Redox Conversion Research Articles

Approaching high rate All-Solid-State Lithium-Sulfur batteries via promoted sulfur conversion with nickel oxide nanoparticle electrocatalyst

All-solid-state lithium-sulfur battery (ASLSB) is deemed a promising next-generation energy storage device owing to its combination of high theoretical specific energy (2600 Wh kg−1) derived from the sulfur active material, and exceptional safety characteristics and the ability to suppress the polysulfide shuttle effect through the use of solid electrolyte (SE). However, the low electronic and ionic conductivity of sulfur, coupled with the poor solid–solid interfacial contact inherent in all-solid-state configuration, has resulted in poor electrochemical performance. Herein, NiO electrocatalyst supported on N-doped sites of super-p was synthesized and incorporated as a carbon additive in the composite cathode of the ASLSB. The direct growth of nanosized NiO electrocatalyst on the N-doped sites of super-p ensures facile electron transfer to the electrocatalyst surface, while maximizing the electrocatalyst’s surface area. As a result, the overpotential during charging and discharging of the ASLSB was significantly reduced, as assessed through galvanostatic intermittent titration technique and cyclic voltammetry, indicating enhanced redox conversion of sulfur. Furthermore, the Li6PS5Cl sulfide SE induces solid–solid conversion of sulfur, eliminating the dissolution issue of polysulfide intermediates and ensuring good cycle performance. The assembled ASLSB exhibits a high reversible capacity of 1845 mAh g−1 at 0.05C at room temperature and enhanced rate capability at high C-rates, operated at 60 °C. Even at a substantially high sulfur loading level of 6.65 mg cm−2, a maximum areal capacity of 9.48 mAh cm−2 was achieved at room temperature, highlighting the important role of electrocatalyst in realizing high performance ASLSBs.

Accelerated Sulfur Redox Kinetics on Transition Metal Sulfide Electrocatalysts by Modulating Electronic‐State of Active Sites

AbstractLithium‐sulfur (Li‐S) batteries are considered a competitive next‐generation electrochemical energy storage device, while the shuttle effect of soluble lithium polysulfides (LiPSs) resulting from the sluggish redox kinetics severely impedes their practical applications. Herein, a novel cation doping strategy is demonstrated for substantially accelerating the sulfur redox kinetics on the transition metal sulfide (TMS) electrocatalysts by partially substituting cobalt atoms with in situ dissolved Ni dopants (NixCo3‐xS4, 0<x≤1). Theoretical calculations revealed that the doping of Ni in the spinel Co3S4 phase enables the electronic‐state modulation of metal active sites by realizing the upshift of the d‐orbital center, thus leading to good chemical adsorption of intermediates and low redox conversion barriers between LiPSs and solid Li2S products. This is confirmed by in‐depth electrochemical dynamics and in situ Raman characterizations, in which the obtained Ni0.5Co2.5S4 with hierarchical nanosheet structure delivers the stronger chemical affinity of Li2S6 and higher precipitation/dissociation capacity of Li2S in comparison to monometallic cobalt sulfides. Benefiting from these outstanding attributes, the assembled Li‐S batteries by incorporating Ni0.5Co2.5S4 electrocatalysts into S@carbon nanotube cathode (S@Ni0.5Co2.5S4/CNT) exhibit a high specific capacity of 1189 mAh g−1 with excellent rate performance of 596 mAh g−1 at 5 C and long‐term cycling performance over 600 cycles with a capacity decay of 0.06% per cycle at 1 C. More importantly, an ultrahigh reversible areal capacity of 6.6 mAh cm−2 can be achieved for S@Ni0.5Co2.5S4/CNT cathode even with a high sulfur loading of 6.1 mg cm−2. This work demonstrates a new insight into designing TMS electrocatalysts toward rapid redox conversion kinetics in Li‐S batteries.

A Tellurium-Boosted High-Areal-Capacity Zinc-Sulfur Battery.

