A New rGO‐Overcoated Sb2Se3 Nanorods Anode for Na+ Battery: In Situ X‐Ray Diffraction Study on a Live Sodiation/Desodiation Process

Sodium ion batteries (SIBs) are a promising alternative to lithium ion batteries for a broader range of energy storage applications in the future. However, the development of high‐performance anode materials is a bottleneck of SIBs advancement. In this work, Sb₂Se₃ nanorods uniformly wrapped by reduced graphene oxide (rGO) as a promising anode material for SIBs are reported. The results show that such Sb₂Se₃/rGO hybrid anode yields a high reversible mass‐specific energy capacity of 682, 448, and 386 mAh g^?1 at a rate of 0.1, 1.0, and 2.0 A g^?1, respectively, and sustains at least 500 stable cycles at a rate of 1.0 A g^?1 with an average mass‐specific energy capacity of 417 mAh g^?1 and capacity retention of 90.2%. In situ X‐ray diffraction study on a live SIB cell reveals that the observed high performance is a result of the combined Na⁺ intercalation, conversion reaction between Na⁺ and Se, and alloying reaction between Na⁺ and Sb. The presence of rGO also plays a key role in achieving high rate capacity and cycle stability by providing good electrical conductivity, tolerant accommodation to volume change, and strong electron interactions to the base Sb₂Se₃ anode.     

Reconstruction of Conformal Nanoscale MnO on Graphene as a High‐Capacity and Long‐Life Anode Material for Lithium Ion Batteries

To tackle the issue of inferior cycle stability and rate capability for MnO anode materials in lithium ion batteries, a facile strategy is explored to prepare a hybrid material consisting of MnO nanocrystals grown on conductive graphene nanosheets. The prepared MnO/graphene hybrid anode exhibits a reversible capacity as high as 2014.1 mAh g^?1 after 150 discharge/charge cycles at 200 mA g^?1, excellent rate capability (625.8 mAh g^?1 at 3000 mA g^?1), and superior cyclability (843.3 mAh g^?1 even after 400 discharge/charge cycles at 2000 mA g^?1 with only 0.01% capacity loss per cycle). The results suggest that the reconstruction of the MnO/graphene electrodes is intrinsic due to conversion reactions. A long‐term stable nanoarchitecture of graphene‐supported ultrafine manganese oxide nanoparticles is formed upon cycling, which yields a long‐life anode material for lithium ion batteries. The lithiation and delithiation behavior suggests that the further oxidation of Mn(II ) to Mn(IV ) and the interfacial lithium storage upon cycling contribute to the enhanced specific capacity. The excellent rate capability benefits from the presence of conductive graphene and a short transportation length for both lithium ions and electrons. Moreover, the as‐formed hybrid nanostructure of MnO on graphene may help achieve faster kinetics of conversion reactions.     

Enhanced Reversible Sodium‐Ion Intercalation by Synergistic Coupling of Few‐Layered MoS2 and S‐Doped Graphene

Sodium‐ion batteries (SIBs) are regarded as the best alternative to lithium‐ion batteries due to their low cost and similar Na⁺ insertion chemistry. It is still challenging but greatly desired to design and develop novel electrode materials with high reversible capacity, long cycling life, and good rate capability toward high‐performance SIBs. This work demonstrates an innovative design strategy and a development of few‐layered molybdenum disulfide/sulfur‐doped graphene nanosheets (MoS₂/SG) composites as the SIB anode material providing a high specific capacity of 587 mA h g^?1 calculated based on the total composite mass and an extremely long cycling stability over 1000 cycles at a current density of 1.0 A g^?1 with a high capacity retention of ≈85%. Systematic characterizations reveal that the outstanding performance is mainly attributed to the unique and robust composite architecture where few‐layered MoS₂ and S‐doped graphene are intimately bridged at the hetero‐interface through a synergistic coupling effect via the covalently doped S atoms. The design strategy and mechanism understanding at the molecular level outlined here can be readily applied to other layered transition metal oxides for SIBs anode and play a key role in contributing to the development of high‐performance SIBs.     

