Aqueous Zinc Batteries Research Articles

Construction of VO2@V2C MXene heterostructure toward superior-rate rechargeable aqueous zinc batteries

V2C MXene delivers excellent metallic properties and robust mechanical stability. However, its low capacity, easy volume expansion during charge/discharge and relatively short cycle life limits its further development. It is an effective strategy to build Van der Waals heterostructures that can shield the monolithic materials from defects and integrate the advantages of the monolithic materials. Herein, via a one-step hydrothermal method, a VO2@V2C heterostructure is successfully constructed by the controllable oxidation of V2C, which allows for shorter ion diffusion distances, faster ion transport and enhancement of hydrophilic properties of the material. The VO2@V2C heterostructures have incredible reversibility (440.9 mAh/g at 0.2 A/g), remarkable cycling stability (142.7 mAh/g at 1.0 A/g after 900 cycles) and superior-rate capacity (255.3 mAh/g at 6.0 A/g). Density functional theory (DFT) calculations revealed that VO2@V2C possesses excellent adsorption capacity for zinc ions and outstanding electrical conductivity. The heterogeneous interface between the two materials is conducive to the increase of the embedding sites of zinc ions, which promotes the homogeneous distribution and rapid diffusion of zinc ions in the materials, and consequently enhances the capacity and cycling reliability of the electrodes. It provides a new idea for the selection of cathode electrodes for aqueous zinc ion batteries (ZIBs) in present study.

Cyclodextrin-assisted synthesis of nanostructured manganese oxide cathodes for high-performance aqueous Zn-ion batteries

Secondary aqueous zinc batteries (AZIBs) have gained substantial interest recently because of their excellent safety, affordability, and minimal ecological footprint. This study introduced a novel approach for synthesizing MnO2 using a straightforward one-step hydrothermal method in the presence of β-cyclodextrin and was employed as a cathode material for secondary AZIBs for the first time. The study systematically investigated the influence of β-cyclodextrin concentration on the morphology, crystal orientation, and electrochemical properties of MnO2 electrodes. The research found that varying the concentration of β-cyclodextrin resulted in different nanostructured MnO2 morphologies, namely δ-MnO2 and α-MnO2. This is the first time such distinct morphologies have been linked to β-cyclodextrin concentration. According to our experimental findings, the optimal β-cyclodextrin concentration for this study was 1.0wt%. The optimized 1.0wt%-CDM electrode exhibited an impressive discharge capacity of 205.2 mAh g-1 and 177.2 mAh g-1 when operated at 0.5 A g-1 and 1 A g-1, respectively. Notably, the 1.0wt%-CDM electrode maintained an impressive capacity of 129.2 mAh g-1 even after 1000 cycles, surpassing the performance of the pristine δ-MnO2 electrode (14.8 mAh g-1). This research highlights the potential of MnO2 nanostructures as promising candidates for developing commercial electrode materials.

Eco-friendly multi-function electrolyte additive enabling dendrite-free Zn anodes for rechargeable aqueous zinc batteries

Aqueous zinc ion batteries (AZIBs) are increasingly developing on account of their safety, high energy density, affordability and scalability. Nevertheless, the zinc anode encounters notable obstacles, including disruptive side reactions, unregulated dendrite growth and persistent hydrogen evolution. These challenges present barriers to the widespread adoption of AZIBs technology in practical applications. This study incorporates aspartame (ASPT) into the aqueous electrolyte to establish a novel interface between the anode and electrolyte, improve steric effects, and adjust the solvation structure of Zn2+. Theoretical computations elucidate how the ASPT additive interacts with both the electrolyte and Zinc anode. Experimental findings additionally validate the significant role of ASPT in concurrently managing the chemistry between the electrolyte environment and Zinc interface. Accordingly, Zn//Zn symmetric cells exhibit an enduring operational lifespan exceeding 3600 hours under a current of 1 mA cm−2 and 1 mA cm−2. Moreover, Zn//Ti asymmetric cells demonstrate prolonged durability with highly efficient Zn deposition and dissolution processes sustained over more than 300 cycles. Finally, the Zn//MnO2 full cells, upon assembly, demonstrate consistent cycling stability and retain high capacity throughout their operational cycle.