Aqueous rechargeable zinc-sulfur (Zn-S) batteries are a promising, cost-effective, and high-capacity energy storage technology. Still, they are challenged by the poor reversibility of S cathodes, sluggish redox kinetics, low S utilization, and unsatisfactory areal capacity. This work develops a facile strategy to achieve an appealing high-areal-capacity (above 5mAhcm-2) Zn-S battery by molecular-level regulation between S and high-electrical-conductivity tellurium (Te). The incorporation of Te as a dopant allows for manipulation of the Zn-S electrochemistry, resulting in accelerated redox conversion, and enhanced S utilization. Meanwhile, accompanied by the S-ZnS conversion, Te is converted to zinc telluride during the discharge process, as revealed by ex-situ characterizations. This additional redox reaction contributes to the S cathode's total excellent discharge capacity. With this unique cathode structure design, the carbon-confined TeS cathode (denoted as Te1S7/C) delivers a high reversible capacity of 1335.0mAhg-1 at 0.1Ag-1 with a mass loading of 4.22mgcm-2, corresponding to a remarkable areal capacity of 5.64mAhcm-2. Notably, a hybrid electrolyte design uplifts discharge plateau, reduces overpotential, suppresses Zn dendrites growth, and extends the calendar life of Zn-Te1S7 batteries. This study provides a rational S cathode structure to realize high-capacity Zn-S batteries for practical applications.

An NADH/NAD+-favored aldo-keto reductase facilitates avilamycin A biosynthesis by primarily catalyzing oxidation of avilamycin C.

Avilamycins, which possess potent inhibitory activity against Gram-positive bacteria, are a group of oligosaccharide antibiotics produced by Streptomyces viridochromogenes. Among these structurally related oligosaccharide antibiotics, avilamycin A serves as the main bioactive component in veterinary drugs and animal feed additives, which differs from avilamycin C only in the redox state of the two-carbon branched-chain of the terminal octose moiety. However, the mechanisms underlying assembly and modification of the oligosaccharide chain to diversify individual avilamycins remain poorly understood. Here, we report that AviZ1, an aldo-keto reductase in the avilamycin pathway, can catalyze the redox conversion between avilamycins A and C. Remarkably, the ratio of these two components produced by AviZ1 depends on the utilization of specific redox cofactors, namely NADH/NAD+ or NADPH/NADP+. These findings are inspired by gene disruption and complementation experiments and are further supported by in vitro enzymatic activity assays, kinetic analyses, and cofactor affinity studies on AviZ1-catalyzed redox reactions. Additionally, the results from sequence analysis, structure prediction, and site-directed mutagenesis of AviZ1 validate it as an NADH/NAD+-favored aldo-keto reductase that primarily oxidizes avilamycin C to form avilamycin A by utilizing abundant NAD+ in vivo. Building upon the biological function and catalytic activity of AviZ1, overexpressing AviZ1 in S. viridochromogenes is thus effective to improve the yield and proportion of avilamycin A in the fermentation profile of avilamycins. This study represents, to our knowledge, the first characterization of biochemical reactions involved in avilamycin biosynthesis and contributes to the construction of high-performance strains with industrial value.IMPORTANCEAvilamycins are a group of oligosaccharide antibiotics produced by Streptomyces viridochromogenes, which can be used as veterinary drugs and animal feed additives. Avilamycin A is the most bioactive component, differing from avilamycin C only in the redox state of the two-carbon branched-chain of the terminal octose moiety. Currently, the biosynthetic pathway of avilamycins is not clear. Here, we report that AviZ1, an aldo-keto reductase in the avilamycin pathway, can catalyze the redox conversion between avilamycins A and C. More importantly, AviZ1 exhibits a unique NADH/NAD+ preference, allowing it to efficiently catalyze the oxidation of avilamycin C to form avilamycin A using abundant NAD+ in cells. Thus, overexpressing AviZ1 in S. viridochromogenes is effective to improve the yield and proportion of avilamycin A in the fermentation profile of avilamycins. This study serves as an enzymological guide for rational strain design, and the resulting high-performance strains have significant industrial value.

