Towards Operando Secondary Ion Mass Spectrometry Imaging of Lithium Redistribution in Solid-State Lithium-Ion Batteries—Correlation of Structural, Chemical and Electrochemical Characteristics

Innovations in lithium-ion batteries rely crucially on the availability of advanced characterization techniques. High-resolution chemical imaging of low-Z elements e.g., lithium (Li) is often difficult in many conventional chemical analysis techniques such as Energy-Dispersive X-ray Spectroscopy. High-resolution Secondary Ion Mass Spectrometry (SIMS) imaging is a well-known technique for the analysis of all elements including isotopes. For this reason, SIMS imaging is used in numerous studies related to Li-ion battery research. While direct imaging of Li in post-mortem battery components is helpful to understand parts of the degradation mechanisms, a complete dynamic view of the evolution of the Li distribution at high resolution during operation (‘operando’) of batteries is required to fully understand the local interfacial processes, charge transport characteristics and the degradation mechanisms. A few reports presenting operando Time-of-Flight SIMS imaging of batteries have recently been published [1], but the lateral resolution demonstrated in these reports is not adequate to study local processes that occur at nanoscale.

In order to demonstrate operando SIMS chemical imaging with sub-20 nm lateral resolution, we developed a novel operando methodology suitable for Focused Ion Beam (FIB)-SIMS imaging and analysis. An in-house designed magnetic-sector mass spectrometer [2] attached to a ThermoFisher SCIOS Ga⁺ FIB is used for SIMS chemical imaging. A special operando sample holder was designed to enable electrochemical cycling of batteries within the FIB-SIMS instrument. The micromanipulator inside the FIB (typically used for preparing thin lamellae for Transmission Electron Microscopy) is used to contact one of the battery electrodes through the operando sample holder and complete the electrical circuit. An external potentiostat is then connected to the instrument to drive the charging/discharging of batteries. The proof-of-concept experiments were performed using Li|Li₇La₃Zr₂O₁₂|Li symmetric half-cells. Galvanostatic cycling was performed in-situ inside the FIB-SIMS instrument until the sample failed. SIMS chemical mapping revealed a redistribution of Li during cycling. Lithium rich phases appeared during cycling which likely percolated through grain-boundaries and pores of the solid electrolyte causing a short-circuit failure. These results validate our methodology for operando analysis of Li-ion batteries with the possibility to obtain SIMS chemical images with sub-20 nm lateral resolution [3, 4].

This work was funded by Horizon Europe project OPINCHARGE and by the Luxembourg National Research Fund (FNR) through the grant INTER/MERA/20/13992061 (INTERBATT).

[1] Y. Yamagishi et al., J. Phys. Chem. Lett. 2021, 12, 19, 4623–4627
[2] O. De Castro et al., Analytical Chemistry, 2022, 94, 30, 10754–10763.
[3] L. Cressa et al., Analytical Chemistry, 2023, 95, 9932–9939
[4] L. Cressa et al., Electrochimica Acta 494 (2024) 144397