Journal of Applied Electrochemistry

, Volume 48, Issue 11, pp 1221–1230 | Cite as

Effect of electrolyte additives on high-temperature cycling performance of spinel LiMn2O4 cathode

  • Shuangcai Wang
  • Huiping HuEmail author
  • Peifeng Yu
  • Haiying Yang
  • Xinhui Cai
  • Xianglian Wang
Research Article
Part of the following topical collections:
  1. Batteries


Lithium difluoroborate (LiDFOB), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFBOP) and lithium difluorophosphate (LiPF2O2) are investigated as electrolyte additives to alleviate the severe cycle capacity fading of spinel LiMn2O4 cathode of lithium-ion batteries, especially at elevated temperatures. Compared with that of the routine electrolyte, the capacity retention is significantly improved at both room temperature and 55 °C by adding LiBOB and LiDFOB as electrolyte additives. Moreover, surface layer formation processes on the LiMn2O4 electrode in the presence of the LiBOB, LiDFOB, LiDFBOP and LiPF2O2 are investigated by photoelectron spectroscopy (XPS) and X-ray diffraction. According to the analysis results, BOB anions from LiBOB or LiDFOB bond with the dissolved Mn2+ to form an insoluble and stable surface layer on the LiMn2O4 surface, which is beneficial to the suppression of the LiMn2O4 dissolution and electrolyte decomposition, and eventually to the improvement of the cycling performance at elevated temperatures.

Graphical abstract


LiMn2O4 Electrolyte additive Lithium-ion battery Cycling performance 



This research was supported by a grant from the Huzhou Chuangya Power Battery Materials Co., Ltd.


