Quantifying Changes to the Electrolyte and Negative Electrode in Aged NMC532/Graphite Lithium-Ion Cells

Abstract

A set of LiNi0.5Mn0.3Co0.2O2/graphite lithium-ion cells underwent 750 charge-discharge cycles during about 8 months at 55°C to upper cutoff potentials of 4.0, 4.1, 4.2, 4.3, and 4.4 V. The electrolyte in these cells was extracted using a centrifuge method and studied using gas chromatography/mass spectrometry to determine the changes to the solvents and by inductively coupled plasma-mass spectrometry to determine the changes to the salt content in the electrolyte. The negative electrodes from the cells were harvested and studied by micro-X-ray fluorescence to quantify the amount of transition metals which migrated from the positive electrode to the negative electrode during the testing. Emphasis is given to a detailed description of the quantitative methods used in the hope that others will adopt them in similar studies of different types of aged lithium-ion cells. The cells studied here initially had 1.1 molal LiPF6 ethylene carbonate (EC): ethyl methyl carbonate (EMC) (3:7 by weight) electrolyte. The aged cells showed increasing amounts of dimethyl carbonate and diethyl carbonate created by transesterification as the upper cutoff potential increased. Only extremely small amounts of Mn, less than 0.1% of the total Mn in the positive electrode, were found on the negative electrode after this aggressive testing.