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Purification of Bipyridyl Ruthenium Dye and Its Application in Dye-Sensitized Solar Cells

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 2006 Plasma Sci. Technol. 8 531 ( View the table of contents for this issue, or go to the journal homepage for more

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2 2 .48 X lo4 L . 81.47 X lo4 L . The solvents were puriss grade and used without further purification. . We subsequently measured the standard curve of UV-Vis absorbance against concentration and provided a way to determine the concentration of the dye in ethanolic solution after the coating of the Ti02 films repeatedly. purified by the gel chromatogram method and characterized by the proton NMR and UV-Vis spectra.20. Pharmadex LH-20was purchased from Amersham Biosciences.l Experimental setup Materials In dye-sensitized solar cells. dye and their industrialization [18J9~24~251 has been reported recently in China. In this work. 2'bipyridine. the electrolyte systems [12N191. trifluoroacetate acid (TFA) and tetrabutylammonium hydroxide (TBAOH) were obtained from Flukaand used as received. This method was employed to determine the concentration of the dye solution after coating of Ti02 films. In 1993 Gratzel and co-workers [2] developed DSCs with an efficiency of over 10% under AM 1.) with * supported by the National Basic Research Program of China (No. The linear concentration range of the N3 dye was 6.4'-dimethyl-2.4'-dicarboxylicacid. L-' with E of 1.concentration of N719 wasbetween6. as the sensitizer. UV-Vis spectrophotometric analysis.50 X lo4 L .Plasma Science & Technology. where dcbpy = 2. known as the N3 dye. DSC modules with a size of 15 cm X 20 cm and an active area of more than 60% have been achieved with a photoelectric conversion efficiency around 6% and almost the same performance level with the panel sized 40 cm X 60 cm for a primary 500 W DSC power station L'5].5. cm-' at a wavelength of 538 535 nm and 1. Chinese Academy of Sciences. 4.Ym 1 Introduction ' Dye-sensitized solarcells (DSCs) have received much attention since 1991 when a photo-electric conversion efficiency of 7. WANG K o n g j i a ( E 3 L S ) Division of Solar Energy Materials and Engineering. After the purification most of the impurities that decreased the photoelectrochemical properties were removedand the open-circuit voltage (Voc).1% was announced [l]. accordingly. Basic research about the components of DSCs such as Ti02 films [9w111. - - - - Keywords: bipyridyl ruthenium dye. The purification of the N3 and N719 dye. which will ensure the performance of large scale DSCs and reduce the cost of dye for the commercialization of DSCs. L-' with the molar extinction coefficient ( E ) 1. L-' and 1 X l O . L-' to 1. concentration of N3 and N719 dye was achieved by using UV-Vis quantitative analytic spectrophotometry. Hence. cm-' at a wavelength of 399 393 nm. 2006CB202600) Hydrated ruthenium trichloride. Hefei 230031. mol-' . Institute of Plasma Physics. the dye was purified by using the jing Purkinje General Instrument Co. Abstract Bipyridyl ruthenium dye N3 and N719 was synthesized. Ltd. short-circuit photocurrent density ( J s c ) and overall photo-electric conversion efficiency (v) of the dye-sensitized solar cells (DSCs) increased dramatically. mol-' * cm-' at a wavelength of 393 384 nm . Beiture.No. solar cell. dye-sensitized. mol-' . Sept. China (an&).8.2 Analyticalmeasurements electric conversion efficiency. the dye was one of the key components for solar cells with a high photo2.25 X 1O-6 mol . the amount of dye absorbed on Ti02 films can be well controlled.58 X lo4 L . purification PACS: 42.79. vo1.-t. mol-'cm-' at a wavelength of 533 531 nm and 1. [6N8920N231 gel chromatogram and method the photovoltaic performance of DSCs was greatlyimproved.5 X lop4 mol . 2'-bipyridyl-4. 81.4 mol . has not been reported in the literaquartz cell on a spectrophotometer (TU1901. The linear concentration rangeof absorbance vs.5 solarirradiationusing ci~-Ru(dcbpy)~(NCS)~.05. which was widely used as sensiUV-Vis spectra were recorded in a 1 cm path tizers in DSCs. The standard curve of absorbance vs.Ek.Thisresulthas attracted widespreadacademicandcommercialinterest for its low cost and high efficiency [3N81. 2006 Purification of Bipyridyl Ruthenium Dye and Its Application in Dye-Sensitized Solar Cells* KONG Fantai DAI Songyuan($&fiz).25 X 1O-6 mol .

