聚合物电解质中导电物质含量对准固态电池光电性能的影响
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摘要
将聚乙烯吡咯烷酮(PVP)和聚环氧乙烷(PEO)共混用作胶凝剂,制备(PEO-PVP)/LiI/I2凝胶电解质并组装成准固态敏化太阳电池。研究了电池中导电物质的含量对电解质的导电性能和TiO_2/电解质界面的电子复合动力学的影响,以及电池光电性能的变化规律。结果表明,随着导电物质含量的提高TiO_2上光生电子与电解质中I3-之间的复合电阻和复合反应因子逐渐减小,复合反应更加容易进行,使电池的开路电压(Voc)逐渐降低。随导电物质含量的提高电池的短路电流(Jsc)先增大后减小,其原因是:当导电物质含量(质量分数)较低(<15%)时Jsc受电解质的导电性能控制,导电物质含量提高引起的电导率增大使Jsc值增大;当含量较高(>15%)时电池中较大的暗电流(j0)成为影响Jsc的主导因素,导电物质含量提高引起的j0值增大使Jsc值相应减小。随着导电物质含量的提高电池的光电转化效率(η)先增加后减小,并在含量为15%时达到最佳值5.6%。
Novel(PEO-PVP)/LiI/I2 gel electrolyte was prepared by blending polyvinylpyrrolidone(PVP) and polyethylene oxide(PEO), and then the quasi-solid-state sensitized solar cell was prepared with the electrolyte. The effect of the amount of conductive substance on the conductivity of electrolyte, interfacial recombination kinetics between TiO_2 and electrolyte, and the photoelectric performance of the DSSC was investigated. It follows that with the increase amount of the conductive substance, the recombination resistance and recombination reaction factor decrease gradually for the recombination between the light-generated electrons on TiO_2 with the I3-in the electrolyte, thereby the recombination reaction is facilitated, correspondingly the open circuit voltage(VOC) of the dye-sensitized solar cells(DSSC) also re-duced gradually. When the conductive substance is less than 15%(in mass fraction), the short-circuit current(Jsc) is controlled by the conductivity of the electrolyte, and the increase of the conductive substance may result in enhancement of the conductivity and the Jscvalue. When the conductive substance is more than 15%, the dark current(j0) of the DSSC becomes the dominant factor affecting the Jscvalue, and the increase of the conductive substance caused increase of j0 while decrease of the Jsc. The conversion efficiency(η) of the DSSC increases first and then decreases with the increase of the conductive substance and which reaches the optimum value of 5.6% when the amount of conductive substance is 15%.
Novel(PEO-PVP)/LiI/I2 gel electrolyte was prepared by blending polyvinylpyrrolidone(PVP) and polyethylene oxide(PEO), and then the quasi-solid-state sensitized solar cell was prepared with the electrolyte. The effect of the amount of conductive substance on the conductivity of electrolyte, interfacial recombination kinetics between TiO_2 and electrolyte, and the photoelectric performance of the DSSC was investigated. It follows that with the increase amount of the conductive substance, the recombination resistance and recombination reaction factor decrease gradually for the recombination between the light-generated electrons on TiO_2 with the I3-in the electrolyte, thereby the recombination reaction is facilitated, correspondingly the open circuit voltage(VOC) of the dye-sensitized solar cells(DSSC) also re-duced gradually. When the conductive substance is less than 15%(in mass fraction), the short-circuit current(Jsc) is controlled by the conductivity of the electrolyte, and the increase of the conductive substance may result in enhancement of the conductivity and the Jscvalue. When the conductive substance is more than 15%, the dark current(j0) of the DSSC becomes the dominant factor affecting the Jscvalue, and the increase of the conductive substance caused increase of j0 while decrease of the Jsc. The conversion efficiency(η) of the DSSC increases first and then decreases with the increase of the conductive substance and which reaches the optimum value of 5.6% when the amount of conductive substance is 15%.
