Electrolytes and electrolyte additives for energy storage devices are disclosed. The energy storage device comprises a first electrode and a second electrode, where one or both of the first electrode and the second electrode is a Si-based electrode, a separator between the first electrode and the second electrode, an electrolyte, and at least one electrolyte additive compound selected from a carbonate, oxalate, trioxidane, peroxide, peroxoate, dioxetanone, oxepane dione, oxetane dione, anhydride, oxalate or 1,4-dioxane-2,3-dione; each of which may be optionally substituted.