Engineering Defect‐Rich Bimetallic Telluride with Dense Heterointerfaces for High‐Performance Lithium–Sulfur Batteries

AbstractRechargeable lithium–sulfur (Li–S) batteries have received ever‐increasing attention owing to their ultrahigh theoretical energy density, low cost, and environmental friendliness. However, their practical application is critically plagued by the sluggish reaction kinetics, shuttling of soluble polysulfide intermediates, and uncontrollable growth of Li dendrites. Herein, a bimetallic telluride electrocatalyst with dense heterointerfaces and rich defects embedded in hollow carbon polyhedron bunches (N⊂CoTe1‐x/ZnTe1‐y@NC, abbreviated as NCZTC) is rationally designed to simultaneously address the S cathode and Li anode problems. Both experimental and computational results substitute the integration of dense heterointerfaces and rich defects can synergistically modulate the electronic structure, enhance the electrical conductivity, promote the Li+ transportation, strengthen the polysulfides adsorption and improve the catalytic activity, thereby significantly accelerating the redox conversion kinetics and prevent the dendrite growth. Consequently, Li–S batteries with NCZTC‐modified separators demonstrate excellent electrochemical performance including high specific discharge capacity, remarkable rate capability, good long‐term cycling stability, and competitive areal capacity even at high sulfur loading and lean electrolyte conditions. This study not only provides valuable guidance for designing efficient sulfur electrocatalysts with transition metal tellurides but also emphasizes the importance of heterostructure design and defect engineering for high‐performance Li–S batteries.

Heterostructured nickel–cobalt metal alloy and metal oxide nanoparticles as a polysulfide mediator for stable lithium–sulfur full batteries with lean electrolyte

AbstractBatteries that utilize low‐cost elemental sulfur and light metallic lithium as electrodes have great potential in achieving high energy density. However, building a lithium–sulfur (Li–S) full battery by controlling the electrolyte volume generally produces low practical energy because of the limited electrochemical Li–S redox. Herein, the high energy/high performance of a Li–S full battery with practical sulfur loading and minimum electrolyte volume is reported. A unique hybrid architecture configured with Ni–Co metal alloy (NiCo) and metal oxide (NiCoO2) nanoparticles heterogeneously anchored in carbon nanotube‐embedded self‐standing carbon matrix is fabricated as a host for sulfur. This work demonstrates the considerable improvement that the hybrid structure's high conductivity and satisfactory porosity promote the transport of electrons and lithium ions in Li–S batteries. Through experimental and theoretical validations, the function of NiCo and NiCoO2 nanoparticles as an efficient polysulfide mediator is established. These particles afford polysulfide anchoring and catalytic sites for Li–S redox reaction, thus improving the redox conversion reversibility. Even at high sulfur loading, the nanostructured Ni–Co metal alloy and metal oxide enable to have stable cycling performance under lean electrolyte conditions both in half‐cell and full‐cell batteries using a graphite anode.

Deep Multiphase Conversion Derived from NiTe2 Nanosheets with Preferred Kinetics for Highly Reversible Mild Aqueous Zinc–Tellurium Batteries

AbstractConversion‐type tellurium‐based cathodes have attracted great attention in aqueous zinc‐ion batteries (AZIBs) due to potentially high capacity with impressive Te4+/Te0/Te2− conversion. However, impeded by the low‐conductivity Te4+ species and unpreferred kinetics, realizing deep zinc‐tellurium redox remains a major challenge. Herein, energetic NiTe2 nanosheets are first proposed and implemented as preprepared tellurium‐based deep redox cathodes in AZIBs with accelerated electron transport and favorable kinetics. Operando synchrotron X‐ray diffraction and comprehensive ex situ characterizations demonstrate that Te4+ species from direct oxidation of NiTe2 in dilute mild‐aqueous electrolyte undergo a thermodynamic two‐step TeO2→Te→ZnTe discharge process, while the intertwined tellurium oxides and high‐conductivity nickel monomers derived in situ from NiTe2 nanosheets promote a kinetics‐preferred one‐step ZnTe→TeO2 charging conversion with significantly boosted reversibility. Therefore, a high capacity of 510 mAh g−1 at 50 mA g−1 and 93% capacity retention over 400 cycles at 2000 mA g−1 are established. Operando pH tracking and electrode‐electrolyte engineering analyses define that the mild electrolyte environment rich in moisture and electrode conductivity optimization are both critical for achieving reversible tellurium deep redox conversion.

Electrochemical Redox Conversion of Formate to CO via Coupling Fe-Co Layered Double Hydroxides and Au Catalysts.

