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ConspectusLithium-sulfur (Li-S) batteries have attracted worldwide attention as promising next-generation rechargeable batteries due to their high theoretical energy density of 2600 Wh kg -1 . The actual energy density of Li-S batteries at the pouch cell level has significantly exceeded that of state-of-the-art Li-ion batteries. However, the overall performances of Li-S batteries under practical working conditions are limited by the sluggish conversion kinetics of the sulfur cathodes. To overcome the above challenge, various kinetic promotion strategies have been proposed to accelerate the multiphase and multi-electron cathodic redox reactions between sulfur, lithium polysulfides (LiPSs), and lithium sulfide. Nowadays, kinetic promoters have been massively employed in sulfur cathodes to achieve Li-S batteries with high energy densities, high rates, and long lifespans. A comprehensive and timely summary of cutting-edge kinetic promoters for sulfur cathodes is of great essence to afford an in-depth understanding of the unique Li-S electrochemistry.In this Account, we outline the recent efforts on the design of sulfur cathode kinetic promoters for advanced Li-S batteries. The latest progress is discussed in detail regarding heterogeneous, homogeneous, and semi-immobilized kinetic promoters. Heterogeneous promoters, representatively known as electrocatalysts, function mainly by reducing the energy barriers of the interfacial electrochemical reactions. The working mechanism, activity regulation strategies, and reconstitution/deactivation processes of the heterogeneous promoters are reviewed to provide guiding principles for rational design. In comparison, homogeneous promoters are able to fully contact with the reaction interfaces and regulate the electron/ion-inaccessible reactants in working Li-S batteries. Redox mediators and redox comediators are typical homogeneous promoters. The former establishes extra chemical reaction pathways to circumvent the originally sluggish steps and boost the overall kinetics, while the latter fundamentally modifies the LiPS molecules to enhance their redox kinetics. For semi-immobilized promoters, the active units are generally anchored on the cathode substrate through flexible chains with mobile characteristics. Such a design endows the promoter with both heterogeneous and homogeneous characteristics to comprehensively regulate the multiphase sulfur redox reactions involving both mobile and immobile reactants.Overall, this Account summarizes the fundamental electrochemistry, design principles, and practical promotion effects of the various kinetic promoters used for the sulfur cathodes in Li-S batteries. We believe that this Account will provide an in-depth and cutting-edge understanding of the unique sulfur electrochemistry, thereby providing guidance for further development of high-performance Li-S batteries and analogous rechargeable battery systems.

Single-atom catalysts exhibit promising electrocatalytic activity, a trait that can be further enhanced through the introduction of heteroatom doping within the carbon skeleton. Nonetheless, the intricate relationship between the doping positions and activity remains incompletely elucidated. This contribution sheds light on an inductive effect of single-atom sites, showcasing that the activity of the oxygen reduction reaction (ORR) can be augmented by reducing the spatial gap between the doped heteroatom and the single-atom sites. Drawing inspiration from this inductive effect, we propose a synthesis strategy involving ligand modification aimed at precisely adjusting the distance between dopants and single-atom sites. This precise synthesis leads to optimized electrocatalytic activity for the ORR. The resultant electrocatalyst, characterized by Fe-N 3 P 1 single-atom sites, demonstrates remarkable ORR activity, thus exhibiting great potential in zinc-air batteries and fuel cells.

Selective electroreduction of CO 2 to C 1 feed gas provides an attractive avenue to store intermittent renewable energy. However, most of the CO 2 -to-CO catalysts are designed from the perspective of structural reconstruction, and it is challenging to precisely design a meaningful confining microenvironment for active sites on the support. Herein, we report a local sulfur doping method to precisely tune the electronic structure of an isolated asymmetric nickel-nitrogen-sulfur motif (Ni 1 -NSC). Our Ni 1 -NSC catalyst presents >99% faradaic efficiency for CO 2 -to-CO under a high current density of -320 mA cm -2 . In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy and differential electrochemical mass spectrometry indicated that the asymmetric sites show a significantly weaker binding strength of *CO and a lower kinetic overpotential for CO 2 -to-CO. Further theoretical analysis revealed that the enhanced CO 2 reduction reaction performance of Ni 1 -NSC was mainly due to the effectively decreased intermediate activation energy.