Symmetry Donor-Acceptor Molecule Regulating Hydrogen-Bonding Network for Improved Metal Zinc Anode.

The issues of zinc dendrites and side reactions caused by active water molecules have seriously affected the development of aqueous zinc batteries (AZBs). Herein, a symmetry hydrogen-bond donor-acceptor molecule additive named 1,3-bis(hydroxymethyl)urea (BHMU) can preferentially adsorb on the anode surface and lock up water molecules through hydrogen bonding, thus isolating water molecules and reducing side reactions caused by active water molecules. With these advantages, the mixed electrolyte containing BHMU additive impels a reversible Zn anode with a high Coulombic efficiency (99.7% over 1000 cycles at 1 mA cm-2), while it also enables a stable symmetric cell operated at 1 mA cm-2 (1 mAh cm-2, 6.89% DODZn) for 2250 h and 10 mA cm-2 (10 mAh cm-2, 68.9% DODZn) for 350 h. More importantly, the Zn||PTO full battery also delivered superior cycling stability and higher capacity after 3000 consecutive 3000 cycles of circulation at 5 A g-1. This study has great significance for the use of symmetry donor-acceptor molecules to modulate the solvation structure and the interface stability of the Zn anode in aqueous electrolytes.

Interlayer expanded magnesium vanadium bronze for high capacity stable aqueous zinc batteries and method for proton contribution calculation

Magnesium vanadium bronze, MgV6O16·6H2O, is demonstrated as a cathode material for aqueous zinc batteries. Its remarkable electrochemical performance is attributed to the hydrated magnesium pillar layer, which enhances zinc ion diffusion into the structure, yielding a high initial discharge capacity of 298 mAh g−1 and capacity retention above 97 % after 300 cycles. Zinc ions and protons are co-intercalated into the MgV6O16·6H2O structure, while zinc hydroxide sulfate forms on the surface during the discharge process. Ex-situ X-ray diffraction results and elemental analyses confirm the zinc and proton co-intercalation reaction within the MgV6O16·6H2O structure during cycling, providing detailed insights into the electrochemical mechanisms. These findings demonstrate the potential of MgV6O16·6H2O as a high-energy cathode material for aqueous zinc batteries and offer a comprehensive understanding of the zinc ion and proton co-intercalation mechanism in the MgV6O16·6H2O structure.

High-voltage and highly reversible redox chemistry of in situ cross-linked polydiphenylamine as an aqueous zinc battery cathode

Organic redox-active materials are promising electrode candidates for the next generation of rechargeable batteries owing to their versatile redox chemistry, sustainability, and potential low cost. Here, we present polydiphenylamine as a moderately high-voltage (1.25 V vs. Zn) and highly reversible organic cathode for aqueous zinc batteries. As revealed by cyclic voltammetry and spectroscopic analysis, the chemical oxidation–derived diphenylamine dimer electrochemically transforms into a cross-linked polymeric material during the first electrochemical oxidation (charge), which then operates by p-doping/dedoping redox of the amine center and a pseudocapacitor-like solid-state charge storage mechanism during the subsequent discharge-charge cycles. With an 80 wt% active loading, the polymer cathode delivers a specific capacity of 138 mAh/g at 100 mA/g, with 73% retention over 1000 cycles at a 99.8% Coulombic efficiency. Excellent rate capability is evidenced by 87 mAh/g capacity at 400 mA/g and highly stable cycling of over 1200 cycles under variable current rates. Facile one-step synthesis, fast charge storage kinetics, and attractive electrochemical performance establish polydiphenylamine as a notable organic cathode candidate for aqueous zinc batteries.

