Nonaqueous Li-Mediated Nitrogen Reduction: Taking Control of Potentials

[Image: see text] The performance of the Li-mediated ammonia synthesis has progressed dramatically since its recent reintroduction. However, fundamental understanding of this reaction is slower paced, due to the many uncontrolled variables influencing it. To address this, we developed a true nonaqueous LiFePO(4) reference electrode, providing both a redox anchor from which to measure potentials against and estimates of sources of energy efficiency loss. We demonstrate its stable electrochemical potential in operation using different N(2)- and H(2)-saturated electrolytes. Using this reference, we uncover the relation between partial current density and potentials. While the counter electrode potential increases linearly with current, the working electrode remains stable at lithium plating, suggesting it to be the only electrochemical step involved in this process. We also use the LiFePO(4)/Li(+) equilibrium as a tool to probe Li-ion activity changes in situ. We hope to drive the field toward more defined systems to allow a holistic understanding of this reaction.