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.     

Transitional metal-doped 8 mol% yttria-stabilized zirconia electrolytes

The sintering, grain growth and ionic conductivities (especially the grain-boundary (GB) conductivity), of 8YSZ electrolytes with various silica levels (~ 30 ppm, ~ 500 ppm and ~ 3000 ppm), doped with 1 at% transitional metal oxides (TMOs), have been systematically investigated by means of dilatometer, electron microscopy and impedance analyzer. It is confirmed that small additions of TMOs (i.e., Fe, Mn, Co or Ni) promote the densification and grain growth of both the pure and Si-containing 8YSZ. The effect of TMOs on the ionic conductivities could be negative or positive, relying on the type of TMOs, sintered density and impurity level. For the dense and pure 8YSZ (with ~ 30 ppm SiO₂), the addition of 1 at% TMOs led to a reduction in grain interior (GI) conductivity by ~ 25–33% with little effect on the GB conduction. For the impure 8YSZ (with ~ 500 ppm or 3000 ppm SiO₂), except for FeO_1.5, the other TMOs (i.e., Mn, Co or Ni) are extremely detrimental to the total conductivity by significantly reducing the GB conduction. Moreover, it is also found that the GB conductivity of the impure 8YSZ doped with Co or Ni is less sensitive to sintering temperature. FeO_1.5 showed a scavenging effect on SiO₂ in the impure 8YSZ, which is specially beneficial to the total conductivity of samples with higher silica levels and/or sintered at relatively low temperatures.     

A preliminary study on a new LiBOB/acetamide solid phase transition electrolyte

New solid electrolytes containing acetamide and lithium bioxalato borate (LiBOB) with different molar ratios have been investigated. Their melting points (T_m) are around 42 °C. The ionic conductivities and activation energies vary drastically below and above T_m, indicating a typical feature of phase transition electrolyte. The ionic conductivity of the LiBOB/acetamide electrolyte with a molar ratio of 1:8 is 5 × 10^? 8 S cm^? 1 at 25 °C but increases to 4 × 10^? 3 S cm^? 1 at 60 °C. It was found that anode materials, such as graphite and Li₄Ti₅O₁₂, could not discharge and charge properly in this electrolyte at 60 °C due to the difficulty in forming a stable passivating layer on the anodes. However, a Li/LiFePO₄ cell with this electrolyte can be charged properly after heating to 60 °C, but cannot be charged at room temperature. Although the LiBOB/acetamide electrolytes are not suitable for Li-ion batteries due to poor electrode compatibility, the current results indicate that a solid electrolyte with a slightly higher phase transition temperature than room temperature may find potential application in stationary battery for energy storage where the electrolyte is at high conductive liquid state at elevated temperature and low conductive solid state at low temperature. The interaction between acetamide and LiBOB in the electrolyte is also studied by Raman and FTIR spectroscopy.     

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.     

Polymer electrolytes based on copolymer of poly(ethylene glycol) dimethacrylate and imidazolium ionic liquid

Polymer electrolytes based on the copolymer of N-vinylimidazolium tetrafluoroborate (VyImBF₄) and poly(ethylene glycol) dimethacrylate (PEGDMA) have been prepared. Ethylene carbonate (EC) and LiClO₄ are added to form gel polymer electrolytes. The chemical structure of the samples and the interactions between the various constituents are studied by FT-IR. TGA results show that these polymer electrolytes have acceptable thermal stability, are stable up to 155 °C. Measurements of conductivity are carried out as a function of temperature, VyImBF₄ content in poly(VyImBF₄-co-PEGDMA), and the concentration of EC and LiClO₄. The conductivity increases with PEGDMA and EC content. The highest conductivity is obtained with a value of 2.90 × 10^? 6 S cm^? 1 at room temperature for VP1/EC(25 wt.%)–LiClO₄ system, corresponding to the LiClO₄ concentration of 0.70 mol kg^? 1 polymer.     

