Enhanced Cyclability of Lithium–Oxygen Batteries with Electrodes Protected by Surface Films Induced via In Situ Electrochemical Process

Although the rechargeable lithium–oxygen (Li–O₂) batteries have extremely high theoretical specific energy, the practical application of these batteries is still limited by the instability of their carbon‐based air‐electrode, Li metal anode, and electrodes, toward reduced oxygen species. Here a simple one‐step in situ electrochemical precharging strategy is demonstrated to generate thin protective films on both carbon nanotubes (CNTs), air‐electrodes and Li metal anodes simultaneously under an inert atmosphere. Li–O₂ cells after such pretreatment demonstrate significantly extended cycle life of 110 and 180 cycles under the capacity‐limited protocol of 1000 mA h g^?1 and 500 mA h g^?1, respectively, which is far more than those without pretreatment. The thin‐films formed from decomposition of electrolyte during in situ electrochemical precharging processes in an inert environment, can protect both CNTs air‐electrode and Li metal anode prior to conventional Li–O₂ discharge/charge cycling, where reactive reduced oxygen species are formed. This work provides a new approach for protection of carbon‐based air‐electrodes and Li metal anodes in practical Li–O₂ batteries, and may also be applied to other battery systems.     

Amorphous MoS3 Infiltrated with Carbon Nanotubes as an Advanced Anode Material of Sodium‐Ion Batteries with Large Gravimetric,Areal, and Volumetric Capacities

The search for earth‐abundant and high‐performance electrode materials for sodium‐ion batteries represents an important challenge to current battery research. 2D transition metal dichalcogenides, particularly MoS₂, have attracted increasing attention recently, but few of them so far have been able to meet expectations. In this study, it is demonstrated that another phase of molybdenum sulfide—amorphous chain‐like MoS₃—can be a better choice as the anode material of sodium‐ion batteries. Highly compact MoS₃ particles infiltrated with carbon nanotubes are prepared via the facile acid precipitation method in ethylene glycol. Compared to crystalline MoS₂, the resultant amorphous MoS₃ not only exhibits impressive gravimetric performance—featuring excellent specific capacity (≈615 mA h g^?1), rate capability (235 mA h g^?1 at 20 A g^?1), and cycling stability but also shows exceptional volumetric capacity of ≈1000 mA h cm^?3 and an areal capacity of >6.0 mA h cm^?2 at very high areal loadings of active materials (up to 12 mg cm^?2). The experimental results are supported by density functional theory simulations showing that the 1D chains of MoS₃ can facilitate the adsorption and diffusion of Na⁺ ions. At last, it is demonstrated that the MoS₃ anode can be paired with an Na₃V₂(PO₄)₃ cathode to afford full cells with great capacity and cycling performance.     

Vertically Aligned MoS2 Nanosheets Patterned on Electrochemically Exfoliated Graphene for High‐Performance Lithium and Sodium Storage

Molybdenum disulfide (MoS₂) has been recognized as a promising anode material for high‐energy Li‐ion (LIBs) and Na‐ion batteries (SIBs) due to its apparently high capacity and intriguing 2D‐layered structure. The low conductivity, unsatisfied mechanical stability, and limited active material utilization are three key challenges associated with MoS₂ electrodes especially at high current rates and mass active material loading. Here, vertical MoS₂ nanosheets are controllably patterned onto electrochemically exfoliated graphene (EG). Within the achieved hierarchical architecture, the intimate contact between EG and MoS₂ nanosheets, interconnected network, and effective exposure of active materials by vertical channels simultaneously overcomes the above three problems, enabling high mechanical integrity and fast charge transport kinetics. Serving as anode material for LIBs, EG‐MoS₂ with 95 wt% MoS₂ content delivered an ultrahigh‐specific capacity of 1250 mA h g^?1 after 150 stable cycles at 1 A g^?1, which is among the highest values in all reported MoS₂ electrodes, and excellent rate performance (970 mA h g^?1 at 5 A g^?1). Moreover, impressive cycling stability (509 mA h g^?1 at 1 A g^?1 after 250 cycles) and rate capability (423 mA h g^?1 at 2 A g^?1) were also achieved for SIBs. The area capacities reached 1.27 and 0.49 mA h cm^?2 at ≈1 mA cm^?2 for LIBs and SIBs, respectively. This work may inspire the development of new 2D hierarchical structures for high efficiency energy storage and conversion.     