引文
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[20]Jin H R, Jin J, Xu J, et al. Preparation of iodine-free ionic liquid gel electrolyte using polyethylene oxide(PEO)-polyethylene glycol(PEG)and its application in Ti-foil-based dye-sensitized solar cells[J]. Electrochim. Acta, 2016, 201:251
[21]Takikawa K, Nakano M, Arita T. Change in Apparent Permeability of Iodine in the Presence of Polyvinylpyrrolidone[J]. Chem.Pharm. Bull., 2008, 26(3):874
[22]Xu N, Ding D. Preparation and antibacterial activity of chitosan derivative membrane complexation with iodine[J]. Rsc Adv.,2015, 5(97):79820
[23]Xu J, Zhao P, Zhang Y. Iodine-responsive poly(HEMA-PVP)hydrogel for self-regulating burst-free extended release[J]. J. Biomat. Sci-Polym. E., 2017, 28(5):470
[24]Liu Y, Hagfeldt A, Xiao X R, et al. Investigation of influence of redox species on the interfacial energetics of a dye-sensitized nanoporous TiO2solar cell[J]. Sol. Energ. Mater. Sol. C., 1998, 55(3):267
[25]Li R, Liu D X, Zhou D F, et al. Influence of the electrolyte cation in organic dye-sensitized solar cells:lithium versus dimethylimidazolium[J]. Energ. Environ. Sci., 2010, 3(11):1765
[26]Jung N E, Lee D K, Kim Y R, et al. Effect of iodine concentration in the quasi-solid state electrolyte on the photovoltaic performance of dye-sensitized solar Cells[J]. Mol. Cryst. Liq. Cryst., 2015, 620(1):123
[27]Mathew A, Anand V, Rao G M, et al. Effect of iodine concentration on the photovoltaic properties of dye sensitized solar cells for various I2/LiI ratios[J]. Electrochim. Acta, 2013, 87(1):92
[28]Fukui A, Komiya R, Yamanaka R, et al. Effect of a redox electrolyte in mixed solvents on the photovoltaic performance of a dyesensitized solar cell[J]. Sol. Energ. Mater. Sol. C., 2006, 90(5):649
[29]Boschloo G, Leif H?ggman A, Hagfeldt A. Quantification of the Effect of 4-tert-Butylpyridine Addition to I-/I3-Redox Electrolytes in Dye-Sensitized Nanostructured TiO2Solar Cells[J]. J. Phys.Chem. B, 2006, 110(26):13144
[30]Kang M S, Kim J H, Won J, et al. Dye-sensitized solar cells based on crosslinked poly(ethylene glycol)electrolytes[J]. J. Photochem. Photobio. A, 2006, 183(1):15
[31]Sakaguchi S, Ueki H, Kato T, et al. Quasi-solid dye sensitized solar cells solidified with chemically cross-linked gelators[J]. J. Photochem. Photobio. A, 2004, 164(1-3):117
[32]Nazeeruddin M K, Kay A, Rodicio I, et al. Conversion of light to electricity by cis-X2bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II)charge-transfer sensitizers(X=Cl-, Br-, I-, CN-and SCN-)on nanocrystalline titanium dioxide electrodes[J]. J. Am. Chem. Soc.,1993, 115(14):6382
[33]Huang S Y, Schlichth?rl G, Nozik A J, et al. Charge recombination in dye-sSensitized nanocrystalline TiO2solar cells[J]. J. Phys.Chem. B, 1997, 101(14):2576
[34]Wang Q, Ito S, Gr?tzel M, et al. Characteristics of high efficiency dye-sensitized solar cells[J]. J. Phys. Chem. B, 2006, 110(50):25210
[35]Xu X Q, Xu G. Electrochemical impedance spectra of CdSe quantume dots sensitized nanocrystalline TiO2solar cells[J]. Sci. China. Chem., 2011, 41(1):37(徐雪青,徐刚. CdSe量子点敏化纳米二氧化钛太阳电池的电化学交流阻抗谱[J].中国科学:化学, 2011, 41(1):37)
[2]Gr?tzel M. Photoelectrochemical cells[J]. Nature, 2001, 414(6861):338
