Thermochemical Cyclization Constructs Bridged Dual-Coating of Ni-Rich Layered Oxide Cathodes for High-Energy Li-Ion Batteries.

Enhancing microstructural and electrochemical stabilities of Ni-rich layered oxides is critical for improving the safety and cycle-life of high-energy Li-ion batteries. Here we propose a thermochemical cyclization strategy where heating polyacrylonitrile with LiNi0.8Co0.1Mn0.1O2 can simultaneously construct a cyclized polyacrylonitrile outer layer and a rock-salt bridge-like inner layer, forming a compact dual-coating of LiNi0.8Co0.1Mn0.1O2. Systematic studies demonstrate that the mild cyclization reaction between polyacrylonitrile and LiNi0.8Co0.1Mn0.1O2 induces a desirable "layered to rock-salt" structural transformation to create a nano-intermedium that acts as the bridge for binding cyclized polyacrylonitrile to layered LiNi0.8Co0.1Mn0.1O2. Because of the improvement of the structural and electrochemical stability and electrical properties, this cathode design remarkably enhances the cycling performance and rate capability of LiNi0.8Co0.1Mn0.1O2, showing a high reversible capacity of 183 mAh g-1 and a high capacity retention of 83% after 300 cycles at 1 C rate. Notably, this facile and scalable surface engineering makes Ni-rich cathodes potentially viable for commercialization in high-energy Li-ion batteries.

Crystal Phase-Controlled Modulation of Binary Transition Metal Oxides for Highly Reversible Li-O2 Batteries.

Reducing charge-discharge overpotential of transition metal oxide catalysts can eventually enhance the cell efficiency and cycle life of Li-O2 batteries. Here, we propose that crystal phase engineering of transition metal oxides could be an effective way to achieve the above purpose. We establish controllable crystal phase modulation of the binary MnxCo1-xO by adopting a cation regulation strategy. Systematic studies reveal an unprecedented relevancy between charge overpotential and crystal phase of MnxCo1-xO catalysts, whereas a dramatically reduced charge overpotential (0.48 V) via a rational optimization of Mn/Co molar ratio = 8/2 is achieved. Further computational studies indicate that the different morphologies of Li2O2 should be related to different electronic conductivity and binding of Li2O2 on crystal facets of MnxCo1-xO catalysts, finally leading to different charge overpotential. We anticipate that this specific crystal phase engineering would offer good technical support for developing high-performance transition metal oxide catalysts for advanced Li-O2 batteries.

Synthesis of microflower-like vacancy defective copper sulfide/reduced graphene oxide composites for highly efficient lithium-ion batteries.

Copper sulfide (CuS) is considered a promising anode material for lithium-ion batteries (LIBs) due to its high theoretical capacity and good electrical conductivity. However, the inferior cycle performance and low coulombic efficiency of CuS caused by structure detoriation and degradation and the 'shuttling effect' of polysulfide intermediates are restricting its practical application. In this work, we report a facile method to generate S vacancies (Vs) in CuS nanoflowers by thermal annealing in Ar. The obtained CuS was composited with reduced graphene oxide (rGO) to prepare an anode for LIBs. The existence of vacancy defects in CuS leads to electron delocalization and excitation, which is responsible for the conductivity improvement and fast charge transport kinetics. Meanwhile, the graphene coating layer ensures fast pathways for Li+ ion diffusion and provides strong physical adsorption of the polysulfides. Furthermore, hierarchical CuS spheres composed of ultrathin nanosheets provide large void spaces to accommodate the volume expansion of CuS. The synthesized composite exhibited a high initial discharge capacity of 882 mAh g-1 and demonstrated stable cyclability along with around 99% coulombic efficiency over 100 cycles. The results of this work reveal that Vs-CuS/rGO composites are promising anodes to enhance the performance of next-generation lithium-ion batteries.

Healable and Conductive Two-Dimensional Sulfur Iodide for High-Rate Sodium Batteries.

Self-healing functional materials can repair cracks and damage inside the battery, ensuring the stability of the battery material structure. This feature minimizes performance degradation during the charging and discharging processes, improving the efficiency and stability of the battery. Here, we have developed a novel healing conductive two-dimensional sulfur iodide (SI4) composite cathode. This process integrates both sulfur and iodine compounds into carbon nanocages, forming a SI4@C core-shell structure. This cathode design improves electrical conductivity and repairability, facilitates rapid activation, and ensures structural integrity, resulting in a typical Na-SI4 battery with high capacity and an exceptionally long cycle life. At 10.0 A g-1, the capacity of the Na-SI4 battery can still reach 217.4 mAh g-1 after more than 500 cycles, and the capacity decay rate per cycle is only 0.06%. In addition, the cathode exhibits a cascade redox reaction involving S and I, contributing to its high capacity. The in situ growth of a carbon shell further enhances the conductivity and structural robustness of the entire cathode. The flexibility and bendability of SI4@C-carbon cloth make it applicable for flexible electronic devices, providing more possibilities for battery design. The strategy of engineering a two-dimensional self-healing structure to construct a superior cathode is expected to be widely applied to other electrode materials. This study provides a new pathway for designing novel binary-conversion-type sodium-ion batteries with excellent long-term cycling performance.

