Skip to main content
Log in

Improving cyclic stability and rate capability of LiNi0.5Mn1.5O4 cathode via protective film and conductive polymer formed from thiophene

  • Original Paper
  • Published:
Journal of Solid State Electrochemistry Aims and scope Submit manuscript

Abstract

In this work, we report a new finding that thiophene can be used as an electrolyte additive to form simultaneously protective cathode film and conductive polymer and thus to improve significantly the cyclic stability and rate capability of LiNi0.5Mn1.5O4 cathode for a high-voltage lithium-ion battery. The contribution of thiophene is evaluated in a Li/LiNi0.5Mn1.5O4 cell, with charge/discharge test, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electron microscope (SEM), X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier-transformed infrared spectra (FTIR), and X-ray photoelectron spectroscopy (XPS). The charge/discharge tests demonstrate that the capacity retention of LiNi0.5Mn1.5O4 with 1-C (1 C = 147 mA g−1) rate is improved from 37.2 to 78.8 % at 55 °C after 100 cycles, and the discharge capacity with 10-C rate is enhanced from 83 to 111 mAh g−1 when adding 0.5 % thiophene into 1 M LiPF6 in ethylene carbonate (EC)/ dimethyl carbonate (DMC) (1/2, v/v) solution. CV shows that thiophene is oxidized at 4.5 V (vs. Li/Li+), forming a protective film on and conductive polymer among LiNi0.5Mn1.5O4 particles, which can be confirmed by EIS, XRD, SEM, TEM, FTIR, and XPS.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  1. Kim T-H, Park J-S, Chang SK, Choi S, Ryu JH, Song H-K (2012) The current move of lithium ion batteries towards the next phase. Adv Energy Mater 2:860–872

  2. Kraytsberg A, Ein-Eli Y (2012) A review of 5 volt cathode materials for advanced lithium-ion batteries. Adv Energy Mater 2:922–939

  3. Li B, Xing L, Xu M, Lin H, Li W (2013) New solution to instability of spinel LiNi0.5Mn1.5O4 as cathode for lithium ion battery at elevated temperature. Electrochem Commun 34:48–51

  4. Lin HB, Zhang YM, Hu JN, Wang YT, Xing LD, Xu MQ, Li XP, Li WS (2014) LiNi0.5Mn1.5O4 nanoparticles: synthesis with synergistic effect of polyvinylpyrrolidone and ethylene glycol and performance as cathode of lithium ion battery. J Power Sources 257:37–44

  5. Azib T, Ammar S, Nowak S, Lau-Truing S, Groult H, Zaghib K, Mauger A, Julien CM (2012) Crystallinity of nano C-LiFePO4 prepared by the polyol process. J Power Sources 217:220–228

  6. Ying J, Jiang C, Wan C (2004) Preparation and characterization of high-density spherical LiCoO2 cathode material for lithium ion batteries. J Power Sources 129:264–269

  7. Zhang Z, Zeng T, Lai Y, Jia M, Li J (2014) A comparative study of different binders and their effects on electrochemical properties of LiMn2O4 cathode in lithium ion batteries. J Power Sources 247:1–8

  8. Zhuo H, Wan S, He C, Zhang Q, Li C, Gui D, Zhu C, Niu H, Liu J (2014) Improved electrochemical performance of spinel LiMn2O4 in situ coated with graphene-like membrane. J Power Sources 247:721–728

  9. Arrebola JC, Caballero A, Hernan L, Morales J (2010) Re-examining the effect of ZnO on nanosized 5V LiNi0.5Mn1.5O4 spinel: an effective procedure for enhancing its rate capability at room and high temperatures. J Power Sources 195:4278–4284

  10. Santhanam R, Rambabu B (2010) Research progress in high voltage spinel LiNi0.5Mn1.5O4 material. J Power Sources 195:5442–5451

  11. Aoshima T, Okahara K, Kiyohara C, Shizuka K (2001) Mechanisms of manganese spinels dissolution and capacity fade at high temperature. J Power Sources 97–98:377–380

  12. Zheng H, Zhang H, Fu Y, Abe T, Ogumi Z (2005) Temperature effects on the electrochemical behavior of spinel LiMn2O4 in quaternary ammonium-based ionic liquid electrolyte. J Phys Chem B 109:13676–13684

