Producing Bilayer Graphene Oxide via Wedge Ion-Assisted Anodic Exfoliation: Implications for Energy and Electronics

Electrochemical synthesis has emerged as a promising approach for the large-scale production of graphene-based two-dimensional (2D) materials. Electrochemical intercalation of ions and molecules between graphite layers plays a key role in the synthesis of graphene with controllable thickness. However, there is still a limited understanding regarding the impact of intercalant molecules. Herein, we investigated a series of anionic species (i.e., ClO₄^-, PF₆^-, BF₄^-, HSO₄^-, CH₃SO₃^-, and TsO^-) and examined their wedging process between the weakly bonded layered materials driven by electrochemistry. By combining cyclic voltammetry, X-ray diffraction (XRD), and Raman spectroscopy, along with density functional theory (DFT) calculations, we found that stage-2 graphite intercalation compounds (GICs) can be obtained through intercalation of ClO₄^-, PF₆^-, or BF₄^- anions into the adjacent graphene bilayers. The anodic exfoliation step based on ClO₄^--GIC in (NH₄)₂SO₄ (aq.) resulted in the formation of bilayer-rich (>57%) electrochemically exfoliated graphene oxide (EGO), with a high yield (∼85 wt %). Further, the physicochemical properties of these EGO can be readily customized through electrochemical reduction and modification with different surfactants. This versatility allows for precise tailoring of EGO, making it feasible for energy and electronic applications such as electrodes in electrochemical capacitors and functional composites in wearable electronics.