聚合时间对染料敏化太阳能电池中聚苯胺对电极结构和性能的影响

doi:10.3866/PKU.WHXB201301092

物理化学学报 >> 2013, Vol. 29 >> Issue (03): 516-524.doi: 10.3866/PKU.WHXB201301092

聚合时间对染料敏化太阳能电池中聚苯胺对电极结构和性能的影响

王莎莎^1,2, 芦姗^2,3, 苏佳², 郭正凯², 李学敏^2,3, 张雪华², 何声太¹, 贺涛²

1 天津工业大学材料科学与工程学院, 天津 300387;
2 国家纳米科学中心, 北京 100190;
3 中国科学院大学, 北京 100049

收稿日期:2012-11-05 修回日期:2013-01-09 发布日期:2013-02-25
通讯作者: 张雪华, 何声太, 贺涛 E-mail:zhangxh@nanoctr.cn; het@nanoctr.cn; sht-he@tjpu.edu.cn
基金资助:
科技部(2010DFB63530); 国家自然科学基金(51043010, 21203039); 中国科学院项目百人; 中国科学院光化学转换与功能材料重点实验室(理化技术研究所); 天津市应用基础及前沿技术研究计划(09JCYBJC27200)资助项目

Influences of Polymerization Time on Structure and Properties of Polyaniline Counter Electrodes in Dye-Sensitized Solar Cells

WANG Sha-Sha^1,2, LU Shan^2,3, SU Jia², GUO Zheng-Kai², LI Xue-Min^2,3, ZHANG Xue-Hua², HE Sheng-Tai¹, HE Tao²

1 School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin 300387, P. R. China;
2 National Center for Nanoscience and Technology, Beijing 100190, P. R. China;
3 University of Chinese Academy of Sciences, Beijing 100049, P. R. China

Received:2012-11-05 Revised:2013-01-09 Published:2013-02-25
Supported by:
The project was supported by the Ministry of Science and Technology of China (2010DFB63530), National Natural Science Foundation of China (51043010, 21203039), Hundred-Talent Program of Chinese Academy of Sciences, Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physical Chemistry, Chinese Academy of Sciences, and Tianjin Research Program of Applied Basic & Cutting-edge Technologies, China (09JCYBJC27200).

摘要/Abstract

摘要：

采用恒电压方法, 以掺杂氟的SnO₂ (FTO)导电玻璃为基底, 采用不同的聚合时间制备SO₄^2?掺杂的聚苯胺对电极(PANI CEs). 利用扫描电子显微镜(SEM)、紫外-可见(UV-Vis)吸收光谱、循环伏安法(CV)和电化学阻抗谱(EIS)等技术详细研究了聚合时间对PANI CEs的表面形貌、结构(如掺杂度、共轭性、氧化态等)和对I^?/I³^?的催化活性的影响. SEM结果表明PANI在FTO上的生长分两个阶段. 适当增加聚合时间可以增加PANI CEs的比表面积, 为催化I^?/I³^?反应提供更多的活性位点, 同时聚苯胺链的共轭性、半氧化态聚苯胺(EB)结构的含量和对阴离子SO₄^2?的掺杂度会随着增加, 进而PANI 的导电率也逐渐增大. 然而, 聚合时间过长会引起薄膜厚度的增加和氧化结构的过多, 使PANI CEs的导电率降低, 电子在PANI 薄膜中的传输阻抗增加, 进而影响其对I^?/I³^?的催化性能. 聚合时间为300 s 时制备出的PANI 薄膜作为染料敏化太阳能电池(DSSCs)对电极和以D149 为染料时, 获得的最高电池光电转换效率为5.30%, 可达到基于Pt 对电极电池效率的88%. 因此, 通过电化学方法制备的PANI CEs有望代替贵金属Pt CEs用于DSSCs中.

