The effect of functionalization of the carbon additive (acetylene black) of a composite LiMn 1.5 Ni 0.5 O 4 cathode, with benzo-15-crown-5 ether, on the electrode/ electrolyte interfaces and electrochemical behavior of a LiMn 1.5 Ni 0.5 O 4 /Li half-cell and LiMn 1.5 Ni 0.5 O 4 /graphite cell is investigated. Functionalization was achieved by spontaneous reduction of 4âČ-aminobenzo-15-crown-5 ether by acetylene black (AB). The resulting materials were characterized by infrared spectroscopy and thermogravimetric analysis. Complexation of manganese by benzo-15-crown-5 was investigated using ultravioletâvisible spectroscopy. The electrochemical behavior of cells was studied by galvanostatic cycling and electrochemical impedance spectroscopy. The LiMn 1.5 Ni 0.5 O 4 /Li half-cells with modified acetylene black showed improved capacity retention and Coulombic efficiency compared to LiMn 1.5 Ni 0.5 O 4 /Li half-cells with unmodified acetylene black. A similar behavior was observed for LiMn 1.5 Ni 0.5 O 4 âAB/graphite cells with modified AB. Postmortem energy dispersive X-ray spectroscopy analysis of the graphite anode following constant current cycling showed smaller amounts of fluorine, oxygen, phosphorus (resulting from decomposition products of electrolyte), manganese, and nickel for the full-cell made with crown ether modified AB. The increased cycling performance of the LiMn 1.5 Ni 0.5 O 4 âAB/graphite cell with modified AB can be associated with the presence of grafted groups on the carbon additive of the composite cathode surface, which can trap a fraction of metallic ions dissolving from cathode, thus decreasing the amount of transition metal deposited on the graphite anode. Furthermore, benzo-15-crown-5 crown ether groups on the carbon additive can mitigate parasitic reactions such as electrolyte decomposition and carbon degradation.