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Direct synthesis of highly conductive poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS)/graphene composites and their applications in energy harvesting systems

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Abstract

We report for the first time highly conductive poly(3,4-ethylenedioxythiophene): poly(4-styrenesulfonate) (PEDOT:PSS)/graphene composites fabricated by in situ polymerization and their applications in a thermoelectric device and a platinum (Pt)-free dye-sensitized solar cell (DSSC) as energy harvesting systems. Graphene was dispersed in a solution of poly(4-styrenesulfonate) (PSS) and polymerization was directly carried out by addition of 3,4-ethylenedioxythiophene (EDOT) monomer to the dispersion. The content of the graphene was varied and optimized to give the highest electrical conductivity. The composite solution was ready to use without any reduction process because reduced graphene oxide was used. The fabricated film had a conductivity of 637 S·cm−1, corresponding to an enhancement of 41%, after the introduction of 3 wt.% graphene without any further complicated reduction processes of graphene being required. The highly conductive composite films were employed in an organic thermoelectric device, and the device showed a power factor of 45.7 μW·m−1K−2 which is 93% higher than a device based on pristine PEDOT:PSS. In addition, the highly conductive composite films were used in Pt-free DSSCs, showing an energy conversion efficiency of 5.4%, which is 21% higher than that of a DSSC based on PEDOT:PSS.

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References

  1. Garnett, E. C.; Cai, W.; Cha, J. J.; Mahmood, F.; Connor, S. T.; Greyson Christoforo, M.; Cui, Y.; McGehee, M. D.; Brongersma, M. L. Self-limited plasmonic welding of silver nanowire junctions. Nat. Mater. 2012, 11, 241–249.

    Article  Google Scholar 

  2. De, S.; Higgins, T. M.; Lyons, P. E.; Doherty, E. M.; Nirmalraj, P. N.; Blau, W. J.; Boland, J. J.; Coleman, J. N. Silver nanowire networks as flexible, transparent, conducting films: Extremely high DC to optical conductivity ratios. ACS Nano 2009, 3, 1767–1774.

    Article  Google Scholar 

  3. Lee, J.-Y.; Connor, S. T.; Cui, Y.; Peumans, P. Solution-processed metal nanowire mesh transparent electrodes. Nano Lett. 2008, 8, 689–692.

    Article  Google Scholar 

  4. Wu, H.; Kong, D.; Ruan, Z.; Hsu, P.-C.; Wang, S.; Yu, Z.; Carney, T. J.; Hu, L.; Fan, S.; Cui, Y. A transparent electrode based on a metal nanotrough network. Nat. Nanotechnol. 2013, 8, 421–425.

    Article  Google Scholar 

  5. Park, T.; Park, C.; Kim, B.; Shin, H.; Kim, E. Flexible PEDOT electrodes with large thermoelectric power factors to generate electricity by the touch of fingertips. Energy Environ. Sci. 2013, 6, 788–792.

    Article  Google Scholar 

  6. De, S.; Lyons, P. E.; Sorel, S.; Doherty, E. M.; King, P. J.; Blau, W. J.; Nirmalraj, P. N.; Boland, J. J.; Scardaci, V.; Joimel, J.; et al. Transparent, flexible, and highly conductive thin films based on polymer-nanotube composites. ACS Nano 2009, 3, 714–720.

    Article  Google Scholar 

  7. Wu, Y.; Wang, B.; Ma, Y.; Huang, Y.; Li, N.; Zhang, F.; Chen, Y. Efficient and large-scale synthesis of few-layered graphene using an arc-discharge method and conductivity studies of the resulting films. Nano Res. 2010, 3, 661–669.

    Article  Google Scholar 

  8. Chang, H.; Wang, G.; Yang, A.; Tao, X.; Liu, X.; Shen, Y.; Zheng, Z. A transparent, flexible, low-temperature, and solution-processible graphene composite electrode. Adv. Funct. Mater. 2010, 20, 2893–2902.

    Article  Google Scholar 

  9. Hsiao, Y.-S.; Whang, W.-T.; Chen, C.-P.; Chen, Y.-C. High-conductivity poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) film for use in ITO-free polymer solar cells. J. Mater. Chem. 2008, 18, 5948–5955.

    Article  Google Scholar 

  10. Bubnova, O.; Khan, Z. U.; Malti, A.; Braun, S.; Fahlman, M.; Berggren, M.; Crispin, X. Optimization of the thermoelectric figure of merit in the conducting polymer poly(3,4-ethylenedioxythiophene). Nat. Mater. 2011, 10, 429–433.

