Lithium‐sulfur (Li‐S) batteries are one of the most promising next‐generation energy‐storage systems. Nevertheless, the sluggish sulfur redox and shuttle effect in Li‐S batteries are the major obstacles to their commercial application. Previous investigations on adsorption for LiPSs have made great progress but cannot restrain the shuttle effect. Catalysts can enhance the reaction kinetics, and then alleviate the shuttle effect. The synergistic relationship between adsorption and catalysis has become the hotspot for research into suppressing the shuttle effect and improving battery performance. Herein, the adsorption‐catalysis synergy in Li‐S batteries is reviewed, the adsorption‐catalysis designs are divided into four categories: adsorption‐catalysis for LiPSs aggregation, polythionate or thiosulfate generation, and sulfur radical formation, as well as other adsorption‐catalysis. Then advanced strategies, future perspectives, and challenges are proposed to aim at long‐life and high‐efficiency Li‐S batteries.

despite all these promises, three intrinsic drawbacks need to be resolved before fulfilling the promise of the market potential.First, the most stable but electronically insulating S 8 (≈10 −14 S cm −2 ) with cyclic configuration is used as the starting material in Li-S cathode, significantly limiting the full utilization of the active materials to reach the theoretical capacity. Therefore, it is the first priority to design the cathode that ensures the maximum usage of the starting materials, which sets the upper limit of the capacity performance. Second, the muti-step reduction process releases highly soluble lithium polysulfides (LiPSs) intermediates (Li 2 S x , where x = 4-8) into the organic electrolyte. [6] Unlike the batteries based on ion-insertion mechanism, [7,8] Li-S battery possesses unique and complex electrochemical/chemical processes during operation. During galvanostatic discharge process, two distinct plateaus can be verified at about 2.4 and 2.1 V in the voltage profile, corresponding to the reduction of sulfur into long-chain polysulfides and subsequent reaction from short-chain polysulfides to Li 2 S, respectively. [9] Further investigations about the reaction mechanism of Li-S battery based on experimental and theoretical studies reveal that the existence of various intermediates during electrochemical processes, indicating much more complex battery chemistry compared to the simple stepwise reaction model. [10,11] As a result, the soluble intermediates can diffuse through the polymeric separator to the anode surface, causing the loss of active materials and degradation of anode. Third, the density difference between the starting material (sulfur, 2.07 g cm −3 ) and discharge product (Li 2 S, 1.66 g cm −3 ) causes significant volumetric change during continuous cycling, damaging the integrity of the cathode structure and leading to serious capacity fading. [12] Besides above problems concerning the cathode side of the Li-S battery, other issues arose on the anode side, such as the unstable solid-electrolyte interphase (SEI), surface passivation, and uncontrolled lithium dendrite growth. [13][14][15] Stemmed from the basic problems mentioned above from the very beginning of the designed Li-S battery systems, various derivative problems were gradually unraveled during persistent efforts for improving the battery performance to approach the ultimate goal for commercialization. In the past decade, fundamental studies about Li-S battery were carried in laboratories all over the world, and it gradually put the puzzle together while brought promising performance improvement. [11,[16][17][18][19][20] However, to date, most of the lab-scale progresses have been based on batteries with sulfur loading lower than 2 mg cm −2 , Lithium-sulfur (Li-S) batteries, due to the high theoretical energy density, are regarded as one of the most promising candidates for breaking the limitations of energy-storage system based on Li-ion batteries. Tremendous efforts have been made to meet the challenge of high-performan...

Fast lithium ion transport with a high current density is critical for thick sulfur cathodes, stemming mainly from the difficulties in creating effective lithium ion pathways in high sulfur content electrodes. To develop a high-rate cathode for lithium-sulfur (Li-S) batteries, extenuation of the lithium ion diffusion barrier in thick electrodes is potentially straightforward. Here, a phyllosilicate material with a large interlamellar distance is demonstrated in high-rate cathodes as high sulfur loading. The interlayer space (≈1.396 nm) incorporated into a low lithium ion diffusion barrier (0.155 eV) significantly facilitates lithium ion diffusion within the entire sulfur cathode, and gives rise to remarkable nearly sulfur loading-independent cell performances. When combined with 80% sulfur contents, the electrodes achieve a high capacity of 865 mAh g at 1 mA cm and a retention of 345 mAh g at a high discharging/charging rate of 15 mA cm , with a sulfur loading up to 4 mg. This strategy represents a major advance in high-rate Li-S batteries via the construction of fast ions transfer paths toward real-life applications, and contributes to the research community for the fundamental mechanism study of loading-independent electrode systems.

recognized that the safety of LiBs is closely associated with the highly flammable separator and liquid organic electrolytes, for example, polypropylene (PP), ethylene carbonate (EC), and diethyl carbonate (DEC). To this date, considerable efforts have been focused on overcoming the inflammable problem, such as: (1) adding refractories into electrolytes, [11] (2) tracing dendrite evolution via a smart separator for early warning, [12] (3) coating the separator with a ceramic layer for thermal-switching the current collector. [13] Although it is efficient to reduce the flammability, the risk of battery fire still exists, especially for lithium metal battery with excessive metal lithium. In addition, these batteries were mostly traditional LiBs (LiFePO 4 , LiCoO 2 , LiMn 2 O 4 , etc.), which still cannot meet the increasing energy density requirement of next-generation batteries. [7,14,15] Owning a specific capacity as high as 1675 mA h g −1 , lithium-sulfur (Li-S) batteries are promising for next-generation energy storage. Despite great promise, the shuttle effect, due to the dissolution of polysulfides (PS) in the electrolyte, leading to a rapidly fading capacity with recharge process, still impedes the commercialization of Li-S batteries. Tremendous efforts have been devoted to developing advanced cathodes with suppressed shuttle Lithium-sulfur (Li-S) batteries are of considerable research interest for their application potentials in high-density energy storage. However, the practical application of Li-S batteries is severely plagued by polysulfide (PS) dissolution and serious safety concerns caused by flammable sulfur and polymer separators. Herein, a nonflammable multifunctional separator for efficient suppression of PS dissolution and high-temperature performance of Li-S batteries is reported. Polyacrylonitrile (PAN) and ammonium polyphosphate (APP) are electrospun into a multifunctional separator (PAN@APP) for stable and safe Li-S batteries. Owing to the abundant amine groups and phosphate radical in APP, the PAN@APP separator has strong binding interactions with PS, which exerts strong charge repulsion to suppress the transport of negatively charged PS ions and free radicals. Furthermore, refractory APP ensures the stability of the battery at high temperatures. Using the PAN@APP separator, the Li-S battery demonstrates a capacity retention of 83% over 800 cycles. This work provides a robust materials platform for stable and safe Li-S batteries and points to a direction to close the current gap facing the commercialization of high-energy next-generation electrochemical conversion/storage devices.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/aenm.201802441.With the rapidly increasing demand for electric vehicles, lithium-ion batteries (LiBs) have attracted extensive attention owing to their high specific energy density, low cost, and rechargeable performances. [1][2][3][4][5][6][7][8][9][10] However, increased complexity of application conditio...

A boron dopant is experimentally and theoretically confirmed to effectively modulate the d-band center of a single-atom catalyst, enabling favorable adsorption kinetics of oxygen intermediates and thus greatly improving the ORR performance.