[3]Mathew S, Yella A, Gao P, et al. Dye-sensitized solar cells with13%efficiency achieved through the molecular engineering of porphyrin sensitizers[J]. Nat. Chem., 2014, 6(3):242
[4]Kim J, Koh J K, Kim B, et al. Enhanced performance of I2-Free solid-state dye-sensitized solar cells with conductive polymer up to6.8%[J]. Adv. Funct. Mater., 2015, 21(24):4633
[5]Rong Y G, Mei A Y, Liu L F, et al. All-solid-state mesoscopic solar cells:from dye-sensitized to perovskite[J]. Acta Chim. Sinica,2015, 73(3):237(荣耀光,梅安意,刘林峰等.全固态介观太阳能电池:从染料敏化到钙钛矿[J].化学学报, 2015, 73(3):237)
[6]Kumara G R A, Kaneko S, Okuya M, et al. Fabrication of dye-sensitized solar cells using triethylamine hydrothiocyanate as a CuI crystal growth inhibitor[J]. Langmuir, 2002, 18(26):10493
[7]Perera V P S, Senevirathna M K I, Pitigala P K D D P, et al. Doping CuSCN films for enhancement of conductivity:Application in dyesensitized solid-state solar cells[J]. Sol. Energ. Mat. Sol. C., 2005,86(3):443
[8]Ding I K, Tétreault N, Brillet J, et al. Pore-filling of spiro-OMeTAD in solid-state dye sensitized solar cells:quantification, mechanism,and consequences for device performance[J]. Adv. Funct. Mater.,2009, 19(15):2431
[9]Jiang K J, Manseki K, Yu Y H, et al. Photovoltaics based on hybridization of effective dye-sensitized titanium oxide and hole-conductive polymer P3HT[J]. Adv. Funct. Mater., 2009, 19(15):2481
[10]Murakoshi K, Kogure R, Wada Y, et al. Fabrication of solid-state dye-sensitized TiO2, solar cells combined with polypyrrole[J]. Sol.Energ. Mat. Sol. C., 1998, 55(1-2):113
[11]Duan Y, Tang Q, Chen Y, et al. Solid-state dye-sensitized solar cells from poly(ethylene oxide)/polyaniline electrolytes with catalytic and hole-transporting characteristics[J]. J. Mater. Chem. A,2015, 3(10):5368
[12]Li X P, Fang S B, Kang J J, et al. Quasi solid state dye-sensitized solar cells with polymer electrolytes based on polysiloxanes[J]. Acta Energi. Sin., 2007, 28(8):929(李学萍,方世璧,康俊杰等.聚硅氧烷为基体的聚合物电解质准固态染料敏化太阳电池[J].太阳能学报, 2007, 28(8):929)
[13]Kang J, Li W, Wang X, et al. Polymer electrolytes from PEO and novel quaternary ammonium iodides for dye-sensitized solar cells[J].Electrochim. Acta, 2003, 48(17):2487
[14]Li M, Feng S, Fang S, et al. The use of poly(vinylpyridine-co-acrylonitrile)in polymer electrolytes for quasi-solid dye-sensitized solar cells[J]. Electrochim. Acta, 2007, 52(14):4858
[15]Zhang Y H, Zhu J, Dai S Y. Recent research development on solid state and quasi-solid state electrolyte for dye-sensitized Solar Cells[J]. Chem., 2010, 73(12):1059(张耀红,朱俊,戴松元.染料敏化太阳能电池用固态及准固态电解质的研究进展[J].化学通报, 2010, 73(12):1059)
[16]Zhang Y X, Huo Z P, Zhang C N, et al. Research on the dye-sensitized solar cells based on P(VDF-HFP)-type polymer gel electrolyte[J]. Acta chim. Sinica, 2009, 67(19):2253(张玉香,霍志鹏,张昌能等.基于偏氟乙烯-六氟丙烯共聚物凝胶电解质的染料敏化太阳电池光电性能研究[J].化学学报,2009, 67(19):2253)
[17]Fenton D E, Parker J M, Wright P V. Complexes of alkali metal ions with poly(ethylene oxide)[J]. Polymer, 1973, 14(11):589
[18]Ren Y, Zhang Z, Fang S, et al. Application of PEO based gel network polymer electrolytes in dye-sensitized photoelectrochemical cells[J]. Sol. Energ. Mat. Sol. C., 2002, 71(2):253
