Raman Spectroscopy of Practical LIB Cathodes: A Study of Humidity-Induced Degradation.

Exposure of LIB materials to ambient conditions with some level of humidity, either accidentally owing to imperfect fabrication or cell damage, or deliberately due to battery opening operations for analytical or recycling purposes, is a rather common event. As far as humidity-induced damage is concerned, on the one hand the general chemistry is well known, but on the other hand, concrete structural details of these processes have received limited explicit attention. The present study contributes to this field with an investigation centered on the use of Raman spectroscopy for the assessment of structural modifications using common lithium iron phosphate (LFP) and nickel-cobalt-manganese/lithium-manganese oxide (NCM-LMO) cathodes. The impact of humidity has been followed through the observation of differences in Raman bands of pristine and humidity-exposed cathode materials. Vibrational spectroscopy has been complemented with morphological (SEM), chemical (EDS), and electrochemical analyses. We have thus pinpointed the characteristic morphological and compositional changes corresponding to corrosion and active material dissolution. Electrochemical tests with cathodes reassembled in coin cells allowed for the association of specific capacity losses with humidity damaging.