High Sulfur Loading Research Articles

Engineering Triple-Phase Interfaces with Hierarchical Carbon Nanocages for High-Areal-Capacity All-Solid-State Li-S Batteries.

All-solid-state lithium-sulfur batteries (ASSLSBs) have garnered widespread attention due to their advantages of high energy density and enhanced safety. However, the typical composite structure composed of solid-state electrolyte (SE), discrete conducting carbon black, and microsized sulfur (μ-S) with long-range Li+/e- conducting path and huge volume changes, suffers from sluggish charge transport and severe electrochemical-mechanical failure. In this work, a unique hierarchical carbon nanocage (hCNC) is applied as a continuous conducting network where nanosized sulfur are confined. Due to the synergistic effects of multi-dimensional (particle, interface, and electrode) structural engineering, this new sulfur-carbon composite cathode (S@hCNC39) can achieve uniform distribution of sulfur and carbon, and efficiently constructs triple-phase interfaces, showing enhanced charge-carrier transport and improved electrochemical-mechanical stability. Remarkable cycling performance of 89% after 300 cycles at 0.2C at 30°C is realized in ASSLSBs assembled with S@hCNC39. Notably, ASSLSBs achieve an ultrahigh areal capacity of 9.95 mAh cm-2 with stable cycling at 60°C with high sulfur contents of 40% and high sulfur loadings of 6mg cm-2. These results provide critical insights into the design of rational sulfur-carbon composites and offer a viable approach to enhance the overall performance of ASSLSBs.

Multifunctional Ultrathin Ti3C2Tx MXene@CuCo2O4 /PE Separator for Ultra-High-Energy-Density and Large-Capacity Lithium-Sulfur Pouch Cells.

The shuttling of lithium polysulfides (LiPSs), sluggish reaction kinetics, and uncontrolled lithium deposition/stripping remain the main challenges in lithium-sulfur batteries (LSBs), which are aggravated under practical working conditions, i.e., high sulfur loading and lean electrolyte in large-capacity pouch cells. This study introduces a Ti3C2Tx MXene@CuCo2O4 (MCC) composite on a polyethylene (PE) separator to construct an ultrathin MXene@CuCo2O4/PE (MCCP) film. The MCCP functional separator can deliver superior LiPSs adsorption/catalysis capabilities via the MCC composite and regulate the Li+ deposition through a conductive Ti3C2Tx MXene framework, enhancing redox kinetics and cycling lifetime. When paired with sulfur/carbon (S/C) cathode and lithium metal anode, the resultant 10 Ah-level pouch cell with the ultrathin MCCP separator achieves an energy density of 417Wh kg-1 based on the whole cell and a stable running of 100 cycles under practical operation conditions (cathode loading = 10.0 mg cm-2, negative/positive areal capacity ratio (N/P ratio) = 2, and electrolyte/sulfur weight ratio (E/S ratio) = 2.6 µL mg-1). Furthermore, through a systematic evaluation of the as-prepared Li-S pouch cell, the study unveils the operational and failure mechanisms of LSBs under practical conditions. The achievement of ultrahigh energy density in such a large-capacity lithium-sulfur pouch cell will accelerate the commercialization of LSBs.

Highly Solvating Electrolytes with Core‐Shell Solvation Structure for Lean‐Electrolyte Lithium‐Sulfur Batteries

The practical energy density of lithium‐sulfur batteries is limited by the low sulfur utilization at lean electrolyte conditions. The highly solvating electrolytes (HSEs) promise to address the issue at harsh conditions, but the conflicting challenges of long‐term stability of radical‐mediated sulfur redox reactions (SRR) and the poor stability with lithium metal anode (LMA) have dimmed the efforts. We now present a unique core‐shell solvation structured HSE formulated with classical ether‐based solvents and phosphoramide co‐solvent. The unique core‐shell solvation structure features confinement of the phosphoramide in the first solvation shell, which prohibits severe contact reactions with LMA and endows prolonged stability for [S3]•– radical, favoring a rapid radical‐mediated solution‐based SRR. The cell with the proposed electrolyte showing a high capacity of 864 mA h gsulfur−1 under high sulfur loading of 5.5 mgsulfur cm−2 and low E/S ratio of 4 µL mgsulfur−1. The strategy further enables steady cycling of a 2.71‐A h pouch cell with a high specific energy of 307 W h kg−1. Our work highlights the fundamental chemical concept of tuning the solvation structure to simultaneously tame the SRR and LMA stability for metal‐sulfur batteries wherein the electrode reactions are heavily coupled with electrolyte chemistry.

