Transition metals can deliver high lithium storage capacity, but the reason behind this remains elusive. Herein, the origin of this anomalous phenomenon is uncovered by in situ magnetometry taking metallic Co as a model system. It is revealed that the lithium storage in metallic Co undergoes a two-stage mechanism involving a spin-polarized electron injection to the 3d orbital of Co and subsequent electron transfer to the surrounding solid electrolyte interphase (SEI) at lower potentials. These effects create space charge zones for fast lithium storage on the electrode interface and boundaries with capacitive behavior. Therefore, the transition metal anode can enhance common intercalation or pseudocapacitive electrodes at high capacity while showing superior stability to existing conversion-type or alloying anodes. These findings pave the way for not only understanding the unusual lithium storage behavior of transition metals but also for engineering high-performance anodes with overall enhancement in capacity and long-term durability.
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