Computational study identifies key improvements for Na2FeSiO4– a promising cathode material for sodium-ion batteries

Researchers from the University of Jaffna and Imperial College London have uncovered critical insights into optimizing Na₂FeSiO₄, a low-cost, abundant cathode material for sodium-ion batteries (SIBs). Published in Front. Energy, their computational study pinpoints ideal dopants and reveals favorable ion transport properties, bringing SIBs— a sustainable alternative to lithium-ion batteries—closer to large-scale energy storage applications.

Why Sodium-Ion Batteries Matter

Lithium-ion batteries (LIBs) dominate today’s energy storage market, but limited lithium resources, uneven global distribution, and high costs hinder their scalability for grid storage and heavy-duty applications. Sodium-ion batteries offer a compelling solution: sodium is Earth’s sixth most abundant element, widely available and low-cost, with electrochemical mechanisms similar to LIBs.

Among potential SIB cathode materials, Na₂FeSiO₄ stands out. It boasts a high theoretical capacity (276 mAh/g), thermal stability up to 1000°C, and minimal volume change during charge-discharge cycles. However, optimizing its ionic conductivity and structural performance has been a key challenge—one the research team addresses through advanced computational modeling.

Key Discoveries from Atomic-Scale Simulations

Using atomistic simulations and density functional theory (DFT), the team analyzed Na₂FeSiO₄’s crystal structure, intrinsic defects, sodium-ion migration, and dopant behavior:

• Efficient Sodium Transport: The material favors vacancy-mediated Na-ion migration, with low activation energy barriers of 0.38 eV and 0.41 eV. This enables faster ion movement than many similar silicate materials, includingNa₂MnSiO₄ (0.81 eV) and lithium-based Li₂Na₂FeSiO₄ (0.83 eV).
• Critical Intrinsic Defects: The Na Frenkel pair (a combination of a sodium vacancy and interstitial sodium) has the lowest formation energy (1.71 eV) among native defects, supporting efficient ion diffusion.
• Optimal Dopants for Performance:
  • Isovalent dopants: Potassium (K) at Na sites, zinc (Zn) at Fe sites, and germanium (Ge) at Si sites are the most energetically favorable, preserving charge neutrality without disrupting the lattice.
  • Aliovalent dopants: Gallium (Ga) at Fe sites promotes sodium vacancy formation, enhancing ionic conductivity. Aluminum (Al) at Si sites increases the material’s sodium content, potentially boosting battery capacity.

These dopants were selected for their ability to improve structural stability, ion transport, and electrochemical behavior without introducing harmful electronic defects.

Advancing Sustainable Energy Storage

Na₂FeSiO₄’s appeal extends beyond its performance: it is non-toxic, uses Earth-abundant elements (iron, silicon, sodium), and maintains structural integrity even at high temperatures. The monoclinic polymorph studied—with a 3D framework of interconnected tetrahedra—provides a stable scaffold for sodium-ion diffusion, addressing a key limitation of many polyanionic cathode materials.

“Our computational work bridges the gap between theoretical potential and practical application for Na₂FeSiO₄,” said Poobalasuntharam Iyngaran, corresponding author of the study. “By identifying optimal dopants and understanding ion transport at the atomic level, we provide a roadmap for developing high-performance, low-cost sodium-ion batteries that can compete with lithium-ion technology for grid storage and beyond.”

Future Directions

The team’s findings lay the groundwork for experimental validation, including testing doped Na₂FeSiO₄ in full battery cells. Future research will explore co-doping strategies, temperature-dependent defect dynamics, and long-term cycling behavior to further optimize the material for commercial use.

As the global shift to renewable energy accelerates, sodium-ion batteries powered by optimized materials like Na₂FeSiO₄ could play a pivotal role in storing solar and wind energy, reducing reliance on fossil fuels and enabling a more sustainable energy future.

About the Research

This work was supported by computational resources from Imperial College London and the University of Jaffna, Sri Lanka. The full research article is available at https://doi.org/10.1007/s11708-025-1040-2.