Tuning the Solvation Structure in Water-Based Solution Enables Surface Reconstruction of Layered Oxide Cathodes toward Long Lifespan Sodium-Ion Batteries.

Layered oxides of sodium-ion batteries suffer from severe side reactions on the electrode/electrolyte interface, leading to fast capacity degradation. Although surface reconstruction strategies are widely used to solve the above issues, the utilization of the low-cost wet chemical method is extremely challenging for moisture-sensitive Na-based oxide materials. Here, the solvation tuning strategy is proposed to overcome the deterioration of NaNi1/3Mn1/3Fe1/3O2 in water-based solution and conduct the surface reconstruction. When capturing the water molecules by the solvation structure of cations, here is Li+, the structural collapse and degradation of layered oxides in water-based solvents are greatly mitigated. Furthermore, Li(H2O)3EA+ promotes the profitable Li+/Na+ exchange to build a robust surface, which hampers the decomposition of electrolytes and the structural evolution upon cycling. Accordingly, the lifespan of Li-reinforced materials is prolonged to three times that of the pristine one. This work represents a step forward in understanding the surface reconstruction operated in a water-based solution for high-performance sodium layered oxide cathodes.

Adsorption, natural attenuation, and microbial community response of ofloxacin and oxolinic acid in marine sediments.

The pollution of quinolone antibiotics in the marine environment has attracted widespread attention, especially for ofloxacin (OFL) and oxolinic acid (OXO) due to their frequent detection. However, few studies have been conducted to assess the behaviors and microbial community response to these antibiotics in marine sediments, particularly for potential antibiotic-resistant bacteria. In this work, the adsorption characteristics, natural attenuation characteristics, and variation of microbial communities of OFL and OXO in marine sediments were investigated. The adsorption process of antibiotics in sediments occurred on the surface and internal pores of organic matter, where OFL was more likely to be transferred from seawater to sediment compared with OXO. Besides, the adsorption of two antibiotics on sediment surfaces was attributed to physisorption (pore filling, electrostatic interaction) and chemisorption (hydrogen bonding). The natural attenuation of OFL and OXO in marine sediment followed second-order reaction kinetics with half-lives of 6.02 and 26.71 days, respectively, wherein biodegradation contributed the most to attenuation, followed by photolysis. Microbial community structure in marine sediments exposure to antibiotics varied by reducing abundance and diversity of microbial communities, as a whole displaying as an increase in the relative abundance of Firmicutes whereas a decrease of Proteobacteria. In detail, Escherichia-Shigella sp., Blautia sp., Bifidobacterium sp., and Bacillus sp. were those antibiotic-resistant bacteria with potential ability to degrade OFL, while Bacillus sp. may be resistant to OXO. Furthermore, functional predictions indicated that the microbial communities in sediment may resist the stress caused by OFL and OXO through cyano-amino acid metabolism, and ascorbate and aldarate metabolism, respectively. The research is key to understanding fate and bacterial resistance of antibiotics in marine sediments.

Ordered planar plating/stripping enables deep cycling zinc metal batteries.

Metal anodes are emerging as culminating solutions for the development of energy-dense batteries in either aprotic, aqueous, or solid battery configurations. However, unlike traditional intercalation electrodes, the low utilization of "hostless" metal anodes due to the intrinsically disordered plating/stripping impedes their practical applications. Herein, we report ordered planar plating/stripping in a bulk zinc (Zn) anode to achieve an extremely high depth of discharge exceeding 90% with negligible thickness fluctuation and long-term stable cycling. The Zn can be plated/stripped with (0001)Zn preferential orientation throughout the consecutive charge/discharge process, assisted by a self-assembled supramolecular bilayer at the Zn anode-electrolyte interface. Through real-time tracking of the Zn atoms migration, we reveal that the ordered planar plating/stripping is driven by the construction of in-plane Zn─N bindings and the gradient energy landscape at the reaction fronts. The breakthrough results provide alternative insights into the ordered plating/stripping of metal anodes toward rechargeable energy-dense batteries.

