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/2MoxO2(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.
Original language | English |
---|---|
Pages (from-to) | 7259-7267 |
Number of pages | 9 |
Journal | ACS Applied Energy Materials |
Volume | 4 |
Issue number | 7 |
DOIs | |
State | Published - Jul 26 2021 |
Funding
This manuscript has been jointly authored with UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). Partial support for this research was provided by US DOD’s Air Force Office of Scientific Research (AFOSR) under the award number: FA9550-19-1-0366. Part of the research carried out at Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the U.S. Department of Energy (DOE) under contract DE-AC05-00OR22725, was sponsored by the Energy Efficiency and Renewable Energy (EERE), and Vehicle Technologies Office (VTO).
Keywords
- calibration-free quantitative analysis
- cathode materials
- dopant elemental ratios
- laser-induced breakdown spectroscopy (LIBS)
- lithium-ion battery