LAUSR

While organic batteries have attracted great attention due to their high theoretical capacities, high‐voltage organic active materials (> 4 V vs Li/Li+) remain unexplored. Here, density functional theory calculations are combined with cyclic voltammetry measurements to investigate the electrochemistry of croconic acid (CA) for use as a lithium‐ion battery cathode material in both dimethyl sulfoxide and γ‐butyrolactone (GBL) electrolytes. DFT calculations demonstrate that CA dilitium salt (CA–Li2) has two enolate groups that undergo redox reactions above 4.0 V and a material‐level theoretical energy density of 1949 Wh kg–1 for storing four lithium ions in GBL—exceeding the value of both conventional inorganic and known organic cathode materials. Cyclic‐voltammetry measurements reveal a highly reversible redox reaction by the enolate group at ≈4 V in both electrolytes. Battery‐performance tests of CA as lithium‐ion battery cathode in GBL show two discharge voltage plateaus at 3.9 and 3.1 V, and a discharge capacity of 102.2 mAh g–1 with no capacity loss after five cycles. With the higher discharge voltages compared to the known, state‐of‐the‐art organic small molecules, CA promises to be a prime cathode‐material candidate for future high‐energy‐density lithium‐ion organic batteries.