, Volume 24, Issue 8, pp 2287–2294 | Cite as

Thermal and electrochemical properties of poly(butylene sulfite)-based polymer electrolyte

  • Takahito ItohEmail author
  • Satoshi Niihara
  • Takahiro Uno
  • Masataka Kubo
Original Paper


Poly(butylene sulfite) (poly-1) was synthesized by cationic ring-opening polymerization of butylene sulfite (1), which was prepared by the reaction of 1,4-butanediol and thionyl chloride, with trifluoromethanesulfonic acid (TfOH) in bulk. The polymer electrolytes composed of poly-1 with lithium salts such as bis(trifluoromethanesulfonyl)imide (LiN(SO2CF3)2, LiTFSI) and bis(fluorosulfonyl)imide (LiN(SO2F)2, LiFSI) were prepared, and their ionic conductivities, thermal, and electrochemical properties were investigated. Ionic conductivities of the polymer electrolytes for the poly-1/LiTFSI system increased with lithium salt concentrations, reached maximum values at the [LiTFSI]/[repeating unit] ratio of 1/10, and then decreased in further more salt concentrations. The highest ionic conductivity values at the [LiTFSI]/[repeating unit] ratio of 1/10 were 2.36 × 10−4 S/cm at 80 °C and 1.01 × 10−5 S/cm at 20 °C. On the other hand, ionic conductivities of the polymer electrolytes for the poly-1/LiFSI system increased with an increase in lithium salt concentrations, and ionic conductivity values at the [LiFSI]/[repeating unit] ratio of 1/1 were 1.25 × 10−3 S/cm at 80 °C and 5.93 × 10−5 S/cm at 20 °C. Glass transition temperature (T g) increased with lithium salt concentrations for the poly-1/LiTFSI system, but T g for the poly-1/LiFSI system was almost constant regardless of lithium salt concentrations. Both polymer electrolytes showed high transference number of lithium ion: 0.57 for the poly-1/LiTFSI system and 0.56 for the poly-1/LiFSI system, respectively. The polymer electrolytes for the poly-1/LiTFSI system were thermally more stable than those for the poly-1/LiFSI system.


Polysulfite Polymer electrolyte Ionic conductivity Transference number Thermal property 


