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Solar Energy 83 (2009) 108112 www.elsevier.com/locate/solener

An improved preparation of 3-ethyl-1-methylimidazolium triuoroacetate and its application in dye sensitized solar cells
Chengwu Shi a,*, Qian Ge a, Fang Zhou a, Molang Cai a, Xiaoran Wang a, Xiaqin Fang b, Xu Pan b
a

School of Chemical Engineering, Hefei University of Technology, Hefei, Anhui 230009, PR China b Institute of Plasma Physics, Chinese Academy of Sciences, Hefei, Anhui 230031, PR China Received 29 February 2008; accepted 8 July 2008 Available online 20 August 2008 Communicated by: Associate Editor Sam-Shajing Sun

Abstract In this paper, we reported an improved preparation of 3-ethyl-1-methylimidazolium triuoroacetate (EMITA), which proceeded via ecient reaction of 1-methylimidazole and ethyl triuoroacetate under solvent-free conditions using Teon-lined, stainless steel autoclaves. It was shown that the procedure was simple and eco-friendly. The apparent diusion coecients of triiodide and iodide in binary ionic liquids, EMITA and 1-methyl-3-propylimidazolium iodide (MPII) with various weight ratios, were demonstrated by cyclic voltammetry using a Pt ultramicroelectrode. It was found that the apparent diusion coecients of triiodide slightly increased and those of iodide decreased with the weight ratio increase of EMITA and MPII. The dye sensitized solar cells with the electrolyte, which was composed of 0.13 M I2, 0.10 M LiI, 0.50 M 4-tert-butylpyrdine in the binary ionic liquid electrolyte of EMITA and MPII (weight ratio 1:2), gave short circuit photocurrent density of 7.88 mA cm2, open circuit voltage of 0.61 V, and ll factor of 0.67, corresponding to the photoelectric conversion eciency of 3.22% at the illumination (Air Mass 1.5, 100 mW cm2). 2008 Published by Elsevier Ltd.
Keywords: 3-Ethyl-1-methylimidazolium triuoroacetate; Preparation; Autoclave; Dye-sensitized solar cell

1. Introduction During the past decades, dye sensitized solar cells (DSCs) have attracted much attention as low-cost alternatives to conventional pn junction photovoltaic devices (ORegan and Gratzel, 1991; Hagfeldt and Gratzel, 1995; Kambe et al., 2002; Dai et al., 2005, 2004; Shi et al., 2005,). Electrolytes are the critical components in DSCs. Some binary ionic liquid electrolytes have been investigated due to their negligible volatility, low viscosity and high thermostability (Kuang et al., 2006; Fei et al., 2006; Wang et al., 2004; Ryuji et al., 2004). Usually, the preparation of alkylimidazolium triuoroacetate is the metathesis reaction
*

Corresponding author. Tel./fax: +86 551 2901450. E-mail address: shicw506@mail.hf.ah.cn (C. Shi).

between alkylimidazolium halide and silver triuoroacetate in aqueous solution or the quaternization reaction of the appropriate alkyl triuoroacetate and alkylimidazole derivatives via a conventional heating method in reuxing organic solvents. The metathesis approach is obviously limited by the relatively high cost of silver salts and the large quantities of solid by-product. Although there is the very low solubility of these silver halides (AgCl, AgBr, AgI) in aqueous solution, the resulting product has been shown to contain residual silver (Rika and Yasuhiko, 2000; Bonhote et al., 1996; Wasserscheid and Welton, 2002). The quaternization procedure requires an excess of alkyl triuoroacetate and several days in reuxing organic solvents to aord reasonable yields (Bonhote et al., 1996). In this paper, we reported an improved preparation of 3ethyl-1-methylimidazolium triuoroacetate (EMITA, 35 cP

0038-092X/$ - see front matter 2008 Published by Elsevier Ltd. doi:10.1016/j.solener.2008.07.002

