Chemical Characterization Using Laser-Induced Breakdown Spectroscopy of Products Released from Lithium-Ion Battery Cells at Thermal Runaway Conditions

Abstract

Laser-induced breakdown spectroscopy (LIBS) was used to characterize the materials released by lithium-ion (Li-ion) cells at thermal runaway conditions. Commercial AAA-size, rechargeable, 3.7-V, 350-mAh, Li-ion battery cells were heated in a N2-atmosphere tubular chamber up to about 165 °C to induce thermal decomposition. Through measurements of the chamber internal temperature and LIBS emission intensities over time the onset temperature of thermal runaway (≈143 °C) and the duration of the cells outgassing (> 40 minutes) were determined. Relatively high intensity atomic emissions from C, H, F, Li, Na, and P were detected at different times during the heating experiments. The detection of analytes such as C and H was continuous over time. On the contrary, detection of F, Na, Li, and P was more irregular, indicating the presence of solid-phase analytes or analyte-bearing particles. A calibration scheme for estimation of the total mass/volume concentration of all carbon-based species sampled within the laser-induced plasma was developed.

Detection of Off-Gassed Products From Molten Salts Using Laser-Induced Breakdown Spectroscopy

“…Although such intensity variations are common in LIBS sampling of other substances (see for example the analysis of solids 48 ), they are intensified while analyzing aerosols due to the inherent discrete nature of aerosol streams and LIBS sampling characteristics. Such intensity variations have been previously reported during the analysis of aerosol streams under laboratory 44,46,47 and industrial conditions. 43 Third, the ensemble-averaged spectrum of multiple single-shot spectra was flat or featureless at the analyte wavelengths, indicating that discrete sampling of aerosol particles occurred.…”

“…4-6 are representative of LIBS aerosol sampling. 12,[43][44][45][46][47] First, only a small portion of the total single-shot spectra displayed the analyte emission lines. Second, the intensity of the particle hits (i.e., the occurrence of analyte-plasma interaction and signal detection) varied considerably from low to high intensities.…”

Vapor-Phase Contribution to Laser-Induced Plasma Emission of Magnesium in Liquid Aluminum

“…It is clear, however, that studies of the temperature dependence of the LIBS signal of volatile species in molten metals can provide valuable information about their behavior in the melt, for example, the effects of microalloying for the mitigation of oxidative loss of Mg. 25 In a recent study, LIBS measurements on off-gassed Na and Ca from molten salts were reported, where the analysis was performed in a chamber that was separated from the molten salt reactor. 26 Such studies, as well as experimental configurations where a breakdown is localized in the vapor phase above a liquid surface, will be of value to further elucidate the mechanisms of evaporation, without contributions from the liquid phase.…”

Atomic spectrometry update: review of advances in the analysis of metals, chemicals and materials

“…Diaz and Hahn used LIBS to characterise products released from lithium ion battery cells at thermal runaway conditions . 232 Commercial AAA-sized 3.7 V, 350 mA h lithium ion batteries were placed in a heating chamber and heated to 165 °C to induce thermal decomposition (this starts at 143 °C) in a nitrogen atmosphere. Any gases emitted over a 40 minute period were then analysed on-line using LIBS which employed a Nd:YAG laser, optics, a chamber in which the LIBS analysis occurred and a spectrometer equipped with an intensified CCD.…”