Journal of Applied Electrochemistry

, Volume 48, Issue 11, pp 1205–1211 | Cite as

Improvement of cycling performance in bismuth fluoride electrodes by controlling electrolyte composition in fluoride shuttle batteries

  • Hiroaki KonishiEmail author
  • Taketoshi MinatoEmail author
  • Takeshi AbeEmail author
  • Zempachi Ogumi
Research Article


We have developed a fluoride shuttle battery (FSB) which is a promising candidate for the next-generation high-energy-density secondary batteries. Using the bis [2-(2-methoxyethoxy) ethyl] ether (tetraglyme: G4) solvent containing 0.45 mol dm−3 cesium fluoride (CsF) and 0.5 mol dm−3 fluorobis (2,4,6-trimethylphenyl) borane (FBTMPhB) as an electrolyte for FSB, we have successfully conducted the discharge (BiF3 + 3e → Bi + 3F) and charge (Bi + 3F → BiF3 + 3e) reactions for a BiF3 electrode; however, the discharge and charge capacities significantly decreased during cycling. Atomic absorption spectrometry results indicated that, in addition to the formation of BiF3, dissolution of Bi (Bi → Bi3+ + 3e) occurred during the charge process. The dissolution of Bi indicated that the active material was lost from the electrode, which decreased the capacity during cycling. An increased CsF/FBTMPhB ratio in the electrolyte was found to suppress the dissolution of Bi during the charge process and, therefore, improve the cycling performance.

Graphical Abstract


Fluoride shuttle battery Bismuth fluoride Anion acceptor Cycle performance XPS 



This work was supported by the Research and Development Initiative for Scientific Innovation of New Generation Batteries (RISING) and Research and Development Initiative for Scientific Innovation of New Generation Batteries 2 (RISING2) projects from the New Energy and Industrial Technology Development Organization (NEDO), Japan. The authors thank Ms. Kiyomi Ishizawa, Ms. Ryoko Masuda, and Ms. Hisayo Ikeda for their experimental support.