Formate has been considered an inactive molecule and thus cannot be further reduced under CO2 reduction conditions, which limits its widespread application as feedstock. Here we present an electrochemical redox conversion of formate to CO through the potential-dependent generation of carbon dioxide radical anions (CO2 ⋅- ) on Fe-Co layered double hydroxides (Fe-Co LDHs) and the subsequent reduction of CO2 ⋅- to CO on Au catalysts. We present an electrodeposition protocol for the synthesis of Fe-Co LDHs with precise composition control and find that Fe1 Co4 exhibits a promising potential window for CO2 ⋅- formation between 1.14 and 1.4 V and an optimized potential at 1.24 V at a neutral pH condition. We further determined the formation of CO2 ⋅- at 1.24 V via electron paramagnetic resonance and CO2 at >1.4 V through differential electrochemical mass spectrometry. This work provides a redox chemistry route for converting formate into CO through a coupled slit parallel-plate electrode system.

High-Entropy MXene as Bifunctional Mediator toward Advanced Li-S Full Batteries.

The development of high-energy-density Li-S batteries (LSBs) is still hindered by the disturbing polysulfide shuttle effect. Herein, with clever combination between "high entropy" and MXene, an HE-MXene doped graphene composite containing multiple element quasi-atoms as bifunctional mediator for separator modification (HE-MXene/G@PP) in LSBs is proposed. The HE-MXene/G@PP offers high electrical conductivity for fast lithium polysulfide (LiPS) redox conversion kinetics, abundant metal active sites for efficient chemisorption with LiPSs, and strong lipophilic characteristics for uniform Li+ deposition on lithium metal surface. As demonstrated by DFT theoretical calculations, in situ Raman, and DRT results successively, HE-MXene/G@PP efficiently captures LiPSs through synergistic modulation of the cocktail effect and accelerates the LiPSs redox reaction, and the lattice distortion effect effectively induces the homogeneous deposition of dendritic-free lithium. Therefore, this work achieves excellent long-term cycling performance with a decay rate of 0.026%/0.031% per cycle after 1200 cycles at 1 C/2 C. The Li||Li symmetric cell still maintains a stable overpotential after 6000 h under 40 mA cm-2/40 mAh cm-2. Furthermore, it delivers favorable cycling stability under 7.8 mg cm-2 and a low E/S ratio of 5.6 μL mg-1. This strategy provides a rational approach to resolve the sulfur cathode and lithium anode problems simultaneously.

Metal-organic-framework derived NiS2/C hollow structures for enhanced polysulfide redox kinetics in lithium-sulfur batteries.

To cope with the shuttling of soluble lithium polysulfides in lithium-sulfur batteries, confinement tactics, such as trapping of sulfur within porous carbon structures, have been extensively studied. Although performance has improved a bit, the slow polysulfide conversion inducing fast capacity decay remains a big challenge. Herein, a NiS2/carbon (NiS2/C) composite with NiS2 nanoparticles embedded in a thin layer of carbon over the surface of micro-sized hollow structures has been prepared from Ni-metal-organic frameworks. These unique structures can physically entrap sulfur species and also influence their redox conversion kinetics. By improving the reaction kinetics of polysulfides, the NiS2/carbon@sulfur (NiS2/C@S) composite cathode with a suppressed shuttle effect shows a high columbic efficiency and decent rate performance. An initial capacity of 900 mAh g-1 at the rate of 1 C (1 C = 1675 mA g-1) and a low-capacity decline rate of 0.132% per cycle after 500 cycles are obtained, suggesting that this work provides a rational design of a sulfur cathode.

Hybrid Membrane Composed of Nickel Diselenide Nanosheets with Carbon Nanotubes for Catalytic Conversion of Polysulfides in Lithium-Sulfur Batteries.

