Skip to main content
SpringerLink
Log in

Microgravimetric study of electrochemical properties of PEDOT/WO3 composite films in diluted sulfuric acid

  • Original Paper
  • Published:
Journal of Solid State Electrochemistry Aims and scope Submit manuscript

Abstract

Poly-3,4-ethylenedioxythiophene composite films with tungsten oxide (PEDOT/WO3) were obtained by potentiodynamic deposition of tungsten oxide from acidic metastable solution of isopolytungstates into poly-3,4-ethylenedioxythiophene film, pre-deposited on an Au-quartz crystal. The electrochemical deposition of tungsten oxide into poly-3,4-ethylenedioxythiophene was investigated by electrochemical quartz microgravimetry (EQCM), the masses of PEDOT and tungsten oxide deposits were estimated. The electrochemical behavior of PEDOT/WO3 composite films with different masses of deposited tungsten oxide was studied by cyclic voltammetry and EQCM in the 0.5 M sulfuric acid electrolyte. The change of the fraction of tungsten oxide in the PEDOT/WO3 composite film results in the change of the slope of the Δf–E dependency in the potential region, corresponding to WVI/WV redox process. It is due to an oppositely directed mass transport (anion and cation) during the redox process in the composite film. The average molar mass of transferred species involved in the redox process in tungsten oxide was estimated to be 26 ± 4 g mol−1. It was shown that the fraction of electrochemically active tungsten oxide deposit is dependent on its mass in the composite, with increase of the mass of tungsten oxide in PEDOT/WO3, the fraction of electroactive tungsten oxide WO3 decreases due to decrease in its active area.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Lokhande VC, Lokhande AC, Lokhande CD, Kim JH, Ji T (2016) Supercapacitive composite metal oxide electrodes formed with carbon, metal oxides and conducting polymers. J Alloys Compd 685:381–403

    Article  Google Scholar 

  2. Meng Q, Cai K, Chen Y, Chen L (2017) Research progress on conducting polymer-based supercapacitor electrode materials. Nanomater Energy 36:268–285

    Article  CAS  Google Scholar 

  3. Holze R (2017) Metal oxide/conducting polymer hybrids for application in supercapacitors. In: Dubal DP, Gomez-Romero P (eds) Metal oxides in supercapacitors. Elsevier, Amsterdam, pp 219–245

    Chapter  Google Scholar 

  4. Granqvist CG, Avendaño E, Azens A (2003) Electrochromic coatings and devices: survey of some recent advances. Thin Solid Films 442:201–211

    Article  CAS  Google Scholar 

  5. Somani PR, Radhakrishnan S (2002) Electrochromic materials and devices: present and future. Mater Chem Phys 77:117–133

    Article  Google Scholar 

  6. Monk PMS, Mortimer RJ, Rosseinsky DR (2007) Electrochromism and electrochromic devices. Cambridge University Press, Cambridge

    Book  Google Scholar 

  7. Darmawi S, Burkhardt S, Leichtweiss T, Weber DA, Wenzel S, Janek J, Elm MT, Klar PJ (2015) Correlation of electrochromic properties and oxidation states in nanocrystalline tungsten trioxide. Phys Chem Chem Phys 17(24):15903–15911

    Article  CAS  Google Scholar 

  8. Chen KY, Tseung A (1996) Effect of nafion dispersion on the stability of Pt/WO3 electrodes. J Electrochem Soc 143:2703–2707

    Article  CAS  Google Scholar 

  9. Komaba S, Kumagai N, Kato K, Yashiro H (2000) Hydrothermal synthesis of hexagonal tungsten trioxide from Li2WO4 solution and electrochemical lithium intercalation into the oxide. Solid State Ionics 135:193–197

    Article  CAS  Google Scholar 

  10. Freedman ML (1959) The tungstic acids. J Am Chem Soc 81:3834–3839

    Article  CAS  Google Scholar 

  11. Reichman B, Bard AJ (1979) The electrochromic process at WO3 electrodes prepared by vacuum evaporation and anodic oxidation of W. J Electrochem Soc 126:583–591

    Article  CAS  Google Scholar 

  12. Kulesza PJ, Faulkner LR (1989) Electrocatalytic properties of bifunctional Pt/W(VI,V) oxide microstructures electrodeposited on carbon substrates. J Electroanal Chem 259:81–98

    Article  CAS  Google Scholar 

  13. Ling H, Liu L, Lee PS, Mandler D, Lu X (2015) Layer-by-layer assembly of PEDOT:PSS and WO3 nanoparticles: enhanced electrochromic coloration efficiency and mechanism studies by scanning electrochemical microscopy. Electrochim Acta 174:57–65

