Lithium Sulfur Research Articles

Advanced MXene materials: Paving the way for next-generation lithium-sulfur batteries in energy storage

Advanced MXene materials: Paving the way for next-generation lithium-sulfur batteries in energy storage

Empowering Low-Temperature Lithium-Sulfur Batteries: Unlocking the Potential of Transition Metal Alloy-Based Cathode Materials.

At low temperatures, lithium-sulfur (Li-S) batteries have poor kinetics, resulting in extreme polarization and decreased capacity. In this study, we investigated the electrochemical performance of Li-S batteries utilizing transition metal alloy-based cathode materials. Specifically, binary transition metal alloys (FeNi, FeCo, and NiCo) are integrated into a porous carbon nanofiber (CNF) matrix as composite cathode material. Our findings reveal that alloying metallic Ni with Fe in the FeNi@CNFs composite enhances the catalytic conversion of sulfur species, mitigating the shuttle effect and improving battery performance even under low temperatures. Li-S batteries employing a Li2S6/FeNi@CNFs cathode exhibited a significantly high initial discharge capacity of 1655 mAh g-1 at 0.1 C. Even at the higher current density of 10 C, the Li2S6/FeNi@CNFs composite can still reach an ultrahigh specific capacity of 828 mAh g-1. In addition, Li2S6/FeNi@CNFs demonstrated exceptional initial discharge capacities of 890.5 and 382.7 mAh g-1 at 0.1 C under -20 and -40 °C, respectively. With an initial capacity of 392.02 mAh g-1 and a capacity retention rate of 88.86% (after 60 cycles) at 0.2 C, the conversion of LiPSs in Li2S6/FeNi@CNFs is significantly enhanced even at ultralow temperatures of -40 °C. The findings of this study hold significant implications for the advancement of extremely low-temperature Li-S batteries.

An Electron-Coupled Co-ZrO2 Nanodot Heterojunction Electrocatalyst with Lewis Acid-Base Site Pairs Enables High Redox Reaction Kinetics of Li-S Batteries.

Using electrocatalysts is effective in solving the slow reaction kinetics of polysulfides in Li-S batteries, but designing stable electrocatalysts with an integrated adsorption-catalysis-desorption system is challenging. Here, we report a stable metal-semiconductor (Co-ZrO2) heterojunction electrocatalyst fabricated by assembling electron-coupled Co-ZrO2 nanodots into macroporous carbon nanofibers. The Co-ZrO2 contact causes interfacial electron enrichment and electron transfer from Co to ZrO2, which creates abundant Lewis-acid sites on Co that can adsorb polysulfides. Simultaneously, the enriched interfacial electrons can activate the S-S bond and boost the catalytic conversion of long-chain polysulfides, while the ZrO2 with Lewis-base sites facilitate the desorption of short-chain polysulfides from the electrocatalyst. Moreover, the nanodot heterojunctions show great chemical stability and high redox reaction kinetics of polysulfides. Li-S batteries show high discharge capacities of 954.5 mA h·g-1 at 0.5 C with a retention of 84.9% over 200 cycles, and 710.2 mA hg-1 at 1 C with a retention of 98.6% over 200 cycles. This study provides an effective strategy for developing active and durable electrocatalysts for Li-S batteries.

A Nitrogen/Oxygen Dual-Doped Porous Carbon with High Catalytic Conversion Ability toward Polysulfides for Advanced Lithium–Sulfur Batteries

Lithium–sulfur batteries (LSBs) have attracted widespread attention due to their high theoretical energy density and low cost. However, their development has been constrained by the shuttle effect of lithium polysulfides and their slow reaction kinetics. In this work, a nitrogen/oxygen dual-doped porous carbon (N/O-PC) was synthesized by annealing the precursor of zeolitic imidazolate framework-8 grown in situ on MWCNTs (ZIF-8/MWCNTs). Then, the N/O-PC composite served as an efficient host for LSBs through chemical adsorption and providing catalytic conversion sites of polysulfides. Moreover, the interconnected porous carbon-based structure facilitates electron and ion transfer. Thus, the S/N/O-PC cathode exhibits high cycling stability (a stable capacity of 685.9 mA h g−1 at 0.2 C after 100 cycles). It also demonstrates excellent rate performance with discharge capacities of 1018.2, 890.2, 775.1, 722.7, 640.4, and 579.6 mAh g−1 at 0.2, 0.5, 1.0, 2.0, 3.0, and 5.0 C, respectively. This work provides an effective strategy for designing and developing high energy density, long cycle life LSBs.

