Synthesis of New Bio-Based Solid Polymer Electrolyte Polyurethane-LiClO4 via Prepolymerization Method: Effect of NCO/OH Ratio on Their Chemical, Thermal Properties and Ionic Conductivity
Novel bio-based polymer electrolyte was synthesized
with LiClO4 as the main source of charge carrier. Initially,
polyurethane-LiClO4 polymer electrolytes were synthesized via
prepolymerization method with different NCO/OH ratios and labelled
them as PU1, PU2, PU3 and PU4. Fourier transform infrared (FTIR)
analysis indicates the co-ordination between Li+ ion and polyurethane
in PU1. Differential scanning calorimetry (DSC) analysis indicates
PU1 has the highest glass transition temperature (Tg) corresponds to
the most abundant urethane group which is the hard segment in PU1.
Scanning electron microscopy (SEM) shows the good miscibility
between lithium salt and the polymer. The study found that PU1
possessed the greatest ionic conductivity and the lowest activation
energy, Ea. All the polyurethanes exhibited linear Arrhenius
variations indicating ion transport via simple lithium ion hopping in
polyurethane. This research proves the NCO content in polyurethane
plays an important role in affecting the ionic conductivity of this
polymer electrolyte.
[1] N. Ataollahi, A. Ahmad, H. Hamzah, M.Y.A. Rahman.and N.S.
Mohamed, “Ionic conductivity of PVDF-HFP/MG49 based solid
polymer Electrolyte,” Advanced Materials Research, vol 501 pp 29-33,
April 2012.
[2] M. Ulaganathan and S. Rajendran, “Effect of different salts on
PVAc/PVdF-co-HFP based polymer blend electrolytes,” J. Applied
Polymer Science, vol 118 pp 646–651, 2010.
[3] M. Wetjen, G.T Kim, M. Joost, M. Winter, and S. Passerini,
“Temperature dependence of electrochemical properties of cross-linked
poly(ethylene oxide)–lithium bis(trifluoromethanesulfonyl)imide–Nbutyl-
N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide solid
polymer electrolytes for lithium batteries,” Electrochimica Acta vol 87
pp 779-787, 2013.
[4] A. Lewandowski, A.S. Mocek and L. Waliszewski, “Li+ conducting
polymer electrolyte based on ionic liquid for lithium and lithium-ion
batteries,” Electrochimica Acta vol 92 pp 404-411, 2013.
[5] C.S. Wong and K.H. Badri, “Chemical Analyses of Palm kernel oilbased
polyurethane prepolymer,” Materials Sciences and Applications,
vol 3 pp 78-86, 2012.
[6] J.H. Yang, B.C. Chun, Y.C. Chung and J.H. Cho. “Comparison of
thermal/mechanical properties and shape memory effect of polyurethane
block-copolymers with planar or bent shape of hard segment.” Polymer,
vol 44 pp 3251-3258, 2013.
[7] R.L. Lavall, S. Ferrari, C. Tomasi, M. Marzantowicz, E. Quartarone, M.
Fagnoni, P. Mustarelli and M.L. Saladino, “MCM-41 silica effect on gel
polymer electrolytes based on thermoplastic polyurethane,”
Electrochimica Acta vol 60 pp 359-365, 2012.
[8] M.S. Su’ait, A. Ahmad, K.H. Badri, N.S. Mohamed, M.Y.A. RahmaN,
C.L. Azanza Ricardo and P. Scardi, “The potential of polyurethane biobased
solid polymer electrolyte for photoelectrochemical cell
application,” Journal of Hydrogen Energy, vol 39 pp 3005-3017, 2014.
[9] Libin Liu, Xiwen Wu and Tianduo Li, “Novel polymer electrolytes
based on cationic polyurethane with different alkyl chain length,”
Journal of Power Sources, vol249 pp 397-404, 2014.
[10] Shao-Ming Lee, Chuh-Yung Chen, Cheng-Chien Wang and Yao-Hui
Huang, “The effect of EPIDA units on the conductivity of poly(ethylene
glycol)–4,4$-diphenylmethane diisocyanate-EPIDA polyurethane
electrolytes,” Electrochimica Acta, vol 48 pp 669-677, 2003.
[11] K. Nakamae, T. Nishino, S. Asaoka and Sudaryanto, “Microphase
separation and surface properties of segmented polyurethane - Effect of
hard segment content,” 16 Adhesion and Adhesives, pp 233-239, 1996.
