Sulfur-Rich Graphene Nanoboxes with Ultra-High Potassiation Capacity at Fast Charge: Storage Mechanisms and Device Performance

Abstract

It is a major challenge to achieve fast charging and high reversible capacity in potassium ion storing carbons. Here, we synthesized sulfur-rich graphene nanoboxes (SGNs) by one-step chemical vapor deposition to deliver exceptional rate and cyclability performance as potassium ion battery and potassium ion capacitor (PIC) anodes. The SGN electrode exhibits a record reversible capacity of 516 mAh g^-1 at 0.05 A g^-1, record fast charge capacity of 223 mA h g^-1 at 1 A g^-1, and exceptional stability with 89% capacity retention after 1000 cycles. Additionally, the SGN-based PIC displays highly favorable Ragone chart characteristics: 112 Wh kg^-1at 505 W kg^-1 and 28 Wh kg^-1 at 14618 W kg^-1 with 92% capacity retention after 6000 cycles. X-ray photoelectron spectroscopy analysis illustrates a charge storage sequence based primarily on reversible ion binding at the structural-chemical defects in the carbon and the reversible formation of K-S-C and K₂S compounds. Transmission electron microscopy analysis demonstrates reversible dilation of graphene due to ion intercalation, which is a secondary source of capacity at low voltage. This intercalation mechanism is shown to be stable even at cycle 1000. Galvanostatic intermittent titration technique analysis yields diffusion coefficients from 10^-10 to 10^-12 cm² s^-1, an order of magnitude higher than S-free carbons. The direct electroanalytic/analytic comparison indicates that chemically bound sulfur increases the number of reversible ion bonding sites, promotes reaction-controlled over diffusion-controlled kinetics, and stabilizes the solid electrolyte interphase. It is also demonstrated that the initial Coulombic efficiency can be significantly improved by switching from a standard carbonate-based electrolyte to an ether-based one.