  1. 1.
    Nishi Y (2001) Lithium ion secondary batteries; past 10 years and the future. J Power Sources 100:101–106CrossRefGoogle Scholar
  2. 2.
    Wang Y, Liu B, Li Q, Cartmell S, Ferrara S, Deng ZD, Xiao J (2015) Lithium and lithium ion batteries for applications in microelectronic devices: a review. J Power Sources 286:330–345CrossRefGoogle Scholar
  3. 3.
    Minato T, Abe T (2017) Surface and interface sciences of Li-ion batteries—research progress in electrode-electrolyte interface. Prog Surf Sci 92:240–280CrossRefGoogle Scholar
  4. 4.
    Delmas C, Braconnier JJ, Fouassier C, Hagenmuller P (1981) Electrochemical intercalation of sodium inNaxCoO2 bronzes. Solid State Ion 3–4:165–169CrossRefGoogle Scholar
  5. 5.
    Aurbach D, Lu Z, Schechter A, Gofer Y, Gizbar H, Turgeman R, Cohen Y, Moshkovich M, Levi E (2000) Prototype systems for rechargeable magnesium batteries. Nature 407:724–727CrossRefGoogle Scholar
  6. 6.
    Abraham KM, Jiang Z (1996) A polymer electrolyte-based rechargeable lithium/oxygen battery. J Electrochem Soc 143:1–5CrossRefGoogle Scholar
  7. 7.
    Kim TB, Choi JW, Ryu HS, Cho GB, Kim KW, Ahn JH, Cho KK, Ahn HJ (2007) Electrochemical properties of sodium/pyrite battery at room temperature. J Power Sources 174:1275–1278CrossRefGoogle Scholar
  8. 8.
    Eftekhari A (2004) Potassium secondary cell based on Prussian blue cathode. J Power Sources 126:221–228CrossRefGoogle Scholar
  9. 9.
    Zhao X, Zhao-Karger Z, Wang D, Fichtner M (2013) Metal oxychlorides as cathode materials for chloride ion batteries. Angew Chem Int Ed 52:13621–13624CrossRefGoogle Scholar
  10. 10.
    Zhao X, Li Q, Zhao-Karger Z, Gao P, Fink K, Shen X, Fichtner M (2014) Magnesium anode for chloride ion batteries. Appl Mater Interfaces 6:10997–11000CrossRefGoogle Scholar
  11. 11.
    Zhao X, Ren S, Bruns M, Fichtner M (2014) Chloride ion battery: a new member in the rechargeable battery family. J Power Sources 245:706–711CrossRefGoogle Scholar
  12. 12.
    Gao P, Zhao X, Zhao-Karger Z, Diemant T, Behm RJ, Fichtner M (2014) Vanadium oxychloride/magnesium electrode systems for chloride ion batteries. Appl Mater Interfaces 6:22430–22435CrossRefGoogle Scholar
  13. 13.
    Reddy MA, Fichtner M (2011) Batteries based on fluoride shuttle. J Mater Chem 21:17059–17062CrossRefGoogle Scholar
  14. 14.
    Rongeat C, Reddy MA, Witter R, Fichtner M (2013) Nanostructured fluoride-type fluorides as electrolytes for fluoride ion batteries. J Phys Chem C 117:4943–4950CrossRefGoogle Scholar
  15. 15.
    Rongeat C, Reddy MA, Diemant T, Behm RJ, Fichtner M (2014) Development of new anode composite materials for fluoride ion batteries. J Mater Chem A 2:20861–20872CrossRefGoogle Scholar
  16. 16.
    Gschwind F, Zhao-Karger Z, Fichtner M M (2014) A fluoride-doped PEG matrix as an electrolyte for anion transportation in a room-temperature fluoride ion battery. J Mater Chem A 2:1214–1218CrossRefGoogle Scholar
  17. 17.
    Gschwind F, Bastien J (2015) Parametric investigation of room-temperature fluoride-ion batteries: assessment of electrolytes, Mg-based anodes, and BiF3-cathodes. J Mater Chem A 3:5628–5634CrossRefGoogle Scholar
  18. 18.
    Konishi H, Minato T, Abe T, Ogumi Z (2017) Electrochemical performance of a bismuth fluoride electrode in a reserve-type fluoride shuttle battery. J Electrochem Soc 164:A3702–A3708CrossRefGoogle Scholar
  19. 19.
    Lee HS, Yang XQ, Xiang CL, McBreen J (1998) The synthesis of a new family of boron-based anion receptors and the study of their effect on ion pair dissociation and conductivity of lithium salts in nonaqueous solutions. J Electrochem Soc 145:2813–2818CrossRefGoogle Scholar
  20. 20.
    Lee HS, Sun X, Yang XQ, McBreen J (2002) Synthesis and study of new cyclic boronate additives for lithium battery electrolytes. J Electrochem Soc 149:A1460–A1465CrossRefGoogle Scholar
  21. 21.
    Li LF, Lee HS, Li H, Yang XQ, Nam KW, Yoon WS, McBreen J, Huang XJ (2008) New electrolytes for lithium ion batteries using LiF salt and boron based anion receptors. J Power Sources 184:517–521CrossRefGoogle Scholar
  22. 22.
    Bervas M, Badway F, Klein LC, Amatucci GG (2005) Bismuth fluoride nanocomposite as a positive electrode material for rechargeable lithium batteries. Electrochem Solid-State Lett 8:A179–A183CrossRefGoogle Scholar
  23. 23.
    Bervas M, Mansour AN, Yoon WS, Al-Sharab JF, Badway F, Cosandey F, Klein LC, Amatucci GG (2006) Investigation of the lithiation and delithiation conversion mechanisms of bismuth fluoride nanocomposites. J Electrochem Soc 153:A799–A808CrossRefGoogle Scholar
  24. 24.
    Gmitter AJ, Badway F, Rangan S, Bartynski RA, Halajko A, Pereira N, Amatucci GG (2010) Formation, dynamics, and implication of solid electrolyte interphase in high voltage reversible conversion fluoride nanocomposites. J Mater Chem 20:4149–4161CrossRefGoogle Scholar
  25. 25.
    Hu B, Wang X, Shu H, Yang X, Liu L, Song Y, Wei Q, Hu H, Wu H, Jiang L, Liu X (2013) Improved electrochemical properties of BiF3/C cathode via adding amorphous AlPO4 for lithium-ion batteries. Electrochim Acta 102:8–18CrossRefGoogle Scholar
  26. 26.
    Konishi H, Minato T, Abe T, Ogumi Z (2017) Cycling fading mechanism for a bismuth fluoride electrode in a lithium-ion battery. Chem Sel 2:3504–3510Google Scholar
  27. 27.
    Konishi H, Minato T, Abe T, Ogumi Z (2017) Electrochemical reaction mechanism for Bi1−xBaxF3−x (x = 0, 0.1, 0.2, and 0.4) electrodes in lithium-ion batteries. Chem Sel 2:6399–6406Google Scholar
  28. 28.
    Konishi H, Minato T, Abe T, Ogumi Z (2017) Difference of rate performance between discharge and charge reactions for bismuth fluoride electrode in lithium-ion battery J. Electroanal Chem 806:82–87CrossRefGoogle Scholar
  29. 29.
    Pavlishchuk VV, Addison AW (2000) Conversion constants for redox potentials measured versus different reference electrodes in acetonitrile solutions at 25 °C. Inorg Chim Acta 298:97–102CrossRefGoogle Scholar
  30. 30.
    Gmitter AJ, Halajko A, Sideris PJ, Greenbaum SG, Amatucci GG (2013) Subsurface diffusion of oxide electrolyte decomposition products in metal fluoride nanocomposite electrodes. Electrochim Acta 88:735–744CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  1. 1.Office of Society-Academia Collaboration for InnovationKyoto UniversityUjiJapan
  2. 2.Office of Society-Academia Collaboration for InnovationKyoto UniversityNishikyoJapan
  3. 3.Graduate School of Global Environmental StudiesKyoto UniversityNishikyoJapan
  4. 4.Research & Development GroupHitachi LtdHitachiJapan

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