High-Throughput Description of Infinite Composition–Structure–Property–Performance Relationships of Lithium–Manganese Oxide Spinel Cathodes

Abstract

Lithium−manganese oxide based spinel is attractive as cathode materials in lithium ion batteries. A wide range of spinel solid solution can be directly sintered and result in different properties of identical compositions during the battery operation, making it extremely difficult to understand the intrinsic properties and evaluate the battery performance. In this work, a high-throughput computational framework combining ab initio calculations and a CALPHAD (Calculation of Phase Diagrams) approach is developed to systematically describe infinite composition− structure−property−performance relationships under sintered and battery states of spinel cathodes. Depending on composition and crystallography, various properties (physical, thermochemical, and electrochemical) relating key factors (cyclability, safety, and energy density) are quantitatively mapped. The overall performance is consequently evaluated and validated by key experiments. Finally, 4 V spinel cathodes with codoping of reasonable Li and vacancies on the octahedral sites have been proposed. The presented strategy provides a general guide to evaluate the performance of cathodes with wide composition ranges.

Exceptional Cycling Performance Enabled by Local Structural Rearrangements in Disordered Rocksalt Cathodes

“…This leads to the distinct evolution of voltage regions near 4 V and 3 V, [64,65] similar to what was observed on metastable DRX materials such as Li 4 Mn 2 O 5 . [66][67][68] The arrangements not only create excellent percolation pathways of low activation energy Li migration channels [69][70][71] but also mitigate Jahn-teller distortion and enhance structural stability, [63,72] leading to better material utilization at a given current density, increased accessible capacity and more than 100% of capacity retention with cycling. It is conceivable that over-lithiation of the off-stoichiometry spinel-like domains occurs upon discharging below 3 V, enabling additional capacity not accounted in the pristine material and contributing to additional discharge capacity.…”

Boosting Rechargeable Batteries R&D by Multiscale Modeling: Myth or Reality?

“…Additionally, Zhang et al 121 exploited the potential of combining ab initio calculations and a CALPHAD approach (as already mentioned in section 2.1 115 ) to systematically probe infinite composition−structure−property−performance relationships under sintered and battery states of spinel cathodes. By calling to this high-throughput computational framework and with the aim to find the overall best performance for 4 V cathode materials, they conducted a systematic search for the best compromise for three key factors: energy density, cyclability, and safety, within the LiMn 2 O 4 -Li 4 Mn 5 O 12 -Li 2 Mn 4 O 9 triangle and were able to identify favorable compositions for each of these three properties.…”

Transition Metal Substitution of Hollandite α-MnO2: Enhanced Potential and Structural Stability on Lithiation from First-Principles Calculation

“…The application of manganese oxide (MnO x )-based materials in lithium batteries (LB) has attracted considerable attention. − Mn is environmentally friendly, capable of accommodating 3+ and 4+ oxidation states, and thus of interest as a material class. , Manganese oxide-based materials have a rich structural diversity . When considering ion insertion materials, a common structural form is layered motif providing ion diffusion in two dimensions. , However, lattice expansion and contraction associated with ion movement and electron transfer can also be accompanied by structural degradation and amorphization with loss of functional capacity.…”