关键词: 聚苯胺, 电化学聚合, 聚合时间, 电催化活性, 对电极, 染料敏化太阳能电池

Abstract:

SO₄^2? doped polyaniline (PANI) counter electrodes (CEs) on fluorine-doped tin oxide (FTO) glass substrates were fabricated, using electrochemical method under constant bias for different polymerization time. The effect of polymerization time on surface morphology, structure (such as doping level, conjugation and oxidization state), and electrocatalytic activity for I^?/I₃^? redox reaction of the obtained PANI CEs was investigated by scanning electron microscopy (SEM), UV-Vis absorption spectroscopy, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). SEM results indicated that the growth of PANI films on FTO substrate occurred in two phases. Properly increasing polymerization time could increase the specific surface area of PANI CEs, affording more electrocatalytic sites for the I^?/I₃^? redox reaction. Meanwhile, the conductivity of the PANI CEs increased gradually because of enhanced conjugation, emeraldine base (EB) structure, and SO₄^2? doping degree. If the polymerization time was too long, however, the CE conductivity would decrease due to the formation of a thick film and superabundance of oxidized structure, resulting in an increase in the electron transfer resistance and decrease in the electrocatalytic activity of PANI CEs for I^?/I₃^? redox reaction. Dye-sensitized solar cells (DSSCs) based on PANI CEs with a polymerization time of 300 s and D149 dye showed the best photovoltaic performance, with a solar-to-energy conversion efficiency of 5.30%. This result is approximately 88% of the efficiency of Pt CE based-solar cells, suggesting that PANI CEs polymerized with electrochemical method may replace Pt CEs in DSSCs.

Key words: Polyaniline, Electrochemical polymerization, Polymerization time, Electrocatalytic activity, Counter electrode, Dye-sensitized solar cell

王莎莎, 芦姗, 苏佳, 郭正凯, 李学敏, 张雪华, 何声太, 贺涛. 聚合时间对染料敏化太阳能电池中聚苯胺对电极结构和性能的影响[J]. 物理化学学报, 2013, 29(03), 516-524. doi: 10.3866/PKU.WHXB201301092

WANG Sha-Sha, LU Shan, SU Jia, GUO Zheng-Kai, LI Xue-Min, ZHANG Xue-Hua, HE Sheng-Tai, HE Tao. Influences of Polymerization Time on Structure and Properties of Polyaniline Counter Electrodes in Dye-Sensitized Solar Cells[J]. Acta Phys. -Chim. Sin. 2013, 29(03), 516-524. doi: 10.3866/PKU.WHXB201301092

