Versatile separators toward advanced lithium-sulfur batteries: status, recent progress, challenges and perspective.

Lithium-sulfur batteries (LSBs) have recently gained extensive attention due to their high energy density, low cost, and environmental friendliness. However, serious shuttle effect and uncontrolled growth of lithium dendrites restrict them from further commercial applications. As "the third electrode", functional separators are of equal significance as both anodes and cathodes in LSBs. The challenges mentioned above are effectively addressed with rational design and optimization in separators, thereby enhancing their reversible capacities and cycle stability. The review discusses the status/operation mechanism of functional separators, then primarily focuses on recent research progress in versatile separators with purposeful modifications for LSBs, and summarizes the methods and characteristics of separator modification, including heterojunction engineering, single atoms, quantum dots, and defect engineering. From the perspective of the anodes, distinct methods to inhibit the growth of lithium dendrites by modifying the separator are discussed. Modifying the separators with flame retardant materials or choosing a solid electrolyte is expected to improve the safety of LSBs. Besides, in-situ techniques and theoretical simulation calculations are proposed to advance LSBs. Finally, future challenges and prospects of separator modifications for next-generation LSBs are highlighted. We believe that the review will be enormously essential to the practical development of advanced LSBs.

Engineering Triple-Phase Interfaces Enabled by Layered Double Perovskite Oxide for Boosting Polysulfide Redox Conversion.

The electrocatalytic conversion of polysulfides is crucial to lithium-sulfur batteries and mainly occurs at triple-phase interfaces (TPIs). However, the poor electrical conductivity of conventional transition metal oxides results in limited TPIs and inferior electrocatalytic performance. Herein, a TPI engineering approach comprising superior electrically conductive layered double perovskite PrBaCo2O5+δ (PBCO) is proposed as an electrocatalyst to boost the conversion of polysulfides. PBCO has superior electrical conductivity and enriched oxygen vacancies, effectively expanding the TPI to its entire surface. DFT calculation and in situ Raman spectroscopy manifest the electrocatalytic effect of PBCO, proving the critical role of enhanced electrical conductivity of this electrocatalyst. PBCO-based Li-S batteries exhibit an impressive reversible capacity of 612 mAh g-1 after 500 cycles at 1.0 C with a capacity fading rate of 0.067% per cycle. This work reveals the mechanism of the enriched TPI approach and provides novel insight into designing new catalysts for high-performance Li-S batteries.

Ultrafast Self-Healing, Highly Stretchable, Adhesive, and Transparent Hydrogel by Polymer Cluster Enhanced Double Networks for Both Strain Sensors and Environmental Remediation Application.

Stretchable, healable, biocompatible, and conductive hydrogels are one of the promising candidates for both wearable electronics and environmental remediation applications. To date, the design of hydrogels that integrate ultrafast self-healing with high efficiency (seconds), high stretchability, and biocompatibility and reversibility into one system is not an easy task. Herein, we demonstrate a general oxidation approach to accelerate the hydrogelation of hPEI-based double network gels via the generation of fluorescent polymer clusters at room temperature or triggered by the heating-cooling process. The resulting ohPEI hydrogel has the merit of biocompatibility over most reported hPEI hydrogels for strain sensors. It shows a high conductivity (1.3 S/m), an ultrafast self-healing ability (<3 s, 98% healing efficiency within 60 s), a high stretchability (∼1850 and ∼7000% in deformation), and reversible adhesivity on various material surfaces. The excellent performance of the hydrogel is ascribed to the cooperative and hierarchical interactions of four types of dynamic combinations, including the reversible borate bond, hydrogen bonding, electrostatic interaction, and polymer cluster interactions. The reversible fabrication process by the one-spot method (just by simple mixing of the components) and superior properties of the hydrogel make it an ideal candidate for a wearable strain sensor to monitor human motions and physiological activities. Moreover, it is also a good hydrogel absorbent for phase separation absorption of volatile organic compounds with a high capacity (for acetone: 4.75 g g-1), reusability, and an easy handling process.

Catalytic Mechanism of Oxygen Vacancies in Perovskite Oxides for Lithium-Sulfur Batteries.

Defective materials have been demonstrated to possess adsorptive and catalytic properties in lithium-sulfur (Li-S) batteries, which can effectively solve the problems of lithium polysulfides (LiPSs) shuttle and sluggish conversion kinetics during charging and discharging of Li-S batteries. However, there is still a lack of research on the quantitative relationship between the defect concentration and the adsorptive-catalytic performance of the electrode. In this work, perovskites Sr0.9 Ti1- x Mnx O3- δ (STMnx ) (x = 0.1-0.3) with different oxygen-vacancy concentrations are quantitatively regulated as research models. Through a series of tests of the adsorptive property and electrochemical performance, a quantitative relationship between oxygen-vacancy concentration and adsorptive-catalytic properties is established. Furthermore, the catalytic mechanism of oxygen vacancies in Li-S batteries is investigated using density functional theory calculations and in situ experiments. The increased oxygen vacancies can effectively increase the binding energy between perovskite and LiPSs, reduce the energy barrier of LiPSs decomposition reaction, and promote LiPSs conversion reaction kinetics. Therefore, the perovskite STMn0.3  with high oxygen-vacancy concentrations exhibits excellent LiPSs adsorptive and catalytic properties, realizing high-efficiency Li-S batteries. This work is helpful to realize the application of the quantitative regulation strategy of defect engineering in Li-S batteries.