P-doped RuSe2 on Porous N-doped Carbon Matrix as Catalysts for Accelerated Sulfur Redox Reactions.

Monocomponent catalysts exhibit the limited catalytic conversion of polysulfides due to their intrinsic electronic structure, but their catalytic activity can be improved by introducing heteroatoms to regulate its electronic structure. However, the rational selection principles of doping elements remain unclear. Here, we are guided by theoretical calculations to select the suitable doping elements based on the balanced relationship between the adsorption strength of lithium polysulfides (LiPSs) and catalytic activity of lithium sulfide. We apply the screening method to develop a new catalyst of phosphorus doped RuSe2, manifesting the further enhanced conductivity compared with original RuSe2, facilitating charge transfer and further modulating the d-band center of RuSe2, thereby augmenting its effectiveness in interacting with LiPSs. Consequently, the assembled cell exhibits an areal capacity of 7.7 mAh cm-2, even under high sulfur loading of 8.0 mg cm-2 and a lean electrolyte condition (5.0 µL mg-1). This rational screening strategy offers a robust solution for the design of advanced catalysts in the field of lithium-sulfur batteries and potentially other domains as well.

Bifunctional Role of High-Entropy Selenides in Accelerating Redox Conversion and Modulating Lithium Plating towards Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries, recognized as one of the most promising next-generation energy storage systems, are still limited by the "shuttle effect" of soluble polysulfides (LiPSs) on the cathode and the uncontrolled growth of lithium dendrites on the anode. These issues are critical obstacles to their practical application. Currently, many researchers have addressed these challenges from a unilateral perspective. Herein, we propose bifunctional hosts based on high-entropy selenides (HE-Se) to simultaneously tackle the persistent problems on both the positive and negative electrodes of Li-S batteries. On the one hand, HE-Se interacts with polysulfides to promote their conversion, effectively mitigating the shuttle effect. On the other hand, HE-Se provides multiple lithophilic sites during the initial nucleation of Li+, which reduces overpotential and exhibits excellent lithophilicity and cyclic stability. As a result, Li-S batteries incorporating the HE-Se host demonstrate outstanding performance in terms of rate capability and cycling stability. Additionally, the porous lithophilic HE-Se structure offers sufficient nucleation sites, inhibits the growth of dendritic lithium, and accommodates volume changes during charging and discharging cycles. This study highlights the potential of sulphophilic/lithophilic high-entropy materials in designing advanced Li-S batteries and encourages further exploration in this area.

Modulating the Coordination Chemistry of Cobalt Catalytic Sites by Ruthenium Species to Accelerate the Polysulfide Conversion Kinetics in Lithium-Sulfur Batteries.

The performance of lithium-sulfur batteries is compromised by the loss of sulfur as dissolved polysulfides in the electrolyte and consequently the polysulfide redox shutting effect. Accelerating the conversion kinetics of polysulfide intermediates into sulfur or lithium sulfide through electrocatalysis has emerged as a root-cause solution. Co-N-C composite electrocatalyst is commonly used for this purpose. It is illustrated here that how the effectiveness can be improved by modulating the coordination chemistry of Co-N-C catalytic sites through introducing Ru species (RuCo-NC). The well-dispersed Ru in the Co-NC carbon matrix altered the total charge distribution over the Co-N-C catalytic sites and led to the formation of electron-rich Co-N, which is highly active for the polysulfide conversion reactions. Using Ru to modulate the electronic structure in the Co-N-C configuration and the additional catalytic sites over the Ru-Nx species can manifest optimal adsorption behavior of polysulfides. Consequently, the sulfur cathode with RuCo-NC can reduce the capacity fade rate from 0.11 % per cycle without catalyst (initial capacity of 701 mAh g-1) to 0.054 % per cycle (initial capacity of 1074 mAh g-1) over 400 cycles at 0.2 C rate. The results of this study provide the evidence for a feasible catalyst modification strategy for the polysulfide electrocatalysis.

Multifunctional Heterostructured Fe3O4-FeTe@MCM Electrocatalyst Enabling High-Performance Practical Lithium-Sulfur Batteries Via Built-in Electric Field.