High‐performance vanadium oxide‐based aqueous zinc batteries: Organic molecule modification, challenges, and future prospects

AbstractAqueous Zn‐vanadium batteries have been attracting significant interest due to the high theoretical capacity, diverse crystalline structures, and cost‐effectiveness of vanadium oxide cathodes. Despite these advantages, challenges such as low redox potential, sluggish reaction kinetics, and vanadium dissolution lead to inferior energy density and unsatisfactory lifespan of vanadium oxide cathodes. Addressing these issues, given the abundant redox groups and flexible structures in organic compounds, this study comprehensively reviews the latest developments of organic‐modified vanadium‐based oxide strategies, especially organic interfacial modification, and pre‐intercalation. The review presents detailed analyses of the energy storage mechanism and multiple electron transfer reactions that contribute to enhanced battery performance, including boosted redox kinetics, higher energy density, and broadened lifespan. Furthermore, the review emphasizes the necessity of in situ characterization and theoretical calculation techniques for the further investigation of appropriate organic “guest” materials and matched redox couples in the organic‐vanadium oxide hybrids with muti‐energy storage mechanisms. The review also highlights strategies for Zn anode protection and electrolyte solvation regulation, which are critical for developing advanced Zn‐vanadium battery systems suitable for large‐scale energy storage applications.

Enhancing the efficiency of two-electron zinc-manganese batteries enabled by Glycine complexation of manganese ions and compatibility with zinc anodes

Aqueous Zn//MnO2 batteries, leveraging the Mn2+/MnO2 conversion reaction, are gaining significant interest for their high redox potential and cost-effectiveness. However, they typically require a highly acidic environment to initiate this redox process. Herein, Glycine (Gly), a gentle and safe amino acid, is employed to enhance the effectiveness of depositing and dissolving Mn2+/MnO2. On one hand, Gly can complex with Mn2+, reducing its concentration and releasing H+. This not only promotes the dissolution of MnO2 but also increases the electrode potential. On the other hand, the Gly attaches to the Zn metal anode’s surface, shielding it from unwanted reactions. Hence, the assembled aqueous Zn//MnO2 battery exhibits an elevated output voltage during the discharge of 1.5 V with high coulombic efficiency (0.5 mAh cm−2 capacity), a long cycling life and excellent rate. This work showcases an efficient approach to enable the two-electron process of MnO2 cathode materials in aqueous zinc batteries.

Revealing the intricacies of natural convection: A key factor in aqueous zinc battery design

Aqueous zinc-based batteries offer high safety, abundant resources, low cost, and environmental friendliness, making them a promising alternative to lithium-ion batteries for large-scale energy storage markets. However, the natural convection in the electrolyte during operation, which can greatly affect the battery performance, is overlooked for a long time. Through particle tracing experiments, this study demonstrates that in the vertical placement of the battery, natural convection occurs due to the variation of electrolyte density, whereas it does not happen when the cathode is on top. Besides, there is a significant difference in electrochemical performance between these two configurations, with a voltage difference of up to 0.25 V at 10 mA cm⁻² and a peak current difference of up to 3.4 mA in linear sweep voltammetry. Simulation results show that convective mass transfer can be up to 100 times greater than diffusive mass transfer in a bulk solution. This highlights the importance of considering natural convection to improve model accuracy. Further, to increase energy density, batteries are scaled up in practical applications to reduce the weight of the casing. This work simulates mass transfer conditions under various scenarios, illustrating the trade-off between current density and battery size, and offering new guidance for the design of aqueous zinc-based batteries.