    Article  Google Scholar 

  11. Kim, G. H.; Shao, L.; Zhang, K.; Pipe, K. P. Engineered doping of organic semiconductors for enhanced thermoelectric efficiency. Nat. Mater. 2013, 12, 719–723.

    Article  Google Scholar 

  12. Kumar, A.; Zhou, C. The race to replace tin-doped indium oxide: Which material will win? ACS Nano 2010, 4, 11–14.

    Article  Google Scholar 

  13. Kim, J.; You, J.; Kim, B.; Park, T.; Kim, E. Solution processable and patternable poly(3,4-alkylenedioxythiophene)s for large-area electrochromic films. Adv. Mater. 2011, 23, 4168–4173.

    Article  Google Scholar 

  14. Koh, J. K.; Kim, J.; Kim, B.; Kim, J. H.; Kim, E. Highly efficient, iodine-free dye-sensitized solar cells with solid-state synthesis of conducting polymers. Adv. Mater. 2011, 23, 1641–1646.

    Article  Google Scholar 

  15. Kim, J.; You, J.; Kim, E. Flexible conductive polymer patterns from vapor polymerizable and photo-cross-linkable EDOT. Macromolecules 2010, 43, 2322–2327.

    Article  Google Scholar 

  16. Kim, J.; Koh, J. K.; Kim, B.; Ahn, S. H.; Ahn, H.; Ryu, D. Y.; Kim, J. H.; Kim, E. Enhanced performance of I2-free solid-state dye-sensitized solar cells with conductive polymer up to 6.8%. Adv. Funct. Mater. 2011, 21, 4633–4639.

    Article  Google Scholar 

  17. Meng, H.; Perepichka, D. F.; Wudl, F. Facile solid-state synthesis of highly conducting poly(ethylenedioxythiophene). Angew. Chem. Int. Ed. 2003, 42, 658–661.

    Article  Google Scholar 

  18. Xia, Y.; Sun, K.; Ouyang, J. Solution-processed metallic conducting polymer films as transparent electrode of optoelectronic devices. Adv. Mater. 2012, 24, 2436–2440.

    Article  Google Scholar 

  19. Kim, H.; Abdala, A. A.; Macosko, C. W. Graphene/polymer nanocomposites. Macromolecules 2010, 43, 6515–6530.

    Article  Google Scholar 

  20. Gaynor, W.; Lee, J.-Y.; Peumans, P. Fully solution-processed inverted polymer solar cells with laminated nanowire electrodes. ACS Nano 2009, 4, 30–34.

    Article  Google Scholar 

  21. Coates, N. E.; Yee, S. K.; McCulloch, B.; See, K. C.; Majumdar, A.; Segalman, R. A.; Urban, J. J. Effect of interfacial properties on polymer-nanocrystal thermoelectric transport. Adv. Mater. 2013, 25, 1629–1633.

    Article  Google Scholar 

  22. Yu, C.; Choi, K.; Yin, L.; Grunlan, J. C. Light-weight flexible carbon nanotube based organic composites with large thermoelectric power factors. ACS Nano 2011, 5, 7885–7892.

    Article  Google Scholar 

  23. Kim, G. H.; Hwang, D. H.; Woo, S. I. Thermoelectric properties of nanocomposite thin films prepared with poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) and graphene. Phys. Chem. Chem. Phys. 2012, 14, 3530–3536.

    Article  Google Scholar 

  24. Geim, A. K.; Novoselov, K. S. The rise of graphene. Nat. Mater. 2007, 6, 183–191.

    Article  Google Scholar 

  25. Zhang, Y.; Tan, Y.-W.; Stormer, H. L.; Kim, P. Experimental observation of the quantum Hall effect and Berry’s phase in graphene. Nature 2005, 438, 201–204.

    Article  Google Scholar 

  26. Wang, X.; Zhi, L.; Mullen, K. Transparent, conductive graphene electrodes for dye-sensitized solar cells. Nano Lett. 2007, 8, 323–327.

    Article  Google Scholar 

  27. Yin, Z.; Wu, S.; Zhou, X.; Huang, X.; Zhang, Q.; Boey, F.; Zhang, H. Electrochemical deposition of ZnO nanorods on transparent reduced graphene oxide electrodes for hybrid solar cells. Small 2010, 6, 307–312.

    Article  Google Scholar 

  28. Xia, J.; Chen, F.; Li, J.; Tao, N. Measurement of the quantum capacitance of graphene. Nat. Nanotechnol. 2009, 4, 505–509.

    Article  Google Scholar 

  29. Chang, H.; Tang, L.; Wang, Y.; Jiang, J.; Li, J. Graphene fluorescence resonance energy transfer aptasensor for the thrombin detection. Anal. Chem. 2010, 82, 2341–2346.

