Journal of Solid State Electrochemistry

, Volume 23, Issue 2, pp 407–417 | Cite as

Analysis on the constant-current overcharge electrode process and self-protection mechanism of LiCoO2/graphite batteries

  • Yaoming Deng
  • Tianxing Kang
  • Xiaona Song
  • Zhen Ma
  • Xiaoxi Zuo
  • Dong Shu
  • Junmin NanEmail author
Original Paper


With the expanding applications, concerns about the charging safety of lithium-ion batteries (LIBs) have become more significant. In this paper, the constant-current (CC) overcharge electrode process of pouch LiCoO2/graphite batteries are analyzed at 0.25 C, and then, a self-protection mechanism for decreasing the overcharge risk of batteries is evaluated. As for the batteries passing the safety test, their typical overcharge behaviors show the battery voltage and temperature begin to dramatically increase to about 5.2 V and 65 °C from about 155% state of charge (SOC) and then decrease slowly after a short fluctuating period. The element analysis of two electrodes and separator reveals that besides the well-known metal lithium, cobalt precipitation pierces the separator and subsequently forms an internal micro-short circuit at about 155% SOC to consume the charge energy and subsequently avoid the overcharge explosion and ignition. As a conclusion, a self-protection mechanism based on an internal micro-short circuit model, which is closely related with the deposited electric lithium and cobalt and the separator porosity, is proposed and experimentally verified. These results offer an idea and method to decrease the CC overcharge risk of LIBs and can advance the safe application of LIBs.


Analysis Electrode process Overcharge safety LiCoO2/graphite battery Self-protection mechanism 


Funding information

This work was financially supported by the science and technology projects of Guangzhou (201604016131) and the science and technology projects of Dongguan (201521511902).


