Effects of compositions on properties of PEO–KI–I2 salts polymer electrolytes for DSSC

The effects of compositions on properties of PEO/KI/I₂ salts polymer electrolytes were investigated to optimize the photovoltaic performance of solid state DSSCs. XRD pattern for the mole ratio 12:1 of [EO:KI] was showed the formation of complete amorphous complex. DSC results also confirmed the amorphous nature of the polymer electrolyte. The highest value of ionic conductivity is 8.36 × 10^− 5 S/cm at 303 K (ambient temperature) and 2.32 × 10^− 4 S/cm at 333 K (moderate temperature) for the mole ratio 12:1 of EO:KI complex. The effect of contribution of [I⁻] and [I₃⁻] concentration with conductivity were also evaluated. FTIR spectrum reveals that the alkali metal cations were co-ordinated to ether oxygen of PEO. The formation of polyiodide ions, such as symmetric I₃⁻ (114 cm^− 1) and I₅⁻ (145 cm^− 1) caused by the addition of iodine was confirmed by FT Raman spectroscopic measurements. The optimum composition of PEO–KI–I₂ polymer electrolyte system for higher conductivity at ambient and moderate temperatures was reported. A linear Arrhenius type behaviour was observed for all the PEO–KI polymer complexes. Transport number measurements were carried out for several polymer electrolyte compositions. Dye-sensitized solar cells were fabricated by using higher conductivity polymer electrolyte compositions and its photoelectrochemical performance was investigated. The fill factor, short-circuit current, photovoltage and energy conversion efficiency of the DSSC assembled with optimized electrolyte composition were calculated to be 0.563, 6.124 mA/cm², 593 mV and 2.044% respectively.     

Influence of pyrazole on the photovoltaic performance of dye-sensitized solar cell with polyvinylidene fluoride polymer electrolytes

We investigate the influence of the pyrazole content on the polyvinylidene fluoride (PVDF)/KI/I₂ electrolytes for dye-sensitized solar cells (DSSCs). The solid polymer electrolyte films consisting of different weight percentage ratios (0 20, 30, 40, and 50 %) of pyrazole doped with PVDF/KI/I₂ have been prepared by solution casting technique using N,N-dimethyl formamide (DMF) as a solvent. The as-prepared polymer electrolyte films were characterized by various techniques such as Fourier transform infrared spectroscopy (FT-IR spectroscopy), differential scanning calorimetry (DSC), X-ray diffractometer (XRD), alternate current (AC)-impedance analysis, and scanning electron microscopy (SEM). The 40 wt% pyrazole-PVDF/KI/I₂ electrolyte exhibited the highest ionic conductivity value of 9.52?×?10^?5 Scm^?1 at room temperature. This may be due to the lower crystallinity of PVDF and higher ionic mobility of iodide ions in the electrolyte. The DSSC fabricated using this highest ion conducting electrolyte showed an enhanced power conversion efficiency of 3.30 % under an illumination of 60 mW/cm² than that of pure PVDF/KI/I₂ electrolyte (1.42 %).     

AZO/Ag/AZO multilayer films prepared by DC magnetron sputtering for dye-sensitized solar cell application

Ag films were deposited on Al-doped ZnO (AZO) films and coated with AZO to fabricate AZO/Ag/AZO multilayer films by DC magnetron sputtering on glass substrates without heating of glass substrates. The best multilayer films have low sheet resistance of 19.8 Ω/Sq and average transmittance values of 61% in visible region. It was found that the highest figure of merit (F_TC) is 6.9 × 10⁻⁴ Ω⁻¹. For the dye-sensitized solar cell (DSSC) application, the multilayer films were used as transparent conductive electrode (multilayer films/ZnO + Eosin-Y/LiI + I₂/Pt/FTO). The best DSSC based on the multilayer films showed that open circuit voltage (V_oc) of 0.47 V, short circuit current density (J_sc) of 2.24 mA/cm², fill factor (FF) of 0.58 and incident photon-to-current conversion efficiency (η) of 0.61%. It was shown that the AZO/Ag/AZO multilayer films have potential for application in DSSC.     