Hydrophobic Interface Engineering for Highly Reversible and Stable Zn Anodes

AbstractRechargeable aqueous zinc batteries (AZIBs) with merits of high safety and high theoretical capacity are regarded as next‐generation energy storage devices. However, their practical application is hindered by the instable Zn anodes associated with the dendrite growth, parasite corrosion and side reactions. Developing a stable solid electrolyte interface is crucial for improving the cycling stability of Zn anodes. Herein, a hydrophobic interface is constructed on Zn anode through a simple heptafluorobutyrate acid etching route. The hydrophobic interface containing organic C─F, O─C═O and inorganic Zn─F bonds effectively address the issues of dendrites growth and parasitic reactions. Consequently, symmetric cells with acid‐treated Zn‐HA anodes achieve a prolonged lifespan of over 2000 h at 4.0 mA cm−2 and 1100 h at 10.0 mA cm−2. When paired with MnO2 cathode, the full cells deliver lower overpotential and outstanding cycling stability. This strategy provides a simple and feasible method to construct stable Zn anode for achieving high performance AZIBs.

Electrolyte Additive l-Lysine Stabilizes the Zinc Electrode in Aqueous Zinc Batteries for Long Cycling Performance.

Rechargeable aqueous Zn-ion batteries (AZIBs) have been recognized as competitive devices for large-scale energy storage due to their characteristics of low cost, safe operation, and environmental friendliness. Nevertheless, their practical applications are greatly limited by zinc dendrite growth and side reactions occurring at the anode/electrolyte interface. Herein, we propose an effective and simple electrolyte engineering strategy, which is the introduction of l-lysine additive containing two amino groups and one carboxyl group into a ZnSO4 electrolyte to achieve stable and reversible Zn depositions. Theoretical calculations and experimental results reveal that the l-lysine can adsorb on the Zn anode surface due to the strong coordination effects between amino groups and Zn metal (Zn-N binding) and induce the reduction of ZnSO4 into inorganic ZnS, which can not only prevent interfacial side reactions but also regulate interfacial electric field on the zinc electrode surface to guide uniform Zn2+ electrodeposition to inhibit zinc dendrites. Consequently, the l-lysine additive in the electrolyte enables Zn||Zn symmetric cells to achieve an ultralong stable cycling up to 2400 h at 1 mA cm-2 with a low polarization of only about 16 mV and Zn||Cu asymmetric cells to obtain a high average Coulombic efficiency of 99.80% after stably cycling for more than 2000 h at 2 mA cm-2 (1 mAh cm-2). In addition, the Zn||MnO2@CNT full cell in an l-lysine-containing electrolyte also exhibits good cycling performance. This study offers a new perspective on multifunctional electrolyte additive for achieving highly reversible Zn metal anodes in AZIBs.

Rational design of epoxy functionalized ionic liquids electrolyte additive for hydrogen-free and dendrite-free aqueous zinc batteries

Despite the high safety and low cost associated with aqueous Zn-ion batteries (ZIBs), uncontrolled Zn dendrite growth and parasitic reactions induced by water significantly diminish their stability. Herein, a new epoxy functionalized ionic liquid, 4-methyl-4-glycidylmorpholin bis[(trifluoromethyl)sulfonyl]imide (MGM[TFSI]), has been developed to mitigate water reactivity for stable ZIBs. It was found that the MGM+ cation disrupts the hydrogen bond network of water, hindering its adsorption on Zn anodes, thereby suppressing water decomposition and enhancing anode stability. Additionally, preferential adsorption of MGM+ cations on the Zn anode surface mitigates tip effects, suppresses dendrite growth, and promotes the formation of a ZnF2 solid electrolyte interphase layer, effectively isolating the anode from the bulk electrolyte. As a result, benefiting from the well-designed MGM+-based electrolyte, Zn//Zn cells achieve significantly enhanced cycling stability, lasting over 2000 h at 1 mA cm−2 with 1 mAh cm−2. Furthermore, Zn//MnO2 full cells deliver remarkable stability, retaining approximately 89 % of their initial capacity after 3000 cycles at 5 A/g. This work proposes that the MGM[TFSI] additive can effectively regulate the interfacial chemistry of the Zn anode, providing an opportunity to design advanced electrolytes for highly reversible ZIBs and beyond.

