Preparation of PVP-based Iodine-iodide Gel-electrolyte and Its Application in DSSCs†

doi:10.7503/cjcu20131250

Abstract

Abstract:

In the preparation of gel polymer electrolyte(GPE) for dye-sensitized solar cell(DSSCs), lithium iodide was used as the I^- source, ethylene carbonate(EC) and propylene carbonate(PC) were used as the solvent, polyvinyl pyrrolidone(PVP) and polyvinylidene fluoride(PVDF) were used as the gelling agent. Raman spectroscopy, cyclic voltammetry and alternate current(AC) impedance were used to characterize the gel electrolyte. The results show that the concentration(mass fraction) of polymer and the ratios of PVP to PVDF and iodine to iodide have great influence on the performance of the GPE. The prepared GPE comes to the highest ion conductivity of 3.27 mS/cm at room temperature when the concentration of polymer is 10%[m(PVP)/m(PVDF)=80∶20] and the molar ratio of LiI/I₂ is 30∶1 with the concentration of iodide as 0.042 mol/L. DSSC with the PVP-based GPE achieves a good output performance with open circuit voltage of 0.64 V, short circuit current density of 13.6 mA/cm², fill factor of 0.595, the overall photoelectric conversion efficiency of 5.18% under 100 mW/cm² of simulated sunlight and exhibits a good stability during the test time of 30 d. The new GPE which is cheap and available overcomes the problem of liquid electrolytes leakage in DSSCs.

Key words: Poly(vinylpyrrolidone), Polymer gel-electrolyte, Ionic conductivity, Dye-sensitized solar cell

CLC Number:

O641
O649

TrendMD:

LU Shanfu, LIU Yiyang, XIANG Yan. Preparation of PVP-based Iodine-iodide Gel-electrolyte and Its Application in DSSCs^†[J]. Chem. J. Chinese Universities, 2014, 35(6): 1293.

Figures/Tables 11

Fig.1 Influence of the polymer concentration on ionic conductivity of the gel electrolytem(PVP)∶m(PVDF)=80∶20; c(LiI)=1.26 mol/L; c(I2)=0.042 mol/L.

Fig.2 Cyclic voltammetry curves of the gel electrolyte based on different polymer concentrationw(Polymer)(%): a. 8; b. 10; c. 12; d. 13.5; e. 15.

Fig.3 Influence of the PVP concentration in polymer on ionic conductivity of the gel electrolytew(Polymer)=10%; c(LiI)=1.26 mol/L; c(I2)=0.042 mol/L.

Fig.4 Influence of molar ratio of iodide/iodine on ionic conductivity of the gel electrolytew(Polymer)=10%; m(PVP)∶m(PVDF)=80∶20; c(I2)=0.042 mol/L.

Fig.5 Raman spectra of the gel electrolyte based on different molar ratios of LiI/I2(A) and the intensity of the band at 111 cm-1(B) c(I2)=0.042 mol/L.

Fig.6 J-V curves of DSSCs based on different gel electrolytes(A) Photocurrent-voltage curves; (B) dark current-voltage curves. a. w(Polymer)=10%, n(LiI)∶n(I2)=30∶1; b. w(Polymer)=10%, n(LiI)∶n(I2)=20∶1; c. w(Polymer)=12%, n(LiI)∶n(I2)=30∶1; d. w(Polymer)=10%, n(LiI)∶n(I2)=35∶1.

Fig.7 EIS spectra of DSSCs based on different gel electrolytesThe lines are the fitting results. The inset is the equivalent circuit to fit the DSSCs impedance spectroscopy[26-29] ; CPE1, CPE2 and CPEW: non-ideal frequency dependent capacitance.

Table 1 Performance of DSSCs based on different gel electrolytes*

w(Polymer)(%)	n(LiI)∶n(I₂)	σ/ (mS·cm^-1)	V_oc/V	J_sc/ (mA·cm^-2)	FF(%)	η(%)	R_s/Ω	R₁/Ω	R₂/Ω	R_w/Ω
10	20∶1	2.77	0.693	9.66	52.4	3.51	20.4	39.6	10.6	42.1
10	30∶1	3.27	0.737	11.54	53.1	4.52	18.5	29.6	10.1	24.3
10	35∶1	2.95	0.680	10.56	48.2	3.46	17.7	23.5	10.3	45.3
12	30∶1	2.89	0.706	8.49	53.4	3.20	21.3	31.8	10.3	27.7

Fig.8 Performance of DSSCs in a long time(A) Photocurrent-voltage curves. Time/d: a. 0, b. 6, c. 15, d. 34; (B) conversion efficiency vs. time.

