Intermolecular π-π stacking of oligomeric naphthalene cathodes facilitate high performance aluminum ion battery.

• A brand-new two-step reaction mechanism of ONA electrode is proposed in AIB. • The π-π stacking structures of π-COCs can contribute capacity directly. • The ONA show the co-existence of high capacity and excellent cycle stability in AIB. Π-conjugated organic compounds (π-COCs), as a potential electrode material, mainly emphasized the effects of functional groups and intramolecular π-conjugated system on charge storage in the past studies. In this work, we discovered a brand-new two step energy storage mechanism for π-COCs using oligomeric naphthalene (ONA) with intermolecular π-π stacking structure as electrode material in Al ion battery system. The electrochemical reaction of ONA is identified as the synergistic work of the chemical-adsorption of AlCl 4 - anions at low potential and the π···[AlCl 4 ]···π interaction at high potential. Based on this, the Al-ONA battery exhibits an excellent electrochemical performance (high specific capacity of 450 mAh/g at 0.1 A/g, long cycle life without attenuation for 4000 cycles at 1 A/g). This discovery of the energy storage mechanism, especially for the π···anion···π interaction, for π-COCs materials opens the door to exploring high performance organic electrode materials in energy storage field. [ABSTRACT FROM AUTHOR]