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Nano Lett. 2019 Jan 9;19(1):29-37. doi: 10.1021/acs.nanolett.8b02902. Epub 2018 Oct 26.

Unveiling the Intrinsic Cycle Reversibility of a LiCoO2 Electrode at 4.8-V Cutoff Voltage through Subtractive Surface Modification for Lithium-Ion Batteries.

Author information

1
Department of Materials Science and Engineering, Research Institute of Advanced Materials (RIAM) , Seoul National University , Seoul 08826 , Republic of Korea.
2
Center for Nanoparticle Research , Institute for Basic Science (IBS) , Seoul 08826 , Republic of Korea.

Abstract

The thermodynamic instability of the LiCoO2 layered structure at >0.5Li extraction has been considered an obstacle for the reversible utilization of its near theoretical capacity at high cutoff voltage (>4.6 V vs Li/Li+) in lithium-ion batteries. Many previous studies have focused on resolving this issue by surface modification of LiCoO2, which has proven to be effective in suppressing phase transformation. To determine the extent to which surface protection of LiCoO2 is effective despite its thermodynamic instability and presumably incomplete reversibility involving the O1 phase, here we verify the intrinsic reversibility of bulk LiCoO2 with extended lithium extraction by ruling out the effect of a surface. Specifically, first, we show that, contrary to conventional belief, electrochemical cycling of LiCoO2 at a cutoff voltage of 4.8 V (vs Li/Li+) results in better cycle stability and lower polarizations than those at 4.6 V. We demonstrate, using an exhaustive suite of characterization tools, that the rapid cycle degradation under high-voltage cycling is mostly caused by the formation of a surface resistive layer; however, these damaged surfaces are leached out faster than they are accumulated above a certain potential, which results in superior cyclability compared with that achieved for less oxidative 4.6-V cycling. This beneficial leaching out of the resistive surface layer serves as a "subtractive" surface modification and plays a role in enhancing the cycle stability and is distinguished from conventional "additive" surface modification such as coating. This approach allows us to decouple factors of the bulk and surface degradations that contribute to the capacity fade and leads to the finding that, in the absence of a resistive surface, the capacity retention of a LiCoO2 electrode with 4.8-V cutoff cycling can be intrinsically high, indicating that the instability of the crystalline Li xCoO2 ( x < 0.5) has a limited effect on the cycle stability. Our findings also explain why the strategy of coating foreign materials on the surface of LiCoO2 can improve the high-voltage cycling to some extent despite the expected thermodynamic instability of the highly charged phase.

KEYWORDS:

LiCoO2; high-voltage cycling; intrinsic cycle reversibility; lithium-ion batteries; subtractive surface modification

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