Li3+ ion irradiation effects on ionic conduction in P(VDF–HFP)–(PC + DEC)–LiClO4 gel polymer electrolyte system

Swift heavy ion irradiation of P(VDF–HFP)–(PC + DEC)–LiClO₄ gel polymer electrolyte system with 48 MeV Li³⁺ ions having five different fluences was investigated with a view to increase the Li⁺ ion diffusivity in the electrolyte. Irradiation with swift heavy ion (SHI) shows enhancement of conductivity at lower fluences and decrease in conductivity at higher fluences with respect to unirradiated polymer electrolyte films. Maximum room temperature (303 K) ionic conductivity is found to be 2.2 × 10^− 2 S/cm after irradiation with fluence of 10¹¹ ions/cm². This interesting result could be ascribed to the fluence-dependent change in porosity and to the fact that for a particular ion beam with a given energy higher fluence provides critical activation energy for cross-linking and crystallization to occur, which results in the decrease in ionic conductivity. The XRD results show decrease in the degree of crystallinity upon ion irradiation at low fluences (≤ 10¹¹ ions/cm²) and increase in crystallinity at high fluences (> 10¹¹ ions/cm²). The scanning electron micrographs (SEM) exhibit increased porosity of the polymer electrolyte films after low fluence ion irradiation.     

Synthesis and ionic conductivity of polymeric ion gel containing room temperature ionic liquid and phosphotungstic acid

Composite electrolyte comprising phosphotungstic acid (PWA) filler and 1-butyl-3-methyl-imidazolium-tetrafluoroborate (BMImBF₄) room temperature ionic liquid (RTIL) in poly(2-hydroxyethyl methacrylate) (PHEMA) matrix has been prepared. The polymer matrix was formed by free radical polymerization of 2-hydroxyethyl methacrylate (HEMA) monomers. BMImBF₄ was used as both ionic source and plasticizer, and PWA filler provided the proton conductivity in this system. The interactions and structure changes of the PHEMA-RTIL-PWA composites were investigated by Fourier transform infrared spectra, differential scanning calorimetry, and X-ray diffraction. PWA fillers maintained their Keggin structure within a limited range and enhanced the ionic conductivity of the composite electrolyte. The electrolyte with PWA at the 2 wt.% showed the highest ionic conductivity of 8 × 10^− 4 S cm^− 1 at room temperature and 96% relative humidity.     

Study on ionic conductivity of polymer electrolyte plasticized with PEG–aluminate ester for rechargeable lithium ion battery

We have synthesized poly(ethylene glycol) (PEG)-aluminate ester as a plasticizer for solid polymer electrolytes. The thermal stability, ionic conductivity and electrochemical stability of the polymer electrolyte which consist of poly(ethylene oxide) (PEO)-based copolymer, PEG–aluminate ester and lithium bis-trifluoromethanesulfonimide (LiTFSI) were investigated. Addition of PEG–aluminate ester increased the ionic conductivity of the polymer electrolyte, showing greater than 10^− 4 S cm^− 1 at 30 °C. The polymer electrolyte containing PEG–aluminate ester retained thermal stability of the non-additive polymer electrolyte and exhibited electrochemical stability up to 4.5 V vs. Li⁺/Li at 30 °C.     