[12] C.W. Peng, C. Hsu, K.H. Lin, P.L. Li, M.F. Hsieh, Y. Wei, J.M. Yeh
and Y.H. Yu, “Electrochemical corrosion protection studies of anilinecapped
trimer-based electroactive polyurethane coatings,”
Electrochimica Acta, vol 58 pp 614-620, 2011.
[13] T.C. Wen, S.S. Luo and C.H. Yang, “Ionic conductivity of polymer
electrolytes derived from various diisocyanate-based waterborne
polyurethanes,” Polymer, vol 41 pp 6755-6764, 2000.
[14] K. Petcharoen and A. Sirivat, “Electrostrictive properties of
thermoplastic polyurethane elastomer: Effects of urethane type and soft–
hard segment composition,” Current Applied Physics, vol 13 pp 1119-
1127, 2013.
[15] Huang, J. and L. Zhang, “Effects of NCO/OH molar ratio on structure
and properties of graft-interpenetrating polymer networks from
polyurethane and nitrolignin,” Polymer, vol 43 pp 2287-2294, 2002.
[16] Anthony, J.R., Carme, M.C.F. & David, B, “Characterization of
polyurethane networks based on vegetable derived polyol,” Polymer, vol
49 pp 3279-3287, 2008.
[17] R.C. Agrawal and G.P. Pandey, “Solid polymer electrolytes: materials
designing and all-solid-state battery applications: an overview,” Physics
D: Applied Physics, vol 41 pp 223001, 2008.
[18] N.N. Mobarak, A.Ahmad, M.P. Abdullah, N. Ramli and M.Y.A
Rahman, “Conductivity enhancement via chemical modification of
chitosan based green polymer electrolyte,” Electrochimica Acta, vol 92
pp 161-167, 2013.
[19] S. Sang, J.Zhang, Q. Wu and Y, “Liao Influences of Bentonite on
conductivity of composite solid alkaline polymer electrolyte PVABentonite-
KOH-H2O,” Electrochimica Acta, vol 52 pp 7315-732, 2007.
[20] S. Haddad, N. Zanina, A. Othmane and L. Mora, “Polyurethane films
modified by antithrombin–heparin complex to enhance
endothelialization: An original impedimetric analysis,” Electrochimica
Acta,, vol 56 pp 7303-7011, 2011.
[21] Mutsuhisa, F, Ken, K, Shohei, N, “Microphase-separated structure and
mechanical properties of norbornane diisocyanate-based polyurethanes”,
Polymer, vol 48 pp 997-1004, 2007.
[22] K. Mishra, R. Narayan, K.V.S.N. Raju and T.M. Aminabhavi,
“Hyperbranched polyurethane (HBPU)-urea and HBPU-imide coatings:
Effect of chain extender and NCO/OH ratio on their properties,”
Progress in Organic Coatings, vol 74 pp 134-141, 2012.
[23] S. Xiong, F. Yang, G. Ding, K.Y. Mya, J. Ma and X. Lu, “Covalent
bonding of polyaniline on fullerene: Enhanced electrical, ionic
conductivities and electrochromic performances,” Electrochimica Acta,
vol 67 pp 194-200, 2012.
[24] F. Gaudin and N.S. Zydowiz, “Correlation between the polymerization
kinetics and the chemical structure of poly(urethane–urea) nanocapsule
membrane obtained by interfacial step polymerization in miniemulsion,”
Colloids and Surfaces A: Physiochemical and Engineering Aspects, vol
415 pp 328-342, 2012.
[25] C.S. Wong and K.H. Badri, “Thermal, Mechanical and Chemical
Analyses Of Rapid And Self-Cured Prepolymerized Polyurethane
Coatings,” Applied Mechanics and Materials, vol 313-314 pp 227-231,
2013.
[26] F. Gaudin and N.S. Zydowiz, “Core–shell biocompatible polyurethane
nanocapsules obtained by interfacial step polymerisation in
miniemulsion,” Colloids and Surfaces A: Physiochemical and
Engineering Aspects, vol 331 pp 133-142, 2008.
[27] L. Cuve, J.P. Pascault, G. Boiteux and G. Seytre, “Synthesis and
properties of polyurethanes based on polyolefine: 1. Rigid polyurethanes
and amorphous segmented polyurethanes prepared in polar solvents
under homogeneous conditions,” Polymer, vol 32 pp 343-352, 1991.
[28] D, Ren and C.E. Frazier, “Structure–property behaviour of moisture-cure
polyurethane wood adhesives: Influence of hard segment content,”.
Adhesion and Adhesives, vol 45 pp 118-124, 2013.
