Abstract
Proton-conducting solid polymer blend electrolytes based on methylcellulose-polyvinyl alcohol:ammonium nitrate (MC-PVA:NH4NO3) were prepared by the solution cast technique. The structural and electrical properties of the samples were examined by X-ray diffraction (XRD), Fourier transform infrared (FTIR), and electrical impedance (EI) spectroscopy. The shifting and change in the intensity of FTIR bands of the electrolyte samples confirm the complex formation between the MC-PVA polymer blend and the NH4NO3 added salt. The observed broadening in the XRD pattern of the doped samples reveals the increase of the amorphous fraction of polymer electrolyte samples. The increase in electrical conductivity of polymer electrolyte samples with increasing salt concentration attributed to the formation of charge-transfer complexes, and to increase in the amorphous domains. A maximum ionic conductivity of about 7.39 × 10−5 S cm−1 was achieved at room temperature for the sample incorporating 20 wt% of NH4NO3. The DC conductivity of the present polymer system exhibits Arrhenius-type dependence with temperature. The decrease in the values of activation energies with increasing salt concentration indicates the ease mobility of ions. The decrease in dielectric constant with increasing frequency was observed at all temperatures. Optical properties such as absorption edge, optical band gap, and tail of localized state were estimated for polymer blend and their electrolyte films. It was found that the optical band gap values shifted towards lower photon energy from 6.06 to 4.75 eV by altering the NH4NO3 salt content.
Similar content being viewed by others
References
Albu AM, Maior I, Nicolae CA, Bocaneala FL (2016) Novel PVA proton conducting membranes doped with polyaniline generated by in-situ polymerization. Electrochim Acta 211:911–917
Saroj AL, Singh RK (2012) Thermal, dielectric and conductivity studies on PVA/ionic liquid [EMIM][EtSO4] based polymer electrolytes. J Phys Chem Solids 73:162–168
Rajendran S, Sivakumar M, Subadevi R (2004) Li-ion conduction of plasticized PVA solid polymer electrolytes complexed with various lithium salts. Solid State Ionics 167:335–339
Mohan VM, Raja V, Bhargav PB, Sharma AK, Rao VVRN (2007) Structural, electrical and optical properties of pure and NaLaF4 doped PEO polymer electrolyte films. J Polym Res 14:283–290
Achari VB, Reddy TJR, Sharma AK, Rao VVRN (2007) Electrical, optical, and structural characterization of polymer blend (PVC/PMMA) electrolyte films. Ionics 13:349–354
Saroj AL, Singh RK (2011) Studies on ionic liquid 1-ethyl-3-methyl imidazolium ethylsulphate complexed with PVA. Phase Transit 84:231–242
Yamada T, Sadakiyo M, Shigematsu A, Kitagawa H (2016) Proton-conductive metal organic frameworks. Bull Chem Soc Jpn 89:1–10
Kochetova N, Animitsa I, Medvedev D, Deminb A, Tsiakaras P (2016) Recent activity in the development of proton-conducting oxides for high-temperature applications. RSC Adv 6:73222–73268
Colomban P (1992) Proton conductors: solids, membrane and gels-materials and devices. Cambridge University, Cambridge
Ali AMM, Mohamed NS, Arof AK (1998) Polyethylene oxide (PEO)-ammonium sulfate ((NH4)2SO4) complexes and electrochemical cell performance. J Power Sources 74:135–141
Maurya KK, Srivastava N, Hashmi SA, Chandra S (1992) Proton conducting polymer electrolyte: II poly ethylene oxide + NH4l system. J Mater Sci 27:6357–6364