The development of capable of simultaneously modulating the sluggish electrochemical kinetics, shuttle effect, and lithium dendrite growth is a promising strategy for the commercialization of lithium-sulfur batteries. Consequently, an elaborate preparation method is employed to create a host material consisting of multi-channel carbon microspheres (MCM) containing highly dispersed heterostructure Fe3O4-FeTe nanoparticles. The Fe3O4-FeTe@MCM exhibits a spontaneous built-in electric field (BIEF) and possesses both lithophilic and sulfophilic sites, rendering it an appropriate host material for both positive and negative electrodes. Experimental and theoretical results reveal that the existence of spontaneous BIEF leads to interfacial charge redistribution, resulting in moderate polysulfide adsorption which facilitates the transfer of polysulfides and diffusion of electrons at heterogeneous interfaces. Furthermore, the reduced conversion energy barriers enhanced the catalytic activity of Fe3O4-FeTe@MCM for expediting the bidirectional sulfur conversion. Moreover, regulated Li deposition behavior is realized because of its high conductivity and remarkable lithiophilicity. Consequently, the battery exhibited long-term stability for 500 cycles with 0.06% capacity decay per cycle at 5 C, and a large areal capacity of 7.3 mAh cm-2 (sulfur loading: 9.73 mg cm-2) at 0.1 C. This study provides a novel strategy for the rational fabrication of heterostructure hosts for practical Li-S batteries.

Polysulfide regulation by defect-modulated Ta3N5-x electrocatalyst toward superior room-temperature sodium-sulfur batteries.

Resolving low sulfur reaction activity and severe polysulfide dissolution remains challenging in metal-sulfur batteries. Motivated by a theoretical prediction, herein, we strategically propose nitrogen-vacancy tantalum nitride (Ta3N5-x) impregnated inside the interconnected nanopores of nitrogen-decorated carbon matrix as a new electrocatalyst for regulating sulfur redox reactions in room-temperature sodium-sulfur batteries. Through a pore-constriction mechanism, the nitrogen vacancies are controllably constructed during the nucleation of Ta3N5-x. The defect manipulation on the local environment enables well-regulated Ta 5d-orbital energy level, not only modulating band structure toward enhanced intrinsic conductivity of Ta-based materials, but also promoting polysulfide stabilization and achieving bifunctional catalytic capability toward completely reversible polysulfide conversion. Moreover, the interconnected continuous Ta3N5-x-in-pore structure facilitates electron and sodium-ion transport and accommodates volume expansion of sulfur species while suppressing their shuttle behavior. Due to these attributes, the as-developed Ta3N5-x-based electrode achieves superior rate capability of 730 mAh g-1 at 3.35 A g-1, long-term cycling stability over 2000 cycles, and high areal capacity over 6 mAh cm-2 under high sulfur loading of 6.2 mg cm-2. This work not only presents a new sulfur electrocatalyst candidate for metal-sulfur batteries, but also sheds light on the controllable material design of defect structure in hopes of inspiring new ideas and directions for future research.

Interfacial Synergy in Mo2C/MoC Heterostructure Promoting Sequential Polysulfide Conversion in High-Performance Lithium-Sulfur Battery.

A rational design of sulfur host is the key to conquering the"polysulfide shuttle effects" by accelerating the polysulfide conversion. Since the process involves solid-liquid-solid multistep phase transitions, purposely-engineered heterostructure catalysts with various active regions for catalyzing conversion steps correspondingly are beneficial to promote the overall conversion process. However, the functionalities of the materials surface and interface in heterostructure catalysts remain unclear. In this work, an Mo2C/MoC catalyst with abundant Mo2C surface-interface-MoC surface tri-active-region is developed by in situ converting the MoZn-metal organic framework. The experimental and simulation studies demonstrate the interface can catch long-chain polysulfides and promote their conversion. Instead, the Mo2C and MoC tend to accommodate the short-chain polysulfide and accelerate their conversion and the Li2S dissociation. Benefitting from the high catalytic ability, the Li-S battery assembled with the Mo2C/MoC-S cathode shows more discrete redox reactions and delivers a high initial capacity of 1603.6 mAh g-1 at 1 C charging-discharging rate, which is over twofolds of the one assembled using individual hosts, and 80.4% capacity can be maintained after 1000 cycles at 3 C rate. This work has demonstrated a novel synergy between the interface and material surface, which will help the future design of high-performance Li-S batteries.

Undercoordination Chemistry of Sulfur Electrocatalyst in Lithium-Sulfur Batteries.

