Electrical and Structural Properties of Li1.3Al0.3Ti1.7(PO4)3-Based Ceramics Prepared with the Addition of Li4SiO4.

The currently studied materials considered as potential candidates to be solid electrolytes for Li-ion batteries usually suffer from low total ionic conductivity. One of them, the NASICON-type ceramic of the chemical formula Li1.3Al0.3Ti1.7(PO4)3, seems to be an appropriate material for the modification of its electrical properties due to its high bulk ionic conductivity of the order of 10-3 S∙cm-1. For this purpose, we propose an approach concerning modifying the grain boundary composition towards the higher conducting one. To achieve this goal, Li4SiO4 was selected and added to the LATP base matrix to support Li+ diffusion between the grains. The properties of the Li1.3Al0.3Ti1.7(PO4)3-xLi4SiO4 (0.02 ≤ x ≤ 0.1) system were studied by means of high-temperature X-ray diffractometry (HTXRD); 6Li, 27Al, 29Si, and 31P magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR); thermogravimetry (TG); scanning electron microscopy (SEM); and impedance spectroscopy (IS) techniques. Referring to the experimental results, the Li4SiO4 additive material leads to the improvement of the electrical properties and the value of the total ionic conductivity exceeds 10-4 S∙cm-1 in most studied cases. The factors affecting the enhancement of the total ionic conductivity are discussed. The highest value of σtot = 1.4 × 10-4 S∙cm-1 has been obtained for LATP-0.1LSO material sintered at 1000 °C for 6 h.

B2O3-Doped LATP Glass-Ceramics Studied by X-ray Diffractometry and MAS NMR Spectroscopy Methods.

Two families of glasses in the Li2O-Al2O3-B2O3-TiO2-P2O5 system were prepared via two different synthesis routes: melt-quenching and ball-milling. Subsequently, they were submitted to crystallization and yielded the Li1.3Al0.3Ti1.7(PO4)3 (LATP)-based glass-ceramics. Glasses and corresponding glass-ceramics were studied by complementary X-ray diffraction (XRD) and 27Al, 31P, 7Li, 11B magic-angle spinning nuclear magnetic resonance (MAS NMR) methods in order to compare their structure and phase composition and elucidate the impact of boron additive on their glass-forming properties and crystallization process. XRD studies show that the addition of B2O3 improves the glass-forming properties of glasses prepared by either method and inhibits the precipitation of unwanted phases during heat treatment. MAS NMR studies allowed us to distinguish two LATP phases of slightly different chemical composition suggesting that LATP grains might not be homogeneous. In conclusion, the crystallization of boron-incorporated LATP glasses can is an effective way of obtaining LATP-based solid state electrolytes for the next generation of lithium-ion batteries provided the proper heat-treatment conditions are chosen.