, Volume 23, Issue 11, pp 3111–3123 | Cite as

The order of addition of corn starch/lithium perchlorate/glycerol affects the optical, mechanical, and electrical properties of a solid polymer electrolyte

  • E.J. Vernon-Carter
  • J. Alvarez-Ramirez
  • L.A. Bello-Perez
  • C. Roldan-Cruz
  • A. Garcia-Hernandez
  • L. Huerta
Original Paper


Optical, mechanical, and electric properties of solid polymer electrolyte (SPE) were affected by the order of addition of corn starch (S), lithium perchlorate (Li), and glycerol (G) during the preparation process. Four formulations were made based on whether Li was added prior to S gelatinization (simultaneous formulations SGLi and SLi+G) or whether it was added after S was gelatinized (sequential formulations SG+Li and S+LiG). Simultaneous formulations produced films with smaller elongation-at-break response (60–75%) relative to their sequential counterparts (75–82%). The simultaneous formulations exhibited higher electrical conductivity (∼0.7 mS cm−1) and capacitance (∼0.017 F cm−2) and electrochemical stability than the sequential formulations (∼0.9 mS cm−1 and ∼0.012 F cm−2) at room temperature. Results from FTIR and DSC analyses indicated that starch re-crystallization in casting phase could lead to variations on electrical properties for the different SPE formulations. It was postulated that Li cations replace hydrogen ions inside starch molecules, retarding the re-crystallization of starch molecules.


Solid polymer electrolyte Corn starch Lithium perchlorate Order of addition Re-crystallization 



The authors thank the Consejo Nacional de Ciencia y Tecnología (CONACyT) for partially financing this work through project 236500.

Author’s contribution

E. J. Vernon-Carter proposed the use of contact angle and EIS for monitoring film stability. J. Alvarez-Ramirez organized results and discussion. L.A. Bello-Perez helped with the characterization of starch-based films. C. Roldan-Cruz (Ph.D. student) designed and performed the EIS experiments. A. Garcia-Hernandez (Ph.D. student) carried out conductivity, opacity, and mechanical response tests. L. Huerta carried out and interpreted XPS studies. All authors contributed to the writing of the manuscript.

Compliance with ethical standards

Conflict of interest

The authors declare no competing financial interest.


