Electronic Structure of Nitrogen- and Phosphorus-Doped Graphenes Grown by Chemical Vapor Deposition Method

Heteroatom doping is a widely used method for the modification of the electronic and chemical properties of graphene. A low-pressure chemical vapor deposition technique (CVD) is used here to grow pure, nitrogen-doped and phosphorous-doped few-layer graphene films from methane, acetonitrile and methane-phosphine mixture, respectively. The electronic structure of the films transferred onto SiO2/Si wafers by wet etching of copper substrates is studied by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy using a synchrotron radiation source. Annealing in an ultra-high vacuum at ca. 773 K allows for the removal of impurities formed on the surface of films during the synthesis and transfer procedure and changes the chemical state of nitrogen in nitrogen-doped graphene. Core level XPS spectra detect a low n-type doping of graphene film when nitrogen or phosphorous atoms are incorporated in the lattice. The electrical sheet resistance increases in the order: graphene < P-graphene < N-graphene. This tendency is related to the density of defects evaluated from the ratio of intensities of Raman peaks, valence band XPS and NEXAFS spectroscopy data. View Full-Tex

Optical Absorption and Raman Spectroscopy Study of the Fluorinated Double-Wall Carbon Nanotubes

Double-wall carbon nanotube (DWNT) samples have been fluorinated at room temperature with varied concentration of a fluorinating agent BrF3. Content of the products estimated from X-ray photoelectron data was equal to CF0.20 and CF0.29 in the case of deficit and excess of BrF3. Raman spectroscopy showed considerable decrease of carbon nanotube amount in the fluorinated samples. Analysis of optical absorption spectra measured for pristine and fluorinated DWNT samples revealed a selectivity of carbon nanotube fluorination. Nanotubes with large chiral angle are more inert to the fluorinating agent used

X-ray Spectroscopy Study of Defect Contribution to Lithium Adsorption on Porous Carbon

Lithium adsorption on high-surface-area porous carbon (PC) nanomaterials provides superior electrochemical energy storage performance dominated by capacitive behavior. In this study, we demonstrate the influence of structural defects in the graphene lattice on the bonding character of adsorbed lithium. Thermally evaporated lithium was deposited in vacuum on the surface of as-grown graphene-like PC and PC annealed at 400 °C. Changes in the electronic states of carbon were studied experimentally using surface-sensitive X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. NEXAFS data in combination with density functional theory calculations revealed the dative interactions between lithium sp2 hybridized states and carbon π*-type orbitals. Corrugated defective layers of graphene provide lithium with new bonding configurations, shorter distances, and stronger orbital overlapping, resulting in significant charge transfer between carbon and lithium. PC annealing heals defects, and as a result, the amount of lithium on the surface decreases. This conclusion was supported by electrochemical studies of as-grown and annealed PC in lithium-ion batteries. The former nanomaterial showed higher capacity values at all applied current densities. The results demonstrate that the lithium storage in carbon-based electrodes can be improved by introducing defects into the graphene layers

Electron spectroscopy of carbon materials: Experiment and theory

We present a comparative spectroscopic study of carbon as graphite, diamond and C60 using C1s K-edge electron energy-loss spectroscopy (EELS), X-ray emission spectroscopy, and theoretical modelling. The first principles calculations of these spectra are obtained in the local density approximation using a self-consistent Gaussian basis pseudo-potential method. Calculated spectra show excellent agreement with experiment and are able to discriminate not only between various carbon hybridisations but also local variation in environment. Core-hole effects on the calculated spectra are also investigated. For the first time, the EEL spectrum of carbyne is calculated

Brominated Porous Nitrogen-Doped Carbon Materials for Sodium-Ion Storage

Chemical modification improves the performance of the carbon anode in sodium-ion batteries (SIBs). In this work, porous nitrogen-doped carbon (PNC) was obtained by removing template nanoparticles from the thermal decomposition products of calcium glutarate and acetonitrile vapor. The treatment of PNC with a KOH melt led to the etching of the carbon shells at the nitrogen sites, which caused the replacement of some nitrogen species by hydroxyl groups and the opening of pores. The attached hydroxyl groups interacted with Br2 molecules, resulting in a higher bromine content in the brominated pre-activated sample (5 at%) than in the brominated PNC (3 at%). Tests of the obtained materials in SIBs showed that KOH activation has little effect on the specific capacity of PNC, while bromination significantly improves the performance. The largest gain was achieved for brominated KOH-activated PNC, which was able to deliver 234 and 151 mAh g−1 at 0.05 and 1 A g−1, respectively, and demonstrated stable long-term operation at 0.25 and 0.5 A g−1. The improvement was related to the separation of graphitic layers due to Br2 intercalation and polarization of the carbon surface by covalently attached functional groups. Our results suggest a new two-stage modification strategy to improve the storage and high-rate capability of carbon materials in SIBs

Hydrothermal Activation of Porous Nitrogen-Doped Carbon Materials for Electrochemical Capacitors and Sodium-Ion Batteries

Highly porous nitrogen-doped carbon nanomaterials have distinct advantages in energy storage and conversion technologies. In the present work, hydrothermal treatments in water or ammonia solution were used for modification of mesoporous nitrogen-doped graphitic carbon, synthesized by deposition of acetonitrile vapors on the pyrolysis products of calcium tartrate. Morphology, composition, and textural characteristics of the original and activated materials were studied by transmission electron microscopy, X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, infrared spectroscopy, and nitrogen gas adsorption method. Both treatments resulted in a slight increase in specific surface area and volume of micropores and small mesopores due to the etching of carbon surface. Compared to the solely aqueous medium, activation with ammonia led to stronger destruction of the graphitic shells, the formation of larger micropores (1.4 nm vs. 0.6 nm), a higher concentration of carbonyl groups, and the addition of nitrogen-containing groups. The tests of nitrogen-doped carbon materials as electrodes in 1M H2SO4 electrolyte and sodium-ion batteries showed improvement of electrochemical performance after hydrothermal treatments especially when ammonia was used. The activation method developed in this work is hopeful to open up a new route of designing porous nitrogen-doped carbon materials for electrochemical applications