MXene Supported Electrodeposition Engineering of Layer Double Hydroxide for Alkaline Zinc Batteries

AbstractThe main challenges faced by aqueous rechargeable nickel‐zinc batteries are their comparatively low energy density and poor cycling stability, mainly due to the limited capacity and reversibility of existing Ni‐based cathodes. Moreover, the preparation procedures of these cathodes are complex and not easily scalable, which makes them less promising for large‐scale energy storage. Herein, we utilized MXene as a functional additive to effectively improve the electrodeposition preparation of NiCo layered double hydroxides (LDH). Benefiting from the improved interfacial contact between nickel foam (NF) and platting solution and the enhanced ionic conductivity of platting product based on MXene additives, the resulting binder‐free NiCo LDH electrode can achieve ultrahigh areal loading (~65 mg cm−2) with abundant active surface for redox reactions and maintained short transport pathway for ion diffusion and charge transfer. Furthermore, the as‐fabricated alkaline NiCo LDH‐based battery delivers high discharge capacity, up to 20.2 mAh cm−2 (311 mAh g−1), accompanied by remarkable rate performance (9.6 mAh cm−2 or 148 mAh g−1 at 120 mA cm−2). Due to the high structural and chemical stability of MXenes/LDH‐based electrode, excellent cycling life can also be achieved with 88.6 % capacity retention after 10000 cycles. In addition, ultrahigh areal energy density (31.2 mWh cm−2) and gravimetric energy density (465 Wh kg−1) can be simultaneously achieved. This work has inspired the design of advanced cathode materials to develop high‐performance aqueous zinc batteries.

Superhydrophobic metal-organic framework layers as multifunctional ion-conducting interfaces for ultra-stable Zn anodes

Aqueous zinc batteries (AZBs) show great promise for cost-effective, high-safety, and large-scale energy storage. Yet, corrosion and dendrite formation at the Zn anode interface undermine its stability, shortening the cycle life. In this work, a fluorosilane-modified metal-organic framework layer (F-MOF) is successfully prepared as a multifunctional ion-conductive interface to stabilize the Zn anode. The designed MOF-based artificial layer provides a uniform pathway for Zn deposition, while its hydrophobic nature prevents negative effects such as hydrogen evolution and corrosion. According to density functional theory (DFT) calculations, the hydration energy of Zn2+ in F-MOF@Zn(002) is reduced while the adsorption energy for Zn2+ is increased. This facilitates the desolvation process on the Zn anode surface, promoting uniform Zn deposition. Consequently, the lifespan of the F-MOF-coated Zn anode extends beyond 2000 h at a current density of 1 mA cm−2 (areal capacity: 0.5 mAh cm−2), significantly outlasting both bare Zn (225 h) and MOF-coated Zn (751 h) anodes. Additionally, the assembled coin cells and pouch-type full cells prove the practical availability of F-MOF@Zn anodes for AZBs. The F-MOF@Zn//MnO2 full cell maintains a high-capacity retention exceeding 91.9 % even after 1000 cycles. This work highlights the practical application potential of hydrophobic MOF coatings for AZBs.

Revitalizing Dead Zinc with Ferrocene/Ferrocenium Redox Chemistry for Deep-Cycle Zinc Metal Batteries.