Lithium-sulfur batteries demonstrate enormous energy density are promising forms of energy storage. Unfortunately, the slow redox kinetics and polysulfides shuttle effect are some of the factors that prevent the its development. To address these issues, the hybrid membrane with combination of nickel diselenide nanosheets modified carbon nanotubes (NSN@CNTs) and utilized Li2 S6 catholyte for lithium sulfur battery. The conductive CNTs facilitates fast electronic/ionic transport, while the polarity of NSN as a strong affinity to lithium polysulfides, effectively anchoring them, facilitating the redox conversion of polysulfide species, and effectively diminishing reaction barriers. The cell with NSN@CNTs delivers the first discharge capacity of 1123.8 mAh g-1 and maintains 786.5 mAh g-1 after 300 cycles (0.2 C) at the sulfur loading 5.4 mg. Its rate capability is commendable, enabling it to sustain a capacity of 559.8 mAh g-1 even at a high discharge rate of 2 C. In addition, its initial discharge capacity can remain 8.33 mAh even at 10.8 mg for duration of 100 cycles. This research indicates the potential application of NSN@CNTs hybrid materials in lithium-sulfur batteries.

Carbon nanotubes integrated with multiphasic molybdenum diselenide nanosheets as hybrid membrane accomplish highly efficient electrocatalysts for lithium-sulfur batteries

Lithium sulfur (Li-S) batteries are considered a promising application device due to their high theoretical capacity and energy density. However, the commercialization of Li-S batteries is hindered by the rapid capacity fading caused by the shuttle effect of lithium polysulfide (LiPSs) and the sluggish redox reaction of sulfur cathodes. To address these issues, the hybrid membrane with combination of multiphasic molybdenum diselenide nanosheets (MMS) modified carbon nanotubes (MMS@CNTs) and utilized Li2S6 catholyte for Li-S batteries. The conductivity CNTs facilitate fast electronic/ionic transport, while the polarity of MMS has a strong affinity for LiPSs, effectively anchoring them, facilitating the redox conversion of lithium polysulfides, and effectively diminishing reaction barriers. The cell with MMS@CNTs displays an initial discharge capacity of 1036.2 mAh g−1 and maintains 810.5 mAh g−1 after 300 cycles at 0.2 C with 5.4 mg sulfur loading. Remarkably, even at 10.8 mg sulfur loading, the MMS@CNTs membrane displays high capacity of 8.1 mAh and maintains 6.7 mAh over 100 cycles. The results show that the efficient chemical anchoring polysulfides and catalyzing redox reaction by multifunctional MMS@CNTs hybrid composites is promising for assembling with a high sulfur loading electrode, which exhibits a superior electrochemical performance in Li-S batteries.

Fast redox conversion in lithium–sulfur batteries enabled by Cu-doped W18O49 with abundant oxygen defects

Abundant oxygen defects in W18O49 nanorods are designed via Cu doping, which can not only provide abundant suspended unsaturated metal atoms but also promote electron transfer, greatly accelerating the redox conversion of LiPS in Li//S batteries.

Ti3C2Tx nanosheet@Cu/Fe-MOF separators for high-performance lithium-sulfur batteries: an experimental and density functional theory study.

Lithium-sulfur (Li-S) batteries have attracted much attention due to their superior theoretical specific capacity and high theoretical energy density. However, rapid capacity fading originating from the shuttle effect, insulating the S cathode and the dendrite formation on the Li anode restrict the practical applications of Li-S batteries. Herein, we suggest novel coatings on glass fiber separators to satisfy all high-performance Li-S battery requirements. A conductive Ti3C2Tx (MXene) nanosheet/Fe-MOF or Ti3C2Tx (MXene) nanosheet/Cu-MOF layer was coated on a glass fiber separator to act as a polysulfide trapping layer. The MXene layer with high conductivity and polar surface functional groups could confine polysulfides and accelerate the redox conversions. The porous MOF layer acts as a Li ion sieve, thereby leading to the interception of polysulfides and mitigation of Li dendrite growth. The cells with the Cu-MOF/MXenes and Fe-MOF/MXene separators display superior capacities of 1100 and 1131 mA h g-1 after 300 cycles, respectively, whereas the cell with a pure glass fiber separator delivers a very low capacity of 309 mA h g-1 after 300 cycles. With Fe-MOF/MXene and Cu-MOF/MXene configurations, the discharge capacity, coulombic efficiency, cycling stability, and electrochemical conversion reactions are significantly improved. Our ab initio calculations demonstrate that the MXene layer dissociates lithium polysulfides into adsorbed S and mobile Li ions, which explains the experimental findings.

