Deposition of nano-crystalline graphite films by cathodic plasma electrolysis

Atmospheric pressure plasma deposition of nano-crystalline graphite films on titanium substrates from a predominantly ethanolic liquid phase was carried out under varying applied voltage. A thorough study of the plasma electrolytic deposition mechanisms has been performed. The investigation of the composition, structural properties, and the morphology of these graphite coatings have been performed by visible and ultraviolet Raman spectroscopy, X-ray Photoelectron Spectroscopy, Scanning Electron Microscopy and X-ray elemental microanalysis. The experimental evidence of the reduction of the work function and the enhancement of the plasma intensity with the presence of the carbon film has been reported. These properties make such nano-crystalline graphite coatings very attractive for the production of inexpensive cold cathodes for electronics and plasma devices.     

Graphene Physics in Graphite

Single layers of carbon dubbed “graphene”, from which graphite is built, have attracted broad interest in the scientific community because of recent exciting experimental results. Graphene is interesting from a fundamental research perspective, as well as for potential technological applications. Here, we provide a brief overview of recent developments in this field, focusing especially on the electronic properties of graphite. Experimental evidence indicates that high‐quality graphite is a multi‐layer system with nearly decoupled 2D graphene planes. Based on experimental observations, we anticipate that thin graphite samples and not single layers will be the most promising candidates for graphene‐based electronics.     

A new route to graphene starting from heavily ozonized fullerenes: Part 3 – an electron spin resonance study

It is shown that graphite oxide (GO) and both heavily ozonized C₆₀ and C₇₀ fullerenes, known as “fullerene ozopolymers,” are paramagnetic materials with a very strong electron spin resonance (ESR) signal at room temperature. When thermally annealed, the paramagnetic centers are gradually lost in large part. This occurs at 350°C in the case of GO, while for fullerene ozopolymers, a higher temperature is required, reaching the same results in the end. The half-width of ESR signal is linked to the distribution of paramagnetic centers. Once again, striking analogies were found in the half-width of the ESR signal measured on GO and fullerene ozopolymers, at least in the temperature range of 25–450°C. Similarly, the same g-factor values, which are diagnostic for understanding the chemical nature of paramagnetic centers, were found on both GO and fullerene ozopolymers in all ranges of temperature considered.     

A novel perspective on the formation of the solid electrolyte interphase on the graphite electrode for lithium-ion batteries

In this paper, we describe how the mechanism of formation of a protective film [the solid electrolyte interphase (or interface) (SEI)] on a graphite electrode for Li-ion batteries was investigated from the novel perspective of precipitation of the final decomposition products that arise from the reduction of a nonaqueous electrolyte solution in contact with the graphite electrode. Within the framework of this new perspective, we can elegantly account for the compositional and structural differences between the basal-plane and edge-plane SEIs and for the origins of the multi-layer structure and the parabolic growth law of the SEIs on both the edge-plane and basal-plane surfaces of the graphite electrode.     

Oblique hypervelocity impacts into graphite

Investigations have been conducted into the morphology of craters formed by impacts of aluminium and HDPE projectiles at oblique angles to graphite target plates. The experiments were conducted with a two-stage gas gun capable of launching projectiles of differing density and strength to speeds of about 6 kms⁻¹ at right angles into target plates. It was found that, as the impact angle is decreased from the normal, the crater dimensions scaled as the normal component of the impact velocity as predicted by the ‘2/3 power law’ until a critical normal velocity was reached below which the conditions for a hypervelocity impact no longer apply. In this regime, new scaling laws were derived for the crater dimensions. It was also possible to identify a fragmentation angle below which the projectile remains intact as it ricochets across the target surface.     

Hybridized synergy effect among TiO2, Pt and graphite silica on photocatalytic hydrogen production from water–methanol solution

The photocatalytic production of hydrogen gas from aqueous methanol solution was performed using powdered mixtures of graphite silica (GS) and platinized TiO₂ (Pt/TiO₂) or those of GS, Pt and TiO₂. The addition of GS to Pt/TiO₂ resulted in the decrease of the amount of H₂ gas, whereas the addition of GS to mixtures of TiO₂ and Pt led to the incremental production of H₂ gas. This effect is attributed to the aggregation of GS, TiO₂ and Pt in suspension. The new additional electron transfer process of TiO₂ → Pt → GS caused the increment of the amount of hydrogen gas.     