Undercoordination chemistry is an effective strategy to modulate the geometry-governed electronic structure and thereby regulate the activity of sulfur electrocatalysts. Efficient sulfur electrocatalysis is requisite to overcome the sluggish kinetics in lithium-sulfur (Li-S) batteries aroused by multi-electron transfer and multi-phase conversions. Recent advances unveil the great promise of undercoordination chemistry in facilitating and stabilizing sulfur electrochemistry, yet a related review with systematicness and perspectives is still missing. Herein, it is carefully combed through the recent progress of undercoordination chemistry in sulfur electrocatalysis. The typical material structures and operational strategies are elaborated, while the underlying working mechanism is also detailly introduced and generalized into polysulfide adsorption behaviors, polysulfide conversion kinetics, electron/ion transport, and dynamic reconstruction. Moreover, perspectives on the future development of undercoordination chemistry are further proposed.

A Facilely Synthesized NiCo2S4 with Two Mutually Reinforcing Active Sites for High-Performance Lithium-Sulfur Batteries.

The shuttle effect and slow conversion kinetics of soluble polysulfides hinder the commercial application of lithium-sulfur batteries (LSBs). In this context, we propose a three-dimensional lamellar-stacked nanostructure of nickel cobalt sulfide (D-NiCo2S4) enriched with lattice defects by manipulating the cations in spinel sulfides. It has an obvious synergistic promotion mechanism for the adsorption and catalysis of lithium sulfides. Specifically, Ni3+ on tetrahedral (Td) sites with strong Ni-S covalency anchors LiPSs, whereas Co3+ on octahedral (Oh) sites promotes a highly efficient catalytic conversion of LiPSs, which is confirmed by experimental results and density functional theory (DFT) calculations. Besides, the crystal defects and distortions in the lamellar region could expose more active sites and enhance the redox reaction kinetics of polysulfides. Hence, Li-S batteries with D-NiCo2S4@S as the cathode show outstanding cycle stability; upon cycling at 1 A/g, the battery achieves a high initial specific capacity of 1001.12 and 655.31 mAh g-1 after 1000 cycles (decay rate as low as 0.05% per cycle), as well as a high initial areal capacity of 3.15 mAh cm-2 under high S loading (4.2 mg cm-2). This work provides a viable scheme for designing efficient bimetal sulfide catalysts and furnishes a rational strategy for constructing LSB cathodes with high specific capacity and high area capacity.

Highly stable lithium sulfur batteries enhanced by flocculation and solidification of soluble polysulfides in routine ether electrolyte.

Lithium-sulfur batteries (LSBs) are among the most promising next-generation high energy density energy-storage systems. However, practical application has been hindered by fundamental problems, especially shuttling by the higher-order polysulfides (PSs) and slow redox kinetics. Herein, a novel electrolyte-based strategy is proposed by adding an ultrasmall amount of the low-cost and commercially available cationic antistatic agent octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate (SN) into a routine ether electrolyte. Due to the strong cation-anion interaction and bridge-bonding with SN, rapid flocculation of the soluble polysulfide intermediates into solid-state polysulfide-SN sediments is found, which significantly inhibited the adverse shuttling effect. Moreover, a catalytic effect was also demonstrated for conversion of the polysulfide-SN intermediates, which enhanced the redox kinetics of Li-S batteries. Encouragingly, for cells with only 0.1 % added SN, an initial specific capacity of 783.6 mAh/g and a retained specific capacity of 565.7 mAh/g were found at 2C after 200 cycles, which corresponded to an ultralow capacity decay rate of only 0.014 % per cycle. This work may provide a simple and promising regulation strategy for preparing highly stable Li-S batteries.

Steering Bidirectional Sulfur Redox via Geometric/Electronic Mediator Comodulation for Li-S Batteries.

Mediator design has stimulated ever-increasing attention to help tackle a surge of detrimental caveats in Li-S realms, mainly pertaining to rampant polysulfide shuttling and sluggish redox kinetics. Nevertheless, universal designing philosophy, despite being highly sought-after, remains still elusive to date. Herein, we present a generic and simple material strategy to allow the target fabrication of advanced mediator toward boosted sulfur electrochemistry. This trick is done by the geometric/electronic comodulation of a prototype VN mediator, where the interplay of its triple-phase interface, favorable catalytic activity, and facile ion diffusivity is conducive to steering bidirectional sulfur redox kinetics. In laboratory tests, the thus-derived Li-S cells manifest impressive cyclic performances with a capacity decay rate of 0.07% per cycle over 500 cycles at 1.0 C. Moreover, under a sulfur loading of 5.0 mg cm-2, the cell could sustain a durable areal capacity of 4.63 mAh cm-2. Our work is anticipated to lay a theory-to-application foundation for rationalizing the design and modulation of reliable polysulfide mediators in working Li-S batteries.

