Calibration-Free Quantitative Analysis of Lithium-Ion Battery (LiB) Electrode Materials Using Laser-Induced Breakdown Spectroscopy (LIBS)

Abstract

Recent years have seen a surge in the demand for high-performance battery electrode materials for automotive and various electronic device applications. Improving battery performance requires precise knowledge of the structure–composition properties of active electrode materials. To this effect, quantitative and precise estimation of the composition of advanced electrode materials, containing trace amounts of dopants, provide immense value toward developing next-generation high-capacity battery materials. Herein, we demonstrate the application of calibration-free laser-induced breakdown spectroscopy (LIBS) as a powerful analytical tool for rapid and reliable quantitative spectrochemical characterizations of layered Li metal oxide cathodes containing Mo and Cr dopants (<5 atom %). Specifically, we employ the LIBS using an internal calibration methodology to establish the quantitative elemental ratios of major (Ni, Mn, Co) and trace dopant (Cr, Mo) transition metals to bulk Li contents in diverse cathode material samples such as LiNi0.5Mn0.5O2 (NM-50/50), LiNi0.33Mn0.33Co0.33O2 (NMC), LiNi0.317Mn0.317Co0.317Cr0.05O2 (Cr-doped NMC), and LiNi0.5–x/2Mn0.5–x/2Mo x O2 (x = 0.03, 0.04, 0.05) (Mo-doped NM-50/50) that were synthesized via sol–gel routes. The LIBS-estimated elemental compositions are in good agreement with the nominal stoichiometric values. Ex situ LIBS characterizations presented here pave the path for future high-efficacy application of calibration-free quantitative LIBS for rapid in situ analyses of elemental composition changes in battery electrode materials under operation that need not resort to off-site analytical techniques requiring cumbersome sample preparations and/or external standards.

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

“…A calibration-free LIBS method was reported by Pamu et al for the analysis of assorted lithium ion battery cathode materials . 231 This is a continuation of previous work and so the paper refers to previous papers for the LIBS setup and much of the theory. However, the method was used successfully for the determination of the ratios of the major electrode materials (Ni, Co and Mn) as well as some of the dopants, e.g.…”

Depth-Resolved Elemental Analysis on Moving Electrode Foils with Laser-Induced Breakdown Spectroscopy

“…This measurement could be of great interest for the production of electrode foils for lithium-ion batteries to monitor the homogeneity of its constituents. The feasibility of LIBS for the 2D and 3D measurement of the elemental distribution in electrode foils has been shown in several publications [ 5 , 14 , 15 , 16 , 17 , 18 ]. In all publications, the used samples were not in movement.…”

Sensitive Detection of the Human Epididymis Protein-4 (HE4) Ovarian Cancer Biomarker through a Sandwich-Type Immunoassay Method with Laser-Induced Breakdown Spectroscopy

“…The emitted photons can be collected by fiber optics coupled to a spectrometer and analyzed for sample composition and content. , LIBS has been used in many fields, including the biomedical field, for quantitative and qualitative analyses due to its unique features, such as minimal or no sample preparation and being a relatively fast analysis tool. Also, it requires a tiny amount of samples for the measurements. , In quantitative analysis, calibration curves or multivariate techniques are typically utilized to get the sample’s compositional information. On the other hand, reproducibility is a problem with LIBS as the spectral intensity is sensitive to laser parameters, sample distribution, and atmospheric conditions.…”

“…Also, it requires a tiny amount of samples for the measurements. 34,35 In quantitative analysis, calibration curves or multivariate techniques are typically utilized to get the sample's compositional information. On the other hand, reproducibility is a problem with LIBS as the spectral intensity is sensitive to laser parameters, sample distribution, and atmospheric conditions.…”