van der Waals gap modulation of graphene oxide through mono-Boc ethylenediamine anchoring for superior Li-ion batteries.

Li-ion batteries stand out among energy storage systems due to their higher energy and power density, cycle life, and high-rate performance. Development of advanced, high-capacity anodes is essential for enhancing their performance, safety, and durability, and recently, two-dimensional materials have garnered extensive attention in this regard due to distinct properties, particularly their ability to modulate van der Waals gap through intercalation. Covalently intercalated Graphene oxide interlayer galleries with mono-Boc-ethylenediamine (GO-EnBoc) was synthesized via the ring opening of epoxide, forming an amino alcohol moiety. This creates three coordination sites for Li ion exchange on the graphene oxide nanosheets' surface. Consequently, the interlayer d-spacing expands from 8.47 Å to 13.17 Å, as anticipated. When explored as an anode, Li-GO-EnBoc shows a significant enhancement in the stable and reversible capacity of 270 mA h g-1 at a current density of 25 mA g-1 compared to GO (80 mA h g-1), without compromising the mechanical or chemical stability. Through 13C, 7Li and 6Li MAS NMR, XPS, IR, Raman microscopy, and density functional theory (DFT) calculations, we confirm the positioning of Li+ ions at multiple sites of the interlayer gallery, which enhances the electrochemical performance. Our findings suggest that these novel systematically modulated van der Waals gap GO-engineered materials hold promise as efficient anodes for Li-ion batteries.

Effect of hetero-atom doping on the electrocatalytic properties of graphene quantum dots for oxygen reduction reaction.

Oxygen reduction is an important reaction involved in a diverse variety of energy storage devices and also in many chemical and biological processes. However, the high cost of suitable catalysts like platinum, rhodium, and iridium proves to be a major obstacle for its commercialization. Consequently, many new materials have emerged in recent years such as various forms of carbon, carbides, nitrides, core-shell particles, Mxenes, and transition metal complexes as alternatives to platinum and other noble metals for oxygen reduction reaction (ORR). Among these, Graphene Quantum Dots (GQDs) as metal-free alternatives have captured universal attention, since electrocatalytic properties can be tuned not only by size and functionalization but by heteroatom doping also. We discuss electrocatalytic properties of GQDs (approximate size 3-5 nm) with specific dopants such as N and S focusing on their synergistic effects of co-doping, prepared by solvothermal routes. Cyclic Voltammetry shows benefits of doping as lowering of the onset potentials while steady-state Galvanostatic Tafel polarization measurements show a clear difference in the apparent Tafel slope, along with enhanced exchange current densities, suggesting higher rate constants.