Quasi-solid state polymer electrolytes for dye-sensitized solar cells: Effect of the electrolyte components variation on the triiodide ion diffusion properties and charge-transfer resistance at platinum electrode

Quasi-solid state polymer electrolytes have been prepared from poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) as gelator for 1-ethyl-3-methylimidazolium based ionic liquids (with anions like trifluoromethanesulfonate [EMIM][TfO], bis(trifluoromethanesulfonyl)imide [EMIM][Tf₂N]) and polyacrylonitrile (PAN) for gelation of 1-ethyl-3-methylimidazolium dicyanamide [EMIM][DCA] as well as I⁻/I₃⁻ as the redox couple. All electrolytes exhibit high ionic conductivity in the range of 10^− 3 S/cm. The effect of gelation, redox couple concentration, I⁻/I₃⁻ ratio, choice of cations and additives on the triiodide diffusion and charge-transfer resistance of the platinum/electrolyte interface (R_ct) were studied. The apparent diffusion coefficient of triiodide ion (D(I₃⁻)) at various iodide/triiodide ratios in liquid and gelified electrolytes has been calculated from measurements of the diffusion limited current (I_lim) in electrochemical cell resembling the set-up of a dye-sensitized solar cell. The charge-transfer resistance of the platinum/electrolyte interface as well as the capacitance of the electrical double layer (C_dl) have been calculated from impedance measurements. Electrolytes with reduced content of polymer (2.5 wt.%) were doped with Al₂O₃ particles of different sizes (50 nm, 300 nm, 1 μm). The dispersion of the particles proceeds by speedy stirring of the hot electrolyte and the addition of PAN provides a homogeneous suspension. The addition of Al₂O₃ particles causes a slight increase of the triiodide diffusion constants. Furthermore the suggested enhancement of the charge transfer rate shows a dependence on the size of the particles.     

Synthesis and properties of a new class of fluorine-containing dilithium salts for lithium-ion batteries

A facile synthetic route for the development of a new class of dilithium salts is described. Because of the presence of two lithium ions per molecule, these salts require lower concentrations than commonly used salts to achieve comparable ionic conductivities at ambient temperatures. An ionic conductivity of 3.55 × 10^− 3 S/cm at 30 °C was obtained using 0.5 M salt solution in 1:1 wt/wt ethylene carbonate:dimethyl carbonate. The salts exhibit excellent thermal stabilities to at least 350 °C and are electrochemically stable below 4.2 V versus lithium metal. The best salt was tested with a polymer electrolyte system. Incorporation of a polyethylene glycol-based borate ester plasticizer improved the ionic conductivity of the solid polymer electrolyte film up to 1.36 × 10^− 5 S/cm at 30 °C, which is 10 times higher than that of un-plasticized electrolyte films.     

Synthesis,ionic conductivity,and thermal properties of proton conducting polymer electrolyte for high temperature fuel cell

Hyperbranched polymer (poly-1a) with sulfonic acid groups at the end of chains was successfully synthesized. Interpenetration reaction of poly-1a with a hyperbranched polymer with acryloyl groups at the end of chains (poly-1b) as a cross-linker afforded a tough electrolyte membrane. The poly-1a and the resulting electrolyte membrane showed the ionic conductivities of 7 × 10^− 4 and 8 × 10^− 5 S/cm, respectively, at 150 °C under dry condition. The ionic conductivities of the poly-1a and the electrolyte membrane exhibited the VTF type temperature dependence. And also, both poly-1a and the resulting electrolyte membrane were thermally stable up to 200 °C.     

High ionic conductive behavior of cyanoethylated polyvinylalcohol- and polyacrylonitrile-based electrolytes

New type polymer electrolyte films based on poly(acrylonitrile), (PAN), and cyanoethylated poly(vinyl alcohol), (CN-PVA), were prepared and their conducting behaviors were investigated. CN-PVA was prepared from poly(vinyl alcohol), (PVA) and acrylonitrile in the presence of sodium hydroxide and quaternary ammonium halide as a phase transfer catalyst. Free standing PAN- and CN-PVA-based electrolyte films were prepared by casting the propylene carbonate (PC) solution containing PAN, CN-PVA and LiClO₄ and removing some amount of PC. Ionic conductivity of the electrolyte film, (PAN)10(CN-PVA) 10(LiClO₄)8(PC)4 composite film was 14.6 mS cm^− 1 at 30 °C and 22.4 mS cm^− 1 at 60 °C. FTIR results for the electrolyte films suggest that the nitrile groups in the CN-PVA matrix mainly interact with the lithium ions in the films and enhance dissolution of the lithium salt in the electrolyte films.     