[29] S. Kaur, D. Rana, T. Matsuura, S. Sundarrajan and S. Ramakrishna,
“Preparation and characterization of surface modified electrospun
membranes for higher filtration flux,” Membrane Science, vol 390-391
pp 235-242, 2012.
[30] J. Saunier, N. Chaix, F. Alloin, J.P. Belieres and J.Y. Sanchez,
“Electrochemical study of polymethacrylonitrile electrolytes:
Conductivity study of polymer/salt complexes and plasticized polymer
electrolytes. Part I,” Electrochimica Acta, vol 47 pp 1321-1326, 2002.
[31] X. Ma, X. Huang, J. Gao, S. Zhang, Z. Deng and J. Suo, “Compliant gel
polymer electrolyte based on poly(methyl acrylate-coacrylonitrile)/
poly(vinyl alcohol) for flexible lithium-ion batteries,”
Electrochimica Acta, vol 115 pp 216-222, 2014.
[32] N. Ataollahi, A. Ahmad, H. Hamzah, M.Y.A Rahman, N.S Mohamed,
“Ionic conduction of blend poly (vinylidene fluoride-hexafluoro
propylene) and poly (methyl methacrylate) grafted natural rubber based
solid polymer electrolyte,” International Journal of Electrochemical
Science, vol 8: pp 7875-7884 June 2013.
[33] N. Ataollahi, A. Ahmad, T.K Lee, A.R Abdullah, M.Y.A Rahman,
“Prepration and characterization of PVDF-MG49-NH4CF3SO3 based
solid polymer electrolyte,” E-polymers vol 14(2) pp 115-120, March
2014.
[34] M.J. da Silva, D.H.F. Kanda and H.N. Nagashima, “Mechanism of
charge transport in castor oil-based polyurethane/carbon black
composite (PU/CB),” Non Crystalline Solids. Vol 358 pp 270-275, 2012.
[35] K.H. Badri, S.H. Ahmad and S. Zakaria. “Development of zero ODP
rigid polyurethane foam from RBD palm kernel oil,” Journal of Applied
Polymer Science. Vol 19 pp 1355-1356, 2000.
[1] N. Ataollahi, A. Ahmad, H. Hamzah, M.Y.A. Rahman.and N.S.
Mohamed, “Ionic conductivity of PVDF-HFP/MG49 based solid
polymer Electrolyte,” Advanced Materials Research, vol 501 pp 29-33,
April 2012.
[2] M. Ulaganathan and S. Rajendran, “Effect of different salts on
PVAc/PVdF-co-HFP based polymer blend electrolytes,” J. Applied
Polymer Science, vol 118 pp 646–651, 2010.
[3] M. Wetjen, G.T Kim, M. Joost, M. Winter, and S. Passerini,
“Temperature dependence of electrochemical properties of cross-linked
poly(ethylene oxide)–lithium bis(trifluoromethanesulfonyl)imide–Nbutyl-
N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide solid
polymer electrolytes for lithium batteries,” Electrochimica Acta vol 87
pp 779-787, 2013.
[4] A. Lewandowski, A.S. Mocek and L. Waliszewski, “Li+ conducting
polymer electrolyte based on ionic liquid for lithium and lithium-ion
batteries,” Electrochimica Acta vol 92 pp 404-411, 2013.
[5] C.S. Wong and K.H. Badri, “Chemical Analyses of Palm kernel oilbased
polyurethane prepolymer,” Materials Sciences and Applications,
vol 3 pp 78-86, 2012.
[6] J.H. Yang, B.C. Chun, Y.C. Chung and J.H. Cho. “Comparison of
thermal/mechanical properties and shape memory effect of polyurethane
block-copolymers with planar or bent shape of hard segment.” Polymer,
vol 44 pp 3251-3258, 2013.
[7] R.L. Lavall, S. Ferrari, C. Tomasi, M. Marzantowicz, E. Quartarone, M.
Fagnoni, P. Mustarelli and M.L. Saladino, “MCM-41 silica effect on gel
polymer electrolytes based on thermoplastic polyurethane,”
Electrochimica Acta vol 60 pp 359-365, 2012.
[8] M.S. Su’ait, A. Ahmad, K.H. Badri, N.S. Mohamed, M.Y.A. RahmaN,
C.L. Azanza Ricardo and P. Scardi, “The potential of polyurethane biobased
solid polymer electrolyte for photoelectrochemical cell
application,” Journal of Hydrogen Energy, vol 39 pp 3005-3017, 2014.