Bottom‐Up Confined Synthesis of Nanorod‐in‐Nanotube Structured Sb@N‐C for Durable Lithium and Sodium Storage

Antimony (Sb) has emerged as an attractive anode material for both lithium and sodium ion batteries due to its high theoretical capacity of 660 mA h g^?1. In this work, a novel peapod‐like N‐doped carbon hollow nanotube encapsulated Sb nanorod composite, the so‐called nanorod‐in‐nanotube structured Sb@N‐C, via a bottom‐up confinement approach is designed and fabricated. The N‐doped‐carbon coating and thermal‐reduction process is monitored by in situ high‐temperature X‐ray diffraction characterization. Due to its advanced structural merits, such as sufficient N‐doping, 1D conductive carbon coating, and substantial inner void space, the Sb@N‐C demonstrates superior lithium/sodium storage performance. For lithium storage, the Sb@N‐C exhibits a high reversible capacity (650.8 mA h g^?1 at 0.2 A g^?1), excellent long‐term cycling stability (a capacity decay of only 0.022% per cycle for 3000 cycles at 2 A g^?1), and ultrahigh rate capability (343.3 mA h g^?1 at 20 A g^?1). For sodium storage, the Sb@N‐C nanocomposite displays the best long‐term cycle performance among the reported Sb‐based anode materials (a capacity of 345.6 mA h g^?1 after 3000 cycles at 2 A g^?1) and an impressive rate capability of up to 10 A g^?1. The results demonstrate that the Sb@N‐C nanocomposite is a promising anode material for high‐performance lithium/sodium storage.     

Nanoparticles Encapsulated in Porous Carbon Matrix Coated on Carbon Fibers: An Ultrastable Cathode for Li‐Ion Batteries

Nanostructured V₂O₅ is emerging as a new cathode material for lithium ion batteries for its distinctly high theoretic capacity over the current commercial cathodes. The main challenges associated with nanostructured V₂O₅ cathodes are structural degradation, instability of the solid‐electrolyte interface layer, and poor electron conductance, which lead to low capacity and rapid decay of cyclic stability. Here, a novel composite structure of V₂O₅ nanoparticles encapsulated in 3D networked porous carbon matrix coated on carbon fibers (V₂O₅/3DC‐CFs) is reported that effectively addresses the mentioned problems. Remarkably, the V₂O₅/3DC‐CF electrode exhibits excellent overall lithium‐storage performance, including high Coulombic efficiency, excellent specific capacity, outstanding cycling stability and rate property. A reversible capacity of ≈183 mA h g^?1 is obtained at a high current density of 10 C, and the battery retains 185 mA h g^?1 after 5000 cycles, which shows the best cycling stability reported to date among all reported cathodes of lithium ion batteries as per the knowledge. The outstanding overall properties of the V₂O₅/3DC‐CF composite make it a promising cathode material of lithium ion batteries for the power‐intensive energy storage applications.     

In Situ Revealing the Electroactivity of P?O and P?C Bonds in Hard Carbon for High‐Capacity and Long‐Life Li/K‐Ion Batteries

The low capacity and unsatisfactory rate capability of hard carbon still restricts its practical application for Li/K‐ion batteries. Herein, a low‐cost and large‐scale method is developed to fabricate phosphorus‐doped hard carbon (PHC‐700) by crosslinking phosphoric acid and epoxy resin and followed by annealing at 700 °C. H₃PO₄ acts not only as a crosslinker to solidify epoxy resin for promoting the degree of graphitization and lowering the specific surface area, but also as phosphorus source for forming P? C and P? O bonds, thus providing more active sites for Li/K storage. As a result, the PHC‐700 electrode delivers a highly reversible capacity of 1294.8 mA h g^?1 at 0.1 A g^?1 and a capacity of 214 mA h g^?1 after 10 000 cycles at 10 A g^?1. As for potassium‐ion batteries, PHC‐700 exhibits a reversible capacity of 381.9 mA h g^?1 at 0.1 A g^?1 and a capacity of 260 mA h g^?1 after 1000 cycles at 0.2 A g^?1. In situ Raman and in situ NMR measurements reveal that the P‐containing bonds can enhance the adsorption to alkali metal ions, and the P? C bond can participate in electrochemical redox reaction by forming Li_x PC_y . Additionally, P‐doped hard carbon shows better structural/interfacial stability for improved long‐term cycling stability.     

