Abstract
Eco-friendly and cost-effective solid biopolymer electrolytes based on tamarind seed polysaccharide (TSP) as host polymer with different concentrations of lithium perchlorate (LiClO4) as ionic dopant salt and different wt% of ethylene carbonate (EC) as plasticizer have been synthesized via solution casting technique. The amorphous nature and complexation of the salt with the polymer matrix have been confirmed by XRD and FTIR analysis, respectively. The change in glass transition temperature (Tg) of the polymer electrolyte has been measured using DSC analysis. Maximum ionic conductivity of 8.77 × 10−4 S cm−1 is obtained for the polymer electrolyte composition of 1 g TSP/0.45 g LiClO4 at ambient temperature, whereas the ionic conductivity improved to 1 order of magnitude (1.06 × 10−3 S cm−1) through the incorporation of 0.3 wt% EC plasticizer into the above polymer electrolyte composition determined by AC impedance analysis. The activation energy (Ea) is observed to be low for the highest conducting EC plasticizer incorporated polymer electrolyte. The value of ionic transference number estimated by Wagner’s dc polarization method reveals that the conducting species are predominantly Li+ ions. The electrochemical stability window of the highest conducting biopolymer electrolytes has been determined by LSV. From the constructed battery, the open circuit cell potentials of 1.6 and 1.9 V have been observed for the TSP-LiClO4 and TSP-LiClO4-EC polymer electrolyte systems, respectively. The performance of the constructed battery has been compared with the commercially available lithium battery.
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Jeong SK, Inaba M, Iriyama Y, Abe T, Ogumi Z (2008) Interfacial reactions between graphite electrodes and propylene carbonate-based solutions: electrolyte-concentration dependence of electrochemical lithium intercalation reaction. J Power Sources 175:540–546
Arya A, Sharma AL (2017) Polymer electrolytes for lithium ion batteries: a critical study. Ionics 23(3):497–540
Singh R, Polu AR, Bhattacharya B, Rhee HW, Varlikli C, Singh PK (2016) Perspectives for solid biopolymer electrolytes in dye sensitized solar cell and battery application. Renew Sust Energ Rev 65:1098–1117
Zhang HP, Zhang P, Li ZH, Sun M, Wu YP, Wu HQ (2007) A novel sandwiched membrane as polymer electrolyte for lithium ion battery. Electrochem Commun 9(7):1700–1703
Shamsudin IA, Ahmad A, Hassan NH, Kaddami H (2015) Biopolymer electrolytes based on carboxymethyl O-carrageenan and imidazolium ionic liquid. Ionics 22(6):841–851
Avachat AM, Dash RR, Shrotriya SN (2011) Recent investigations of plant based natural gums, mucilages and resins in novel drug delivery systems. Indian J Pharm Educ Res 45:86–99
Shukur MF, Kadir MFZ (2015) Electrical & transport properties of NH4Br doped corn starch based solid biopolymer electrolyte. Ionics 21:111–124
Majid SR, Arof AK (2005) Proton-conducting polymer electrolyte films based on chitosanacetate complexed with NH4NO3 salt. Phys B Condens Matter 355(1–4):78–82
Pasini Cabello SD, Ochoa NA, Takara EA, Molla S, Compan V (2017) Influence of pectin as a green polymer electrolyte on the transport properties of chitosan-pectin membranes. Carbohydr Polym 57:1759–1768
Moniha V, Alagar M, Selvasekarapandian S, Sundaresan B, Hemalatha R, Boopathi G (2018) Synthesis and characterization of bio polymer electrolyte based on iota-carrageenan with ammonium thiocyanate and its applications. J Solid State Electrochem 22:3209–3223
