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Improving the self-discharge behavior of sulfur-polypyrrole cathode material by LiNO3 electrolyte additive

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Abstract

Self-discharge characteristics of Li/S cells using pure sulfur and sulfur-polypyrrole (S-PPy) cathode materials and lithium bis(trifluoromethane)sulfonimide (LiTFSI) as the electrolyte salt were investigated by monitoring the open circuit voltage, the electrochemical impedance change, and the capacity loss during or after storage at room temperature. Corrosion behavior of the aluminum current collector was studied using linear sweep voltammetry and optical microscope observations of aluminum substrate in aged cells. The results showed that the cell with a pure sulfur cathode suffered from severe self-discharge, which is attributed to the corrosion of the current collector by LiTFSI and a rapid shuttle mechanism. However, a PPy coating on the surface of sulfur particles can suppress the shuttle effect, giving better self-discharge performance. LiNO3 was investigated as a suitable electrolyte additive to prevent the self-discharge of Li/S cells. A self-discharge rate of 3.1 % was obtained for a cell with an S-PPy cathode and a modified electrolyte containing 0.4 M LiNO3. It was found that LiNO3 acts both as a corrosion inhibitor and a shuttle inhibitor. This respectively reduces the transformation of solid sulfur to soluble lithium polysulfides and prevents the dissolved sulfur and generated polysulfides from chemical reaction with the Li anode.

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References

  1. Kim JW, Ocon JD, Park DW, Lee J (2013) Enhanced reversible capacity of Li-S battery cathode based on graphene oxide. J Energy Chem 22:336–340

    Article  CAS  Google Scholar 

  2. Xiong S, Xie K, Diao Y, Hong X (2012) Oxidation process of polysulfides in charge process for lithium–sulfur batteries. Ionics 18:867–872

    Article  CAS  Google Scholar 

  3. Bao W, Zhang Z, Zhou C, Lai Y, Li J (2014) Multi-walled carbon nanotubes @ mesoporous carbon hybrid nanocomposites from carbonized multi-walled carbon nanotubes @ metal-organic framework for lithium sulfur battery. J Power Sources 248:570–576

    Article  CAS  Google Scholar 

  4. Lee JT, Zhao Y, Kim H, Cho WI, Yushin G (2014) Sulfur infiltrated activated carbon cathodes for lithium sulfur cells: the combined effects of pore size distribution and electrolyte molarity. J Power Sources 248:752–761

    Google Scholar 

  5. Zhang SS (2013) New insight into liquid electrolyte of rechargeable lithium/sulfur battery. Electrochim Acta 97:226–230

    Article  CAS  Google Scholar 

  6. Utsunomiya T, Hatozaki O, Yoshimoto N, Egashira M, Morita M (2011) Influence of particle size on the self-discharge behavior of graphite electrodes in lithium-ion batteries. J Power Sources 196:8675–8682

    Article  CAS  Google Scholar 

  7. Yazami R, Reynier YF (2002) Mechanism of self-discharge in graphite–lithium anode. Electrochim Acta 47:1217–1223

    Article  CAS  Google Scholar 

  8. Wang L, He X, Li J, Gao J, Fang M, Tian G, Wang J, Fan S (2013) Graphene-coated plastic film as current collector for lithium/sulfur batteries. J Power Sources 239:623–627

    Article  CAS  Google Scholar 

  9. Chung SH, Manthiram A (2013) Lithium–sulfur batteries with superior cycle stability by employing porous current collectors. Electrochim Acta 107:569–576

    Article  CAS  Google Scholar 

  10. Azimi N, Weng W, Takoudis C, Zhang Z (2013) Improved performance of lithium–sulfur battery with fluorinated electrolyte. Electrochem Commun 37:96–99

    Article  CAS  Google Scholar 

  11. Ryu HS, Ahn HJ, Kim KW, Ahn JH, Cho KK, Nam TH (2006) Self-discharge characteristics of lithium/sulfur batteries using TEGDME liquid electrolyte. Electrochim Acta 52:1563–1566

    Article  CAS  Google Scholar 

  12. Ryu HS, Ahn HJ, Kim KW, Ahn JH, Lee JY, Cairns EJ (2005) Self-discharge of lithium–sulfur cells using stainless-steel current-collectors. J Power Sources 140:365–369

    Article  CAS  Google Scholar 

  13. Barchasz C, Lepretre JC, Patoux S, Alloin F (2013) Electrochemical properties of ether-based electrolytes for lithium/sulfur rechargeable batteries. Electrochim Acta 89:737–743

    Article  CAS  Google Scholar 

  14. Zhang SS (2013) Liquid electrolyte lithium/sulfur battery: fundamental chemistry, problems, and solutions. J Power Sources 231:153–162

    Article  CAS  Google Scholar 

  15. Wang J, Chen J, Konstantinov K, Zhao L, Ng SH, Wang GX, Guo ZP, Liu HK (2006) Sulphur-polypyrrole composite positive electrode materials for rechargeable lithium batteries. Electrochim Acta 51:4634–4638