Developing Cathode Films for Practical All-Solid-State Lithium-Sulfur Batteries.

The development of all-solid-state lithium-sulfur batteries (ASSLSBs) toward large-scale electrochemical energy storage is driven by the higher specific energies and lower cost in comparison with the state-of-the-art Li-ion batteries. Yet, insufficient mechanistic understanding and quantitative parameters of the key components in sulfur-based cathode hinders the advancement of the ASSLSB technologies. This review offers a comprehensive analysis of electrode parameters, including specific capacity, voltage, S mass loading and S content toward establishing the specific energy (Wh kg-1) and energy density (Wh L-1) of the ASSLSBs. Additionally, this work critically evaluates the progress in enhancing lithium ion and electron percolation and mitigating electrochemical-mechanical degradation in sulfur-based cathodes. Last, a critical outlook on potential future research directions is provided to guide the rational design of high-performance sulfur-based cathodes toward practical ASSLSBs.

Tuning p‐Band Centers and Interfacial Built‐In Electric Field of Heterostructure Catalysts to Expedite Bidirectional Sulfur Redox for High‐Performance Li–S Batteries

AbstractTransition‐metal compound based heterostructures hold promise but challenge in expediting stepwise sulfur redox because of their inferior adsorption‐catalysis activity and unclear mechanism in Li–S batteries (LSBs). Herein, the p‐band centers and interfacial charge rearrangement of Mo‐doped VS2/MXene heterostructure are tuned through Mo doping and built‐in electric field (BIEF) effect to boost dual‐directional sulfur redox. Experimental and theoretical calculations demonstrate that Mo doping tunes the p‐band center of active S in VS2, shifting it positively toward the Fermi level to enhance the polysulfide adsorption ability and electrocatalytic activity. Whereas BIEF between Mo‐VS2 and MXene accelerates electrons transfer from MXene to Mo‐VS2 surface, generating more electrons accumulation at the surface‐S sites. Their synergy accelerates sulfur‐species conversion by reducing the energy barrier of polysulfide reduction and Li2S oxidation. Ultimately, S/Mo‐VS2/MXene cathode exhibits large initial capacity of 1387 mAh g−1at 0.2 C and stable 500‐cycle long‐term lifespan at 0.5 C. Impressively, the thick S/Mo‐VS2/MXene cathode (S loading: 5.4 mg cm−2, lean electrolyte: 4.5 µL mgsulfur−1) achieves a high areal capacity of 6.44 mAh cm−2 with 91.5% retention for 61 cycles. This work highlights the synergistic strategy of doping engineering and BIEF to tune the p‐band centers and interfacial charge rearrangement for designing high‐performance LSBs.

Amorphous bimetallic-organic framework enable accelerated redox kinetics and polysulfide trapping for lithium-sulfur batteries

Severe polysulfide dissolution and shuttling during charging and discharging are the main challenges hindering the practical application of lithium-sulfur (Li-S) batteries. Constructing functional separators is considered as an economical and convenient way to suppress the shuttle effect and improve the kinetics of Li-S chemistry. In this work, partially ligand-deficient amorphous bimetallic MOF material (aFeNi-MOF) is designed via a ligand competition strategy and employed as a separator modifier. The aFeNi-MOF not only promotes the rapid transportation of ions, but also enhances the chemisorption and catalytic capability on sulfur species, enabling accelerated redox kinetics and polysulfide trapping in Li-S batteries. Consequently, the assembled coin cell using aFeNi-MOF-modified separator delivered a high reversible capacity of 931.1 mAh/g at 1C, a long cycle life of more than 500 cycles and a low capacity decay of 0.084 % per cycle. Meanwhile, the areal capacity of 3.70 mAh cm−2 can be achieved under a high sulfur loading of 4.5 mg cm−2 and low electrolyte usage, meeting the requirement of areal capacity for commercial applications of Li-S batteries.

A Review of Electrospun Carbon-based Nanofibers Materials Used in Lithium-Sulfur Batteries.