Selvakumar M, Bhat DK (2008) LiClO4 doped cellulose acetate as biodegradable polymer electrolyte for supercapacitors. J Appl Polym Sci 110:594–602
Sharma M, Mondal D, Mukesh C, Prasad K (2014) Preparation of tamarind gum based soft ion gels having thixotropic properties. Carbohydr Polym 102:467–471
Chawananorasest K, Saengtongdee P, Kaemchantuek P (2016) Extraction and characterization of tamarind (Tamarind indica L.) seed polysaccharides (TSP) from three difference sources. Molecules 775:1–9
Premalatha M, Mathavan T, Selvasekarapandian S, Monisha S, Pandi DV, Selvalakshmi S (2016) Investigations on proton conducting biopolymer membranes based on tamarind seed polysaccharide incorporated with ammonium thiocyanate. J Non-Cryst Solids 453:131–140
Premalatha M, Mathavan T, Selvasekarapandian S, Selvalakshmi S (2017) Incorporation of NH4Br in tamarind seed polysaccharide biopolymer and its potential use in electrochemical energy storage devices. Org Electron 50:418–425
Premalatha M, Mathavan T, Selvasekarapandian S, Monisha S, Selvalakshmi S, Vinoth Pandi D (2017) Tamarind seed polysaccharide (TSP)-based Li-ion conducting membranes. Ionics 23:2677–2684
Kumar LS, Christopher P, Selvasekarapandian S, Manjuladevi S, Monisha S, Perumal P (2018) Tamarind seed polysaccharide biopolymer membrane for lithium-ion conducting battery. Ionics 24:3793–3803
Sudhakar YN, Selvakumar M (2012) Lithium perchlorate doped plasticized chitosan and starch blend as biodegradable polymer electrolyte for supercapacitors. Electrochim Acta 78:398–405
Monisha S, Mathavan T, Selvasekarapandian S, Milton Franklin Benial A, Premalatha M (2016) Preparation and characterization of cellulose acetate and lithium nitrate for advanced electrochemical devices. Ionics 23:2677–2684
Prabakaran P, Manimuthu RP, Gurusamy S, Sebasthiyan E (2017) Plasticized polymer electrolyte membranes based on PEO/PVdF-HFP for use as an effective electrolyte in lithium-ion batteries. Chin J Polym Sci 35:407–421
Kim D (1996) Conductivity and thermal studies of solid polymer electrolytes prepared by blending poly(ethylene oxide), poly(oligo[oxyethylene]oxysebacoyl) and lithium perchlorate. Solid State Ionics 83:49–56
Watanabe M, Nagano S, Sanui K, Ogata N (1987) Structure-conductivity relationship in polymer electrolytes formed by network polymers from poly [dimethylsiloxane-g-poly (ethylene oxide)] and lithium perchlorate. J Power Sources 20:327–332
Wieczorek W, Stevens JR (1997) Impedance spectroscopy and phase structure of polyether-poly (methyl methacrylate)-LiCF3SO3 blend-based electrolytes. J Phys Chem B 101(9):1529–1534
Nagasubramanian G, Attia AI, Halpert G (1994) A polyacrylonitrile-based gelled electrolyte: electrochemical kinetic studies. J Appl Electrochem 24:298–302
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
Przyluski J, Wieczorek W (1989) Increasing the conductivity of polymer sold electrolytes—a review. Solid State Ionics 36:165–169
Sun XG, Liu G, Xie J, Han Y, Kerr JB (2004) New gel polyelectrolytes for rechargeable lithium batteries. Solid State Ionics 175:713–716
Labreche C, Prud’homme J (1999) Preferential solvation and free volume as interrelated features governing ion conduction in plasticized polyether electrolytes. J Power Sources 82:130–136
Li T, Balbuena PB (1999) Theoretical studies of lithium perchlorate in ethylene carbonate, propylene carbonate, and their mixtures. J Electrochem Soc 146:3613–3622