    Article  Google Scholar 

  30. Kim, K. S.; Zhao, Y.; Jang, H.; Lee, S. Y.; Kim, J. M.; Kim, K. S.; Ahn, J.-H.; Kim, P.; Choi, J.-Y.; Hong, B. H. Large-scale pattern growth of graphene films for stretchable transparent electrodes. Nature 2009, 457, 706–710.

    Article  Google Scholar 

  31. Wu, J.; Agrawal, M.; Becerril, H. A.; Bao, Z.; Liu, Z.; Chen, Y.; Peumans, P. Organic light-emitting diodes on solution-processed graphene transparent electrodes. ACS Nano 2009, 4, 43–48.

    Article  Google Scholar 

  32. Jo, K.; Lee, T.; Choi, H. J.; Park, J. H.; Lee, D. J.; Lee, D. W.; Kim, B.-S. Stable aqueous dispersion of reduced graphene nanosheets via non-covalent functionalization with conducting polymers and application in transparent electrodes. Langmuir 2011, 27, 2014–2018.

    Article  Google Scholar 

  33. Trang, L. K. H.; Thanh Tung, T.; Young Kim, T.; Yang, W. S.; Kim, H.; Suh, K. S. Preparation and characterization of graphene composites with conducting polymers. Polym. Int. 2012, 61, 93–98.

    Article  Google Scholar 

  34. Stankovich, S.; Piner, R. D.; Chen, X.; Wu, N.; Nguyen, S. T.; Ruoff, R. S. Stable aqueous dispersions of graphitic nanoplatelets via the reduction of exfoliated graphite oxide in the presence of poly(sodium 4-styrenesulfonate). J. Mater. Chem. 2006, 16, 155–158.

    Article  Google Scholar 

  35. Qi, X.; Pu, K.-Y.; Zhou, X.; Li, H.; Liu, B.; Boey, F.; Huang, W.; Zhang, H. Conjugated-polyelectrolyte-functionalized reduced graphene oxide with excellent solubility and stability in polar solvents. Small 2010, 6, 663–669.

    Article  Google Scholar 

  36. Xu, Y.; Bai, H.; Lu, G.; Li, C.; Shi, G. Flexible graphene films via the filtration of water-soluble noncovalent functionalized graphene sheets. J. Am. Chem. Soc. 2008, 130, 5856–5857.

    Article  Google Scholar 

  37. Si, Y.; Samulski, E. T. Synthesis of water soluble graphene. Nano Lett. 2008, 8, 1679–1682.

    Article  Google Scholar 

  38. Li, D.; Muller, M. B.; Gilje, S.; Kaner, R. B.; Wallace, G. G. Processable aqueous dispersions of graphene nanosheets. Nat. Nanotechnol. 2008, 3, 101–105.

    Article  Google Scholar 

  39. Bolotin, K. I.; Sikes, K. J.; Jiang, Z.; Klima, M.; Fudenberg, G.; Hone, J.; Kim, P.; Stormer, H. L. Ultrahigh electron mobility in suspended graphene. Solid State Commun. 2008, 146, 351–355.

    Article  Google Scholar 

  40. Lee, C.; Wei, X.; Kysar, J. W.; Hone, J. Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 2008, 321, 385–388.

    Article  Google Scholar 

  41. Zuev, Y. M.; Chang, W.; Kim, P. Thermoelectric and magnetothermoelectric transport measurements of graphene. Phys. Rev. Lett. 2009, 102, 096807.

    Article  Google Scholar 

  42. Tung, N.; Khai, T.; Jeon, M.; Lee, Y.; Chung, H.; Bang, J.-H.; Sohn, D. Preparation and characterization of nanocomposite based on polyaniline and graphene nanosheets. Macromol. Res. 2011, 19, 203–208.

    Article  Google Scholar 

  43. Reddy, B. N.; Deepa, M.; Joshi, A. G.; Srivastava, A. K. Poly(3,4-ethylenedioxypyrrole) enwrapped by reduced graphene oxide: How conduction behavior at nanolevel leads to increased electrochemical activity. J. Phys. Chem. C 2011, 115, 18354–18365.

    Article  Google Scholar 

  44. Wang, X. J.; Wong, K. Y. Effects of a base coating used for electropolymerization of poly(3,4-ethylenedioxythiophene) on indium tin oxide electrode. Thin Solid Films 2006, 515, 1573–1578.

    Article  Google Scholar 

  45. Zhang, J.; Zhao, X. S. Conducting polymers directly coated on reduced graphene oxide sheets as high-performance supercapacitor electrodes. J. Phys. Chem. C 2012, 116, 5420–5426.