Fabrication and tribological properties of titanium nitride coatings incorporating solid lubricant microreservoirs

The concept of incorporating microscopic reservoirs within a hard coating for the purpose of solid lubricant storage and supply during wear of interacting surfaces has been investigated in this study. A novel method was devised using ceramic beads (1.5-10 μm diameter) as placeholders during the deposition of a TiN coating by reactive sputter deposition. A pin-on-disk wear test was used to test these coatings using graphite and sputter-deposited carbon as the solid lubricant, and an alumina counterface. When tested without any lubricant, the presence of the microreservoirs in the TiN coating appeared to degrade the mechanical integrity of the coating leading to rapid failure. With the graphite lubricant present, the frictional behavior ranged from levels similar to the TiN coating alone, to that of graphite alone. Tests of the TiN coating made using 10 μm beads running against an aluminum counterface showed substantial improvement when the microreservoirs were present. Optical microscopy examination of the wear tracks showed the microreservoirs were generally successful at trapping the graphite lubricant during wear. With a sufficient density and appropriate distribution of the microreservoirs significant improvements in tribological performance can be realized.     

Manganese distribution and effect on graphite shape in advanced cast irons

The manganese contribution to a change of the graphite shape (in nodular graphite cast irons) has never been revealed. We made obvious the negative action of this element on the nodularization of graphite. Using SEM, we observe a significant change of the shape of the precipitated graphite (decrease of the shape coefficient values), depending on the cooling rate, the nature and the quantity of the nodularizing elements. The distribution of manganese and silicon in the metallic matrix and in the nodular graphite of cast irons with various amounts of manganese was studied using Castaing Scanning X-ray Microprobe. The distribution profiles of (K_α^Mn and K_α^Si) show that polycarbides appear on the graphite periphery in the cast iron with manganese contents over 1.0% (confirmed by SEM-EDX analysis). These chemical compounds influence the slowing down of the expected growth of graphite during the austenitic decomposition. This allows us to suggest that manganese would be added to the referenced antinodularizing elements group (O, S, halogens and Pb, Te, Ti, Cu, Al, Sn, Sb, Bi).     

Stabilisation of lithiated graphite in an electrolyte based on ionic liquids: an electrochemical and scanning electron microscopy study

1-Ethyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide (EMI-TFSI) is shown to reversibly permit lithium intercalation into standard TIMREX^® SFG44 graphite when vinylene carbonate (VC) is used in small amounts as additive. The best performance was obtained when 5% of VC was added to a 1 M solution of LiPF₆ in EMI-TFSI. Intercalation of lithium in the SFG44 graphite host was demonstrated over 100 cycles without noticeable capacity fading. The reversible charge capacity was around 350 mA h g⁻¹ and an only small irreversible capacity loss per cycle could be observed. Li₄Ti₅O₁₂ was used as counter electrode material. Scanning electron microscopy indicates the reduction of the electrolyte without graphite exfoliation in the neat electrolyte and the formation of a passivation film in the case of a VC-containing electrolyte. Other additives that were tested comprise ethylene sulphite and acrylonitrile which show also a positive effect, but a smaller one than vinylene carbonate. LiCoO₂ positive electrodes were cycled in a 1 M solution of LiPF₆ in EMI-TFSI with good charge capacity retention over more than 300 cycles, when Li₄Ti₅O₁₂ was used as counter electrode. The formation of a passivation film is proven on the LiCoO₂-electrodes, when the electrolyte contained VC, but not in the neat ionic liquid. Finally, the stable cycling of a full cell configuration is proven in this electrolyte system. An ammonium-containing ionic liquid (methyltrioctylammonium-bis(trifluoromethylsulfonyl)-imide, MTO-TFSI) is shown to permit the cycling of both, graphite and lithium cobalt oxide when VC is used as additive in small amounts, but at slightly elevated temperatures.     

Group 15 element-graphite composites synthesized by reduction of chlorides by KC8: Characterization and electrochemical lithiation

Group 15 element-graphite M/C composites were prepared by reduction of MCl_x chlorides (AsCl₃, SbCl₅, BiCl₃) by KC₈ in THF. Arsenic and antimony were both amorphous: antimony appeared as a film-like material, formed of aggregated nano-sized particles covering parts of the graphite surface; arsenic was present as large graphite supported particles. On the contrary, bismuth was present as crystalline metal nanoparticles distributed on the graphite surface. Amorphous As and Sb-graphite composites displayed stable reversible capacities of 310 and 420 mA h/g, respectively while that of crystalline Bi-graphite materials decreased regularly upon cycling. Although these practical capacities were lower than the expected theoretical ones corresponding to the formation of Li₃M compounds, it appeared that, in the presence of graphite, amorphous solids exhibiting a (partly) covalent character like As and Sb gave better long life cycling properties than the crystalline and metallic bismuth. It was very likely that our one step synthesis could generate bonds between graphite and (partly) covalent solids reducing consequently the volume expansion effects occurring during cycling. On the contrary, metallic solids like bismuth that were not inclined to bond with graphite behave, upon cycling, as corresponding massive metals.