Abstract
Li1+x (Ni1/3Mn1/3Co1/3)1−x O2 (NMC) oxides are among the most promising positive electrode materials for future lithium–ion batteries. A voltage “plateau” was observed on the first galvanostatic charging curve of NMC in the extended voltage region positive to 4.5 V vs. Li/Li+ for compounds with x > 0 (overlithiated compounds). Differences were observed in the cycling stability of the overlithiated and stoichiometric (x = 0) NMC oxides in this potential region. A differential plot of the charge vs. potential profile in the first cycle revealed that, for the overlithiated compounds, a large irreversible oxidative peak arises positive to 4.5 V vs. Li/Li+, while in the same potential region only a small peak due to the electrolyte oxidation is detected for the stoichiometric material. Differential Electrochemical Mass Spectrometry (DEMS) was used to investigate the high voltage region for both compounds and experimental evidence for oxygen evolution was provided for the overlithiated compounds at potentials positive to 4.5 V vs. Li/Li+. No oxygen evolution was detected for the stoichiometric compound.
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References
Winter M, Besenhard JO, Spahr ME et al (1998) Adv Mater 725:10
Lu ZH, MacNeil DD, Dahn JR (2001) Electrochem Solid State Lett A191:4
Lee CW, Sun YK, Prakash J (2004) Electrochim Acta 4425:49
Tran N, Croguennec L, Labrugere C et al (2006) J Electrochem Soc A261:153
Ohzuku T, Makimura Y (2001) Chem Lett 642
Lu ZH, Dahn JR (2002) J Electrochem Soc A815:149
Park YJ, Hong YS, Wu XL et al (2004) J Electrochem Soc A720:151
Grincourt Y, Storey C, Davidson IJ (2001) J Power Sources 711:97
Storey C, Kargina I, Grincourt Y et al (2001) J Power Sources 541:97
Ammundsen B, Paulsen J, Davidson I et al (2002) J Electrochem Soc A431:149
Armstrong AR, Bruce PG (2004) Electrochem Solid State Lett A1:7
Rosciano F, La Mantia F, Tran N et al (2008) J Electrochem Soc (submitted)
Novák P, Goers D, Hardwick L et al (2005) J Power Sources 15:146
Wuersig A, Scheifele W, Novák P (2007) J Electrochem Soc A449:154
Vetter J, Holzapfel M, Würsig A et al (2006) J Power Sources 277:159
Armstrong AR, Holzapfel M, Novák P et al (2006) J Am Chem Soc 8694:128
Acknowledgments
The authors thank Professor Reinhard Nesper (ETH Zurich) and the Swiss National Science Foundation for fruitful discussions and financial support, respectively.
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La Mantia, F., Rosciano, F., Tran, N. et al. Direct evidence of oxygen evolution from Li1+x (Ni1/3Mn1/3Co1/3)1−x O2 at high potentials. J Appl Electrochem 38, 893–896 (2008). https://doi.org/10.1007/s10800-008-9491-9
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DOI: https://doi.org/10.1007/s10800-008-9491-9