Identification and Quantification of Lithium Ion Battery Electrolyte Residues in Blackmass Via Headspace-GC-MS/FID

Abstract

Due to the increasing demand for lithium-ion batteries (LIBs) in recent years, the demand for resources has also risen. As a result, the amount of LIBs that have reached the end of their life is increasing, leading to stricter guidelines that require certain proportions of recycled materials in the production of new LIBs. Typical recycling strategies start by deactivating, dismantling and shredding LIBs, thereby generating blackmass consisting of active and inactive materials (e.g. Li, Mn, Ni, Co, Cu and organic carbonates). However, black mass is a non-standardized resource, and its composition and purity vary depending on the respective process. 1,2 Therefore, it is essential to characterize and quantify its composition in order to make use of this highly variable resource stream while maintaining quality and safety.This work aims to identify and quantify organic electrolyte residues in black mass without further sample preparation. To achieve this, the samples were agitated using a headspace sampler and then analyzed by gas chromatography-mass spectrometry (GC-MS) and flame ionization detector (FID). Linear and cyclic carbonates such as dimethyl carbonate, ethyl methyl carbonate, and ethylene carbonate, as well as aging products such as 2,5-dioxahexanedioic acid dimethyl ester (DMDOHC), were detected. The identification results were compared to those achieved by thermodesorption and solid-phase microextraction.Overall, this study demonstrates a method for identifying and quantifying organic electrolyte residues in black mass, which can aid in the development of more efficient and sustainable recycling processes for LIBs.References(1) Peschel, C.; van Wickeren, S.; Preibisch, Y.; Naber, V.; Werner, D.; Frankenstein, L.; Horsthemke, F.; Peuker, U.; Winter, M.; Nowak, S. Comprehensive Characterization of Shredded Lithium-Ion Battery Recycling Material. Chemistry (Weinheim an der Bergstrasse, Germany) 2022, 28, e202200485.(2) Neumann, J.; Petranikova, M.; Meeus, M.; Gamarra, J. D.; Younesi, R.; Winter, M.; Nowak, S. Recycling of Lithium‐Ion Batteries—Current State of the Art, Circular Economy, and Next Generation Recycling. Advanced Energy Materials 2022, 761, 2102917.