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High-Voltage Electrolyte Additive for High-Energy Lithium-Ion Batteries
The Li1.2Mn0.525Ni0.175Co0.1O2 cathode material was synthesized at 900 oC in air using the carbonate coprecipitate precursor. The crystal structure of coprecipitate precursor and cathode material were identified by X-ray diffraction analysis, measured in the 2θ range of 10 - 80o with the scan rate of 2o/min. Lithium coin cells, consisted of Li1.2Mn0.525Ni0.175Co0.1O2 as a working electrode, a lithium foil as counter electrode and the electrolyte of 1M LiPF6/EC:EMC (3:7 volume ratio) with 5 wt% additive of fluorinated carbonate was assembled in the Ar-filled glove box. The 2016 coin half- and full-cells were evaluated for their cycling ability at C/5 rate between 2.5 and 4.8 V. AC impedance spectra were also collected during cycling. For characterization of solid electrolyte interface (SEI) composition, attenuated total reflection FTIR combined with X-ray photoelectron spectroscopic (XPS) analyses were conducted.
Figure 1a compares the cycling ability of Li1.2Mn0.525Ni0.175Co0.1O2 cathode without and with additive. With additive, the initial charge and discharge capacities are 350 and 256 mAh/g, respectively, with initial coulombic efficiency of 73%. The cathode delivers the capacity retention of 89% with the discharge capacity of 227 mAh/g at the 50th cycle. On the contrary, without additive, inferior capacities of 222 – 156 mAh/g and capacity retention of 70% over 50 cycles are observed. The use of additive is found to be very effective in enabling high-voltage cycling performance of Li1.2Mn0.525Ni0.175Co0.1O2 cathode. Our spectroscopic surface chemistry studies suggest that with additive, the cathode surface is effectively passivated with a stable SEI layer with maintained surface cathode structure (Figure 1b-iii), leading to a suppressed change in charge transfer resistance with cycling. On the contrary, the occurrence of surface structural degradation by the formation of dissolvable Mn2+proably followed by oxygen loss is observed when cycled without additive (Figure 1b-ii). Further discussion of the SEI formation mechanism and stability, their correlation to interfacial resistance and cycling performance, and the cycling performance of full-cells would be presented in the meeting.
Acknowledgements: This research was financially supported by the Korean Ministry of Education and National Research Foundation (2012026203) and by the Ministry of Trade, Industry & Energy (A0022-00725).