Understanding Excess Li Storage beyond LiC₆ in Reduced Dimensional Scale Graphene

A phenomenon is observed in which the electrochemical performances of porous graphene electrodes show unexpectedly increasing capacities in the Li storage devices. However, despite many studies, the cause is still unclear. Here, we systematically present the reason for the capacity enhancements of the pristine graphene anode under functional group exclusion through morphological control and crystal structure transformation. The electrochemical synergy of both the edge effect and surface effect of the reduced dimensional scale graphene in an open-porous structure facilitates significantly enhanced capacity through multidimensional Li-ion accessibility and accumulation of Li atoms. Furthermore, the Stone–Wales defects boosted during Li insertion and extraction promote a capacity elevation beyond the theoretical capacity of the carbon electrode even after long-term cycles at high C-rates. As a result, the morphologically controlled graphene anode delivers the highest reversible capacity of 3074 mA h g^–1 with a 163% capacity increase after 2000 cycles at 5 C. It also presents a gradually increasing capacity up to 1102 mA h g^–1 even at 50 C without an evident capacity fading tendency. This study provides valuable information into the practical design of ultralight and high-rate energy storage devices.