A Novel Potassium Salt Regulated Solvation Chemistry Enabling Excellent Li-Anode Protection in Carbonate Electrolytes.

In lithium-metal batteries (LMBs), the compatibility of Li anode and conventional lithium hexafluorophosphate-(LiPF6 ) carbonate electrolyte is poor owing to the severe parasitic reactions. Herein, to resolve this issue, a delicately designed additive of potassium perfluoropinacolatoborate (KFPB) is unprecedentedly synthesized. On the one hand, KFPB additive can regulate the solvation structure of the carbonate electrolyte, promoting the formation of Li+ FPB- and K+ PF6 - ion pairs with lower lowest unoccupied molecular orbital (LUMO) energy levels. On the other hand, FPB- anion possesses strong adsorption ability on Li anode. Thus, anions can preferentially adsorb and decompose on the Li-anode surface to form a conductive and robust solid-electrolyte interphase (SEI) layer. Only with a trace amount of KFPB additive (0.03 m) in the carbonate electrolyte, Li dendrites' growth can be totally suppressed, and Li||Cu and Li||Li half cells exhibit excellent Li-plating/stripping stability upon cycling. Encouragingly, KFPB-assisted carbonate electrolyte enables high areal capacity LiCoO2 ||Li, LiNi0.8 Co0.1 Mn0.1 O2 (NCM811)||Li, and LiNi0.8 Co0.05 Al0.15 O2 (NCA)||Li LMBs with superior cycling stability, showing its excellent universality. This work reveals the importance of designing novel additives to regulate the solvation structure of carbonate electrolytes in improving its interface compatibility with the Li anode.

Mixture of Pb, Zn and Cu on root permeability and radial oxygen loss in the mangrove Bruguiera gymnorrhiza.

A short term pot trail was employed to evaluate the exposure of mixed heavy metals (Cu, Pb and Zn) on growth, radial oxygen loss (ROL) and root anatomy in Bruguiera gymnorrhiza. The possible function of BgC4H, a cytochrome P450 gene, on root lignification was also discussed. The exposures of mixed Cu, Pb and Zn directly reduce O2 leakage at root surface. The reduced ROL inhibited by heavy metals was mainly ascribed by the changes in root anatomical features, such as decreased root porosity together with increased lignification within the exodermis. BgC4H was found to be up-regulated after 0.5-day metal exposure, and remained higher transcript levels within 3-day metal exposure when compared to control roots. Besides, the inhibited photosynthesis may also result in less oxygen can be transported to the underground roots. In summary, the mangrove B. gymnorrhiza appeared to react to external mixed metal contaminants by developing a lignified and impermeable exodermis, and such a root barrier induced by mixed Cu, Pb and Zn appeared to be an adaptive response to block metal ions enters into the roots.

Iron vacancy in tetragonal Fe1-xS crystals and its effect on the structure and superconductivity.

Understanding the effects of non-stoichiometry on the structure and physical properties of tetragonal Fe chalcogenides is of great importance, especially for developing fascinating superconductivity in this system, which might be very sensitive to the non-stoichiometry. In this study, a series of Fe1-xS single crystals were synthesized by a hydrothermal method, which show varying concentrations of Fe vacancies (0 ≤ x ≤ 0.1) in the structure. Based on the crystal samples, the effects of vacancies on the crystal structure and physical properties were studied. The vacancy-free sample (x = 0) showed a metallic state in resistance and superconductivity below 4.5 K, whereas for the samples with Fe vacancies (x ≥ 0.05), the SC was degraded and the sample exhibited semiconducting behavior. Structural analysis showed that the Fe vacancy decreases the lattice parameter a, but elongates c, leading to enhanced tetragonality in Fe1-xS. Selected-area electron diffraction showed that the vacancy in Fe1-xS was disordered, which is different from the scenario in FeSe-based materials. On combining the abovementioned results with the first-principles calculations, it was speculated that the disappearance of SC in non-stoichiometric Fe1-xS resulted from the localization of the 3d electrons of Fe. Moreover, the accompanied metal-insulator transition induced by Fe vacancy mainly belonged to the Mott mechanism because the vacancy did not significantly alter the band structure. These results not only provide deep insight into the effect of Fe vacancy in Fe chalcogenides, but also provide a basis to effectively induce SC in Fe sulfides by decreasing the number of Fe vacancies.