Ramesh S, Shanti R, Durairaj R (2011) Effect of ethylene carbonate in poly (methyl methacrylate)-lithium tetraborate based polymer electrolytes. J Non-Cryst Solids 357:1357–1363
Rajendran S, Sivakumar P (2008) An investigation of PVdF/PVC-based blend electrolytes with EC/PC as plasticizers in lithium battery applications. Phys B 403:509–516
Shukur MF, Majid NA, Ithnin R, Kadir MFZ (2013) Effect of plasticization on the conductivity and dielectric properties of starch-chitosan blend biopolymer electrolytes infused with NH4Br. Phys Scr T157:014051. https://doi.org/10.1088/0031-8949/2013/T157/014051
Sudhakar YN, Selvakumar M, Bhat DK (2013) LiClO4 doped plasticized chitosan and poly (ethylene glycol) blend as biodegradable polymer electrolyte for supercapacitors. Ionics 19:277–285
Samsudin AS, Isa MIN (2014) Conductivity and transport properties study of plasticized carboxymethyl cellulose (CMC) based solid biopolymer electrolytes (SBE). Adv Mater Res 856:118–122
Perumal P, Christopher Selvin P, Selvasekarapandian S, Sivaraj P, Abhilash KP, Moniha V, Manjula Devi R (2018) Plasticizer incorporated, novel eco-friendly bio-polymer based solid bio-membrane for electrochemical clean energy applications. J Polym Degrad stab 159:43–53. https://doi.org/10.1016/j.polymdegradstab.2018.11.013
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. J Polym 9:187
Rajendran S, Ramesh Prabhu M (2010) Effect of different plasticizer on structural and electrical properties of PEMA-based polymer electrolytes. J Appl Electrochem 4:327–332
Selvasekarapandian S (2013) Analysis of lithium ion conducting P(VdCl-co-AN-co-MMA)-LiClO4-DMF tri block copolymer electrolytes. Indian J Applied Res 4:498–505
Flora XH, Ulaganathan M, Rajendran S (2012) Influence of lithium salt concentration on PAN-PMMA blend polymer electrolytes. Int J Electrochem Sci 7:7451–7462
Baskaran R, Selvasekarapandian S, Kuwata N, Kawamura J, Hattori T (2007) Structure, thermal and transport properties of PVAc-LiClO4 solid polymer electrolytes. J Phys Chem Solids 68:407–412
Awadhia A, Agrawal SL (2007) Structural, thermal and electrical characterizations of PVA:DMSO:NH4SCN gel electrolytes. Solid State Ionics 178:951–958
Shukur MF, Ithnin R, Kadir MFZ (2014) Electrical properties of proton conducting solid biopolymer electrolytes based on starch-chitosan blend. Ionics 20:977–999
Rathod SG, Bhajantri R, Ravindrachary V (2016) Influence of transport parameters on conductivity of lithium poly (vinyl alcohol)/chitosan composites. J Elastomers Plast 48(5):442–455
Monisha S, Mathavan T, Selvasekarapandian S, Benial AMF, Latha MP (2017) Preparation and characterization of cellulose acetate and lithium nitrate for advanced electrochemical devices. Ionics 23:2697–2706
Bhuvaneswari R, Karthikeyan S, Selvasekarapandian S, Vinoth Pandi D, Vijaya N, Araichimani A, Sanjeeviraja C (2014) Preparation and characterization of PVA complexed with amino acid, proline. Ionics 21:387–399
Kim JH, Min BR, Won J, Kang YS (2003) Analysis of the glass transition behavior of polymer-salt complexes: an extended configurational entropy model. J Phys Chem B 107:5901–5905
Huh PH, Choi MG, Jo NJ, Lee JK, Lee JO, Yang W (2004) Effect of salt concentration on the glass transition temperature and ionic conductivity of poly (ethylene glycol) polyurethane/LiClO4 complexes. Macromol Res 12:422–426