[9] Libin Liu, Xiwen Wu and Tianduo Li, “Novel polymer electrolytes
based on cationic polyurethane with different alkyl chain length,”
Journal of Power Sources, vol249 pp 397-404, 2014.
[10] Shao-Ming Lee, Chuh-Yung Chen, Cheng-Chien Wang and Yao-Hui
Huang, “The effect of EPIDA units on the conductivity of poly(ethylene
glycol)–4,4$-diphenylmethane diisocyanate-EPIDA polyurethane
electrolytes,” Electrochimica Acta, vol 48 pp 669-677, 2003.
[11] K. Nakamae, T. Nishino, S. Asaoka and Sudaryanto, “Microphase
separation and surface properties of segmented polyurethane - Effect of
hard segment content,” 16 Adhesion and Adhesives, pp 233-239, 1996.
[12] C.W. Peng, C. Hsu, K.H. Lin, P.L. Li, M.F. Hsieh, Y. Wei, J.M. Yeh
and Y.H. Yu, “Electrochemical corrosion protection studies of anilinecapped
trimer-based electroactive polyurethane coatings,”
Electrochimica Acta, vol 58 pp 614-620, 2011.
[13] T.C. Wen, S.S. Luo and C.H. Yang, “Ionic conductivity of polymer
electrolytes derived from various diisocyanate-based waterborne
polyurethanes,” Polymer, vol 41 pp 6755-6764, 2000.
[14] K. Petcharoen and A. Sirivat, “Electrostrictive properties of
thermoplastic polyurethane elastomer: Effects of urethane type and soft–
hard segment composition,” Current Applied Physics, vol 13 pp 1119-
1127, 2013.
[15] Huang, J. and L. Zhang, “Effects of NCO/OH molar ratio on structure
and properties of graft-interpenetrating polymer networks from
polyurethane and nitrolignin,” Polymer, vol 43 pp 2287-2294, 2002.
[16] Anthony, J.R., Carme, M.C.F. & David, B, “Characterization of
polyurethane networks based on vegetable derived polyol,” Polymer, vol
49 pp 3279-3287, 2008.
[17] R.C. Agrawal and G.P. Pandey, “Solid polymer electrolytes: materials
designing and all-solid-state battery applications: an overview,” Physics
D: Applied Physics, vol 41 pp 223001, 2008.
[18] N.N. Mobarak, A.Ahmad, M.P. Abdullah, N. Ramli and M.Y.A
Rahman, “Conductivity enhancement via chemical modification of
chitosan based green polymer electrolyte,” Electrochimica Acta, vol 92
pp 161-167, 2013.
[19] S. Sang, J.Zhang, Q. Wu and Y, “Liao Influences of Bentonite on
conductivity of composite solid alkaline polymer electrolyte PVABentonite-
KOH-H2O,” Electrochimica Acta, vol 52 pp 7315-732, 2007.
[20] S. Haddad, N. Zanina, A. Othmane and L. Mora, “Polyurethane films
modified by antithrombin–heparin complex to enhance
endothelialization: An original impedimetric analysis,” Electrochimica
Acta,, vol 56 pp 7303-7011, 2011.
[21] Mutsuhisa, F, Ken, K, Shohei, N, “Microphase-separated structure and
mechanical properties of norbornane diisocyanate-based polyurethanes”,
Polymer, vol 48 pp 997-1004, 2007.
[22] K. Mishra, R. Narayan, K.V.S.N. Raju and T.M. Aminabhavi,
“Hyperbranched polyurethane (HBPU)-urea and HBPU-imide coatings:
Effect of chain extender and NCO/OH ratio on their properties,”
Progress in Organic Coatings, vol 74 pp 134-141, 2012.
[23] S. Xiong, F. Yang, G. Ding, K.Y. Mya, J. Ma and X. Lu, “Covalent
bonding of polyaniline on fullerene: Enhanced electrical, ionic
conductivities and electrochromic performances,” Electrochimica Acta,
vol 67 pp 194-200, 2012.
[24] F. Gaudin and N.S. Zydowiz, “Correlation between the polymerization
kinetics and the chemical structure of poly(urethane–urea) nanocapsule
membrane obtained by interfacial step polymerization in miniemulsion,”
Colloids and Surfaces A: Physiochemical and Engineering Aspects, vol
415 pp 328-342, 2012.
[25] C.S. Wong and K.H. Badri, “Thermal, Mechanical and Chemical
Analyses Of Rapid And Self-Cured Prepolymerized Polyurethane
Coatings,” Applied Mechanics and Materials, vol 313-314 pp 227-231,
2013.
