Room temperature solid-state synthesis of a conductive polymer for applications in stable I2-free dye-sensitized solar cells

Byeonggwan Kim, Jong Kwan Koh, Jeonghun Kim, Won Seok Chi, Jong Hak Kim, Eunkyoung Kim

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

A solid-state polymerizable monomer, 2,5-dibromo-3,4- propylenedioxythiophene (DBProDOT), was synthesized at 25°C to produce a conducting polymer, poly(3,4-propylenedioxythiophene) (PProDOT). Crystallographic studies revealed a short interplane distance between DBProDOT molecules, which was responsible for polymerization at low temperature with a lower activation energy and higher exothermic reaction than 2,5-dibromo-3,4- ethylenedioxythiophene (DBEDOT) or its derivatives. Upon solid-state polymerization (SSP) of DBProDOT at 25°C, PProDOT was obtained in a self-doped state with tribromide ions and an electrical conductivity of 0.05 S cm-1, which is considerably higher than that of chemically- polymerized PProDOT (2×10-6 S cm-1). Solid-state 13C NMR spectroscopy and DFT calculations revealed polarons in PProDOT and a strong perturbation of carbon nuclei in thiophenes as a result of paramagnetic broadening. DBProDOT molecules deeply penetrated and polymerized to fill nanocrystalline TiO2 pores with PProDOT, which functioned as a hole-transporting material (HTM) for I2-free solid-state dye-sensitized solar cells (ssDSSCs). With the introduction of an organized mesoporous TiO2 (OM-TiO2) layer, the energy conversion efficiency reached 3.5 % at 100 mW cm-2, which was quite stable up to at least 1500 h. The cell performance and stability was attributed to the high stability of PProDOT, with the high conductivity and improved interfacial contact of the electrode/HTM resulting in reduced interfacial resistance and enhanced electron lifetime.

Original languageEnglish
Pages (from-to)2173-2180
Number of pages8
JournalChemSusChem
Volume5
Issue number11
DOIs
Publication statusPublished - 2012 Nov 1

Fingerprint

dye
Polymers
polymer
polymerization
temperature
Polymerization
Polarons
Temperature
Molecules
Exothermic reactions
Conducting polymers
Thiophene
Thiophenes
Energy conversion
Discrete Fourier transforms
activation energy
Nuclear magnetic resonance spectroscopy
Conversion efficiency
electrical conductivity
nuclear magnetic resonance

All Science Journal Classification (ASJC) codes

  • Environmental Chemistry
  • Chemical Engineering(all)
  • Materials Science(all)
  • Energy(all)

Cite this

Kim, Byeonggwan ; Koh, Jong Kwan ; Kim, Jeonghun ; Chi, Won Seok ; Kim, Jong Hak ; Kim, Eunkyoung. / Room temperature solid-state synthesis of a conductive polymer for applications in stable I2-free dye-sensitized solar cells. In: ChemSusChem. 2012 ; Vol. 5, No. 11. pp. 2173-2180.
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abstract = "A solid-state polymerizable monomer, 2,5-dibromo-3,4- propylenedioxythiophene (DBProDOT), was synthesized at 25°C to produce a conducting polymer, poly(3,4-propylenedioxythiophene) (PProDOT). Crystallographic studies revealed a short interplane distance between DBProDOT molecules, which was responsible for polymerization at low temperature with a lower activation energy and higher exothermic reaction than 2,5-dibromo-3,4- ethylenedioxythiophene (DBEDOT) or its derivatives. Upon solid-state polymerization (SSP) of DBProDOT at 25°C, PProDOT was obtained in a self-doped state with tribromide ions and an electrical conductivity of 0.05 S cm-1, which is considerably higher than that of chemically- polymerized PProDOT (2×10-6 S cm-1). Solid-state 13C NMR spectroscopy and DFT calculations revealed polarons in PProDOT and a strong perturbation of carbon nuclei in thiophenes as a result of paramagnetic broadening. DBProDOT molecules deeply penetrated and polymerized to fill nanocrystalline TiO2 pores with PProDOT, which functioned as a hole-transporting material (HTM) for I2-free solid-state dye-sensitized solar cells (ssDSSCs). With the introduction of an organized mesoporous TiO2 (OM-TiO2) layer, the energy conversion efficiency reached 3.5 {\%} at 100 mW cm-2, which was quite stable up to at least 1500 h. The cell performance and stability was attributed to the high stability of PProDOT, with the high conductivity and improved interfacial contact of the electrode/HTM resulting in reduced interfacial resistance and enhanced electron lifetime.",
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Room temperature solid-state synthesis of a conductive polymer for applications in stable I2-free dye-sensitized solar cells. / Kim, Byeonggwan; Koh, Jong Kwan; Kim, Jeonghun; Chi, Won Seok; Kim, Jong Hak; Kim, Eunkyoung.

In: ChemSusChem, Vol. 5, No. 11, 01.11.2012, p. 2173-2180.

Research output: Contribution to journalArticle

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