57(d) ppm.0 6.5 8. The structure and purity of N3 and N719was confirmed with proton NMR.l/m/mAcmz) FF q x 10 Fig.0 5. then the main band of the chromatape was collected and the pH was lowered to 2.2 3. and 6 7. It is shown that the open circle voltage (Voc).5 5.4’-dicarboxylate acid ligand [271. the solid was washed with a TFA aqueous solution with pH a of 2.6 0. The peaks at 6 8.5.8. vo1.0 4.64(s) ppm and 6 2.57(s) ppm. + 2. 3 UV-Vis spectra of N719 dye with various concentrations All these impurities were removed and the spectrum of the sample after two-time purification was consistent with that of pure N3 in Ref.0 2.o 0.2 Performance of DSCs withdifferentbandin chromatogram process I. Fig.6 1.72(s) ppm. The process of purification was repeated. the short circle current density ( J s c ) and the photo-current conversion efficiency (7) of DSCs based on the third band of the chromatape (pure N3 dye) are improved remarkably compared to those based on the second band of chromatape (impure N3 dye).. 6 8.Thenthe product then was dried under vacuum for 24 h to afford a high purity N3 dye.3 Synthesis andpurificationof N3 and N719 : : 4 1. The reported chemical shifts were against TMS in D20 NaOD solution.T* transition of 2.2 0.2 I m Band2 1 9. 3 3.0 PPm O’O V d J.Plasma Science & Technology. 300 1 400 500 Wavelengh(nm) 600 700 I Fig. 532 Fig. 3 displays the UV-Vis spectra of N719 with different concentrations.5 with a TFA aqueous solution to precipitate a dark brownish-red solid.5.0 8.5 2.8 0.2 the a wavelength scan range from 300 nm to 700 nm at room temperature.2. byusing the procedure and purified by using the gel chromatogram methods as follows. [27] with highpurity N3 as the starting material.4 0. It can be seen that the lowest energy MLCT( metal-ligand charge transfer ) absorption centred on 533 531 nm and the peak centred on 393 384 nm are also the MLCT absorption of the complex while the absorption band at 313 312 nm is T .4 1.5. The peak at 6 2. [27].5 3.6 0.5 6.6 1. were assigned to rudimental DMF. This can also be seen from the data of N719 (in Table 1) based sensitizers before and after purification. Proton NMR was measured on a Bruker 600 MHz spectrometer.(xO. The signals of crude N3 dye at 6 7.5 7.2 1.1 UV-Vis spectrophotometric analysis of N3 and N719 UV-Vis spectra of N719 with different concentrations Fig.4 1.5 4.8 0.4 0. After filtration the solution was transferred onto a pharmadex LH-20 column eluting with distilled water. 1 shows the proton NMR spectra of N3 before and after purification.59. N N N . No.1 Result and discussion Influenceofpurification of sensitizers on photovoItaic performance of DSCs 3.0 7.2’-bipyridyl-4. 2 shows the photovoltaic performance of DSCs basedon different bandsduringthe purification.2’-bipyridine-4. 6 2.0 3. 2006 1.0 2.56 (d) ppm were assigned to the unreacted dcbpy.42(s) may be due to the existence of a spot of acetic acid in TFA. 4’-dicarboxylic acid (dcbpy) was synthesized L’6] and N3 dye was synthesized. N719 is the bis-(tetra-butyl ammonium salt) of N3 and was synthesizedusing the methods specified in Ref. Sept.1 ‘H-NMR spectra of N3 beforeandafterpurification Fig.09(s) ppm.a 1. Crude N3 dye was dissolved in a sodium hydroxide aqueous solution and the pH was adjusted to 7.o 0. After centrifugation. [2727].

