# Density-dependent sodium-storage mechanisms in hard carbon materials

## TL;DR

This study explores how the density of hard carbon materials affects sodium storage in batteries, revealing how porosity influences performance and capacity.

## Contribution

A multiscale methodology combining machine learning and simulations to uncover density-dependent sodium-storage mechanisms in hard carbon.

## Key findings

- Low-density carbons favor pore-filling, achieving high capacities at near-zero voltages.
- Intermediate-density carbons (1.3–1.6 g cm−3) offer balanced performance with moderate capacity and minimal volume expansion.
- High-density carbons store sodium mainly through adsorption and intercalation, yielding lower but more stable capacities.

## 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.

Coupling machine-learning potential with grand-canonical Monte Carlo, we simulated hard carbon from structure generation to electrochemical evaluation (0.7–1.9 g cm−3), revealing how porosity governs sodium storage mechanisms and overall performance.