Solid polymer electrolytes based on chitosan NaCF3SO3 have been prepared by the solution cast technique. X-ray diffraction shows that the crystalline phase of the pure chitosan membrane has been partially disrupted. The fourier transform infrared (FTIR) results reveal the complexation between the chitosan polymer and the sodium triflate (NaTf) salt. The dielectric constant and DC conductivity follow the same trend with NaTf salt concentration. The increase in dielectric constant at different temperatures indicates an increase in DC conductivity. The ion conduction mechanism follows the Arrhenius behavior. The dependence of DC conductivity on both temperature and dielectric constant ( ) is also demonstrated. 1. Introduction Ion conducting polymers are an active area of study in materials research. They are prepared by complexing polymers containing polar groups with alkali metal salts [1]. Being light weight and flexible [2, 3], attempts have been made to use solid polymer electrolytes in solid-state electrochemical devices such as batteries, fuel cells, electrochromic displays, and smart windows [4]. Polymer electrolytes usually contain both crystalline and amorphous phases. It has been reported that the ion conduction takes place primarily in the amorphous phase [5]. Chitosan is a derivative of chitin which can be obtained from crab and shrimp shells. Chitosan is produced from deacetylation of chitin to overcome the solubility limitation of chitin in common solvents [6]. Due to the NH2 and OH functional groups that can serve as conjunction sites, chitosan is a good sorbent with high affinity for transition metal ions [7]. Chitosan has good film forming ability, porous scaffolds, and hydrogels [8]. Ion-conducting polymer electrolytes based on chitosan have also been reported [9–16]. From the fundamental point of view, ionic conduction in polymer electrolytes is still poorly understood. Ion transport is complex and depends on factors such as salt concentration, dielectric constant of host polymer, degree of salt dissociation and ion aggregation, and mobility of polymer chains [17]. Dielectric analysis of ion conducting polymer electrolytes can provide information on ion transport behavior and ionic/molecular interaction in solid polymer electrolytes [18]. This is due to the fact that dielectric constant is both frequency and temperature dependent [19]. Recently Petrowsky and Frech [20, 21] hypothesized that the DC conductivity is not only a function of temperature, but also is dependent on the dielectric constant in organic liquid electrolytes. They have
References
[1]
A. K. Thakur and S. A. Hashmi, “Polymer matrix-filler interaction mechanism for modified ion transport and glass transition temperature in the polymer electrolyte composites,” Solid State Ionics, vol. 181, no. 27-28, pp. 1270–1278, 2010.
[2]
R. N. Mason, L. Hu, D. T. Glatzhofer, and R. Frech, “Infrared spectroscopic and conductivity studies of poly(N-methylpropylenimine)/lithium triflate electrolytes,” Solid State Ionics, vol. 180, no. 40, pp. 1626–1632, 2010.
[3]
R. C. Agrawal, Y. K. Mahipal, and R. Ashrafi, “Materials and ion transport property studies on hot-press casted solid polymer electrolyte membranes: [(1?-?x) PEO: x KIO3],” Solid State Ionics, vol. 192, no. 1, pp. 6–8, 2011.
[4]
H. M. J. C. Pitawala, M. A. K. L. Dissanayake, and V. A. Seneviratne, “Combined effect of Al2O3 nano-fillers and EC plasticizer on ionic conductivity enhancement in the solid polymer electrolyte (PEO)9LiTf,” Solid State Ionics, vol. 178, no. 13-14, pp. 885–888, 2007.
[5]
P.-L. Kuo, W.-J. Liang, and T.-Y. Chen, “Solid polymer electrolytes V: microstructure and ionic conductivity of epoxide-crosslinked polyether networks doped with LiClO4,” Polymer, vol. 44, no. 10, pp. 2957–2964, 2003.
[6]
R. Jayakumar, M. Prabaharan, S. V. Nair, and H. Tamura, “Novel chitin and chitosan nanofibers in biomedical applications,” Biotechnology Advances, vol. 28, no. 1, pp. 142–150, 2010.
[7]
P. Bai, F. Cao, X. Lan, et al., “Chitosan gel beads immobilized Cu (II) for selective adsorption of amino acids,” Journal of biochemical and biophysical methods, vol. 70, no. 6, pp. 903–908, 2008.
