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Microstructural, dielectric, and transport properties of proton-conducting solid polymer electrolyte for battery applications

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Abstract

Poly (vinyl alcohol) (PVA) complexed with ammonium chloride (NH4Cl) solid polymer electrolyte films was prepared using solution casting technique. Complexation of dopant with polymer was studied using Fourier transform infrared spectroscopy (FTIR). X-ray diffraction (XRD) results reflect that degree of crystallinity of the polymer increases with doping level. Surface morphology and topology of the electrolyte were studied using Scanning electron microscopy (SEM) and atomic force microscopy (AFM). Thermogravimetric analysis (TGA) results accounts for the increase of thermal stability of PVA due to the incorporation of NH4Cl. Impedance analysis was carried out to understand relaxation phenomena of polymer electrolyte. Dielectric studies revealed that the mobility of charge carriers follows non-Debye nature of ionic relaxation. Electrical studies reveal that proton conduction occurs in this polymer electrolyte through Grotthus mechanism and maximum conductivity of the polymer electrolyte (7.5 wt% NH4Cl/PVA) has been observed to be 1.81 × 10−3 S/cm at 353 K. Transport parameters have been determined using Wagner’s polarization technique. The observed highest conductivity of polymer electrolyte indicates utilizing this electrolyte for the fabrication of proton battery applications, and accordingly, the cell parameters have been measured.

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References

  1. Kumar A, Logapperumal S, Sharma R, Das MK, Kar KK (2016) Li-ion transport, structural and thermal studies on lithium triflate and barium titanate incorporated poly (vinylidene fluoride-co-hexafluoropropene) based polymer electrolyte. Solid State Ionics 289:150–158. https://doi.org/10.1016/j.ssi.2016.03.008

    Article  CAS  Google Scholar 

  2. Naga G, Vani S, Raja V, Sharma AK, Rao VVRN (2013) Development of PVP based polymer electrolytes for solid state battery applications. Int J Res Eng Adv Technol 1(3) ISSN: 2320–8791. https://www.researchgate.net/publication/317003139

  3. Chew KW, Ng TC, How ZH (2013) Conductivity and microstructure study of PLA-based polymer electrolyte salted with Lithium Perchloride, LiClO4. Int J Electrochem Sci 8:6354–6364

    CAS  Google Scholar 

  4. Bamford D, Dlubek G, Reiche A, Alam MA, Meyer W, Galvosas P, Rittig F (2001) The local free volume, glass transition, and ionic conductivity in a polymer electrolyte: a positron lifetime study. J Chem Phys 115:7260. https://doi.org/10.1063/1.1402633

    Article  CAS  Google Scholar 

  5. Rana P, Singh B, Chandra S (2006) Polymeric rechargeable solid-state proton battery. J Power Sources 161:702–706. https://doi.org/10.1016/j.jpowsour.2006.04.020

    Article  CAS  Google Scholar 

  6. Agrawal RC, Hashmi SA, Pandey GP (2007) Electrochemical cell performance studies on all-solid-state battery using nano-composite polymer electrolyte membrane. Ionics 13:295–298. https://doi.org/10.1007/s11581-007-0112-0

    Article  CAS  Google Scholar 

  7. Hema M, Selvasekerapandian S, Hirankumar G (2009) A. Sakunthala, D. Arunkumar, H. Nithya, structural and thermal studies of PVA:NH4I. J Phys Chem Solids 70:1098–1103. https://doi.org/10.1016/j.jpcs.2009.06.005

    Article  CAS  Google Scholar 

  8. Ahmad NH, Isa MIN (2015) Structural and ionic conductivity studies of CMC based polymer electrolyte doped with NH4Cl. Adv Mater Res ISSN: 1662-8985 1107:247–252. https://doi.org/10.4028/www.scientific.net/AMR.1107.247

    Article  Google Scholar 

  9. Radha KP, Selvasekarapandian S, Karthikeyan S, Hema M, Sanjeeviraja C (2013) Synthesis and impedance analysis of proton-conducting polymer electrolyte PVA:NH4F. Ionics 19:1437–1447. https://doi.org/10.1007/s11581-013-0866-5

    Article  CAS  Google Scholar 

  10. Manjunath A, Deepa T, Supreetha NK, Irfan M (2015) Studies on AC electrical conductivity and dielectric properties of PVA/NH4NO3 solid polymer electrolyte films. Adv Mater Phys Chem 5:295–301. https://doi.org/10.4236/ampc.2015.58029

    Article  CAS  Google Scholar 

  11. Praveena SD, Ravindrachary V, Bhajantri RF, Ismayil (2016) Dopant-induced microstructural, optical, and electrical properties of TiO2/PVA composite. Polym Compos 37:987–997. https://doi.org/10.1002/pc.23258

