Atomistic-Scale Simulations Toward the Understanding of the Conversion–Alloying Mechanism in Li-Ion Battery Anodes
Authors: Park Heesoo , van Duin Adri , Koposov Alexey 
Published: February 2024

The increasing demands for energy storage call for improved capacity and cycling stability of modern Li-ion batteries (LIBs). However, the application of the state-of-the-art LIB anode material – graphite is limited as graphite underperforms as a high-rate/high-storage-capacity anode. Alternatively, materials capable of alloying with Li-ions have attracted attention as a promising pathway to solve high-rate and high-capacity challenges. Furthermore, when alloying reaction in a material is coupled with irreversible conversion reaction, the materials operating under such mechanism exhibit a high Li-ion storage capacity and long-term stability during electrochemical cycling. However, despite the optimistic performance of these materials, a number of parameters need to be optimized and fundamentally understood.
Among the unknowns for the conversion/alloying materials are the atomistic details of the reaction mechanism - understanding the atomistic structure during transformations is a pre-requisite for the future rational optimization of the materials. Furthermore, amorphization, which is prevalent in these materials, severely limits the conventional characterization methods essentially impeding further development and understanding the degradation mechanisms. Hence, to investigate the atomistic structure changes, we proposed a computational methodology for these conversion-alloying materials and their reaction mechanism by taking amorphous substoichiometric silicon nitride as a showcase system [1]. The molecular dynamics (MD) simulations utilized the ReaxFF parameter set which was specifically developed for the investigation. Subsequently, the experimental pair distribution functions (PDF) were used to verify the modeling results.
While the reactive molecular dynamics was coupled with the PDF simulation to complement the experimental measurements, the effective and practical approach guided us to the atomistic structure evolution understanding for LIBs in a conversion–alloying process, revealing the bond coordinations around the Si atoms in the active material. Consequently, the analysis opened an in-depth understanding of the cycling stability of substoichiometric a-SiNx anode materials by revealing the atomistic features relevant to the changes this material undergoes during lithiation and delithiation processes in a LIB. Furthermore, the proposed approach allows modeling of the changes at the atomistic scale for the amorphous materials and predicting the experimental PDF at different cycling stages, verifying the modeling outcome. The topic also addresses the applications of the approach for other anode materials.
References
[1] Park, H., Duin, A. C. T. van & Koposov, A. Y. Toward Atomistic Understanding of Materials with the Conversion–Alloying Mechanism in Li-Ion Batteries. Chem Mater
35, 2835–2845 (2023).
Acknowledgement
This work was performed with the support of MoZEES, a Norwegian Centre for Environment-friendly Energy Research (FME), co-sponsored by the Research Council of Norway (project number 257653). The authors acknowledge the Research Council of Norway for providing the computer time (under the project numbers NN2875k and NS2875k) at the Norwegian supercomputer facility.

Figure 1