Journal of Applied Electrochemistry

, Volume 46, Issue 11, pp 1099–1107 | Cite as

Solid electrolyte interphase formation in propylene carbonate-based electrolyte solutions for lithium-ion batteries based on the Lewis basicity of the co-solvent and counter anion

  • Hee-Youb Song
  • Tomokazu Fukutsuka
  • Kohei Miyazaki
  • Takeshi Abe
Research Article
Part of the following topical collections:
  1. Batteries

Abstract

Propylene carbonate (PC) is widely regarded as the superior organic solvent for lithium-ion batteries used in cold areas owing to its low melting point. However, an effective solid electrolyte interphase (SEI) is not formed in PC-based electrolyte solutions and reversible intercalation and de-intercalation of the lithium ions at the graphite negative electrode do not proceed. This leads to decomposition of the electrolyte solution and exfoliation of the graphite electrode. One solution to this problem is to control the structure of the solvated lithium ions. In this study, we focused on the Lewis basicity of the co-solvent and counter anion in the lithium salt to control the solvation in a PC-based electrolyte solution and form an effective SEI. Triglyme and tetraglyme were used as the co-solvents, and lithium bis(fluorosulfonyl)amide and lithium trifluoromethanesulfonate were used as the anion sources. SEI formation was investigated by charge and discharge measurements and in situ scanning probe microscopy; the obtained results indicated that SEI formation is strongly influenced by the Lewis basicity of the co-solvent and counter anion.

Graphical Abstract

Keywords

Lithium-ion batteries Graphite negative electrodes Propylene carbonate Solid electrolyte interphase In situ scanning probe microscopy 