Adaptively Reforming Natural Enzyme to Activate Catalytic Microenvironment for Polysulfide Conversion in Lithium-Sulfur Batteries.

Catalyzing polysulfide conversion is a promising way toward accelerating complex and sluggish sulfur redox reactions (SRRs) in lithium-sulfur batteries. Reasonable alteration of an enzyme provides a new means to expand the natural enzyme universe to catalytic reactions in abiotic systems. Herein, we design and fabricate a denatured hemocyanin (DHc) to efficiently catalyze the SRR. After denaturation, the unfolded ß-sheet architectures with exposed rich atomically dispersed Cu, O, and N sites and intermolecular H-bonds are formed in DHc, which not only provides the polysulfides for a strong spatial confinement effect in microenvironment via S-O and Li···N interactions but also activates chemical channels for electron/Li+ transport into the Cu active center via H/Li-bonds to catalyze polysulfide conversion. As expected, the charge/discharge kinetics of DHc-containing cathodes is fundamentally improved in cyclability with nearly 100% Coulombic efficiency and capacity even under high sulfur loading (4.3 mg cm-2) and lean-electrolyte (8 µL mg-1) conditions.

Single-Atom Vanadium Catalyst Boosting Reaction Kinetics of Polysulfides in Na-S Batteries.

The practical application of the room-temperature sodium-sulfur (RT Na-S) batteries is hindered by the insulated sulfur, the severe shuttle effect of sodium polysulfides, and insufficient polysulfide conversion. Herein, on the basis of first principles calculations, single-atom vanadium anchored on a 3D nitrogen-doped hierarchical porous carbon matrix (denoted as 3D-PNCV) is designed and fabricated to enhance sulfur reactivity, and adsorption and catalytic conversion performance of sodium polysulfide. The 3D-PNCV host with abundant and active V sites, hierarchical porous structure, high electrical conductivity, and strong chemical adsorption/conversion ability of V-N bonding can immobilize the polysulfides and promote reversibly catalytic conversion of polysulfides toward Na2 S. Therefore, as-fabricated RT Na-S batteries can achieve a high reversible capacity (445 mAh g-1 over 800 cycles at 5 A g-1 ) and excellent rate capability (224 mAh g-1 at 10 A g-1 ). The electrocatalysis mechanism of sodium polysulfides is further experimentally and theoretically revealed, which provides a new strategy to develop the highly stable RT Na-S batteries.

Dual-Functional Hosts for Polysulfides Conversion and Lithium Plating/Stripping towards Lithium-Sulfur Full Cells.

The practical application of lithium-sulfur (Li-S) batteries is greatly hindered by the shuttle effect of dissolved polysulfides in the sulfur cathode and the severe dendritic growth in the lithium anode. Adopting one type of effective host with dual-functions including both inhibiting polysulfide dissolution and regulating Li plating/stripping, is recently an emerging research highlight in Li-S battery. This review focuses on such dual-functional hosts and systematically summarizes the recent research progress and application scenarios. Firstly, this review briefly describes the stubborn issues in Li-S battery operations and the sophisticated counter measurements over the challenges by dual-functional behaviors. Then, the latest advances on dual-functional hosts for both cathode and anode in Li-S full cells are catalogued as species, including metal chalcogenides, metal carbides, metal nitrides, heterostuctures, and the possible mechanisms during the process. Besides, we also outlined the theoretical calculation tools for the dual-functional host based on the first principles. Finally, several sound perspectives are also rationally proposed for fundamental research and practical development as guidelines.

Mesoporous hierarchical NiCoSe2-NiO composite self-supported on carbon nanoarrays as synergistic electrocatalyst for flexible lithium-sulfur batteries.

