Preparation of MoS2‐Coated Three‐Dimensional Graphene Networks for High‐Performance Anode Material in Lithium‐Ion Batteries

A novel composite, MoS₂‐coated three‐dimensional graphene network (3DGN), referred to as MoS₂/3DGN, is synthesized by a facile CVD method. The 3DGN, composed of interconnected graphene sheets, not only serves as template for the deposition of MoS₂, but also provides good electrical contact between the current collector and deposited MoS₂. As a proof of concept, the MoS₂/3DGN composite, used as an anode material for lithium‐ion batteries, shows excellent electrochemical performance, which exhibits reversible capacities of 877 and 665 mAh g^?1 during the 50^th cycle at current densities of 100 and 500 mA g^?1, respectively, indicating its good cycling performance. Furthermore, the MoS₂/3DGN composite also shows excellent high‐current‐density performance, e.g., depicts a 10^th‐cycle capacity of 466 mAh g^?1 at a high current density of 4 A g^?1.     

Construction of Complex Co3O4@Co3V2O8 Hollow Structures from Metal–Organic Frameworks with Enhanced Lithium Storage Properties

A novel metal–organic‐framework‐engaged strategy is demonstrated for the preparation of multishelled Co₃O₄@Co₃V₂O₈ hybrid nanoboxes. This strategy relies on the unique reaction of zeolitic imidazolate framework‐67 with the vanadium source of vanadium oxytriisopropoxide. Benefitting from the synthetic versatility, a series of nanostructures can be realized including triple‐shelled and double‐shelled Co₃O₄@Co₃V₂O₈ nanoboxes and single‐shelled Co₃V₂O₈ nanoboxes. When evaluated as electrode materials for lithium‐ion batteries, these unique hollow structures demonstrate remarkable lithium storage properties. For example, the triple‐shelled Co₃O₄@Co₃V₂O₈ nanoboxes retain a high capacity of 948 mAh g^?1 after 100 cycles at 100 mA g^?1.     

3D Hollow α‐MnO2 Framework as an Efficient Electrocatalyst for Lithium–Oxygen Batteries

Lithium–oxygen (Li–O₂) batteries are attracting more attention owing to their superior theoretical energy density compared to conventional Li‐ion battery systems. With regards to the catalytically electrochemical reaction on a cathode, the electrocatalyst plays a key role in determining the performance of Li–O₂ batteries. Herein, a new 3D hollow α‐MnO₂ framework (3D α‐MnO₂) with porous wall assembled by hierarchical α‐MnO₂ nanowires is prepared by a template‐induced hydrothermal reaction and subsequent annealing treatment. Such a distinctive structure provides some essential properties for Li–O₂ batteries including the intrinsic high catalytic activity of α‐MnO₂, more catalytic active sites of hierarchical α‐MnO₂ nanowires on 3D framework, continuous hollow network and rich porosity for the storage of discharge product aggregations, and oxygen diffusion. As a consequence, 3D α‐MnO₂ achieves a high specific capacity of 8583 mA h g^?1 at a current density of 100 mA g^?1, a superior rate capacity of 6311 mA h g^?1 at 300 mA g^?1, and a very good cycling stability of 170 cycles at a current density of 200 mA g^?1 with a fixed capacity of 1000 mA h g^?1. Importantly, the presented design strategy of 3D hollow framework in this work could be extended to other catalytic cathode design for Li–O₂ batteries.     

Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles embedded in 3D reduced graphene oxide network as anode for high-performance lithium ion batteries

Mn₃O₄ nanoparticles were in-situ synthesized in the 3D framework of reduced graphene oxide (RGO) by a facile one-step hydrothermal method. In the reduced graphene-Mn₃O₄ (RGM) composite, the RGO network not only serves as a mechanical support to construct a self-supported and binder-free electrode, but also offers 3D continuous conductive network for effective electron transfer. The Mn₃O₄ nanoparticles anchored uniformly across the RGO framework, which provided high capacity and prevented the restacking of the RGO thin sheets. Based on the unique composite structures, strong synergistic effect was achieved between Mn₃O₄ and RGO, resulting in superior specific capacity, enhanced rate capability, stable cycling performance and nearly 100% Coulombic efficiency in the RGM2 composites. With an optimal Mn₃O₄ composition of 44% by weight (similarly hereinafter), the composite exhibits high specific capacities of 696–795 mAh g¹ based on the overall weight of the electrode in 60 cycles at 200 mA g^?1, with a large coulombic efficiency of around 98%. Even at a high current density of 10,000 mA g^?1, the composite can still deliver a capacity of 383 mAh g^?1, demonstrating its excellent rate performance. The outstanding performances of the composites are attributed to the synergistic effect of both components and the hierarchical structure of the composite.     