    Article  CAS  Google Scholar 

  14. Ling H, Lu J, Phua S, Liu H, Liu L, Huang Y, Mandler D, Lee PS, Lu X (2014) One-pot sequential electrochemical deposition of multilayer poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonic acid)/tungsten trioxide hybrid films and their enhanced electrochromic properties. J Mater Chem A 2:2708–2717

    Article  CAS  Google Scholar 

  15. Wang F, Zhan X, Cheng Z, Wang Z, Wang Q, Xu K, Safdar M, He J (2014) Tungsten oxide@polypyrrole core-shell nanowire arrays as novel negative electrodes for asymmetric supercapacitors. Small 11:749–755

    Article  Google Scholar 

  16. Asim N, Syuhami MF, Badiei M, Ambar Yarmo M (2014) WO3 modification by synthesis of nanocomposites. APCBEE Procedia 9:175–180

    Article  CAS  Google Scholar 

  17. Bernard MC, Hugot-Le Goff A, Zeng W (1998) Elaboration and study of a PANI/PAMPS/WO3 all solid-state electrochromic device. Electrochim Acta 44:781–796

    Article  CAS  Google Scholar 

  18. Li B, Li X, Li W, Wang Y, Uchaker E, Pei Y, Cao X, Li S, Huang B, Cao G (2016) Mesoporous tungsten trioxide polyaniline nanocomposite as an anode material for high-performance lithium-ion batteries. Chem Nano Mat 2:281–289

    CAS  Google Scholar 

  19. Szymanska D, Rutkowska IA, Adamczyk L, Zoladek S, Kulesza PJ (2010) Effective charge propagation and storage in hybrid films of tungsten oxide and poly(3,4-ethylenedioxythiophene). J Solid State Electrochem 14:2049–2056

    Article  CAS  Google Scholar 

  20. Plieth W, Bund A, Rammelt U, Neudeck S, Duc LM (2006) The role of ion and solvent transport during the redox process of conducting polymers. Electrochim Acta 51:2366–2372

    Article  CAS  Google Scholar 

  21. Niu L, Kvarnström C, Ivaska A (2004) Mixed ion transfer in redox processes of poly(3,4-ethylenedioxythiophene). J Electroanal Chem 569:151–160

    Article  CAS  Google Scholar 

  22. Hillman AR, Daisley SJ, Bruckenstein S (2007) Kinetics and mechanism of the electrochemical p-doping of PEDOT. Electrochem Commun 9:1316–1322

    Article  CAS  Google Scholar 

  23. Babinec SJ (1992) A quartz crystal microbalance analysis of ion insertion into WO3. Sol Energy Mater Sol Cells 25:269–291

    Article  CAS  Google Scholar 

  24. Martín AJ, Maffiotte C, Chaparro AM (2015) Mechanisms for the growth of thin films of WO3 and bronzes from suspensions of WO3 nanoparticles. ECS Trans 64(29):43–56

    Article  Google Scholar 

  25. Bueno PR, Faria RC, Avellaneda CO, Leite ER, Bulhões LOS (2003) Li+ insertion into pure and doped amorphous WO3 films. Correlations between coloration kinetics, charge and mass accumulation. Solid State Ionics 158:415–426

    Article  CAS  Google Scholar 

  26. Kim DJ, Pyun SI, Choi YM (1998) A study on the hydrogen intercalation into rf-magnetron sputtered amorphous WO3 film using cyclic voltammetry combined with electrochemical quartz crystal microbalance technique. Solid State Ionics 109:81–87

    Article  CAS  Google Scholar 

  27. Ohtsuka T, Wakabayashi T, Einaga H (1994) Electrochemical quartz crystal microbalance study of polypyrrole and tungstate polyanion composite films. J Electroanal Chem 377:107–114

    Article  CAS  Google Scholar 

  28. Zhuzhelskii DV, Tolstopjatova EG, Eliseeva SN, Ivanov AV, Miao S, Kondratiev VV (2019) Electrochemical properties of PEDOT/WO3 composite films for high performance supercapacitor application. Electrochim Acta 299:182–190

