Phthaloylchitosan-Based Gel Polymer Electrolytes for Efficient Dye-Sensitized Solar Cells

Phthaloylchitosan-based gel polymer electrolytes were prepared with tetrapropylammonium iodide, Pr 4 NI, as the salt and optimized for conductivity. The electrolyte with the composition of 15.7 wt.% phthaloylchitosan, 31.7 wt.% ethylene carbonate (EC), 3.17wt.% propylene carbonate (PC), 19.0 wt.% of Pr 4 NI, and 1.9wt.% iodine exhibits the highest room temperature ionic conductivity of 5.27 x 10 -3 S cm -1. The dye-sensitized solar cell (DSSC) fabricated with this electrolyte exhibits an efficiency of 3.5% with.. SC of 7.38mAcm -2,.. OC of 0.72V, and fill factor of 0.66. When various amounts of lithium iodide (LiI) were added to the optimized gel electrolyte, the overall conductivity is observed to decrease. However, the efficiency of the DSSC increases to a maximum value of 3.71% when salt ratio of Pr 4 NI : LiI is 2 : 1. This cell has.. SC,.. OC and fill factor of 7.25mAcm -2, 0.77V and 0.67, respectively

Polyacrylonitrile gel polymer electrolyte based dye sensitized solar cells for a prototype solar panel

Polyacrylonitrile (PAN) based gel polymer electrolytes (GPE) were prepared using lithium iodide (LiI), 1-butyl-3-methylimidazolium iodide (BMII) and tetrapropyl ammonium iodide (TPAI). The LiI mass fraction in the electrolyte was varied while keeping the masses of other components constant in order to enhance the solar cell performance. The addition of 4.61 wt.% LiI in the GPE increased the electrolyte room temperature ionic conductivity from (2.32 ± 0.02) to (3.91 ± 0.04) mS cm−1. The increase in conductivity with the addition of LiI salts was attributed to the increase in diffusion coefficient, mobility and number density of charge carriers as determined from Nyquist plot fitting. The incorporation of LiI salts in PAN-based GPE has enhanced the efficiency of the DSSC as expected. The best cell performance was obtained with an electrolyte containing 4.61 wt.% LiI sandwiched between a single mesoporous layer of TiO2 soaked in N3 dye sensitizer and a platinum counter electrode, which showed a power conversion efficiency (PCE) of (5.4 ± 0.1) % with a short circuit current density (Jsc) of (21.0 ± 1.1) mA cm−2, an open circuit voltage (Voc) of (0.48 ± 0.02) V and a fill factor (FF) of (53.4 ± 0.9) %. The DSSCs with 4.61 wt.% of LiI have been used to fabricate prototype solar panels for operating small devices. The panels were assembled using a number of cells, each having an area of 2 cm × 2 cm, connected in series and parallel. The panel, consisting of a set of eight cells in series which was connected in parallel with another set of eight cells in series, produces an average power conversion efficiency of (3.7 ± 0.2)% with a maximum output power of (17.1 ± 0.9) mW

Effect of thermal history and characterization of plasticized, composite polymer electrolyte based on PEO and tetrapropylammonium iodide salt (Pr4N+I-).

The search for anionic conductors based on solid polymer electrolytes is important for the development of photo-electrochemical (PEC) solar cells due to their many favourable chemical and physical properties. Although solid polymer electrolytes have been extensively studied as cation, mainly lithium ion, conductors for applications in secondary batteries, their use as anionic conductors have not been studied in greater detail. In a previous paper we reported the application of a PEO based iodide ion conducting electrolyte in a PEC solar cell. This electrolyte had the composition PEO: Pr4N+I- = 9:1 with 50 wt.% ethylene carbonate (EC). In this work we have studied the effect of incorporating alumina filler on the properties of this electrolyte. The investigation was extended to electrical and dielectric measurements including high frequency impedance spectroscopy and thermal analysis. In the DSC themograms two endothermic peaks have been observed on heating, one of these peaks is attributed with the melting of the PEO crystallites, while the other peak with a melting temperature similar to 30 degrees C is attributed to the melting of the EC rich phase. The melting temperature of both these peaks shows a marked variation with alumina content in the electrolyte. The temperature dependence of the conductivity shows that there is an abrupt conductivity increase in the first heating run evidently due to the melting of the EC rich phase. High conductivity values are retained at lower temperatures in the second heating. Conductivity isotherms show the existence of two maxima, one at -5% Al2O3 content and the other at similar to 15%. The occurrence of these two maxima has been explained in terms of the interactions caused by alumina grains, the crystallinity and melting of the PEO rich phase. As seen from latent heat of melting, the crystallinity of the electrolyte has reduced considerably during the first heating run. In contrast to the conductivity enhancement caused by ceramic fillers in PEO-based cation containing electrolytes, no conductivity enhancement has been observed in the present PEO based anionic conducting materials by adding alumina except at low temperatures. (C) 2009 Elsevier B.V. All rights reserved

