Anion-exchange membrane (AEM) water electrolysis could allow inexpensive and greener hydrogen production than other alternatives, such as steam methane reforming. To increase performance, hydroxide salts are often added to the water feed, with the tradeoff of corrosivity and complexity. Recently, carbonate salts that are less corrosive have shown promise, but their specific functionality remains unknown. In this paper, we use a mathematical model to compare an AEM electrolyzer with added potassium carbonate to an AEM electrolyzer with added potassium hydroxide. We show that the conductivity of the carbonate-form membrane has little impact on the performance of the device, but that carbonate ions replace hydroxide in the ionomer, which creates a Nernstian voltage difference across the membrane. The replacement of hydroxide anions with carbonate also reduces utilization of the catalyst in the anode, resulting in an additional voltage loss.