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Mott Transition in the A15 Phase of Cs3C60: Absence of a Pseudogap and Charge Order

We present a detailed NMR study of the insulator-to-metal transition induced by an applied pressure p in the A15 phase of Cs3C60. We evidence that the insulating antiferromagnetic (AFM) and superconducting (SC) phases coexist only in a narrow p range. At fixed p, in the metallic state above the SC transition Tc, the 133Cs and 13C NMR spin-lattice relaxation data are seemingly governed by a pseudogaplike feature. We prove that this feature, also seen in the 133Cs NMR shift data, is rather a signature of the Mott transition which broadens and smears out progressively for increasing (p, T). The analysis of the variation of the quadrupole splitting νQ of the 133Cs NMR spectrum precludes any cell symmetry change at the Mott transition and only monitors a weak variation of the lattice parameter. These results open an opportunity to consider theoretically the Mott transition in a multiorbital three-dimensional system well beyond its critical point.

Reproduced with permission. Copyright 2017, American Physical Society

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Mechanisms of Sodium Insertion/Extraction on the Surface of Defective Graphenes

Two chemically synthesized defective graphene materials with distinctly contrasting extended structures and surface chemistry are used to prepare sodium-ion battery electrodes. The difference in electrode performance between the chemically prepared graphene materials is qualified based on correlations with intrinsic structural and chemical dissimilarities. The overall effects of the materials physical and chemical discrepancies are quantified by measuring the electrode capacities after repeated charge/discharge cycles. Solvothermal synthesized graphene (STSG) electrodes produce capacities of 92 mAh/g in sodium-ion batteries after 50 cycles at 10 mA/g, while thermally exfoliated graphite oxide (TEGO) electrodes produce capacities of 248 mAh/g after 50 cycles at 100 mA/g. Solid-state 23Na nuclear magnetic resonance spectroscopy is employed to locally probe distinct sodium environments on and between the surface of the graphene layers after charge/discharge cycles that are responsible for the variations in electrode capacities. Multiple distinct sodium environments of which at least 3 are mobile during the charge–discharge cycle are found in both cases, but the majority of Na is predominantly located in an immobile site, assigned to the solid electrolyte interface (SEI) layer. Mechanisms of sodium insertion and extraction on and between the defective graphene surfaces are proposed and discussed in relation to electrode performance. This work provides a direct account of the chemical and structural environments on the surface of graphene that govern the feasibility of graphene materials for use as sodium-ion battery electrodes.

Reproduced with permission. Copyright 2016, American Chemical Society