Performance enhancers for gel polymer electrolytes based on LiI and RbI for quasi-solid-state dye sensitized solar cells

In this study, the effect of additives (enhancers) on efficiency enhancement in dye sensitized solar cells (DSSCs) containing two series of gel polymer electrolytes, one based on LiI and the other based on RbI have been systematically studied. Polyacrylonitrile (PAN) was used as the host polymer while the performance enhancers used in each case were tetrapropylammoniumiodide (Pr4NI), the ionic liquid 1-methyl-3-propyl imidazolium iodide (MPII) and 4-tert-butylpyridine (4TBP) respectively. Appropriate amounts of the selected enhancers were incorporated one by one, in LiI based and RbI based gel electrolytes. The incorporation of Pr4NI and MPII led to an increase in conductivity of the electrolyte, while 4TBP showed a decrease in conductivity. The maximum conductivity of 3.85 mS cm(-1) at room temperature was shown by the RbI based-series while for the LiI based series the maximum conductivity was 2.95 mS cm(-1). Each of these electrolytes with respective additives was used to fabricate quasi-solid state DSSCs. For the DSSCs based on the LiI containing series, a significant short circuit current density (J(sc)) enhancement (161%) from 3.65 to 9.54 mA cm(-2) was observed due to the addition of Pr4NI. This J(sc) value further increased to 9.7 mA cm(-2) due to the addition of MPII and 4TBP. For the DSSCs with corresponding Rb based electrolytes with all three additives, the highest J(sc) value obtained was 11.5 mA cm(-2). The incorporation of the three additives Pr4NI, MPII and 4TBP collectively enhanced the open circuit voltages and the efficiencies of both LiI and RbI containing quasi-solid state DSSCs. Another important finding from this work is that rarely used RbI containing electrolytes exhibit superior DSSC performance compared to more frequently used LiI based electrolytes. Hence, RbI appears to be a better candidate compared to LiI to fabricate gel polymer electrolytes for DSSCs in general. The three additives have contributed to a remarkable efficiency enchantment in DSSCs by 449.3% for the LiI based electrolyte and by 35.7% for the RbI based electrolyte

Tetrahexylammonium Iodide Containing Solid and Gel Polymer Electrolytes for Dye Sensitized Solar Cells

AbstractTiO2 dye sensitized solar cells (DSSCs) are emerging as an alternative technology to photovoltaic junction devices. DSSCs conventionally use liquid-type electrolytes but solid and gel polymer electrolytes are more promising due to many advantages. However, their conductivity needs to be enhanced in order to make them useful in practical device applications. In this work, an iodide ion conducting polymer electrolyte was prepared using polyacrylonitrile (PEO), tetrahexylammonium iodide salt with ethylene carbonate and propylene carbonate plasticisers. The salt composition was varied to find the optimum conductivity. The sample containing 120% salt with respect to PEO weight showed the highest conductivity. This optimum electrolyte showed a glass transition at -102.3°C and an ambient temperature conductivity of 2.1×10-3 S cm−1 at 30°C. The optimized gel electrolyte was used in a quasi solid-state DSSC and a ISC of 9.37 mA cm-2, a VOC of 696 mV and an efficiency of 2.8% were achieved under irradiation of 1000 W m−2. In addition, a solid polymer electrolyte was fabricated using the same salt with polyethylene oxide host polymer and ethylene carbonate. The salt composition was varied to obtain the highest conductivity and the best performing sample with composition 65% salt with respect to PEO weight showed a conductivity of 4.7×10-4 S cm-2 at 30°C. This electrolyte was used in a DSSC and it showed a ISC of 1.26 mA cm-2, a VOC of 745 mV and efficiency of 0.6%