Walnut‐Like Multicore–Shell MnO Encapsulated Nitrogen‐Rich Carbon Nanocapsules as Anode Material for Long‐Cycling and Soft‐Packed Lithium‐Ion Batteries

Metal oxide‐based nanomaterials are widely studied because of their high‐energy densities as anode materials in lithium‐ion batteries. However, the fast capacity degradation resulting from the large volume expansion upon lithiation hinders their practical application. In this work, the preparation of walnut‐like multicore–shell MnO encapsulated nitrogen‐rich carbon nanocapsules (MnO@NC) is reported via a facile and eco‐friendly process for long‐cycling Li‐ion batteries. In this hybrid structure, MnO nanoparticles are uniformly dispersed inside carbon nanoshells, which can simultaneously act as a conductive framework and also a protective buffer layer to restrain the volume variation. The MnO@NC nanocapsules show remarkable electrochemical performances for lithium‐ion batteries, exhibiting high reversible capability (762 mAh g^?1 at 100 mA g^?1) and stable cycling life (624 mAh g^?1 after 1000 cycles at 1000 mA g^?1). In addition, the soft‐packed full batteries based on MnO@NC nanocapsules anodes and commercial LiFePO₄ cathodes present good flexibility and cycling stability.     

Few‐Layer MoSe2 Nanosheets with Expanded (002) Planes Confined in Hollow Carbon Nanospheres for Ultrahigh‐Performance Na‐Ion Batteries

Sodium‐ion batteries (SIBs) are considered as a promising alternative to lithium‐ion batteries, due to the abundant reserves and low price of Na sources. To date, the development of anode materials for SIBs is still confronted with many serious problems. In this work, encapsulation‐type structured MoSe₂@hollow carbon nanosphere (HCNS) materials assembled with expanded (002) planes few‐layer MoSe₂ nanosheets confined in HCNS are successfully synthesized through a facile strategy. Notably, the interlayer spacing of the (002) planes is expanded to 1.02 nm, which is larger than the intrinsic value of pristine MoSe₂ (0.64 nm). Furthermore, the few‐layer nanosheets are space‐confined in the inner cavity of the HCNS, forming hybrid MoSe₂@HCNS structures. When evaluated as anode materials for SIBs, it shows excellent rate capabilities, ultralong cycling life with exceptional Coulombic efficiency even at high current density, maintaining 501 and 471 mA h g^?1 over 1000 cycles at 1 and 3 A g^?1, respectively. Even when cycled at current densities as high as 10 A g^?1, a capacity retention of 382 mA h g^?1 can be achieved. The expanded (002) planes, 2D few‐layer nanosheets, and unique carbon shell structure are responsible for the ultralong cycling and high rate performance.     

Rambutan‐Like Hybrid Hollow Spheres of Carbon Confined Co3O4 Nanoparticles as Advanced Anode Materials for Sodium‐Ion Batteries

Transition metal oxides, possessing high theoretical specific capacities, are promising anode materials for sodium‐ion batteries. However, the sluggish sodiation/desodiation kinetics and poor structural stability restrict their electrochemical performance. To achieve high and fast Na storage capability, in this work, rambutan‐like hybrid hollow spheres of carbon confined Co₃O₄ nanoparticles are synthesized by a facile one‐pot hydrothermal treatment with postannealing. The hierarchy hollow structure with ultrafine Co₃O₄ nanoparticles embedded in the continuous carbon matrix enables greatly enhanced structural stability and fast electrode kinetics. When tested in sodium‐ion batteries, the hollow structured composite electrode exhibits an outstandingly high reversible specific capacity of 712 mAh g^?1 at a current density of 0.1 A g^?1, and retains a capacity of 223 mAh g^?1 even at a large current density of 5 A g^?1. Besides the superior Na storage capability, good cycle performance is demonstrated for the composite electrode with 74.5% capacity retention after 500 cycles, suggesting promising application in advanced sodium‐ion batteries.     

Layered P2‐Type K0.65Fe0.5Mn0.5O2 Microspheres as Superior Cathode for High‐Energy Potassium‐Ion Batteries

Potassium‐ion batteries have been regarded as the potential alternatives to lithium‐ion batteries (LIBs) due to the low cost, earth abundance, and low potential of K (?2.936 vs standard hydrogen electrode (SHE)). However, the lack of low‐cost cathodes with high energy density and long cycle life always limits its application. In this work, high‐energy layered P2‐type hierarchical K_0.65Fe_0.5Mn_0.5O₂ (P2‐KFMO) microspheres, assembled by the primary nanoparticles, are fabricated via a modified solvent‐thermal method. Benefiting from the unique microspheres with primary nanoparticles, the K⁺ intercalation/deintercalation kinetics of P2‐KFMO is greatly enhanced with a stabilized cathodic electrolyte interphase on the cathode. The P2‐KFMO microsphere presents a highly reversible potassium storage capacity of 151 mAh g^?1 at 20 mA g^?1, fast rate capability of 103 mAh g^?1 at 100 mA g^?1, and long cycling stability with 78% capacity retention after 350 cycles. A full cell with P2‐KFMO microspheres as cathode and hard carbon as anode is constructed, which exhibits long‐term cycling stability (>80% of retention after 100 cycles). The present high‐performance P2‐KFMO microsphere cathode synthesized using earth‐abundant elements provides a new cost‐effective alternative to LIBs for large‐scale energy storage.     