    Article  CAS  Google Scholar 

  29. Sauerbrey G (1959) Verwendung von Schwingquarzen zur Wägung dünner Schichten und zur Mikrowägung. Z Phys 155:206–222

    Article  CAS  Google Scholar 

  30. Nizhegorodova AO, Eliseeva SN, Tolstopjatova EG, Lang GG, Zalka D, Ujvari M, Kondratiev VV (2018) EQCM study of redox properties of PEDOT/MnO2 composite films in aqueous electrolytes. J Solid State Electrochem 22:2357–2366

    Article  CAS  Google Scholar 

  31. Tolstopjatova EG, Eliseeva SN, Nizhegorodova AO, Kondratiev VV (2015) Electrochemical properties of composite electrodes, prepared by spontaneous deposition of manganese oxide into poly-3,4-ethylendioxythiophene. Electrochim Acta 173:40–49

    Article  CAS  Google Scholar 

  32. QCM200 (2004) Operation and service manual. Stanford Research Systems, Inc

  33. Bobacka J, Lewenstam A, Ivaska A (2000) Electrochemical impedance spectroscopy of oxidized poly(3,4-ethylenedioxythiophene) film electrodes in aqueous solutions. J Electroanal Chem 489:17–27

    Article  CAS  Google Scholar 

  34. Kondratiev VV, Pogulaichenko NA, Tolstopjatova EG, Malev VV (2011) Hydrogen peroxide electroreduction on composite PEDOT films with included gold nanoparticles. J Solid State Electrochem 15(11–12):2383–2393

    Article  CAS  Google Scholar 

  35. Eliseeva SN, Malev VV, Kondrat’ev VV (2009) Electrochemical properties of composite films based on poly-3,4-ethylenedioxythiophene with inclusions of metallic palladium. Russ J Electrochem 45:1045–1051

    Article  CAS  Google Scholar 

  36. Bund A, Neudeck S (2004) Effect of the solvent and the anion on the doping/dedoping behavior of poly(3,4-ethylenedioxythiophene) films studied with the electrochemical quartz microbalance. J Phys Chem B 108:17845–17850

    Article  CAS  Google Scholar 

  37. Zhuzhel’skii DV, Yalda KD, Spiridonov VN, Apraksin RV, Kondrat’ev VV (2018) Synthesis and special features of electrochemical behavior of tungsten oxide deposited on various substrates. Russ J Gen Chem 88:520–527

    Article  Google Scholar 

  38. Pugolovkin LV, Vassiliev SY, Borzenko MI, Laurinavichyute VK, Tsirlina GA (2013) Speciation in strongly acidic metastable solutions of oxotungstate(VI) compounds. Russ Chem Bull 62:1317–1322

    Article  CAS  Google Scholar 

  39. Agrisuelas J, Gabrielli C, García-Jareño JJ, Perrot H, Sel O, Vicente F (2015) Electrochemically induced free solvent transfer in thin poly(3,4- ethylenedioxythiophene) films. Electrochim Acta 164:21–30

    Article  CAS  Google Scholar 

  40. Jiang H, Hong JJ, Wu X, Surta TW, Qi Y, Dong S, Li Z, Leonard DP, Holoubek JJ, Wong JC, Razink JJ, Zhang X, Ji X (2018) Insights on the proton insertion mechanism in the electrode of hexagonal tungsten oxide hydrate. J Am Chem Soc 140(37):11556–11559

    Article  CAS  Google Scholar 

  41. Bóbics L, Sziráki L, Láng GG (2008) The impedance related to the electrochemical hydrogen insertion into WO3 films – on the applicability of the diffusion-trapping model. Electrochem Commun 10:283–287

    Article  Google Scholar 

Download references

Funding

This work was supported by the Saint-Petersburg State University (grant no. 26455158) and Russian Foundation for Basic Research (grant no. 19-03-00593).

Author information

Authors and Affiliations

  1. Saint Petersburg State University, Institute of Chemistry, 7/9 Universitetskaya nab., Saint Petersburg, Russia, 199034

    D. V. Zhuzhelskii, E. G. Tolstopjatova, A. I. Volkov, S. N. Eliseeva & V. V. Kondratiev

Authors
  1. D. V. Zhuzhelskii
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. E. G. Tolstopjatova
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. A. I. Volkov
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. S. N. Eliseeva
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. V. V. Kondratiev
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to V. V. Kondratiev.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhuzhelskii, D.V., Tolstopjatova, E.G., Volkov, A.I. et al. Microgravimetric study of electrochemical properties of PEDOT/WO3 composite films in diluted sulfuric acid. J Solid State Electrochem 23, 3275–3285 (2019). https://doi.org/10.1007/s10008-019-04432-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10008-019-04432-0

Keywords

Search

Navigation