Quasi solid state polymer electrolyte with binary iodide salts for photo-electrochemical solar cells

Quasi-solid-state polymer electrolytes can be used in dye sensitized solar cells (DSSCs) in order to overcome various problems associated with liquid electrolytes. Prior to fabricating commercially viable solar cells, the efficiency of quasi solid state DSSCs needs to be improved. Using electrolytes with a binary iodide mixture is a novel technique used to obtain such efficiency enhancement. In this work we report both conductivity and solar cell performance enhancements due to incorporation of a mixture containing LiI and tetrahexylammonium iodide in a quasi-solid-state electrolyte. The conductivity of the electrolyte increases with added amounts of Lit and thus the highest conductivity, 3.15 x 10(-3) S cm(-2) at 25 degrees C, is obtained for the electrolyte 100 wt% LiI. The predominantly ionic behavior of the electrolytes was established from dc polarization measurements. The iodide ion conductivity, measured using iodine pellet electrodes decreased somewhat with increasing amount of LiI even though the overall conductivity increased. However, the highest efficiency was obtained for the DSSC containing a polymer electrolyte with Hex(4)N(+)I:LiI = 1:2 mass ratio. This cell had the largest short circuit current density of about 13 mA cm(-2) and more than 4% overall energy conversion efficiency. The results thus show that electrolytes with Hex(4)N(+)I/LiI mixed iodide system show better DSSC performance than single iodide systems. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved

Effect of the alkaline cation size on the conductivity in gel polymer electrolytes and their influence on photo electrochemical solar cells

The nature and concentration of cationic species in the electrolyte exert a profound influence on the efficiency of nanocrystalline dye-sensitized solar cells (DSSCs). A series of DSSCs based on gel electrolytes containing five alkali iodide salts (LiI, NaI, KI, RbI and CsI) and polyacrylonitrile with plasticizers were fabricated and studied, in order to investigate the dependence of solar cell performance on the cation size. The ionic conductivity of electrolytes with relatively large cations, K+, Rb+ and Cs+, was higher and essentially constant, while for the electrolytes containing the two smaller cations, Na+ and Li+, the conductivity values were lower. The temperature dependence of conductivity in this series appears to follow the Vogel-Tamman-Fulcher equation. The sample containing the smallest cation shows the lowest conductivity and the highest activation energy of similar to 36.5 meV, while K+, Rb+ and Cs+ containing samples show an activation energy of similar to 30.5 meV. DSSCs based on the gel electrolyte and a TiO2 double layer with the N719 dye exhibited an enhancement in the open circuit voltage with increasing cation size. This can be attributed to the decrease in the recombination rate of electrons and to the conduction band shift resulting from cation adsorption by TiO2. The maximum efficiency value, 3.48%, was obtained for the CsI containing cell. The efficiencies shown in this study are lower compared to values reported in the literature, and this can be attributed to the use of a single salt and the absence of other additives, since the focus of the present study was to analyze the cation effect. The highest short circuit current density of 9.43 mA cm(-2) was shown by the RbI containing cell. The enhancement of the solar cell performance with increasing size of the cation is discussed in terms of the effect of the cations on the TiO2 anode and ion transport in the electrolyte. In liquid electrolyte based DSSCs, the short circuit current density has been reported to decrease with the increasing size of the cation. However, in this work, it follows an opposite trend highlighting a major difference between liquid and quasi-solid electrolytes on the solar cell performance

Efficiency enhancement by mixed cation effect in dye-sensitized solar cells with PAN based gel polymer electrolyte

