Generally, we applied less than -1.0V potential in 0.5M KHCO3 solution in our experiment. Is it safe to apply a high voltage like -3V vs Ag/AgCl? What is the highest applied voltage limit Vs Ag/AgCl?
It is safe to apply any voltage on the working electrode, because through the reference electrode current does not flow, and their potential is independent on the applied voltage between the counter and the working electrode.
It is safe, but not recommended. You are close to the lower limit of the potential window in aqueous solution. Below this limit the current increases a lot because the release of H2 begins. Normally, the potentiostat will stop the measurement when the set maximum current limit or the one in the instrument specification is reached.