Aqueous zinc (Zn) batteries are highly desirable for sustainable and large-scale electrochemical energy storage technologies. However, the ceaseless dendrite growth and the derived dead Zn are principally responsible for the capacity decay and insufficient lifespan. Here, we propose a dissolved oxygen-initiated revitalization strategy to reactivate dead Zn via ferrocene redox chemistry, which can be realized by incorporating a trace amount of poly(ethylene glycol) as a solubilizer to improve the solubility of water-insoluble ferrocene derivatives. Ferrocene scaffold can be spontaneously oxidized to ferricenium cations by dissolved oxygen, which eradicates the dissolved oxygen-involved Zn corrosion and insulating by-product generation. Subsequently, the generated ferricenium cations as the scavenger can rejuvenate electrically isolated dead Zn into electroactive Zn2+ ions to compensate the zinc loss. Through this design, the symmetric cell exhibited improved cycle life of 3700 h at 10 mA cm-2, and 220 h under a high depth of dischargeof 80%. Importantly, the Zn||NaV3O8·1.5H2O full cells demonstrated the impressive cycling stability over 1000 cycles at a low N/P ratio of 3.0. This work presents an innovative solution for the revitalization of dead Zn to extend the lifespan of deep-cycling metal batteries.

Revitalizing Dead Zinc with Ferrocene/Ferrocenium Redox Chemistry for Deep‐Cycle Zinc Metal Batteries

Aqueous zinc (Zn) batteries are highly desirable for sustainable and large‐scale electrochemical energy storage technologies. However, the ceaseless dendrite growth and the derived dead Zn are principally responsible for the capacity decay and insufficient lifespan. Here, we propose a dissolved oxygen‐initiated revitalization strategy to reactivate dead Zn via ferrocene redox chemistry, which can be realized by incorporating a trace amount of poly(ethylene glycol) as a solubilizer to improve the solubility of water‐insoluble ferrocene derivatives. Ferrocene scaffold can be spontaneously oxidized to ferricenium cations by dissolved oxygen, which eradicates the dissolved oxygen‐involved Zn corrosion and insulating by‐product generation. Subsequently, the generated ferricenium cations as the scavenger can rejuvenate electrically isolated dead Zn into electroactive Zn2+ ions to compensate the zinc loss. Through this design, the symmetric cell exhibited improved cycle life of 3700 h at 10 mA cm−2, and 220 h under a high depth of discharge of 80%. Importantly, the Zn||NaV3O8·1.5H2O full cells demonstrated the impressive cycling stability over 1000 cycles at a low N/P ratio of 3.0. This work presents an innovative solution for the revitalization of dead Zn to extend the lifespan of deep‐cycling metal batteries.

Highly reversible Zn anodes enabled by in-situ construction of zincophilic zinc polyacrylate interphase for aqueous Zn-ion batteries

The irreversibility and low utilization of Zn anode stemming from the corrosion and dendrite growth have largely limited the commercialization of aqueous zinc batteries. Here, a carbonyl-rich polymer interphase of zinc polyacrylate (ZPAA) is spontaneously in-situ constructed on Zn anode to address the above-mentioned dilemmas. The ZPAA interlayer enables fast transport kinetics of Zn2+ and tailors the interfacial electric field for realizing the uniform Zn deposition due to superior zincophilicity, high Zn2+ transference number and inherent ion-diffusion channel. Importantly, acting as a buffer interphase with strong adhesion and isolation of electrolytes, this functional layer effectively protects the Zn electrode against the water-induced erosion and passivation. Remarkably, the ZPAA@Zn electrode realizes an enhanced Coulombic efficiency of 99.71 % within 2200 cycles, delivers an ultra-long cycling stability over 7660 h (>319 days, 1 mA cm−2) and 2460 h (5 mA cm−2) with lower voltage hysteresis. Also, the ZPAA@Zn/MnO2 full cell maintains a high capacity of 114 mAh/g after 2000 cycles, much better that of untreated Zn/MnO2 cell (25 mAh/g). This concept of in-situ fabricating ion-sieve-like polymer interphase provides a facile approach to stabilize Zn anode and further paves a way for high-performance aqueous batteries.

Homogeneous Deposition of Zinc on N-Doped Carbon Fibers Interconnected with Sn Nanoparticles for Advanced Aqueous Zinc Batteries.

