Fossil fuel power plants are responsible for a significant portion of anthropogenic atmospheric carbon dioxide (CO2) and due to concerns over global climate change, finding solutions that significantly reduce emissions at their source has become a vital concern. When oxygen (O2) is reduced along with CO2 at the cathode of an anion exchange membrane (AEM) electrochemical cell, carbonate and bicarbonate are formed which are transported through electrolyte by migration from the cathode to the anode where they are oxidized back to CO2 and O2. This behavior makes AEM-based devices scientifically interesting CO2 separation devices or “electrochemical CO2 pumps.” Electrochemical CO2 separation is a promising alternative to state-of-the-art solvent-based methods because they operate at low temperatures and scale with surface area, not volume, suggesting that industrial electrochemical systems could be more compact than amine sorption technologies. In this work, we investigate the impact of the CO2 separator cell potential on the CO2 flux, carbonate transport mechanism and process costs. The applied electrical current and CO2 flux showed a strong correlation that was both stable and reversible. The dominant anion transport pathway, carbonate vs. bicarbonate, undergoes a shift from carbonate to mixed carbonate/bicarbonate with increased potential. A preliminary techno-economic analysis shows that despite the limitations of present cells, there is a clear pathway to meet the US DOE 2025 and 2035 targets for power plant retrofit CO2 capture systems through materials and systems-level advances.