  1. 1.
    Zhu J, Wierzbicki T, Li W (2018) A review of safety-focused mechanical modeling of commercial lithium-ion batteries. J Power Sources 378:153–168CrossRefGoogle Scholar
  2. 2.
    Noelle DJ, Wang M, Le AV, Shi Y, Qiao Y (2018) Internal resistance and polarization dynamics of lithium-ion batteries upon internal shorting. Appl Energy 212:796–808CrossRefGoogle Scholar
  3. 3.
    Ruiz V, Pfrang A, Kriston A, Omar N, Bossche den PV, Boon-Brett L (2018) A review of international abuse testing standards and regulations for lithium ion batteries in electric and hybrid electric vehicles. Renew Sust Energ Rev 81:1427–1452CrossRefGoogle Scholar
  4. 4.
    Larouche F, Demopoulos GP, Amouzegar K, Bouchard P, Zaghib K (2018) Recycling of Li-ion and Li-solid state batteries: the role of hydrometallurgy. Extraction 2541–2553Google Scholar
  5. 5.
    Biensan P, Simon B, Peres JP, Guibert A, Broussely M, Bodet JM, Perton F (1999) On safety of lithium-ion cells. J Power Sources 81:906–912CrossRefGoogle Scholar
  6. 6.
    Tobishima S, Yamaki J (1999) A consideration of lithium cell safety. J Power Sources 81:882–886CrossRefGoogle Scholar
  7. 7.
    Saito Y, Takano K, Negishi A (2001) Thermal behaviors of lithium-ion cells during overcharge. J Power Sources 97-8:693–696CrossRefGoogle Scholar
  8. 8.
    Wen J, Yu Y, Chen C (2012) A review on lithium-ion batteries safety issues: existing problems and possible solutions. Mater Express 2(3):197–212CrossRefGoogle Scholar
  9. 9.
    Spotnitz R, Franklin J (2003) Abuse behavior of high-power lithium-ion cells. J Power Sources 113(1):81–100CrossRefGoogle Scholar
  10. 10.
    Leising RA, Palazzo MJ, Takeuchi ES, Takeuchi KJ (2001) A study of the overcharge reaction of lithium-ion batteries. J Power Sources 97-98:681–683CrossRefGoogle Scholar
  11. 11.
    Ouyang MG, Ren DS, Lu LG, Li JQ, Feng XN, Han XB, Liu GM (2015) Overcharge-induced capacity fading analysis for large format lithium-ion batteries with LiyNi1/3Co1/3Mn1/3O2 + LiyMn2O4 composite cathode. J Power Sources 279:626–635CrossRefGoogle Scholar
  12. 12.
    Ohsaki T, Kishi T, Kuboki T, Takami N, Shimura N, Sato Y, Sekino M, Satoh A (2005) Overcharge reaction of lithium-ion batteries. J Power Sources 146(1-2):97–100CrossRefGoogle Scholar
  13. 13.
    Yuan QF, Zhao FG, Wang WD, Zhao YM, Liang ZY, Yan DL (2015) Overcharge failure investigation of lithium-ion batteries. Electrochim Acta 178:682–688CrossRefGoogle Scholar
  14. 14.
    Ecker M, Sabet PS, Sauer DU (2017) Influence of operational condition on lithium plating for commercial lithium-ion batteries: electrochemical experiments and post-mortem analysis. Appl Energy 206:934–946CrossRefGoogle Scholar
  15. 15.
    Perea A, Paolella A, Dubé J, Champagne D, Mauger A, Zaghib K (2018) State of charge influence on thermal reactions and abuse tests in commercial lithium-ion cells. J Power Sources 399:392–397CrossRefGoogle Scholar
  16. 16.
    Sharma N, Peterson V (2013) Overcharging a lithium-ion battery: effect on the LixC6 negative electrode determined by in situ neutron diffraction. J Power Sources 244:695–701CrossRefGoogle Scholar
  17. 17.
    Sun F, Moronic R, Dong K, Markotter H, Zhou D, Hilger A, Zielke L, Zengerle R, Thiele S, Bahart J, Manke I (2017) Study of the mechanism of internal short circuit in a Li/Li cell by synchrotron X-ray phase contrast tomography. ACS Energy Lett 2(1):94–104CrossRefGoogle Scholar
  18. 18.
    Zhang K, Ren F, Wang XL, Mehta A, Yu XQ, Liu YJ (2017) Finding a needle in the haystack: identification of functionally important minority phases in an operating battery. Nano Lett 17(12):7782–7788CrossRefGoogle Scholar
  19. 19.
    Huang PF, Verm A, Robles DJ, Wang QS, Mukherjee P, Sun JH (2018) Probing the cooling effectiveness of phase change materials on lithium-ion battery thermal response under overcharge condition. Appl Therm Eng 132:521–530CrossRefGoogle Scholar
  20. 20.
    Xiao L, Ai XP, Cao YL, Yang HX (2004) Electrochemical behavior of biphenyl as polymerizable additive for overcharge protection of lithium ion batteries. Electrochim Acta 49(24):4189–4196CrossRefGoogle Scholar
  21. 21.
    Lee H, Lee JH, Ahn S, Kim HK, Cho JJ (2006) Co-use of cyclohexyl benzene and biphenyl for overcharge protection of lithium-ion batteries. Electrochem Solid-State Lett 9(6):A307–A310CrossRefGoogle Scholar
  22. 22.
    Feng XM, Ai XP, Yang HX (2004) Possible use of methylbenzenes as electrolyte additives for improving the overcharge tolerances of Li-ion batteries. J Appl Electrochem 34(12):1199–1203CrossRefGoogle Scholar
  23. 23.
    Huang DH, Liu R, Fan WZ, Yu L (2017) 2,4-difluorobiphenyls as overcharge protection additive of high-voltage Li-ion battery. Chin Batt Mon 47:223–225Google Scholar
  24. 24.
    Zhao MK, Zuo XX, Ma XD, Xiao X, Yu L, Nan JM (2016) Diphenyl disulfide as a new bifunctional film-forming additive for high-voltage LiCoO2/graphite battery charged to 4.4 V. J Power Sources 323:29–36CrossRefGoogle Scholar
  25. 25.
    Ma Y, Wang LS, Zuo XX, Nan JM (2018) Co-precipitation spray-drying synthesis and electrochemical performance of stabilized LiNi0.5Mn1.5O4 cathode materials. J Solid State Electrochem 22:1963–1969CrossRefGoogle Scholar
  26. 26.
    Deng YM, Ma Z, Song XN, Cai ZD, Pang PP, Wang Z, Zeng RH, Shu D, Nan JM (2018) From the charge conditions and internal short-circuit strategy to analyze and improve the overcharge safety of LiCoO2/graphite batteries. Electrochim Acta 282:295–303CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.School of Chemistry and EnvironmentSouth China Normal UniversityGuangzhouPeople’s Republic of China
  2. 2.Dongguan McNair New Power Co. LtdDongguanPeople’s Republic of China

Personalised recommendations