Micro-solid oxide fuel cell using thick-film ceria

A fabrication method that does not use lithography or etching processes for thick-film based micro-SOFCs (Solid Oxide Fuel Cells) was described and discussed. In this study, a new type of micro-SOFC was fabricated using a free-standing thick-film electrolyte with ~ 20 μm thickness. This structure has the advantages of both electrolyte-support and electrode-support type SOFCs. Generally, the electrolyte should be thicker than e.g., ~ 150 μm since a thinner electrolyte easily cracks in a self-supporting mode during the fabrication procedure. Thus, a new mounting method was developed in order to use a thin-electrolyte film. In this study, a ~ 20 μm-thick GDC (Gd-doped ceria) electrolyte film was successfully mounted on a ~ 400 μm-thick GDC ring by sintering these two pieces together. Ni-GDC and Sm_0.5Sr_0.5CoO₃ were brush painted as an anode and a cathode, respectively. With this new configuration, it was possible to construct an electrolyte-supported SOFC using a thick-film ceria-based electrolyte and measure the power density. The open-circuit voltage (OCV) of the cell in 97%H₂ + 3%H₂O/air was ~ 0.87 V and the maximum power density was ~ 270 mW/cm² at 600 °C. The result shows that the high performance is achievable for the micro-SOFCs using a thick-film ceria-electrolyte operating at 600 °C.     

Conductivity and optical studies of plasticized solid polymer electrolytes doped with carbon nanotube

Solid polymer electrolyte films based on Poly(ethylene oxide) (PEO) complexed with lithium hexafluorophosphate (LiPF₆), ethylene carbonate (EC) and amorphous carbon nanotube (αCNTs) were prepared by the solution cast technique. The conductivity increases from 10^?10 to 10^?5 Scm^?1 upon the addition of salt. The incorporation of EC and αCNTs to the salted polymer enhances the conductivity significantly to 10^?4 and 10^?3 Scm^?1. The complexation of doping materials with polymer were confirmed by X-ray diffraction and infrared studies. Optical properties like direct band gap and indirect band gap were investigated for pure and doped polymer films in the wavelength range 200–400 nm. It was found that the energy gaps and band edge values shifted to lower energies on doping.     

Thermal diffusivity and electrical conductivity in fast ion conducting composites: A correlation

The thermal diffusivity and electrical conductivity have been measured for two ion conducting polyethylene oxide (PEO) based polymer–ceramic composites viz. (PEO:NH₄I) + xAl₂O₃, (PEO:LiBF₄) + xBa_0.70Sr_0.30TiO₃ and two solid–solid composites viz. AgI + xAl₂O₃, AgI +xBa_0.70Sr_0.30TiO₃. The thermal diffusivity has been measured by the novel photoacoustic technique while the electrical conductivity has been measured by impedance spectroscopy technique using complex impedance plots. The pattern of variation in the electrical conductivity (σ) vs. composition plot and that in the thermal diffusivity (α_s) vs. composition plot are similar. Interestingly, the correlation between α_s and σ is not only qualitative but is quantitative as well in the sense that the ratio (α_s / σ) remains constant for all the samples within the same system (though their conductivities are different) similar to Wiedmann–Franz law applicable to metallic conductors.     

Development of dry polymer electrolyte based on polyethylene oxide with co-bridging agent crosslinked by electron beam

Polyethylene oxide (PEO)-based electrolytes were crosslinked using electron beam (EB) irradiation. The gel contents of a polymer film were increased after irradiation doses of 0, 140, 280, and 420 kGy, with ionic conductivities of 0.831, 1.55, 6.08, and 7.95 (× 10^? 5) S cm^? 1 at 40 °C, respectively. The slight decrease in conductivity at higher temperatures after irradiation is due to the retardation of polymer motion by crosslinking. The electrolyte with higher EB dose amount exhibits higher conductivity due to stabilization of the amorphous state. The EB crosslinking with a co-bridging agent shows enhanced conductivities of 4.71, 6.59, and 7.18 (× 10^? 5) S cm^? 1 at 40 °C, after irradiation with 140, 280, and 420 kGy. Addition of the co-bridging agent is effective for developing a crosslinked structure with a smaller EB dose. Tensile strength becomes two to three times higher with irradiation compared to the non-treated polymer. Combination of the EB technique with a co-bridging agent is a simple and effective method to prepare strong dry polymer electrolyte films with improved room temperature conductivity.     

Influence of electrolyte temperature on properties and infrared emissivity of MAO ceramic coating on 6061 aluminum alloy

6061 aluminum alloy was treated by MAO at various temperatures of the alkali silicate electrolyte using pulsed bipolar current mode for ten minutes. The surface microstructures and properties were studied using SEM, EDX, and XRD. The infrared emissivities of the MAO ceramic coatings were measured at the 70 °C using FTIR spectrometer. The electrolyte temperature strongly affected all the surface properties. The MAO alumina ceramics prepared in cold electrolytes have volcano-like and accumulated particles microstructures, while those prepared in hot electrolytes were: rougher, thinner and contained grainy spherical hollow bulgy microstructures with more pore density and more sillimanite and cristobalite phases which enhanced the IR emissivity. Also, the increment of sillimanite and cristobalite phases moved the apparent peaks toward longer wavelengths, and broadened the opaque region of the IR spectra. As a result, the increment of electrolyte temperature from 12.3 °C to 90.5 °C increased the average of LWIR emissivity from 80.4% to 94.4%, respectively, for the MAO ceramic coatings.     