Single ion conductors—polyphosphazenes with sulfonimide functional groups

A novel single ion conductive polymer electrolyte was developed by covalently linking an arylsulfonimide substituent to the polyphosphazene backbone. Polymeric single-ion conductors incorporate the anion of a salt either into the polymer backbone or as a pendent group linked to the polymer backbone. Immobilization of the anion could provide access to electrochemical devices that would be less vulnerable to increased resistance associated with salt concentration gradients at the interfaces during charging and discharging. In this work, an immobilized sulfonimide lithium salt is the source of lithium cations, while a cation-solvating cosubstituent, 2-(2-methoxyethoxy)ethoxy, was used to increase free volume and assist cation transport. The ionic conductivities showed a dependence on the percentage of lithiated sulfonimide substituent present. Increasing amounts of the lithium sulfonimide component increased the charge carrier concentration but decreased the ionic conductivity due to decreased macromolecular motion and possible increased shielding of the nitrogen atoms in the polyphosphazene backbone. Maximum ionic conductivity values of 2.45 × 10^− 6 S/cm at ambient temperature and 4.99 × 10^− 5 S/cm at 80 °C were obtained. Gel polymer electrolytes containing N-methyl-2-pyrrolidone gave ionic conductivities in the 10^− 3 S/cm range. The ion conduction process was investigated through model polymers that contained the non-immobilized sulfonimide — systems that had higher conductivities than their single ion counterparts.     

Polymer electrolytes based on cross-linked cyclotriphosphazenes

Substituted cyclotriphosphazenes were used to prepare lithium ion conducting polymer networks. Two types of compounds were synthesized starting with the precursor hexachlorocyclotriphosphazene (HCCP): Type I (CVEEP) in which all the chlorine atoms in HCCP were replaced by vinyloxyethoxyethoxy groups (VEE = –OCH₂CH₂OCH₂CH₂OCHCH₂), and type II (CVMEEP) in which half of the chlorine was replaced by VEE and the other half by methoxyethoxyethoxy groups (MEE = –OCH₂CH₂OCH₂CH₂OCH₃). The terminal vinyl groups were used to build up a network by a thermally initiated cross-linking of lithium salt containing membranes. Polymer electrolytes with dissolved LiSO₃CF₃ and LiN(SO₂CF₃)₂ were investigated by impedance measurements. The ionic conductivity of CVMEEP with 10 wt.% LiSO₃CF₃ was 3.2 × 10^− 5 S/cm at 30 °C and 4.1 × 10^− 4 S/cm at 90 °C. Lower conductivity values in the range 10^− 8–10^− 9 S/cm were obtained at 30 °C for the highly crosslinked CVEEP. An interesting polymer electrolyte with good mechanical properties and a good conductivity of 1.3 × 10^− 5 S/cm (30 °C) was obtained from a solution of MEEP (= poly[bis(methoxy–ethoxy–ethoxy)phosphazene]) and LiSO₃CF₃ in CVEEP as an interpenetrating network.     

Ionic conductivity of polymer electrolyte membranes based on polyphosphazene with oligo(propylene oxide) side chains

A polyphosphazene [NP(NHR)₂]_n with oligo[propylene oxide] side chains − R = –[CH(CH₃)–CH₂O]_m–CH₃ (m = 6 – 10) was synthesized by living cationic polymerisation and polymer-analogue substitution of chlorine from the intermediate precursor [NPCl₂]_n using the corresponding primary amine RNH₂. The polymer had an average molecular weight of 3.3 × 10⁵ D. Polymer electrolytes with different concentrations of dissolved lithium triflate (LiCF₃SO₃) were prepared. Mechanically stable polymer electrolyte membranes were formed using UV radiation induced crosslinking of the polymer salt mixture in the presence of benzophenone as photoinitiator. The glass transition temperature of the parent polymer was found to be − 75 °C before cross linking. It increases after crosslinking and with increasing amounts of salt to a maximum of − 55 °C for 20 wt.% LiCF₃SO₃. The ionic conductivity was determined by impedance spectroscopy in the temperature range 0–80 °C. The highest conductivity was found for a salt concentration of 20 wt.% LiCF₃SO₃: 6.5 × 10^− 6 S·cm^− 1 at 20 °C and 2.8 × 10^− 4 S cm^− 1 at 80 °C. The temperature dependence of the conductivities was well described by the MIGRATION concept.     