Sodium Storage Behavior in Natural Graphite using Ether‐based Electrolyte Systems

This work reports that natural graphite is capable of Na insertion and extraction with a remarkable reversibility using ether‐based electrolytes. Natural graphite (the most well‐known anode material for Li–ion batteries) has been barely studied as a suitable anode for Na rechargeable batteries due to the lack of Na intercalation capability. Herein, graphite is not only capable of Na intercalation but also exhibits outstanding performance as an anode for Na ion batteries. The graphite anode delivers a reversible capacity of ≈150 mAh g^?1 with a cycle stability for 2500 cycles, and more than 75 mAh g^?1 at 10 A g^?1 despite its micrometer‐size (≈100 μm). An Na storage mechanism in graphite, where Na⁺‐solvent co‐intercalation occurs combined with partial pseudocapacitive behaviors, is revealed in detail. It is demonstrated that the electrolyte solvent species significantly affect the electrochemical properties, not only rate capability but also redox potential. The feasibility of graphite in a Na full cell is also confirmed in conjunction with the Na_1.5VPO_4.8F_0.7 cathode, delivering an energy of ≈120 Wh kg^?1 while maintaining ≈70% of the initial capacity after 250 cycles. This exceptional behavior of natural graphite promises new avenues for the development of cost‐effective and reliable Na ion batteries.     

All‐Cellulose‐Based Quasi‐Solid‐State Sodium‐Ion Hybrid Capacitors Enabled by Structural Hierarchy

Na‐ion hybrid capacitors consisting of battery‐type anodes and capacitor‐style cathodes are attracting increasing attention on account of the abundance of sodium‐based resources as well as the potential to bridge the gap between batteries (high energy) and supercapacitors (high power). Herein, hierarchically structured carbon materials inspired by multiscale building units of cellulose from nature are assembled with cellulose‐based gel electrolytes into Na‐ion capacitors. Nonporous hard carbon anodes are obtained through the direct thermal pyrolysis of cellulose nanocrystals. Nitrogen‐doped carbon cathodes with a coral‐like hierarchically porous architecture are prepared via hydrothermal carbonization and activation of cellulose microfibrils. The reversible charge capacity of the anode is 256.9 mAh g^?1 when operating at 0.1 A g^?1 from 0 to 1.5 V versus Na⁺/Na, and the discharge capacitance of cathodes tested within 1.5 to 4.2 V versus Na⁺/Na is 212.4 F g^?1 at 0.1 A g^?1. Utilizing Na⁺ and ClO₄^? as charge carriers, the energy density of the full Na‐ion capacitor with two asymmetric carbon electrodes can reach 181 Wh kg^?1 at 250 W kg^?1, which is one of the highest energy devices reported until now. Combined with macrocellulose‐based gel electrolytes, all‐cellulose‐based quasi‐solid‐state devices are demonstrated possessing additional advantages in terms of overall sustainability.     

Temperature‐Mediated Engineering of Graphdiyne Framework Enabling High‐Performance Potassium Storage

Graphdiyne (GDY), an emerging type of carbon allotropes, possesses fascinating electrical, chemical, and mechanical properties to readily spark energy applications in the realm of Li‐ion and Na‐ion batteries. Nevertheless, rational design of GDY architectures targeting advanced K‐ion storage has rarely been reported to date. Herein, the first example of synthesizing GDY frameworks in a scalable fashion to realize superb potassium storage for high‐performance K‐ion battery (KIB) anodes is showcased. To begin with, first principles calculations provide theoretical guidances for analyzing the intrinsic potassium storage capability of GDY. Meanwhile, the specific capacity is predicted to be as high as 620 mAh g^?1, which is considerably augmented as compared with graphite (278 mAh g^?1). Experimental tests then reveal that prepared GDY framework indeed harvests excellent electrochemical performance as a KIB anode, achieving high specific capacity (≈505 mAh g^?1 at 50 mA g^?1), outstanding rate performance (150 mAh g^?1 at 5000 mA g^?1) and favorable cycling stability (a high capacity retention of over 90% after 2000 cycles at 1000 mA g^?1). Furthermore, kinetic analysis reveals that capacitive effect mainly accounts for the K‐ion storage, with operando Raman spectroscopy/ex situ X‐ray photoelectron spectroscopy identifying good electrochemical reversibility of GDY.     

