Investigation of Li accumulations in LLZO based solid state batteries via operando neutron imaging and ex-situ correlative structural and chemical analysis

Abstract

In this study, we present a comprehensive analysis of lithium dendrite formation in half-cells with lithium garnet-type solid-state electrolyte Li7La3Zr2O12 (LLZO) utilizing operando neutron imaging and subsequent ex-situ correlative structural and chemical analysis. The operando experiment involves cycling a solid-state symmetric half-cell (Li|LLZO|Li) until short-circuit failure, all while being irradiated with neutrons, providing invaluable insights into the dynamic processes within the symmetric half-cell. Post-mortem investigations were carried out, comprising two techniques: 1) secondary electron imaging for structural analysis and 2) secondary ion mass spectrometry (SIMS) for chemical mapping. This multifaceted approach creates complementary datasets, bridging the gap between neutron radiography, known for its quantitative transmission capabilities, and high-resolution, high-sensitivity structural and chemical imaging via scanning electron microscopy (SEM) and SIMS.Central to our investigation is the design and development of an operando neutron imaging approach, enabling the study of lithium penetration during the electrochemical cycling. Furthermore, structural, and chemical analyses through correlative SEM/SIMS unveil various morphologies of lithium accumulations. Specifically, regions with dense LLZO reveal intergranular lithium accumulations, while low-density areas within the LLZO pellet, such as pores and cracks, exhibit distinct types of lithium accumulations (e.g. whiskers).Notably, neutron analysis reveals an accumulation of lithium in selected regions, with a maximum increase of up to 3.6 vol.-%. These regions primarily correspond to the roughened LLZO/Li interface, as observed through neutron imaging, although the SEM/SIMS analysis unequivocally confirms the presence of lithium dendrites (with sizes at or below the resolution limit of neutron imaging) also within the bulk of LLZO.This work offers a comprehensive examination of the intricate dynamics of lithium dendrite formation and behaviour in LLZO-based solid-state half-cells, emphasizing the potential of operando techniques to advance our understanding of critical issues (e.g. degradation, dendrite formation, …) in battery research.