UC Davis

Due to higher packing density, lower working potential, and area specific impedance, the MLi₂Ti₆O₁₄ (M = 2Na, Sr, Ba, and Pb) titanate family is a potential alternative to zero-strain Li₄Ti₅O₁₂ anodes used commercially in Li-ion batteries. However, the exact lithiation mechanism in these compounds remains unclear. Despite its structural similarity, MLi₂Ti₆O₁₄ behaves differently depending on charge and size of the metal ion, hosting 1.3, 2.7, 2.9, and 4.4 Li per formula unit, giving charge capacity values from 60 to 160 mAh/g in contrast to the theoretical capacity trend. However, high-temperature oxide melt solution calorimetry measurements confirm strong correlation between thermodynamic stability and the observed capacity. The main factors controlling energetics are strong acid-base interactions between basic oxides MO, Li₂O and acidic TiO₂, size of the cation, and compressive strain. Accordingly, the energetic stability diminishes in the order Na₂Li₂Ti₆O₁₄ > BaLi₂Ti₆O₁₄ > SrLi₂Ti₆O₁₄ > PbLi₂Ti₆O₁₄. This sequence is similar to that in many other oxide systems. This work exhibits that thermodynamic systematics can serve as guidelines for the choice of composition for building better batteries.