Density-dependent sodium-storage mechanisms in hard carbon materials

TL;DR

This study combines multiscale simulations and machine learning to elucidate how the density of hard carbon materials influences sodium storage mechanisms, guiding the design of better anodes for sodium-ion batteries.

Contribution

It introduces a multiscale methodology integrating GCMC simulations with machine-learning potentials to analyze sodium storage in hard carbons of varying densities, revealing density-dependent storage behaviors.

Findings

Low-density carbons favor pore-filling with high capacities.

High-density carbons mainly store sodium via adsorption and intercalation.

Intermediate-density carbons balance capacity, stability, and volume change.

Abstract

Understanding the sodium-storage mechanism in hard carbon (HC) anodes is crucial for advancing sodium-ion battery (SIB) technology. However, the intrinsic complexity of HC microstructures and their interactions with sodium remain not fully elucidated. We present a multiscale methodology that integrates grand-canonical Monte Carlo (GCMC) simulations with a machine-learning interatomic potential based on the Gaussian approximation potential (GAP) framework to investigate sodium insertion mechanisms in hard carbons with different levels of porosity, achieved by simulating structural models with densities ranging from 0.7 to 1.9 g cm$^{-3}$. Structural and thermodynamic analyses reveal the interplay between pore size and accessibility and the relative contributions of adsorption, intercalation, and pore filling to the overall storage capacity. Low-density carbons favor pore-filling, achieving extremely high capacities at near-zero voltages, whereas high-density carbons primarily store sodium through adsorption and intercalation, leading to lower but more stable capacities. Intermediate-density carbons ($1.3-1.6$ g cm$^{-3}$) provide the most balanced performance, combining moderate capacity (480 and 310 mAh g$^{-1}$), safe operating voltages, and minimal volume expansion ($<10$\%). These findings establish a direct correlation between carbon density and electrochemical behavior, providing atomic-scale insight into how hard carbon morphology governs sodium-storage. The proposed framework offers a rational design principle for optimizing HC-based SIB anodes toward high energy density and long-term cycling stability.