  1. 1.
    Tarascon JM, Armand M (2001) Issues and challenges facing rechargeable lithium batteries. Nature 414(6861):359–367. CrossRefGoogle Scholar
  2. 2.
    Xu K (2004) Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chem Rev 104(10):4303–4418. CrossRefPubMedGoogle Scholar
  3. 3.
    Scrosati B (1993) Applications of electroactive polymers. Chapman & Hall, London, p 251. CrossRefGoogle Scholar
  4. 4.
    Bruce PG (1995) Solid state electrochemistry 95. Cambridge University Press, CambridgeGoogle Scholar
  5. 5.
    Gray FG (1991) Solid polymer electrolytes: fundamentals and technological applications. VCH Publishers, New YorkGoogle Scholar
  6. 6.
    Gray FG (1997) Polymer electrolytes. The Royal Society of Chemistry, CambridgeGoogle Scholar
  7. 7.
    Paunzer MJ, Frisbie CD (2007) Polymer electrolyte-gated organic field-effect transistors: low-voltage, high-current switches for organic electronics and testbeds for probing electrical transport at high charge carrier density. J Am Chem Soc 129(20):6599–6607. CrossRefGoogle Scholar
  8. 8.
    Hu W, Zheng Z, Jiang J (2017) Vertical organic-inorganic hybrid transparent oxide TFTs gated by biodegradable electric-double-layer biopolymer. Org Electron 44:1–5. CrossRefGoogle Scholar
  9. 9.
    Liplowski J, Ross PN (1994) The electrochemistry of novel materials. VHC Publishers, New YorkGoogle Scholar
  10. 10.
    Croce F, Appetecchi GB, Persi L, Scrosati B (1998) Nanocomposite polymer electrolytes for lithium batteries. Nature 394(6692):456–458. CrossRefGoogle Scholar
  11. 11.
    Nishimoto A, Watanabe M, Ikeda Y, Kojiya S (1998) High ionic conductivity of new polymer electrolytes based on high molecular weight polyether comb polymers. Electrochim Acta 43(10-11):1177–1184. CrossRefGoogle Scholar
  12. 12.
    Itoh T, Hirata N, Wen Z, Kubo M, Yamamoto O (2001) Polymer electrolytes based on hyperbranched polymers. J Power Sources 97-98:637–640. CrossRefGoogle Scholar
  13. 13.
    Tominaga Y, Izumi Y, Kwark GH, Asai S, Sumita H (2003) Effect of the supercritical carbon dioxide processing on ionic association and conduction in a crystalline poly(ethylene oxide)-LiCF3SO3 complex. Macromolecules 36(23):8766–8772. CrossRefGoogle Scholar
  14. 14.
    Tominaga Y, Shimomura T, Nakamura M (2010) Alternating copolymers of carbon dioxide with glycidyl ethers for novel ion-conductive polymer electrolytes. Polymer 51(19):4295–4298. CrossRefGoogle Scholar
  15. 15.
    Nakamura M, Tominaga Y (2011) Utilization of carbon dioxide for polymer electrolytes [II]: synthesis of alternating copolymers with glycidyl ethers as novel ion-conductive polymers. Elecrochim Acta 57:36–39. CrossRefGoogle Scholar
  16. 16.
    Tominaga Y, Yamazaki K, Nanthana V (2015) Effect of anions on lithium ion conduction in poly(ethylene carbonate)-based polymer electrolytes. J Electrochem Soc 162(2):A3133–A3136. CrossRefGoogle Scholar
  17. 17.
    Kimura K, Yajima M, Tominaga Y (2016) A highly-concentrated poly(ethylene carbonate)-based electrolyte for all-solid-state Li battery working at room temperature. Electrochem Commun 65:46–48CrossRefGoogle Scholar
  18. 18.
    Smith JM, Silva MM, Cerqueira S, MacCallum JM (2001) Preparation and characterization of a lithium ion conducting electrolyte based on poly(trimethylene carbonate). Solid State Ionics 140(3-4):345–351. CrossRefGoogle Scholar
  19. 19.
    Silva MM, Barbosa P, Evans PA, Smith MJ (2006) Novel solid polymer electrolytes based on poly(trimethylene carbonate) and lithium hexfluoroantimonate. Solid State Sci 8(11):1318–1321. CrossRefGoogle Scholar
  20. 20.
    Sun B, Mindemark J, Edstrom K, Brandell D (2014) Polycarbonate-based solid polymer electrolytes for Li-ion batteries. Solid State Ionics 262:738–742. CrossRefGoogle Scholar
  21. 21.
    Sun B, Mindemark J, Edstrom K, Brandell D (2015) Realization of high performance polycarbonate-based Li polymer batteries. Electrochem Commun 52:71–74. CrossRefGoogle Scholar
  22. 22.
    Mindemark J, Imholt L, Brandell D (2015) Synthesis of high molecular flexibility polycarbonates for solid polymer electrolytes. Electrochim Acta 175:247–253. CrossRefGoogle Scholar
  23. 23.
    Barbora PC, Rodrigues LL, Silva MM, Smith MJ (2011) Characterization of pTMCnLiPF6 solid polymer electrolytes. Solid State Ionics 183:39–42CrossRefGoogle Scholar
  24. 24.
    Mindemark J, Imholt L, Montero J, Brandell D (2016) Allyl ether as combined plasticizing and crosslinkable side groups in polycarbonate-based polymer electrolytes for solid-state Li batteries. J Polym Sci: Part A, Polym Chem 54(14):2128–2135. CrossRefGoogle Scholar
  25. 25.
    Matsumoto M, Uno T, Kubo M, Itoh T (2013) Polymer electrolytes based on polycarbonates and their electrochemical and thermal properties. Ionics 19(4):615–622. CrossRefGoogle Scholar
  26. 26.
    Itoh T, Fujita K, Inoue K, Iwama H, Kondoh K, Uno T, Kubo M (2013) Solidd polymer electrolytes based on alternating copolymers of vinyl ethers with methoxy oligo(ethyleneoxy)ethyl groups and vinylene carbonate. Electrochim Acta 112:221–229. CrossRefGoogle Scholar
  27. 27.
    Itoh T, Nakamura K, Uno T, Kubo M (2017) Thermal and electrochemical properties of poly(2,2-dimethoxypropylene carbonate)-based solid polymer electrolyte for polymer battery. Solid State Ionics (to be submitted)Google Scholar
  28. 28.
    Goodenough JB, Kim Y (2011) Challenges for rechargeable batteries. J Power Sources 196(16):6688–6694. CrossRefGoogle Scholar
  29. 29.
    Bai Y, Tang Y, Wang Z, Jia Z, Wu F, Wu C, Liu G (2015) Electrochemical performance of Si/CeO2/polyaniline composites as anode materials for lithium ion batteries. Solid State Ionics 272:24–29. CrossRefGoogle Scholar
  30. 30.
    Wu T, Zhou H, Bai Y, Wang H, Wu C (2015) Toward 5 V Li-ion batteries: quantum chemical calculation and electrochemical characterization of sulfone-based high-voltage electrolytes. Appl Mater Interface 7(27):15098–15107. CrossRefGoogle Scholar
  31. 31.
    Abouimrane A, Belharouak I, Amine K (2009) Sulfone-based electrolytes for high-voltage Li-ion batteries. Electrochem Commun 11(5):1073–1076. CrossRefGoogle Scholar
  32. 32.
    Sun XG, Angell CA (2005) New sulfone electrolytes for rechargeable lithium batteries. Part I. Oligoether-containing sulfones. Electrochem Commun 7(3):261–266. CrossRefGoogle Scholar
  33. 33.
    Snyder JF (2004) Developing rigid polymer electrolytes. Polym Prepr 45:762–763Google Scholar
  34. 34.
    Azuma N, Sanda F, Takata T, Endo T (1997) First observation of equilibrium polymerization polymerization of cyclic sulfite. J Polym Sci: Part A, Polym Chem 35(17):3673–3682.<3673::AID-POLA6>3.0.CO;2-T CrossRefGoogle Scholar
  35. 35.
    Evans J, Vincent CA, Bruce PG (1987) Electrochemical measurement of transference numbers in polymer electrolytes. Polymer 28(13):2324–2328. CrossRefGoogle Scholar
  36. 36.
    Bruce PG, Evans CA (1987) Steady state current flow in solid binary electrolyte cells. J Electroanal Chem 225(1-2):1–17. CrossRefGoogle Scholar
  37. 37.
    Baril D, Michot C, Armand M (1997) Electrochemistry of liquids vs. solids: polymer electrolytes. Solid State Ionics 94(1-4):35–47. CrossRefGoogle Scholar
  38. 38.
    Calculated with Chem3D (ver. 15.1) of CambridgeSoft CorporationGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2017

Authors and Affiliations

  • Takahito Itoh
    • 1
    Email author
  • Satoshi Niihara
    • 1
  • Takahiro Uno
    • 1
  • Masataka Kubo
    • 1
  1. 1.Division of Chemistry for Materials, Graduate School of EngineeringMie UniversityTsuJapan

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