Potential‑Resolved In Situ Atomic Force Microscopy of Surface Film Formation on Graphite in Ethylene Carbonate with Lithium Perchlorate

Abstract:

Ethylene carbonate (EC) is essential for forming a passivating film on graphite, whereas practical electrolytes dilute EC with linear carbonates that modify that film. Here, we isolate an EC-only medium and track film formation by in situ electrochemical atomic force microscopy during slow-scan cyclic voltammetry on the basal plane of highly oriented pyrolytic graphite in EC with lithium perchlorate. A two-stage pathway is resolved: during the cathodic sweep a subsurface pre-insertion regime develops and transitions near 0.8 V vs Li/Li⁺; the subsequent anodic sweep produces a particulate precipitate layer. After the first cycle, the effective precipitate-layer thickness is approximately 20 nm; a second cycle increases it to approximately 30 nm with marked lateral heterogeneity and edge-proximal coarsening. These observations delineate the potential-dependent switch and provide quantitative benchmarks for the early growth of the EC-derived film. Minimizing the dwell time near the transition may suppress overgrowth and improve interfacial stability, thereby establishing an EC-only baseline for interpreting mixed-carbonate electrolytes.

• Periodical: Defect and Diffusion Forum (Volume 449)
• Pages: 135-141
• DOI: https://doi.org/10.4028/p-Qy7mVD
• Online since: March 2026
• Authors: Soon Ki Jeong*
• Keywords: Highly Oriented Pyrolytic Graphite, In Situ Atomic Force Microscopy, Lithium Secondary Batteries, Solvent Cointercalation, Surface Film Formation

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