[26] F. Gaudin and N.S. Zydowiz, “Core–shell biocompatible polyurethane
nanocapsules obtained by interfacial step polymerisation in
miniemulsion,” Colloids and Surfaces A: Physiochemical and
Engineering Aspects, vol 331 pp 133-142, 2008.
[27] L. Cuve, J.P. Pascault, G. Boiteux and G. Seytre, “Synthesis and
properties of polyurethanes based on polyolefine: 1. Rigid polyurethanes
and amorphous segmented polyurethanes prepared in polar solvents
under homogeneous conditions,” Polymer, vol 32 pp 343-352, 1991.
[28] D, Ren and C.E. Frazier, “Structure–property behaviour of moisture-cure
polyurethane wood adhesives: Influence of hard segment content,”.
Adhesion and Adhesives, vol 45 pp 118-124, 2013.
[29] S. Kaur, D. Rana, T. Matsuura, S. Sundarrajan and S. Ramakrishna,
“Preparation and characterization of surface modified electrospun
membranes for higher filtration flux,” Membrane Science, vol 390-391
pp 235-242, 2012.
[30] J. Saunier, N. Chaix, F. Alloin, J.P. Belieres and J.Y. Sanchez,
“Electrochemical study of polymethacrylonitrile electrolytes:
Conductivity study of polymer/salt complexes and plasticized polymer
electrolytes. Part I,” Electrochimica Acta, vol 47 pp 1321-1326, 2002.
[31] X. Ma, X. Huang, J. Gao, S. Zhang, Z. Deng and J. Suo, “Compliant gel
polymer electrolyte based on poly(methyl acrylate-coacrylonitrile)/
poly(vinyl alcohol) for flexible lithium-ion batteries,”
Electrochimica Acta, vol 115 pp 216-222, 2014.
[32] N. Ataollahi, A. Ahmad, H. Hamzah, M.Y.A Rahman, N.S Mohamed,
“Ionic conduction of blend poly (vinylidene fluoride-hexafluoro
propylene) and poly (methyl methacrylate) grafted natural rubber based
solid polymer electrolyte,” International Journal of Electrochemical
Science, vol 8: pp 7875-7884 June 2013.
[33] N. Ataollahi, A. Ahmad, T.K Lee, A.R Abdullah, M.Y.A Rahman,
“Prepration and characterization of PVDF-MG49-NH4CF3SO3 based
solid polymer electrolyte,” E-polymers vol 14(2) pp 115-120, March
2014.
[34] M.J. da Silva, D.H.F. Kanda and H.N. Nagashima, “Mechanism of
charge transport in castor oil-based polyurethane/carbon black
composite (PU/CB),” Non Crystalline Solids. Vol 358 pp 270-275, 2012.
[35] K.H. Badri, S.H. Ahmad and S. Zakaria. “Development of zero ODP
rigid polyurethane foam from RBD palm kernel oil,” Journal of Applied
Polymer Science. Vol 19 pp 1355-1356, 2000.
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:68278", author = "C. S. Wong and K. H. Badri and N. Ataollahi and K. P. Law and M. S. Su’ait and N. I. Hassan", title = "Synthesis of New Bio-Based Solid Polymer Electrolyte Polyurethane-LiClO4 via Prepolymerization Method: Effect of NCO/OH Ratio on Their Chemical, Thermal Properties and Ionic Conductivity", abstract = "Novel bio-based polymer electrolyte was synthesized
with LiClO4 as the main source of charge carrier. Initially,
polyurethane-LiClO4 polymer electrolytes were synthesized via
prepolymerization method with different NCO/OH ratios and labelled
them as PU1, PU2, PU3 and PU4. Fourier transform infrared (FTIR)
analysis indicates the co-ordination between Li+ ion and polyurethane
in PU1. Differential scanning calorimetry (DSC) analysis indicates
PU1 has the highest glass transition temperature (Tg) corresponds to
the most abundant urethane group which is the hard segment in PU1.
Scanning electron microscopy (SEM) shows the good miscibility
between lithium salt and the polymer. The study found that PU1
possessed the greatest ionic conductivity and the lowest activation
energy, Ea. All the polyurethanes exhibited linear Arrhenius
variations indicating ion transport via simple lithium ion hopping in
polyurethane. This research proves the NCO content in polyurethane
plays an important role in affecting the ionic conductivity of this
polymer electrolyte.
", keywords = "Ionic conductivity, Palm kernel oil-based monoester
polyol, polyurethane, solid polymer electrolyte.", volume = "8", number = "11", pages = "1243-8", }
