Quantum capacitance (QC) is a very important character of the graphene cathode in lithium ion capacitors (LIC), which is a novel kind of electrochemical energy conversion and storage device. However, the QC electronic origin of the graphene cathode, which will affect the electrochemical reaction at the electrode/electrolyte interface, is still unclear. In this article, the QC of various kinds of graphene cathode is investigated systematically by DFT calculation. It was found that the value and origin of QC strongly depend on the defects and alien atoms of graphene. Graphene with pentagon defects possesses a higher QC than pristine graphene due to the contribution from the electronic states localized at the carbon pentagon. The introduction of graphitic B can contribute to QC, while graphitic N and P does not work in the voltage range of the LIC cathode. Single vacant defect graphene and pyrrolic N-doped graphene demonstrate very high QC due to the presence of states associated with the σ orbital of unbonded carbon atoms. However, pyridinic graphene shows an even higher QC because of the states from the N atom. For the residual O in graphene, its QC mainly originated from the pz
states of carbon atoms and the effect of O, especially the O in bridged oxygen functional group (–COC–), is very limited. These results provide new insight into further study of the catalytic behavior and the design of a high performance graphene cathode for LIC.
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