    Article  Google Scholar 

  46. Yao, Q.; Chen, L.; Zhang, W.; Liufu, S.; Chen, X. Enhanced thermoelectric performance of single-walled carbon nanotubes/polyaniline hybrid nanocomposites. ACS Nano 2010, 4, 2445–2451.

    Article  Google Scholar 

  47. Kim, D.; Kim, Y.; Choi, K.; Grunlan, J. C.; Yu, C. Improved thermoelectric behavior of nanotube-filled polymer composites with poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate). ACS Nano 2009, 4, 513–523.

    Article  Google Scholar 

  48. Xu, K.; Chen, G.; Qiu, D. Convenient construction of poly(3,4-ethylenedioxythiophene)-graphene pie-like structure with enhanced thermoelectric performance. J. Mater. Chem. A. 2013, 1, 12395–12399.

    Article  Google Scholar 

  49. Lu, Y.; Song, Y.; Wang, F. Thermoelectric properties of graphene nanosheets-modified polyaniline hybrid nanocomposites by an in situ chemical polymerization. Mater. Chem. Phys. 2013, 138, 238–244.

    Article  Google Scholar 

  50. Du, Y.; Shen, S. Z.; Yang, W.; Donelson, R.; Cai, K.; Casey, P. S. Simultaneous increase in conductivity and Seebeck coefficient in a polyaniline/graphene nanosheets thermoelectric nanocomposite. Synth. Met. 2012, 161, 2688–2692.

    Article  Google Scholar 

  51. Xia, J.; Masaki, N.; Jiang, K.; Yanagida, S. The influence of doping ions on poly(3,4-ethylenedioxythiophene) as a counter electrode of a dye-sensitized solar cell. J. Mater. Chem. 2007, 17, 2845–2850.

    Article  Google Scholar 

  52. Jiang, Q. W.; Li, G. R.; Gao, X. P. Highly ordered TiN nanotube arrays as counter electrodes for dye-sensitized solar cells. Chem. Commun. 2009, 6720–6722.

    Google Scholar 

  53. Hong, W.; Xu, Y.; Lu, G.; Li, C.; Shi, G. Transparent graphene/PEDOT-PSS composite films as counter electrodes of dye-sensitized solar cells. Electrochem. Commun. 2008, 10, 1555–1558.

    Article  Google Scholar 

  54. Lee, K. S.; Lee, Y.; Lee, J. Y.; Ahn, J.-H.; Park, J. H. Flexible and platinum-free dye-sensitized solar cells with conducting-polymer-coated graphene counter electrodes. ChemSusChem 2012, 5, 379–382.

    Article  Google Scholar 

  55. Wang, G.; Zhuo, S.; Xing, W. Graphene/polyaniline nanocomposite as counter electrode of dye-sensitized solar cells. Mater. Lett. 2012, 69, 27–29.

    Article  Google Scholar 

  56. Lee, K. S.; Lee, H. K.; Wang, D. H.; Park, N.-G.; Lee, J. Y.; Park, O. O.; Park, J. H. Dye-sensitized solar cells with Pt- and TCO-free counter electrodes. Chem. Commun. 2010, 46, 4505–4507.

    Article  Google Scholar 

  57. Crispin, X.; Jakobsson, F. L. E.; Crispin, A.; Grim, P. C. M.; Andersson, P.; Volodin, A.; van Haesendonck, C.; Van der Auweraer, M.; Salaneck, W. R.; Berggren, M. The origin of the high conductivity of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) plastic electrodes. Chem. Mater. 2006, 18, 4354–4360.

    Article  Google Scholar 

  58. Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Electric field effect in atomically thin carbon films. Science 2004, 306, 666–669.

    Article  Google Scholar 

  59. Li, X.; Zhang, G.; Bai, X.; Sun, X.; Wang, X.; Wang, E.; Dai, H. Highly conducting graphene sheets and Langmuir-Blodgett films. Nat. Nanotechnol. 2008, 3, 538–542.

    Article  Google Scholar 

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Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul, 120-749, Republic of Korea

    Dohyuk Yoo & Jung Hyun Kim

  2. Electronic Materials Division, R&D Center, Dongjin Semichem Co., Ltd., 625-3 Yodang-Ri, Yanggam-Myeon, Hwaseong-Gun, Gyeonggi-Do, Republic of Korea

    Jeonghun Kim

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  1. Dohyuk Yoo
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Correspondence to Jung Hyun Kim.

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Yoo, D., Kim, J. & Kim, J.H. Direct synthesis of highly conductive poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS)/graphene composites and their applications in energy harvesting systems. Nano Res. 7, 717–730 (2014). https://doi.org/10.1007/s12274-014-0433-z

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