Covalently Anchoring an Ultrathin Conformal SiOx Coating on Polyolefin Separator for Enhanced Lithium Metal Battery Performance

AbstractSurface modification of separators with inorganic oxide ceramics such as SiOx, Al2O3, and TiO2 has emerged as a promising strategy to suppress lithium dendrite growth in lithium metal batteries, thereby enhancing safety and extending battery life. However, the binder‐dependent nature of these modifications often leads to increased separator thickness and a heightened risk of detachment during lithium plating, ultimately compromising both battery performance and energy density. In this study, a conformal, ultrathin (≈20 nm) SiOx coating with strong covalent bonding is grown on a porous separator through a liquid polymer‐derived method. Compared to the pristine polyethylene (PE) separators, this SiOx‐co‐PE separator exhibits significantly improved electrolyte wettability, mechanical strength, and thermal stability without any increase in thickness, leading to vastly enhanced cycling stability and dendrite resistance in cells with Li metal anodes. In a practical demonstration, a 402.9 Wh·kg−1 Li‐S pouch cell, with a high sulfur loading of 9 mg cm−2 and a low E/S ratio of 3.3 µL mg−1, is assembled with the SiOx‐co‐PE separator, achieving stable cycling over 70 cycles at 25 °C.

Highly Solvating Electrolytes with Core-Shell Solvation Structure for Lean-Electrolyte Lithium-Sulfur Batteries.

The practical energy density of lithium-sulfur batteries is limited by the low sulfur utilization at lean electrolyte conditions. The highly solvating electrolytes (HSEs) promise to address the issue at harsh conditions, but the conflicting challenges of long-term stability of radical-mediated sulfur redox reactions (SRR) and the poor stability with lithium metal anode (LMA) have dimmed the efforts. We now present a unique core-shell solvation structured HSE formulated with classical ether-based solvents and phosphoramide co-solvent. The unique core-shell solvation structure features confinement of the phosphoramide in the first solvation shell, which prohibits severe contact reactions with LMA and endows prolonged stability for [S3]•- radical, favoring a rapid radical-mediated solution-based SRR. The cell with the proposed electrolyte showing a high capacity of 864 mA h gsulfur-1 under high sulfur loading of 5.5 mgsulfur cm-2 and low E/S ratio of 4 µL mgsulfur-1. The strategy further enables steady cycling of a 2.71-A h pouch cell with a high specific energy of 307 W h kg-1. Our work highlights the fundamental chemical concept of tuning the solvation structure to simultaneously tame the SRR and LMA stability for metal-sulfur batteries wherein the electrode reactions are heavily coupled with electrolyte chemistry.

Accelerated Ion-Electron Transport in Bi-Heterostructures Constructed Based on Ohmic Contacts for Efficient Bi-Directional Catalysis of Lithium-Sulfur Batteries.

Although lithium-sulfur batteries have satisfactory theoretical specific capacity and energy density, they are difficult to further commercialize due to the shuttle effect of soluble polysulfides and slow sulfur oxidation kinetics. Based on this, in this work, the catalyst MXene-VS4-SnS2 (MVS), a dual heterostructured catalyst with ohmic contacts, is prepared by a one-step hydrothermal method and electrostatic self-adsorption for lithium-sulfur battery cathode materials. Experimental and theoretical results show that the ohmic contact induces spontaneous charge rearrangement, resulting in the formation of a fast charge transfer pathway at the MVS heterojunction interface, which helps to reduce the energy barrier for polysulfide reduction and Li2S oxidation during the discharge/charge process. In addition, the inherent sulfophilicity of VS4 and SnS2 promotes the conversion of S species, while the pleated MXene nanosheets not only provide a highly conductive network for the active sulfur but also retain a rich internal space to maintain the integrity of the cathode structure during the continuous cycling process. As a result, the MVS cathode exhibits excellent electrochemical performance even under high sulfur loading. The integration of excellent performance with a facile synthesis process provides a promising approach for designing highly efficient electrocatalysts suitable for the energy field.