  13. Huang W, Xing L, Wang Y, Xu M, Li W, Xie F, Xia S (2014) 4-(Trifluoromethyl)-Benzonitrile: a novel electrolyte additive for lithium nickel manganese oxide cathode of high voltage lithium ion battery. J Power Sources 267:560–565

  14. Eom J-Y, Jung I-H, Lee J-H (2011) Effects of vinylene carbonate on high temperature storage of high voltage Li-ion batteries. J Power Sources 196:9810–9814

  15. Han Y-K, Jung J, Yu S, Lee H (2009) Understanding the characteristics of high-voltage additives in Li-ion batteries: solvent effects. J Power Sources 187:581–585

  16. Xu K, Zhang S, Jow TR (2005) LiBOB as additive in LiPF6-based lithium ion electrolytes. Electrochem Solid-State Lett 8:A365

  17. Yoon T, Park S, Mun J, Ryu JH, Choi W, Kang Y-S, Park J-H, Oh SM (2012) Failure mechanisms of LiNi0.5Mn1.5O4 electrode at elevated temperature. J Power Sources 215:312–316

  18. Yang T, Zhang N, Lang Y, Sun K (2011) Enhanced rate performance of carbon-coated LiNi0.5Mn1.5O4 cathode material for lithium ion batteries. Electrochim Acta 56:4058–4064

  19. Rong H, Xu M, Xie B, Liao X, Huang W, Xing L, Li W (2014) Tris (trimethylsilyl) borate (TMSB) as a cathode surface film forming additive for 5 V Li/LiNi0.5Mn1.5O4 Li-ion cells. Electrochim Acta 147:31–39

  20. Wu HM, Belharouak I, Abouimrane A, Sun YK, Amine K (2010) Surface modification of LiNi0.5Mn1.5O4 by ZrP2O7 and ZrO2 for lithium-ion batteries. J Power Sources 195:2909–2913

  21. Zhao G, Lin Y, Zhou T, Lin Y, Huang Y, Huang Z (2012) Enhanced rate and high-temperature performance of La0.7Sr0.3MnO3-coated LiNi0.5Mn1.5O4 cathode materials for lithium ion battery. J Power Sources 215:63–68

  22. Zhong GB, Wang YY, Yu YQ, Chen CH (2012) Electrochemical investigations of the LiNi0.45M0.10Mn1.45O4 (M = Fe, Co, Cr) 5 V cathode materials for lithium ion batteries. J Power Sources 205:385–393

  23. Zhong GB, Wang YY, Zhao XJ, Wang QS, Yu Y, Chen CH (2012) Structural, electrochemical and thermal stability investigations on LiNi0.5-xAl2xMn1.5-xO4 (0 ≤ 2x ≤ 1.0) as 5 V cathode materials. J Power Sources 216:368–375

  24. Abouimrane A, Belharouak I, Amine K (2009) Sulfone-based electrolytes for high-voltage Li-ion batteries. Electrochem Commun 11:1073–1076

  25. Wu F, Xiang J, Li L, Chen J, Tan G, Chen R (2012) Study of the electrochemical characteristics of sulfonyl isocyanate/sulfone binary electrolytes for use in lithium-ion batteries. J Power Sources 202:322–331

  26. Xiang J, Wu F, Chen R, Li L, Yu H (2013) High voltage and safe electrolytes based on ionic liquid and sulfone for lithium-ion batteries. J Power Sources 233:115–120

  27. Xu M, Tsiouvaras N, Garsuch A, Gasteiger HA, Lucht BL (2014) Generation of cathode passivation films via oxidation of lithium bis(oxalato) borate on high voltage spinel (LiNi0.5Mn1.5O4). J Phys Chem C 118:7363–7368

  28. Zhou H, Li D, Hibino M, Honma I (2005) A self-ordered, crystalline-glass, mesoporous nanocomposite for use as a lithium-based storage device with both high power and high energy densities. Angew Chem Int Ed 44:797–802

  29. Lee K-S, Sun Y-K, Noh J, Song KS, Kim D-W (2009) Improvement of high voltage cycling performance and thermal stability of lithium-ion cells by use of a thiophene additive. Electrochem Commun 11:1900–1903

