期刊
ELECTROCHIMICA ACTA
卷 180, 期 -, 页码 234-240出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.electacta.2015.08.122
关键词
in-situ neutron diffraction; deuterated ethyl acetate electrolyte; NMC442 degradation at high voltage; gassing
资金
- Walter C. Sumner Foundation
- AINSE Ltd
- 3M Canada
- NSERC
- DREAMS/CREATE
- ANSTO's Energy Materials project
The application of detailed in-situ neutron diffraction studies on lithium ion batteries has been limited in part due to the requirement of expensive deuterated carbonate-based electrolyte. This work presents an in-situ neutron diffraction study of the structural evolution of the Li-x (Ni0.4Mn0.4Co0.2)O-2 (NMC442) positive electrode material using a recently-developed low-cost deuterated ethyl acetate-based electrolyte. Rietveld analysis show that the NMC442 c lattice parameter gradually increases until x = 0.47 (4.03 V) and then decreases during the first charge. The decreasing trend of the c lattice parameter with time during the hold at 4.7 V and 4.9 V agrees very well with the change of current. Overall the structural changes appear highly reversible When 4.7 V is used as an upper cutoff voltage, even following a 10 h hold at 4.7 V. However, the electrode/electrolyte changes dramatically when charged and held at 4.9 V. There is a significant drop in background attributed to electrolyte decomposition and an unexpected increase in the a lattice parameter is noted after the 4.9 V hold. Therefore, the electrolyte system used is both beneficial for in-situ neutron diffraction studies and battery performance until 4.7 V, but appears to degrade in combination with the electrode at 4.9 V. By comparison to Li(Ni0.8Mn0.1Co0.1)O-2 (NMC811), the contraction of the c lattice with increasing voltage and decreasing lithium content of the NMC442 is less rapid. The transition metal composition significantly affects the c lattice contraction above 4.0 V. (C) 2015 Elsevier Ltd. All rights reserved.
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