In order to avoid any presence of air or oxygen, the electrochemical experiment should be done under an inert atmosphere (N2 or Ar). Presence of trace amount of oxygen in all solutions and moisture in nonaqueous solutions may lead to new oxidation and/or reduction peaks in CV.
You can do e-chem in a glovebox/glovebag if you can plumb the wires in or use a wirelessly controlled potentiostat.
Most electrochemistry is done on air-stable precursors to the air-sensitive species. The air-sensitive species are formed in situ upon reduction/oxidation in the cell. You purge with N2 or Ar first and keep a blanket of that gas over the solution and it works fine.