Skip to main content
SpringerLink
Log in

Preparation and characterization of chitosan-based nanocomposite hybrid polymer electrolyte membranes for fuel cell application

  • Original Papers
  • Published:
Ionics Aims and scope Submit manuscript

Abstract

The aim of the work was to synthesize nanocomposite membranes based on sulfonated chitosan and PEO blends containing sulfonated silica dioxide (s-SiO2) nanoparticles and investigated their morphological, structural, mechanical, and thermal properties. The electrolytes were characterized by SEM, FTIR, XRD, TG analysis, and water contact angle. FTIR analysis confirmed the presence of chitosan, PEO, SiO2, and sulfonic acid groups through the chitosan matrix in which the components used had good compatibility. The mechanical and thermal studies emphasized that strong interactions occurred between sulfonated chitosan, PEO, and s-SiO2. Blending sulfonated chitosan with PEO and the addition of s-SiO2 nanoparticles enhanced the hydrophilic property of chitosan membranes. The s-chitosan /PEO-based nanocomposites containing 7.5 wt% of s-SiO2 nanoparticles showed the remarkable improvements in ultimate tensile strength values and an increase in conductivity compared to the chitosan/PEO with s-SiO2 membranes in the order of 10−2 S/cm at room temperature.

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
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11

Similar content being viewed by others

Abbreviations

σ :

Conductivity

σ 0 :

Pre-exponential factor

E a :

Activation energy

k :

Boltzmann constant

t :

Thickness of the prepared polymer electrolyte film

A :

Area of the prepared polymer electrolyte film

R b :

Bulk resistance of the electrolyte film

μ:

Micro

θ :

Theta

λ :

Lambda

°C:

Degree Celsius

Å:

Angstrom

K:

Kelvin

%T:

Percentage of transmittance

References

  1. Dashtimoghadam E, Sadrabadi MMH, Moaddel M (2010) Structural modification of chitosan biopolymer as a novel polyelectrolyte membrane for green power generation. Polym Adv Technol 21:726–734

    Article  CAS  Google Scholar 

  2. Logan B (2005) Generating electricity from wastewater treatment. Water Environ Res 77:211

    CAS  PubMed  Google Scholar 

  3. Ye H, Huang J, Xu JJ, Kodiweera NKAC, Jayakody JRP, Greenbaum SG (2008) New membranes based on ionic liquids for PEM fuel cells at elevated temperatures. J Power Sources 178:651–660

    Article  CAS  Google Scholar 

  4. Meenakshi S, Bhat SD, Sahu AK, Alwin S, Sridhar P, Pichumani S (2012) Natural and synthetic solid polymer hybrid dual network membranes as electrolytes for direct methanol fuel cells. J Solid State Electrochem 16:1709–1721

    Article  CAS  Google Scholar 

  5. Shirdast A, Sharif A, Abdollahi M (2016) Effect of the incorporation of sulfonated chitosan/sulfonated graphene oxide on the proton conductivity of chitosan membranes. J Power Sources 306:541–551

    Article  CAS  Google Scholar 

  6. Mishra AK, Chaattopadhyay S, Rajamohanan PR, Nando GB (2011) Effect of tethering on the structure-property relationship of TPU-dual modified laponite clay nanocomposites prepared by ex-situ and in-situ techniques. Polymer 52:1071–1083

    Article  CAS  Google Scholar 

  7. Seo WJ, Sung YT, Han SH, Kim YH, Ryu OH, Lee HS, Kim WN (2006) Synthesis and properties of polyurethane/clay nanocomposite by clay modified with polymeric methane diisocyanate. J Appl Polym Sci 101:2879–2883

    Article  CAS  Google Scholar 

  8. Lin HL, Yen SH, Yu TL, Chen LC (2009) Silicate and zirconium phosphate modified Nafion/PTFE composite membranes for high temperature PEMFC. J Polym Res 16:519–527

    Article  CAS  Google Scholar 

  9. Safronova EY, Yaroslavtsev AB (2012) Nafion-type membranes doped with silica nanoparticles with modified surface. Solid State Ionics 221:6–10

    Article  CAS  Google Scholar 

  10. Yin Y, Xua T, Shen X, Wu H, Jiang Z (2014) Fabrication of chitosan/zwitterion functionalized titania–silica hybrid membranes with improved proton conductivity. J Membr Sci 469:355–363

    Article  CAS  Google Scholar 

  11. Nagarale RK, Bhattacharya PK (2015) New insights into proton exchange membranes. Dir Ther 15:98–107

    Google Scholar 

  12. Zou L, Roddecha S, Anthamatten M (2009) Morphology, hydration, and proton transport in novel sulfonated polyimide–silica nanocomposites. Polymer 50:3136–3144