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at 20 C), which was the quaternization reaction of ethyl triuoroacetate and 1-methylimidazole under solvent-free conditions by Teon-lined, stainless autoclaves. The redox behavior of I-/I3- in the binary ionic liquids of EMITA and 1-methyl-3-propylimidazolium iodide (MPII) was investigated by cyclic voltammetry using a Pt ultramicroelectrode. The photovoltaic performances of DSCs employing the binary ionic liquid electrolytes with various weight ratios of EMITA and MPII were measured. 2. Experimental 2.1. Materials Anhydrous lithium iodide and 4-tert-butylpyrdine (TBP) were purchased from Fluka and used as received. 1-Methylimidazole, ethyl triuoroacetate and 1,1,1-trichloroethane were commercially available and were distilled under vacuum before used. 1-Methyl-3-propylimidazolium iodide (MPII) was synthesized according to our previous report (Shi et al., 2007). 2.2. Preparation and characterization The mixture of 1-methylimidazole (50.0 mmol) and ethyl triuoroacetate (52.5 mmol) was placed in a 57 mL Teon-lined, stainless steel autoclave (its structure is similar to the literature (Walton, 2002)), and then was heated in an oven at 100 C for 3, 6, 12 and 24 h, respectively. The resulting EMITA was decanted and dried under vacuum at 70 C for 6 h. Some crude products were washed with 1,1,1-trichloroethane before drying, and the weight ratio of crude products and 1,1,1-trichloroethane was 1:2 in every washing. 1 H NMR spectra of EMITA were measured on a Bruker DMX 300 spectrometer using acetone-d6 as solvents. Electrospray ionization mass spectra (ESI-MS) were recorded on a Thermonnigan LCQ Advantage Max, electrospray source, ion trap instrument on a sample diluted in methanol. 2.3. Measurement Conductivity of the mixture of EMITA and MPII were measured by lab conductivity meter (DDS-307) with two platinum black electrode conductance cell (DJS-1, REX, the area of each platinum black electrode was about 0.25 cm2, the distance between two platinum black electrodes was about 0.50 cm, the cell constant was 0.974, determined by aqueous KCl standard solution). Cyclic voltammetry was achieved by using an electrochemical workstation (CHI660B). The working electrode was a 5.0 lm radius Pt disk ultramicroelectrode (CHI107), the auxiliary electrode and the reference electrode were a 1.0 mm radius Pt disk electrode (CHI102). A slow scan rate at 5 mV s1 was used to obtain steady-state current voltage curves. The apparent diusion coecient (Dapp) of triiodide and

iodide in the mixture of EMITA and MPII can be calculated from the steady-state current (Iss) according to the following equation, Iss = 4ncaFDapp (Wang et al., 2004, 2003). The photovoltaic performances of DSCs were measured with a Keithley 2420 source meter controlled by Testpoint software under solar simulator (Xenon lamp, Air Mass 1.5, 100 mW cm2, Changchun institute of Optics Fine Mechanics and Physics, Chinese Academy of Science, calibrated with standard crystalline silicon solar cell). 2.4. DSCs assembly Briey, the TiO2 (anatase) colloidal solution was prepared by hydrolysis of titanium tetra-isopropoxide (Hu et al., 2003). The TiO2 paste was printed on transparent conducting glass sheets (TEC-8, LOF) and sintered in air at 450 C for 30 min. The lm was 10 lm thick, which was determined by prolometer (XP-2, AMBIOS Technology Inc., USA). A 4-lm-thick light scattering layer was used. After cooling to 80 C, the TiO2 lms were immersed in a anhydrous ethanol solution with 5.0 104 M cisdithiocyanate-N,N0 -bis-(4-carboxylate-4-tetrabutylammonium carboxylate-2,20 -bipyridine) ruthenium (II) (N719) overnight. The excess of N719 dye in TiO2 lms was rinsed o with anhydrous ethanol before assembly. The counter electrode was platinized by spraying H2PtCl6 solution to transparent conducting glass and red in air at 410 C for 20 min. Then, it was placed directly on the top of the dye-sensitized TiO2 lms. The gap between the two electrodes was sealed by thermal adhesive (Surlyn, Dupont). The electrolyte was lled from a hole made on the counter electrode and the hole was later sealed by a cover glass and thermal adhesive lms. The total active electrode areas of DSCs was 0.25 cm2. 3. Results and discussion 3.1. Preparation of EMITA Fig. 1 shows the 1H NMR of EMITA prepared at 100 C for dierent reaction times employing a 5% molar excess of ethyl triuoroacetate. Table 1 summarized the yield evolution of EMITA with reaction times. With the increase of reaction times, the content of the residual 1methylimidazole decreased, the yield increased, and the colour became darker in the resulting EMITA. The amount of impurity resulting in darker EMITA was generally small, and was dicult to be detected by 1H NMR. Therefore, 12 h was the optimal reaction time for preparation of EMITA under solvent-free condition at 100 C. Fig. 2 shows the 1H NMR of EMITA before and after washing with 1,1,1-trichloroethane. It was found that the content of the residual 1-methylimidazole in the resulting EMITA decreased with the washing times increased. Moreover, some impurity in the resulting EMITA can be detected by MS, which may be due to the corrosion of Teflon-lined, stainless steel autoclaves, and can be removed by

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washing with 1,1,1-trichloroethane for four times. It was advisable that washing was useful for obtaining pure EMITA.

