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.     

Defect‐Rich Soft Carbon Porous Nanosheets for Fast and High‐Capacity Sodium‐Ion Storage

Soft carbon has attracted tremendous attention as an anode in rocking‐chair batteries owing to its exceptional properties including low‐cost, tunable interlayer distance, and favorable electronic conductivity. However, it fails to exhibit decent performance for sodium‐ion storage owing to difficulties in the formation of sodium intercalation compounds. Here, microporous soft carbon nanosheets are developed via a microwave induced exfoliation strategy from a conventional soft carbon compound obtained by pyrolysis of 3,4,9,10‐perylene tetracarboxylic dianhydride. The micropores and defects at the edges synergistically leads to enhanced kinetics and extra sodium‐ion storage sites, which contribute to the capacity increase from 134 to 232 mAh g^?1 and a superior rate capability of 103 mAh g^?1 at 1000 mA g^?1 for sodium‐ion storage. In addition, the capacitance‐dominated sodium‐ion storage mechanism is identified through the kinetics analysis. The in situ X‐ray diffraction analyses are used to reveal that sodium ions intercalate into graphitic layers for the first time. Furthermore, the as‐prepared nanosheets can also function as an outstanding anode for potassium‐ion storage (reversible capacity of 291 mAh g^?1) and dual‐ion full cell (cell‐level capacity of 61 mAh g^?1 and average working voltage of 4.2 V). These properties represent the potential of soft carbon for achieving high‐energy, high‐rate, and low‐cost energy storage systems.     

Advanced Phosphorus‐Based Materials for Lithium/Sodium‐Ion Batteries: Recent Developments and Future Perspectives

High‐performance and lost‐cost lithium‐ion and sodium‐ion batteries are highly desirable for a wide range of applications including portable electronic devices, transportation (e.g., electric vehicles, hybrid vehicles, etc.), and renewable energy storage systems. Great research efforts have been devoted to developing alternative anode materials with superior electrochemical properties since the anode materials used are closely related to the capacity and safety characteristics of the batteries. With the theoretical capacity of 2596 mA h g^?1, phosphorus is considered to be the highest capacity anode material for sodium‐ion batteries and one of the most attractive anode materials for lithium‐ion batteries. This work provides a comprehensive study on the most recent advancements in the rational design of phosphorus‐based anode materials for both lithium‐ion and sodium‐ion batteries. The currently available approaches to phosphorus‐based composites along with their merits and challenges are summarized and discussed. Furthermore, some present underpinning issues and future prospects for the further development of advanced phosphorus‐based materials for energy storage/conversion systems are discussed.     

Observation of Pseudocapacitive Effect and Fast Ion Diffusion in Bimetallic Sulfides as an Advanced Sodium‐Ion Battery Anode

Sodium‐ion batteries (SIBs) are promising next‐generation alternatives due to the low cost and abundance of sodium sources. Yet developmental electrodes in SIBs such as transition metal sulfides have huge volume expansion, sluggish Na⁺ diffusion kinetics, and poor electrical conductivity. Here bimetallic sulfide (Co₉S₈/ZnS) nanocrystals embedded in hollow nitrogen‐doped carbon nanosheets are demonstrated with a high sodium diffusion coefficient, pseudocapacitive effect, and excellent reversibility. Such a unique composite structure is designed and synthesized via a facile sulfidation of the CoZn‐MOFs followed by calcination and is highly dependant on the reaction time and temperature. The optimized Co₁Zn₁‐S(600) electrode exhibits excellent sodium storage performance, including a high capacity of 542 mA h g^?1 at 0.1 A g^?1, good rate capability at 10 A g^?1, and excellent cyclic stability up to 500 cycles for half‐cell. It also shows potential in full‐cell configuration. Such capabilities will accelerate the adoption of sodium‐ion batteries for electrical energy applications.     