Ionic Liquid‐Controlled Growth of NiCo2S4 3D Hierarchical Hollow Nanoarrow Arrays on Ni Foam for Superior Performance Binder Free Hybrid Supercapacitors

A significant development in the design of a NiCo₂S₄ 3D hierarchical hollow nanoarrow arrays (HNA)‐based supercapacitor binder free electrode assembled by 1D hollow nanoneedles and 2D nanosheets on a Ni foam collector through controlling ionic liquid 1‐octyl‐3‐methylimidazolium chloride ([OMIm]Cl) concentration is reported. The unique NiCo₂S₄‐HNA electrode acquires high specific capacity (1297 C g^?1 at 1 A g^?1, 2.59 C cm^?2 at 2 mA cm^?2), excellent rate capability (maintaining 73.0% at 20 A g^?1), and long operational life (maintaining 92.4% after 10 000 cycles at 5 A g^?1), which are superior to those for 1D hollow nanoneedle arrays (HNN) and 2D porous nanoflake arrays (PNF). The outstanding electrochemical performance is attributed to the novel 3D structure with large specific surface, hollow cores, high porosity as well as stable architecture. In addition, a hybrid supercapacitor applying 3D NiCo₂S₄‐HNA as the positive electrode and active carbon as the negative electrode exhibits a high energy density of 42.5 Wh kg^?1 at a power density of 2684.2 W kg^?1 in an operating voltage of 1.6 V. Robust cycling stability is also expressed with 84.9% retention after repeating 10 000 cycles at 5 A g^?1, implying their great potential in superior‐performance supercapacitors.     

3D Interconnected and Multiwalled Carbon@MoS2@Carbon Hollow Nanocables as Outstanding Anodes for Na‐Ion Batteries

Currently, the specific capacity and cycling performance of various MoS₂/carbon‐based anode materials for Na‐ion storage are far from satisfactory due to the insufficient structural stability of the electrode, incomplete protection of MoS₂ by carbon, difficult access of electrolyte to the electrode interior, as well as inactivity of the adopted carbon matrix. To address these issues, this work presents the rational design and synthesis of 3D interconnected and hollow nanocables composed of multiwalled carbon@MoS₂@carbon. In this architecture, (i) the 3D nanoweb‐like structure brings about excellent mechanical property of the electrode, (ii) the ultrathin MoS₂ nanosheets are sandwiched between and doubly protected by two layers of porous carbon, (iii) the hollow structure of the primary nanofibers facilitates the access of electrolyte to the electrode interior, (iv) the porous and nitrogen‐doping properties of the two carbon materials lead to synergistic Na‐storage of carbon and MoS₂. As a result, this hybrid material as the anode material of Na‐ion battery exhibits fast charge‐transfer reaction, high utilization efficiency, and ultrastability. Outstanding reversible capacity (1045 mAh g^?1), excellent rate behavior (817 mAh g^?1 at 7000 mA g^?1), and good cycling performance (747 mAh g^?1 after 200 cycles at 700 mA g^?1) are obtained.     

Synergistic Effect of Mesoporous Co3O4 Nanowires Confined by N‐Doped Graphene Aerogel for Enhanced Lithium Storage

A one‐step multipurpose strategy is developed to realize a sophisticated design that simultaneously integrates three desirable components of nitrogen dopant, 3D graphene, and 1D mesoporous metal oxide nanowires into one hybrid material. This facile synthetic strategy includes a one‐step hydrothermal reaction followed by topotactic calcination. The utilization of urea as the starting reagent enables the precipitation of precursor nanowires and concurrent doping of nitrogen heteroatoms on graphene during hydrothermal reaction, while at the same time the graphene nanosheets are self‐assembled to afford a 3D scaffold. Detailed characterizations on the final calcined product are conducted to confirm the phase purity, porosity, nitrogen composition, and morphology. The integration of two building blocks, i.e., flexible graphene nanosheets and Co₃O₄ nanowires, enables various intertwining behaviors such as seaming, bridging, hooping, bundling, and sandwiching, of which synergistic effect substantially enhances electrical and electrochemical properties of the resultant hybrid. For lithium ion battery application of the hybrid, a remarkably high capacity more than 1200 mA h g^?1 (at 100 mA g^?1) is stabilized over 100 cycles with coulombic efficiency higher than 97%. Even during rapid discharge/charge processes (1000 mA g^?1), a reversible charge capacity of 812 mA h g^?1 is still retained after 230 cycles.     

