Effect of excess lithium in LiMn2O4 and Li1.15Mn1.85O4 electrodes revealed by quantitative analysis of soft X-ray absorption spectroscopy

Zhuo, Zengqing; Olalde-Velasco, Paul; Chin, Timothy; Battaglia, Vincent; Harris, Stephen J.; Pan, Feng; Yang, Wanli

doi:10.1063/1.4977502

Title: Effect of excess lithium in LiMn₂O₄ and Li_1.15Mn_1.85O₄ electrodes revealed by quantitative analysis of soft X-ray absorption spectroscopy

Journal Article · Tue Feb 28 00:00:00 EST 2017 · Applied Physics Letters

DOI:https://doi.org/10.1063/1.4977502· OSTI ID:1393125

Zhuo, Zengqing ^[1]; Olalde-Velasco, Paul ^[2]; Chin, Timothy ^[2]; Battaglia, Vincent ^[2]; Harris, Stephen J. ^[2]; Pan, Feng ^[3];

^[2]

Peking Univ., Beijing (China); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Peking Univ., Beijing (China)

We performed a comparative study of the soft x-ray absorption spectroscopy of the LiMn2O4 and Li1.15Mn1.85O4 electrode materials with a quantitative analysis of the Mn oxidation states. The revealed redox evolution of Mn upon the electrochemical cycling clarifies the effect of the excess Li in the materials, which naturally explains the different electrochemical performance. The spectral analysis perfectly agrees with the different initial cycling capacities of the two materials. The results show unambiguously that Mn3+ starts to dominate the electrode surface after only one cycle. More importantly, the data show that, while LiMn2O4 electrodes follow the nominal Mn redox evolution, the formation of Mn3+ on the electrode surface is largely retarded for the Li1.15Mn1.85O4 during most of the electrochemical process. Such a different surface Mn redox behavior leads to differences in the detrimental effects of Mn2+ formation on the surface, which is observed directly after only two cycles. Our results provide strong evidence that a key effect of the (bulk) excess Li doping is actually due to processes on the electrode surfaces.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); Shenzhen Municipal Government (China)

Contributing Organization:: Peking University; Shenzhen Graduate School (China)

Grant/Contract Number:: AC02-05CH11231; 2016YFB0700600; 2013N080; KYPT20141016105435850

OSTI ID:: 1393125

Alternate ID(s):: OSTI ID: 1343752; OSTI ID: 1348273

Journal Information:: Applied Physics Letters, Vol. 110, Issue 9; ISSN 0003-6951

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 15 works

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Title: Effect of excess lithium in LiMn2O4 and Li1.15Mn1.85O4 electrodes revealed by quantitative analysis of soft X-ray absorption spectroscopy

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Title: Effect of excess lithium in LiMn₂O₄ and Li_1.15Mn_1.85O₄ electrodes revealed by quantitative analysis of soft X-ray absorption spectroscopy