Shukur MF, Ithnin R, Illias HA, Kadir MFZ (2013) Proton conducting polymer electrolyte based on plasticized chitosan-PEO blend and application in electrochemical devices. Opt Mater 35:1834–1841
Liew CW, Ramesh S, Arof AK (2015) Characterization of ionic liquid added poly(vinyl alcohol)-based proton conducting polymer electrolytes and electrochemical studies on the supercapacitors. Int J Hydrogen Energ 40:852–862
Muthuvinayagam M, Gopinathan C (2015) Characterization of proton conducting polymer blend electrolytes based on PVdF-PVA. Polymer 68:122–130
Woo HJ, Arof AK (2016) Vibrational studies of flexible solid polymer electrolyte based on PCL-EC incorporated with proton conducting NH4SCN. Spectrochim Acta A 161:44–51
Aziz NAN, Idris NK, Isa MIN (2010) Solid polymer electrolytes based on methylcellulose: FT-IR and ionic conductivity studies. Int J Polym Anal Charact 15:319–327
Krumova M, Lopez D, Benavente R, Mijangos C, Parena JM (2000) Effect of crosslinking on the mechanical and thermal properties of poly(vinyl alcohol). Polymer 41:9265–9272
Kuljanin J, Comor MI, Djokovic V, Nedeljkovic JM (2006) Synthesis and characterization of nanocomposite of polyvinyl alcohol and lead sulfide nanoparticles. Mater Chem Phys 95:67–71
Badr S, Sheha E, Bayomi RM, El-Shaarawy MG (2010) Structural and electrical properties of pure and H2SO4 doped (PVA)0.7(NaI)0.3 solid polymer electrolyte. Ionics 16:269–275
Yusof YM, Illias HA, Kadir MFZ (2014) Incorporation of NH4Br in PVA-chitosan blend-based polymer electrolyte and its effect on the conductivity and other electrical properties. Ionics 20:1235–1245
Shuhaimi NEA, Teo LP, Woo HJ, Majid SR, Arof AK (2012) Electrical double-layer capacitors with plasticized polymer electrolyte based on methyl cellulose. Polym Bull 69:807–826
Gauthier M, Armand M, Mulle D (1988) Electrosponsive molecular and polymeric systems, vol 1. Marcel Dekker, New York
Park JS, Park JW, Ruckenstein E (2001) Thermal and dynamic mechanical analysis of PVA/MC blend hydrogels. Polymer 42:4271–4280
Rajendran S, Sivakumar M, Subadevi R (2003) Effect of salt concentration in poly(vinyl alcohol)-based solid polymer electrolytes. J Power Sources 124:225–230
Chandrakala HN, Ramaraj B, Shivakumaraiah, Madhu GM, Siddaramaiah (2012) The influence of zinc oxide-cerium oxide nanoparticles on the structural characteristics and electrical properties of polyvinyl alcohol films. J Mater Sci 47:8076–8084
Bdewi SF, Abdullah OG, Aziz BK, Mutar AAR (2016) Synthesis, structural and optical characterization of MgO nanocrystalline embedded in PVA matrix. J Inorg Organomet Polym Mater 26:326–334
Wu HB, Chan MN, Chan CK (2007) FTIR characterization of polymorphic transformation of ammonium nitrate. Aerosol Sci Technol 41:581–588
Kadir MFZ, Aspanut Z, Majid SR, Arof AK (2011) FTIR studies of plasticized poly(vinyl alcohol)-chitosan blend doped with NH4NO3 polymer electrolyte membrane. Spectrochim Acta A 78:1068–1074
Liu JH, Zhang YH, Wang LY, Wei ZF (2005) Drawing out the structural information of the first layer of hydrated ions: ATR-FTIR spectroscopic studies on aqueous NH4NO3, NaNO3, and Mg(NO3)2 solutions. Spectrochim Acta A 61:893–899
Chintapalli S, Zea C, Frech R (1996) Characterization studies on high molecular weight PEO-ammonium triflate complexes. Solid State Ionics 92:205–212
Hema M, Selvasekerapandian S, Sakunthala A, Arunkumar D, Nithya H (2008) Structural, vibrational and electrical characterization of PVA-NH4Br polymer electrolyte system. Physica B 403:2740–2747