In Situ Encapsulating α‐MnS into N,S‐Codoped Nanotube‐Like Carbon as Advanced Anode Material: α → β Phase Transition Promoted Cycling Stability and Superior Li/Na‐Storage Performance in Half/Full Cells

Incorporation of N,S‐codoped nanotube‐like carbon (N,S‐NTC) can endow electrode materials with superior electrochemical properties owing to the unique nanoarchitecture and improved kinetics. Herein, α‐MnS nanoparticles (NPs) are in situ encapsulated into N,S‐NTC, preparing an advanced anode material (α‐MnS@N,S‐NTC) for lithium‐ion/sodium‐ion batteries (LIBs/SIBs). It is for the first time revealed that electrochemical α → β phase transition of MnS NPs during the 1st cycle effectively promotes Li‐storage properties, which is deduced by the studies of ex situ X‐ray diffraction/high‐resolution transmission electron microscopy and electrode kinetics. As a result, the optimized α‐MnS@N,S‐NTC electrode delivers a high Li‐storage capacity (1415 mA h g^?1 at 50 mA g^?1), excellent rate capability (430 mA h g^?1 at 10 A g^?1), and long‐term cycling stability (no obvious capacity decay over 5000 cycles at 1 A g^?1) with retained morphology. In addition, the N,S‐NTC‐based encapsulation plays the key roles on enhancing the electrochemical properties due to its high conductivity and unique 1D nanoarchitecture with excellent protective effects to active MnS NPs. Furthermore, α‐MnS@N,S‐NTC also delivers high Na‐storage capacity (536 mA h g^?1 at 50 mA g^?1) without the occurrence of such α → β phase transition and excellent full‐cell performances as coupling with commercial LiFePO₄ and LiNi_0.6Co_0.2Mn_0.2O₂ cathodes in LIBs as well as Na₃V₂(PO₄)₂O₂F cathode in SIBs.     

3D composites of ZnSnO<Subscript>3</Subscript> nanoplates/reduced graphene oxide aerogels as an advanced lithium-ion battery anode

Zinc-based bimetal oxides have received considerable attention as anode for lithium-ion batteries (LIBs). A one-pot self-assembly hydrothermal method is developed for the fabrication of 3D hierarchical structure aerogels from zinc stannate (ZnSnO₃) and reduced graphene oxide (rGO). 3D interconnected porous structure with ZnSnO₃ hexagon nanoplates uniformly dispersed on graphene sheets has been constructed successfully, in which the crystalline hexagon nanoplates ZnSnO₃ are firstly used to prepare ZnSnO₃-based anode materials for LIBs. The as-prepared ZnSnO₃ nanoplates/reduced graphene oxide aerogels (ZnSnO₃–rGAs) electrode demonstrates an excellent reversible capacity (780 mAh g^?1) after 200 cycles at a certain current density (100 mA g^?1) and still delivers a specific capacity of 460 mAh g^?1 even at 1000 mA g^?1. The superior performance of lithium storage is attributed to the 3D porous hierarchical structure and the synergistic effects of uniform hexagon nanoplates ZnSnO₃ and rGO sheets.     

Solvent‐Free Synthesis of Uniform MOF Shell‐Derived Carbon Confined SnO2/Co Nanocubes for Highly Reversible Lithium Storage

Tin dioxide (SnO₂) has attracted much attention in lithium‐ion batteries (LIBs) due to its abundant source, low cost, and high theoretical capacity. However, the large volume variation, irreversible conversion reaction limit its further practical application in next‐generation LIBs. Here, a novel solvent‐free approach to construct uniform metal–organic framework (MOF) shell‐derived carbon confined SnO₂/Co (SnO₂/Co@C) nanocubes via a two‐step heat treatment is developed. In particular, MOF‐coated CoSnO₃ hollow nanocubes are for the first time synthesized as the intermediate product by an extremely simple thermal solid‐phase reaction, which is further developed as a general strategy to successfully obtain other uniform MOF‐coated metal oxides. The as‐synthesized SnO₂/Co@C nanocubes, when tested as LIB anodes, exhibit a highly reversible discharge capacity of 800 mAh g^?1 after 100 cycles at 200 mA g^?1 and excellent cycling stability with a retained capacity of 400 mAh g^?1 after 1800 cycles at 5 A g^?1. The experimental analyses demonstrate that these excellent performances are mainly ascribed to the delicate structure and a synergistic effect between Co and SnO₂. This facile synthetic approach will greatly contribute to the development of functional metal oxide‐based and MOF‐assisted nanostructures in many frontier applications.     