Enhanced Performance of Lithium-Sulfur Batteries Using Construction Wastes: A Sustainable Approach to High-Loading Sulfur Cathodes.

Advancing lithium-sulfur battery technology requires addressing both extrinsic cell-fabrication and intrinsic material challenges to improve efficiency, cyclability, and environmental sustainability. A key challenge is the low conductivity of sulfur cathodes, which is typically managed by incorporating conductive carbon materials. These materials enhance the performance of sulfur cathodes by facilitating high sulfur loading and improving polysulfide retention. In line with green chemistry principles and circular economy concepts, this study explores the use of recycled materials-specifically recycled quartz and board-as substrates for graphene coatings in lithium-sulfur cells. Recycled quartz bricks and blocks, predominantly SiO2, and recycled shelf boards, rich in Al2O3, are successfully coated with graphene, which significantly improves polysulfide adsorption and overall battery performance. The graphene-coated quartz exhibits high sulfur loading (8 mg cm-2), exceptional charge-storage capacity (1,114 mA·h g-1), and long cycle stability (200 cycles) with an energy density of 19 mW·h cm-2. This approach enhances the electrochemical performance of the lithium-sulfur cells and also aligns with sustainability goals by repurposing waste materials and minimizing environmental impact. This novel methodology demonstrates that integrating recycled materials can effectively address key challenges in lithium-sulfur battery technology, advancing both performance and environmental sustainability.

HighSpin-State Modulation of Catalytic Centers by Weak Ligand Field for Promoting Sulfur Redox Reaction in Lithium-Sulfur Batteries.

The spin state of transition-metal compounds in lithium-sulfur batteries (LSBs) significantly impacts the electronic properties and the kinetics of sulfur redox reactions (SRR). However, accurately designing the spin state remains challenging, which is crucial for understanding the structure-performance relationship and developing high-performance electrocatalysts. Herein, the CoF2, specifically the Co2+ with 3d7 electrons in a high-spin state distribution (t2g5eg2), were tailored predictably for the first time through the weak coordination field effect of the F element. Both DFT calculations and experimental results confirm that the spin state of Co2+ transitions from low- to high-spin configurations and strongly interacts with sulfur species through Co-S and Li-F bonds during the SRR process. This interaction weakens the S-S bond, promoting its facile cleavage from both ends while also facilitating the rapid and uniform nucleation of Li2S2/Li2S, thus resulting in LSBs with a capacity of 447.7 mAh g-1 at 10 C rates and stable cycling for 1000 cycles, with an acceptable practical capacity of 585 mAh g-1 at a high sulfur loading mass of 10 mg cm-2. This work achieves rational control of the active Co2+ d electron state through the field effect and enriches the application of spin control to accelerate SRR in LSBs.

Targeted Electrocatalysis for High‐Performance Lithium–Sulfur Batteries

The intricate sulfur redox chemistry involves multiple electron transfers and complicated phase changes. Catalysts have been previously explored to overcome the kinetic barrier in lithium–sulfur batteries (LSBs). This work contributes to closing the knowledge gap and examines electrocatalysis for enhancing LSB kinetics. With a strong chemical affinity for polysulfides, the electrocatalyst enables efficient adsorption and accelerated electron transfer reactions. Resulting cells with catalyzed cathodes exhibit improved rate capability and excellent stability over 500 cycles with 91.9% capacity retention at C/3. In addition, cells were shown to perform at high rates up to 2C and at high sulfur loadings up to 6 mg cm−2. Various electrochemical, spectroscopic, and microscopic analyses provide insights into the mechanism for retaining high activity, coulombic efficiency, and capacity. This work delves into crucial processes identifying pivotal reaction steps during the cycling process at commercially relevant areal capacities and rates.

