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Zicun Li

Publications and source records attributed to Zicun Li.

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Influence of Exchange-Correlation Functionals and Neural Network Architectures on Li$^+$-Ion Conductivity in Solid-State Electrolyte from Molecular Dynamics Simulations with Machine-Learning Force Fields

With the rapid advancement of machine learning techniques for materials simulations, machine-learned force fields (MLFFs) have become a powerful tool that complements first-principles calculations by enabling high-accuracy molecular dynamics simulations over extended timescales. Typically, MLFFs are trained on data generated from density functional theory (DFT) using a specific exchange-correlation (XC) functional, with the goal of reproducing DFT-level properties. However, the uncertainties in MLFF-based simulations--arising from variations in both MLFF model architectures and the choice of XC functionals--remain insufficiently understood. In this work, we construct MLFF models of different architectures trained on DFT data from both semilocal and hybrid functionals to describe Li$^+$ diffusion in the solid-state electrolyte Li$_6$PS$_5$Cl. We systematically investigate how different XC functionals influence the Li$^+$ diffusion coefficient. To reduce statistical uncertainty, the mean squared displacements are averaged over 300 independent molecular dynamics (MD) trajectories of 70 ps each, yielding statistical variations below $1\%$. This enables a clear assessment of the respective influences of the functional and the MLFF model. Due to its tendency to underestimate band gaps and migration barriers, the semilocal functional predicts consistently higher Li$^+$ diffusion coefficients, compared to the hybrid functional. Furthermore, comparisons among various neural network methods reveal that the differences in predicted diffusion coefficients arising from different network architectures are of the same order of magnitude as those caused by different functionals, indicating that the choice of the network model itself substantially influences the MLFF predictions. This observation calls from an urgent need for standardized protocols to minimize model-dependent biases in MLFF-based MD.

cond-mat.mtrl-sci

Revealing the Staging Structural Evolution and Li (De)Intercalation Kinetics in Graphite Anodes via Machine Learning Potential

Revealing the dynamic structural evolution and lithium transport properties during the charge/discharge processes is crucial for optimizing graphite anodes in lithium-ion batteries, enabling high stability and fast-charging performance. However, the dynamic coupling mechanisms among carbon layer kinetics, lithium (de)intercalation/diffusion, and defects regulation remain insufficiently understood. In this study, we developed a universal automated workflow based on machine learning potentials to simulate the dynamic lithium (de)intercalation process. With this approach, the staging structural evolution of lithium-graphite intercalation compounds and their lithium transport behavior were resolved through molecular dynamics simulations. By introducing stacking faults into the graphite structure, we successfully simulated stage transitions driven by carbon layer sliding and reorganization, accompanied by stress release and structural stabilization. The dynamics of carbon layers regulate the lithium (de)intercalation positional selectivity, producing intermediate states with varying lithium concentrations and distributions during cycling. This facilitates the formation and transformation of stage structures while mitigating residual stress accumulation. A fundamental kinetic asymmetry arises between lithium intercalation and deintercalation, driven by the continuous and heterogeneous lithium transport and carbon layer sliding during charge/discharge processes. The carbon defects regulate lithium transport, in which the atomic-scale defects confine intralayer lithium transport and carbon sliding while enabling interlayer transport via dynamic lithium trapping/release mechanisms. Accordingly, for the future design, it is critical to construct structural units with controllable carbon layer sliding/reorganization, and tunable defects to enhance lithium-ion transport.

cond-mat.mtrl-sci

Gas-solid Reaction Dynamics on Li$_6$PS$_5$Cl Surfaces: A Case Study of the Influence of CO$_2$ and CO$_2$/O$_2$ Atmospheres Using AIMD and MLFF Simulations

In recent years, rapid progress has been made in solid-state lithium batteries. Among various technologies, coating the surface of electrodes or electrolytes has proven to be an effective method to enhance interfacial stability and improve battery cycling performance. Recent experimental studies showed that gas-solid reactions offer a convenient approach to form modified coating layers on the solid electrolyte. Here, we performed computational simulations to investigate this surface reaction process. Specifically, we simulated the gas-solid reactions of Li$_6$PS$_5$Cl(LPSC) solid-state electrolytes in pure CO$_2$ and in mixed CO$_2$/O$_2$ atmospheres using ab-initio molecular dynamics (AIMD) and machine-learning force fields (MLFF)-accelerated molecular dynamics (MD) approaches. In the former case, LPSC surfaces primarily form Li$_2$CO$_2$S because it is difficult to dissociate another oxygen atom from the second CO$_2$ molecule. While in CO$_2$/O$_2$ mixed atmosphere, O$_2$ molecules preferentially adsorb onto LPSC, which supplies oxygen sites for subsequent CO$_2$ adsorption to form carbonate -CO$_3$ units. This reaction pathway ultimately generates an interfacial product dominated by Li$_2$CO$_3$. These coatings exhibit distinct electronic and ionic conductivity characteristics, allowing the possibility to control coating compositions and configurations by adjusting the gas-solid reactions. Key criteria for applying this strategy are extracted from the current research.

physics.chem-ph

Mechanistic Insights into Temperature Effects for Ionic Conductivity in Li6PS5Cl

Ensuring solid-state lithium batteries perform well across a wide temperature range is crucial for their practical use. Molecular dynamics (MD) simulations can provide valuable insights into the temperature dependence of the battery materials, however, the high computational cost of ab initio MD poses challenges for simulating ion migration dynamics at low temperatures. To address this issue, accurate machine-learning interatomic potentials were trained, which enable efficient and reliable simulations of the ionic diffusion processes in Li6PS5Cl over a large temperature range for long-time evolution. Our study revealed the significant impact of subtle lattice parameter variations on Li+ diffusion at low temperatures and identified the increasing influence of surface contributions as the temperature decreases. Our findings elucidate the factors influencing low temperature performance and present strategic guidance towards improving the performance of solid-state lithium batteries under these conditions.

cond-mat.mtrl-sci