[19]Wang M, Xiao X, Zhou X, et al. Investigation of PEO-imidazole ionic liquid oligomer electrolytes for dye-sensitized solar cells[J]. Key Eng. Mater., 2007, 91(9):785
[20]Jin H R, Jin J, Xu J, et al. Preparation of iodine-free ionic liquid gel electrolyte using polyethylene oxide(PEO)-polyethylene glycol(PEG)and its application in Ti-foil-based dye-sensitized solar cells[J]. Electrochim. Acta, 2016, 201:251
[21]Takikawa K, Nakano M, Arita T. Change in Apparent Permeability of Iodine in the Presence of Polyvinylpyrrolidone[J]. Chem.Pharm. Bull., 2008, 26(3):874
[22]Xu N, Ding D. Preparation and antibacterial activity of chitosan derivative membrane complexation with iodine[J]. Rsc Adv.,2015, 5(97):79820
[23]Xu J, Zhao P, Zhang Y. Iodine-responsive poly(HEMA-PVP)hydrogel for self-regulating burst-free extended release[J]. J. Biomat. Sci-Polym. E., 2017, 28(5):470
[24]Liu Y, Hagfeldt A, Xiao X R, et al. Investigation of influence of redox species on the interfacial energetics of a dye-sensitized nanoporous TiO2solar cell[J]. Sol. Energ. Mater. Sol. C., 1998, 55(3):267
[25]Li R, Liu D X, Zhou D F, et al. Influence of the electrolyte cation in organic dye-sensitized solar cells:lithium versus dimethylimidazolium[J]. Energ. Environ. Sci., 2010, 3(11):1765
[26]Jung N E, Lee D K, Kim Y R, et al. Effect of iodine concentration in the quasi-solid state electrolyte on the photovoltaic performance of dye-sensitized solar Cells[J]. Mol. Cryst. Liq. Cryst., 2015, 620(1):123
[27]Mathew A, Anand V, Rao G M, et al. Effect of iodine concentration on the photovoltaic properties of dye sensitized solar cells for various I2/LiI ratios[J]. Electrochim. Acta, 2013, 87(1):92
[28]Fukui A, Komiya R, Yamanaka R, et al. Effect of a redox electrolyte in mixed solvents on the photovoltaic performance of a dyesensitized solar cell[J]. Sol. Energ. Mater. Sol. C., 2006, 90(5):649
[29]Boschloo G, Leif H?ggman A, Hagfeldt A. Quantification of the Effect of 4-tert-Butylpyridine Addition to I-/I3-Redox Electrolytes in Dye-Sensitized Nanostructured TiO2Solar Cells[J]. J. Phys.Chem. B, 2006, 110(26):13144
[30]Kang M S, Kim J H, Won J, et al. Dye-sensitized solar cells based on crosslinked poly(ethylene glycol)electrolytes[J]. J. Photochem. Photobio. A, 2006, 183(1):15
[31]Sakaguchi S, Ueki H, Kato T, et al. Quasi-solid dye sensitized solar cells solidified with chemically cross-linked gelators[J]. J. Photochem. Photobio. A, 2004, 164(1-3):117
[32]Nazeeruddin M K, Kay A, Rodicio I, et al. Conversion of light to electricity by cis-X2bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II)charge-transfer sensitizers(X=Cl-, Br-, I-, CN-and SCN-)on nanocrystalline titanium dioxide electrodes[J]. J. Am. Chem. Soc.,1993, 115(14):6382
[33]Huang S Y, Schlichth?rl G, Nozik A J, et al. Charge recombination in dye-sSensitized nanocrystalline TiO2solar cells[J]. J. Phys.Chem. B, 1997, 101(14):2576
[34]Wang Q, Ito S, Gr?tzel M, et al. Characteristics of high efficiency dye-sensitized solar cells[J]. J. Phys. Chem. B, 2006, 110(50):25210
[35]Xu X Q, Xu G. Electrochemical impedance spectra of CdSe quantume dots sensitized nanocrystalline TiO2solar cells[J]. Sci. China. Chem., 2011, 41(1):37(徐雪青,徐刚. CdSe量子点敏化纳米二氧化钛太阳电池的电化学交流阻抗谱[J].中国科学:化学, 2011, 41(1):37)