We investigate the contribution of pseudocapacitance to the overall capacitance of MnO2 electrodes in pure and alkaline-doped ionic liquids via two spectroscopic methods: step potential electrochemical spectroscopy (SPECS) and in situ Raman spectroscopy. For both characterization methods, thin-film electrodes of birnessite-like amorphous MnO2 were cycled in Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, pure or doped with lithium or sodium. SPECS allows determination of the influence of the electrolyte composition on the electrochemical behavior of the MnO2 electrodes. Pseudocapacitive charge storage can account for over half of the total capacitance with alkaline-doped ionic liquids. In situ Raman spectroscopy provided insight into the reversible ion intercalation in the MnO2 structure, which appears to be controlled by EMIm+ cations. These findings are supported by density functional theory (DFT) calculations, which further help unveil the charge storage mechanism in birnessite-like amorphous MnO2 thin films operated in pure and alkaline-doped ionic liquids.

Dislocations are a central concept in materials science, which dictate the plastic deformation and damage evolution in materials. Layered materials such as graphite admit two general types of interlayer dislocations: basal and prismatic dislocations, of which prismatic dislocations have been relatively less studied. Using density functional theory (DFT) calculations, we have examined different prismatic core structures in graphite and evaluated their structure, energetics and mobility. We find close energetic interplay between bonded and “free-standing” core structures in both zigzag and armchair directions, with a reconstructed stable zigzag core identified. We explore grain boundaries and prismatic dislocation pile-up, identifying metastable structures which may be important in energy storage. The role of interlayer stacking in core structure, dislocation glide and climb is also considered in-depth. Our calculations suggest that the prismatic dislocation core is stable up to high temperatures of approximately 1500K in bulk graphite. Above this temperature, the breaking of bonds in the dislocation core can facilitate climb, grain-boundary motion, and the annealing of damage through prismatic dislocation glide.

We report the intercalation of iodine chains in highly crystalline arc-discharge multiwalled carbon nanotubes (MWCNTs), not in the central cavity but instead between the concentric graphene shells. High-resolution transmission electron microscopy demonstrated that the intercalation was asymmetric with respect to the longitudinal axis of the nanotubes. This filling is explained through the existence of asymmetric intershell channels which formed as the tubes shrank upon cooling after growth. Shrinkage occurred because the geometrically constrained equilibrium intershell spacing was higher at growth than room temperature, due to the highly anisotropic coefficient of thermal expansion of graphite (or graphene stacks). Computational modelling supported the formation of such cavities and explained why they all formed on the same side of the tubes. The graphene shells were forced to bend outward, thereby opening aligned intergraphene nanocavities, and subsequently allowing the intercalation with iodine once the tube ends were opened by oxidative treatment. These observations are specific to catalyst-free processes because catalytic processes use too low temperatures, but they are generally applicable in geometrically closed carbon structures grown at high temperatures and so should be present in all arc-grown MWCNTs. They are likely to explain multiple observations in the literature of asymmetric interlayer spacings in multiple-shell graphenic carbon structures.

Folded regions are commonly encountered in a number of hexagonal boron nitride (h-BN) based bulk and nanostructured materials. Two types of structural modifications occur in folded h-BN layers: local curvature at the folded edges and interlayer shear of the layers which changes the stacking of the overlapping flat regions. In this work we discuss, via density functional theory simulations, the impact of these structural modifications on the ground state electronic structure of the pristine monolayer. We show that, depending on the fold orientation, the overlapping region might present different stacking configurations with subsequent variations of the fundamental band gap; further gap changes occur at the folded regions. The overall electronic structure of a BN folded monolayer can finally be described as a type-II junction between two wide gap semiconductors located at the curved and flat overlapping zones.

Cutting and folding 2D systems is one of the explored paths to tune physical and chemical properties in one-atom-thick matter. Contrary to graphene, boron nitride (BN) nanoribbons are difficult to obtain, and folded BN nanoribbon structures have not been reported yet. Here, we show that pressure application in multiwalled boron nitride nanotubes leads to different types of tube internal organizations including BN nanoribbon formation and folds. The new structures are associated with the breaking of a number of the internal tubes, leading to either nonorganized structures in the form of internal tube alveoli or an organized stacking of folded h-BN nanoribbons. Irreversible changes in the morphology of multiwalled BN nanotubes (MWBNNTs) take place from similar to 7 GPa, and morphologically modified tubes could be observed up to pressures of at least 49 GPa. The experimental probes utilized included high-resolution transmission microscopy, electron tomography, and Raman spectroscopy. Atomistic modeling shows the formation of pinch structures along the tubes that favor pressure-induced bond-breaking and hybridization changes and confirm the folded structure. Both experiments and modeling show that tube polygonization is a prominent characteristic of MWBNNTs even at ambient pressure. Overall, the pressure evolution of MWBNNTs strongly differs from their carbon analogues. The high mechanical stability of BN tube geometry is of interest for composite-based structural materials. On the other side, the availability of h-BN nanoribbons and folded structures opens new prospects to produce physically modified BN properties.

Above a critical diameter, single- or few-walled carbon nanotubes spontaneously collapse as flattened carbon nanotubes. Raman spectra of isolated flattened and cylindrical carbon nanotubes have been recorded. The collapse provokes an intense and narrow D band, despite the absence of any lattice disorder. The curvature change near the edge cavities activates a D band, despite framework continuity. Theoretical calculations based on Placzek approximation fully corroborate this experimental finding. Usually used as a tool to quantify defect density in graphenic structures, the D band cannot be used as such in the presence of a graphene fold. This conclusion should serve as a basis to revisit materials comprising structural distortion where poor carbon organization was concluded on a Raman basis. Our finding also emphasizes the different visions of a defect between chemists and physicists, a possible source of confusion for researchers working in nanotechnologies.

The structure of iodine monochloride (ICl) intercalated into graphite (GIC) has been revisited, and a stage 1 stoichiometry of about 10 carbon atoms to 1 ICl molecule is determined. Intercalation proceeds readily at room temperature without additional energy input. A chainlike structure of alternating halogen species is proposed for the intercalation layer based on detailed Raman spectroscopic analysis and ab initio calculations. Long-range ordering is observed, reaching beyond one layer of carbon. The calculated density of states shows p-doping of the carbon layers upon intercalation, in agreement with Raman spectroscopic analysis. The intercalation is reversible upon heating and can be cycled several times. While iodine chains have been observed in other nanocarbons, ICl is the first example of extended halogen chains intercalated in graphite. Indeed, intercalant phases of acceptor GICs have rarely been studied to date, and the current findings are of potential interest in structural chemistry, materials science, solid-state batteries, and other areas.

We show that polar molecules (water, ammonia, and nitrogen dioxide) adsorbed solely at the exposed edges of an encapsulated graphene sheet exhibit ferroelectricity, collectively orienting and switching reproducibly between two available states in response to an external electric field. This ferroelectric molecular switching introduces drastic modifications to the graphene bulk conductivity and produces a large and ambipolar charge bistability in micrometer-size graphene devices. This system comprises an experimental realization of envisioned memory capacitive ("memcapacitive") devices whose capacitance is a function of their charging history, here conceived via confined and correlated polar molecules at the one-dimensional edge of a two-dimensional crystal.