Current transport mechanism and photovoltaic properties of photoelectrochemical cells of ITO/TiO2/PVC–LiClO4/graphite

This paper deals with the current transport mechanism of solid state photoelectrochemical cells of ITO/TiO₂/PVC–LiClO₄/graphite as well as the physical properties of a component of a device affecting its performance. The principle of operation and a schematic energy level diagram for the materials used in the photoelectrochemical cells are presented. The device makes use of ITO films, TiO₂ films, PVC–LiClO₄ and graphite films as photoanode, photovoltaic material, solid electrolyte and counter electrode, respectively. The device shows rectification. The J_sc and V_oc obtained at 100 mW cm⁻² were 0.95 μAcm⁻² and 180 mV, respectively.     

Study of EVOH based single ion polymer electrolyte: Composition and microstructure effects on the proton conductivity

A comb-like EVOH based single ion polymer electrolyte (EVOH-g-SPEG) was synthesized by sulfonification of EVOH grafts 2-(2-chloroethoxy) ethanol (C₄H₉O₂Cl)/2-[2-(2-chloroethxy) ethoxy] ethanol (C₆H₁₃O₃Cl) with 1, 3-propane sultone. The main chain of the comb-like polymer is hydrophobic polyethylene segments; the side chain is hydrophilic poly (ethylene glycol) (PEG) segment, which can solubilize large amounts of inorganic salts. The sulfonic acid group was introduced onto the end of the PEG side chain. The acid form of SPE was successfully obtained by being dialyzed from the products with acid solution. The saturation water sorption of EVOH-g-SPEG membrane increased with the side chain length and the immersion time. The XRD results indicate that the water in SPE membrane region can destroy the membrane crystalline structure and the water absorption membranes are nearly amorphous. AFM phase images of the hydration membranes clearly show the hydrophilic domains, with sizes increasing from 10 to 35 nm as a function of the side chain length. A phase inversion could be observed when n ≥ 5, which was consistent with a rapid increase in water absorption. And the ion conductivity is also measured by AC impedance. The conductivity is greatly influenced by ion exchange capacity and water sorption. The comb-like EVOH-g-SPEG polymer electrolyte grafts with 2 PEG side chain provides the highest ionic conductivity (1.65 × 10^− 3 S cm^− 1). The comb-like polymer could be a candidate as new polymeric electrolyte material for fuel cells and other electrochemical devices.     

Characterization of LSGM films obtained by electrophoretic deposition (EPD)

The application of the electrophoretic deposition (EPD) technique to the preparation of high quality electrolyte films for intermediate temperature solid oxide fuel cells (IT-SOFCs) was investigated. Films of La_0.83Sr_0.17Ga_0.83Mg_0.17O_2.83 (LSGM) were deposited on Pt and La_0.8Sr_0.2MnO₃ (LSM) substrates from suspensions in acetone/ethanol (3:1 by volume) mixture solvent and sintered at 1300 °C. Pt supported LSGM films, 10–20 μm thick, exhibited good adhesion to the Pt substrate, well-distributed microporosity and some surface roughness. LSM supported films exhibited cracking after sintering at 1300 °C for 3 h. Up to 900 °C the bulk conductivity of the Pt supported LSGM film showed the same behaviour of LSGM pellet (E_a = 0.93 eV and 0.99 eV, respectively). The LSGM film exhibited lower bulk electrical conductivity than the latter (4.1 × 10^− 3 and 4.4 × 10^− 2 Ω^− 1 cm^− 1, respectively, at 700 °C). This difference should be ascribed to the slight Ga depletion in the LSGM film. An important issue remains the selection of adequate electrode for LSGM electrolyte films.     