Lithium-sulfur batteries (LSBs) have enormous application potential in the flexible energy storage field due to their large theoretical specific capacities and high energy densities. However, lithium-sulfur batteries face a notorious shuttle effect problem. To address this challenge, this work reports a three-dimensional (3D) structure of binary transition metal selenides (B-TMSe) hierarchical composites (CC/NiCoSe2-NiO) on carbon cloth as a self-supporting sulfur host for flexible LSBs. According to the density functional theory (DFT) calculations, NiCoSe2can exert a synergetic effect of high affinity with Lithium polysulfides (LiPSs) and electrocatalytic activity to lower the adsorption energy barrier and accelerate the sluggish reaction kinetics of polysulfides. Consequently, the CC/NiCoSe2-NiO-based electrodes realize a large specific capacity of approximately 1363 mAh/g at a current density of 0.1C, excellent rate performance (454.66 mAh/g at 5C) and a reversible specific capacity of 978.9 mAh/g at 1C, along with impressive cycling stability with an attenuation rate of 0.038% per cycle for 1000 cycles. They also achieve a large reversible cycle capacity of 919.43 mAh/g at 0.2C even at a high sulfur loading (3.5 mg/cm2). With a lean electrolyte (E/S ratio 10 µL/mg) and a high sulfur loading of 2.65 mg/cm2, a large capacity of 934.1 mAh/g is retained after 150 cycles at 0.5C. The assembled pouch cells from S@CC/NiCoSe2-NiO electrodes show a high initial discharge capacity of 1039.5 mAh/g at 1C at a sulfur loading of 2.65 mg/cm2 and maintain strong stability under high twisting and buckling.

Crystal phase engineering of nanoflower-like hollow MoSe2boosting polysulfide conversion for lithium-sulfur batteries.

The battery performance of sulfur cathode has obviously depended on the redox reaction kinetics of polysulfides upon cycling. Herein, an effective strategy was proposed to achieve the conversion from 2H (semiconductor phase) to 1T (metal phase) in hollow nano-flowered molybdenum selenide sphere (HFSMS) through crystal phase engineering. The HFSMS with different phase ratio was realized by regulating the proportion of reducing agents. Specifically, the 1T phase content can reach up to 60.8%, and then subsequently decreased to 59.1% with the further increase of the reducing agent. The as-prepared HFSMS with the 1T phase content of 60.8% showed a smallest Tafel slopes (49.99 and 79.65 mV/dec in reduction and oxidation process, respectively), fastest response time and highest response current (520 s, 0.459 mA in Li2S deposition test), which further exhibited excellent catalytic activity and faster reaction kinetics. This result was verified by electrochemical performance, which manifested as stable cycle life with only 0.112% capacity decay per cycle. It was found that the hollow structure can ensures a rich sulfur storage space, and effectually buffer the volume changes of the active substance. More importantly, the improved performance is attributed to the introduction of the 1T phase, which significantly improves the catalytic activity of MoSe2with promoting the polysulfide conversion.

Carbon-Nitride-Based Materials for Advanced Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are promising candidates for next-generation energy storage systems owing to their high energy density and low cost. However, critical challenges including severe shuttling of lithium polysulfides (LiPSs) and sluggish redox kinetics limit the practical application of Li-S batteries. Carbon nitrides (CxNy), represented by graphitic carbon nitride (g-C3N4), provide new opportunities for overcoming these challenges. With a graphene-like structure and high pyridinic-N content, g-C3N4 can effectively immobilize LiPSs and enhance the redox kinetics of S species. In addition, its structure and properties including electronic conductivity and catalytic activity can be regulated by simple methods that facilitate its application in Li-S batteries. Here, the recent progress of applying CxNy-based materials including the optimized g-C3N4, g-C3N4-based composites, and other novel CxNy materials is systematically reviewed in Li-S batteries, with a focus on the structure-activity relationship. The limitations of existing CxNy-based materials are identified, and the perspectives on the rational design of advanced CxNy-based materials are provided for high-performance Li-S batteries.

Desolvation Synergy of Multiple H/Li-Bonds on an Iron-Dextran-Based Catalyst Stimulates Lithium-Sulfur Cascade Catalysis.

Traditional lithium-sulfur battery catalysts are still facing substantial challenges in solving sulfur redox reactions, which involve multistep electron transfer and multiphase transformations. Here, inspired by the combination of iron dextran (INFeD) and ascorbic acid (VC) as a blood tonic for the treatment of anemia, a highly efficient VC@INFeD catalyst is developed in the sulfur cathode, accomplishing the desolvation and enrichment of high-concentration solvated lithium polysulfides at the cathode/electrolyte interface with the assistance of multiple H/Li-bonds and resolving subsequent sulfur transformations through gradient catalysis sites where the INFeD promotes long-chain lithium polysulfide conversions and VC accelerates short-chain lithium polysulfide conversions. Comprehensive characterizations reveal that the VC@INFeD can substantially reduce the energy barrier of each sulfur redox step, inhibit shuttle effects, and endow the lithium-sulfur battery with high sulfur utilization and superior cycling stability even under a high sulfur loading (5.2 mg cm-2 ) and lean electrolyte (electrolyte/sulfur ratio, ≈7 µL mg-1 ) condition.

