Lawrence Berkeley National Laboratory
Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi0.5Mn1.5O4 Electrodes
- Author(s): Qiao, Ruimin
- Wray, L Andrew
- Kim, Jung-Hyun
- Pieczonka, Nicholas PW
- Harris, Stephen J
- Yang, Wanli
- et al.
Published Web Locationhttps://doi.org/10.1021/acs.jpcc.5b07479
© 2015 American Chemical Society. The LiNi0.5Mn1.5O4 spinel is an appealing cathode material for next generation rechargeable Li-ion batteries due to its high operating voltage of ∼4.7 V (vs Li/Li+). Although it is widely believed that the full range of electrochemical cycling involves the redox of Ni(II)/(IV), it has not been experimentally clarified whether Ni(III) exists as the intermediate state or a double-electron transfer takes place. Here, combined with theoretical calculations, we show unambiguous spectroscopic evidence of the Ni(III) state when the LiNi0.5Mn1.5O4 electrode is half charged. This provides a direct verification of single-electron-transfer reactions in LiNi0.5Mn1.5O4 upon cycling, namely, from Ni(II) to Ni(III), then to Ni(IV). Additionally, by virtue of its surface sensitivity, soft X-ray absorption spectroscopy also reveals the electrochemically inactive Ni2+ and Mn2+ phases on the electrode surface. Our work provides the long-awaited clarification of the single-electron transfer mechanism in LiNi0.5Mn1.5O4 electrodes. Furthermore, the experimental results serve as a benchmark for further spectroscopic characterizations of Ni-based battery electrodes.