Dual-functional mediators of high-entropy Prussian blue analogues for lithiophilicity and sulfiphilicity in Li-S batteries.

Lithium-sulfur (Li-S) batteries are considered promising next-generation energy storage systems due to their high energy density (2600 W h kg-1) and cost-effectiveness. However, the shuttle effect of lithium polysulfides in sulfur cathodes and uncontrollable Li dendrite growth in Li metal anodes significantly impede the practical application of Li-S batteries. In this study, we address these challenges by employing a high-entropy Prussian blue analogue Mn0.4Co0.4Ni0.4Cu0.4Zn0.4[Fe(CN)6]2 (HE-PBA) composite containing multiple metal ions as a dual-functional mediator for Li-S batteries. Specifically, the HE-PBA composite provides abundant metal active sites that efficiently chemisorb lithium polysulfides (LiPSs) to facilitate fast redox conversion kinetics of LiPSs. In Li metal anodes, the exceptional lithiophilicity of the HE-PBA ensures a homogeneous Li ion flux, resulting in uniform Li deposition while mitigating the growth of Li dendrites. As a result, our work demonstrates outstanding long-term cycling performance with a decay rate of only 0.05% per cycle over 1000 cycles at 2.0 C. The HE-PBA@Cu/Li anode maintains a stable overpotential even after 600 h at 0.5 mA cm-2 under the total areal capacity of 1.0 mA h cm-2. This study showcases the application potential of the HE-PBA in Li-S batteries and encourages further exploration of prospective high-entropy materials used to engineer next-generation batteries.

Self-tandem catalysis of fast Mg2+ desolvation and sulfur conversions for ultrahigh-performance Mg–S batteries via serially-assembled atomic reactors

Serially-assembled train-like atomic reactors employed in long-conductive nanocarbons were initially designed to achieve fast interfacial Mg2+ desolvation kinetics for improving subsequent sulfur redox conversion kinetics.

Cobalt-zinc carbides embedded in N-doped porous carbon nanospheres as polysulfide mediators for efficient lithium-sulfur batteries.

Developing high-efficiency interlayer catalysts is a promising tactic for improving the cycling performance of rechargeable lithium-sulfur (Li-S) batteries. Herein, using the Prussian blue analogue as the precursor, cobalt-zinc carbide nanocrystal-embedded N-doped porous carbon (Co3ZnC@NC) is synthesized via simple post-carbonization. The obtained Co3ZnC@NC nanospheres exhibit a robust core-shell structure showing good conductivity, high porosity and available metal active sites, favoring the interfacial charge transfer and the electron transport upon electrochemical reactions. The results demonstrate that the Co3ZnC@NC catalyst is quite suitable for boosting the adsorption and redox conversion kinetics of soluble polysulfides. When acting as the separator interlayer, Co3ZnC@NC contributes to improved Li-S batteries with a high discharge specific capacity of 1659.8 mA h g-1 at 0.1C and superior cycling stability of over 250 cycles at 1.0C (high capacity retention of 84.1% after 100 cycles at 0.5C). Furthermore, the Co3ZnC@NC-based battery can maintain a high discharge capacity of 734.0 mA h g-1 at 5.0C, along with delivering a stable reversible capacity of 805.4 mA h g-1 (∼5 mA h cm-2) after 50 cycles even under a high sulfur loading of 6.2 mg cm-2. This study affords a viable way to construct highly dispersed bimetal/carbon composites for efficient catalysts and renewable energy devices.

