Additives for energy storage devices comprising cyclodextrin-based compounds and their derivatives are disclosed. The energy storage device comprises a first electrode and a second electrode, where at least one of the first electrode and the second electrode is a Si-based electrode, a separator between the first electrode and the second electrode, and an electrolyte composition. Cyclodextrin-based compounds may serve as additives to the first electrode, the second electrode, and/or the electrolyte.