When the lithium-salt concentration increases, the electrode potential often shifts upward, and one usually starts from the coordination structure around Li⁺. This JACS work finds that in ionic liquids, the first coordination shell changes very little, yet the potential still rises substantially, showing that looking only at the anions immediately next to Li⁺ may miss the key contribution. Atsuo Yamada’s group at the University of Tokyo extends liquid Madelung theory to ionic liquids and, using all-atom molecular dynamics (MD) to calculate the electrostatic interactions between Li⁺ and surrounding species, shows that enhanced repulsion from an increased number of Li⁺ ions in the second coordination shell is an important reason for the potential upshift in such systems.