Probing Capacity Trends in MLi2Ti6O14 Lithium-Ion Battery Anodes Using Calorimetric Studies

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 thermody-namic 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.

Automated summary

The titanate family MLi2Ti6O14 (M = 2Na, Sr, Ba, and Pb) shows potential as an alternative to commercial zero-strain Li4Ti5O12 anodes in Li-ion batteries due to its higher packing density, lower working potential, and area specific impedance. The lithiation mechanism in these compounds remains unclear, but there is a strong correlation between thermodynamic stability and observed capacity. The choice of composition for building better batteries can be guided by thermodynamic systematics.