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.     

Expanded graphite/polyaniline electrical conducting composites: Synthesis, conductive and dielectric properties

Expanded graphite/polyaniline electrical conducting composites were prepared by emulsion polymerization of aniline in the presence of expanded graphite. The phase composition and morphology of the composites were characterized by X-ray diffractometer and scanning electron microscopy, respectively. The electrical conductivities were measured by a four-probe resistivity instrument. The dielectric loss factor was performed on an impedance/material analyzer. The electrical conductivities of the composites were enhanced dramatically to 298.51 S cm^− 1 compared to polyaniline. The composites also showed excellent dielectric loss behavior in the frequency range from 1 MHz to 3 GHz, and the maximum of the dielectric loss factor approximated to 15,000.     

Synergistic Effects of Carbon Fillers of Phenolic Resin Based Composite Bipolar Plates on the Performance of PEM Fuel Cell

The most essential and costly component of polymer electrolyte membrane fuel cells is the bipolar plate. The production of suitable composite bipolar plates for polymer electrolyte membrane fuel cell with good mechanical properties and high electrical conductivity is scientifically and technically very challenging. This paper reports the development of composite bipolar plates using exfoliated graphite, carbon black, and graphite powder in resole‐typed phenol formaldehyde. The exfoliated graphite with maximum exfoliated volume of 570 ± 10 mL g⁻¹ used in this study was prepared by microwave irradiation of chemically intercalated natural flake graphite in a few minutes. The composite plates were prepared by varying exfoliated graphite content from 10 to 35 wt.% in phenolic resin along with fixed weight percentage of carbon black (5 wt.%) and graphite powder (3 wt.%) by compression molding. The composite plates with filler weight percentage of 35/5/3/exfoliated graphite/carbon black/graphite powder offer in‐plane and trough‐plane electrical conductivities of 374.42 and 97.32 S cm⁻¹, bulk density 1.58 g cm⁻³, compressive strength 70.43 MPa, flexural strength 61.82 MPa, storage modulus 10.25 GPa, microhardness 73.23 HV and water absorption 0.22%. Further, I–V characteristics notify that exfoliated graphite/carbon black/graphite powder/resin composite bipolar plates in unit fuel cell shows better cell performance compared exfoliated graphite/resin composite bipolar plates. The composite plates own desired mechanical properties with low bulk density, high electrical conductivity, and good thermal stability as per the U.S. department of energy targets at low filler concentration and can be used as bipolar plates for proton exchange membrane fuel cells.     

Polypropylene-graphite nanocomposites made by solid-state shear pulverization: Effects of significantly exfoliated, unmodified graphite content on physical, mechanical and electrical properties

Nanocomposites made from polypropylene and as-received graphite were prepared by solid-state shear pulverization (SSSP) as a function of graphite loading (0.3-8.4 wt%). X-ray diffraction indicates that SSSP employing harsh pulverization conditions yields substantial graphite exfoliation at 0.3-2.7 wt% graphite content with less exfoliation being achieved at higher graphite content. With increasing graphite content, thermal degradation temperature and non-isothermal onset crystallization temperature increase substantially (by as much as 35 and 23 °C relative to neat polypropylene) while isothermal crystallization half-time decreases dramatically. In contrast, Young’s modulus and tensile yield strength exhibit maxima (∼100% and ∼60% increases, respectively, relative to neat polypropylene) at 2.7 wt% graphite content, with all nanocomposites retaining high elongation at break values except at the highest filler loading. Electrical conductivity measurements indicate percolation of graphite at 2.7 wt% and higher graphite content, consistent with rheology measurements showing the presence of a solid-like response of melt-state shear storage modulus as a function of frequency. Significant tunability of graphite exfoliation and property enhancements is demonstrated as a function of SSSP processing.     

Effect of fluoroethylene carbonate on high temperature capacity retention of LiMn2O4/graphite Li-ion cells

In order to overcome severe capacity fading of LiMn₂O₄/graphite Li-ion cells at high temperature at 60 °C, fluoroethylene carbonate (FEC) was newly evaluated as an electrolyte additive. With 2 wt.% FEC addition into the electrolyte (EC/DEC/PC with 1 M LiPF₆), the capacity retention at 60 °C after 130 cycles was significantly improved by about 20%. To understand the underlying principle on the capacity retention enhancement, the electrochemical properties of the cells including cell performance, impedance behavior as well as the characteristics of the interfacial properties were examined. Based on these results, it is suggested that the improved capacity retention of LiMn₂O₄/graphite Li-ion cells with addition of FEC especially at high temperature is mainly originated from the thin and stable SEI layer formed on the graphite anode surface.     

On the electrochemical performance of anthracite-based graphite materials as anodes in lithium-ion batteries

The electrochemical performance as potential negative electrode in lithium-ion batteries of graphite materials that were prepared from two Spanish anthracites of different characteristics by heat treatment in the temperature interval 2400-2800 °C are investigated by galvanostatic cycling. The interlayer spacing, d₀₀₂, and crystallite sizes along the c axis, L_c, and the a axis, L_a, calculated from X-ray diffractometry (XRD) as well as the relative intensity of the Raman D-band, I_D/I_t, are used to assess the degree of structural order of the graphite materials. The galvanostatic cycling are carried out in the 2.1-0.003 V potential range at a constant current and C/10 rate during 50 cycles versus Li/Li⁺. Larger reversible lithium storage capacities are obtained from those anthracite-based graphite materials with higher structural order and crystal orientation. Reasonably good linear correlations were attained between the electrode reversible charge and the materials XRD and Raman crystal parameters. The graphite materials prepared show excellent cyclability as well as low irreversible charge; the reversible capacity being up to ∼250 mA h g⁻¹. From this study, the utilization of anthracite-based graphite materials as negative electrode in lithium-ion batteries appears feasible. Nevertheless, additional work should be done to improve the structural order of the graphite materials prepared and therefore, the reversible capacity.