  30. Lee Y-S, Lee K-S, Sun Y-K, Lee YM, Kim D-W (2011) Effect of an organic additive on the cycling performance and thermal stability of lithium-ion cells assembled with carbon anode and LiNi1/3Co1/3Mn1/3O2 cathode. J Power Sources 196:6997–7001

  31. Xing LY, Hu M, Tang Q, Wei JP, Qin X, Zhou Z (2012) Improved cyclic performances of LiCoPO4/C cathode materials for high-cell-potential lithium-ion batteries with thiophene as an electrolyte additive. Electrochim Acta 59:172–178

  32. Hu M, Wei J, Xing L, Zhou Z (2013) Improving electrochemical performance of Li3V2(PO4)3 in a thiophene-containing electrolyte. J Power Sources 222:373–378

  33. Hu M, Pang X, Zhou Z (2013) Recent progress in high-voltage lithium ion batteries. J Power Sources 237:229–242

  34. Osório WR, Cheung N, Spinelli JE, Goulart PR, Garcia A (2007) The effects of a eutectic modifier on microstructure and surface corrosion behavior of Al-Si hypoeutectic alloys. J Solid State Electrochem 11:1421–1427

    Article  Google Scholar 

  35. Costa CM, Sencadas V, Rocha JG, Silva MM, Lanceros-Méndez S (2013) Evaluation of the main processing parameters influencing of performance of poly(vinylidene fluoride-trifluoroethylene) lithium-ion battery separators. J Solid State Electrochem 17:861–870

    Article  CAS  Google Scholar 

  36. Apostolova R, Peskov R, Shembel E (2014) Comparative performance of LiMn2O4 spinel compositions with carbon nanotubes and graphite in Li prototype battery. J Solid State Electrochem 18:2315–2324

    Article  CAS  Google Scholar 

  37. Rong H, Xu M, Xing L, Li W (2014) Enhanced cyclability of LiNi0.5Mn1.5O4 cathode in carbonate based electrolyte with incorporation of tris(trimethylsilyl)phosphate (TMSP). J Power Sources 261:148–155

    Article  CAS  Google Scholar 

  38. Li B, Wang Y, Rong H, Wang Y, Liu J, Xing L, Xu M, Li W (2013) A novel electrolyte able to form solid state interface on anode and cathode of LiMn2O4/graphite battery. J Mater Chem A 1:12954–12961

    Article  CAS  Google Scholar 

  39. Rong H, Xu M, Xie B, Huang W, Liao X, Xing L, Li W (2015) Performance improvement of graphite/LiNi0.4Co0.2Mn0.4O2 battery at high voltage with added Tris (trimethylsilyl) phosphate. J Power Sources 274:1155–1161

    Article  CAS  Google Scholar 

  40. Deepa M, Agnihotry SA, Gupta D, Chandra R (2004) Ion-pairing effects and ion–solvent–polymer interactions in LiN(CF3SO2)2–PC–PMMA electrolytes: a FTIR study. Electrochim Acta 49:373–383

    Article  CAS  Google Scholar 

  41. Ramesh S, Yuen TF, Shen CJ (2008) Conductivity and FTIR studies on PEO-LiX [X: CF3SO3 -, SO2-] polymer electrolytes, Spectrochimica acta. Part A. Mol Biomol Spectrosc 69:670–675

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work is supported by the National Natural Science Foundation of China (21273084 and 21373092), the Joint Project of the National Natural Science Foundation of China and Natural Science Foundation of Guangdong (No. U1401248), the Natural Science Foundation of Guangdong Province (10351063101000001), the key project of Science and Technology in Guangdong Province (Grant No. 2012A010702003), and the scientific research project of the Department of Education of Guangdong Province (Grant No. 2013CXZDA013).

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to L. D. Xing or W. S. Li.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Lin, H.B., Huang, W.Z., Rong, H.B. et al. Improving cyclic stability and rate capability of LiNi0.5Mn1.5O4 cathode via protective film and conductive polymer formed from thiophene. J Solid State Electrochem 19, 1123–1132 (2015). https://doi.org/10.1007/s10008-014-2717-3

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10008-014-2717-3

Keywords

Navigation