[8]
G. Lu, L. Kong, B. Sheng, G. Wang, Y. Gong, and X. Zhang, “Degradation of covalently cross-linked carboxymethyl chitosan and its potential application for peripheral nerve regeneration,” European Polymer Journal, vol. 43, no. 9, pp. 3807–3818, 2007.
[9]
L. S. Ng and A. A. Mohamad, “Protonic battery based on a plasticized chitosan-NH4NO3 solid polymer electrolyte,” Journal of Power Sources, vol. 163, no. 1, pp. 382–385, 2006.
[10]
A. S. A. Khiar, R. Puteh, and A. K. Arof, “Conductivity studies of a chitosan-based polymer electrolyte,” Physica B, vol. 373, no. 1, pp. 23–27, 2006.
[11]
Z. Osman, Z. A. Ibrahim, and A. K. Arof, “Conductivity enhancement due to ion dissociation in plasticized chitosan based polymer electrolytes,” Carbohydrate Polymers, vol. 44, no. 2, pp. 167–173, 2001.
[12]
M. H. Buraidah, L. P. Teo, S. R. Majid, and A. K. Arof, “Ionic conductivity by correlated barrier hopping in NH4I doped chitosan solid electrolyte,” Physica B, vol. 404, no. 8–11, pp. 1373–1379, 2009.
[13]
M. F. Z. Kadir, S. R. Majid, and A. K. Arof, “Plasticized chitosan-PVA blend polymer electrolyte based proton battery,” Electrochimica Acta, vol. 55, no. 4, pp. 1475–1482, 2010.
[14]
R. H. Y. Subban, A. K. Arof, and S. Radhakrishna, “Polymer batteries with chitosan electrolyte mixed with sodium perchlorate,” Materials Science and Engineering B, vol. 38, no. 1-2, pp. 156–160, 1996.
[15]
N. M. Morni, N. S. Mohamed, and A. K. Arof, “Silver nitrate doped chitosan acetate films and electrochemical cell performance,” Materials Science and Engineering B, vol. 45, no. 1–3, pp. 140–146, 1997.
[16]
S. B. Aziz, Z. H. Z. Abidin, and A. K. Arof, “Effect of silver nanoparticles on the DC conductivity in chitosansilver triflate polymer electrolyte,” Physica B, vol. 405, no. 21, pp. 4429–4433, 2010.
[17]
S. L. Agrawal, M. Singh, M. Tripathi, M. M. Dwivedi, and K. Pandey, “Dielectric relaxation studies on [PEO-SiO2]:NH4SCN nanocomposite polymer electrolyte films,” Journal of Materials Science, vol. 44, no. 22, pp. 6060–6068, 2009.
[18]
D. K. Pradhan, R. N. P. Choudhary, and B. K. Samantaray, “Studies of dielectric relaxation and AC conductivity behavior of plasticized polymer nanocomposite electrolytes,” International Journal of Electrochemical Science, vol. 3, pp. 597–608, 2008.
[19]
M. Okutan and E. ?entürk, “β dielectric relaxation mode in side-chain liquid crystalline polymer film,” Journal of Non-Crystalline Solids, vol. 357, no. 14, pp. 1526–1530, 2008.
[20]
M. Petrowsky and R. Frech, “Temperature dependence of ion transport: the compensated arrhenius equation,” Journal of Physical Chemistry B, vol. 113, no. 17, pp. 5996–6000, 2009.
[21]
M. Petrowsky and R. Frech, “Salt concentration dependence of the compensated Arrhenius equation for alcohol-based electrolytes,” Electrochimica Acta, vol. 55, no. 4, pp. 1285–1288, 2010.
[22]
F. G?ktepe, S. ü. ?elik, and A. Bozkurt, “Preparation and the proton conductivity of chitosan/poly(vinyl phosphonic acid) complex polymer electrolytes,” Journal of Non-Crystalline Solids, vol. 354, no. 30, pp. 3637–3642, 2008.
[23]
Y. Wan, K. A. M. Creber, B. Peppley, and V. T. Bui, “Chitosan-based solid electrolyte composite membranes. I. Preparation and characterization,” Journal of Membrane Science, vol. 280, no. 1-2, pp. 666–674, 2006.