Polymer electrolytes based on poly(vinylidene fluoride-co-hexafluoropropylene) with crosslinked poly(ethylene glycol) for lithium batteries

The combination of a poly(ethylene glycol) (PEG) network and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) copolymer chains is one of the most efficient means for modifying PVDF-HFP gel electrolytes. Previous preparations tend to introduce contamination into the polymer gel electrolyte because of irradiation, high temperature or the initiator needed for crosslinking which might result in the electrochemical degradation. In order to overcome the above disadvantages, a new method has been developed to successfully prepare the semi-interpenetrating polymer networks of PVDF-HFP based electrolytes with crosslinked diepoxy polyethylene glycol (DIEPEG). In this process, impurities are avoided because of a moderate reaction temperature at 50 °C and poly(ethylenimine) (PEI) as the crosslinking agent. Microporous films with various compositions are prepared and characterized. Thermal, mechanical, swelling and electrochemical properties, as well as microstructures of the prepared polymer electrolytes have been investigated using thermogravimetric analysis, electrochemical impedance spectroscopy, linear sweep voltammetry, and scanning electron microscopy. The results show that the blend polymer electrolyte with PVDF-HFP/PEI + DIEPEG (60:40 w/w) has an ionic conductivity of 2.3 mS cm^? 1 at room temperature in the presence of 1 M LiPF₆ in EC and DMC (1:1 w/w). All the blend electrolytes are electrochemically stable up to 4.8 V versus Li/Li⁺. The results reveal that this new method may be very promising for improving PVDF-HFP based electrolytes.     

Preparation and characterization of solid polymer electrolytes based on PHEMO and PVDF-HFP

Polymer electrolyte membranes consisting of a novel hyperbranched polyether PHEMO (poly(3-{2-[2-(2-hydroxyethoxy) ethoxy] ethoxy}methyl-3′-methyloxetane)), PVDF-HFP (poly(vinylidene fluoride-hexafluoropropylene)) and LiTFSI have been prepared by solution casting technique. X-ray diffraction of the PHEMO/PVDF-HFP polymer matrix and pure PVDF-HFP revealed the difference in crystallinity between them. The effect of different amounts of PVDF-HFP and lithium salts on the conductivity of the polymer electrolytes was studied. The ionic conductivity of the prepared polymer electrolytes can reach 1.64 × 10^? 4 S·cm^? 1 at 30 °C and 1.75 × 10^? 3 S·cm^? 1 at 80 °C. Thermogravimetric analysis informed that the PHEMO/PVDF-HFP matrix exhibited good thermal stability with a decomposition temperature higher than 400 °C. The electrochemical experiments showed that the electrochemical window of the polymer electrolyte was around 4.2 V vs. Li⁺/Li. The PHEMO/PVDF-HFP polymer electrolyte, which has good electrochemical stability and thermal stability, could be a promising solid polymer electrolyte for polymer lithium ion batteries.     

Synthesis and electrical transport properties of Lu2+xTi2−xO7−x/2 oxide-ion conductors

The Lu_2+xTi_2−xO_7−x/2 (x = 0; 0.052; 0.096; 0.286; 0.44; 0.63; 33.3–49 mol% Lu₂O₃) nanoceramics with partly disordered pyrochlore-type structure are prepared by sintering freeze-dried powders obtained by a co-precipitation technique with 1600 °C annealing. Similar to pyrochlore-like compositions in the zirconate system, some of the new titanates are good oxide-ion conductors in air. The new solid-state electrolytes have oxide-ion conductivity in the interval of 1.0 × 10^− 3 – 2.5 × 10^− 3 S/cm at 740 °C in air. This value of conductivity is comparable with that of ZrO₂/Y₂O₃ ceramics. The conductivity of Lu_2+xTi_2−xO_7−x/2 depends on the chemical composition. The highest ionic conductivity is exhibited by nearly stoichiometric Lu_2+xTi_2−xO_7−x/2 (x = 0.096; 35.5 mol% Lu₂O₃) material containing ∼ 4.8 at.% Lu_Ti anti-site defects.     