  1. 1.
    Croce F, Appetecchi GB, Persi L, Scrosati B (1998) Nanocomposite polymer electrolytes for lithium batteries. Nature 394:456–458CrossRefGoogle Scholar
  2. 2.
    Wu JH, Lan Z, Lin JM, Huang ML, Hao SC, Sato T, Yin S (2007) A novel thermosetting gel electrolyte for stable quasi-solid-state dye-sensitized solar cells. Adv Mater 19:4006–4011CrossRefGoogle Scholar
  3. 3.
    Meng C, Liu C, Chen L, Hu C, Fan S (2010) Highly flexible and all-solid-state paperlike polymer supercapacitors. Nano Lett 10(10):4025–4031CrossRefGoogle Scholar
  4. 4.
    Khiar AA, Arof AK (2010) Conductivity studies of starch-based polymer electrolytes. Ionics 16:123–129CrossRefGoogle Scholar
  5. 5.
    Khiar ASA, Puteh R, Arof AK (2006) Conductivity studies of a chitosan-based polymer electrolyte. Physica B 373:23–27CrossRefGoogle Scholar
  6. 6.
    Yamazaki A, Takegawa R, Kaneko Y, Kadokawa JI, Yamagata M, Ishikawa M (2009) An acidic cellulose–chitin hybrid gel as novel electrolyte for an electric double layer capacitor. Electrochem Commun 11:68–70CrossRefGoogle Scholar
  7. 7.
    Park SJ, Yoo K, Kim JY, Kim JY, Lee DK, Kim B, Ko MJ (2013) Water-based thixotropic polymer gel electrolyte for dye-sensitized solar cells. ACS Nano 7:4050–4056CrossRefGoogle Scholar
  8. 8.
    Vieira DF, Avellaneda CO, Pawlicka A (2007) Conductivity study of a gelatin-based polymer electrolyte. Electrochim Acta 53:1404–1408CrossRefGoogle Scholar
  9. 9.
    Zobel HF (1988) Molecules to granules: a comprehensive starch review. Starch-Stärke 40:44–50CrossRefGoogle Scholar
  10. 10.
    Marcondes RF, D’Agostini PS, Ferreira J, Girotto EM, Pawlicka A, Dragunski DC (2010) Amylopectin-rich starch plasticized with glycerol for polymer electrolyte application. Solid State Ionics 181:586–591CrossRefGoogle Scholar
  11. 11.
    Sudhakar YN, Selvakumar M (2012) Lithium perchlorate doped plasticized chitosan and starch blend as biodegradable polymer electrolyte for supercapacitors. Electrochim Acta 78:398–405CrossRefGoogle Scholar
  12. 12.
    Sudhakar YN, Selvakumar M (2013) LiClO4-doped plasticized chitosan and poly (ethylene glycol) blend as biodegradable polymer electrolyte for supercapacitors. Ionics 19:277–285CrossRefGoogle Scholar
  13. 13.
    Kumar M, Tiwari T, Srivastava N (2012) Electrical transport behaviour of bio-polymer electrolyte system: potato starch+ammonium iodide. Carbohydr Polym 88:54–60CrossRefGoogle Scholar
  14. 14.
    Lin Y, Li J, Liu K, Liu Y, Liu J, Wang X (2016) Unique starch polymer electrolyte for high capacity all-solid-state lithium sulfur battery. Green Chem 18:3796–3803CrossRefGoogle Scholar
  15. 15.
    Biliaderis CG, Maurice TJ, Vose JR (1980) Starch gelatinization phenomena studied by differential scanning calorimetry. J Food Sci 45(6):1669–1674CrossRefGoogle Scholar
  16. 16.
    Ratnayake WS, Jackson DS (2007) A new insight into the gelatinization process of native starches. Carbohydr Polym 67:511–529CrossRefGoogle Scholar
  17. 17.
    Ning W, Xingxiang Z, Haihui L, Benqiao H (2009) 1-Allyl-3-methylimidazolium chloride plasticized-corn starch as solid biopolymer electrolytes. Carbohydr Polym 76:482–484CrossRefGoogle Scholar
  18. 18.
    Ramesh S, Liew CW, Arof AK (2011) Ion conducting corn starch biopolymer electrolytes doped with ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate. J Non-Cryst Solids 357(21):3654–3660CrossRefGoogle Scholar
  19. 19.
    Khanmirzaei MH, Ramesh S (2014) Nanocomposite polymer electrolyte based on rice starch/ionic liquid/TiO2 nanoparticles for solar cell application. Measurement 58:68–72CrossRefGoogle Scholar
  20. 20.
    Wang S, Li C, Copeland L, Niu Q, Wang S (2015) Starch retrogradation: a comprehensive review. Compr Rev Food Sci Food Saf 14:568–585CrossRefGoogle Scholar
  21. 21.
    Li G, Li Z, Zhang P, Zhang H, Wu Y (2008) Research on a gel polymer electrolyte for Li-ion batteries. Pure Appl Chem 80:2553–2563Google Scholar
  22. 22.
    ASTM D1003-00 (2000) Standard test method for haze and luminous transmittance of transparent plastics. ASTM International, West ConshohockenGoogle Scholar
  23. 23.
    ASTM D882-00 (2000) Standard test method for tensile properties of thin plastic sheeting. ASTM International, West ConshohockenGoogle Scholar
  24. 24.
    Hermans PH, Weidinger A (1949) X-ray studies on the crystallinity of cellulose. J Polym Sci 4:135–144CrossRefGoogle Scholar
  25. 25.
    Ahvenainen P, Kontro I, Svedström K (2016) Comparison of sample crystallinity determination methods by X-ray diffraction for challenging cellulose I materials. Cellulose 23:1073–1086CrossRefGoogle Scholar
  26. 26.
    Roldan-Cruz C, Garcia-Hernandez A, Vernon-Carter EJ, Alvarez-Ramirez J (2017) Impact of insoluble starch remnants on the behavior of corn starch/glycerol/LiCl solid electrolyte. Ionics. doi: 10.1007/s11581-017-2014-0 Google Scholar
  27. 27.
    Romero-Bastida CA, Bello-Perez LA, Velazquez G, Alvarez-Ramirez J (2015) Effect of the addition order and amylose content on mechanical, barrier and structural properties of films made with starch and montmorillonite. Carbohydr Polym 127:195–201CrossRefGoogle Scholar
  28. 28.