    Article  CAS  Google Scholar 

  13. Majid SR, Arof AK (2007) Electrical behavior of proton-conducting chitosan-phosphoric acid-based electrolytes. Physica B 390:209–215

    Article  CAS  Google Scholar 

  14. Gumuoglu T, Ari GA, Deligoz H (2011) Investigation of salt addition and acid treatment effects on the transport properties of ionically cross-linked polyelectrolyte complex membranes based on chitosan and polyacrylic acid. J Membr Sci 376:25–34

    Article  Google Scholar 

  15. Wan Y, Creber KAM, Pepply B, Bui VT (2003) Ionic conductivity of chitosan membranes. Polymer 44:1057–1065

    Article  CAS  Google Scholar 

  16. Vincent CA (1995) Ion transport in polymer electrolytes. Electrochim Acta 40:2035–2040

    Article  CAS  Google Scholar 

  17. Johan MR, Ting LM (2011) Structural, thermal and electrical properties of nano manganese-composite polymer electrolytes. Int J Electrochem Sci 6:4737–4748

    CAS  Google Scholar 

  18. Pradeepa P, Prabhu MR (2016) Enhancement of the electrochemical properties with the effect of alkali metal systems on PEO/PVdF-HFP complex polymer electrolytes. Ionics 22:827–839

    Article  Google Scholar 

  19. Prabakaran K, Mohanty S, Nayak SK (2015) Chemically exfoliated nanosilicate platelet hybridized polymer electrolytes for solid state dye sensitized solar cells. New J Chem 39:8602–8613

    Article  CAS  Google Scholar 

  20. Zivanovic S, Li J, Davidson PM, Kit K (2007) Physical, mechanical, and antibacterial properties of chitosan/PEO blend films. Biomacromolecules 8:1505–1510

    Article  CAS  PubMed  Google Scholar 

  21. Pakravan M, Heuzey MC, Ajji A (2011) A fundamental study of chitosan/PEO electrospinning. Polymer 52:4813–4824

    Article  CAS  Google Scholar 

  22. Noor MM, Careem MA, Majid SR, Arof AK (2011) Characterisation of plasticised PVDF–HFP polymer electrolytes. Mater Res Innov 15:S157–s160

    Article  Google Scholar 

  23. Kowsari E, Zare A, Ansari V (2015) Phosphoric acid-doped ionic liquid-functionalized graphene oxide/sulfonated polyimide composites as proton exchange membrane. Int J Hydrog Energy 40:13964–13978

    Article  CAS  Google Scholar 

  24. Palani PB, Abidin KS, Sivakumar M, Wang FM, Rajashabala S, Velraj G (2014) Improvement of proton conductivity in nanocomposite polyvinyl alcohol (PVA)/chitosan (CS) blend membranes. RSC Adv 4:61781–61789

    Article  CAS  Google Scholar 

  25. Smith B, Sridhar S, Khan A (2005) Solid polymer electrolyte membranes for fuel cell applications—a review. J Membr Sci 259:10–26

    Article  Google Scholar 

  26. Tsai HS, Wang YZ, Lin JJ, Lien WF (2010) Preparation and properties of sulfo propyl chitosan derivatives with various sulfonation degree. J Appl Polym Sci 116:1686–1693

    Article  CAS  Google Scholar 

  27. Kumar GG, Senthilarasu S, Lee ON, Kim P, Nahm KS, Lee SH (2008) Synthesis and characterization of aligned SiO2 nanosphere arrays: spray method. Synth Met 158:684–687

    Article  CAS  Google Scholar 

  28. Park YS, Yamazakiy Y (2006) Low water/methanol permeable Nafion/CHP organic–inorganic composite membrane with high crystallinity. Eur Secur 42:375–387

    CAS  Google Scholar 

  29. Kumar GG, Nahm KS, Elizabeth RN (2008) Electro chemical properties of porous PVdF-HFP membranes prepared with different nonsolvents. J Membr Sci 325:117–124

    Article  CAS  Google Scholar 

  30. Selvasekarapandian S, Baskaran R, Hema M (2005) Complex AC impedance, transference number and vibrational spectroscopy studies of proton conducting PVAc–NH 4 SCN polymer electrolytes. Physica B 357:412–419

    Article  CAS  Google Scholar 

  31. Smitha B, Devi DA, Sridhar S (2008) Proton-conducting composite membranes of chitosan and sulfonated polysulfone for fuel cell application. Int J Hydrog Energy 33:4138–4146

    Article  CAS  Google Scholar 

  32. Pereira AGB, Paulino AT, Nakamura CV, Britta EA, Rubira AF, Muniz EC (2011) Effect of starch type on miscibility in poly (ethylene oxide)(PEO)/starch blends and cytotoxicity assays. Mater Sci Eng C 31:443–451

