High-Temperature Phase Behavior of Li2O-MnO with a Focus on the Liquid-to-Solid Transition

Abstract

The Li-Mn-O system is a crucial constituent of cathode materials used in lithium-ion batteries (LIBs). Numerous research teams have focused on enhancing its electrochemical properties and thermal stability at lower temperatures to develop high-performance cathode materials. However, in the recycling of LIBs in pyrometallurgical processing, the high temperature phase behavior of the Li-Mn-O system is important. Today, there is still a lack of systematic understanding regarding the high-temperature phase behavior of the Li-Mn-O system under well-defined atmospheric conditions, which is highly sought after in the pyrometallurgical process route to increase the recycling efficiency of lithium from spent LIBs. In this study, we investigate the high temperature phase behavior of the pseudo binary system Li2O-MnO under inert atmosphere. Thermal and caloric properties are measured as well as the contact angle at high temperatures to identify the solid-liquid transition. Based on the obtained phase behavior, thermodynamic database of Li2O-MnO within the Calphad framework is developed, where the liquid phase is modelled by the Modified Quasichemical Model (MQM).

Engineering Compounds for the Recovery of Critical Elements from Slags: Melt Characteristics of Li5AlO4, LiAlO2, and LiAl5O8

“…Applications are for instance in the understanding of material’s microstructure and solidification predictions . Particularly, in terms of lithium-containing oxide material systems, CALPHAD is widely applied for calculating and predicting the phase diagrams and serves as input for nonequilibrium solidification modeling. ,,− In this work, thermodynamic models and thermodynamic database of the Li 2 O–Al 2 O 3 system are applied according to Konar et al Based on this, essential phase information is provided for synthesizing different lithium-containing samples.…”

Enhancing Lithium Recycling Efficiency in Pyrometallurgical Processing through Thermodynamic-Based Optimization and Design of Spent Lithium-Ion Battery Slag Compositions

“…Consequently, manganese oxidation and the influence of the partial pressure of oxygen are excluded within this study. With the development of CALPHAD databases over the past few decades, ten binary subsystems, Li 2 O–Al 2 O 3 , , Li 2 O–SiO 2 , , Li 2 O–CaO, Li 2 O–MnO, Al 2 O 3 –SiO 2 , Al 2 O 3 –CaO, Al 2 O 3 –MnO, SiO 2 –CaO, SiO 2 –MnO, and CaO–MnO, and seven ternary subsystems, Li 2 O–CaO–Al 2 O 3 , Li 2 O–CaO–SiO 2 , , Li 2 O–Al 2 O 3 –SiO 2 , , CaO–Al 2 O 3 –SiO 2 , Al 2 O 3 –SiO 2 –MnO, CaO–Al 2 O 3 –MnO, and CaO–SiO 2 –MnO, have been critically assessed and optimized by the respective research groups. Despite these efforts, there remains a gap for the development of a comprehensive five-component thermodynamic database tailored specifically for the slag system of LIBs and also for experimental validation.…”

“…Li 2 O− SiO 2 ,40,49 Li 2 O−CaO,50 Li 2 O−MnO,51 Al 2 O 3 −SiO 2 ,52 Al 2 O 3 −CaO,52 Al 2 O 3 −MnO,53 SiO 2 −CaO,54 SiO 2 −MnO,54 and CaO−MnO,55 and seven ternary subsystems, Li 2 O−CaO−Al 2 O 3 ,56 Li 2 O−CaO− SiO 2 , 40,56 Li 2 O−Al 2 O 3 −SiO 2 , 40,57 CaO−Al 2 O 3 −SiO 2 , 52 Al 2 O 3 − SiO 2 −MnO, 58 CaO−Al 2 O 3 −MnO,59 and CaO−SiO 2 −MnO,59 have been critically assessed and optimized by the respective research groups. Despite these efforts, there remains a gap for the development of a comprehensive five-component thermodynamic database tailored Overview of the Selected Stoichiometric Compounds and Liquid and Solid Solutions, Corresponding Thermodynamic Models, and Database of the Li Solid solutions, the Gibbs energies of phases were taken directly from the FT-Oxide database from FactSage.…”

Characterisation of the Grain Morphology of Artificial Minerals (EnAMs) in Lithium Slags by Correlating Multi-Dimensional 2D and 3D Methods

“…This may be due to the assumption used in the simulation that the lithium, silicate, aluminate, and carbonate are treated as an ideal solution, which is not realistic, as indicated by Sommerfeld et al [8]. Additionally, the absence of solid solution database in the simulation strongly contributes to the discrepancy between the thermochemical simulation and the real experiment result [41]. The complexity of the real slag system is yet to be described more accurately by future simulations.…”