In Situ Chemical Modulation of Graphitization Degree of Carbon Fibers and Its Potassium Storage Mechanism

Abstract Graphite is considered to be the most auspicious anode candidate for potassium ion batteries. However, the inferior rate performances and cycling stability restrict its practical applications. Few studies have investigated the modulating the graphitization degree of graphitic materials. Herein, a nitrogen‐doped carbon‐coated carbon fiber composite with tunable graphitization (CNF@NC) through etching growth, in‐situ oxidative polymerization, and subsequent carbonization process is reported. The prepared CNF@NC with abundant electrochemical active sites and a rapid K ⁺ /electron transfer pathway, can effectively shorten the K ⁺ transfer distance and promote the rapid insertion/removal of K ⁺ . Amorphous domains and short‐range curved graphite layers can provide ample mitigation spaces for K ⁺ storage, alleviating the volume expansion of the highly graphitized CNF during repeated K ⁺ insertion/de‐intercalation. As expected, the CNF@NC‐5 electrode presents a high initial coulombic efficiency (ICE) of 69.3%, an unprecedented reversible volumetric capacity of 510.2 mA h cm ⁻³ at 0.1 A g ⁻¹ after 100 cycles with the mass‐capacity of 294.9 mA h g ⁻¹ . The K ⁺ storage mechanism and reaction kinetic analysis are studied by combining in‐situ analysis and first‐principles calculation. It manifests that the K ⁺ storage mechanism in CNF@NC‐5 is an adsorption‐insertion‐insertion mechanism (i.e., the “1+2” model). The solid electrolyte interphase (SEI) film forming is also detected.