Material Selection for Fundamental Investigation of High Temperature Processes in Lithium-Ion Cathode Production
Authors: Coessens Siebe , Bahramian Behnam , Bellemans Inge , Crivits Tijl , Detavernier Christophe , Verbeken Kim 
Published: February 2024

Rapid upscaling of current and near-future lithium-ion battery (LIB) technologies is one of the main remaining challenges for road transport electrification. Among cathode materials high-Ni layered lithium transition metal oxides, Li(NixCoyMn1-x-y)O2 (LNMC, x ≥ 0.7), show large potential for application in next-generation LIB’s because of their high energy density, low cost, and superior electrochemical properties 1–3.
To optimize current cathode production technologies, and to select the most optimal future technologies, a thorough understanding of the synthesis fundamentals of lithium-ion cathode calcination processes is a prerequisite. In this context, in-situ X-ray diffraction (XRD) and thermogravimetric analysis (TGA) have emerged as powerful tools for investigating the high-temperature reaction mechanism of the synthesis of these materials 4,5. However, most research does not address some challenges that come with studying complex high temperature synthesis reactions at the inherit small scale of these in-situ techniques. One issue, is that detailed information on the materials used for supporting the samples is seldomly mentioned, making it difficult to distinguish possible side reactions from the main reactions occurring during high temperature characterization. In only a limited number of studies on the high temperature interaction between ternary lithium-ion battery cathode materials and common substrate materials, evidence of direct contact-corrosion of refractory materials due to lithium compounds has been observed 6. To obtain meaningful insights from these in-situ techniques on the synthesis mechanism of LIB cathode materials that are transferable to mass production processes, these unwanted side reactions must be avoided as much as possible.
The purpose of the current study is to select the optimal support material for high temperature in-situ characterization of LIB calcination processes. Several LNMC blends, containing a Li compound and a NMC precursor, were calcined in different crucible materials under a 100% O2 flow at 900 °C for 10-12 hours. The selected crucibles for this investigation include common oxide refractories: Al2O3, SiO2 (fiber and quartz) and MgO, as well as Au, as a frequently used inert material for lab scale experiments. Chemical composition of the precursor blend and calcined products are compared by inductively coupled plasma optical emission spectroscopy ICP-OES. Additionally, weight increase of each crucible material is tracked over multiple calcination cycles, and the formed corrosion products are characterized with SEM-EDS and XRD. The ICP-OES measurements show that the final Li:TM ratio of the calcined LNMC material is heavily influenced by the used crucible material, indicating that selecting an appropriate support material is crucial to avoid side reactions and thus ensure that small scale in situ characterization methods such as in-situ XRD and TGA provide relevant data.

Nitta, N., Wu, F., Lee, J.T. & Yushin, G. Mater. Today
18, 252–264 (2015).

Schipper, F. et al. J. Electrochem.
Soc.
164, A6220–A6228 (2017).

Julien, C.M. & Mauger, A. Energies
13, 6363 (2020).

Wang, D. et al. Adv. Mater.
29, 1606715 (2017).

Gao, M. et al. Ionics
27, 3729–3737 (2021).

Zhai, P. et al. J. Eur.
Ceram. Soc.
38, 2145–2151 (2018).