Toxicity and endocrine-disrupting potential of PM2.5: Association with particulate polycyclic aromatic hydrocarbons, phthalate esters, and heavy metals.

The adverse effects of fine atmospheric particulate matter with aerodynamic diameters of ≤2.5 µm (PM2.5) are closely associated with particulate chemicals. In this study, PM2.5 samples were collected from highway and industry sites in Hangzhou, China, during the autumn and winter, and their cytotoxicity and pulmonary toxicity and endocrine-disrupting potential (EDP) were evaluated in vitro and in vivo; the particulate polycyclic aromatic hydrocarbons (PAHs), phthalate esters (PAEs), and heavy metals were then characterized. The toxicological results suggested that the PM2.5 from highway site induced higher cytotoxicity (cell viability inhibition, intracellular oxidative stress, and cell membrane injury) and pulmonary toxicity (inflammatory response (IR) and oxidative stress (OS)) than the samples from industry site, while the PM2.5 from industry site exhibited higher EDP (estrogenic and anti-androgenic activity). The cytotoxicity and pulmonary toxicity of PM2.5 in the winter were higher than those in the autumn, while no seasonal difference in the endocrine-disrupting potential was observed (p > 0.05). The Pearson correlation analysis between the biological effects and particulate chemicals revealed that the PM2.5-induced inflammatory response and oxidative stress were closely associated with the particulate PAHs and heavy metals (Pearson correlation coefficients: rIR, PAHs = 0.822-0.988, rIR, heavy metals = 0.895-0.971, rOS, PAHs = 0.843-0.986, and rOS, heavy metals = 0.887-0.933), while particulate di (2-ethylhexyl)phthalate (DEHP) substantially contributed to the EDP of PM2.5 (rEDP, DEHP = 0.981). This study indicated that the toxicity and EDP of PM2.5 could vary with the surrounding environment and season, which was closely associated with the variations of particulate chemicals. Further studies are needed to clarify the associations between the harmful effects of PM2.5 and other contributing factors.

Preparation of ZnO Nanorods/Graphene Composite Anodes for High-Performance Lithium-Ion Batteries.

ZnO is a promising anode material for lithium-ion batteries (LIBs); however, its practical application is hindered primarily by its large volume variation upon lithiation. To overcome this drawback, we synthesized ZnO/graphene composites using the combination of a simple hydrothermal reaction and spray drying. These composites consisted of well-dispersed ZnO nanorods anchored to graphene. The folded three-dimensional graphene spheres provided a high conductivity, high surface area, and abundant defects. LIB with an anode composed of our novel ZnO/graphene material demonstrated a high initial discharge capacity of 1583 mAh g-1 at 200 mA g-1.

A 3D MoS2/Graphene Microsphere Coated Separator for Excellent Performance Li-S Batteries.

Lithium-sulfur (Li-S) batteries are the most prospective energy storage devices. Nevertheless, the poor conductivity of sulfur and the shuttling phenomenon of polysulfides hinder its application. In this paper, flower-like MoS2/graphene nanocomposite is prepared and deposited on a multi-functional separator to enhance the electrochemical behavior of Li-S batteries. The results demonstrated that the MoS2/graphene-coated separator is contributing to inhibit the shuttling phenomenon of polysulfides and improve the integrity of sulfur electrode. The initial discharge capacity of the battery using MoS2/graphene-coated separator at 0.2 C was up to 1516 mAh g-1. After 100 cycles, a reversible capacity of 880 mAh g-1 and a coulombic efficiency of 98.7% were obtained. The improved electrochemical behavior can be due to the nanostructure and Mo-S bond of the MoS2/graphene composite, which can combine physical shielding and chemisorption to prohibit the shuttle effect of polysulfides. The results prove that the MoS2/graphene-coated separator has the potential for feasible application in Li-S batteries to enhance their electrochemical performance.

High Electrochemical Performance of Nanotube Structured ZnS as Anode Material for Lithium⁻Ion Batteries.

By using ZnO nanorods as an ideal sacrificial template, one-dimensional (1-D) ZnS nanotubes with a mean diameter of 10 nm were successfully synthesized by hydrothermal method. The phase composition and microstructure of the ZnS nanotubes were characterized by using XRD (X-ray diffraction), SEM (scanning electron micrograph), and TEM (transmission electronic microscopy) analysis. X-ray photoelectron spectroscopy (XPS) and nitrogen sorption isotherms measurements were also used to study the information on the surface chemical compositions and specific surface area of the sample. The prepared ZnS nanotubes were used as anode materials in lithium-ion batteries. Results show that the ZnS nanotubes deliver an impressive prime discharge capacity as high as 950 mAh/g. The ZnS nanotubes also exhibit an enhanced cyclic performance. Even after 100 charge/discharge cycles, the discharge capacity could still remain at 450 mAh/g. Moreover, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were also carried out to evaluate the ZnS electrodes.