Electrochemically Derived Graphene‐Like Carbon Film as a Superb Substrate for High‐Performance Aqueous Zn‐Ion Batteries

3D graphene, as a light substrate for active loadings, is essential to achieve high energy density for aqueous Zn‐ion batteries, yet traditional synthesis routes are inefficient with high energy consumption. Reported here is a simplified procedure to transform the raw graphite paper directly into the graphene‐like carbon film (GCF). The electrochemically derived GCF contains a 2D–3D hybrid network with interconnected graphene sheets, and offers a highly porous structure. To realize high energy density, the Na:MnO₂/GCF cathode and Zn/GCF anode are fabricated by electrochemical deposition. The GCF‐based Zn‐ion batteries deliver a high initial discharge capacity of 381.8 mA h g^?1 at 100 mA g^?1 and a reversible capacity of 188.0 mA h g^?1 after 1000 cycles at 1000 mA g^?1. Moreover, a recorded energy density of 511.9 Wh kg^?1 is obtained at a power density of 137 W kg^?1. The electrochemical kinetics measurement reveals the high capacitive contribution of the GCF and a co‐insertion/desertion mechanism of H⁺ and Zn²⁺ ions. First‐principles calculations are also carried out to investigate the effect of Na⁺ doping on the electrochemical performance of layered δ‐MnO₂ cathodes. The results demonstrate the attractive potential of the GCF substrate in the application of the rechargeable batteries.     

Ultrathin Layered Hydroxide Cobalt Acetate Nanoplates Face‐to‐Face Anchored to Graphene Nanosheets for High‐Efficiency Lithium Storage

The dramatically increasing demand of high‐energy lithium‐ion batteries (LIBs) urgently requires advanced substitution for graphite‐based anodes. Herein, inspired from the extra capacity of lithium storage in solid‐electrolyte interface (SEI) films, layered hydroxide cobalt acetates (LHCA, Co(Ac)_0.48(OH)_1.52·0.55H₂O) are introduced as novel and high‐efficiency anode materials. Furthermore, ultrathin LHCA nanoplates are face‐to‐face anchored on the surface of graphene nanosheets (GNS) through a facile solvothermal method to improve the electronic transport and avoid agglomeration during repeated cycles. Profiting from the parallel structure, LHCA//GNS nanosheets exhibit extraordinary long‐term and high‐rate performance. At the current densities of 1000 and 4000 mA g^?1, the reversible capacities maintain ≈1050 mAh g^?1 after 200 cycles and ≈780 mAh g^?1 after 300 cycles, respectively, much higher than the theoretical value of LHCA according to the conversion mechanism. Fourier transform infrared spectroscopy confirms the conversion from acetate to acetaldehyde after lithiation. A reasonable mechanism is proposed to elucidate the lithium storage behaviors referring to the electrocatalytic conversion of OH groups with Co nanocatalysts. This work can help further understand the contribution of SEI components (especially LiOH and LiAc) to lithium storage. It is envisaged that layered transition metal hydroxides can be used as advanced materials for energy storage devices.     

Hierarchical NiS2 Modified with Bifunctional Carbon for Enhanced Potassium‐Ion Storage

Potassium‐ion batteries (PIBs) are currently drawing increased attention as a promising alternative to lithium‐ion batteries (LIBs) owing to the abundant resource and low cost of potassium. However, due to the large ionic radius size of K⁺, electrode material that can stably maintain K⁺ insertion/deintercalation is still extremely inadequate, especially for anode material with a satisfactory reversible capacity. As an attempt, nitrogen/carbon dual‐doped hierarchical NiS₂ is introduced as the electrode material in PIBs for the first time. Considering that the introduction of the carbon layer effectively alleviates the volume expansion of the material itself, further improves the electronic conductivity, and finally accelerates the charge transfer of K⁺, not surprisingly, NiS₂ decorated with the bifunctional carbon (NiS₂@C@C) material electrode shows excellent potassium storage performances. When utilized as a PIB anode, it delivers a high reversible capacity of 302.7 mAh g^?1 at 50 mA g^?1 after 100 cycles. The first coulombic efficiency is 78.6% and rate performance is 151.2 mAh g^?1 at 1.6 A g^?1 of the NiS₂@C@C, which are also notable. Given such remarkable electrochemical properties, this work is expected to provide more possibilities for the reasonable design of advanced electrode materials for metal sulfide potassium ion batteries.     

