MCNTs@MnO₂ Nanocomposite Cathode Integrated with Soluble O₂‑Carrier Co-salen in Electrolyte for High-Performance Li–Air Batteries

Li–air batteries (LABs) are promising because of their high energy density. However, LABs are troubled by large electrochemical polarization during discharge and charge, side reactions from both carbon cathode surface/peroxide product and electrolyte/superoxide intermediate, as well as the requirement for pure O₂. Here we report the solution using multiwall carbon nanotubes (MCNTs)@MnO₂ nanocomposite cathode integrated with N,N′-bis­(salicylidene)­ethylenediaminocobalt­(II) (Co^II-salen) in electrolyte for LABs. The advantage of such a combination is that on one hand, the coating layer of δ-MnO₂ with about 2–3 nm on MCNTs@MnO₂ nanocomposite catalyzes Li₂O₂ decomposition during charge and suppresses side reactions between product Li₂O₂ and MCNT surface. On the other hand, Co^II-salen works as a mobile O₂-carrier and accelerates Li₂O₂ formation through the reaciton of (Co^III-salen)₂-O₂^2– + 2Li⁺ + 2e^– → 2Co^II-salen + Li₂O₂. This reaction route overcomes the pure O₂ limitation and avoids the formation of aggressive superoxide intermediate (O₂^– or LiO₂), which easily attacks organic electrolyte. By using this double-catalyst system of Co-salen/MCNTs@MnO₂, the lifetime of LABs is prolonged to 300 cycles at 500 mA g^–1 (0.15 mA cm^–2) with fixed capacity of 1000 mAh g^–1 (0.30 mAh cm^–2) in dry air (21% O₂). Furthermore, we up-scale the capacity to 500 mAh (5.2 mAh cm^–2) in pouch-type batteries (∼4 g, 325 Wh kg^–1). This study should pave a new way for the design and construction of practical LABs.