High and Reversible Lithium Ion Storage in Self‐Exfoliated Triazole‐Triformyl Phloroglucinol‐Based Covalent Organic Nanosheets

Covalent organic framework (COF) can grow into self‐exfoliated nanosheets. Their graphene/graphite resembling microtexture and nanostructure suits electrochemical applications. Here, covalent organic nanosheets (CON) with nanopores lined with triazole and phloroglucinol units, neither of which binds lithium strongly, and its potential as an anode in Li‐ion battery are presented. Their fibrous texture enables facile amalgamation as a coin‐cell anode, which exhibits exceptionally high specific capacity of ≈720 mA h g^?1 (@100 mA g^?1). Its capacity is retained even after 1000 cycles. Increasing the current density from 100 mA g^?1 to 1 A g^?1 causes the specific capacity to drop only by 20%, which is the lowest among all high‐performing anodic COFs. The majority of the lithium insertion follows an ultrafast diffusion‐controlled intercalation (diffusion coefficient, D_Li⁺ = 5.48 × 10^?11 cm² s^?1). The absence of strong Li‐framework bonds in the density functional theory (DFT) optimized structure supports this reversible intercalation. The discrete monomer of the CON shows a specific capacity of only 140 mA h g^?1 @50 mA g^?1 and no sign of lithium intercalation reveals the crucial role played by the polymeric structure of the CON in this intercalation‐assisted conductivity. The potentials mapped using DFT suggest a substantial electronic driving‐force for the lithium intercalation. The findings underscore the potential of the designer CON as anode material for Li‐ion batteries.     

Structural Engineering of Hierarchical Micro‐nanostructured Ge–C Framework by Controlling the Nucleation for Ultralong‐Life Li Storage

The rational design of a proper electrode structure with high energy and power densities, long cycling lifespan, and low cost still remains a significant challenge for developing advanced energy storage systems. Germanium is a highly promising anode material for high‐performance lithium ion batteries due to its large specific capacity and remarkable rate capability. Nevertheless, poor cycling stability and high price significantly limit its practical application. Herein, a facile and scalable structural engineering strategy is proposed by controlling the nucleation to fabricate a unique hierarchical micro‐nanostructured Ge–C framework, featuring high tap density, reduced Ge content, superb structural stability, and a 3D conductive network. The constructed architecture has demonstrated outstanding reversible capacity of 1541.1 mA h g^?1 after 3000 cycles at 1000 mA g^?1 (with 99.6% capacity retention), markedly exceeding all the reported Ge–C electrodes regarding long cycling stability. Notably, the assembled full cell exhibits superior performance as well. The work paves the way to constructing novel metal–carbon materials with high performance and low cost for energy‐related applications.     

Unraveling the Dual Functionality of High‐Donor‐Number Anion in Lean‐Electrolyte Lithium‐Sulfur Batteries

Minimizing electrolyte use is essential to achieve high practical energy density of lithium–sulfur (Li–S) batteries. However, the sulfur cathode is more readily passivated under a lean electrolyte condition, resulting in low sulfur utilization. In addition, continuous electrolyte decomposition on the Li metal anode aggravates the problem, provoking rapid capacity decay. In this work, the dual functionalities of NO₃^? as a high‐donor‐number (DN) salt anion is presented, which improves the sulfur utilization and cycling stability of lean‐electrolyte Li–S batteries. The NO₃^? anion elevates the solubility of the sulfur species based on its high electron donating ability, achieving a high sulfur utilization of above 1200 mA h g^?1. Furthermore, the anion suppresses electrolyte decomposition on the Li metal by regulating the lithium ion (Li⁺) solvation sheath, enhancing the cycle performance of the lean electrolyte cell. By understanding the anionic effects, this work demonstrates the potential of the high‐DN electrolyte, which is beneficial for both the cathode and anode of Li–S batteries.     