3.2. Inuence of the weight ratio of EMITA and MPII on the redox behavior of triiodide and iodide Fig. 3 illustrated the relationship between the conductivity of binary ionic liquid mixture and the weight ratios of EMITA and MPII at 20 C. With the weight ratios increased, the mixture conductivity increased, which may be associated with the decrease of the mixture viscosity. Table 2 listed the apparent diusion coecient of triiodide and iodide in binary ionic liquid mixtures at 20 C. With the increase of weight ratios of EMITA and MPII, the apparent diusion coecients of triiodide slightly increased and those of iodide decreased. 3.3. Photovoltaic performances of DSCs Table 3 listed the photovoltaic performances of DSCs with electrolytes AF and Fig. 4 shows the photocurrent voltage curve of DSCs with electrolyte A, 0.13 M I2, 0.10 M LiI, 0.50 M TBP in the mixture of EMITA and MPII (weight ratio 1:2). The open circuit voltage (Voc) increased with the weight ratio increase of EMITA and MPII in the electrolytes AD. This was consistent with the literature (Ryuji and Masayoshi, 2003). That is, the equilibrium potentials of I-/I3- and open-circuit voltages of DSCs increased with the decrease of total concentrations ([I-] + [I3-]) in the ionic liquid electrolytes. Moreover, the short circuit photocurrent density, ll factor and overall conversion eciency decreased from electrolytes AC,

a
10 8 6 4 2 0

Chemical Shift/ppm

Fig. 1. 1H NMR chemical shifts of 3-ethyl-1-methylimidazolium triuoroacetate in acetone-d6. Reaction temperature: 100 C. Reaction time: (a) 3 h; (b) 6 h; (c) 12 h and (d) 24 h.

Table 1 The yield evolution of 3-ethy-l-methylimidazolium triuoroacetate with reaction times 1-Methylimidazole (mol) 1 1 1 1 Ethyl triuoroacetate (mol) 1.05 1.05 1.05 1.05 Time (h) 3 6 12 24 Yield (%) 64 85 93 $100

10

Conductivity (mS/cm)

2 0
b

m(EMITA) : m( MPII)
Fig. 3. The relationship between the conductivity of binary ionic liquid mixtures and the weight ratios of EMITA and MPII at 20 C.

a
10 8 6 4 2 0

Chemical shift/ppm
Fig. 2. 1H NMR chemical shifts of 3-ethyl-1-methylimidazolium triuoroacetate in acetone-d6: (a) before washing; (b) after washing twice and (c) after washing four times.

Table 2 Apparent diusion coecient of triiodide and iodide in binary ionic liquid mixtures at 20 C m(EMITA): m(MPII) Dapp(I3-, 107 cm2 s1) Dapp(I, 107 cm2 s1) 0.33 2.90 1.21 0.50 3.01 1.09 1.00 3.12 1.00 2.00 3.17 0.84 4.00 3.22 0.55

C. Shi et al. / Solar Energy 83 (2009) 108112 Table 3 Photovoltaic performances of DSCs with electrolytes AF Electrolytea A. m(EMITA): m(MPII) = 0.50, 0.50 M TBP B. m(EMITA): m(MPII) = 1.00, 0.50 M TBP C. m(EMITA): m(MPII) = 2.00, 0.50 M TBP D. m(EMITA): m(MPII) = 4.00, 0.50 M TBP E. m(EMITA): m(MPII) = 0.50, without TBP F. m(EMITA): m(MPII) = 2.00, without TBP Jsc (mA cm2) 7.88 6.76 5.31 5.30 6.19 4.68 Voc (V) 0.61 0.63 0.64 0.66 0.47 0.58 FF 0.67 0.67 0.64 0.66 0.64 0.62

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g (%) 3.22 2.87 2.16 2.32 1.88 1.71

a The other components of electrolytes are the same, 0.13 M I2, 0.10 M LiI. Illumination: Air Mass 1.5, 100 mW cm2. Cell active area of DSCs: 0.25 cm2.

Appendix A. Supplementary data

Photocurrent density / mA cm

Data of 1H NMR and MS, the picture of autoclaves, the photos of products, stead-state voltammograms can be found in the online version. Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.solener.2008.07.002. References

-2

0 0.0

0.2

0.4

0.6

Voltage / V
Fig. 4. The photocurrentvoltage curve of DSCs with electrolyte A.

which may be associated with the decrease of the apparent diusion coecients and content of iodide. Comparing electrolyte with and without TBP, it was demonstrated that the TBP can improve the performance of the DSCs with the binary ionic liquid electrolytes. 4. Conclusion In this paper, an improved preparation of EMITA under solvent-free conditions by Teon-lined, stainless autoclaves was described. It was shown that the procedure was simple and eco-friendly. The DSCs with the electrolyte, which was composed of 0.13 M I2, 0.10 M LiI, 0.50 M 4tert-butylpyrdine in the binary ionic liquid electrolyte of EMITA and MPII (weight ratio 1:2), gave short circuit photocurrent density of 7.88 mA cm2, open circuit voltage of 0.61 V, and ll factor of 0.67, corresponding to the photoelectric conversion eciency of 3.22% at the illumination (Air Mass 1.5, 100 mW cm2). Acknowledgments This work is nancially supported by Hefei University of Technology and the National Key Project of China for Basic Research (2006CB202600).

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