화학공학소재연구정보센터
Journal of the Electrochemical Society, Vol.163, No.3, A546-A551, 2016
Interactions between Positive and Negative Electrodes in Li-Ion Cells Operated at High Temperature and High Voltage
When NMC/graphite Li-ion cells are operated at elevated temperature or at a cutoff potential above 4.2 V, electrolyte oxidation becomes increasingly severe leading to gaseous products and other oxidized species. These generated gas products and oxidized species can migrate to, and then interact with, the negative electrode. A variety of cell formats (pouch cells, symmetric cells and coin cells) as well as pouch bags, containing only a delithiated positive electrode or a lithiated negative electrode, were used to investigate electrode/electrode interactions. Open circuit potential measurements during high temperature storage, ex-situ measurements of gas volume produced versus time, gas chromatography-mass spectrometry (GC-MS) of the gases produced and electrochemical impedance spectroscopy (EIS) of the electrodes versus time were performed. During storage at 60 degrees C, pouch bags containing only a lithiated negative electrode and electrolyte produced no gas while charged full pouch cells produced some gas and pouch bags containing only a delithiated positive electrode and electrolyte produced a significant amount of gas. The predominant gas produced in the positive electrode pouch bags was CO2 while virtually no CO2 was detected in the gases evolved in the charged full cell, suggesting that the negative electrode in the full cell consumes CO2 generated at the charged positive electrode. In addition, the impedance of the surface film on the charged positive electrodes in the pouch bags increased at least three times more than the positive electrodes in the charged pouch cells, even though they were both in contact with electrolyte for the same period of time. These impedance results suggest that oxidized species created at the positive electrode in the pouch bag remain in the vicinity of the positive electrode and create a high impedance film possibly a rock salt surface layer, while the same species migrate to the negative and are "consumed" in the pouch cell where the impedance of the positive electrode remains small. These interactions are apparently essential for the health of a NMC/graphite Li-ion pouch cell when operated at an elevated temperature or at a cutoff voltage above 4.2 V. (C) The Author(s) 2016 Published by ECS. All rights reserved.