    Article  CAS  Google Scholar 

  16. Liang X, Wen Z, Liu Y, Wang X, Zhang H, Wu M, Huang L (2011) Preparation and characterization of sulfur–polypyrrole composites with controlled morphology as high capacity cathode for lithium batteries. Solid State Ionics 192:347–350

    Article  CAS  Google Scholar 

  17. Zhang Y, Bakenov Z, Zhao Y, Konarov A, Doan TNL, Malik M, Paron T, Chen P (2012) One-step synthesis of branched sulfur/polypyrrole nanocomposite cathode for lithium rechargeable batteries. J Power Sources 208:1–8

    Article  CAS  Google Scholar 

  18. Liang X, Liu Y, Wen Z, Huang L, Wang X, Zhang H (2011) Nano-structured and highly ordered polypyrrole-sulfur cathode for lithium–sulfur batteries. J Power Sources 196:6951–6955

    Article  CAS  Google Scholar 

  19. Mikhaylik YV, Akridge JR (2004) Polysulfide shuttle study in the Li/S battery system. J Electrochem Soc 151:A1969–A1976

    Article  CAS  Google Scholar 

  20. Xiong S, Xie K, Diao Y, Hong X (2014) Characterization of the solid electrolyte interphase on lithium anode for preventing the shuttle mechanism in lithium-sulfur batteries. J Power Sources 246:840–845

    Article  CAS  Google Scholar 

  21. Cui X, Shan Z, Cui L, Tian J (2013) Enhanced electrochemical performance of sulfur/carbon nanocomposite material prepared via chemical deposition with a vacuum soaking step. Electrochim Acta 105:23–30

    Article  CAS  Google Scholar 

  22. Liang X, Wen Z, Liu Y, Wu M, Jin J, Zhang H, Wu X (2011) Improved cycling performances of lithium sulfur batteries with LiNO3-modified electrolyte. J Power Sources 196:9839–9843

    Article  CAS  Google Scholar 

  23. Zhang SS (2012) Role of LiNO3 in rechargeable lithium/sulfur battery. Electrochim Acta 70:344–348

    Article  CAS  Google Scholar 

  24. Xiong S, Xie K, Diao Y, Hong X (2012) Properties of surface film on lithium anode with LiNO3 as lithium salt in electrolyte solution for lithium–sulfur batteries. Electrochim Acta 83:78–86

    Article  CAS  Google Scholar 

  25. Kazazi M, Vaezi MR, Kazemzadeh A (2014) Enhanced rate performance of polypyrrole-coated sulfur/MWCNT cathode material: a kinetic study by electrochemical impedance spectroscopy. Ionics. doi:10.1007/s11581-013-1044-5

    Google Scholar 

  26. Li GC, Li GR, Ye SH, Gao XP (2012) A polyaniline-coated sulfur/carbon composite with an enhanced high-rate capability as a cathode material for lithium/sulfur batteries. Adv Energy Mater 2:1238–1245

    Article  CAS  Google Scholar 

  27. Kim CS, Guerfi A, Hovington P, Trottier J, Gagnon C, Barray F, Vijh A, Armand M, Zaghib K (2013) Importance of open pore structures with mechanical integrity in designing the cathode electrode for lithium-sulfur batteries. J Power Sources 241:554–559

    Article  CAS  Google Scholar 

  28. Canas NA, Hirose K, Pascucci B, Wagner N, Friedrich KA, Hiesgen R (2013) Investigations of lithium–sulfur batteries using electrochemical impedance spectroscopy. Electrochim Acta 97:42–51

    Article  CAS  Google Scholar 

  29. Wang L, Zhao J, He X, Wan C (2011) Kinetic investigation of sulfurized polyacrylonitrile cathode material by electrochemical impedance spectroscopy. Electrochim Acta 56:5252–5256

    Article  CAS  Google Scholar 

  30. Ahn W, Kim KB, Jung KN, Shin KH, Jin CS (2012) Synthesis and electrochemical properties of a sulfur-multi walled carbon nanotubes composite as a cathode material for lithium sulfur batteries. J Power Sources 202:394–399

    Article  CAS  Google Scholar 

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Acknowledgments

The first author wishes to gratefully acknowledge Mr. Morteza Vosooghi for designing and fabricating of the battery test system and Dr. Parvaneh Sangpour for her assistance in the electrochemistry laboratory.

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Authors and Affiliations

  1. Division of Nanotechnology and Advanced Materials, Materials and Energy Research Center, P.O. Box 31787-316, Karaj, Iran

    M. Kazazi & M. R. Vaezi

  2. Division of Semiconductors, Materials and Energy Research Center, P.O. Box 31787-316, Karaj, Iran

    A. Kazemzadeh

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  1. M. Kazazi
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  2. M. R. Vaezi
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  3. A. Kazemzadeh
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Correspondence to M. Kazazi.

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Kazazi, M., Vaezi, M.R. & Kazemzadeh, A. Improving the self-discharge behavior of sulfur-polypyrrole cathode material by LiNO3 electrolyte additive. Ionics 20, 1291–1300 (2014). https://doi.org/10.1007/s11581-014-1095-2

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  • DOI: https://doi.org/10.1007/s11581-014-1095-2

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