The Impact of Intergrain Phases on the Ionic Conductivity of the LAGP Solid Electrolyte Material Prepared by Spark Plasma Sintering.

Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) is a promising oxide solid electrolyte for all-solid-state batteries due to its excellent air stability, acceptable electrochemical stability window, and cost-effective precursor materials. However, further improvement in the ionic conductivity performance of oxide solid-state electrolytes is hindered by the presence of grain boundaries and their associated morphologies and composition. These key factors thus represent a major obstacle to the improved design of modern oxide based solid-state electrolytes. This study establishes a correlation between the influence of the grain boundary phases, their 3D morphology, and compositions formed under different sintering conditions on the overall LAGP ionic conductivity. Spark plasma sintering has been employed to sinter oxide solid electrolyte material at different temperatures with high compacity values, whereas a combined potentiostatic electrochemical impedance spectroscopy, 3D FIB-SEM tomography, XRD, and solid-state NMR/materials modeling approach provides an in-depth analysis of the influence of the morphology, structure, and composition of the grain boundary phases that impact the total ionic conductivity. This work establishes the first 3D FIB-SEM tomography analysis of the LAGP morphology and the secondary phases formed in the grain boundaries at the nanoscale level, whereas the associated 31 P and 27 Al MAS NMR study coupled with materials modeling reveals that the grain boundary material is composed of Li 4 P 2 O 7 and disordered Li 9 Al 3 (P 2 O 7 ) 3 (PO 4 ) 2 phases. Quantitative 31 P MAS NMR measurements demonstrate that optimal ionic conductivity for the LAGP system is achieved for the 680 °C SPS preparation when the disordered Li 9 Al 3 (P 2 O 7 ) 3 (PO 4 ) 2 phase dominates the grain boundary composition with reduced contributions from the highly ordered Li 4 P 2 O 7 phases, whereas the 27 Al MAS NMR data reveal that minimal structural change is experienced by each phase throughout this suite of sintering temperatures.