Bhargav PB, Mohan VM, Sharma AK, Rao VVRN (2007) Structural, electrical and optical characterization of pure and doped poly (vinyl alcohol) (PVA) polymer electrolyte films. Int J Polym Mater Polymeric Biomater 56:579–591
Shukur MF, Ithnin R, Kadir MFZ (2014) Electrical properties of proton conducting solid biopolymer electrolytes based on starch–chitosan blend. Ionics 20:977–999
Abdullah OG, Salman YAK, Saleem SA (2015) In-situ synthesis of PVA/HgS nanocomposite films and tuning optical properties. Phys Mater Chem 3:18–24
Majid SR, Arof AK (2005) Proton-conducting polymer electrolyte films based on chitosan acetate complexed with NH4NO3 salt. Physica B 355:78–82
Abdullah GO, Aziz SB, Rasheed MA (2016) Structural and optical characterization of PVA:KMnO4 based solid polymer electrolyte. Results in Physics 6:1103–1108
Aziz SB (2013) Li+ ion conduction mechanism in poly (ε-caprolactone)-based polymer electrolyte. Iran Polym J 22:877–883
Sivadevi S, Selvasekarapandian S, Karthikeyan S, Sanjeeviraja C, Nithya H, Iwai Y, Kawamura J (2015) Proton-conducting polymer electrolyte based on PVA-PAN blend doped with ammonium thiocyanate. Ionics 21:1017–1029
Abdullah OG (2016) Synthesis of single-phase zinc chromite nano-spinel embedded in polyvinyl alcohol films and its effects on energy band gap. J Mater Sci Mater Electron 27:12106–12111
Shuhaimi NEA, Alias NA, Kufian MZ, Majid SR, Arof AK (2010) Characteristics of methyl cellulose-NH4NO3-PEG electrolyte and application in fuel cells. J Solid State Electrochem 14:2153–2159
Hema M, Selvasekarapandian S, Hirankumar G, Sakunthala A, Arunkumar D, Nithya H (2010) Laser Raman and ac impedance spectroscopic studies of PVA: NH4NO3 polymer electrolyte. Spectrochim Acta A 75:474–478
Park CH, Kim DW, Prakash J, Sun YK (2003) Electrochemical stability and conductivity enhancement of composite polymer electrolytes. Solid State Ionics 159:111–119
Reddy TJR, Achari VBS, Sharma AK, Rao VVRN (2007) Preparation and electrical characterization of (PVC + KBrO3) polymer electrolytes for solid state battery applications. Ionics 13:435–439
Reddeppa N, Reddy TJR, Achari VBS, Rao VVRN, Sharma AK (2009) Electrical and optical characterization of (PEO+PVAc) polyblend films. Ionics 15:255–259
Bhargav PB, Mohan VM, Sharma AK, Rao VVRN (2009) Investigations on electrical properties of (PVA:NaF) polymer electrolytes for electrochemical cell applications. Curr Appl Phys 9:165–171
Abdullah OG, Salman YAK, Saleem SA (2016) Electrical conductivity and dielectric characteristics of in-situ prepared PVA/HgS nanocomposite films. J Mater Sci Mater Electron 27:3591–3598
Raj CJ, Varma KBR (2010) Synthesis and electrical properties of the (PVA)0.7(KI)0.3·xH2SO4 (0 ≤ x ≤ 5) polymer electrolytes and their performance in a primary Zn/MnO2 battery. Electrochim Acta 56:649–656
Hema M, Selvasekarapandian S, Nithya H, Sakunthala A, Arunkumar D (2009) Structural and ionic conductivity studies on proton conducting polymer electrolyte based on polyvinyl alcohol. Ionics 15:487–491
Khiar ASA, Arof AK (2010) Conductivity studies of starch-based polymer electrolytes. Ionics 16:123–129
Abdullah OG, Saleem SA (2016) Effect of copper sulfide nanoparticles on the optical and electrical behavior of poly (vinyl alcohol) films. J Electron Mater 45:5910–5920
Aziz SB (2016) Modifying poly(vinyl alcohol) (PVA) from insulator to small-bandgap polymer: a novel approach for organic solar cells and optoelectronic devices. J Electron Mater 45:736–745
Sheha E, El-Mansy MK (2008) A high voltage magnesium battery based on H2SO4-doped (PVA)0.7(NaBr)0.3 solid polymer electrolyte. J Power Sources 185:1509–1513
