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The Co‐free Ni‐rich layered cathode materials with excellent structural stability and low‐cost in Ni‐rich family are emerging as the promising candidates for the next generation of high‐energy density cathodes. Previously, Mn is generally regarded as the structural stabilizer in Co‐free Ni‐rich cathodes, while the role of inevitable Li/Ni intermixing is underestimated. Herein, the study reveals that the real origin of the lattice oxygen/structure stability of Co‐free Ni‐rich cathodes is dominated more by Li/Ni intermixing than the widely accepted Mn. In the Li/Ni intermixing configuration, the intermixed Ni ions can suppress the oxidation of lattice oxygen by increasing the formation energy of oxygen vacancy and reducing charge compensation. Besides, the Li vacancy formed via the delithiation of intermixed Li in transition metal layer can serve as O2 capture sites. This dual stabilization mechanism is proposed and proved to be effectively in enhancing the reversibility of lattice oxygen and the stability of material structural. This work sheds light on the mechanism of stabilizing lattice oxygen through Li/Ni intermixing, which provides new insights for designing better batteries. [ABSTRACT FROM AUTHOR]

As an emerging post‐lithium battery technology, aluminum ion batteries (AIBs) have the advantages of large Al reserves and high safety, and have great potential to be applied to power grid energy storage. But current graphite cathode materials are limited in charge storage capacity due to the formation of stage‐4 graphite‐intercalated compounds (GICs) in the fully charged state. Herein, we propose a new type of cathode materials for AIBs, namely polycyclic aromatic hydrocarbons (PAHs), which resemble graphite in terms of the large conjugated π bond, but do not form GICs in the charge process. Quantum chemistry calculations show that PAHs can bind AlCl4− through the interaction between the conjugated π bond in the PAHs and AlCl4−, forming on‐plane interactions. The theoretical specific capacity of PAHs is negatively correlated with the number of benzene rings in the PAHs. Then, under the guidance of theoretical calculations, anthracene, a three‐ring PAH, was evaluated as a cathode material for AIBs. Electrochemical measurements show that anthracene has a high specific capacity of 157 mAh g−1 (at 100 mA g−1) and still maintains a specific capacity of 130 mAh g−1 after 800 cycles. This work provides a feasible "theory guides practice" research model for the development of energy storage materials, and also provides a new class of promising cathode materials for AIBs. [ABSTRACT FROM AUTHOR]

• 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]