NiCo alloy-decorated nitrogen-doped carbon double-shelled hollow polyhedrons with abundant catalytic active sites to accelerate lithium polysulfides conversion

Lithium-sulfur (Li-S) batteries have received significant attention due to their high theoretical energy density. However, the inherent poor conductivity of S and lithium sulfide (Li2S), coupled with the detrimental shuttle effect induced by lithium polysulfides (LiPSs), impedes their commercialization. In this study, we develop NiCo alloy-decorated nitrogen-doped carbon double-shelled hollow polyhedrons (NC/NiCo DSHPs) as highly efficient catalysts for Li-S batteries. The distribution of NiCo alloy on both the inner and outer shells provides abundant catalytic active sites, effectively adsorbing LiPSs, mitigating the shuttle effect, and promoting the conversion between LiPSs and Li2S, even at high sulfur loadings. This results in enhanced redox kinetics within the Li-S system. Moreover, the highly conductive carbon material framework, enriched with carbon nanotubes and graphitic carbon layers, can greatly promote the efficient electron transportation. Additionally, the improved ion diffusion rates benefiting from the hollow structure can also be realized. By harnessing these synergistic effects, Li-S batteries incorporating the double-shelled NC/NiCo DSHP catalysts achieved a high specific capacity of 1310 mAh/g at 0.2C and a superior rate performance of 621 mAh/g at 4C. Furthermore, excellent cycling performance with ultralow capacity fading rate of only 0.045 % per cycle after 800 cycles at 1C was achieved. When sulfur loading reaches 6 mg cm−2, a high capacity of 4.6 mAh cm−2 at 0.1C after 100 cycles further validates the practical potential of this design. This study presents an innovative approach to alloy catalyst design, offering valuable insights for future research of Li-S batteries.

Natural Polyphenol‐Reinforced Ion‐Selective Separators for High‐Performance Lithium‐Sulfur Batteries with High Sulfur Loading and Lean Electrolyte

Ion‐selective separators are promising to inhibit soluble intermediates shuttle in practical lithium‐sulfur (Li‐S) batteries. However, designing and fabricating such high‐performance ion‐selective separators using cost‐effective, eco‐friendly, and versatile methods remains a formidable challenge. Here we present ion‐selective separators fabricated via the spontaneous deposition of green tea‐derived polyphenols onto a polypropylene separator, aimed at enhancing the stability of Li‐S batteries. The resulting natural polyphenol‐reinforced ion‐selective (NPRIS24) separators exhibit rapid Li ion transport and high soluble intermediates inhibition capability with an ultralow shuttle rate of 0.67% for Li2S4, 0.19% for Li2S6 and 0.10% for Li2S8. This superior ion‐selectivity arises from the high electronegativity and strong lithiophilic nature of the phenolic compounds. Consequently, we have achieved high‐performance Li‐S batteries that are steadily cyclable under the challenging conditions of an S loading of 5.7 mg cm−2, an electrolyte‐to‐S ratio of 5.1 μL mg−1, and a 50 μm Li foil anode. Furthermore, the NPRIS24 separator enhances the performance of other Li metal batteries utilizing commercial LiFePO4 (5.3 mg cm−2) and LiNi0.5Co0.2Mn0.3O2 (9.9 mg cm−2) cathodes. This work underscores the potential of utilizing natural polyphenols for the design of advanced ion‐selective separators in energy storage systems.

Natural Polyphenol-Reinforced Ion-Selective Separators for High-Performance Lithium-Sulfur Batteries with High Sulfur Loading and Lean Electrolyte.

Ion-selective separators are promising to inhibit soluble intermediates shuttle in practical lithium-sulfur (Li-S) batteries. However, designing and fabricating such high-performance ion-selective separators using cost-effective, eco-friendly, and versatile methods remains a formidable challenge. Here we present ion-selective separators fabricated via the spontaneous deposition of green tea-derived polyphenols onto a polypropylene separator, aimed at enhancing the stability of Li-S batteries. The resulting natural polyphenol-reinforced ion-selective (NPRIS24) separators exhibit rapid Li ion transport and high soluble intermediates inhibition capability with an ultralow shuttle rate of 0.67% for Li2S4, 0.19% for Li2S6 and 0.10% for Li2S8. This superior ion-selectivity arises from the high electronegativity and strong lithiophilic nature of the phenolic compounds. Consequently, we have achieved high-performance Li-S batteries that are steadily cyclable under the challenging conditions of an S loading of 5.7 mg cm-2, an electrolyte-to-S ratio of 5.1 μL mg-1, and a 50 μm Li foil anode. Furthermore, the NPRIS24 separator enhances the performance of other Li metal batteries utilizing commercial LiFePO4 (5.3 mg cm-2) and LiNi0.5Co0.2Mn0.3O2 (9.9 mg cm-2) cathodes. This work underscores the potential of utilizing natural polyphenols for the design of advanced ion-selective separators in energy storage systems.