A Universal MOF‐Confined Strategy to Synthesize Atomically Dispersed Metal Electrocatalysts Toward Fast Redox Conversion in Lithium‐Sulfur Batteries

AbstractAccelerating catalytic conversion of lithium polysulfides (LiPSs) is a promising way to address the shuttle effect of lithium‐sulfur (Li‐S) batteries but remains a challenge to date. Herein, a universal metal‐organic framework (MOF)‐confined strategy is proposed to fabricate atomically dispersed metal catalysts (ADMCs) with the help of ethylenediaminetetraacetic acid (EDTA) toward fast redox conversion in Li‐S batteries. In the synthesis, the EDTA acts as not only the coupling agent for the chemical bonding with unsaturated sites of MOF but also the chelating agent for metal ion capture and further confining them into MOF. As a proof of concept, the ADMCs made of transition metal sites anchored on MOF‐808 (named MOF‐808‐M, M = Fe, Co, Ni, Cu, Zn, etc.) are obtained, with well‐defined M‐N2O2 configurations. The in‐depth experiments and theoretical calculations reveal that the atomically dispersed M‐N2O2 sites are capable of enhancing the chemical affinity of MOF‐808‐M toward LiPSs and further accelerating their redox conversion by reducing the energy barrier of the rate‐limiting step. As a result, the assembled Li‐S batteries with S@MOF‐808‐M cathode, represented by S@MOF‐808‐Zn exhibit a high reversible specific capacity of 1192 mAh g−1 at 0.1 C, excellent rate capability of 599 mAh g−1 at 2 C, and remarkable long‐term cycling stability with a capacity retention rate of 94.6% after 300 cycles at 1 C. Moreover, the high areal capacity of 4.79 mAh cm−2 at 0.2 C with a sulfur loading of 5.14 mg cm−2 for S@MOF‐808‐M cathode can be achieved. This work presents a universal strategy to fabricate ADMCs with well‐defined active centers by combining the advantages of MOF for Li‐S batteries.

Pyridyl Porphyrin as Electrocatalyst: Regulating the Redox Conversion of Lithium Polysulfides under Voltage

AbstractThe binding correlation between electrocatalyst and lithium polysulfides (LiPSs) determines the regulation of LiPSs’ redox conversion. However, how the correlation works on the LiPSs under voltage remains obscured. In this paper, the π‐conjugated aromatic pyridyl porphyrin with nitrogen of a lone pair of electrons is introduced as electrocatalyst to accelerate redox kinetics and inhibit polysulfides shuttle. On the foundation of DFT calculation and experimental tests, it is stated that the chemical binding between pyridyl porphyrin and lithium polysulfides is beefed up under higher voltage, which facilitates the charge transfer. Moreover, the molecular dynamics (MD) simulation of the solid‐liquid model shows that the presence of pyridyl porphyrin increases the binding chances between Li+ and S62− and forms clusters rather than dissolving in electrolyte, which is good for charge transfer and polysulfides localization. By hybridizing the pyridyl porphyrin with conductive cathode matrix of carbon nanotube and graphene oxide, the as‐fabricated Li2S‐T4PP‐GO‐CNT cathode delivers a high initial discharge capacity of 996.4 mAh g−1 at 0.1 C. The as‐made batteries with good electrochemical performance therefore show potential for trouble‐shooting and commercial utilization of lithium‐sulfur batteries (LSBs) in the future.

Fast redox conversion and low shuttle effect enabled by functionalized zeolite for high-performance lithium–sulfur batteries

Lithium–sulfur (Li–S) batteries are among the most promising next-generation rechargeable battery systems because of their high theoretical energy density and low cost. Nevertheless, the notorious shuttle effect of polysulfides and poor redox kinetics significantly limit their practical applications. Herein, a metallic cobalt-doped ZSM-5 zeolite with extra-framework Li+ is constructed to inhibit the migration of polysulfides and simultaneously enhance their conversion kinetics via a separator coating strategy. The ZSM-5 zeolite possessing a sub-nanometer channel structure acts as an ionic sieve, and effectively suppresses the undesired polysulfide migration by spatial constraint. The negatively charged zeolite framework with Li+ as counterions helps to facilitate the fast Li+ transport. More importantly, Co dopants further strengthen the interaction with polysulfides and work as active sites to improve the kinetics of sulfur redox reactions, which is verified by theoretical calculations and experiments. As expected, a Li–S battery employing the modified separator delivers superior long-term cyclic stability (only 0.04% capacity decay per cycle over 500 cycles at 1.0 C) and excellent rate capability (706 mAh g−1 at 3.0 C). In addition, the stable operation of an assembled Li–S pouch cell under various bending angles demonstrates its feasibility in practical applications. This work offers a new insight into the design of advanced separator modifiers for high-performance Li–S batteries.