Commercial lithium-ion batteries are gradually approaching their theoretical values (200-250 Wh kg-1), which cannot meet the fast-growing energy storage demands. Lithium-sulfur (Li-S) batteries are anticipated to supersede lithium-ion batteries as the next-generation energy storage system owing to their high theoretical specific capacity (1675 mAh g-1) and energy density (2600 Wh kg-1). Nonetheless, Li-S batteries encounter several challenges, including the inadequate conductivity of sulfur and lithium sulfide, sulfur's volume expansion, and the shuttle effect of lithium polysulfides, all of which significantly impact the practical utilization of Li-S batteries. Electrospun carbon-based nanofibers can simultaneously resolve these issues with their economical preparation, distinctive nanostructure, and exceptional flexibility. This review presents the most recent research findings on electrospun carbon-based nanofibers materials serving as sulfur hosts and interlayer components in Li-S batteries. We analyzed the impact of the material's structural design on the performance of Li-S batteries and the relative underlying mechanism. Finally, the current challenges and issues faced by carbon-based nanofibers composites in the application of Li-S batteries are summarized, and the future development trajectory are outlined.

Enhancing Lithium-Sulfur Battery Performance with MXene: Specialized Structures and Innovative Designs.

Established in 1962, lithium-sulfur (Li-S) batteries boast a longer history than commonly utilized lithium-ion batteries counterparts such as LiCoO2 (LCO) and LiFePO4 (LFP) series, yet they have been slow to achieve commercialization. This delay, significantly impacting loading capacity and cycle life, stems from the long-criticized low conductivity of the cathode and its byproducts, alongside challenges related to the shuttle effect, and volume expansion. Strategies to improve the electrochemical performance of Li-S batteries involve improving the conductivity of the sulfur cathode, employing an adamantane framework as the sulfur host, and incorporating catalysts to promote the transformation of lithium polysulfides (LiPSs). 2D MXene and its derived materials can achieve almost all of the above functions due to their numerous active sites, external groups, and ease of synthesis and modification. This review comprehensively summarizes the functionalization advantages of MXene-based materials in Li-S batteries, including high-speed ionic conduction, structural diversity, shuttle effect inhibition, dendrite suppression, and catalytic activity from fundamental principles to practical applications. The classification of usage methods is also discussed. Finally, leveraging the research progress of MXene, the potential and prospects for its novel application in the Li-S field are proposed.

Mo2C-Co heterostructure with carbon nanosheets decorated carbon microtubules: Different means for high-performance lithium-sulfur batteries

The practical applications of lithium sulfur batteries (LSBs) are hindered by notorious shuttle effect and sluggish conversion kinetics of intermediate polysulfides. Herein, Mo2C-Co heterogeneous particles decorated two-dimensional (2D) carbon nanosheets grown on hollow carbon microtubes (CCC@MCC) are synthesized. Three-dimensional (3D) carbon framework with Mo2C-Co heterogeneous particles combines the conductivity, adsorption and catalysis, effectively trapping and accelerating the conversion of polysulfides. As evidenced experimentally, the hetero-structured Mo2C-Co with high Li+ diffusion coefficient enables uniform precipitation and complete oxidation of Li2S. Meanwhile, CCC@MCC is found to have multiple application possibilities for lithium-sulfur batteries. As an interlayer, the cells deliver an excellent capacity of 881.1 mAh/g at 2C and still retain 438.2 mAh/g after 500 cycles under the low temperature of 0 ℃. As a sulfur carrier, the cell with a sulfur loading of 7.0 mg cm−2 exhibits a high area capacity of 5.3 mAh cm−2. This work provides an effective strategy to prepare heterostructured material and imaginatively exploit the application potential of it.

Design of Coatings for Sulfur-Based Cathode Materials in Lithium-Sulfur Batteries: A review.

Lithium-sulfur batteries (LSBs) are considered next-generation energy storage and conversion solutions owing to their high theoretical specific capacity and the high abundance/low-cost of sulfur-based cathode materials. However, LSBs still encounter significant challenges, including the low conductivities of sulfur-based materials, severe volumetric expansion of sulfur during the discharge process, and the persistent "shuttle effect" of polysulfides. In recent years, a tremendous amount of research has been conducted to address the above challenges by developing coating and compositing materials and corresponding fabrication strategies for sulfur-based cathode materials. In this study, the surface coating, compositing materials, and fabrication methodologies of LSB cathodes are comprehensively reviewed in terms of advanced materials, structure/component characterization, functional mechanisms, and performance validation. Some technical challenges are analyzed in detail, and possible future research directions are proposed to overcome the challenges toward practical applications of lithium-sulfur batteries.