References

  1. 1.
    Ogumi Z, Inaba M (1998) Electrochemical lithium intercalation within carbonaceous materials: intercalation process, surface film formation, and lithium diffusion. Bull Chem Soc Jpn 71:521–553CrossRefGoogle Scholar
  2. 2.
    Aurbach D, Markovsky B, Weissman I, Levi E, Ein-Eli Y (1999) On the correlation between surface chemistry and performance of graphite negative electrodes for Li ion batteries. Electrochim Acta 45:67–86CrossRefGoogle Scholar
  3. 3.
    Agubra VA, Fergus JW (2014) The formation and stability of the solid electrolyte interface on the graphite anode. J Power Sources 268:153–162CrossRefGoogle Scholar
  4. 4.
    Peled E (1979) The electrochemical behavior of alkali and alkaline earth metals in nonaqueous battery systems: the solid electrolyte interphase model. Electrochem Soc 126:2047–2051CrossRefGoogle Scholar
  5. 5.
    Xu K, Cresce A (2012) Li+-solvation/desolvation dictates interphasial processes on graphitic anode in li ion cell. J Mater Res 27:2327–2341CrossRefGoogle Scholar
  6. 6.
    Abe T, Mizutani Y, Tabuchi T, Ikeda K, Asano M, Harada T, Inaba M, Ogumi Z (1997) Intercalation of lithium into natural graphite flakes and heat-treated polyimide films in ether-type solvents by chemical method. J Power Sources 68:216–220CrossRefGoogle Scholar
  7. 7.
    Mizutani Y, Abe T, Inaba M, Ogumi Z (2002) Creation of nanospaces by intercalation of alkali metals into graphite in organic solutions. Synth Met 125:153–159CrossRefGoogle Scholar
  8. 8.
    Wagner MR, Albering JH, Moeller KC, Besenhard JO, Winter M (2005) XRD evidence for the electrochemical formation of Li+(PC)yCn- in PC-based electrolytes. Electrochem Commun 7:947–952CrossRefGoogle Scholar
  9. 9.
    Besenhard JO, Winter M, Yang J, Biberacher W (1995) Filming mechanism of lithium-carbon anodes in organic and inorganic electrolyte. J Power Sources 54:228–231CrossRefGoogle Scholar
  10. 10.
    Jeong SK, Inaba M, Abe T, Ogumi Z (2001) Surface film formation on graphite negative electrode in lithium-ion batteries. J Electrochem Soc 148:A989–A993CrossRefGoogle Scholar
  11. 11.
    Jeong SK, Inaba M, Iriyama Y, Abe T, Ogumi Z (2003) AFM study of surface film formation on a composite graphite electrode in lithium-ion batteries. J Power Sources 119–121:555–560CrossRefGoogle Scholar
  12. 12.
    Abe T, Fukuda H, Iriyama Y, Ogumi Z (2004) Solvated Li-ion transfer at interface between graphite and electrolyte. J Electrochem Soc 151:A1120–A1123CrossRefGoogle Scholar
  13. 13.
    Abe T, Sagane F, Ohtsuka M, Iriyama Y, Ogumi Z (2005) Lithium-ion transfer at the interface between lithium-ion conductive ceramic electrolyte and liquid electrolyte: a key to enhancing the rate capability of lithium-ion batteries. J Electrochem Soc 152:A2151–A2154CrossRefGoogle Scholar
  14. 14.
    Aurbach D, Koltypin M, Teller H (2002) In situ AFM imaging of surface phenomena on composite graphite electrodes during lithium insertion. Langmuir 18:9000–9009CrossRefGoogle Scholar
  15. 15.
    Inaba M, Siroma Z, Kawabata Y, Funabiki A, Ogumi Z (1997) Electrochemical scanning tunneling microscopy analysis of the surface reactions on graphite basal plane in ethylene carbonate-based solvents and propylene carbonate. J Power Sources 68:221–226CrossRefGoogle Scholar
  16. 16.
    Xu K (2009) Whether EC and PC differ in interphasial chemistry on graphitic anode and how. J Electrochem Soc 156:A751–A755CrossRefGoogle Scholar
  17. 17.
    Xu K, Zhang SS, Lee U, Allen JL, Jow TR (2005) LiBOB: is it an alternative salt for lithium ion chemistry? J Power Sources 146:79–85CrossRefGoogle Scholar
  18. 18.
    Jeong SK, Inaba M, Iriyama Y, Abe T, Ogumi Z (2003) Electrochemical intercalation of lithium ion within graphite from propylene carbonate solutions. Electrochem Solid-State Lett 6:A13–A15CrossRefGoogle Scholar
  19. 19.
    Jeong SK, Inaba M, Iriyama Y, Abe T, Ogumi Z (2008) Interfacial reactions between graphite electrodes and propylene carbonate-based solution: electrolyte-concentration dependence of electrochemical lithium intercalation reaction. J Power Sources 175:540–546CrossRefGoogle Scholar
  20. 20.
    Domi Y, Doi T, Yamanaka T, Abe T, Ogumi Z (2013) Electrochemical AFM study of surface films formed on the hopg edge plane in propylene carbonate-based electrolytes. J Electrochem Soc 160:A678–A683CrossRefGoogle Scholar
  21. 21.
    Jeong SK, Song HY, Kim SI, Abe T, Jeon WS, Yin RZ, Kim YS (2013) A simple method of electrochemical lithium intercalation within graphite from a propylene carbonate-based solution. Electrochem Commun 31:24–27CrossRefGoogle Scholar
  22. 22.
    Takeuchi S, Miyazaki K, Sagane F, Fukutsuka T, Jeong SK, Abe T (2011) Electrochemical properties of graphite electrode in propylene carbonate-based electrolytes containing lithium and calcium ions. Electrochim Acta 56:10450–10453CrossRefGoogle Scholar
  23. 23.
    Takeuchi S, Fukutsuka T, Miyazaki K, Abe T (2013) Electrochemical lithium ion intercalation into graphite electrode in propylene carbonate-based electrolytes with dimethyl carbonate and calcium salt. J Power Sources 238:65–68CrossRefGoogle Scholar
  24. 24.
    Henderson WA (2006) Glyme-lithium salt phase behavior. J Phys Chem B 110:13177–13183CrossRefGoogle Scholar
  25. 25.
    Seo DM, Borodin O, Han SD, Boyle PD, Henderson WA (2012) Electrolyte solvation and ionic association II acetonitrile-lithium salt mixtures: highly dissociated salts. J Electrochem Soc 159:A1489–A1500CrossRefGoogle Scholar
  26. 26.
    Yamada Y, Yaegashi M, Abe T, Yamada A (2013) A superconcentrated ether electrolyte for fast-charging li-ion batteries. Chem Commun 49:11194–11196CrossRefGoogle Scholar
  27. 27.
    Yamada Y, Furukawa K, Sodeyama K, Kikuchi K, Yaegashi M, Tateyama Y, Yamada A (2014) Unusual stability of acetonitrile-based superconcentrated electrolytes for fast-charging lithium-ion batteries. J Am Chem Soc 136:5039–5046CrossRefGoogle Scholar
  28. 28.
    Song HY, Fukutsuka T, Miyazaki K, and Abe T (in press) suppression of co-intercalation reaction of propylene carbonate and lithium ion into graphite negative electrode by addition of diglyme. J Electrochem SocGoogle Scholar
  29. 29.
    Webber A (1991) Conductivity and viscosity of solutions of LiCF3SO3, Li(CF3SO2)2N, and their mixtures. J Electrochem Soc 138:2586–2590CrossRefGoogle Scholar
  30. 30.
    Tokuda H, Tsuzuki S, Susan MABH, Hayamizu K, Watanabe M (2006) How ionic are room-temperature ionic liquids? an indicator of the physicochemical properties. J Phys Chem B 110:19593–19600CrossRefGoogle Scholar
  31. 31.
    Ueno K, Yoshida K, Tsuchiya M, Tachikawa N, Dokko K, Watanabe M (2012) Glyme-lithium salt equimolar molten mixtures: concentrated solutions or solvate ionic liquids? J Phys Chem B 116:11323–11331CrossRefGoogle Scholar
  32. 32.
    Inaba M, Siroma Z, Funabiki A, Ogumi Z, Abe T, Mizutani Y, Asano M (1996) Electrochemical scanning tunneling microscopy observation of highly oriented pyrolytic graphite surface reactions in an ethylene carbonate-based electrolyte solution. Langmuir 12:1535–1540CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2016

Authors and Affiliations

  • Hee-Youb Song
    • 1
  • Tomokazu Fukutsuka
    • 1
    • 2
  • Kohei Miyazaki
    • 1
    • 2
  • Takeshi Abe
    • 1
    • 2
  1. 1.Graduate School of EngineeringKyoto UniversityKyotoJapan
  2. 2.Hall of Global Environmental ResearchKyoto UniversityKyotoJapan

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