80° were obtained and lithium ion transference number was 0.29. Compared with traditional ceramic fillers such as SiO₂, the addition of PZS microspheres increased the ionic conductivity of the electrolytes slightly and led to remarkable enhancement in the lithium ion transference number.