Effect of Plasticizers on Ion Transport Properties of PEO+NH4PF6 Polymer Electrolyte System – Dielectric Studies

Abstract:

Dielectric properties of proton conducting polymer electrolyte system, containing polyethylene oxide (PEO) as host polymer and ammonium hexfluorophosphate (NH₄PF₆) as complexing salt plasticized with EC and EC:PC, are investigated. The free standing films of thickness ~ 200 - 300µm are synthesized by solution casting technique. The electrical conductivity studies show that plasticization of the polymer electrolyte results into an enhancement in its conductivity by about two orders of magnitude. The maximum room temperature bulk conductivity is obtained to be ~ 10^-5 S/cm for the plasticized polymer electrolyte. To understand the ion transport mechanism, different frequency dependent parameters are measured like dielectric permittivity, loss tangent and AC conductivity. The ionic transference number of the prepared systems is found to be close to unity which shows ion dominant charge transport in the electrolyte system. The conductivity of the polymer electrolyte has been found to be very sensitive to the relative humidity, which makes it a good candidate for its application for humidity sensor.

• Periodical: Applied Mechanics and Materials (Volumes 110-116)
• Pages: 278-284
• DOI: https://doi.org/10.4028/www.scientific.net/AMM.110-116.278
• Online since: October 2011
• Authors: Kuldeep Mishra, D.K. Rai
• Keywords: Dielectric Studies, Polymer Electrolyte, Proton Conduction

References

[1] J. R. Mac Callum and C. A. Vincent, Polymer Electrolyte Review-I, Elsevier (Eds. ), London, (1987).

[2] Fiona M. Gray, Solid Polymer Electrolytes, CVH, New York, (1991).

[3] J. C. Lasseques, in: P. Colomban (Ed. ), Proton Conductors: Solid Membranes and gel – Materials and Devices, Cambridge University Press, Cambridge, (1992).

[4] Yongku Kang, Junkyoung Lee, Joung-in Lee and Changjin Lee, Ionic conductivity and electrochemical properties of cross-linked solid polymer electrolyte using star-shaped siloxane acrylate, Journal of Power Sources, vol. 165, 2007, pp.92-96.

DOI: 10.1016/j.jpowsour.2006.11.019

[5] Yongku Kang, Wonsil Lee, Dong Hack Suh and Changjin Lee, Solid polymer electrolytes based on cross-linked polysiloxane-g-oligo(ethylene oxide): ionic conductivity and electrochemical properties, Journal of Power Sources, vol. 119-121, 2003, pp.448-453.

DOI: 10.1016/s0378-7753(03)00189-7

[6] M.F.Z. Kadir, S.R. Majid and A.K. Arof, Plasticized chitosan–PVA blend polymer electrolyte based proton battery, Electrochemica Acta, vol. 55, 2010, pp.1475-1482.

DOI: 10.1016/j.electacta.2009.05.011

[7] Takeo Hamaya, Satoko Inoue, Jinli Qiao and Tatsuhiro Okada, Novel proton-conducting polymer electrolyte membranes based on PVA/PAMPS/PEG400 blend, Journal of Power Sources, vol. 156, 2006, pp.311-314.

DOI: 10.1016/j.jpowsour.2005.07.002

[8] Isabella Nicotera, Luigi Coppola, Cesare Oliviero, Marco Castriota and Enzo Cazzanelli, Investigation of ionic conduction and mechanical properties of PMMA–PVdF blend-based polymer electrolytes, Solid State Ionics, vol. 177, 2006, pp.581-588.

DOI: 10.1016/j.ssi.2005.12.028

[9] F. Croce, G. B. Appetecchi, L. Persi and B. Scrosati, Nanocomposite polymer electrolytes for lithium batteries, Nature, vol. 394, 1999, pp.456-458.

DOI: 10.1038/28818

[10] G.P. Pandey, S.A. Hashmi and R.C. Agarwal, Hot-press synthesized polyethylene oxide based proton conducting nanocomposite polymer electrolyte dispersed with SiO2 nanoparticles, Solid State Ionics, vol. 179, 2008, pp.543-549.

DOI: 10.1016/j.ssi.2008.04.006

[11] G.P. Pandey, S.A. Hashmi and R.C. Agarwal, Experimental investigations on a proton conducting nanocomposite polymer electrolyte, J. Phys. D: Apply. Phys., vol. 41, 2008, 055409.

DOI: 10.1088/0022-3727/41/5/055409

[12] M.S. Michael, M.M.E. Jacob, S.R.S. Prabhaharan and S. Radhakrishna, Enhanced lithium ion transport in PEO-based solid polymer electrolytes employing a novel class of plasticizers, Solid State Ionics, vol. 98, 1997, pp.167-174.

DOI: 10.1016/s0167-2738(97)00117-3

[13] Dillip K. Pradhan, R.N.P. Choudhary and B.K. Samantaray, Studies of dielectric and electrical properties of plasticized polymer nanocomposite electrolytes, Materials Chemistry and Physics, vol. 115, 2009, pp.557-561.

DOI: 10.1016/j.matchemphys.2009.01.008

[14] Xinming Qian, Ningyu Gu, Zhiliang Cheng, Xiurong Yang, Erkang Wang and Shaojun Dong, Plasticizer effect on the ionic conductivity of PEO-based polymer electrolyte, Materials Chemistry and Physics, vol. 74, 2002, pp.98-103.

DOI: 10.1016/s0254-0584(01)00408-4

[15] L.S. Ng and A.A. Mohamad, Effect of temperature on the performance of proton batteries based on chitosan–NH4NO3–EC membrane, Journal of Membrane Science, vol. 325, 2008, pp.653-657.

DOI: 10.1016/j.memsci.2008.08.029

[16] Yawen Li, Jinwei Wang, Jinwei Tang, Yupeng Liu and Yedong He, Conductive performances of solid polymer electrolyte films based on PVB/LiClO4 plasticized by PEG200, Journal of Power Sources, vol. 187, 2009, pp.305-311.

DOI: 10.1016/j.jpowsour.2008.11.126

[17] Manoj Kumar and S.S. Sekhon, Role of plasticizer's dielectric constant on conductivity modification of PEO–NH4F polymer electrolytes, European Polymer Journal, vol. 38, 2002, pp.1297-1304.

DOI: 10.1016/s0014-3057(01)00310-x

[18] D.F. Shriver, B.L. Papke, M.A. Ratner, R. Dupon, T. Wong, M. Brodwin, Structure and ion transport in polymer-salt complexes, Solid State Ionics, vol. 5, 1981, pp.83-88.

DOI: 10.1016/0167-2738(81)90199-5

[19] ", Solid State Ionics, vol. 17, 1985, pp.101-106.

[20] C.S. Ramya, S. Selvasekarapandian, G. Hirankumar, T. Savitha and P.C. Angelo, Investigation on dielectric relaxations of PVP–NH4SCN polymer electrolyte, Journal of Non- Crystalline Solids, vol. 354, 2008, pp.1494-1502.

DOI: 10.1016/j.jnoncrysol.2007.08.038

[21] N.K. Karan, D.K. Pradhan, R. Thomas, B. Natesan and R.S. Katiyar, Solid polymer electrolytes based on polyethylene oxide and lithium trifluoro- methane sulfonate (PEO–LiCF3SO3): Ionic conductivity and dielectric relaxation, Solid State Ionics, vol. 179, 2008, pp.689-696.

DOI: 10.1016/j.ssi.2008.04.034