Oxygen-regulated spontaneous solid electrolyte interphase enabling ultra-stable solid-state Na metal batteries.

Solid-state sodium metal batteries utilizing inorganic solid electrolytes (SEs) hold immense potentials such as intrinsical safety, high energy density, and environmental sustainability. However, the interfacial inhomogeneity/instability at the anode-SE interface usually triggers the penetration of sodium dendrites into the electrolyte, leading to short circuit and battery failure. Herein, confronting with the original nonuniform and high-resistance solid electrolyte interphase (SEI) at the Na-Na3Zr2Si2PO12 interface, an oxygen-regulated SEI innovative approach is proposed to enhance the cycling stability of anode-SEs interface, through a spontaneous reaction between the metallic sodium (containing trace amounts of oxygen) and the Na3Zr2Si2PO12 SE. The oxygen-regulated spontaneous SEI is thin, uniform, and kinetically stable to facilitate homogenous interfacial Na+ transportation. Benefitting from the optimized SEI, the assembled symmetric cell exhibits an ultra-stable sodium plating/stripping cycle for over 6600 h under a practical capacity of 3 mAh cm-2. Quasi-solid-state batteries with Na3V2(PO4)3 cathode deliver excellent cyclability over 500 cycles at a rate of 0.5 C (1 C = 117 mA cm-2) with a high capacity retention of 95.4%. This oxygen-regulated SEI strategy may offer a potential avenue for the future development of high-energy-density solid-state metal batteries.

Transient Zwitterions Dynamics Empowered Adaptive Interface for Ultra-Stable Zn Plating/Stripping.

A highly reversible zinc anode is crucial for the commercialization of zinc-ion batteries. However, the change in the microstructure of the electric double layer originated from the dynamic change in charge density on the electrode greatly impacts anode reversibility during charge/discharge, which is rarely considered in previous research. Herein, the zwitterion additive is employed to create an adaptive interface by coupling the transient zwitterion dynamics upon the change of interfacial charge density. Ab initio molecular dynamics simulations suggest the molecular orientation and adsorption groups of zwitterions will be determined by the charging state of the electrode. ZnSO4 electrolyte with zwitterion fulfills a highly reversible Zn anode with an average Coulombic efficiency of up to 99.85%. Zn/Zn symmetric cells achieve greatly enhanced cycling stability for 700 h with extremely small voltage hysteresis of 29 mV under 5 mA cm-2 with 5 mAh cm-2 . This study validates the adaptive interface based on transient dynamics of zwitterions, which sheds new light on developing highly reversible metal anodes with a high utilization rate.

Synergistic "Anchor-Capture" Enabled by Amino and Carboxyl for Constructing Robust Interface of Zn Anode.

While the rechargeable aqueous zinc-ion batteries (AZIBs) have been recognized as one of the most viable batteries for scale-up application, the instability on Zn anode-electrolyte interface bottleneck the further development dramatically. Herein, we utilize the amino acid glycine (Gly) as an electrolyte additive to stabilize the Zn anode-electrolyte interface. The unique interfacial chemistry is facilitated by the synergistic "anchor-capture" effect of polar groups in Gly molecule, manifested by simultaneously coupling the amino to anchor on the surface of Zn anode and the carboxyl to capture Zn2+ in the local region. As such, this robust anode-electrolyte interface inhibits the disordered migration of Zn2+, and effectively suppresses both side reactions and dendrite growth. The reversibility of Zn anode achieves a significant improvement with an average Coulombic efficiency of 99.22% at 1 mA cm-2 and 0.5 mAh cm-2 over 500 cycles. Even at a high Zn utilization rate (depth of discharge, DODZn) of 68%, a steady cycle life up to 200 h is obtained for ultrathin Zn foils (20 µm). The superior rate capability and long-term cycle stability of Zn-MnO2 full cells further prove the effectiveness of Gly in stabilizing Zn anode. This work sheds light on additive designing from the specific roles of polar groups for AZIBs.