Table 2 Performance of DSSCs during a long time

Time/d	V_oc/V	J_sc/(mA·cm^-2)	FF(%)	η(%)	Time/d	V_oc/V	J_sc/(mA·cm^-2)	FF(%)	η(%)
0	0.65	12.9	47.0	3.94	15	0.67	11.0	60.8	4.47
6	0.64	13.6	59.5	5.18	28	0.68	10.0	67.9	4.63
12	0.66	11.1	62.7	4.62	34	0.66	10.2	63.5	4.29

Table 3 Performanceof DSSCs according to the recent reported references*

Type of electrolyte	η(%)	Ref.	Type of electrolyte	η(%)	Ref.
PVP+PVDF+LiI+EC-PC	5.18	This work	Poly(HDT/PEG)+PANi+ NMP-AC	6.81	[20]
PAN+Prop₄NI+EC-PC	4.30	[31]	PVA+KI EC-PC	2.74	[32]
POEM+PMII+EMIBF₄	6.28	[8]	PVB+LiI+GBL-NMP	4.86	[33]

References 33

[1]	O’regan B., Grfitzeli M., Nature, 1991, 353, 737-740
[2]	Yella A., Lee H. W., Tsao H. N., Yi C., Chandiran A. K., Nazeeruddin M. K., Diau E. W. G., Yeh C. Y., Zakeeruddin S. M., Grätzel M., Science, 2011, 334(6056), 629-634
[3]	Dong R. X., Shen S. Y., Chen H. W., Wang C. C., Shih P. T., Liu C. T., Vittal R., Lin J. J., Ho K. C., J. Mater. Chem. A, 2013, 1(29), 8471-8478
[4]	Yin X. O., Tan W. W., Xiang W. C., Lin Y. A., Zhang J. B., Xiao X. R., Li X. P., Zhou X. W., Fang S. B., Electrochim. Acta, 2010, 55(20), 5803-5807
[5]	Lee H. S., Han C. H., Sung Y. M., Sekhon S. S., Kim K. J., Current Applied Physics, 2011, 11(1), S158-S162
[6]	Lim S. J., Kang Y. S., Kim D. W., Electrochim. Acta, 2011, 56(5), 2031-2035
[7]	Wu J. H., Hao S., Lan Z., Lin J. M., Huang M. L., Huang Y. F., Fang L. Q., Yin S., Sato T., Adv. Funct. Mater., 2007, 17(15), 2645-2652
[8]	Chang L. Y., Lee C. P., Vittal R., Lin J. J., Ho K. C., J. Mater. Chem. A, 2013, 1(9), 3055-3060
[9]	Park S. H., Song I. Y., Lim J., Kwon Y. S., Choi J., Song S., Lee J. R., Park T., Energy & Environmental Science, 2013, 6(5), 1559-1564
[10]	Wang Y. M., Sol. Energ. Mat. Sol. C, 2009, 93(8), 1167-1175
[11]	Guo L., Dai S. Y., Wang K. J., Fang X. Q., Shi C. W., Pan X., Chem. J. Chinese Universities, 2005, 26(10), 1934-1937
	(郭力, 戴松元, 王孔嘉, 方霞琴, 史成武, 潘旭.高等学校化学学报, 2005,26(10), 1934-1937)
[12]	Huo Z. P., Dai S. Y., Zhang C. N., Liu W. Q., Fang X. Q., Cai M. L., Guo L., Wang K. J., Jiang N. Q., Zheng Y. Z., Chem. J. Chinese Universities, 2009, 30(6), 1214-1218
	(霍志鹏, 戴松元, 张昌能, 刘伟庆, 方霞琴, 蔡墨朗, 郭磊, 王孔嘉, 姜年权, 郑亦庄.高等学校化学学报, 2009,30(6), 1214-1218)
[13]	Yu Q. J., Yu C. L., Guo F. Y., Wang J. Z., Jiao S. J., Gao S. Y., Li H. T., Zhao L. C., Energy & Environmental Science, 2012, 5(3), 6151-6155