Taib NU, Hayati N (2014) Plastic crystal-solid biopolymer electrolytes for rechargeable lithium batteries. J Membr Sci 468:149–154
Boukamp BA (1986) A nonlinear least squares fit procedure for analysis of immittance data of electrochemical systems. Solid State Ionics 20:31–44
Kumar M, Sekhon SS (2002) Ionic conductance behaviour of plasticized polymer electrolytes containing different plasticizers. Ionics 8:223–233
Chandra MVL, Karthikeyan S, Selvasekarapandian S, Premalatha M, Monisha S (2017) Study of PVAc-PMMA-LiCl polymer blend electrolyte and the effect of plasticizer ethylene carbonate and nanofiller titania on PVAc-PMMA-LiCl polymer blend electrolyte. J Polym Eng 37:617–631
Sekhar PC, Kumar PN, Sharma AK (2012) Effect of plasticizer on conductivity and cell parameters of (PMMA + NaClO4) polymer electrolyte system. J Appl Phys 2:1–6
Ibrahim S, Johan MR (2012) Thermolysis and conductivity studies of poly (ethylene oxide) (PEO) based polymer electrolytes doped with carbon nanotube. Int J Electrochem Sci 7:2596–2615
Johan MR, Ting LM (2011) Structural, thermal and electrical properties of nano manganese-composite polymer electrolytes. Int J Electrochem Sci 6:4737–4748
Armand MB, Chabagno JM, Duclot MJ, Vashita P, Munday LN and Shoney G (1979) Fast-ion transport in solids. Electrodes and Electrolytes. Elsevier, North-Holland, Amsterdam
Rajendran S, Sivakumar M, Subadevi R (2004) Investigations on the effect of various plasticizers in PVA–PMMA solid polymer blend electrolytes. Mater Lett 58:641–649
Genova FKM, Selvasekarapandian S, Karthikeyan S, Vijaya N, Pradeepa R, Sivadevi S (2015) Study on blend polymer (PVA-PAN) doped with lithium bromide. Polym Sci Ser A 57:851–862
Ramly K, Isa MIN, Khiar ASA (2011) Conductivity and dielectric behaviour studies of starch / PEO + x wt-% NH4NO3 polymer electrolyte. Mater Res Innov 15:2–5
Ramesh S, Yahaya AH, Arof AK (2002) Dielectric behaviour of PVC based polymer electrolytes. Solid State Ionics 152–153:291–294
Wagner JB, Wagner C (1957) Electrical conductivity measurements on cuprous halides. J Chem Phys 26:1597–1601
Winnie T, Arof AK (2006) Transport properties of hexanoyl chitosan based gel electrolyte. Ionics 12:149–152
Rudhziah S, Ahmad A, Ahmad I, Mohamed NS (2015) Biopolymer electrolytes based on blend of kappa-carrageenan and cellulose derivatives for potential application in dye sensitized solar cell. Electrochim Acta 175:162–168
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
Kingslin Mary Genova F, Selvasekarapandian S, Karthikeyan S et al (2015) Study on blend polymer (PVA-PAN) doped with lithium bromide. Polym Sci 57:851–862
Kingslin Mary Genova F, Selvasekarapandian S, Vijaya N, Sivadevi S, Premalatha M, Karthikeyan S (2017) Lithium ion-conducting polymer electrolytes based on PVA–PAN doped with lithium triflate. Ionics 23:2727–2734
Perumal P, Christopher Selvin P, Selvasekarapandian S (2018) Characterization of biopolymer pectin with lithium chloride and its applications to electrochemical devices. Ionics 24:3259–3270
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Sampathkumar, L., Christopher Selvin, P., Selvasekarapandian, S. et al. Synthesis and characterization of biopolymer electrolyte based on tamarind seed polysaccharide, lithium perchlorate and ethylene carbonate for electrochemical applications. Ionics 25, 1067–1082 (2019). https://doi.org/10.1007/s11581-019-02857-1
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DOI: https://doi.org/10.1007/s11581-019-02857-1