[24]
S. A. Hashmi and S. Chandra, “Experimental investigations on a sodium-ion-conducting polymer electrolyte based on poly(ethylene oxide) complexed with NaPF6,” Materials Science and Engineering B, vol. 34, no. 1, pp. 18–26, 1995.
[25]
R. A. Sanders, A. G. Snow, R. Frech, and D. T. Glatzhofer, “A spectroscopic and conductivity comparison study of linear poly(N-methylethylenimine) with lithium triflate and sodium triflate,” Electrochimica Acta, vol. 48, no. 14–16, pp. 2247–2253, 2003.
[26]
S. Ramesh, C.-W. Liew, and K. Ramesh, “Evaluation and investigation on the effect of ionic liquid onto PMMA-PVC gel polymer blend electrolytes,” Journal of Non-Crystalline Solids, vol. 357, no. 10, pp. 2132–2138, 2011.
[27]
K. K. Kumar, M. Ravi, Y. Pavani, S. Bhavani, A. K. Sharma, and V. V. R. N. Rao, “Investigations on the effect of complexation of NaF salt with polymer blend (PEO/PVP) electrolytes on ionic conductivity and optical energy band gaps,” Physica B, vol. 406, no. 9, pp. 1706–1712, 2011.
[28]
D. Wei, W. Sun, W. Qian, Y. Ye, and X. Ma, “The synthesis of chitosan-based silver nanoparticles and their antibacterial activity,” Carbohydrate Research, vol. 344, no. 17, pp. 2375–2382, 2009.
[29]
M. H. Buraidah and A. K. Arof, “Characterization of chitosan/PVA blended electrolyte doped with NH4I,” Journal of Non-Crystalline Solids, vol. 357, no. 16-17, pp. 3261–3266, 2011.
[30]
B. C. Ng, H. Y. Wong, K. W. Chew, and Z. Osman, “Development and characterization of Poly-ε-caprolactone-based polymer electrolyte for lithium rechargeable battery,” International Journal of Electrochemical Science, vol. 6, no. 9, pp. 4355–4364, 2011.
[31]
S. Selvasekarapandian, R. Baskaran, and M. Hema, “Complex AC impedance, transference number and vibrational spectroscopy studies of proton conducting PVAc-NH4SCN polymer electrolytes,” Physica B, vol. 357, no. 3-4, pp. 412–419, 2005.
[32]
J. Malathi, M. Kumaravadivel, G. M. Brahmanandhan, M. Hema, R. Baskaran, and S. Selvasekarapandian, “Structural, thermal and electrical properties of PVA-LiCF3SO3 polymer electrolyte,” Journal of Non-Crystalline Solids, vol. 356, no. 43, pp. 2277–2281, 2010.
[33]
Y. W. Chen-Yang, Y. T. Chen, H. C. Chen, W. T. Lin, and C. H. Tsai, “Effect of the addition of hydrophobic clay on the electrochemical property of polyacrylonitrile/LiClO4 polymer electrolytes for lithium battery,” Polymer, vol. 50, no. 13, pp. 2856–2862, 2009.
[34]
A. Awadhia and S. L. Agrawal, “Structural, thermal and electrical characterizations of PVA:DMSO:NH4SCN gel electrolytes,” Solid State Ionics, vol. 178, no. 13-14, pp. 951–958, 2007.
[35]
C. V. S. Reddy, X. Han, Q. Zhu, L. Mai, and W. Chen, “Dielectric spectroscopy studies on (PVP?+?PVA) polyblend film,” Microelectronic Engineering, vol. 83, no. 2, pp. 281–285, 2006.
[36]
J. Y. Kim and S. H. Kim, “Ionic conduction behavior of network polymer electrolytes based on phosphate and polyether copolymers,” Solid State Ionics, vol. 124, no. 1, pp. 91–99, 1999.
[37]
A. Awadhia, S. K. Patel, and S. L. Agrawal, “Dielectric investigations in PVA based gel electrolytes,” Progress in Crystal Growth and Characterization of Materials, vol. 52, no. 1-2, pp. 61–68, 2006.
[38]
A. Karmakar and A. Ghosh, “Dielectric permittivity and electric modulus of polyethylene oxide (PEO)-LiClO4 composite electrolytes,” Current Applied Physics, vol. 12, no. 2, pp. 539–543, 2012.