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201301092

https://www.whxb.pku.edu.cn/CN/Y2013/V29/I03/516

参考文献

(1) Regan, B. O.; Grätzel, M. Nature 1991, 353, 737. doi: 10.1038/353737a0
(2) Grätzel, M. J. Photochem. Photobiol. C: Photochem. Rev. 2003,4, 145. doi: 10.1016/S1389-5567(03)00026-1
(3) Grätzel, M. Accounts Chem. Res. 2009, 42, 1788. doi: 10.1021/ar900141y
(4) Papageorgiou, N.; Maier,W. F.; Grätzel, M. J. Electrochem.Soc. 1997, 144, 876. doi: 10.1149/1.1837502
(5) Papageorgiou, N. Coord. Chem. Rev. 2004, 248, 1421. doi: 10.1016/j.ccr.2004.03.028
(6) Wu, M. X.; Lin, X.;Wang, T. H.; Qiu, J. S.; Ma, T. L. EnergyEnviron. Sci. 2011, 4, 2308. doi: 10.1039/c1ee01059j
(7) Li, J.; Sun, M. X.; Zhang, X. Y.; Cui, X. L. Acta Phys. -Chim.Sin. 2011, 27, 2255. [李靖, 孙明轩, 张晓艳, 崔晓莉. 物理化学学报, 2011, 27, 2255.] doi: 10.3866/PKU.WHXB20110901
(8) Li, Z. P.; Ye, B. X.; Hu, X. D.; Ma, X. Y.; Zhang, X. P.; Deng, Y.Q. Electrochem. Commun. 2009, 11, 1768. doi: 10.1016/j.elecom.2009.07.018
(9) Qin, Q.; Tao, J.; Yang, Y. Synth. Met. 2010, 160, 1167. doi: 10.1016/j.synthmet.2010.03.003
(10) Chen, J. Z.; Li, B.; Zheng J. F.; Zhao, J. H.; Jing, H.W.; Zhu, Z.P. Electrochim. Acta 2011, 56, 4624. doi: 10.1016/j.electacta.2011.02.097
(11) Tian, H. N.; Yu, Z.; Hagfeldt, A.; Kloo, L.; Sun, L. C. J. Am.Chem. Soc. 2011, 133, 9413. doi: 10.1021/ja2030933
(12) Ahmad, S.; Yum, J. H.; Butt, H. J.; Nazeeruddin, M. K.; Grätzel,M. ChemPhysChem 2010, 11, 2814. doi: 10.1002/cphc.201000612
(13) Lee, K. M.; Chen, P. Y.; Hsu, C. Y.; Huang, J. H.; Ho,W. H.;Chen, H. C.; Ho, K. C. J. Power Sources 2009, 188, 313. doi: 10.1016/j.jpowsour.2008.11.075
(14) Xia, J. B.; Chen, L.; Yanagida, S. J. Mater. Chem. 2011, 21,4644. doi: 10.1039/c0jm04116e
(15) Wu, J. H.; Li, Q. H.; Fan, L. Q.; Lan, Z.; Li, P. J.; Lin, J. M.;Hao, S. C. J. Power Sources 2008, 181, 172. doi: 10.1016/j.jpowsour.2008.03.029
(16) Sun, H. C.; Luo, Y. H.; Zhang, Y. D.; Li, D. M.; Yu, Z. X.; Li, K.X.; Meng, Q. B. J. Phys. Chem. C 2010, 114, 11673. doi: 10.1021/jp1030015
(17) Li, Q. H.;Wu, J. H.; Tang, Q.W.; Lan, Z.; Li, P. J.; Lin, J. M.;Fan, L. Q. Electrochem. Commun. 2008, 10, 1299. doi: 10.1016/j.elecom.2008.06.029
(18) Tai, Q. D.; Chen, B. L.; Guo, F.; Xu, S.; Hu, H.; Sebo, B.; Zhao,X. Z. ACS Nano 2011, 5, 3795. doi: 10.1021/nn200133g
(19) Zhang, J.; Hreid, T.; Li, X. X.; Guo,W.;Wang, L. P.; Shi, X. T.;Su, H. Q.; Yuan, Z. B. Electrochim. Acta 2010, 55, 3664. doi: 10.1016/j.electacta.2010.01.115
(20) Bhadra, S.; Khastgir, D.; Singha, N. K.; Lee, J. H. Prog. Polym.Sci. 2009, 34, 783. doi: 10.1016/j.progpolymsci.2009.04.003
(21) MacDiarmid, A. G.; Chiang, J. C.; Richter, A. F.; Epstein, A. J.Synth. Met. 1987, 18, 286.
(22) Nazeeruddin, M. K.; Kay, A.; Rodicio, I.; Humpbry-Baker, R.;Miiller, E.; Liska, P.; Vlachopoulos, N.; Grätzel, M. J. Am.Chem. Soc. 1993, 115, 6382. doi: 10.1021/ja00067a063
(23) Stafström, S.; Sjögren, B.; Brédas, J. L. Synth. Met. 1989, 29,E219.
(24) Xu, Y. T.; Dai, L. Z.;Wu, H. H. Journal of Xiamen University2001, 40, 1073. [许一婷, 戴李宗, 吴辉煌. 厦门大学学报,2001, 40, 1073.]
(25) Huang,W. S.; MacDiarmid, A. G. Polymer 1993, 34, 1833. doi: 10.1016/0032-3861(93)90424-9
(26) Cao, Y.; Smith, P.; Heeger, A. J. Synth. Met. 1989, 32, 263. doi: 10.1016/0379-6779(89)90770-4
(27) Yin,W.; Ruckenstein, E. Synth. Met. 2000, 108, 39. doi: 10.1016/S0379-6779(99)00179-4
(28) Shreepathi, S.; Holze, R. Chem. Mater. 2005, 17, 4078. doi: 10.1021/cm050117s
(29) Qin, Q. Preparation and Properties of Polyaniline Electrolyteand Counter Electrode for DSSCs. Ph.D. Dissertation, NanjingUniversity of Aeronautics and Astronautics, Nanjing, 2010.[秦琦. 染料敏化太阳能电池用聚苯胺电解质及对电极的制备与性能研究[D]. 南京: 南京航空航天大学, 2010.]
(30) Saito, Y.; Kubo,W.; Kitamura, T.;Wada, Y.; Yanagida, S.J. Photochem. Photobiol. A: Chem. 2004, 164, 153. doi: 10.1016/j.jphotochem.2003.11.017
(31) Tang, H.; Kitani, A.; Shiotani, M. J. Appl. Electrochem. 1996,26, 36. doi: 10.1007/BF00248186

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聚合时间对染料敏化太阳能电池中聚苯胺对电极结构和性能的影响

Influences of Polymerization Time on Structure and Properties of Polyaniline Counter Electrodes in Dye-Sensitized Solar Cells

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