Performance of La-doped strontium titanate (LST) anode on LaGaO3-based SOFC

Ni-containing anode is currently used with many electrolytes of solid oxide fuel cells (SOFCs). However, Ni is easily oxidized and deteriorates the LaGaO₃-based electrolyte. A La-doped SrTiO₃ (LST, La_0.2Sr_0.8TiO₃) is a candidate as an anode material to solve the Ni poisoning problem in LaGaO₃-based SOFC. In this study, a single-phase LST and an LST-Gd_0.2Ce_0.8O_2 ? δ (GDC) composite were tested as the possible anodes on La_0.9Sr_0.1Ga_0.8Mg_0.2O_3 ? δ (LSGM) electrolyte. In order to further improve the anodic performance, Ni was impregnated into the LST-GDC composite anode. The performance was examined from 600 °C to 800 °C by measuring impedance of the electrolyte-supported, symmetric (anode/electrolyte/anode) cells. A polarization resistance (R_p) of LST-GDC anode was much reduced from that of LST anode. When Ni was impregnated into LST-GDC composite, the R_p value was further reduced to ~ 10% of the single-phase LST anode, and it was 1 Ωcm² at 800 °C in 97% H₂ + 3% H₂O atmosphere. A single cell with Ni-impregnated LST-GDC as an anode, Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 ? δ (BSCF) as a cathode and LSGM as an electrolyte exhibited the maximum power density of 275 mW/cm² at 800 °C, increased from ~ 60 mW/cm² for the cell using the LST-GDC as an anode. Thus, LST-GDC composite is promising as a component of anode.     

Thin films of molecule-based charge transfer complex cobalt tetracyanoethylene: In situ X-ray photoemission study

Thin films of molecule-based charge transfer magnet, cobalt tetracyanoethylene [Co(TCNE)_x, x ~ 2] consisting of the transition metal Co, and an organic molecule viz. tetracyanoethylene (TCNE) have been deposited by using physical vapor deposition method under ultra-high vacuum conditions at room temperature. X-ray photoelectron spectroscopy (XPS) technique has been used extensively to investigate the electronic properties of the Co(TCNE)_x thin films. The XPS measurements show that the prepared Co(TCNE)_x films are clean, and oxygen free. The stoichiometries of the films, based on atomic sensitive factors, are obtained, and yields a ~ 1:2 ratio between metal Co and TCNE for all films. Interestingly, the positive shift of binding energy position for Co(2p), and negative shifts for C(1s) and N(1s) peaks suggest a charge-transfer from Co to TCNE, and cobalt is assigned to its Co(II) valence state. In the valence band investigation, the highest occupied molecular orbital (HOMO) of Co(TCNE)_x is found to be at ~ 2.4 eV with respect to the Fermi level, and it is derived either from the TCNE^? singly occupied molecular orbital (SOMO) or Co(3d) states. The peaks located at ~ 6.8 eV and ~ 8.8 eV are due to TCNE derived electronic states. The obtained core level and valence band results of Co(TCNE)_x, films are compared with those of V(TCNE)_x thin film magnet: a well known system of M(TCNE)_x type of organic magnet, and important points regarding their electronic properties have been brought out.     

Electrochemical redox supercapacitors using PVdF-HFP based gel electrolytes and polypyrrole as conducting polymer electrode

Electrochemical redox supercapacitors have been fabricated using polymeric gel electrolytes polyvinylidene fluoride co-hexafluoropropylene (PVdF-HFP)–ethylene carbonate (EC)–propylene carbonate (PC)–MClO₄: M = Li, Na, (C₂H₅)₄N and electrochemically deposited polypyrrole as conducting polymer electrode. The performance of the capacitors have been characterized using a.c impedance spectroscopy, cyclic linear sweep voltammetry and galvanostatic charge–discharge techniques. The capacitors shows larger values of overall capacitance of about 14–25 mF cm^− 2 (equivalent to a single electrode specific capacitance of 78–137 F g^− 1 of polypyrrole), which corresponds to the energy density of 11–19 W h kg^− 1 and power density of 0.22–0.44 kW kg^− 1. The values of capacitance have been found to be almost stable up to 5000 cycles and even more. A comparison indicates that the capacitive behaviour and the capacitance values are not much affected with the size of cations of the salts incorporated in gel electrolytes, rather predominant role of anions is possible at the electrode–electrolyte interfaces. Furthermore the coulombic efficiencies of all the cells were found to be nearly 100% that is comparable to the liquid electrolytes based capacitors.     

