Revealing electrolyte oxidation via carbonate dehydrogenation on Ni-based oxides in Li-ion batteries by in situ Fourier transform infrared spectroscopy
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Author(s)
Zhang, Yirui
Katayama, Yu
Tatara, Ryoichi
Giordano, Livia
Yu, Yang
Fraggedakis, Dimitrios
Sun, Jame Guangwen
Maglia, Filippo
Jung, Roland
Bazant, Martin Z
Date Issued
November 2019
Journal
Energy and Environmental Science
Publisher
Royal Society of Chemistry (RSC)
Citation
Zhang, Yirui et al. "Revealing electrolyte oxidation via carbonate dehydrogenation on Ni-based oxides in Li-ion batteries by in situ Fourier transform infrared spectroscopy." Energy and Environmental Science, 13, 1, (2020): 183-199. © 2019 The Royal Society of Chemistry
Version
Final published version
Abstract
Understanding (electro-)chemical reactions at the electrode–electrolyte interface (EEI) is crucial to promote the cycle life of lithium-ion batteries. In this study, we developed an in situ Fourier-transform infrared spectroscopy (FT-IR) method, which provided unprecedented information on the oxidation of carbonate solvents via dehydrogenation on LiNixMnyCo1−x−yO2 (NMC). While ethylene carbonate (EC) was stable against oxidation on Pt up to 4.8 VLi, unique evidence for dehydrogenation of EC on LiNi0.8Co0.1Mn0.1O2 (NMC811) at voltages as low as 3.8 VLi was revealed by in situ FT-IR measurements, which was supported by density functional theory (DFT) results. Unique dehydrogenated species from EC were observed on NMC811 surface, including dehydrogenated EC anchored on oxides, vinylene carbonate (VC) and dehydrogenated oligomers which could diffuse away from the surface. Similar dehydrogenation on NMC811 was noted for EMC-based and LP57 (1 M LiPF6 in 3 : 7 EC/EMC) electrolytes. In contrast, no dehydrogenation was found for NMC111 or surface-modified NMC by coatings such as Al2O3. In addition, while the dehydrogenation of solvents was observed in 1 M electrolytes with different anions, they were not observed on NMC811 in the concentrated electrolyte (EC/EMC with 3.1 M LiPF6), indicating lithium coordination could suppress dehydrogenation. Dehydrogenation of carbonates on NMC811 accompanied with rapid growth of interfacial impedance with increasing voltage revealed by electrochemical impedance spectroscopy (EIS), while the electrode–electrolyte combinations without dehydrogenation did not show significant impedance growth. Therefore, minimizing carbonate dehydrogenation on the NMC surface by tuning electrode reactivity and electrolyte reactivity is critical to develop high-energy Li-ion batteries with long cycle life.
MIT Department
Massachusetts Institute of Technology. Department of Mechanical Engineering
Massachusetts Institute of Technology. Research Laboratory of Electronics
Massachusetts Institute of Technology. Department of Materials Science and Engineering
Massachusetts Institute of Technology. Department of Chemical Engineering
Massachusetts Institute of Technology. Department of Mathematics
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DOI of Published Version
https://doi.org/10.1039/c9ee02543j
