Influence of Dimethyl Carbonate on Graphite Surface Film Formation Revealed by Potential-Resolved in situ Atomic Force Microscopy

Abstract:

Ethylene carbonate (EC) is essential for establishing a passivating surface film on graphite; in practice, however, EC is commonly blended with dimethyl carbonate (DMC), which alters Li⁺ solvation and interfacial chemistry. Here, we compare 1 mol dm⁻³ (M) LiClO₄/EC+DMC with 1 M LiClO₄/DMC using in situ electrochemical atomic force microscopy (AFM) during cyclic voltammetry on the basal plane of highly oriented pyrolytic graphite (HOPG). Both media follow a two-stage pathway—solvent cointercalation (subsurface pre-insertion) followed by surface precipitate formation—yet their electrochemical responses and morphologies diverge. In EC+DMC, pronounced second-cycle suppression of the cathodic current accompanies the development of a laterally continuous, fine particulate precipitate layer after the first cycle. In the DMC‑only electrolyte, large cathodic currents persist and AFM reveals edge-dominated blistering, step disruption, and patchy deposits, indicative of sustained cointercalation and incomplete passivation. Taken together, these results indicate that the principal passivating film is EC-derived, whereas DMC chiefly modulates cointercalation and coalescence kinetics, thereby amplifying lateral heterogeneity. The measurements provide potential-resolved benchmarks for formation-protocol design and a reference for interpreting mixed-carbonate electrolytes.

• Periodical: Advances in Science and Technology (Volume 175)
• Pages: 47-52
• DOI: https://doi.org/10.4028/p-F2m75o
• Online since: May 2026
• Authors: Soon Ki Jeong*
• Keywords: Dimethyl Carbonate, HOPG, In Situ Electrochemical AFM, Precipitate Layer, Solvent Cointercalation, Surface Film Formation

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