On the reduced damage tolerance of fine-grained nuclear graphite at elevated temperatures using in situ 4D tomographic imaging
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Application of advanced anode and cathode materials in commercial lithium-ion batteries is attracting attention due to their high capacity. Silicon (Si)/graphite anodes and nickel (Ni)-rich lithium nickel manganese cobalt oxide with layered structures have been paired in commercial 18650 high energy density cells (~270 Wh/kg). It is crucial to investigate the cell performance and the aging behavior of this commercial cell. In this study, we present commercial cell degradation mechanisms by comparing fresh and aged electrodes, including changes of crystal structure, morphology, elemental composition, and electrochemical properties. The quantitative analysis was done based on dV/dQ incremental capacity analysis of 18650 cells. To determine the amount of cyclable lithium ions (Li + ) and active material loss, the lithiation and delithiation capacity were compared for fresh and aged electrodes in half coin cells. Results showed that even with 5% (by mass) of Si added in the anode, cracks occurred across the anode leading to contact loss and thickening of the solid electrolyte interphase (SEI) layer. Additionally, the average fluorine (F) ratio of the aged anodes was higher compared to that of the fresh anodes. More severely, the F content on the Si aggregations on aged anodes increased to as high as 5 times that of the fresh anode, indicating SEI growth, especially on Si particles. Solid 7 Li nuclear magnetic resonance results showed no detectable Li metal deposition on the aged anode. On the cathode side, cracks on the primary particle interfaces contributed to cathode material loss, contact loss, and impedance rise. Furthermore, Li + loss into the thickened SEI layer, particle cracking, and impedance rise are the main reasons behind cell degradation.
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Here we report a novel synthetic pathway for preparation of Cu-doped g-C{sub 3}N{sub 4} (Cu-g-C{sub 3}N{sub 4}) with nanosheet morphology by using a two dimensional Cu–melamine supramolecular network as both sacrificial template and precursor. The specific surface area of Cu-g-C{sub 3}N{sub 4} is 40.86 m{sup 2} g{sup −1}, which is more than 7 times larger than that of pure g-C{sub 3}N{sub 4}. Cu-g-C{sub 3}N{sub 4} showed strong optical absorption in the visible-light region and expanded the absorption to the near-infrared region. The uniform nanosheet morphology, higher surface area and strong visible-light absorption have enabled Cu-g-C{sub 3}N{sub 4} exhibiting enhanced visible light photocatalytic activity for the photo-degradation of methylene blue (MB). The results indicate that metal–melamine supramolecular network can be promising precursors for the one step preparation of efficient metal-doped g-C{sub 3}N{sub 4} photocatalysts. - Graphical abstract: Cu-doped g-C{sub 3}N{sub 4} (Cu-g-C{sub 3}N{sub 4}) with nanosheet morphology was fabricated via a simple one step preparation by using a two dimensional Cu–melamine supra-molecular network as both sacrificial template and precursor. - Highlights: • Cu-doped g-C{sub 3}N{sub 4} (Cu-g-C{sub 3}N{sub 4}) with nanosheet morphology was prepared. • Cu-g-C{sub 3}N{sub 4} showed strong optical absorption in the visible-light region. • Cu-g-C{sub 3}N{sub 4} exhibits enhanced visible light photocatalytic activity.
Highlights: • Bulk g-C{sub 3}N{sub 4} and its exfoliated form have been synthesized at different temperatures and characterized in detail. • Exfoliation proces increased oxidizing power of holes and enabled direct phenol degradation. • High-power visible LEDs improved significantly photocatalytic production of H{sub 2}O{sub 2} over exfoliated g-C{sub 3}N{sub 4}. • Synergistic effect between LEDs and exfoliated g-C{sub 3}N{sub 4} materials was observed. - Abstract: Exfoliated g-C{sub 3}N{sub 4} materials were prepared by thermal treatment of bulk materials synthesized from melamine at 4 different temperatures in range from 500 to 600 °C. The exfoliated g-C{sub 3}N{sub 4} synergically increased the photocatalytic degradation of phenol as effects like the fast production of H{sub 2}O{sub 2}, the presence of more active holes for direct phenol degradation and the use of high-power visible (416 nm) LEDs as irradiation source. The amount of phenol initially present was 99% converted in 15 min. All materials were also tested for comparison only in UVA region by using high-power UV (370 nm) LEDs. All prepared materials were thoroughly characterized by several analytical methods. In this work, the combination of g-C{sub 3}N{sub 4} after thermal treatment and high-power visible LEDs reduced the time needed for complete phenol degradation from several hours to just a few minutes. The mechanism of phenol degradation was also studied by introducing different active species scavengers into the reaction medium.
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Microstructural evolution of bias-enhanced grown (BEG) ultrananocrystalline diamond (UNCD) films has been investigated using microwave plasma enhanced chemical vapor deposition in gas mixtures of CH{sub 4} and Ar under different negative bias voltages ranging from −50 to −200 V. Scanning electron microscopy and Raman spectroscopy were used to characterize the morphology, growth rate, and chemical bonding of the synthesized films. Transmission electron microscopic investigation reveals that the application of bias voltage induced the formation of the nanographitic filaments in the grain boundaries of the films, in addition to the reduction of the size of diamond grains to ultra-nanosized granular structured grains. For BEG-UNCD films under −200 V, the electron field emission (EFE) process can be turned on at a field as small as 4.08 V/μm, attaining a EFE current density as large as 3.19 mA/cm{sup 2} at an applied field of 8.64 V/μm. But the films grown without bias (0 V) have mostly amorphous carbon phases in the grain boundaries, possessing poorer EFE than those of the films grown using bias. Consequently, the induction of nanographitic filaments in grain boundaries of UNCD films grown in CH{sub 4}/Ar plasma due to large applied bias voltage of −200 V is the prime factor, which possibly forms interconnected paths for facilitating the transport of electrons that markedly enhance the EFE properties.
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