Carbon–Heteroatom Bond Formation by an Ultrasonic Chemical Reaction for Energy Storage Systems

The direct formation of C? N and C? O bonds from inert gases is essential for chemical/biological processes and energy storage systems. However, its application to carbon nanomaterials for improved energy storage remains technologically challenging. A simple and very fast method to form C? N and C? O bonds in reduced graphene oxide (RGO) and carbon nanotubes (CNTs) by an ultrasonic chemical reaction is described. Electrodes of nitrogen‐ or oxygen‐doped RGO (N‐RGO or O‐RGO, respectively) are fabricated via the fixation between N₂ or O₂ carrier gas molecules and ultrasonically activated RGO. The materials exhibit much higher capacitance after doping (133, 284, and 74 F g^?1 for O‐RGO, N‐RGO, and RGO, respectively). Furthermore, the doped 2D RGO and 1D CNT materials are prepared by layer‐by‐layer deposition using ultrasonic spray to form 3D porous electrodes. These electrodes demonstrate very high specific capacitances (62.8 mF cm^?2 and 621 F g^?1 at 10 mV s^?1 for N‐RGO/N‐CNT at 1:1, v/v), high cycling stability, and structural flexibility.     

A Single‐Step Hydrothermal Route to 3D Hierarchical Cu2O/CuO/rGO Nanosheets as High‐Performance Anode of Lithium‐Ion Batteries

As anodes of Li‐ion batteries, copper oxides (CuO) have a high theoretical specific capacity (674 mA h g^?1) but own poor cyclic stability owing to the large volume expansion and low conductivity in charges/discharges. Incorporating reduced graphene oxide (rGO) into CuO anodes with conventional methods fails to build robust interaction between rGO and CuO to efficiently improve the overall anode performance. Here, Cu₂O/CuO/reduced graphene oxides (Cu₂O/CuO/rGO) with a 3D hierarchical nanostructure are synthesized with a facile, single‐step hydrothermal method. The Cu₂O/CuO/rGO anode exhibits remarkable cyclic and high‐rate performances, and particularly the anode with 25 wt% rGO owns the best performance among all samples, delivering a record capacity of 550 mA h g^?1 at 0.5 C after 100 cycles. The pronounced performances are attributed to the highly efficient charge transfer in CuO nanosheets encapsulated in rGO network and the mitigated volume expansion of the anode owing to its robust 3D hierarchical nanostructure.     

Large‐Scale Fabrication of Core–Shell Structured C/SnO2 Hollow Spheres as Anode Materials with Improved Lithium Storage Performance

Due to the high theoretical capacity as high as 1494 mAh g^?1, SnO₂ is considered as a potential anode material for high‐capacity lithium–ion batteries (LIBs). Therefore, the simple but effective method focused on fabrication of SnO₂ is imperative. To meet this, a facile and efficient strategy to fabricate core–shell structured C/SnO₂ hollow spheres by a solvothermal method is reported. Herein, the solid and hollow structure as well as the carbon content can be controlled. Very importantly, high‐yield C/SnO₂ spheres can be produced by this method, which suggest potential business applications in LIBs field. Owing to the dual buffer effect of the carbon layer and hollow structures, the core–shell structured C/SnO₂ hollow spheres deliver a high reversible discharge capacity of 1007 mAh g^?1 at a current density of 100 mA g^?1 after 300 cycles and a superior discharge capacity of 915 mAh g^?1 at 500 mA g^?1 after 500 cycles. Even at a high current density of 1 and 2 A g^?1, the core–shell structured C/SnO₂ hollow spheres electrode still exhibits excellent discharge capacity in the long life cycles. Consideration of the superior performance and high yield, the core–shell structured C/SnO₂ hollow spheres are of great interest for the next‐generation LIBs.     

Graphene Caging Silicon Particles for High‐Performance Lithium‐Ion Batteries

Silicon holds great promise as an anode material for lithium‐ion batteries with higher energy density; its implication, however, is limited by rapid capacity fading. A catalytic growth of graphene cages on composite particles of magnesium oxide and silicon, which are made by magnesiothermic reduction reaction of silica particles, is reported herein. Catalyzed by the magnesium oxide, graphene cages can be conformally grown onto the composite particles, leading to the formation of hollow graphene‐encapsulated Si particles. Such materials exhibit excellent lithium storage properties in terms of high specific capacity, remarkable rate capability (890 mAh g^?1 at 5 A g^?1), and good cycling retention over 200 cycles with consistently high coulombic efficiency at a current density of 1 A g^?1. A full battery test using LiCoO₂ as the cathode demonstrates a high energy density of 329 Wh kg^?1.     