Hierarchically Porous N‐Doped Carbon Fibers as a Free‐Standing Anode for High‐Capacity Potassium‐Based Dual‐Ion Battery

Potassium‐based dual‐ion batteries (KDIBs) have emerged as a new generation of rechargeable batteries, due to their high cell voltage, low cost, and the natural abundance of potassium resources. However, the low capacity and poor cycling stability largely hinder the further development of KDIBs. Herein, the fabrication of hierarchically porous N‐doped carbon fibers (HPNCFs) as a free‐standing anode for high‐performance KDIBs is reported. With a free‐standing hierarchical structure (micro/meso/macropores and nanochannels) and high‐content of nitrogen doping, the HPNCFs not only provide intrinsic electron pathways and efficient ion transport channels, but also afford sufficient free space to tolerate the volume change during cycling. Consequently, the KDIBs made from a graphite cathode and an optimized HPNCFs anode deliver a high reversible capacity of 197 mAh g^?1 at a specific current of 50 mA g^?1, and excellent cycling stability (65 mAh g^?1 after 346 cycles at a specific current of 100 mA g^?1, the capacity calculation of the KDIBs is based on the mass of the anode). These results indicate that the properly designed HPNCFs can effectively improve the capacity and cycling stability of the KDIBs, indicating a great potential for applications in the field of high‐performance energy‐storage devices.     

Vertically Oriented MoS2 with Spatially Controlled Geometry on Nitrogenous Graphene Sheets for High‐Performance Sodium‐Ion Batteries

Inspired by the great success of graphite in lithium‐ion batteries, anode materials that undergo an intercalation mechanism are considered to provide stable and reversible electrochemical sodium‐ion storage for sodium‐ion battery (SIB) applications. Though MoS₂ is a promising 2D material for SIBs, it suffers from deformation of its layered structure during repeated intercalation of Na⁺, resulting in undesirable electrochemical behaviors. In this study, vertically oriented MoS₂ on nitrogenous reduced graphene oxide sheets (VO‐MoS₂/N‐RGO) is presented with designed spatial geometries, including sheet density and height, which can deliver a remarkably high reversible capacity of 255 mA h g^?1 at a current density of 0.2 A g^?1 and 245 mA h g^?1 at a current density of 1 A g^?1, with a total fluctuation of 5.35% over 1300 cycles. These results are superior to those obtained with well‐developed hard carbon structures. Furthermore, a SIB full cell composed of the optimized VO‐MoS₂/N‐RGO anode and a Na₂V₃(PO₄)₃ cathode reaches a specific capacity of 262 mA h g^?1 (based on the anode mass) during 50 cycles, with an operated voltage range of 2.4 V, demonstrating the potentially rewarding SIB performance, which is useful for further battery development.     

In Situ Generation of Artificial Solid‐Electrolyte Interphases on 3D Conducting Scaffolds for High‐Performance Lithium‐Metal Anodes

Rational structure design of the current collector along with further engineering of the solid‐electrolyte interphases (SEI) layer is one of the most promising strategies to achieve uniform Li deposition and inhibit uncontrolled growth of Li dendrites. Here, a Li₂S layer as an artificial SEI with high compositional uniformity and high lithium ion conductivity is in situ generated on the surface of the 3D porous Cu current collector to regulate homogeneous Li plating/stripping. Both simulations and experiments demonstrate that the Li₂S protective layer can passivate the porous Cu skeleton and balance the transport rate of lithium ions and electrons, thereby alleviating the agglomerated Li deposition at the top of the electrode or at the defect area of the SEI layer. As a result, the modified current collector exhibits long‐term cycling of 500 cycles at 1 mA cm^?2 and stable electrodeposition capabilities of 4 mAh cm^?2 at an ultrahigh current density of 4 mA cm^?2. Furthermore, full batteries (LiFePO₄ as cathode) paired with this designed 3D anode with only ≈200% extra lithium show superior stability and rate performance than the batteries paired with lithium foil (≈3000% extra lithium). These explorations provide new strategies for developing high‐performance Li metal anodes.     

Electrokinetic Phenomena Enhanced Lithium‐Ion Transport in Leaky Film for Stable Lithium Metal Anodes

The application of lithium (Li) metal anodes in Li metal batteries has been hindered by growth of Li dendrites, which lead to short cycling life. Here a Li‐ion‐affinity leaky film as a protection layer is reported to promote a dendrite‐free Li metal anode. The leaky film induces electrokinetic phenomena to enhance Li‐ion transport, leading to a reduced Li‐ion concentration polarization and homogeneous Li‐ion distribution. As a result, the dendrite‐free Li metal anode during Li plating/stripping is demonstrated even at an extremely high deposition capacity (6 mAh cm^?2) and current density (40 mA cm^?2) with improved Coulombic efficiencies. A full cell battery with the leaky‐film protected Li metal as the anode and high‐areal‐capacity LiNi_0.8Co_0.1Mn_0.1O₂ (NCM‐811) (≈4.2 mAh cm^?2) or LiFePO₄ (≈3.8 mAh cm^?2) as the cathode shows improved cycling stability and capacity retention, even at lean electrolyte conditions.     