    Article  CAS  Google Scholar 

  12. Vinoth Pandi D, Selvasekarapandian S, Bhuvaneswari R, Premalatha M, Monisha S, Arunkumar D, Junichi K (2016) Development and characterization of proton conducting polymer electrolyte based on PVA, amino acid glycine and NH4SCN. Solid State Ionics 298:15–22. https://doi.org/10.1016/j.ssi.2016.10.016

    Article  CAS  Google Scholar 

  13. Sikkanthar S, Karthikeyan S, Selvasekarapandian S, Arunkumar D, Nithya H, Junichi K (2016) Structural, electrical conductivity, and transport analysis of PAN–NH4Cl polymer electrolyte system. Ionics 22:1085–1094. https://doi.org/10.1007/s11581-016-1645-x

    Article  CAS  Google Scholar 

  14. Bhajantri RF, Ravindrachary V, Harisha A, Crasta V, Nayak SP, Poojary B (2006) Microstructural studies on BaCl2 doped poly (vinyl alcohol). Polymer 47:3591–3598. https://doi.org/10.1016/j.polymer.2006.03.054

    Article  CAS  Google Scholar 

  15. Hari-Bala, Guo Y, Xu Z, Zhao J, Wuyou F, Ding X, Jiang Y, Yu K, Lv X, Wang Z (2006) Controlling the particle size of nanocrystalline titania via a thermal dissociation of substrates with ammonium chloride. Mater Lett 60:494–498. https://doi.org/10.1016/j.matlet.2005.09.030

    Article  CAS  Google Scholar 

  16. Fernandes DM, Aiation A, Winkler H, Job AE, Radovanocic E, Gomez Pineda EA (2006) Thermal and photochemical stability of poly (vinyl alcohol)/modified lignin blends. Polym Degrad Stab 91:1192–1201. https://doi.org/10.1016/j.polymdegradstab.2005.05.024

    Article  CAS  Google Scholar 

  17. Kesavana K, Mathewa CM, Rajendrana S, Ulaganathan M (2014) Preparation and characterization of novel solid polymer blend electrolytes based on poly (vinyl pyrrolidone) with various concentrations of lithium perchlorate. Mater Sci Eng B 184:26–33. https://doi.org/10.1016/j.mseb.2014.01.009

    Article  CAS  Google Scholar 

  18. Ramaraj B, Jaisankar SN (2008) Thermal and morphological properties of poly (vinyl alcohol) and layered double hydroxide (LDH) Nanocomposites. Polym-Plast Technol Eng 47:733–738. https://doi.org/10.1080/03602550802059170

    Article  CAS  Google Scholar 

  19. G. Attia, M.F.H. Abd El-kader, Structural (2013) Optical and thermal characterization of PVA/2HEC Polyblend films. Int J Electrochem Sci 8:5672–5687

  20. Abdelrazek EM, Elashmawi IS (2008) Characterization and physical properties of CoCl2 filled polyethyl methacrylate films. Polym Compos 29:1036–1043. https://doi.org/10.1002/pc.20481

    Article  CAS  Google Scholar 

  21. Coats AW, Redfern JP (1984) Kinetic parameters from Thermogravimetric data. Nature 201:681. https://doi.org/10.1038/201068a0

    Article  Google Scholar 

  22. Abdelaziz M (2011) Cerium (III) doping effects on optical and thermal properties of PVA films. Physica B 406:1300–1307. https://doi.org/10.1016/j.physb.2011.01.021

    Article  CAS  Google Scholar 

  23. Sai Prasanna CM, Austin Suthanthiraraj S (2017) Dielectric, thermal, and electrochemical properties of PVC/PEMA blended polymer electrolytes complexed with zinc triflate salt. Ionics 23:3137–3150. https://doi.org/10.1007/s11581-017-2109-7

    Article  CAS  Google Scholar 

  24. Kalim D, Basheer Ahamed M, Polu AR, Sadasivuni KK, Khadheer Pasha SK, Ponnamma D, AlMaadeed MA-A, Deshmukh RR, Chidambaram K (2016) Impedance spectroscopy, ionic conductivity and dielectric studies of new li+ ion conducting polymer blend electrolytes based on biodegradable polymers for solid state battery applications. J Mater Sci Mater Electron 27:11410–11424. https://doi.org/10.1007/s10854-016-5267-x

    Article  CAS  Google Scholar 

  25. Vidyashree H, Bhajantri RF, Naik J (2017) Physico-chemical properties of bismuth nitrate filled PVA–LiClO4 polymer composites for energy storage application. J Mater Sci Mater Electron 28:5827–5839. https://doi.org/10.1007/s10854-016-6254-y

