Three-Dimensional Mapping of Cycling Changes in Silicon-Graphite Composite Anodes Via Scanning Probe Microscopy

Silicon (Si) anodes have the potential to greatly improve the energy density of lithium-ion batteries due to the greater specific capacity of Si relative to standard graphite (Gr) anodes (1). However, Si anode implementation is limited by issues such as volumetric expansion during cycling and an unstable solid-electrolyte interphase (SEI). Composite anodes with Si and Gr particles can increase capacity while mitigating Si anode degradation. However, these electrodes can be challenging to characterize (and therefore optimize) due to their multiple components, heterogeneous surfaces, and the complex processes occurring there. Scanning spreading resistance microscopy (SSRM) is a form of scanning probe microscopy that measures local resistivity in a sample. By removing material with the probe tip while measuring resistivity, three-dimensional resistivity maps can be determined (2). For Si-Gr composite anodes, the different resistivities of the electrode components (e.g., Si, Gr, carbon, and lithium polyacrylate binder) allows direct identification through SSRM. 3D nanoscale volumes can then be created for both the whole electrode and the individual components. This presentation will demonstrate 3D SSRM mapping of pristine and cycled anodes with three compositions – Si, Gr, and Si-Gr. By comparing changes in the morphology, thickness, and resistivity in the active material and SEI in each single-component electrode, the component distribution and evolution of the Si-Gr composite anode is better understood. SSRM results will be compared to chemical analysis techniques such as scanning transmission electron microscopy, energy dispersive x-ray spectroscopy, and electron energy loss spectroscopy to verify the component identification and to correlate chemical composition to resistivity. These data will then be correlated to electrochemical performance and used to further the development of Si-Gr electrodes with enhanced performance. W.-J. Zhang, Journal of Power Sources, 196, 13 (2011). C. Stetson, Z. Huey, A. Downard, Z. Li, B. To, A. Zakutayev, C. S. Jiang, M. M. Al-Jassim, D. P. Finegan, S. D. Han and S. C. DeCaluwe, Nano Lett (2020). Figure 1