Formation of Uniform N‐doped Carbon‐Coated SnO2 Submicroboxes with Enhanced Lithium Storage Properties

Rational design and preparation of SnO₂‐based materials with superior electrochemical performance for lithium‐ion batteries are highly desirable. In this work, the synthesis of SnO₂/nitrogen‐doped carbon (SnO₂/NC) submicroboxes with excellent lithium storage properties is reported. The as‐synthesized SnO₂/NC submicroboxes are highly porous with a high specific surface area of 125 m² g^?1, well‐defined hollow structure (around 400 nm in size) with a shell thickness of 40 nm, and ultrasmall SnO₂ nanoparticles uniformly coated with nitrogen‐doped carbon layer. As a result, the SnO₂/NC submicroboxes show outstanding electrochemical performance as an anode material for lithium‐ion batteries. A high reversible capacity of 491 mAh g^?1 can be retained after 100 cycles at a current density of 0.5 A g^?1.     

Li+ Pre‐Insertion Leads to Formation of Solid Electrolyte Interface on TiO2 Nanotubes That Enables High‐Performance Anodes for Sodium Ion Batteries

Recently, sodium ion batteries (SIBs) have been widely investigated as one of the most promising candidates for replacing lithium ion batteries (LIBs). For SIBs or LIBs, designing a stable and uniform solid electrolyte interphase (SEI) at the electrode–electrolyte interface is the key factor to provide high capacity, long‐term cycling, and high‐rate performance. In this paper, it is described how a remarkably enhanced SEI layer can be obtained on TiO₂ nanotube (TiO₂ NTs) arrays that allows for a strongly improved performance of sodium battery systems. Key is that a Li⁺ pre‐insertion in TiO₂ NTs can condition the SEI for Na⁺ replacement. SIBs constructed with Li‐pre‐inserted NTs deliver an exceptional Na⁺ cycling stability (e.g., 99.9 ± 0.1% capacity retention during 250 cycles at a current rate of 50 mA g^?1) and an excellent rate capability (e.g., 132 mA h g^?1 at a current rate of 1 A g^?1). The key factor in this outstanding performance is that Li‐pre‐insertion into TiO₂ NTs leads not only to an enhanced electronic conductivity in the tubes, but also expands the anatase lattice for facilitated subsequent Na⁺ cycling.     

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.     

Dial the Mechanism Switch of VN from Conversion to Intercalation toward Long Cycling Sodium‐Ion Battery

Transition metal nitrides are promising energy storage materials in regard to good metallic conductivity and high theoretical specific capacity, but their cycling stability is impeded by the huge volume change caused by the conversion reaction mechanism. Here, a simple strategy to produce an intercalation pseudocapacitive‐type vanadium nitride (VN) by one‐step ammonification of V₂C MXene for sodium‐ion batteries is reported. Profiting from a distinctive layered structure pillared by Al atoms in the layer spacing, it delivers a high capacity of 372 mA h g^?1 at 50 mA g^?1 and a desirable rate performance. More importantly, it shows remarkably long cycling stability over 7500 cycles without capacity attenuation at 500 mA g^?1. As expected, it is found that the intercalation pseudocapacitance plays an important role in the excellent performance, by using in situ X‐ray diffraction and ex situ X‐ray absorption structure characterization. Even more remarkable, are the high energy and power density of the sodium‐ion capacitor after coupling with a carbon‐based cathode. The hybrid device possesses an energy density of 78.43 Wh kg^?1 at power density of 260 W kg^?1. The results clearly show that such a unique‐layered VN with outstanding Na storage capability is an excellent new material for energy storage systems.     

Fabrication of Hierarchical Potassium Titanium Phosphate Spheroids: A Host Material for Sodium‐Ion and Potassium‐Ion Storage

Identifying suitable electrode materials for sodium‐ion and potassium‐ion storage holds the key to the development of earth‐abundant energy‐storage technologies. This study reports an anode material based on self‐assembled hierarchical spheroid‐like KTi₂(PO₄)₃@C nanocomposites synthesized via an electrospray method. Such an architecture synergistically combines the advantages of the conductive carbon network and allows sufficient space for the infiltration of the electrolyte from the porous structure, leading to an impressive electrochemical performance, as reflected by the high reversible capacity (283.7 mA h g^?1 for Na‐ion batteries; 292.7 mA h g^?1 for K‐ion batteries) and superior rate capability (136.1 mA h g^?1 at 10 A g^?1 for Na‐ion batteries; 133.1 mA h g^?1 at 1 A g^?1 for K‐ion batteries) of the resulting material. Moreover, the different ion diffusion behaviors in the two systems are revealed to account for the difference in rate performance. These findings suggest that KTi₂(PO₄)₃@C is a promising candidate as an anode material for sodium‐ion and potassium‐ion batteries. In particular, the present synthetic approach could be extended to other functional electrode materials for energy‐storage materials.     

