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Lithium ion transport was accelerated within graphite by controlling its d-spacing as well as its functional groups. By oxidizing bare graphite under a mild condition, expanded graphites (EG* where * = functional groups) were obtained with increasing d-spacing from 0.3359 nm to 0.3395 nm as well as with functional groups formed on the plane or at the edges of graphites. The subsequent thermal reduction of EG* led to an insignificant change of d-spacing (0.3390 nm), simultaneously eliminating a portion of the functional groups (EG). The enlargement of d-spacing reduced kinetic hindrance of lithium ion movement within the expanded graphites (EG* and EG) by reserving more space for the ionic transport route. In addition, the activation energy of lithium ion intercalation in EG* was reduced by surface charge polarization of graphites induced by hydrogen bonds between oxygen atoms of carbonates in electrolytes …