    Article  CAS  Google Scholar 

  26. Shreedatta H, Ravindrachary V, Praveena SD, Guruswamy B, Sagar RN (2018) Optical and Dielectric Properties of Li+ ion conducting solid polymer electrolyte. Ind J Adv Chem Sci 6(2):83–87. https://doi.org/10.22607/IJACS.2018.602004

    Article  Google Scholar 

  27. Mahendia S, Goyal PK, Tomar AK, Chahal RP, Kumar S (2016) Study of dielectric behavior and charge conduction mechanism of poly(Vinyl Alcohol) (PVA)-Copper (Cu) and gold (Au) nanocomposites as a bio-resorbable material for organic electronics. J Electron Mater 45(10). https://doi.org/10.1007/s11664-016-4677-0

  28. Ragab HM (2011) Spectroscopic investigations and electrical properties of PVA/PVP blend filled with different concentrations of nickel chloride. Physica B 406:3759–3767. https://doi.org/10.1016/j.physb.2010.11.030

    Article  CAS  Google Scholar 

  29. Buraidah MH, Teo LP, Majid SR, Arof AK (2009) Ionic conductivity by correlated barrier hopping in NH4I doped chitosan solid electrolyte. Physica B 404:1373–1379. https://doi.org/10.1016/j.physb.2008.12.027

    Article  CAS  Google Scholar 

  30. Tahalyania J, Rahangdalea KK, Aepurua R, Balasubramanian K, Datar S (2016) Dielectric investigation of conducting fibrous nonwoven porous mat fabricated by one-step facile electrospinning process. RSC Adv 6:36588. https://doi.org/10.1039/C5RA23012H

    Article  CAS  Google Scholar 

  31. Ben Taher Y, Oueslati A, Maaloul NK, Khirouni K, Gargouri M (2015) Conductivity study and correlated barrier hopping (CBH) conduction mechanism in diphosphate compound. Appl Phys A Mater Sci Process 120:1537–1543. https://doi.org/10.1007/s00339-015-9353-3

    Article  CAS  Google Scholar 

  32. Rathod SG, Bhajantri RF, Ravindrachary V, Naik J, Madhu Kumar DJ (2016) High mechanical and pressure sensitive dielectric properties of Graphene oxide doped PVA Nanocomposites. RSC Adv 6:77977–77986. https://doi.org/10.1039/C6RA16026C

    Article  CAS  Google Scholar 

  33. Bi L, Shafi SP, Da’as EH, Traversa E (2018) Tailoring the cathode–electrolyte Interface with nanoparticles for boosting the solid oxide fuel cell performance of chemically stable proton-conducting electrolytes. Small 14:1801231. https://doi.org/10.1002/smll.201801231

    Article  CAS  Google Scholar 

  34. Ma J, Tao Z, Kou H, Fronzi M, Bi L (2019) Evaluating the effect of Pr-doping on the performance of strontium-doped lanthanum ferrite cathodes for protonic SOFCs. Ceram Int. https://doi.org/10.1016/j.ceramint.2019.10.017

  35. Xu X, Wang H, Jinming M, Liu W, Wang X, Fronzi M, Bi L (2019) Impressive performance of proton-conducting solid oxide fuel cells using a first-generation cathode with tailored cations. J Mater Chem A 7:18792–18798. https://doi.org/10.1039/C9TA06676D

    Article  CAS  Google Scholar 

  36. Xia Y, Jin Z, Wang H, Zheng G, Lv H, Peng R, Liu W, Bi L (2019) A novel cobalt-free cathode with triple-conduction for proton-conducting solid oxide fuel cells with unprecedented performance. J Mater Chem A 7:16136–16148. https://doi.org/10.1039/c9ta02449b

    Article  CAS  Google Scholar 

  37. Xu X, Lei B, Zhao XS (2018) Highly-conductive proton-conducting electrolyte membranes with a low sintering temperature for solid oxide fuel cells. J Membr Sci 558:17–25. https://doi.org/10.1016/j.memsci.2018.04.037

    Article  CAS  Google Scholar 

  38. Krishna Kumar V, Shanmugam G (2012) Electrical and optical properties of pure and Pb2+ ion doped PVA−PEG polymer composite electrolyte films. Ionics 18:403–411. https://doi.org/10.1007/s11581-011-0643-2

    Article  CAS  Google Scholar 

  39. Du JF, Bai Y, Chu WY, Qiao LJ (2010) Synthesis and performance of proton ConductingChitosan/NH4Cl electrolyte. J Polym Sci B Polym Phys 48:260–266. https://doi.org/10.1002/polb.21866