Layer‐by‐Layer Na3V2(PO4)3 Embedded in Reduced Graphene Oxide as Superior Rate and Ultralong‐Life Sodium‐Ion Battery Cathode

Na₃V₂(PO₄)₃ (NVP) is regarded as a promising cathode for advanced sodium‐ion batteries (SIBs) due to its high theoretical capacity and stable sodium (Na) super ion conductor (NASICON) structure. However, strongly impeded by its low electronic conductivity, the general NVP delivers undesirable rate capacity and fails to meet the demands for quick charge. Herein, a novel and facile synthesis of layer‐by‐layer NVP@reduced graphene oxide (rGO) nanocomposite is presented through modifying the surface charge of NVP gel precursor. The well‐designed layered NVP@rGO with confined NVP nanocrystal in between rGO layers offers high electronic and ionic conductivity as well as stable structure. The NVP@rGO nanocomposite with merely ≈3.0 wt% rGO and 0.5 wt% amorphous carbon, yet exhibits extraordinary electrochemical performance: a high capacity (118 mA h g^?1 at 0.5 C attaining the theoretical value), a superior rate capability (73 mA h g^?1 at 100 C and even up to 41 mA h g^?1 at 200 C), ultralong cyclability (70.0% capacity retention after 15 000 cycles at 50 C), and stable cycling performance and excellent rate capability at both low and high operating temperatures. The proposed method and designed layer‐by‐layer active nanocrystal@rGO strategy provide a new avenue to create nanostructures for advanced energy storage applications.     

Carbon Coated Bimetallic Sulfide Hollow Nanocubes as Advanced Sodium Ion Battery Anode

Sodium ion battery (SIB) as a next‐generation battery has been drawing much attention due to the abundance and even distribution of sodium source. Metal sulfides with high theoretical capacity and good electrical conductivity are promising anode candidates for SIB, however, the structural collapse caused by severe volume change during the de/sodiation process typically results in a fast capacity decay, limited rate capability, and cycling stability. In this work, by careful composition and structure design, polydopamine coated Prussian blue analogs derived carbon coated bimetallic sulfide hollow nanocubes (PBCS) are prepared with distinguished morphology, higher surface area, smaller charge transfer resistance, and higher sodium diffusion coefficient than the uncoated bimetallic sulfides. An optimum carbon coated bimetallic sulfide hollow nanocube anode delivers a specific capacity of ≈500 mA h g^?1 at 50 mA g^?1 with ethylene carbonate/dimethyl carbonate (1:1, vol%) electrolyte in the presence of fluoroethylene carbonate additives. A capacity of 122.3 mA h g^?1 can be realized at 5000 mA g^?1, showing good rate performance. In addition the carbon coated bimetallic sulfide hollow nanocubes can maintain capacity of 87 mA h g^?1 after being cycled at 500 mA g^?1 for 150 times, indicating its good cycling stability. The structure integrity, high specific capacity, good rate performance, and cycling stability of PBCS render it a promising anode material for advanced SIB.     

Realizing Three‐Electron Redox Reactions in NASICON‐Structured Na3MnTi(PO4)3 for Sodium‐Ion Batteries

Developing multielectron reaction electrode materials is essential for achieving high specific capacity and high energy density in secondary batteries; however, it remains a great challenge. Herein, Na₃MnTi(PO₄)₃/C hollow microspheres with an open and stable NASICON framework are synthesized by a spray‐drying‐assisted process. When applied as a cathode material for sodium‐ion batteries, the resultant Na₃MnTi(PO₄)₃/C microspheres demonstrate fully reversible three‐electron redox reactions, corresponding to the Ti^3+/4+ (≈2.1 V), Mn^2+/3+ (≈3.5 V), and Mn^3+/4+ (≈4.0 V vs Na⁺/Na) redox couples. In situ X‐ray diffraction results reveals that both solid‐solution and two‐phase electrochemical reactions are involved in the sodiation/desodiation processes. The high specific capacity (160 mAh g^?1 at 0.2 C), outstanding cyclability (≈92% capacity retention after 500 cycles at 2 C), and the facile synthesis make the Na₃MnTi(PO₄)₃/C a prospective cathode material for sodium‐ion batteries.     

