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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 Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 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, Li 4 SiO 4 was selected and added to the LATP base matrix to support Li + diffusion between the grains. The properties of the Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 - x Li 4 SiO 4 (0.02 ≤ x ≤ 0.1) system were studied by means of high-temperature X-ray diffractometry (HTXRD); 6 Li, 27 Al, 29 Si, and 31 P 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 Li 4 SiO 4 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 σ tot  = 1.4 × 10 -4 S∙cm -1 has been obtained for LATP-0.1LSO material sintered at 1000 °C for 6 h.

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