2.4 0. k is also called the molar extinction coefficient with the sign of c .T * and d7r .3 N N N N N 3. In a special range of concentration the absorbance of N3 and N719 against their concentration is linear. the molar extinction coefficient E is 1.62 f 0. the linear concentration range of absorbance against the concentration of N719 is 6.2 1.2 1. L-l with E of 5.8 0. 3.61% f 0..7r*) charge transfer transitions.01 Pure woduct N719 77 (%l 4. where l is 1 cm.6 0.02 0. For the absorbance at the wavelength of 533 531 nm and 393 384 nm.1 6.2 so the concentrationof N3 and N719 dye inthe ethanolic solution can be calculated based on the LambertBeer law from the absorbance of the samples.6 0.5 mol .2 0.4 0.5 UV-Vis spectra of N3 dye with various concentrations 3.2.02 0. is the ratio between the intensity of transmission light I t and the intensity of incidence light l o .crn-') L(V) 10.58 X lo4 L .0 -0. L-' 1 X lO-4 mol . L-' to 2.00.12 f 0.72 f 0.2.2 Concentration of N719(~lO4molL') 1.5 x l O .8 2 0.4 nm 531 393 nm 384 nm A 313nm-312nm 0 m nm 533 -- 0. Performance ofDSCs with dye N719 FF Jsc (mA.22 0.50 x lo4 L .4 Relationshipbetweenabsorbance and concentration of N 3 dye at various wavelengths As is shown in Fig. cm-'. While the linear concentration of the absorbance at the wavelength of 313 312 nm is 6.02 Crude product 15.4 1. : Purification of Bipyridyl Ruthenium Dye and ItsApplicationin Dye-Sensitized SolarCells Table 1. Fig. Both A and T are a ruler to characterize the absorption of the sample to light.66 f 0.84% f 0.0 0. N N N N Curve of absorbanceagainst concentration of N719 Based on the Lambert-Beer law. 4 shows the relationship between the absorbance and concentration at some special wavelength.. when c is characterized in the unit of mol .causing the 7r .25 X lop6 mol .69 f 0. The absorption spectra of N719 is blueshifted by 3 5 nm compared with that of N3 dye. T . A = lgl/T = lgIo/lt = k d . and c is the concentration of the sample.81. The lowest energy transitions' wavelength centred at 538 535 nm and the absorption at 399 393 nm are assigned to the metal-ligand charge transfer transition together with the absorption at 399 393 nm. k is the absorbance coefficient.01.25 x lo-6 mol .41. which is related to the property of the solution. the transmission ratio of the sample. 0.2 0. while the absorption band at 315 314 nm is assigned to the intraligand (T . where A is the absorbance of the sample.33 f 0. the linear concentration range of absorbance-concentration curve for the absorbance at the wavelength of 538 535 nm and 399 393 nm - N 533 . temperature and wavelength of the incidence light.KONG Fantai et al. mol-' * cm-' and 1. 1 is the thickness of the liquid in the sample cell in centimetres.accordingly. 5 presents the UV-Vis spectra of N3 dye varied in concentration.o m 538 nm 535 nm 399 nm 393 nm A 315 nm 315 nm 0 -- .6 1.4 Absorbance vs.6 Concentration of N3 (x104mol L') of N3 dye at Fig. UV-Vis spectra of N 3 dye with various concentrations Fig.0 0. This is due to an increase in the energy of the LUMO of the ligand.6 Absorbancevsconcentrationcurve different wavelengths 9 (0 I I I I I I I I I I I I I I I I I 400 350 300 450 500 550 650 600 Wavelength(nm) 700 Fig. mol-' . 6. L-l. L-' .71 X lo4 L mol-'cm-'.281.6 0.7r* transitions to occur at higher energies [27.2 1.2 1. concentration curve of N719 dye at different wavelengths - Fig.25 0.2 0.