Carbon Coated Metal-Based Composite Electrode Materials for Lithium Sulfur Batteries: A Review.

Lithium-sulfur battery is one of the most promising secondary battery systems due to their high energy density and low material cost. During the past decade, great progress has been achieved in promoting the performances of Li-S batteries by addressing the challenges at the laboratory-level model systems. With growing attention paid to the application of Li-S batteries, new challenges at practical cell scales emerge as the bottleneck. However, challenges remain for the commercialization of lithium-sulfur batteries. The current review mainly focused on metal-based catalysts decorated-carbon materials for enhanced lithium sulfur battery performance. Firstly, the synthesis methods of various carbon-sulfur composites are discussed, as well as the influence of different material structures on the electrochemical performance. Secondly, a variety of catalysts, including metal atoms, metal oxides, sulfides, phosphides, nitrides, and carbide-decorated carbon nanomaterials, are systematically introduced to determine how lithium can be enhanced by suppressing polysulfides and promoting redox conversion reactions. Also, analyzed the multi-step electrochemical reaction mechanism of the battery during the charging and discharging process, and provide a feasible path for the practical application of high energy density lithium-sulfur batteries.

Sacrificial Template Method to Synthesize Atomically Dispersed Mn Atoms on S, N-Codoped Carbon as a Separator Modifier for Advanced Li-S Batteries.

Efficient and durable electrocatalysts are important for polysulfide conversion in high-performance Li-S batteries. Herein, we report a sacrificial template strategy to synthesize a sulfur/nitrogen-codoped carbon-supported manganese (Mn) single-atom catalyst (Mn/SNC). The synthesis is enabled by fabricating a novel precursor, i.e., cadmium sulfide (CdS) wrapped with Mn ion-impregnated polyporrole (CdS@Mn-PPy), and subsequent pyrolysis. During pyrolysis, the CdS template is decomposed into Cd and S, PPy-derived carbon is doped with N and S, and Mn ions are reduced to Mn atoms, forming Mn-N active sites. The evaporation of Cd atoms/clusters creates abundant pores in the carbon substrate to expose the active sites and facilitate ion transport, and S atoms can form edge C-S-C bonds to improve the activity of Mn-N sites. Benefiting from the above advantages, the Mn/SNC catalyst markedly enhances the performance of Li-S batteries, delivering an initial capacity of 1563.7 mAh g-1 at 0.1C, a capacity decay of only 0.037% per cycle after 1600 cycles at 2C; a capacity of 1045.1 mAh g-1 at a high sulfur loading of 7.44 mg cm-2 at 0.2C, and a capacity retention of 73.1% after 180 cycles. This work provides a strategy that may benefit further the rational design and development of single-atom catalysts for application in renewable energy.

Oxidation States Regulation of Cobalt Active Sites through Crystal Surface Engineering for Enhanced Polysulfide Conversion in Lithium-Sulfur Batteries.

In this work, unique Co3 O4 /N-doped reduced graphene oxide (Co3 O4 /N-rGO) composites as favorable sulfur immobilizers and promoters for lithium-sulfur (Li-S) batteries are developed. The prepared Co3 O4  nanopolyhedrons (Co3 O4 -NP) and Co3 O4  nanocubes mainly expose (112) and (001) surfaces, respectively, with different atomic configurations of Co2+ /Co3+ sites. Experiments and theoretical calculations confirm that the octahedral coordination Co3+ (Co3+ Oh ) sites with different oxidation states from tetrahedral coordination Co2+ sites optimize the adsorption and catalytic conversion of lithium polysulfides. Specially, the Co3 O4 -NP crystals loaded on N-rGO expose (112) planes with ample Co3+ Oh active sites, exhibiting stronger adsorbability and superior catalytic activity for polysulfides, thus inhibiting the shuttle effect. Therefore, the S@Co3 O4 -NP/N-rGO cathodes deliver excellent electrochemical properties, for example, stable cyclability at 1 C with a low capacity decay rate of 0.058% over 500 cycles, superb rate capability up to 3 C, and high areal capacity of 4.1 mAh cm-2 . This catalyst's design incorporating crystal surface engineering and oxidation state regulation strategies also provides new approaches for addressing the complicated issues of Li-S batteries.