Understanding the Improved High-Temperature Cycling
Stability of a LiNi0.5Mn0.3Co0.2O2/Graphite Cell with Vinylene Carbonate: A Comprehensive Analysis
Approach Utilizing LC-MS and DART-MS
An
analysis approach utilizing liquid chromatography mass spectrometry
(LC-MS) and direct analysis in real time mass spectrometry (DART-MS)
is applied to discern the influence of vinylene carbonate (VC) on
the cycling performance of a LiNi0.5Mn0.3Co0.2O2 (NMC)/graphite cell at elevated temperature.
The VC-containing cell exhibits much improved cycling performance
against the elevated temperature rather than the VC-free one. On the
basis of the LC-MS results, more decomposition compounds including
carbonate oligomers and organophosphates are present in the electrolyte
without VC after the initial cycling, while they are less identifiable
in the VC-containing electrolyte. On the other hand, the DART-MS results
show that a thermally resistant film, which is primarily composed
of the cyclic organophosphates, favors forming on the graphite anode
surface of the VC-containing cell rather than the VC-free one, preventing
further electrolyte decomposition. Moreover, a reaction scheme is
proposed to reasonably explain the formation of the decomposition
compounds, in which it is understood that VC can trap the free alkoxide
anions and meanwhile allow more EC to react with POF3 during
the initial cycling, thus reducing the decomposition compounds in
the electrolyte and facilitating the formation of thermally stable
organophosphates. Consequently, the cell’s cycling performance
is improved at elevated temperature.