Heterostructure Mo2C/α-MoO3/G catalyst based heterogeneous catalysis/deposition mechanism for high-performance Li-S battery

Lithium-sulfur batteries (LSBs) have been recognized as a promising energy device due to their outstanding theoretical energy density and abundant resources. However, the commercial application remains obstruction by the sluggish redox kinetics and serious shuttle effect of polysulfides. Herein, a heterostructural Mo2C/α-MoO3/graphene (Mo2C/α-MoO3/G) catalyst based on a heterogeneous catalysis/deposition mechanism is proposed to address these issues. The prepared Mo2C/α-MoO3/G catalyst is feature with high-activity facet, fast electron delocalization and build-in electric field, which drastically promotes the redox kinetics of polysulfides on the surface of crystal phase. Simultaneously, the heterostructural Mo2C/α-MoO3/G catalyst is capable of capturing polysulfides effectively and eliciting the heterogeneous deposition of Li2S on the surface of amorphous phase, of which guarantee the efficient catalytic characteristic during the charge/discharge processes. In addition, the shuttle effect is restricted with a lower shuttle factor (∼0.02). Therefore, the assembled LSBs based Mo2C/α-MoO3/G catalyst modifying separator exhibits an impressive specific capacity of 1311.4 mAh g−1 at 0.2 C and excellent rate capability of 580.3 mAh g−1 at 4 C. More importantly, it demonstrated satisfied cycling stability even at a high sulfur loading mass (4.2 mgS cm−2) and lean electrolyte conditions (9.3 μL gS-1). This work reveals a novel paradigm for optimizing the kinetics behaviors to achieve the commercialization of LSBs.

Application of Y-MOF-CNT-Derived Y2O3-C@CNT Composites in Lithium-Sulfur Battery Separators.

In order to mitigate the shuttle effect of lithium polysulfides in lithium-sulfur batteries, we propose a yttrium-metal-organic framework-carbon nanotube (Y-MOF-CNT)-derived Y2O3-C@CNT composite for modifying the separator in this study. The Y-MOFs, comprising yttrium (Y) rare earth metal and terephthalic acid, exemplify a prototypical category of metal-organic framework (MOF) materials. They manifest the advantageous attributes associated with MOFs while concurrently possessing distinctive catalytic traits ascribed to rare earth elements. In this study, Y-MOF nanoparticles were synthesized on carbon nanotube (CNT) substrates via a facile aqueous solution method, succeeded by high-temperature carbonization to yield Y2O3-C@CNT composite materials. These composites were subsequently employed as coatings on one side of polyethylene (PE) separators. The resultant Y2O3-C@CNT composite inherits the particle-like morphology and porosity from its precursor Y-MOF, alongside the inherent conductivity in carbon-based materials. This amalgamation is conducive to polysulfide capture and catalytic conversion processes within lithium-sulfur batteries. The application of the Y2O3-C@CNT-coated PE separator effectively mitigated polysulfide shuttle effects and significantly enhanced the battery electrochemical performance. At a sulfur loading level of 3 mg cm-2 under a 0.5 C rate, an initial discharge specific capacity of 900 mAh g-1 was achieved. After 400 cycles, the discharge specific capacity remained at 483.85 mAh g-1 with a capacity retention rate of 53.7%. Upon increasing sulfur loading to 5 mg cm-2, the discharge specific capacity at a lower rate (0.1 C) reached 817.8 mAh g-1; even after 100 cycles, it maintained a value of 700 mAh g-1 with a capacity retention rate of 85.6%. Notably, our modified Y2O3-C@CNT separator demonstrated exceptional cycling stability, even under conditions involving high sulfur loading.

