Quasi in situ XPS study of electrochemical oxidation and reduction of highly oriented pyrolytic graphite in [1-ethyl-3-methylimidazolium][BF4] electrolytes

Highly oriented pyrolytic graphite (HOPG) electrodes were electrochemically oxidised and reduced in 1-ethyl-3-methylimidazolium tetrafluoroborate [EMIM][BF4] electrolytes and studied by X-ray photoelectron spectroscopy (XPS). Sample preparation and transfer have been performed under inert nitrogen atmosphere in a preparation chamber directly attached to an ultra high vacuum system. After electrochemical treatment, both, the electrolyte and the electrode surface were investigated. While on the oxidised HOPG surface the core levels of the detected elements shift towards lower energies, on the reduced samples a shift towards higher binding energies is observed. These shifts refer to a Fermi level shift proving that graphite intercalation compounds were formed. Intercalation occurs together with co-intercalation of the ionic liquid. XPS analysis of the ionic liquids before and after electrochemical treatment reveals changes in electrolyte composition. The influence of impurities on electrochemical behaviour and XPS data is discussed.

► Quasi in situ XPS study of oxidation and reduction of HOPG in [EMIM][BF4] electrolytes.
► HOPG: Core level shifts prove that graphite intercalation compounds were formed.
► [EMIM][BF4]: Core level shifts are attributed to electrochemically induced shifts.
► Changes of the C 1s line shapes of [EMIM][BF4] suggest a stability window of <3.7 V.