Suppressing sulfur crosstalk lowers the bar of lithium metal anode for practical Li-S pouch cells

The obscure cause of early failure in lithium-sulfur batteries has long hindered their practicality. In this work, the shortboard factor has been ascertained as the lithium metal anode. Capacity-type sulfur cathode amplifies the intrinsic dendrite growth of Li metal through higher capacity requirements (> 8 mAh/cm2). More significantly, sulfur crosstalk seriously destroys the chemical-electrochemical stability of Li metal and directly leads to the unexpected capacity diving, which has been identified as more dominant and crucial. Herein, to lower the bar of the Li metal anode for the practicality of Li-S batteries, we proposed a hybrid sulfur-rich cathode to suppress the sulfur crosstalk. Our innovations reduced the lithium porosity by 26.7 % and the lithium corrosion rate by 27.4 % after cycling. As a result, our demonstrated pouch cells achieved superior energy densities of 460 Wh/kg and 985 Wh/L, and a stable cycle life above 75 cycles with an excellent capacity retention of 80 %. Our work is anticipated to provide a meticulous and thorough view to let the community rethink how to realize the practicality of Li-S batteries.

Simple Framework for Simultaneous Analysis of Both Electrodes in Stoichiometric Lithium-Sulfur Batteries.

A battery is composed of two electrodes that depend on and interact with each other. However, galvanostatic charging-discharging measurement, the most widely used method for battery evaluation, cannot simultaneously reflect performance metrics [capacity, Coulombic efficiency (CE), and cycling stability] of both electrodes because the result is generally governed by the lower-capacity electrode of the cell, namely the limiting reagent of the battery reaction. In studying stoichiometric Li-S cells operating under application-relevant high-mass-loading and lean-electrolyte conditions, we take advantage of the two-stage discharging behavior of sulfur to construct a simple framework that allows us to analyze both electrodes simultaneously. The cell capacity and its decay are anode performance descriptors, whereas the first plateau capacity and cell CE are cathode performance descriptors. Our analysis within this frame identifies Li stripping/plating and polysulfide shuttling to be the limiting factors for the cycling performance of the stoichiometric Li-S cell. Using our newly developed framework, we examine various previously reported strategies to mitigate these bottleneck problems and find modifying the separator with a reduced graphene oxide layer to be an effective means, which improves the capacity retention rate of the cell to 99.7% per cycle.

The study on the reason why ZnS catalyst cannot suppress the shuttle effect of polysulfides in lithium-sulfur (Li–S) battery

The catalytic effect of zinc sulfide (ZnS) on the transformation of polysulfides (Li2S8) to lithium sulfide (Li2S) has been proven by the enhancement in the rate performance of lithium-sulfur (Li–S) batteries incorporating ZnS particles into the cathode. Accordingly, the shuttling effect of polysulfide should also be suppressed. However, the expected phenomenon is not found in the Li–S batteries with ZnS particles being added in the cathodes. In order to find the intrinsic mechanism of this phenomenon, detailed catalytic effects of ZnS particles on different polysulfide molecules are investigated. It is shown that ZnS can only enhance the reaction from Li2S4 to Li2S and it has almost no catalytic effect on the reaction from Li2S6 to Li2S4. This is why the shuttle effect of Li2S6 cannot be effectively prohibited. This mechanism is further verified via combining ZnS particles with S–C@PVA yolk-shell particles containing sulfur (S) and carbon black (C) as the core and PVA as the shell. Although the reaction from Li2S6 to Li2S4 cannot be directly catalysed by ZnS particles, it can still be enhanced when ZnS particles are distributed within the S–C@PVA yolk-shell structure (S–C–ZnS@PVA) because the reaction speed from the Li2S4 to Li2S is accelerated. The fast consumption of Li2S4 will result in the enhancement of the reaction from Li2S6 to Li2S4, which will largely reduce the diffusion of Li2S6 out of the PVA shell. While if ZnS particles are located outside the S–C@PVA yolk-shell structure (S–C@PVA-ZnS), large amount of Li2S6 can still diffuse out of the PVA shell and enter into the electrolyte since the transformation from is Li2S6 to Li2S4 relatively low. Both the rate performance and cycle stability of the batteries with S–C–ZnS@PVA cathodes are higher than those with S–C@PVA-ZnS ones. These results will give a guidance for the preparation of Li–S battery with high performance.