Currently, inhomogeneous distribution of Zn2+ on the surface of the Zn anode is still the essential reason for dendrite formation and unsatisfactory stability of zinc ion batteries. Given the merits of strong interaction between Sn and Zn, as well as a low nucleation barrier during Zn deposition, the combination of metallic Sn with carbon material is expected to improve the deposition of zinc ions and inhibit the growth of zinc dendrites by guiding the homogeneous plating/stripping of zinc on the electrode surface. In this article, zincophilic Sn nanoparticles with low nucleation barriers and strong interaction with Zn2+ were embedded into 3D N-doped carbon nanofibers using a simple electrostatic spinning technique. Accordingly, when serving as an artificial coating layer for the zinc metal anode, an ultrastable Sn@NCNFs@Zn||Sn@NCNFs@Zn symmetric cell can be achieved for over 3500 h with a low nucleation overpotential of 29.1 mV. Significantly, the full cell device assembled with the as-prepared anode and MnO2 cathode exhibits desirable electrochemical behaviors. Moreover, this simple method could be extended to other metal-carbon composites, and to ensure ease in scaling up as required. Such significant approach can provide an effective strategy for the design of high-performance zinc anodes.

Constructing a Fluoride‐Ion Tunnel‐Structured Interface to Stabilize the Zn Metal Chemistry at 50 °C

AbstractHigh‐temperature aqueous zinc batteries have recently garnered significant attention for large‐scale energy storage. However, spontaneous hydrogen evolution and passivation on the Zn metal anode severely affect its cycling stability under elevated temperature conditions. Herein, a facile strategy is employed to construct a bifunctional composite protective layer comprising an insulating ZnF2 layer combined with Zn affinity conductive tin (Sn) metal. This combination optimally distributes Zn ions (Zn2+) and maintains consistent thermal field distribution around Zn anodes. Moreover, the presence of fluorides on the interface efficiently suppresses the hydrogen evolution reaction, while the Sn metal serves as nucleation seeds with reversible alloying and dealloying process to endow dendrite‐free morphology and fast reaction kinetics. Specifically, the symmetric cell with the coated electrode exhibits excellent stability at a current density of 3 mA cm−2 over 420 h at 50 °C. When coupled with the modified Zn anode and I2 cathode, the Zn//I2 full cells deliver high areal capacity and substantiate their practical application, exhibiting remarkable high‐temperature resilience over 2000 cycles with 97.8% capacity retained at 50 °C.

Synergistic Electrocatalysis and Spatial Nanoconfinement to Accelerate Sulfur Conversion Kinetics in Aqueous Zn−S Battery

AbstractAqueous zinc batteries based on the conversion‐type sulfur cathodes are promising in energy storage system due to the high theoretical energy density, low cost, and good safety. However, the multi‐electron solid‐state intermediate conversion reaction of sulfur cathodes generally possess sluggish kinetics, which leads to lower discharge voltage and inefficient sulfur utilization, thus suppressing the practical energy density. Herein, sulfur nanoparticles derived from metal–organic frameworks confined in situ within electrospun fibers derived sulfur and nitrogen co‐doped carbon nanofibers (S@S,N−CNF) composite, which possesses yolk–shell S@C nanostructure, is fabricated through successive sulfidation, pyrolysis, and sulfide oxidation processes, and served as a high‐performance cathode material for Zn−S battery. The S and N dopants on carbon can collectively catalyse sulfur reduction reaction (SRR) by lowering energy barrier and accelerating kinetics to increase discharge voltage and specific capacity. Meanwhile, the yolk–shell S@C structure with spatially confined S nanoparticle yolks is beneficial to improve charge transfer and lower activation energy, thus further expediting SRR kinetics. Furthermore, extensive density functional theory (DFT) calculations reveal that S and N dual‐doping can thermodynamically and dynamically reduce the energy barrier of rate‐determining step (i.e., the transformation of *ZnS4 into *ZnS2) for the overall SRR, thereby significantly accelerating SRR kinetics.