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.

Room temperature manipulation of long lifetime spins in metallic-like carbon nanospheres.

The time-window for processing electron spin information (spintronics) in solid-state quantum electronic devices is determined by the spin-lattice and spin-spin relaxation times of electrons. Minimizing the effects of spin-orbit coupling and the local magnetic contributions of neighbouring atoms on spin-lattice and spin-spin relaxation times at room temperature remain substantial challenges to practical spintronics. Here we report conduction electron spin-lattice and spin-spin relaxation times of 175 ns at 300 K in 37±7 nm carbon spheres, which is remarkably long for any conducting solid-state material of comparable size. Following the observation of spin polarization by electron spin resonance, we control the quantum state of the electron spin by applying short bursts of an oscillating magnetic field and observe coherent oscillations of the spin state. These results demonstrate the feasibility of operating electron spins in conducting carbon nanospheres as quantum bits at room temperature.

Site-specific synthesis of a hybrid boron-graphene salt.

We report the first example of an ionic graphene salt containing boron. An anionic charge is introduced to the graphene surface by means of 7,8-nido-[C2B9H11](-) carborane clusters covalently and electronically bound to the graphene lattice, and this new material was isolated as its Cs(+) salt.

Strong interplay between the electron spin lifetime in chemically synthesized graphene multilayers and surface-bound oxygen.

The electron spin lifetime in an assembly of chemically synthesized graphene sheets was found to be extremely sensitive to oxygen. Introducing small concentrations of physisorbed O2 onto the graphene surface reduced the exceptionally long 140 ns electron spin lifetime by an order of magnitude. This effect was completely reversible: Removing the O2 by using a dynamic vacuum restored the spin lifetime. The presence of covalently bound oxygen also decreased the electron spin lifetime in graphene, although to a far lesser extent compared to physisorbed O2 . The conduction electrons in graphene were found to play a significant role by counter-balancing the spin depolarization caused by oxygen molecules. Our results highlight the importance of chemical environment control and device packing in practical graphene-based spintronic applications.

Carborane functionalization of the aromatic network in chemically-synthesized graphene.

The conjugated aromatic system of graphene was used to trap the reactive, boron-rich 1,2-carborane cluster. Functionalization of the graphene surface was confirmed by solid-state MAS (11)B NMR spectroscopy and quantified by X-ray photoelectron spectroscopy. This work represents the first confirmed example of direct functionalization of a graphene lattice with carboranes.

Muons probe strong hydrogen interactions with defective graphene.

Here, we present the first muon spectroscopy investigation of graphene, focused on chemically produced, gram-scale samples, appropriate to the large muon penetration depth. We have observed an evident muon spin precession, usually the fingerprint of magnetic order, but here demonstrated to originate from muon-hydrogen nuclear dipolar interactions. This is attributed to the formation of CHMu (analogous to CH(2)) groups, stable up to 1250 K where the signal still persists. The relatively large signal amplitude demonstrates an extraordinary hydrogen capture cross section of CH units. These results also rule out the formation of ferromagnetic or antiferromagnetic order in chemically synthesized graphene samples.

Gram-scale production of graphene based on solvothermal synthesis and sonication.

Carbon nanostructures have emerged as likely candidates for a wide range of applications, driving research into novel synthetic techniques to produce nanotubes, graphene and other carbon-based materials. Single sheets of pristine graphene have been isolated from bulk graphite in small amounts by micromechanical cleavage, and larger amounts of chemically modified graphene sheets have been produced by a number of approaches. Both of these techniques make use of highly oriented pyrolitic graphite as a starting material and involve labour-intensive preparations. Here, we report the direct chemical synthesis of carbon nanosheets in gram-scale quantities in a bottom-up approach based on the common laboratory reagents ethanol and sodium, which are reacted to give an intermediate solid that is then pyrolized, yielding a fused array of graphene sheets that are dispersed by mild sonication. The ability to produce bulk graphene samples from non-graphitic precursors with a scalable, low-cost approach should take us a step closer to real-world applications of graphene.