Hydrogenated Core–Shell MAX@K2Ti8O17 Pseudocapacitance with Ultrafast Sodium Storage and Long‐Term Cycling

Sodium‐ion batteries are considered alternatives to lithium‐ion batteries for energy storage devices due to their competitive cost and source abundance. However, the development of electrode materials with long‐term stability and high capacity remains a great challenge. Here, this paper describes for the first time the synthesis of a new class of core–shell MAX@K₂Ti₈O₁₇ by alkaline hydrothermal reaction and hydrogenation of MAX, which grants high sodium ion‐intercalation pseudocapacitance. This composite electrode displays extraordinary reversible capacities of 190 mA h g^?1 at 200 mA g^?1 (0.9 C, theoretical value of ≈219 mA h g^?1) and 150 mA h g^?1 at 1000 mA g^?1 (4.6 C). More importantly, a reversible capacity of 75 mA h g^?1 at 10 000 mA g^?1 (46 C) is retained without any apparent capacity decay even after more than 10 000 cycles. Experimental tests and first‐principle calculations confirm that the increase in Ti³⁺ on the surface layers of MAX@K₂Ti₈O₁₇ by hydrogenation increases its conductivity in addition to enhancing the sodium‐ion intercalation pseudocapacitive process. Furthermore, the distorted dodecahedrons between Ti and O layers not only provide abundant sites for sodium‐ion accommodation but also act as wide tunnels for sodium‐ion transport.     

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.     

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 Hollow‐Shell Structured V2O5 Electrode‐Based Symmetric Full Li‐Ion Battery with Highest Capacity

The symmetric batteries with an electrode material possessing dual cathodic and anodic properties are regarded as an ideal battery configuration because of their distinctive advantages over the asymmetric batteries in terms of fabrication process, cost, and safety concerns. However, the development of high‐performance symmetric batteries is highly challenging due to the limited availability of suitable symmetric electrode materials with such properties of highly reversible capacity. Herein, a triple‐hollow‐shell structured V₂O₅ (THS‐V₂O₅) symmetric electrode material with a reversible capacity of >400 mAh g^?1 between 1.5 and 4.0 V and >600 mAh g^?1 between 0.1 and 3.0 V, respectively, when used as the cathode and anode, is reported. The THS‐V₂O₅ electrodes assembled symmetric full lithium‐ion battery (LIB) exhibits a reversible capacity of ≈290 mAh g^?1 between 2 and 4.0 V, the best performed symmetric energy storage systems reported to date. The unique triple‐shell structured electrode makes the symmetric LIB possessing very high initial coulombic efficiency (94.2%), outstanding cycling stability (with 94% capacity retained after 1000 cycles), and excellent rate performance (over 140 mAh g^?1 at 1000 mA g^?1). The demonstrated approach in this work leaps forward the symmetric LIB performance and paves a way to develop high‐performance symmetric battery electrode materials.     

Promoting Highly Reversible Sodium Storage of Iron Sulfide Hollow Polyhedrons via Cobalt Incorporation and Graphene Wrapping

Sodium ion batteries (SIBs) have drawn significant attention owing to their low cost and inherent safety. However, the absence of suitable anode materials with high rate capability and long cycling stability is the major challenge for the practical application of SIBs. Herein, an efficient anode material consisting of uniform hollow iron sulfide polyhedrons with cobalt doping and graphene wrapping (named as CoFeS@rGO) is developed for high‐rate and long‐life SIBs. The graphene‐encapsulated hollow composite assures fast and continuous electron transportation, high Na⁺ ion accessibility, and strong structural integrity, showing an extremely small volume expansion of only 14.9% upon sodiation and negligible volume contraction during the desodiation. The CoFeS@rGO electrode exhibits high specific capacity (661.9 mAh g^?1 at 100 mA g^?1), excellent rate capability (449.4 mAh g^?1 at 5000 mA g^?1), and long cycle life (84.8% capacity retention after 1500 cycles at 1000 mA g^?1). In situ X‐ray diffraction and selected‐area electron diffraction patterns show that this novel CoFeS@rGO electrode is based on a reversible conversion reaction. More importantly, when coupled with a Na₃V₂(PO₄)₃/C cathode, the sodium ion full battery delivers a superexcellent rate capability (496.8 mAh g^?1 at 2000 mA g^?1) and ≈96.5% capacity retention over 200 cycles at 500 mA g^?1 in the 1.0–3.5 V window. This work indicates that the rationally designed anode material is highly applicable for the next generation SIBs with high‐rate capability and long‐term cyclability.     