A General Metal‐Organic Framework (MOF)‐Derived Selenidation Strategy for In Situ Carbon‐Encapsulated Metal Selenides as High‐Rate Anodes for Na‐Ion Batteries

On account of increasing demand for energy storage devices, sodium‐ion batteries (SIBs) with abundant reserve, low cost, and similar electrochemical properties have the potential to partly replace the commercial lithium‐ion batteries. In this study, a facile metal‐organic framework (MOF)‐derived selenidation strategy to synthesize in situ carbon‐encapsulated selenides as superior anode for SIBs is rationally designed. These selenides with particular micro‐ and nanostructured features deliver ultrastable cycling performance at high charge–discharge rate and demonstrate ultraexcellent rate capability. For example, the uniform peapod‐like Fe₇Se₈@C nanorods represent a high specific capacity of 218 mAh g^?1 after 500 cycles at 3 A g^?1 and the porous NiSe@C spheres display a high specific capacity of 160 mAh g^?1 after 2000 cycles at 3 A g^?1. The current simple MOF‐derived method could be a promising strategy for boosting the development of new functional inorganic materials for energy storage, catalysis, and sensors.     

Stable Cycling of Phosphorus Anode for Sodium‐Ion Batteries through Chemical Bonding with Sulfurized Polyacrylonitrile

Sodium‐ion batteries are attracting increasing interests as a promising alternative to lithium‐ion batteries due to the abundant resource and low cost of sodium. Despite phosphorus (P) has extremely high theoretical capacity of 2595 mAh g^?1, its wide application for sodium‐ion battery is highly hampered by its fast capacity fading and low Coulombic efficiency as a result of large volume change upon cycling. Herein, a robust phosphorus anode with long cycle life for sodium‐ion battery via hybridization with functional conductive polymer is presented. To this end, the polyacrylonitrile is first dehydrogenated by sulfur via a facile thermal treatment, forming a conductive main chain embedded with C–S–S moieties. This functional conductive polymer enables the formation of P? S bonds between phosphorus and functional conductive matrix, leading to a robust electrode that can accommodate the large volume change upon substantial volume change in cycling. Consequently, this hybrid anode delivers a high capacity of ≈1300 mAh g^?1 at a current density of 520 mA g^?1 with high Coulombic efficiency (>99%) and good cycling performance (91% capacity retention after 100 cycles).     

Lithium Accommodation in a Redox‐Active Covalent Triazine Framework for High Areal Capacity and Fast‐Charging Lithium‐Ion Batteries

The synthesis of a new type of redox‐active covalent triazine framework (rCTF) material, which is promising as an anode for Li‐ion batteries, is reported. After activation, it has a capacity up to ≈1190 mAh g^?1 at 0.5C with a current density of 300 mA g^?1 and a high cycling stability of over 1000 discharge/charge cycles with a stable Coulombic efficiency in an rCTF/Li half‐cell. This rCTF has a high rate performance, and at a charging rate of 20C with a current density of 12 A g^?1 and it functions well for over 1000 discharge/charge cycles with a reversible capacity of over 500 mAh g^?1. By electrochemical analysis and theoretical calculations, it is found that its lithium‐storage mechanism involves multi‐electron redox‐reactions at anthraquinone, triazine, and benzene rings by the accommodation of Li. The structural features and progressively increased structural disorder of the rCTF increase the kinetics of infiltration and significantly shortens the activation period, yielding fast‐charging Li‐ion half and full cells even at a high capacity loading.     

Covalently Tethered Polyoxometalate–Pyrene Hybrids for Noncovalent Sidewall Functionalization of Single‐Walled Carbon Nanotubes as High‐Performance Anode Material

A covalently tethered polyoxometalate (POM)–pyrene hybrid (Py–SiW₁₁) is utilized for the noncovalent functionalization of single‐walled carbon nanotubes (SWNTs). The resulting SWNTs/Py–SiW₁₁ nanocomposite shows that both SiW₁₁ and pyrene moieties could interact with SWNTs without causing any chemical decomposition. When used as anode material in lithium‐ion batteries, the SWNTs/Py–SiW₁₁ nanocomposite exhibits higher discharge capacities, and better rate capacity and cycling stability than the individual components. When the current density is 0.5 mA cm^?2, the nanocomposite exhibits the initial discharge capacity of 1569.8 mAh g^?1, and a high discharge capacity of 580 mAh g^?1 for up to 100 cycles.     

