B(2)O(3)-Doped LATP Glass-Ceramics Studied by X-ray Diffractometry and MAS NMR Spectroscopy Methods

Two families of glasses in the Li(2)O-Al(2)O(3)-B(2)O(3)-TiO(2)-P(2)O(5) system were prepared via two different synthesis routes: melt-quenching and ball-milling. Subsequently, they were submitted to crystallization and yielded the Li(1.3)A(l0).(3)Ti(1.7)(PO(4))(3) (LATP)-based glass-ceramics. Glasses and corresponding glass-ceramics were studied by complementary X-ray diffraction (XRD) and (27)Al, (31)P, (7)Li, (11)B 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 B(2)O(3) 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.