Frogspawn‐Coral‐Like Hollow Sodium Sulfide Nanostructured Cathode for High‐Rate Performance Sodium–Sulfur Batteries

Room‐temperature (RT) sodium–sulfur (Na–S) batteries are attractive cost‐effective platforms as the next‐generation energy storage systems by using all earth‐abundant resources as electrode materials. However, the slow kinetics of Na–S chemistry makes it hard to achieve high‐rate performance. Herein, a facile and scalable approach has been developed to synthesize hollow sodium sulfide (Na₂S) nanospheres embedded in a highly hierarchical and spongy conductive carbon matrix, forming an intriguing architecture similar to the morphology of frogspawn coral, which has shown great potential as a cathode for high‐rate performance RT Na–S batteries. The shortened Na‐ion diffusion pathway benefits from the hollow structures together with the fast electron transfer from the carbon matrix contributes to high electrochemical reactivity, leading to superior electrochemical performance at various current rates. At high current densities of 1.4 and 2.1 A g^?1, high initial discharge capacities of 980 and 790 mAh g^?1_sulfur can be achieved, respectively, with reversible capacities stabilized at 600 and 400 mAh g^?1_sulfur after 100 cycles. As a proof of concept, a Na‐metal‐free Na–S battery is demonstrated by pairing the hollow Na₂S cathode with tin‐based anode. This work provides guidance on rational materials design towards the success of RT high‐rate Na–S batteries.     

Insights into the Na+ Storage Mechanism of Phosphorus‐Functionalized Hard Carbon as Ultrahigh Capacity Anodes

Hard carbon as a typical anode material for sodium ion batteries has received much attention in terms of its low cost and renewability. Herein, phosphorus‐functionalized hard carbon with a specific “honeycomb briquette” shaped morphology is synthesized via electrospinning technology. When applied as an anode material for Na⁺ storage, it exhibits an impressively high reversible capacity of 393.4 mA h g^?1 with the capacity retention up to 98.2% after 100 cycles. According to first‐principle calculation, the ultrahigh capacity of the as‐prepared anode is ascribed to the enhancement of Na‐absorption through formation of P?O and P? C bonds in graphitic layers when doped with phosphorus. Moreover, the increase of electron density around the Fermi level is found to be mainly caused by O atoms instead of P atoms.     

New Binder‐Free Metal Phosphide–Carbon Felt Composite Anodes for Sodium‐Ion Battery

Metal phosphides are promising anode candidates for sodium‐ion batteries (SIBs) due to their high specific capacity and low operating potential but suffer from poor cycling stability caused by huge volume expansion and poor solid‐state ion transfer rate. Herein, a new strategy to grow a new class of mesoporous metal phosphide nanoarrays on carbon felt (CF) as binder‐free anodes for SIBs is reported. The resultant integrated electrodes demonstrate excellent cycling life up to 1000 times (>90% retention rate) and high rate capability of 535 mAh g^?1 at a current density of 4 A g^?1. Detailed characterization reveals that the synergistic effect of unique mesoporous structure for accommodating huge volume expansion during sodiation/desodiation process, ultrasmall primary particle size (≈10 nm) for providing larger electrode/electrolyte contact area and shorter ion diffusion distance, and 3D conductive networks for facilitating the electrochemical reaction, leads to the extraordinary battery performance. Remarkably, a full SIB using the new CoP₄/CF anode and a Na₃V₂(PO₄)₂F₃ cathode delivers an average operating voltage of ≈3.0 V, a reversible capacity of 553 mAh g^?1, and very high energy density of ≈280 Wh kg^?1 for SIBs. A flexible SIB with outstanding mechanical strength based on this binder‐free new anode is also demonstrated.