    Oosten BJ (1982) Tentative hypothesis to explain how electrolytes affect the gelatinization temperature of starches in water. Starch-Stärke 34:233–239CrossRefGoogle Scholar
  29. 29.
    Lobato-Calleros C, Hernandez-Jaimes C, Chavez-Esquivel G, Meraz M, Sosa E, Lara VH, Alvarez-Ramirez J, Vernon-Carter EJ (2015) Effect of lime concentration on gelatinized maize starch dispersions properties. Food Chem 172:353–360CrossRefGoogle Scholar
  30. 30.
    Xian-Zhong H, Hamaker BR (2002) Association of starch granule proteins with starch ghosts and remnants revealed by confocal laser scanning microscopy. Cereal Chem 79:892–896CrossRefGoogle Scholar
  31. 31.
    Debet MR, Gidley MJ (2007) Why do gelatinized starch granules not dissolve completely? Roles for amylose, protein, and lipid in granule “ghost” integrity. J Agric Food Chem 55:4752–4760CrossRefGoogle Scholar
  32. 32.
    Ma X, Yu J, He K, Wang N (2007) The effects of different plasticizers on the properties of thermoplastic starch as solid polymer electrolytes. Macromol Mat Eng 292:503–510CrossRefGoogle Scholar
  33. 33.
    Liew CW, Ramesh S, Ramesh K, Arof AK (2012) Preparation and characterization of lithium ion conducting ionic liquid-based biodegradable corn starch polymer electrolytes. J Solid State Electrochem 16:1869–1875CrossRefGoogle Scholar
  34. 34.
    Utrilla-Coello RG, Hernández-Jaimes C, Carrillo-Navas H, González F, Rodríguez E, Bello-Perez LA, Alvarez-Ramirez J (2014) Acid hydrolysis of native corn starch: morphology, crystallinity, rheological and thermal properties. Carbohydr Polym 103:596–602CrossRefGoogle Scholar
  35. 35.
    Karim AA, Norziah MH, Seow CC (2000) Methods for the study of starch retrogradation. Food Chem 71:9–36CrossRefGoogle Scholar
  36. 36.
    Sevenou O, Hill SE, Farhat IA, Mitchell JR (2002) Organisation of the external region of the starch granule as determined by infrared spectroscopy. Int J Biol Macromol 31(1):79–85CrossRefGoogle Scholar
  37. 37.
    van Soest JJ, Tournois H, de Wit D, Vliegenthart JF (1995) Short-range structure in (partially) crystalline potato starch determined with attenuated total reflectance Fourier-transform IR spectroscopy. Carbohydr Res 279:201–214CrossRefGoogle Scholar
  38. 38.
    Beck M, Jekle M, Becker T (2011) Starch re-crystallization kinetics as a function of various cations. Starch-Stärke 63:792–800CrossRefGoogle Scholar
  39. 39.
    Al-Muhtaseb AH, McMinn WAM, Magee TRA (2004) Water sorption isotherms of starch powders. Part 2: thermodynamic characteristics. J Food Eng 62:135–142CrossRefGoogle Scholar
  40. 40.
    Liu H, Chaudhary D, Yusa S, Tadé MO (2011) Glycerol/starch/Na+-montmorillonite nanocomposites: a XRD, FTIR, DSC and 1H NMR study. Carbohydr Polym 83:1591–1597CrossRefGoogle Scholar
  41. 41.
    Talja RA, Helén H, Roos YH, Jouppila K (2007) Effect of various polyols and polyol contents on physical and mechanical properties of potato starch-based films. Carbohydr Polym 67:288–295CrossRefGoogle Scholar
  42. 42.
    Huang X, Kocaefe D, Kocaefe Y, Boluk Y, Pichette A (2012) Study of the degradation behavior of heat-treated jack pine (Pinus banksiana) under artificial sunlight irradiation. Polym Degrad Stab 97:1197–1214CrossRefGoogle Scholar
  43. 43.
    Samsudin AS, Khairul WM, Isa MIN (2012) Characterization on the potential of carboxy methylcellulose for application as proton conducting biopolymer electrolytes. J Non-Cryst Solids 358:1104–1112CrossRefGoogle Scholar
  44. 44.
    Shukur MF, Kadir MFZ (2015) Hydrogen ion conducting starch-chitosan blend based electrolyte for application in electrochemical devices. Electrochim Acta 158:152–165CrossRefGoogle Scholar
  45. 45.
    Selvakumar M, Bhat DK (2008) LiClO4 doped cellulose acetate as biodegradable polymer electrolyte for supercapacitors. J Appl Polym Sci 110:594–602CrossRefGoogle Scholar
  46. 46.
    Stephan AM, Thirunakaran RN, Renganathan G, Sundaram V, Pitchumani S, Muniyandi N, Ramamoorthy P (1999) A study on polymer blend electrolyte based on PVC/PMMA with lithium salt. J Power Sources 81:752–758CrossRefGoogle Scholar
  47. 47.
    Jaipal Reddy M, Sreekanth T, Subba Rao UV (1999) Study of the plasticizer effect on a (PEO+NaYF4) polymer electrolyte and its use in an electrochemical cell. Solid State Ionics 126:55–63CrossRefGoogle Scholar
  48. 48.
    Teoh KH, Lim CS, Ramesh S (2014) Lithium ion conduction in corn starch based solid polymer electrolytes. Measurement 48:87–95CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2017

Authors and Affiliations

  • E.J. Vernon-Carter
    • 1
  • J. Alvarez-Ramirez
    • 1
  • L.A. Bello-Perez
    • 2
  • C. Roldan-Cruz
    • 3
  • A. Garcia-Hernandez
    • 1
  • L. Huerta
    • 4
  1. 1.Departamento de Ingeniería de Procesos e HidráulicaUniversidad Autónoma Metropolitana-IztapalapaCiudad de MéxicoMexico
  2. 2.Centro de Desarrollo de Productos BioticosInstituto Politécnico NacionalYautepecMexico
  3. 3.Departamento BiotecnologíaUniversidad Autónoma Metropolitana-IztapalapaCiudad de MéxicoMexico
  4. 4.Instituto de Investigación en MaterialsUniversidad Nacional Autónoma de MéxicoCiudad de MéxicoMexico

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