SILAR deposited Bi2S3 thin film towards electrochemical supercapacitor

Bi₂S₃ thin film electrode has been synthesized by simple and low cost successive ionic layer adsorption and reaction (SILAR) method on stainless steel (SS) substrate at room temperature. The formation of interconnected nanoparticles with nanoporous surface morphology has been achieved and which is favourable to the supercapacitor applications. Electrochemical supercapacitive performance of Bi₂S₃ thin film electrode has been performed through cyclic voltammetry, charge-discharge and stability studies in aqueous Na₂SO₄ electrolyte. The Bi₂S₃ thin film electrode exhibits the specific capacitance of 289 Fg⁻¹ at 5 mVs⁻¹ scan rate in 1 M Na₂SO₄ electrolyte.     

Fabrication of thin-film transistor based on self-assembled single-walled carbon nanotube network

Thin-film transistor based on controllable electrostatic self-assembled monolayer single-wall carbon nanotubes (SWNTs) network has been fabricated by varying the density of nanotubes on the silicon substrate. The densities of SWNTs network have been investigated as a function of concentration and assembly time. It has been observed that the density of SWNTs network increases from 0.6 µm⁻² to 2.1 µm⁻², as the average on-state current (I_on) increases from 0.5 mA to 1.47 mA. The device has a current on/off ratio (I_on/I_off) of 1.3×10⁴ when I_on reaches to 1.34 mA.     

Ionic conductance of composite electrolytes based on network polymer with ceramic powder

Effects of ceramic fillers (α-Al₂O₃, γ-Al₂O₃ and BaTiO₃) have been investigated on the ionic conductance of polymeric complexes consisting of poly(ethylene oxide)-modified poly(methacrylate) (PEO-PMA) and lithium bis(trifluoromethylsulfonyl)imide, Li(CF₃SO₂)₂N, and ceramic powder. The addition of ceramic powder increased the ionic conductivity over an ambient temperature range. Conductivity of 4.9 × 10^− 5 S cm^− 1 at 333 K (60 °C) was obtained for the composite containing 15 wt.% α-Al₂O₃ prepared by photo-polymerization. The optimum content of Al₂O₃ was different among the methods of polymerization. The highest conductivity was obtained for the composite containing 5 wt.% of α-, or γ-Al₂O₃ prepared by thermal polymerization. The addition of the ceramic filler scarcely influenced the thermal properties of the polymer matrix. XRD and NMR experiments showed that the ionic mobility could be enhanced in the composites by addition of α-Al₂O₃. The addition of small amounts of ferroelectric BaTiO₃ also increased the ionic conductivity of the polymeric complex, but its extent was smaller than the case of the Al₂O₃ addition.     

Polyphosphazene based composite polymer electrolytes

Composite salt-in-polymer electrolyte membranes were prepared from poly[(bis(2-methoxyethyl)amino)_1−x(n-propylamino)_x-phosphazene] (BMEAP) with dissolved LiCF₃SO₃ and dispersed Al₂O₃ nanoparticles (40 nm). Membranes with good mechanical stability were obtained. Low ionic conductivities were found in particle free membranes with maximum conductivities at 10 wt.% LiCF₃SO₃ ranging from 3.1 × 10^− 7 S/cm at 30 °C to 1.8 × 10^− 5 S/cm at 90 °C. For the composite membranes, addition of 2 wt.% Al₂O₃ nanoparticles leads to a steep increase of the conductivity by almost two orders of magnitude as compared to the homogeneous membranes. The highest room temperature conductivity for the investigated BMEAP–LiCF₃SO₃–Al₂O₃ composite systems was 10^− 5 S/cm.