Conductivities of electrolytes based on PEI-b-PEO-b-PEI triblock copolymers with lithium and copper TFSI salts

Tri block-copolymer poly(iminoethylene)-b-poly(oxyethylene)-b-poly(iminoethylene) with a poly(oxyethylene) central block (PEI-b-PEO-b-PEI) were used as a “dual” matrix for polymer electrolytes having selectivity for hard cations (Li⁺/PEO) in one phase and for soft cations (Cu²⁺/PEI) in the other. Conductivity measurements were recorded for 20:1, 12:1 and 8:1 coordinating atom (O or/and N) to cation (Li⁺, Cu²⁺) ratios, for each of the three complexes studied: PEI-b-PEO-LiTFSI-b-PEI, PEI-Cu(TFSI)₂-b-PEO-b-PEI-Cu(TFSI)₂ and PEI-Cu(TFSI)₂-b-PEO-LiTFSI-b-PEI-Cu(TFSI)₂. For either low (20 °C) or high temperature (80 °C) the highest conductivity was given by the polymer electrolyte based on Cu(TFSI)₂ with N/Cu²⁺ = 20:1 (10^− 6, respectively 2 × 10^− 4 S cm^− 1). In the present paper, the conductivity evolution is discussed in relation with the polymer structure, the type and the concentration of the salt and the thermal behavior of our systems.     

Pressure and compositional dependence of electric conductivity in the (Mg1 − xFex)1 − δO (x = 0.01–0.40) solid-solution

(Mg_1 ? xFe_x)_1 ? δO (x = 0.01–0.43) single crystals (~ 8 mm in diameter) were made by a melt-growth method. Electrical conductivity measurements were carried out as functions of temperature and frequency by a complex impedance method under pressure (~ 43 GPa and ~ 673 K and at 0.1 MPa and ~ 1400 K). Our experimental results show a change in charge transport mechanism in the (Mg_1 ? xFe_x)_1 ? δO solid solution at high temperature. The temperature of inflection point of the slope in Arrhenius plots depend greatly on both composition and extrinsic factors of crystals. The low-temperature conduction mechanism in (Mg_1 ? xFe_x)_1 ? δO solid solution is small polaron. Pressure effect of the electric conductivity was observed and the conductivity increased to 0.5 at log scale of S/m with increasing pressure up to 43.4 GPa. The activation energy was decreased linearly with increasing pressure. Chemical composition and homogeneity of specimen rather than pressure greatly influence the electric conductivity. The activation energy of 2.37(4) eV for the (Mg_0.99Fe_0.01)_1 ? δO solid solution might correspond to a migration enthalpy of O ions through thermally formed defects. It is proposed that a possible dominant electrical conduction mechanism in ferropericlase under the lower mantle conditions, at least in the higher temperature region, is super ionic conduction.     

Synthesis and characterization of Ge and Sn(II) iodide-doped thioborate anhydrous proton conductors

Metal iodide-doped anhydrous proton conductors in the series xMI₂ + (1 − x)(HBS₂)₃, where M = Ge and Sn, have been prepared. These samples improve upon the anhydrous proton conductivity shown previously in the H₂S + B₂S₃ + GS_y series, where G = Si, Ge, and As, through a displacement reaction to incorporate HI into the materials. This is analogous to doping a silver halide salt into fast ion conducting chalcogenide glasses, such as AgI + Ag₂S + B₂S₃ + SiS₂, which results in a one to two orders of magnitude improvement in the ionic conductivity. The structural modification of the boroxol ring units in the thioboric acid is discussed based on the infrared and Raman spectroscopy. The DC conductivity, estimated from AC impedance spectra, of the metal iodide-doped (HBS₂)₃ samples is reported as a function of temperature and related back to the underlying structural chemistry of these materials. The static solid state proton NMR spectra were also used to identify the proton environment and proton dynamics. These materials represent an improvement upon previous anhydrous proton-conducting materials and represent an important step in finding intermediate temperature proton conductors.     

Effect of Ni doping on the phase stability and conductivity of scandia-stabilized zirconia

The effect of Ni doping on the phase stability and conductivity of scandia-stabilized zirconia (SSZ) thick film was studied. A free-standing 10SSZ thick-film (10 mol% Sc₂O₃-stabilized zirconia, ~ 10 μm thick) that was previously in contact with a Ni layer during co-firing was fabricated. The 10SSZ thick-film showed a cubic phase in contrast to the rhombohedral phase shown for a bulk 10SSZ sample. The Ni content in the SSZ thick film was ~ 1.7 mol%. The effect of Ni on the cubic phase formation was also confirmed by the similar observation of the cubic phase in the Ni-doped bulk 10SSZ sample. The observed conductivity behavior also supported the XRD observation. Ni was found to hinder the transformation of the cubic phase to the rhombohedral on cooling in 10SSZ samples after a reduction treatment.