    Article  CAS  Google Scholar 

  40. Shreedatta H, Ravindrachary V, Praveena SD, Guruswamy B, Sagar RN, Sanjeev G (2018) Relaxation and transport properties of li+ conducting biocompatible material for battery application. Ion AIP Conf Proc 1942:110043. https://doi.org/10.1063/1.5029026

    Article  CAS  Google Scholar 

  41. Nadimicherla R, Sharma AK, Narasimha Rao VVR, Chen W (2014) AC conduction mechanism and battery discharge characteristics of (PVC/PEO) polyblend films complexed with potassium chloride. Measurement 47:33–41. https://doi.org/10.1016/j.measurement.2013.08.047

    Article  Google Scholar 

  42. Hemalatha R, Alagar M, Selvasekarapandian S, Sundaresan B, Moniha V, Boopathi G, Christopher Selvin P (2019) Preparation and characterization of proton-conducting polymer electrolyte based on PVA, amino acidproline, and NH4Cl and its applications to electrochemical devices. Ionics 25:141–154. https://doi.org/10.1007/s11581-018-2564-9

    Article  CAS  Google Scholar 

  43. Kathayat K, Panigrahi A, Pandey A, Kar S (2012) Characterization of electrical behavior of Ba5HoTi3V7O30 ceramic using impedance analysis. Mater Sci Appl 3:390–397. https://doi.org/10.4236/msa.2012.36056

    Article  CAS  Google Scholar 

  44. Chawla M, Shekhawat N, Aggarwa S, Sharma A, Nair KGM (2014) Cole-cole analysis and electrical conduction mechanism of N+ implanted polycarbonate. J Appl Phys 115:184104. https://doi.org/10.1063/1.4876123

    Article  CAS  Google Scholar 

  45. 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. https://doi.org/10.1016/j.jpcs.2011.11.012

    Article  CAS  Google Scholar 

  46. Sahoo PS, Panigrahi A, Patri SK, Choudhary RNP (2009) Structural and impedance properties of Ba5 DyTi3V7O30. J Mater Sci Mater Electron 20:565–570. https://doi.org/10.1007/s10854-008-9766-2

    Article  CAS  Google Scholar 

  47. Wagner B, Wagner C (1957) Electrical conductivity measurements on cuprous halides. J Chem Phys 26:1597. https://doi.org/10.1063/1.1743590

    Article  CAS  Google Scholar 

  48. Prajapati GK, Roshan R, Gupta PN (2010) Effect of plasticizer on ionic transport and dielectric properties of PVA–H3PO4 proton conducting polymeric electrolytes. J Phys Chem Solids 71:1717–1723. https://doi.org/10.1016/j.jpcs.2010.08.023

    Article  CAS  Google Scholar 

  49. Bhavani S, Ravi M, Rao VVRN (2014) Studies on electrical properties of PVA: NiBr2 complexed polymer electrolyte films for battery applications. Int J Eng Sci Innov Technol 3(4) ISSN: 2319–5967

  50. Anantha PS, Hariharan K (2005) Physical and ionic transport studies on poly (ethylene oxide)–NaNO3 polymer electrolyte system. Solid State Ionics 176:155–162. https://doi.org/10.1016/j.ssi.2004.07.006

    Article  CAS  Google Scholar 

  51. Leena Chandra MV, Karthikeyan S, Selvasekarapandian S, Vinoth Pandi D, Monisha S, Arulmozhi Packiaseeli S (2016) Characterization of high ionic conducting PVAc–PMMA blend-based polymer electrolyte for electrochemical applications. Ionics 22:2409–2420. https://doi.org/10.1007/s11581-016-1763-5

    Article  CAS  Google Scholar 

  52. 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. https://doi.org/10.1007/s11581-014-1259-0

    Article  CAS  Google Scholar 

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Acknowledgements

The authors are thankful to Prof. Ganesh Sanjeev, Microtron Center, Mangalore University, for providing instruments to carry out electrical studies and PURSE Lab Mangalore University for providing SEM and TGA facility.

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Authors and Affiliations

  1. Department of Physics, Mangalore University, Mangalagangotri, Konaje, 574199, India

    Shreedatta Hegde, V. Ravindrachary, B. Guruswamy & Rohan N. Sagar

  2. Department of Physics, K. V. G. College of Engineering, Kurunjibhag, Sullia, 574327, India

    S. D. Praveena

  3. Department of Physics, Manipal Institute of Technology, Manipal Academy of Higher Education, Manipal, 576104, India

    Ismayil

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  1. Shreedatta Hegde
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Hegde, S., Ravindrachary, V., Praveena, S.D. et al. Microstructural, dielectric, and transport properties of proton-conducting solid polymer electrolyte for battery applications. Ionics 26, 2379–2394 (2020). https://doi.org/10.1007/s11581-019-03383-w

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