Michael MS, Jacob MME, Prabaharan SRS, Radhakrishna S (1997) Enhanced lithium ion transport in PEO-based solid polymer electrolytes employing a novel class of plasticizers. Solid State Ionics 98:167–174
Wintersgill MC, Fontanella JJ, Pak YS, Greenbaum SG, Al-Mudaris A, Chadwick AV (1989) Electrical conductivity, differential scanning calorimetry and nuclear magnetic resonance studies of amorphous poly(ethylene oxide) complexed with sodium salts. Polymer 30:1123–1126
Aziz SB, Abdullah OG, Rasheed MA, Ahmed HM (2017) Effect of high salt concentration (HSC) on structural, morphological and electrical characteristics of chitosan based solid polymer electrolytes. Polymers 9:187
Zangina T, Hassan J, Matori KA, Azis RS, Ahmadu U, See A (2016) Sintering behavior, ac conductivity and dielectric relaxation of Li1.3Ti1.7Al0.3(PO4)3 NASICON compound. Results in Physics 6:719–725
Buruiana LI, Avram E, Popa A, Musteata VE, Ioan S (2012) Electrical conductivity and optical properties of a new quaternized polysulfone. Polym Bull 68:1641–1661
Aziz SB, Abdullah OG, Saber DR, Rasheed MA, Ahmed HM (2017) Investigation of metallic silver nanoparticles through UV-vis and optical micrograph techniques. Int J Electrochem Sci 12:363–373
Rao CVS, Ravi M, Raja V, Bhargav PB, Sharma AK, Rao VVRN (2012) Preparation and characterization of PVP-based polymer electrolytes for solid-state battery applications. Iran Polym J 21:531–536
Abdullah OG, Aziz SB, Rasheed MA (2017) Effect of silicon powder on the optical characterization of poly(methyl methacrylate) polymer composites. J Mater Sci Mater Electron 28:4513–4520
Abdulwahid RT, Abdullah OG, Aziz SB, Hussein SA, Muhammad FF, Yahya MY (2015) The study of structural and optical properties of PVA:PbO2 based solid polymer nanocomposites. J Mater Sci Mater Electron 27:12112–12118
Reddy CVS, Sharma AK, Rao VVRN (2006) Electrical and optical properties of a polyblend electrolyte. Polymer 47:1318–1323
Aziz SB, Abdullah OG, Rasheed MA (2017) A novel polymer composite with a small optical band gap: new approaches for photonics and optoelectronics. J Appl Polym Sci 134:44847
Mohan KR, Achari VBS, Rao VVRN, Sharma AK (2011) Electrical and optical properties of (PEMA/PVC) polymer blend electrolyte doped with NaClO4. Polym Test 30:881–886
Devi CU, Sharma AK, Rao VVRN (2002) Electrical and optical properties of pure and silver nitrate-doped polyvinyl alcohol films. Mater Lett 56:167–174
Aziz SB, Abdullah OG, Hussein AM, Abdulwahid RT, Rasheed MA, Ahmed HM, Abdalqadir SW, Mohammed AR (2017) Optical properties of pure and doped PVA: PEO based solid polymer blend electrolytes: two methods for band gap study. J Mater Sci Mater Electron 28:7473–7479
Aziz SB, Rasheed MA, Saeed SR, Abdullah OG (2017) Synthesis and characterization of CdS nanoparticles grown in a polymer solution using in-situ chemical reduction technique. Int J Electrochem Sci 12:3263–3274
Acknowledgements
The authors are indebted to the Ministry of Higher Education and Scientific Research in Kurdistan Region, University of Sulaimani, and University of Human Development for the financial support given to this research.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Abdullah, O.G., Aziz, S.B. & Rasheed, M.A. Incorporation of NH4NO3 into MC-PVA blend-based polymer to prepare proton-conducting polymer electrolyte films. Ionics 24, 777–785 (2018). https://doi.org/10.1007/s11581-017-2228-1
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11581-017-2228-1