This review provides the research progress on a comprehensive, first-principles-based examination in elemental-doped graphene as electrode materials for sodium-ion batteries. It examines the governing mechanisms behind the physical properties and electrochemical performance of doped graphene anode materials. The microscopic physicochemical nature of doped graphene's characteristics is revealed via the detailed atomic-scale simulations and analysis.

The first-principles calculations reveal the distinct mechanisms by which different main-group element dopants affect the physical properties of graphene. Nitrogen (N) and boron (B) doping significantly enhance a sodium-ion adsorption capability and a diffusion performance via modifying the electronic structure of graphene, while maintaining a good structural integrity, thus exhibiting excellent overall performance. Sulfur (S) doping optimizes diffusion kinetics via expanding the interlayer spacing, though its adsorption capability and cycling stability require improvement. Fluorine (F) doping enhances adsorption capability via charge transfer mechanisms but suffers from a lower structural stability. Silicon (Si) doping increases the open-circuit voltage, however, its volumetric effect leads to degraded diffusion performance and structural stability.

The electrochemical performance analysis reveals that nitrogen-doped graphene exhibits a balanced performance in terms of specific capacity and capacity retention rate, making it suitable as a high-performance anode material for sodium-ion batteries. Boron-doped graphene achieves the maximum discharge specific capacity, however, its lower capacity retention rate limits its use to scenarios prioritizing a high energy density. Sulfur-doped graphene demonstrates the optimum cycling stability, but its relatively low specific capacity makes it suitable for applications demanding exceptionally long cycle life. Fluorine-doped graphene and silicon-doped graphene require a further performance optimization. Specifically, fluorine-doped graphene suffers from a low specific capacity and a poor capacity retention, limiting its practical viability. Silicon-doped graphene experiences degraded diffusion performance and structural stability due to its volumetric effect, necessitating a further investigation into doping concentration and structural design.

Based on the first-principles calculations, this review delves into the interactions between doped graphene and the electrolyte, predicting the composition and structure of the solid electrolyte interphase (SEI) film. Some strategies are explored to engineer a more stable SEI layer via simulating the SEI formation process, thereby suppressing the electrolyte decomposition and enhancing the cycling stability and safety of batteries.

Based on the research on doped graphene anode materials, novel doping elements and co-doping strategies can be explored to develop sodium-ion battery anodes with an enhanced adsorption capacity, a reduced diffusion energy barriers, and a superior structural stability. Leveraging the first-principles calculations to predict electrochemical performance of emerging dopants, we optimize doping concentrations and atomic configurations to improve electronic conductivity and ion diffusivity, thus propelling the performance enhancement of sodium-ion batteries.

The research on elemental doping of graphene anode materials for sodium-ion batteries synergistically integrates big data analytics, leveraging extensive experimental and computational datasets to identify and predict dopant effects on the material performance. This data-driven approach enables an accelerated translation from laboratory prototypes to industrial-scale production, reducing manufacturing costs and expediting the commercialization of sodium-ion battery technologies. Consequently, it establishes a robust support framework for developing eco-friendly energy materials and their sustainable implementation.