  1. 1.
    Wang Y, Chen L, Wang Y, Xia Y (2015) Cycling stability of spinel LiMn2O4 with different particle sizes in aqueous electrolyte. Electrochim Acta 173:178–183CrossRefGoogle Scholar
  2. 2.
    Zhang X, Zheng H, Battaglia V, Axelbaum RL (2011) Electrochemical performance of spinel LiMn2O4 cathode materials made by flame-assisted spray technology. J Power Sources 196:3640–3645CrossRefGoogle Scholar
  3. 3.
    Wang H-Q, Lai F-Y, Li Y, Zhang X-H, Huang Y-G, Hu S-J, Li Q-Y (2015) Excellent stability of spinel LiMn2O4-based cathode materials for lithium-ion batteries. Electrochim Acta 177:290–297CrossRefGoogle Scholar
  4. 4.
    Liu Y, Tan L, Li L (2013) Tris(trimethylsilyl) borate as an electrolyte additive to improve the cyclability of LiMn2O4 cathode for lithium-ion battery. J Power Sources 221:90–96CrossRefGoogle Scholar
  5. 5.
    Leung K (2012) First-principles modeling of the initial stages of organic solvent decomposition on LixMn2O4 (100) surfaces. J Phys Chem C 116:9852–9861CrossRefGoogle Scholar
  6. 6.
    Wang R, Li X, Wang Z, Guo H (2016) Manganese dissolution from LiMn2O4 cathodes at elevated temperature: methylene methanedisulfonate as electrolyte additive. J Solid State Electrochem 20:19–28CrossRefGoogle Scholar
  7. 7.
    Wu X, Wang Z, Li X, Guo H, Zhang Y, Xiao W (2012) Effect of lithium difluoro(oxalato)borate and heptamethyldisilazane with different concentrations on cycling performance of LiMn2O4. J Power Sources 204:133–138CrossRefGoogle Scholar
  8. 8.
    Shieh DT, Hsieh PH, Yang MH (2007) Effect of mixed LiBOB and LiPF 6 salts on electrochemical and thermal properties in LiMn2O4 batteries. J Power Sources 174:663–667CrossRefGoogle Scholar
  9. 9.
    Amine K, Liu J, Kang S, Belharouak I, Hyung Y, Vissers D, Henriksen G (2004) Improved lithium manganese oxide spinel/graphite Li-ion cells for high-power applications. J Power Sources 129:14–19CrossRefGoogle Scholar
  10. 10.
    Chen Z, Amine K (2006) Capacity fade of Li1+xMn2−xO4-based lithium-ion cells. J Electrochem Soc 153:A316–A320CrossRefGoogle Scholar
  11. 11.
    Qin B, Liu Z, Ding G, Duan Y, Zhang C, Cui G (2014) A single-ion gel polymer electrolyte system for improving cycle performance of LiMn2O4 battery at elevated temperatures. Electrochim Acta 141:167–172CrossRefGoogle Scholar
  12. 12.
    Fu MH, Huang KL, Liu SQ, Liu JS, Li YK (2010) Lithium difluoro(oxalato)borate/ethylene carbonate + propylene carbonate + ethyl(methyl) carbonate electrolyte for LiMn2O4 cathode. J Power Sources 195:862–866CrossRefGoogle Scholar
  13. 13.
    Kusachi Y, Dong J, Zhang Z, Amine K (2011) Tri(ethylene glycol)-substituted trimethylsilane/lithium bis(oxalate)borate electrolyte for LiMn2O4/graphite system. J Power Sources 196:8301–8306CrossRefGoogle Scholar
  14. 14.
    Sirenko VI, Potapenko AV, Prisiazshnyi VD (2008) Cost-effective and ecologically safe electrolyte for lithium batteries. J Power Sources 175:581–585CrossRefGoogle Scholar
  15. 15.
    Liu Y, Lei T, Lei L (2013) Tris(trimethylsilyl) borate as an electrolyte additive to improve the cyclability of LiMn2O4 cathode for lithium-ion battery. J Power Sources 221:90–96CrossRefGoogle Scholar
  16. 16.
    Ha SY, Han JG, Song YM, Chun MJ, Han SI, Shin WC, Choi NS (2013) Using a lithium bis(oxalato) borate additive to improve electrochemical performance of high-voltage spinel LiNi0.5Mn1.5O4 cathodes at 60 °C. Electrochim Acta 104:170–177CrossRefGoogle Scholar
  17. 17.
    Xu M, Liu Z, Hao L, Xing L, Li W, Lucht BL (2011) Investigation and application of lithium difluoro(oxalate)borate (LiDFOB) as additive to improve the thermal stability of electrolyte for lithium-ion batteries. J Power Sources 196:6794–6801CrossRefGoogle Scholar
  18. 18.
    Yang B, Zhang H, Yu L, Fan WZ, Huang D (2016) Lithium difluorophosphate as an additive to improve the low temperature performance of LiNi0.5Co0.2Mn0.3O2/graphite cells. Electrochim Acta 221:107–114CrossRefGoogle Scholar
  19. 19.
    Whittingham MS (2004) Lithium batteries and cathode materials. ChemInform 104:4271Google Scholar
  20. 20.
    Sheng SZ (2006) A review on electrolyte additives for lithium-ion batteries. J Power Sources 162:1379–1394CrossRefGoogle Scholar
  21. 21.
    Xu M, Hao L, Liu Y, Li W, Xing L, Li B (2011) Experimental and theoretical investigations of dimethylacetamide (DMAc) as electrolyte stabilizing additive for lithium ion batteries. J Phys Chem C 115:6085–6094CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  • Shuangcai Wang
    • 1
    • 2
  • Huiping Hu
    • 1
    Email author
  • Peifeng Yu
    • 2
  • Haiying Yang
    • 3
  • Xinhui Cai
    • 2
  • Xianglian Wang
    • 2
  1. 1.School of Chemistry and Chemical Engineering of Central South UniversityChangshaChina
  2. 2.Fujian Shanshan Science Technology Co., LTDNingdeChina
  3. 3.Dongguan Shanshan Battery Materials Co., LtdDongguanChina

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