Tuning bimetallic effects is a promising strategy to guide catalytic properties. However, the nature of these effects can be difficult to assess and compare due to the convolution with other factors such as the catalyst surface structure and morphology and differences in testing environments. Here, we investigate the impact of atomic-scale bimetallic effects on the electrochemical CO 2 reduction performance of Cu-based catalysts by leveraging a systematic approach that unifies protocols for materials synthesis and testing and enables accurate comparisons of intrinsic catalytic activity and selectivity. We used the same physical vapor deposition method to epitaxially grow Cu(100) films decorated with a small amount of noble or base metal atoms and a combination of experimental characterization and first-principles calculations to evaluate their physicochemical and catalytic properties. The results indicate that the metal atoms segregate to under-coordinated Cu sites during physical vapor deposition, suppressing CO reduction to oxygenates and hydrocarbons and promoting competing pathways to CO, formate, and hydrogen. Leveraging these insights, we rationalize bimetallic design principles to improve catalytic selectivity for CO 2 reduction to CO, formate, oxygenates, or hydrocarbons. Our study provides one of the most extensive studies on Cu bimetallics for CO 2 reduction, establishing a systematic approach that is broadly applicable to research in catalyst discovery.

By application of a newly designed T-shaped ligand 5-(4-pyridin-4-yl-benzoylamino)isophthalic acid (H 2 PBAI) to assemble with Zn(II) ions under solvothermal conditions, a novel porous polyhedral metal-organic framework (Zn-PBAI) with pcu topology has been obtained. When treated as a precursor by annealing of Zn-PBAI at various temperatures, porous carbon polyhedra (PCP) were prepared and tested as an anode material for lithium-ion batteries. The results show that PCP carbonized at 1000 °C (PCP-1000) manifest the highest reversible specific capacity of about 1125 mAh g -1 at a current of 500 mA g -1 after 200 cycles, which is supposed to benefit from the large accessible specific area and high electric conductivity. Moreover, PCP-1000 electrode materials also exhibit superior cyclic stability and good rate capacity.

Self-healing capability helps biological systems to maintain their survivability and extend their lifespan. Similarly, self-healing is also beneficial to next-generation secondary batteries because high-capacity electrode materials, especially the cathodes such as oxygen or sulfur, suffer from shortened cycle lives resulting from irreversible and unstable phase transfer. Herein, by mimicking a biological self-healing process, fibrinolysis, we introduced an extrinsic healing agent, polysulfide, to enable the stable operation of sulfur microparticle (SMiP) cathodes. An optimized capacity (∼3.7 mAh cm -2 ) with almost no decay after 2000 cycles at a high sulfur loading of 5.6 mg (S) cm -2 was attained. The inert SMiP is activated by the solubilization effect of polysulfides whereas the unstable phase transfer is mediated by mitigated spatial heterogeneity of polysulfides, which induces uniform nucleation and growth of solid compounds. The comprehensive understanding of the healing process, as well as of the spatial heterogeneity, could further guide the design of novel healing agents (e.g., lithium iodine) toward high-performance rechargeable batteries.

Lithium-sulfur (Li-S) battery system is endowed with tremendous energy density, resulting from the complex sulfur electrochemistry involving multielectron redox reactions and phase transformations. Originated from the slow redox kinetics of polysulfide intermediates, the flood of polysulfides in the batteries during cycling induced low sulfur utilization, severe polarization, low energy efficiency, deteriorated polysulfide shuttle, and short cycling life. Herein, sulfiphilic cobalt disulfide (CoS2) was incorporated into carbon/sulfur cathodes, introducing strong interaction between lithium polysulfides and CoS2 under working conditions. The interfaces between CoS2 and electrolyte served as strong adsorption and activation sites for polar polysulfides and therefore accelerated redox reactions of polysulfides. The high polysulfide reactivity not only guaranteed effective polarization mitigation and promoted energy efficiency by 10% but also promised high discharge capacity and stable cycling performance during 2000 cycles. A slow capacity decay rate of 0.034%/cycle at 2.0 C and a high initial capacity of 1368 mAh g(-1) at 0.5 C were achieved. Since the propelling redox reaction is not limited to Li-S system, we foresee the reported strategy herein can be applied in other high-power devices through the systems with controllable redox reactions.

