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

Sorina Cretu; David G Bradley; Li Patrick Wen Feng; Omer Ulas Kudu; Linh Lan Nguyen; Tuan Tu Nguyen; Arash Jamali; Jean-Noel Chotard; Vincent Seznec; John V Hanna; Arnaud Demortière; Martial Duchamp

doi:10.1021/acsami.3c03839

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

ACS Appl Mater Interfaces. 2023 Aug 23;15(33):39186-39197. doi: 10.1021/acsami.3c03839. Epub 2023 Aug 9.

Authors

Sorina Cretu^{1

2

3}, David G Bradley⁴, Li Patrick Wen Feng¹, Omer Ulas Kudu^{2

3}, Linh Lan Nguyen¹, Tuan Tu Nguyen^{2

3}, Arash Jamali^{2

3}, Jean-Noel Chotard^{2

3

5}, Vincent Seznec^{2

3}, John V Hanna^{1

4}, Arnaud Demortière^{2

3

5}, Martial Duchamp¹

Affiliations

¹ School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798, Singapore.
² Laboratoire de Réactivité et de Chimie des solides (LRCS), Université de Picardie Jules Verne, CNRS UMR 7314, 33 rue Saint Leu, Amiens Cedex 80039, France.
³ Réseau sur le stockage Electrochimique de l'Energie, CNRS FR 3459, 33 rue Saint Leu, Amiens Cedex 80039, France.
⁴ Department of Physics, University of Warwick, Coventry CV4 7AL, U.K.
⁵ ALISTORE-European Research Institute, CNRS FR 3104, Hub de l'Energie, Rue Baudelocque, Amiens Cedex 80039, France.

PMID: 37556356
DOI: 10.1021/acsami.3c03839

Abstract

Li_1.5Al_0.5Ge_1.5(PO₄)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 ³¹P and ²⁷Al MAS NMR study coupled with materials modeling reveals that the grain boundary material is composed of Li₄P₂O₇ and disordered Li₉Al₃(P₂O₇)₃(PO₄)₂ phases. Quantitative ³¹P MAS NMR measurements demonstrate that optimal ionic conductivity for the LAGP system is achieved for the 680 °C SPS preparation when the disordered Li₉Al₃(P₂O₇)₃(PO₄)₂ phase dominates the grain boundary composition with reduced contributions from the highly ordered Li₄P₂O₇ phases, whereas the ²⁷Al MAS NMR data reveal that minimal structural change is experienced by each phase throughout this suite of sintering temperatures.

Keywords: FIB-SEM tomography; NASICON; SPS influence of microstructure; grain boundaries; intergrain phase; ionic conductivity; multinuclear solid-state NMR; solid electrolyte.