Dye-sensitized solar cells based on nano-porous TiO2 photo-anode and quasi-solid polymer (or gel) electrolytes are emerging as low cost alternatives to conventional inorganic photovoltaic devices. Although many attempts have been made in order to improve the relatively low power conversion efficiencies of these solar cells, to our knowledge there are very few reports aimed at using a binary system of two different iodide salts toward efficiency enhancement in these cells. In this paper we report for the first time in detail, the effect of using a binary iodide salt mixture with different size cations on the efficiency enhancement in dye sensitized solar cells with polyacrylonitrile (PAN) based gel polymer electrolyte and suggest a possible mechanism for this enhancement, based on short circuit photocurrent which is directly related to the iodide ion concentration [I-]. The gel electrolyte was made of PAN, ethelene carbonate (EC), Propylene carbonate (PC), salt mixture and I-2. The binary iodide salt mixture consists of potassium iodide (KI) and Tetra propyl ammonium iodide (Pr4NI). Although the gel electrolyte with 100% (w/w) KI exhibited the highest overall ionic conductivity at room temperature, it showed the lowest iodide ion (I-) contribution to conductivity. On the other hand, the electrolyte with 100% (w/w) Pr4NI exhibited the lowest overall ionic conductivity but had the highest iodide ion(I-) contribution. The dye-sensitized solar cells of configuration Glass/FTO/TiO2/N-719 Dye/electrolyte/Pt/FTO/glass were fabricated using the gel electrolytes of different salt ratios and with nanoporous TiO2 electrode sensitized with Ruthenium dye (N719). With identical electrolyte compositions, the solar cell with 100% (w/w) KI showed an efficiency of 4.98% and the cell with 100% (w/w) Pr4NI showed an efficiency of 4.47%. However, the cell with the mixed iodide system, 16.6% (w/w) KI + 83.4%(w/w) Pr4NI showed the highest efficiency of 5.36% with maximum short circuit current density (J(SC)) of 13.79 mA cm(-2), open circuit voltage (V-OC) of 679.10 mV and a fill factor of 57.25%. The variation of efficiency (eta) with iodide ion concentration [I-] follows the same trend as the J(SC) which appears to be governed by the iodide ion conductivity of the gel electrolyte. The dependence of the short circuit photocurrent and the open circuit photovoltage on the cation type generally agrees with reported data for related systems. However, the occurrence of a maximum in the solar cell efficiency and short circuit photocurrent at 16.6% (w/w)10 + 83.4% (w/w) Pr4NI salt composition is an important finding. The efficiency enhancement of about 8% achieved by employing the binary iodide mixture in the gel electrolyte instead of a single iodide salt, could be utilized for achieving efficiency enhancement in many dye sensitized solar cell systems based on polymeric, gel or solvent electrolytes

N719 and N3 dyes for quasi-solid state dye sensitized solar cells - A comparative study using polyacrylonitrile and CsI based electrolytes

Dye sensitized solar cells offer a low cost alternative technology for solar energy harvesting. However, there are long term stability issues connected with these cells due to the liquid electrolytes normally used. Gel or solid polymer electrolytes which do not contain volatile solvents have been used in this investigation in order to alleviate these problems. Two types of solar cells were assembled using a double layered TiO2 film sensitized with two types of dye sensitizers, namely N719 (Ruthenizer 535-bisTBA) and N3 (Ruthenizer 535) in order to compare their performance. Quasi-solid-state electrolytes based on PAN (polyacrylonitrile) as the host polymer and CsI as the iodide salt were prepared by incorporating ethylene carbonate (EC) and propylene carbonate (PC) as plasticizers. The conductivity of the electrolyte was further improved by adding tetrapropylammonium iodide (Pr4NI), 1-methyl 3-propyl imidazolium iodide (MPII) and 4-tert-butylpyridine (4TBP). The incorporation of these additives resulted in 17% enhancement in ionic conductivity.  This improved electrolyte was used to fabricate the solar cells with N3 and N719 dyes. The efficiency of the N3 dye based solar cell was 3.85% whereas the efficiency of the N719 dye based solar cell was 4.14% representing a significant efficiency enhancement by 7.53% by the N719 dye. In addition, due to additives the solar cell efficiency has enhanced by 19% compared to the solar cell without any additive