Dynamically Regulating Polysulfide Degradation via Organic Sulfur Electrolyte Additives in Lithium‐Sulfur Batteries

AbstractLithium‐sulfur (Li‐S) batteries offer promising prospects due to their high energy density and cost‐effectiveness. However, the sluggish kinetics of lithium polysulfides (LiPSs) conversion, particularly the crucial stage from LiPSs to lithium sulfide (Li2S), hampers their development. Herein, a novel strategy for dynamically regulating LiPSs conversion by incorporating 4‐mercaptopyridine (4Mpy), as a LiPSs Redox Regulator (RR) in the electrolyte is introduced. This organic sulfur additive actively interacts with LiPSs during discharge, facilitating rapid conversion and promoting the formation of a three‐dimensional (3D) Li2S structure, thereby enhancing reaction kinetics. Both theoretical and experimental results reveal that the redox conversion mechanism with the 4Mpy additive differs from traditional electrolytes. Upon lithiation, 4Mpy forms lithium‐pyridinethiolate (Li‐pyS), which reversibly engages in the LiPSs conversion during the charging/discharging cycles, significantly improving the redox process. As a result, the Li‐S battery with 4Mpy additive demonstrates superior performances, achieving 10.05 mAh cm−2 under a high sulfur loading of 10.88 mg cm−2, surpassing industrial benchmarks. This study not only presents an approach to mitigating the shuttle effect in Li‐S batteries but also offers valuable insights into electrolyte design for other metal batteries.

Nanosized CeO2C2 with rich oxygen vacancies embedded in hollow mesoporous carbon as a multifunctional sulfur-loaded matrix for lithium-sulfur batteries

The innovative structural and compositional design of sulfur-loaded matrices is an effective strategy to improve the performance of lithium-sulfur batteries (LSBs). Herein, nanosized CeO2C2 with rich oxygen vacancies embedded in hollow mesoporous carbon composites (HMC/CeO2C2) were synthesized by hydrothermal and annealing reduction processes. This structure has several advantages: the large specific surface area and mesoporous carbon walls facilitate sulfur penetration and electron/ion transport; the abundant mesopores and hollow inner cavities provide the structural basis for sulfur storage and buffer its volume expansion; the oxygen vacancy-rich CeO2C2 nanoparticles grown in situ in HMC and in close contact with carbon form an electrically favorable CeO2C2/C heterointerface as an efficient catalyst, which is conducive to catalyzing the redox reaction of sulfur. Consequently, the retention capacity of the HMC/CeO2C2/S electrode is 728 mAh g−1 after 500 cycles at 0.5 C with a decay rate of 0.056 % per cycle, and it maintains a high reversible area capacity of 3.18 mAh cm−2 and excellent cycling performance even under a high sulfur loading of 4.7 mg cm−2. It provides an idea for the development of multifunctional sulfur-loaded materials with high sulfur loading, high conductivity, and high catalytic activity.

Developing Rapid-Charging Li-S Batteries via "Target Catalysis" of Cations and Anions Modified Electrocatalyst.

The shuttle effect and sluggish sulfur reduction reaction have resulted in significantly low efficiency and poor high current cycling stability in lithium-sulfur batteries, impeding their practical applications. To address these challenges, the introduction of Ni cations into MoS2 grown on reduced graphene oxide (MoS2/rGO) induces the formation of impurity energy levels between the conduction and valence bands of MoS2. Additionally, the introduction of anionic Se expands the interlayer spacing, enhances intrinsic conductivity, and improves ion diffusion rates. Simultaneously introducing anionic and cationic species into the MoS2/rGO causes the center of the d-band to shift upward, reducing the occupancy of electrons in antibonding orbitals. This modification leads to a rearrangement of the electronic structure of Mo, accelerating the redox reactions of lithium polysulfides. It particularly enhances the binding energy and lowers the conversion energy barrier of Li2S4. Consequently, the Li||S coin cell with the Ni-MoSSe/rGO cathode demonstrates an initial capacity of 446 mAh g-1 at 20 C, with a remarkable capacity retention of ≈96.7% after 200 cycles. Moreover, even under high sulfur loading conditions (6.45 mg cm-2) and a low electrolyte/sulfur ratio (5.4 µL mg-2), it maintains a high areal capacity of 6.42 mAh cm-2.

