Yolk-Shell Nano ZnO@Co-Doped NiO with Efficient Polarization Adsorption and Catalysis Performance for Superior Lithium-Sulfur Batteries.

Achieving strong adsorption and catalytic ability toward polar lithium polysulfide species (LiPSs) of the sulfur host in lithium-sulfur (Li-S) batteries is essential for their electrochemical cyclic stability. Herein, a strategy of "self-termination of ion exchange" is put forward to synthesize the novel yolk-shell sulfur host composed of ZnO nanoparticles confined in Co-doped NiO (CDN) polyhedron (ZCCDN). After sulfur infiltration, the obtained S/ZCCDN cathode achieves excellent performance of 738.56 mAh g-1 after 500 cycles at 0.5 C with a very low capacity decay rate of only 0.048% per cycle. Even at 1 C, 501.05 mAh g-1 could be retained after 500 cycles, suggesting a capacity decay ratio of only 0.076% per cycle. The good cycle performance is attributed to the improved LiPSs' conversion kinetics, which originates from ZCCDN's sturdy chemical affinity and strong catalytic ability to polar LiPSs. For the first time, by electron holography, the local interfacial polarization electric field is clarified to be existed in the material which is conducive to the capture of LiPSs and the migration of electrons and Li+ from the mesopores. This work provides a rational way for the use of zeolitic imidazolate frameworks (ZIFs) and development of cathode materials for Li-S batteries.

Mirror Plane Effect of Magnetoplumbite-Type Oxide Restraining Long-Chain Polysulfides Disproportionation for High Loading Lithium Sulfur Batteries.

A facile solid-state approach is employed to synthesize a novel magnetoplumbite-type oxide of NdMgAl11O19, which integrates spinel-stacking layers (MgAl2O4) with Nd-O6 mirror plane structures. The resulting NdMgAl11O19 exhibits remarkable catalytic activity and conversion efficiency during the sulfur reduction reaction (SRR) in lithium-sulfur batteries. By employing the 2D projection mapping technique of in situ confocal Raman spectroscopy and electrochemical technique, it is discovered that the exposed mirror plane structure of Nd-O6 can effectively suppress the undesiring disproportionation reaction (S8 2-→S6 2-+1/4 S8) of long-chain lithium polysulfides at the initial stages of sulfur reduction, thereby promoting the positive process of sulfur to lithium sulfide. This not only mitigates the issue of sulfur shuttle loss but also significantly improve the kinetics of the conversion process. Leveraging these advantages, the NdMgAl11O19/S cathode delivered an impressive initial capacity of up to 1398 mAh g-1 at an electrolyte/sulfur (E/S) ratio of 5.1 µL mg-1 and a sulfur loading of 2.3 mg cm-2. Even when the sulfur loading is increased to 10.02 mg cm-2, the cathode retained a reversible areal capacity of 10.01 mAh cm-2 after 200 cycles. This mirror engineering strategy provides valuable and universal insights into enhancing the efficiency of cathodes in Li-S battery.

Multiscale Assessment of Nanoscale Manufacturing Process on the Freeform Copper Surface.

The nanocutting has been paid great attention in ultra-precision machining and high sealing mechanical devices due to its nanometer level machining accuracy and surface quality. However, the conventional methods applicable to reproduce the cutting process numerically such as finite element (FE) and molecular dynamics (MD) are challenging to unveil the cutting machining mechanism of the nanocutting due to the limitation of the simulation scale and computational cost. Here a modified quasi-continuous method (QC) is employed to analyze the dynamic nanocutting behavior (below 10 nm) of the copper sample. After preliminary validation of the effectiveness via the wave propagation on the copper ribbon, we have assessed the effects of cutting tool parameters and back-engagement on the cutting force, stress distribution and surface metamorphic layer depth during the nanocutting process of the copper sample. The cutting force and depth of the surface metamorphic layer is susceptible to the back-engagement, and well tolerant to the cutting tool parameters such as the tool rank angle and tool rounded edge diameter. The results obtained by the QC method are comparable to those from the MD method, which indicate the effectiveness and applicability of the modified QC method in the nanocutting process. Overall, our work provides an applicable and efficient strategy to investigate the nanocutting machining mechanism of the large-scale workpiece and shed light on its applications in the super-precision and high surface quality devices.

Dandelion-like Mn/Ni Co-doped CoO/C Hollow Microspheres with Oxygen Vacancies for Advanced Lithium Storage.

Hollow structures have attracted great attention based on the advantage to accommodate volume expansion. However, template removal usually results in structure destruction. Herein, dandelion-like Mn/Ni co-doped CoO/C hollow microspheres (CMNC-10h) are synthesized via an Ostwald ripening process without templates. The high-angle annular dark field mapping images at the atomic level indicate the successful doping of Mn and Ni into CoO. Via an annular bright field image, oxygen vacancies induced by doping can be clearly observed. The residual two electrons in the oxygen vacancy site are highly delocalized, as confirmed by density functional theory calculations, effectively improving electrical conductivity. According to electron holography analysis, the dielectric polarization field in superficial regions of primary nanoparticles can facilitate insertion of Li+ ions into nanoparticles and thus enhance electrochemical kinetics. Combining those advantages, CMNC-10h demonstrates a high capacity of 1126 mAh g-1 at 1 A g-1 after 1000 cycles as anode material for a lithium-ion battery. Additionally, based on the strong adsorption toward polysulfide, the porous structure to accommodate sulfer/polysulfide, and the effects of oxygen vacancies to immobilize and catalyze polysulfide, CMNC-10h-S as cathode material for a lithium-sulfur battery also displays a high capacity of 642 mAh g-1 after 500 cycles at 1 C.