A universal graphitic interlayered centroid intercalation theory for intercalation chemistry

Abstract Neither of the two widely used staging models in the long history of intercalation chemistry, namely the classical Rüdorff-Hofmann model proposed in 1938 and the pleated-layer domain-modified one in 1969, can explain the intercalation reaction phenomena and mechanism logically. Taking the landmark potassium-intercalation reaction of graphite as a model case and two advanced monolithic graphitic/graphenic carbon foams as model electrodes, here we have revealed that the electrochemical storage of potassium in graphitic/graphenic carbon (as that of lithium) obeys a simple interlayered centroid intercalation (ICIC) rule to achieve the staged potassium intercalation into each graphitic interlayer: C → KC72 → KC24 → KC8. Moreover, judging from the typical potassium-storage behaviors and crystal texture of graphitic electrodes, nitrogen doping and pre-embedded K atoms would enable incoming K+ ions to perform fast pseudocapacitive diffusion in graphitic gallery. This study not only makes clear the basic K-storage mechanism and phenomena in graphitic carbon, but also establishes a more reasonable ICIC model for intercalation chemistry, and thus may help open a new research era for this field as well as graphite-based metal-ion batteries.