261: 129 140 Zhang L. cm-'. Acta Phys. et al. Chem. et al. 2003... Sui Y F. 17:992 Yanagida M. Li X P. Shan L. al. mol-' . 9: 430 439 N N N N N N N N N N N N N (Manuscript received 12 May 2005) E-mail address of DAI Songyuan: sydai@ipp. 1997. Chem. Soc. b. Chinese Universities.. Energy. Dai S. Wang K. et al. 54(4): 1919 1926 20 Yao Q H. ZhangH. Acta.WangK J. Chem..Xiao S F. 1991. 38: 6298 6305 K. 2006 is 6.. et al. Li F Y. Chem. Wang K. Chem. 21(10): 1543 1546 (in Chinese) N N Shi C. Acta Phys. L-l. Sui Y. Chem. 24(5): 888 891 (in Chinese) 24 Pan K. Gao E Q. mol-'. Acta Energiae Solaris Sinica.5 X lO-4 mol L-l.58 X lo4 L . 2063 2064 22 Dai S Y.. Energy Mater. mol-'. Dalton. J. Chinese Universities. et al. KalyanasundaramK. Wei T X. Kohle 0. Chim.Phys. Plasma Science & Technology. Rodicio I. et al. 2005.Dai S. 48(2): 129 131 (in Chinese) Shi C. Wang K J. HouY J.Phys. Chem. 9 1 ~ lo4 L . Inorg..Commun. 2000. 2003. WangK J. Inorg. 2004. while the linear concentration range of N 3 at the wavelength of 315 314 nm is 6. 2000.25 X 1O-6 mol . J.. L-' with E of 5 . Electrochimica Acta. cm-' and 1.5 x lop4 mol . 2004.NazeeruddinM al. Wang K. Kay A.. 104: 9676 9682 Xie P H. 2004. 2005. 39 : 99 105 16 Shi C. J.Chem. HuangCH. et al. Wang K J. Chem. Sol. Liu Z Y. 2001. 2005. Chem.5. Cells. 19(7): 635 640 (in Chinese) 21 Wang Z S. YangM. Nature. Chem. 353: 737 Nazeeruddin Md K. The linear concentration range of absorbance against the concentration of N719 at the wavelength of 533 531 nm and 393 384 nm is 6.. 25: 807 810 (in Chinese) 23 Liu Z Y. The concentration of N3 and N719 can be measured by the UV-Vis photometrymethodandthe amount of dye absorbed ontoTi02 was-controlled. Huang C H. Sol. Kong F T. The purityof the dye was sharply increased after two times of purification and the photovoltaic performance such as V. 2000.. 2005. Yang M Z. HumphryBaker R. J. et al. while the linear concentration range of absorbance-concentration curve for N3 at the wavelength of 538 535 nm and 399 393 nm is 6. (in Chinese) 19 Dai S Y. Gratzel M. 2005. e t al. cm-' and 1.25 X lop6 mol .et al. The performance of large scaleDSCs can be consistent with each other. ShiC W. of ~ DSCs with the dye after purification was greatly improved.Sin. Cells. et al. J. Sin. Vibrational Spectroscopy. Sin. Mater. L-l.Dai S Y. HuL' and 1.. 86: 527 535 17 GuoL. Chinese J. et al. Sept. Chem. cm-'. Chem. with the molar extinction coefficient E of 1. 2002.25 X low6 mol . B.47x lo4 L . 84:105 133 26 NazeeruddinM K. Inorg. et al...Sugihara H. Chinese Science Bulletin. mol-' .Soc. mol-'. Dai S. Trans. 25(5): 934 937 (in Chinese) 25 Dai S. Wang K. 20. 2005. Li F Y. et al. 26(3): 518 521. Gratzel M. Weng J. J.48 x lo4 L. 32:181 27 Nazeeruddin Md K. Inorg. Sol. Acta. Wang K. Singh L P. Am. 2005. 26 (10): 1934 1937 18 Dai S Y. L-' to 1. Sayama K. 6(5): 2467 2474 Li W Y.Dai S Y. Pan K. 1999. 534 . mol-'. Acta. L-l to 5 x loW5 mol . The absorption spectra of N719 is blue-shifted by 3 5 nm compared with N3 dye. Langmuir. mol-'. 2003. cm-'. Chin. N 23 (3): 251 N 254 N - - 1 N N - References 1 2 3 4 5 6 O'Regan B. 50(13): 2597 2602 15 Shi C. Chinese Universities. PBchy P. 1997. Dai S. Synthesis. 308: 73 79 HuLH. et al. Zakeeruddin S M. Dai S.47 x lo4 L . J. Zakeeruddin S M.8..Plasma Science & Technology. cm-'. L-' to 1. et 28 ShkloverV.50 X lo4 L . 1993. Chinese Universities. 115:6382 Hara K.Chim. V0l. et al. Chinese Universities. J s c . Lett. Sol. et al. 1997. Li F Y. 2003. No. 52(9): 2135 2139 (in Chinese) Dai S Y. + 7 8 N 9 10 11 12 13 14 Wang Z S. with E of 1. Phys. et al. 2000: 2 8 1 7 ~ 2822 Ruile S. with E of 1. et al.25 X lop6 mol L-l to 1 X lO-4 mol . XU J J. 2004. 20(6): N N N 4 Conclusions 953 N 955 N a.48 x lo4 L . Mater.. Kang J J.