Ionic Conductivity of Na₃Al₂P₃O₁₂ Glass Electrolytes-Role of Charge Compensators

In glasses, a sodium ion (Na⁺) is a significant mobile cation that takes up a dual role, that is, as a charge compensator and also as a network modifier. As a network modifier, Na⁺ cations modify the structural distributions and create nonbridging oxygens. As a charge compensator, Na⁺ cations provide imbalanced charge for oxygen that is linked between two network-forming tetrahedra. However, the factors controlling the mobility of Na⁺ ions in glasses, which in turn affects the ionic conductivity, remain unclear. In the current work, using high-fidelity experiments and atomistic simulations, we demonstrate that the ionic conductivity of the Na₃Al₂P₃O₁₂ (Si0) glass material is dependent not only on the concentration of Na⁺ charge carriers but also on the number of charge-compensated oxygens within its first coordination sphere. To investigate, we chose a series of glasses formulated by the substitution of Si for P in Si0 glass based on the hypothesis that Si substitution in the presence of Na⁺ cations increases the number of Si-O-Al bonds, which enhances the role of Na as a charge compensator. The structural and conductivity properties of bulk glass materials are evaluated by molecular dynamics (MD) simulations, magic angle spinning-nuclear magnetic resonance, Raman spectroscopy, and impedance spectroscopy. We observe that the increasing number of charge-imbalanced bridging oxygens (BOs) with the substitution of Si for P in Si0 glass enhances the ionic conductivity by an order of magnitude-from 3.7 × 10^-8 S.cm^-1 to 3.3 × 10^-7 S.cm^-1 at 100 °C. By rigorously quantifying the channel regions in the glass structure, using MD simulations, we demonstrate that the enhanced ionic conductivity can be attributed to the increased connectivity of Na-rich channels because of the increased charge-compensated BOs around the Na atoms. Overall, this study provides new insights for designing next-generation glass-based electrolytes with superior ionic conductivity for Na-ion batteries.