Sulfur/Oxygen Codoped Porous Hard Carbon Microspheres for High‐Performance Potassium‐Ion Batteries

Potassium‐ion batteries (KIBs) are very promising alternatives to lithium‐ion batteries (LIBs) for large‐scale energy storage. However, traditional carbon anode materials usually show poor performance in KIBs due to the large size of K ions. Herein, a carbonization‐etching strategy is reported for making a class of sulfur (S) and oxygen (O) codoped porous hard carbon microspheres (PCMs) material as a novel anode for KIBs through pyrolysis of the polymer microspheres (PMs) composed of a liquid crystal/epoxy monomer/thiol hardener system. The as‐made PCMs possess a porous architecture with a large Brunauer–Emmett–Teller surface area (983.2 m² g^?1), an enlarged interlayer distance (0.393 nm), structural defects induced by the S/O codoping and also amorphous carbon nature. These new features are important for boosting potassium ion storage, allowing the PCMs to deliver a high potassiation capacity of 226.6 mA h g^?1 at 50 mA g^?1 over 100 cycles and be displaying high stability by showing a potassiation capacity of 108.4 mA h g^?1 over 2000 cycles at 1000 mA g^?1. The density functional theory calculations demonstrate that S/O codoping not only favors the adsorption of K to the PCMs electrode but also reduces its structural deformation during the potassiation/depotassiation. The present work highlights the important role of hierarchical porosity and S/O codoping in potassium storage.     

An Ion‐Exchange Promoted Phase Transition in a Li‐Excess Layered Cathode Material for High‐Performance Lithium Ion Batteries

A new approach to intentionally induce phase transition of Li‐excess layered cathode materials for high‐performance lithium ion batteries is reported. In high contrast to the limited layered‐to‐spinel phase transformation that occurred during in situ electrochemical cycles, a Li‐excess layered Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ is completely converted to a Li₄Mn₅O₁₂‐type spinel product via ex situ ion‐exchanges and a post‐annealing process. Such a layered‐to‐spinel phase conversion is examined using in situ X‐ray diffraction and in situ high‐resolution transmission electron microscopy. It is found that generation of sufficient lithium ion vacancies within the Li‐excess layered oxide plays a critical role for realizing a complete phase transition. The newly formed spinel material exhibits initial discharge capacities of 313.6, 267.2, 204.0, and 126.3 mAh g^?1 when cycled at 0.1, 0.5, 1, and 5 C (1 C = 250 mA g^?1), respectively, and can retain a specific capacity of 197.5 mAh g^?1 at 1 C after 100 electrochemical cycles, demonstrating remarkably improved rate capability and cycling stability in comparison with the original Li‐excess layered cathode materials. This work sheds light on fundamental understanding of phase transitions within Li‐excess layered oxides. It also provides a novel route for tailoring electrochemical performance of Li‐excess layered cathode materials for high‐capacity lithium ion batteries.     

Mesoporous TiO2‐Sn/C Core‐Shell Nanowire Arrays as High‐Performance 3D Anodes for Li‐Ion Batteries

Three‐dimensional mesoporous TiO₂‐Sn/C core‐shell nanowire arrays are prepared on Ti foil as anodes for lithium‐ion batteries. Sn formed by a reduction of SnO₂ is encapsulated into TiO₂ nanowires and the carbon layer is coated onto it. For additive‐free, self‐supported anodes in Li‐ion batteries, this unique core‐shell composite structure can effectively buffer the volume change, suppress cracking, and improve the conductivity of the electrode during the discharge‐charge process, thus resulting in superior rate capability and excellent long‐term cycling stability. Specifically, the TiO₂‐Sn/C nanowire arrays display rechargeable discharge capacities of 769, 663, 365, 193, and 90 mA h g^?1 at 0.1C, 0.5C, 2C 10C, and 30C, respectively (1C = 335 mA g^?1). Furthermore, the TiO₂‐Sn/C nanowire arrays exhibit a capacity retention rate of 84.8% with a discharge capacity of over 160 mA h g^?1, even after 100 cycles at a high current rate of 10C.     

