How to Measure Solid State Lithium-ion Diffusion using the Atlung Method for Intercalant Diffusion

A systematic investigation of the factors that affect lithium diffusion coefficient measurements in the Atlung Method for Intercalant Diffusion (AMID) is carried out. Single crystal LiNi0.6Mn0.2Co0.2O2 is used for method development. The factors include electrode mass loading, separator thickness, electrolyte solvent choice and salt molarity, voltage interval sizes, open circuit relaxation time, C-rate choice, and charge vs discharge direction. In an ideal diffusivity measurement method, none of these factors listed should impact the true material diffusivity since it should be a purely material property. However, as we demonstrate here, all these experimental parameters should be selected carefully to minimize cell and electrode resistance contributions so that one can measure true lithium diffusivity in a material that is independent of current direction. We propose a low electrode loading cell design that is applicable for all diffusion measurement methods consisting of an ultrathin electrode coating (0.2 mAh cm(-2)), thin separator and 1.5 M LiPF6 ethylene carbonate: dimethyl carbonate 1:1 electrolyte. Additionally, we show diffusivity is not dependent on charge or discharge direction in NMC622, and we compare AMID results to Galvanostatic Intermittent Titration. Specific to AMID 15 min OCV time with 0.1 V intervals are suitable for this measurement.

Automated summary

A systematic investigation was conducted on the factors affecting lithium diffusion coefficient measurements in the Atlung Method for Intercalant Diffusion (AMID). It was found that electrode mass loading, separator thickness, electrolyte solvent choice and salt molarity, voltage interval sizes, open circuit relaxation time, C-rate choice, and charge vs discharge direction all have an impact on the measured material diffusivity. A low electrode loading cell design was proposed to minimize resistance contributions and achieve true lithium diffusivity measurements. AMID results were compared to Galvanostatic Intermittent Titration.