A Universal Strategy for Hollow Metal Oxide Nanoparticles Encapsulated into B/N Co‐Doped Graphitic Nanotubes as High‐Performance Lithium‐Ion Battery Anodes

Yolk–shell nanostructures have received great attention for boosting the performance of lithium‐ion batteries because of their obvious advantages in solving the problems associated with large volume change, low conductivity, and short diffusion path for Li⁺ ion transport. A universal strategy for making hollow transition metal oxide (TMO) nanoparticles (NPs) encapsulated into B, N co‐doped graphitic nanotubes (TMO@BNG (TMO = CoO, Ni₂O₃, Mn₃O₄) through combining pyrolysis with an oxidation method is reported herein. The as‐made TMO@BNG exhibits the TMO‐dependent lithium‐ion storage ability, in which CoO@BNG nanotubes exhibit highest lithium‐ion storage capacity of 1554 mA h g^?1 at the current density of 96 mA g^?1, good rate ability (410 mA h g^?1 at 1.75 A g^?1), and high stability (almost 96% storage capacity retention after 480 cycles). The present work highlights the importance of introducing hollow TMO NPs with thin wall into BNG with large surface area for boosting LIBs in the terms of storage capacity, rate capability, and cycling stability.     

Flexible and Binder‐Free Electrodes of Sb/rGO and Na3V2(PO4)3/rGO Nanocomposites for Sodium‐Ion Batteries

Flexible power sources have shown great promise in next‐generation bendable, implantable, and wearable electronic systems. Here, flexible and binder‐free electrodes of Na₃V₂(PO₄)₃/reduced graphene oxide (NVP/rGO) and Sb/rGO nanocomposites for sodium‐ion batteries are reported. The Sb/rGO and NVP/rGO paper electrodes with high flexibility and tailorability can be easily fabricated. Sb and NVP nanoparticles are embedded homogenously in the interconnected framework of rGO nanosheets, which provides structurally stable hosts for Na‐ion intercalation and deintercalation. The NVP/rGO paper‐like cathode delivers a reversible capacity of 113 mAh g^?1 at 100 mA g^?1 and high capacity retention of ≈96.6% after 120 cycles. The Sb/rGO paper‐like anode gives a highly reversible capacity of 612 mAh g^?1 at 100 mA g^?1, an excellent rate capacity up to 30 C, and a good cycle performance. Moreover, the sodium‐ion full cell of NVP/rGO//Sb/rGO has been fabricated, delivering a highly reversible capacity of ≈400 mAh g^?1 at a current density of 100 mA g^?1 after 100 charge/discharge cycles. This work may provide promising electrode candidates for developing next‐generation energy‐storage devices with high capacity and long cycle life.     

Multidimensional Integrated Chalcogenides Nanoarchitecture Achieves Highly Stable and Ultrafast Potassium‐Ion Storage

Potassium‐ion batteries (KIBs) have come into the spotlight in large‐scale energy storage systems because of cost‐effective and abundant potassium resources. However, the poor rate performance and problematic cycle life of existing electrode materials are the main bottlenecks to future potential applications. Here, the first example of preparing 3D hierarchical nanoboxes multidimensionally assembled from interlayer‐expanded nano‐2D MoS₂@dot‐like Co₉S₈ embedded into a nitrogen and sulfur codoped porous carbon matrix (Co₉S₈/NSC@MoS₂@NSC) for greatly boosting the electrochemical properties of KIBs in terms of reversible capacity, rate capability, and cycling lifespan, is reported. Benefiting from the synergistic effects, Co₉S₈/NSC@MoS₂@NSC manifest a very high reversible capacity of 403 mAh g^?1 at 100 mA g^?1 after 100 cycles, an unprecedented rate capability of 141 mAh g^?1 at 3000 mA g^?1 over 800 cycles, and a negligible capacity decay of 0.02% cycle^?1, boosting promising applications in high‐performance KIBs. Density functional theory calculations demonstrate that Co₉S₈/NSC@MoS₂@NSC nanoboxes have large adsorption energy and low diffusion barriers during K‐ion storage reactions, implying fast K‐ion diffusion capability. This work may enlighten the design and construction of advanced electrode materials combined with strong chemical bonding and integrated functional advantages for future large‐scale stationary energy storage.     