    Article  CAS  Google Scholar 

  33. Tseng CY, Ye YS, kao KY, Joseph J, Shen WC, Rick J, Hwang BJ (2011) Interpenetrating network-forming sulfonated poly (vinyl alcohol) proton exchange membranes for direct methanol fuel cell applications. J Hydrog Energy 36:11936–11945

    Article  CAS  Google Scholar 

  34. Wu TM, Wu CY (2006) Biodegradable poly (lactic acid)/chitosan-modified montmorillonite nanocomposites: preparation and characterization. Polym Degrad Stab 91:2198–2204

    Article  CAS  Google Scholar 

  35. Song R, Xue R, He LH, Liu Y, Xiao Q (2008) The structure and properties of chitosan/polyethylene glycol/silica ternary hybrid organic-inorganic films. Chin J Polym Sci 26:621–630

    Article  CAS  Google Scholar 

  36. Kumar GG, Kim AR, Nahm KS, Elizabeth R (2009) Nafion membranes modified with silica sulfuric acid for the elevated temperature and lower humidity operation of PEMFC. Int J Hydrog Energy 34:9788–9794

    Article  CAS  Google Scholar 

  37. Qu X, Wirsen A, Albertsson AC (2000) Novel pH-sensitive chitosan hydrogels swelling behavior and states of water. Polymer 41:4589–4598

    Article  CAS  Google Scholar 

  38. Sivasankaran A, Sangeetha D (2015) Influence of sulfonated SiO2 in sulfonated polyether ether ketone nanocomposite membrane in microbial fuel cell. Fuel 159:689–696

    Article  CAS  Google Scholar 

  39. Martinova L, Lubasova D (2008) Electrospun chitosan based nanofibers. RJTA 12:72–79

    CAS  Google Scholar 

  40. Pandey GP, Hashmi SA, Agrawal RC (2008) Hot-press synthesized polyethylene oxide based proton conducting nanocomposite polymer electrolyte dispersed with SiO2 nanoparticles. Solid State Ionics 179:543–549

    Article  CAS  Google Scholar 

  41. Du L, Yan X, He G, Wu X, Hu Z, Wang Y (2012) SPEEK proton exchange membranes modified with silica sulfuric acid nanoparticles. Int J Hydrog Energy 37:11853–11861

    Article  CAS  Google Scholar 

  42. Kannan R, Kakade BA, Pillai VK (2008) Polymer electrolyte fuel cells using nafion-based composite membranes with functionalized carbon nanotubes. Angew Chem 120:2653–2656

    Article  Google Scholar 

  43. Lanfredi S, Sara PS, Lebullengu R (2002) Electric conductivity and relaxation in fluoride, fluorophosphate and phosphate glasses: analysis by impedance spectroscopy. Solid State Ionics 146:329–339

    Article  CAS  Google Scholar 

  44. Wan Y, Creber KAM, Peppley B, Bui VT (2006) Chitosan-based electrolyte composite membranes: II. Mechanical properties and ionic conductivity. J Membr Sci 284:331–338

    Article  CAS  Google Scholar 

  45. Rajendran S, Mahalingam T, Kannan R (2000) Experimental investigations on PAN–PEO hybrid polymer electrolytes. Solid State Ionics 130:143–148

    Article  CAS  Google Scholar 

  46. Kim KM, Ryu KS, Kang SG, Chang SH, Chung IJ (2001) The effect of silica addition on the properties of poly ((vinylidene fluoride)-co-hexafluoropropylene)-based polymer electrolytes. Macromol Chem Phys 202:866–872

    Article  CAS  Google Scholar 

  47. Kim JH, Kim SK, Nam K, Kim DW (2012) Composite proton conducting membranes based on Nafion and sulfonated SiO 2 nanoparticles. J Membr Sci 416:696–701

    Article  Google Scholar 

  48. Huang X, Huang D, Ou X, Ding F, Chen Z (2012) Synthesis and properties of side-chain type ion exchange membrane PEEK-g-StSO3Na for bipolar membranes. Appl Surf Sci 258:2312–2318

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Physics, Alagappa University, Karaikudi, 630 003, India

    J. Kalaiselvimary & M. Ramesh Prabhu

  2. Department of Industrial Chemistry, Alagappa University, Karaikudi, 630 003, India

    M. Sundararajan

Authors
  1. J. Kalaiselvimary
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. Sundararajan
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. M. Ramesh Prabhu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to M. Ramesh Prabhu.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kalaiselvimary, J., Sundararajan, M. & Prabhu, M.R. Preparation and characterization of chitosan-based nanocomposite hybrid polymer electrolyte membranes for fuel cell application. Ionics 24, 3555–3571 (2018). https://doi.org/10.1007/s11581-018-2485-7

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11581-018-2485-7

Keywords

Search

Navigation