Advanced Separator Materials for Enhanced Electrochemical Performance of Lithium-Sulfur Batteries: Progress and Prospects.

Lithium-sulfur (Li-S) batteries are promising energy storage devices owing to their high theoretical specific capacity and energy density. However, several challenges, including volume expansion, slow reaction kinetics, polysulfide shuttle effect and lithium dendrite formation, hinder their commercialization. Separators are a key component of Li-S batteries. Traditional separators, made of polypropylene and polyethylene, have certain limitations that should be addressed. Therefore, this review discusses the basic properties and mechanisms of Li-S battery separators, focuses on preparing different functionalized separators to mitigate the shuttle effect of polysulfides. This review also introduces future research trends, emphasizing the potential of separator functionalization in advancing the Li-S battery technology.

Multifunctional TiN‐MXene‐Co@CNTs Networks as Sulfur/Lithium Host for High‐Areal‐Capacity Lithium‐Sulfur Batteries

AbstractThe inevitable shuttling and slow redox kinetics of lithium polysulfides (LiPSs) as well as the uncontrolled growth of Li dendrites have strongly limited the practical applications of lithium‐sulfur batteries (LSBs). To address these issues, we have innovatively constructed the carbon nanotubes (CNTs) encapsulated Co nanoparticles in situ grown on TiN‐MXene nanosheets, denoted as TiN‐MXene‐Co@CNTs, which could serve simultaneously as both sulfur/Li host to kill “three birds with one stone” to (1) efficiently capture soluble LiPSs and expedite their redox conversion, (2) accelerate nucleation/decomposition of solid Li2S, and (3) induce homogeneous Li deposition. Benefiting from the synergistic effects, the TiN‐MXene‐Co@CNTs/S cathode with a sulfur loading of 2.5 mg cm−2 could show a high reversible specific capacity of 1129.1 mAh g−1 after 100 cycles at 0.1 C, and ultralong cycle life over 1000 cycles at 1.0 C. More importantly, it even achieves a high areal capacity of 6.3 mAh cm−2 after 50 cycles under a sulfur loading as high as 8.9 mg cm−2 and a low E/S ratio of 5.0 μL mg−1. Besides, TiN‐MXene‐Co@CNTs as Li host could deliver a stable Li plating/striping behavior over 1000 h.

Nitrogen-Doped TiO2- x(B)/MXene Heterostructures for Expediting Sulfur Redox Kinetics and Suppressing Lithium Dendrites.

Practical application of lithium-sulfur (Li-S) batteries is severely impeded by the random shuttling of soluble lithium polysulfides (LiPSs), sluggish sulfur redox kinetics, and uncontrollable growth of lithium dendrites, particularly under high sulfur loading and lean electrolyte conditions. Here, nitrogen-doped bronze-phase TiO2(B) nanosheets with oxygen vacancies (OVs) grown in situ on MXenes layers (N-TiO2- x(B)-MXenes) as multifunctional interlayers are designed. The N-TiO2- x(B)-MXenes show reduced bandgap of 1.10eV and high LiPSs adsorption-conversion-nucleation-decomposition efficiency, leading to remarkably enhanced sulfur redox kinetics. Moreover, they also have lithiophilic nature that can effectively suppress dendrites growth. The cell based on the N-TiO2- x(B)-MXenes interlayer under sulfur loading of 2.5mg cm-2 delivers superior cycling performance with a high specific capacity of 690.7 mAh g-1 over 600 cycles at 1.0 C. It still has a notable areal capacity of 6.15 mAh cm-2 after 50 cycles even under a high sulfur loading of 7.2mg cm-2 and a low electrolyte-to-sulfur (E/S) ratio of 6.4 µL mg-1. The Li-symmetrical battery with the N-TiO2- x(B)-MXenes interlayer showcases a low over-potential fluctuation with 21.0mV throughout continuous lithium plating/stripping for 1000h. This work offers valuable insights into the manipulation of defects and heterostructures to achieve high-energy Li-S batteries.