Elimination of tetracyclines in seawater by laccase-mediator system.

Long-term exposure of antibiotics at low level leads to the accumulation of antibiotics in environmental media and organisms, inducing the formation of antibiotic resistance genes. Seawater is an important sink for many contaminants. Here, laccase from Aspergillus sp. and mediators that follow different oxidation mechanisms were combined to degrade tetracyclines (TCs) at environmentally relevant levels (ng·L-1-µg·L-1) in coastal seawater. The high salinity and alkaline of seawater changed the enzymatic structure of laccase, resulting in a reduced affinity of laccase to the substrate in seawater (Km of 0.0556 mmol·L-1) than that in buffer (Km of 0.0181 mmol·L-1). Although the stability and activity of the laccase decreased in seawater, laccase at a concentration of 200 U·L-1 with a laccase/syringaldehyde (SA) ratio of 1 U: 1 µmol could completely degrade TCs in seawater at initial concentrations of less than 2 µg·L-1 in 2 h. Molecular docking simulation showed that the interaction between TCs and laccase mainly includes hydrogen bond interaction and hydrophobic interaction. TCs were degraded into small molecular products through a series of reactions: demethylation, deamination, deamidation, dehydration, hydroxylation, oxidation, and ring-opening. Prediction of the toxicity of intermediates showed that the majority of TCs can be degraded into low-toxic or non-toxic, small-molecule products within 1 h, indicating that the degradation process of TCs by a laccase-SA system has good ecological safety. The successful removal of TCs by the laccase-SA system demonstrates its potential for the elimination of pollutants in marine environment.

Precise Phase Control of Large-Scale Inorganic Perovskites via Vapor-Phase Anion-Exchange Strategy.

Anion exchange offers great flexibility and high precision in phase control, compositional engineering, and optoelectronic property tuning. Different from previous successful anion exchange process in liquid solution, herein, a vapor-phase anion-exchange strategy is developed to realize the precise phase and bandgap control of large-scale inorganic perovskites by using gas injection cycle, producing some perovskites such as CsPbCl3 which has never been reported in thin film morphology. Ab initio calculations also provide the insightful mechanism to understand the impact of anion exchange on tuning the electronic properties and optimizing the structural stability. Furthermore, because of precise control of specific atomic concentrations, intriguing tunable photoluminescence is observed and photodetectors with tunable photoresponse edge from green to ultraviolet light can be realized accurately with an ultrahigh spectral resolution of 1 nm. Therefore, a new, universal vapor-phase anion exchange method is offered for inorganic perovskite with fine-tunable optoelectronic properties.

Unexpected bowing band evolution in an all-inorganic CsSn1-x Pb x Br3 perovskite.

We theoretically investigated the structural and electronic properties of the all-inorganic perovskite CsSn1-x Pb x Br3, compared with the mixed perovskite compound MA y Cs1-y Sn1-x Pb x Br3, based on first-principle calculations. It has been demonstrated that Pb and Sn atoms are inclined to occupy the lattice sites uniformly in the all-inorganic perovskite, and this is distinguished from the most stable configurations observed in the mixed Cs-MA system. It is interesting that small Sn atoms prefer to stay close to the large MA+ cations, leading to smaller local structural distortion. Through spin-orbital coupling calculations, we found non-linear bowing band evolution in the all-inorganic mixed Sn-Pb system with a small bowing parameter (b = 0.35), while the band gap of MA y Cs1-y Sn1-x Pb x Br3 was clearly reduced as the ratio of MA was around 0.5 (y ≥ 0.25). We determined the bowing band evolution in the mixed cation perovskites and the intrinsic electronic deficiency of the all-inorganic perovskite to obtain the optimal band gap.