[14]	De Faria D., Gil H., de Queiroz A., J. Mol. Struct., 1999, 478(1), 93-98
[15]	Wu J. H., Li P. J., Hao S. C., Yang H. X., Lan Z., Electrochim. Acta, 2007, 52(17), 5334-5338
[16]	Cha S. Y., Lee Y. G., Kang M. S., Kang Y. S., J. Photochem. Photobiol. A: Chem., 2010, 211(2), 193-196
[17]	Benedetti J. E., Correa A. A., Carmello M., Almeida L. C. P., Goncalves A. S., Nogueira A. F., J. Power Sources, 2012, 208, 263-270
[18]	Chen C. L., Chang T. W., Teng H. S., Wu C. G., Chen C. Y., Yang Y. M., Lee Y. L., Phys. Chem. Chem. Phys., 2013, 15(10), 3640-3645
[19]	Hsu S. Y., Tsai C. H., Lu C. Y., Tsai Y. T., Huang T. W., Jhang Y. H., Chen Y. F., Wu C. C., Chen Y. S., Org. Electron., 2012, 13(5), 856-863
[20]	Li Q. H., Chen H. Y., Lin L., Li P. J., Qin Y. C., Li M. J., He B. L., Chu L., Tang Q. W., J. Mater. Chem. A, 2013, 1(17), 5326-5332
[21]	Ganesan S., Mathew V., Paul B. J., Maruthamuthu P., Suthanthiraraj S. A., Electrochim. Acta, 2013, 102, 219-224
[22]	Jerman I., Jovanovski V., Šurca Vuk A.,Houek M., Jesih A., Orel B., Electrochim. Acta, 2008, 53(5), 2281-2288
[23]	Lan Z., Wu J., Wang D., Hao S., Lin J., Huang Y., Sol. Energy, 2006, 80(11), 1483-1488
[24]	Eschen T., Kösters J., Schönhoff M., Stolwijk N. A., J. Phys. Chem. B, 2012, 116(28), 8290-8298
[25]	Nazeeruddin M. K., Kay A., Rodicio I., Humphry-Baker R., Müller E., Liska P., Vlachopoulos N., Grätzel M., J. Am. Chem. Soc., 1993, 115(14), 6382-6390
[26]	Liu W. Q., Kou D. X., Hu L. H., Dai S. Y., Chem. J. Chinese Universities, 2012, 33(9), 2051-2055
	(刘伟庆, 寇东星, 胡林华, 戴松元.高等学校化学学报, 2012,33(9), 2051-2055)
[27]	Lai Y. H., Lin C. Y., Chen J. G., Wang C. C., Huang K. C., Liu K. Y., Lin K. F., Lin J. J., Ho K. C., Sol. Energ. Mat. Sol. C, 2010, 94(4), 668-674
[28]	Zhang Y. G., Zhao J., Sun B. Q., Chen X. J., Li Q., Qiu L. H., Yan F., Electrochim. Acta, 2012, 61, 185-190
[29]	Wang Q., Moser J. E., Grätzel M., J. Phys. Chem. B, 2005, 109(31), 14945-14953
[30]	Rong Y., Li X., Liu G., Wang H., Ku Z., Xu M., Liu L., Hu M., Yang Y., Zhang M., Liu T., Han H., J. Power Sources, 2013, 235, 243-250
[31]	Bandara T., Jayasundara W., Dissanayake M., Furlani M., Albinsson I., Mellander B. E., Electrochim. Acta, 2013, 109, 609-616
[32]	Aziz M. F., Noor I. M., Sahraoui B., Arof A. K., Opt. Quant. Electron., 2014, 46(1), 133-141
[33]	Chen K. F., Liu C. H., Hsieh C. K., Lin C. L., Huang H. K., Tsai C. H., Chen F. R., J. Power Sources, 2014, 247, 939-946