No abstract

Banana peel pseudographite (BPPG) offers superb dual functionality for sodium ion battery (NIB) and lithium ion battery (LIB) anodes. The materials possess low surface areas (19-217 m(2) g(-1)) and a relatively high electrode packing density (0.75 g cm(-3) vs ∼1 g cm(-3) for graphite). Tested against Na, BPPG delivers a gravimetric (and volumetric) capacity of 355 mAh g(-1) (by active material ∼700 mAh cm(-3), by electrode volume ∼270 mAh cm(-3)) after 10 cycles at 50 mA g(-1). A nearly flat ∼200 mAh g(-1) plateau that is below 0.1 V and a minimal charge/discharge voltage hysteresis make BPPG a direct electrochemical analogue to graphite but with Na. A charge capacity of 221 mAh g(-1) at 500 mA g(-1) is degraded by 7% after 600 cycles, while a capacity of 336 mAh g(-1) at 100 mAg(-1) is degraded by 11% after 300 cycles, in both cases with ∼100% cycling Coulombic efficiency. For LIB applications BPPG offers a gravimetric (volumetric) capacity of 1090 mAh g(-1) (by material ∼2200 mAh cm(-3), by electrode ∼900 mAh cm(-3)) at 50 mA g(-1). The reason that BPPG works so well for both NIBs and LIBs is that it uniquely contains three essential features: (a) dilated intergraphene spacing for Na intercalation at low voltages; (b) highly accessible near-surface nanopores for Li metal filling at low voltages; and (c) substantial defect content in the graphene planes for Li adsorption at higher voltages. The <0.1 V charge storage mechanism is fundamentally different for Na versus for Li. A combination of XRD and XPS demonstrates highly reversible Na intercalation rather than metal underpotential deposition. By contrast, the same analysis proves the presence of metallic Li in the pores, with intercalation being much less pronounced.

We demonstrate that peat moss, a wild plant that covers 3% of the earth's surface, serves as an ideal precursor to create sodium ion battery (NIB) anodes with some of the most attractive electrochemical properties ever reported for carbonaceous materials. By inheriting the unique cellular structure of peat moss leaves, the resultant materials are composed of three-dimensional macroporous interconnected networks of carbon nanosheets (as thin as 60 nm). The peat moss tissue is highly cross-linked, being rich in lignin and hemicellulose, suppressing the nucleation of equilibrium graphite even at 1100 °C. Rather, the carbons form highly ordered pseudographitic arrays with substantially larger intergraphene spacing (0.388 nm) than graphite (c/2 = 0.3354 nm). XRD analysis demonstrates that this allows for significant Na intercalation to occur even below 0.2 V vs Na/Na(+). By also incorporating a mild (300 °C) air activation step, we introduce hierarchical micro- and mesoporosity that tremendously improves the high rate performance through facile electrolyte access and further reduced Na ion diffusion distances. The optimized structures (carbonization at 1100 °C + activation) result in a stable cycling capacity of 298 mAh g(-1) (after 10 cycles, 50 mA g(-1)), with ∼150 mAh g(-1) of charge accumulating between 0.1 and 0.001 V with negligible voltage hysteresis in that region, nearly 100% cycling Coulombic efficiency, and superb cycling retention and high rate capacity (255 mAh g(-1) at the 210th cycle, stable capacity of 203 mAh g(-1) at 500 mA g(-1)).