A Robust Ion‐Conductive Biopolymer as a Binder for Si Anodes of Lithium‐Ion Batteries

Binders have been reported to play a key role in improving the cycle performance of Si anode materials of lithium‐ion batteries. In this study, the biopolymer guar gum (GG) is applied as the binder for a silicon nano­particle (SiNP) anode of a lithium‐ion battery for the first time. Due to the large number of polar hydroxyl groups in the GG molecule, a robust interaction between the GG binder and the SiNPs is achieved, resulting in a stable Si anode during cycling. More specifically, the GG binder can effectively transfer lithium ions to the Si surface, similarly to polyethylene oxide solid electrolytes. When GG is used as a binder, the SiNP anode can deliver an initial discharge capacity as high as 3364 mAh g^?1, with a Coulombic efficiency of 88.3% at the current density of 2100 mA g^?1, and maintain a capacity of 1561 mAh g^?1 after 300 cycles. The study shows that the electrochemical performance of the SiNP anode with GG binder is significantly improved compared to that of a SiNP anode with a sodium alginate binder, and it demonstrates that GG is a promising binder for Si anodes of lithium‐ion batteries.     

Electrochemical Mechanism Investigation of Cu2MoS4 Hollow Nanospheres for Fast and Stable Sodium Ion Storage

Sodium ion batteries (SIBs) are promising alternatives to lithium ion batteries with advantages of cost effectiveness. Metal sulfides as emerging SIB anodes have relatively high electronic conductivity and high theoretical capacity, however, large volume change during electrochemical testing often leads to unsatisfactory electrochemical performance. Herein bimetallic sulfide Cu₂MoS₄ (CMS) with layered crystal structures are prepared with glucose addition (CMS1), resulting in the formation of hollow nanospheres that endow large interlayer spacing, benefitting the rate performance and cycling stability. The electrochemical mechanisms of CMS1 are investigated using ex situ X‐ray photoelectron spectroscopy and in situ X‐ray absorption spectroscopy, revealing the conversion‐based mechanism in carbonate electrolyte and intercalation‐based mechanism in ether‐electrolyte, thus allowing fast and reversible Na⁺ storage. With further introduction of reduced graphene oxide (rGO), CMS1–rGO composites are obtained, maintaining the hollow structure of CMS1. CMS1–rGO delivers excellent rate performance (258 mAh g^?1 at 50 mA g^?1 and 131.9 mAh g^?1 at 5000 mA g^?1) and notably enhanced cycling stability (95.6% after 2000 cycles). A full cell SIB is assembled by coupling CMS1–rGO with Na₃V₂(PO₄)₃‐based cathode, delivering excellent cycling stability (75.5% after 500 cycles). The excellent rate performance and cycling stability emphasize the advantage of CMS1–rGO toward advanced SIB full cells assembly.     

Bamboo‐Like Hollow Tubes with MoS2/N‐Doped‐C Interfaces Boost Potassium‐Ion Storage

Potassium‐ion batteries (KIBs) are new‐concept of low‐cost secondary batteries, but the sluggish kinetics and huge volume expansion during cycling, both rooted in the size of large K ions, lead to poor electrochemical behavior. Here, a bamboo‐like MoS₂/N‐doped‐C hollow tubes are presented with an expanded interlayer distance of 10 Å as a high‐capacity and stable anode material for KIBs. The bamboo‐like structure provides gaps along axial direction in addition to inner cylinder hollow space to mitigate the strains in both radial and vertical directions that ultimately leads to a high structural integrity for stable long‐term cycling. Apart from being a constituent of the interstratified structure the N‐doped‐C layers weave a cage to hold the potassiation products (polysulfide and the Mo nanoparticles) together, thereby effectively hindering the continuing growth of solid electrolyte interphase in the interior of particles. The density functional theory calculations prove that the MoS₂/N‐doped‐C atomic interface can provide an additional attraction toward potassium ion. As a result, it delivers a high capacity at a low current density (330 mAh g^?1 at 50 mA g^?1 after 50 cycles) and a high‐capacity retention at a high current density (151 mAh g^?1 at 500 mA g^?1 after 1000 cycles).