Soft Carbon as Anode for High‐Performance Sodium‐Based Dual Ion Full Battery

Sodium‐based dual ion full batteries (NDIBs) are reported with soft carbon as anode and graphite as cathode for the first time. The NDIBs operate at high discharge voltage plateau of 3.58 V, with superior discharge capacity of 103 mA h g^?1, excellent rate performance, and long‐term cycling stability over 800 cycles with capacity retention of 81.8%. The mechanism of Na⁺ and PF₆^? insertion/desertion during the charging/discharging processes is proposed and discussed in detail, with the support of various spectroscopies.     

Ion Transport Nanotube Assembled with Vertically Aligned Metallic MoS2 for High Rate Lithium‐Ion Batteries

Metallic phase molybdenum disulfide (MoS₂) is well known for orders of magnitude higher conductivity than 2H semiconducting phase MoS₂. Herein, for the first time, the authors design and fabricate a novel porous nanotube assembled with vertically aligned metallic MoS₂ nanosheets by using the scalable solvothermal method. This metallic nanotube has the following advantages: (i) intrinsic high electrical conductivity that promotes the rate performance of battery and eliminates the using of conductive additive; (ii) hierarchical, hollow, porous, and aligned structure that assists the electrolyte transportation and diffusion; (iii) tubular structure that avoids restacking of 2D nanosheets, and therefore maintains the electrochemistry cycling stability; and (iv) a shortened ion diffusion path, that improves the rate performance. This 1D metallic MoS₂ nanotube is demonstrated to be a promising anode material for lithium‐ion batteries. The unique structure delivers an excellent reversible capacity of 1100 mA h g^?1 under a current density of 5 A g^?1 after 350 cycles, and an outstanding rate performance of 589 mA h g^?1 at a current density of 20 A g^?1. Furthermore, attributed to the material's metallic properties, the electrode comprising 100% pure material without any additive provides an ideal system for the fundamental electrochemical study of metallic MoS₂. This study first reveals the characteristic anodic peak at 1.5 V in cyclic voltammetry of metallic MoS_2. This research sheds light on the fabrication of metallic 1D, 2D, or even 3D structures with 2D nanosheets as building blocks for various applications.     

A Novel α‐MoO3/Single‐Walled Carbon Nanohorns Composite as High‐Performance Anode Material for Fast‐Charging Lithium‐Ion Battery

Orthorhombic α‐MoO₃ is a potential anode material for lithium‐ion batteries due to its high theoretical capacity of 1100 mAh g^?1 and excellent structural stability. However, its intrinsic poor electronic conductivity and high volume expansion during the charge–discharge process impede it from achieving a high practical capacity. A novel composite of α‐MoO₃ nanobelts and single‐walled carbon nanohorns (SWCNHs) is synthesized by a facile microwave hydrothermal technique and demonstrated as a high‐performance anode material for lithium‐ion batteries. The α‐MoO₃/SWCNH composite displays superior electrochemical properties (654 mAh g^?1 at 1 C), excellent rate capability (275 mAh g^?1 at 5 C), and outstanding cycle life (capacity retention of >99% after 3000 cycles at 1 C) without any cracking of the electrode. The presence of SWCNHs in the composite enhances the electrochemical properties of α‐MoO₃ by acting as a lithium storage material, electronic conductive medium, and buffer against pulverization.     

Heteroatom‐Doped Mesoporous Hollow Carbon Spheres for Fast Sodium Storage with an Ultralong Cycle Life

Carbon materials have attracted significant attention as anode materials for sodium ion batteries (SIBs). Developing a carbon anode with long‐term cycling stability under ultrahigh rate is essential for practical application of SIBs in energy storage systems. Herein, sulfur and nitrogen codoped mesoporous hollow carbon spheres are developed, exhibiting high rate performance of 144 mA h g^?1 at 20 A g^?1, and excellent cycling durability under ultrahigh current density. Interestingly, during 7000 cycles at a current density of 20 A g^?1, the capacity of the electrode gradually increases to 180 mA h g^?1. The mechanisms for the superior electrochemical performance and capacity improvement of the cells are studied by electrochemical tests, ex situ transmission electron microscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy, and Raman analysis of fresh and cycled electrodes. The unique and robust structure of the material can enhance transport kinetics of electrons and sodium ions, and maintain fast sodium storage from the capacitive process under high rate. The self‐rearrangement of the carbon structure, induced by continuous discharge and charge, lead to the capacity improvement with cycles. These results demonstrate a new avenue to design advanced anode materials for SIBs.