Fence‐type Molecular Electrocatalysts for High‐Performance Lithium‐Sulfur Batteries

Improving the slow redox kinetics of sulfur species and shuttling issues of soluble intermediates induced from the multiphase sulfur redox reactions are crucial factors for developing the next‐generation high‐energy‐density lithium‐sulfur (Li‐S) batteries. In this study, we successfully constructed a novel molecular electrocatalyst through in situ polymerization of bis(3,4‐dibromobenzene)‐18‐crown‐6 (BD18C6) with polysulfide anions on the cathode interface. The crown ether (CE)‐based polymer acts as a spatial "fence" to precisely control the unique redox characteristics of sulfur species, which could confine sulfur substance within its interior and interact with lithium polysulfides (LiPSs) to optimize the reaction barrier of sulfur species. The "fence" structure and the double‐sided Li+ penetrability of the CE molecule may also prevent the CE catalytic sites from being covered by sulfur during cycling. This new fence‐type electrocatalyst mitigates the “shuttle effect”, enhances the redox activity of sulfur species, and promotes the formation of three‐dimensional stacked lithium sulfide (Li2S) simultaneously. It thus enables lithium‐sulfur batteries to exhibit superior rate performance and cycle stability, which may also inspire development facing analogous multiphase electrochemical energy‐efficient conversion process.

Breaking the Passivation Effect for MnO2Catalysts in Li-S Batteries by Anion-Cation Doping.

Transition metal oxides (TMOs) are recognized as high-efficiency electrocatalyst systems for restraining the shuttle effect in lithium-sulfur (Li-S) batteries, owing to their robust adsorption capabilities for polysulfides. However, the sluggish catalytic conversion of Li2S redox and severe passivation effect of TMOs exacerbate polysulfide shuttling and reducethe cyclability of Li-S batteries, which significantly hinders the development of TMOs electrocatalysts. Here, through the anion-cation doping approach, dual incorporation of phosphorus and molybdenum into MnO2(P,Mo-MnO2) was engineered, demonstrating effective mitigation of the passivation effect and allowing for the simultaneous immobilization of polysulfides and rapid redox kinetics of Li2S.Both experimental and theoretical investigations reveal the pivotal role of dopants in fine-tuning the d-band center and optimizing the electronic structure of MnO2. Furthermore, this well-designed configuration processes catalytic selectivity. Specifically, P-doping expedites rapid Li2S nucleation kinetics by minimizing reaction-free energy, while Mo-doping facilitates robust Li2S dissolution kinetics by mitigating decomposition barriers.This dual-doping approach equips P,Mo-MnO2with robust bi-directional catalytic activity, effectively overcoming passivation effect and suppressing the notorious shuttle effect. Consequently, Li-S batteries incorporating P,Mo-MnO2-based separatorsdemonstrate favorable performance thanpristine TMOs. This design offers rational viewpoint for the development of catalytic materials with superior bi-directional sulfur electrocatalytic in Li-S batteries.

Breaking the Passivation Effect for MnO2 Catalysts in Li‐S Batteries by Anion‐Cation Doping

Transition metal oxides (TMOs) are recognized as high‐efficiency electrocatalyst systems for restraining the shuttle effect in lithium‐sulfur (Li‐S) batteries, owing to their robust adsorption capabilities for polysulfides. However, the sluggish catalytic conversion of Li2S redox and severe passivation effect of TMOs exacerbate polysulfide shuttling and reduce the cyclability of Li‐S batteries, which significantly hinders the development of TMOs electrocatalysts. Here, through the anion‐cation doping approach, dual incorporation of phosphorus and molybdenum into MnO2 (P,Mo‐MnO2) was engineered, demonstrating effective mitigation of the passivation effect and allowing for the simultaneous immobilization of polysulfides and rapid redox kinetics of Li2S. Both experimental and theoretical investigations reveal the pivotal role of dopants in fine‐tuning the d‐band center and optimizing the electronic structure of MnO2. Furthermore, this well‐designed configuration processes catalytic selectivity. Specifically, P‐doping expedites rapid Li2S nucleation kinetics by minimizing reaction‐free energy, while Mo‐doping facilitates robust Li2S dissolution kinetics by mitigating decomposition barriers. This dual‐doping approach equips P,Mo‐MnO2 with robust bi‐directional catalytic activity, effectively overcoming passivation effect and suppressing the notorious shuttle effect. Consequently, Li‐S batteries incorporating P,Mo‐MnO2‐based separators demonstrate favorable performance than pristine TMOs. This design offers rational viewpoint for the development of catalytic materials with superior bi‐directional sulfur electrocatalytic in Li‐S batteries.