In Situ Electrochemical Evolution of Amorphous Metallic Borides Enabling Long Cycling Room-/Subzero-Temperature Sodium-Sulfur Batteries.

Room temperature sodium-sulfur batteries (RT Na-S) have garnered significant attention for their high energy density and cost-effectiveness, positioning them as a promising alternative to lithium-ion batteries. However, they encounter challenges such as the dissolution of sodium polysulfides and sluggish kinetics. Introducing high-activity electrocatalysts and enhancing the density of active sites represents an efficient strategy to enhance reaction kinetics. Here, an amorphous Ni-B material that undergoes electrochemical evolution to generate the NiSx phase within an operational sodium-sulfur battery, contrasting with the crystalline NiB counterpart is fabricated. Electrochemical cycling facilitated the establishment of an interface between the amorphous Ni-B and NiSx, leading to heightened catalytic activity and improved reaction kinetics. Consequently, batteries utilizing the amorphous Ni-B showcased a notable initial specific capacity of 1487 mAh g-1 at 0.2 A g-1, exhibiting exceptional performance under high current densities of 5 A g-1, in low-temperature conditions (-10°C), with high sulfur loading, and in pouch cell configurations.

Regional Electron Delocalization Regulation Internalizes the Reduced‐Order‐Transformation of Polysulfides

AbstractThe step‐order or disproportionation conversion of lithium polysulfides (LiPSs) is still a blind box in LiS batteries (LSBs) system. The cation‐doped electrocatalyst (Fe‐CoS2@HCNF) is designed through modulating electron‐surrounding situation of the central atomic d‐band to promote regional electron‐directed LiPSs reduced‐order‐transformation (especially, Li2S4Li2S). Fe‐CoS2@HCNF satisfies the requirement of mass (electron/ion) transfer reaction, quantizing as multi‐osmosis‐connected transportation channels and an all‐encompassing interior space for sulfur reduction occurring. Based on experiments and DFT calculations, the introduced Fe presents a local electron deficiency state toward regulating regional electron delocalization between Fe and Co matrix, which induces the d‐band state of the metal site, strengthening the metal 3d orbital coupling interaction with S2−of LiPSs, further guiding the order‐transformation of intermediate LiPSs. Consequently, the Fe‐CoS2@HCNF electrode has excellent electrochemical properties, performing at 3.0 C with 0.064 % capacity decay per cycle, and even maintaining super cycle stability at a high sulfur loadings. In addition, the pouch cell assembled can also reach an initial specific capacity of 1070.3 mAh g−1 at 0.1 C, which can still show good long‐term cycle stability. This work provides a valuable prospect for analyzing SRR intermediate state by regional electron flow regulation of electrocatalyst in practical LSBs.

Controllable assembly of polysulfides mediator induced by host-guest chemistry for upgrading energy density and longevity of lithium-sulfur batteries

Rechargeable lithium-sulfur (Li-S) batteries are deemed to one potential candidate for next-generation energy storage systems due to high theoretical energy density and environmental friendliness of sulfur. However, the sluggish redox kinetics and the inevitable shuttle effect of soluble polysulfides impede their commercialization process. Herein, the host–guest chemistry strategy has been proposed to fabricate ultrafine Co9S8/CoO nanoparticles embedded in porous carbon nanosheets (Co9S8/CoO@PC) for improving reversible conversion kinetics and adsorption ability toward polysulfides. Benefiting from bidirectional catalysis of Co9S8/CoO heterostructure and the fully exposed active sites on porous carbon nanosheets, the resultant Co9S8/CoO@PC-S electrode exhibits high specific capacity of 1549 mA h/g at 0.1C as well as outstanding cyclic stability with low average capacity decay of 0.021 % in 1000 cycles at high rate of 3C. Remarkably, the electrode delivers high specific capacities of 1209 and 756 mA h/g at 0.1C after 100 cycles with high sulfur loadings of 4.0 and 7.5 mg cm−2, respectively. This work provides new methodology for the controllable assembly of multiple dimensional composites to realize high energy density and long lifetime of Li-S batteries.