Ultrathin Nitrogen‐Doped Carbon Layer Uniformly Supported on Graphene Frameworks as Ultrahigh‐Capacity Anode for Lithium‐Ion Full Battery

The designable structure with 3D structure, ultrathin 2D nanosheets, and heteroatom doping are considered as highly promising routes to improve the electrochemical performance of carbon materials as anodes for lithium‐ion batteries. However, it remains a significant challenge to efficiently integrate 3D interconnected porous frameworks with 2D tunable heteroatom‐doped ultrathin carbon layers to further boost the performance. Herein, a novel nanostructure consisting of a uniform ultrathin N‐doped carbon layer in situ coated on a 3D graphene framework (NC@GF) through solvothermal self‐assembly/polymerization and pyrolysis is reported. The NC@GF with the nanosheets thickness of 4.0 nm and N content of 4.13 at% exhibits an ultrahigh reversible capacity of 2018 mA h g^?1 at 0.5 A g^?1 and an ultrafast charge–discharge feature with a remarkable capacity of 340 mA h g^?1 at an ultrahigh current density of 40 A g^?1 and a superlong cycle life with a capacity retention of 93% after 10 000 cycles at 40 A g^?1. More importantly, when coupled with LiFePO₄ cathode, the fabricated lithium‐ion full cells also exhibit high capacity and excellent rate and cycling performances, highlighting the practicability of this NC@GF.     

Novel 2D Layered Molybdenum Ditelluride Encapsulated in Few‐Layer Graphene as High‐Performance Anode for Lithium‐Ion Batteries

Molybdenum ditelluride nanosheets encapsulated in few‐layer graphene (MoTe₂/FLG) are synthesized by a simple heating method using Te and Mo powder and subsequent ball milling with graphite. The as‐prepared MoTe₂/FLG nanocomposites as anode materials for lithium‐ion batteries exhibit excellent electrochemical performance with a highly reversible capacity of 596.5 mAh g^?1 at 100 mA g^?1, a high rate capability (334.5 mAh g^?1 at 2 A g^?1), and superior cycling stability (capacity retention of 99.5% over 400 cycles at 0.5 A g^?1). Ex situ X‐ray diffraction and transmission electron microscopy are used to explore the lithium storage mechanism of MoTe₂. Moreover, the electrochemical performance of a MoTe₂/FLG//0.35Li₂MnO₃·0.65LiMn_0.5Ni_0.5O₂ full cell is investigated, which displays a reversible capacity of 499 mAh g^?1 (based on the MoTe₂/FLG mass) at 100 mA g^?1 and a capacity retention of 78% over 50 cycles, suggesting the promising application of MoTe₂/FLG for lithium‐ion storage. First‐principles calculations exhibit that the lowest diffusion barrier (0.18 eV) for lithium ions along pathway III in the MoTe₂ layered structure is beneficial for improving the Li intercalation/deintercalation property.     

Porous Carbon Nanofibers Encapsulated with Peapod‐Like Hematite Nanoparticles for High‐Rate and Long‐Life Battery Anodes

Fe₂O₃ is regarded as a promising anode material for lithium‐ion batteries (LIBs) and sodium‐ion batteries (SIBs) due to its high specific capacity. The large volume change during discharge and charge processes, however, induces significant cracking of the Fe₂O₃ anodes, leading to rapid fading of the capacity. Herein, a novel peapod‐like nanostructured material, consisting of Fe₂O₃ nanoparticles homogeneously encapsulated in the hollow interior of N‐doped porous carbon nanofibers, as a high‐performance anode material is reported. The distinctive structure not only provides enough voids to accommodate the volume expansion of the pea‐like Fe₂O₃ nanoparticles but also offers a continuous conducting framework for electron transport and accessible nanoporous channels for fast diffusion and transport of Li/Na‐ions. As a consequence, this peapod‐like structure exhibits a stable discharge capacity of 1434 mAh g^?1 (at 100 mA g^?1) and 806 mAh g^?1 (at 200 mA g^?1) over 100 cycles as anode materials for LIBs and SIBs, respectively. More importantly, a stable capacity of 958 mAh g^?1 after 1000 cycles and 396 mAh g^?1 after 1500 cycles can be achieved for LIBs and SIBs, respectively, at a large current density of 2000 mA g^?1. This study provides a promising strategy for developing long‐cycle‐life LIBs and SIBs.