Lithium-sulfur (Li-S) batteries, with a theoretical energy density of 2600 Wh kg(-1), are a promising platform for high-energy and cost-effective electrochemical energy storage. However, great challenges such as fast capacity degradation and safety concerns prevent it from widespread application. With the adoption of Li metal as the anode, dendritic and mossy metal depositing on the negative electrode during repeated cycles leads to serious safety concerns and low Coulombic efficiency. Herein, we report a distinctive graphene framework structure coated by an in situ formed solid electrolyte interphase (SEI) with Li depositing in the pores as the anode of Li-S batteries. The graphene-based metal anode demonstated a superior dendrite-inhibition behavior in 70 h of lithiation, while the cell with a Cu foil based metal anode was short-circuited after only 4 h of lithiation at 0.5 mA cm(-2). The graphene-modified Li anode with SEI induced by the polysulfide-containing electrolyte improved the Coulombic efficiency to ∼97% for more than 100 cycles, while the control sample with Cu foil as the current collector exhibited huge fluctuations in Coulombic efficiency. The unblocked ion pathways and high electron conductivities of frameworks in the modified metal anode led to the rapid transfer of Li ions through the SEI and endowed the anode framework with an ion conductivity of 7.81 × 10(-2) mS cm(-1), nearly quintuple that of the Cu foil based Li metal anode. Besides, the polarization in the charge-discharge process was halved to 30 mV. The stable and efficient Li deposition was maintained after 2000 cycles. Our results indicated that nanoscale interfacial electrode engineering could be a promising strategy to tackle the intrinsic problems of lithium metal anodes, thus improving the safety of Li-S cells.

Lithium-sulfur batteries hold great promise for serving as next generation high energy density batteries. However, the shuttle of polysulfide induces rapid capacity degradation and poor cycling stability of lithium-sulfur cells. Herein, we proposed a unique lithium-sulfur battery configuration with an ultrathin graphene oxide (GO) membrane for high stability. The oxygen electronegative atoms modified GO into a polar plane, and the carboxyl groups acted as ion-hopping sites of positively charged species (Li(+)) and rejected the transportation of negatively charged species (Sn(2-)) due to the electrostatic interactions. Such electrostatic repulsion and physical inhibition largely decreased the transference of polysulfides across the GO membrane in the lithium-sulfur system. Consequently, the GO membrane with highly tunable functionalization properties, high mechanical strength, low electric conductivity, and facile fabrication procedure is an effective permselective separator system in lithium-sulfur batteries. By the incorporation of a permselective GO membrane, the cyclic capacity decay rate is also reduced from 0.49 to 0.23%/cycle. As the GO membrane blocks the diffusion of polysulfides through the membrane, it is also with advantages of anti-self-discharge properties.

Hollow nanostructures afford intriguing structural features ranging from large surface area and fully exposed active sites to kinetically favorable mass transportation and tunable surface permeability. The unique properties and potential applications of graphene nanoshells with well-defined small cavities and delicately designed graphene shells are strongly considered. Herein, a mesoscale approach to fabricate graphene nanoshells with a single or few graphene layers and quite small diameters through a catalytic self-limited assembly of nanographene on in situ formed nanoparticles was proposed. The graphene nanoshells with a diameter of ca. 10-30 nm and a pore volume of 1.98 cm(3) g(-1) were employed as hosts to accommodate the sulfur for high-rate lithium-sulfur batteries. A very high initial discharge capacity of 1520 mAh g(-1), corresponding to 91% sulfur utilization rate at 0.1 C, was achieved on a graphene nanoshell/sulfur composite with 62 wt % loading. A very high retention of 70% was maintained when the current density increased from 0.1 C to 2.0 C, and an ultraslow decay rate of 0.06% per cycle during 1000 cycles was detected.

In this study, a novel recombinant type I antifreeze protein analogue (rAFP) was produced and secreted by Lactococcus lactis, a food-grade microorganism of major commercial importance. Antifreeze proteins are potent cryogenic protection agents for the cryopreservation of food and pharmaceutical materials. A food-grade expression and fermentation system (BSE- and antibiotic-free) for the production and secretion of high levels of rAFP was developed. Lyophilized, crude rAFP produced by L. lactis was tested in a frozen meat and frozen dough processing model. The frozen meat treated with the antifreeze protein showed less drip loss, less protein loss, and a high score on juiciness by sensory evaluation. Frozen dough treated with the rAFP showed better fermentation capacity than untreated frozen dough. Breads baked from frozen dough treated with rAFP acquired the same consumer acceptance as fresh bread.