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.     

A New P2‐Type Layered Oxide Cathode with Extremely High Energy Density for Sodium‐Ion Batteries

Herein, a new P2‐type layered oxide is proposed as an outstanding intercalation cathode material for high energy density sodium‐ion batteries (SIBs). On the basis of the stoichiometry of sodium and transition metals, the P2‐type Na_0.55[Ni_0.1Fe_0.1Mn_0.8]O₂ cathode is synthesized without impurities phase by partially substituting Ni and Fe into the Mn sites. The partial substitution results in a smoothing of the electrochemical charge/discharge profiles and thus greatly improves the battery performance. The P2‐type Na_0.55[Ni_0.1Fe_0.1Mn_0.8]O₂ cathode delivers an extremely high discharge capacity of 221.5 mAh g^?1 with a high average potential of ≈2.9 V (vs Na/Na⁺) for SIBs. In addition, the fast Na‐ion transport in the P2‐type Na_0.55[Ni_0.1Fe_0.1Mn_0.8]O₂ cathode structure enables good power capability with an extremely high current density of 2400 mA g^?1 (full charge/discharge in 12 min) and long‐term cycling stability with ≈80% capacity retention after 500 cycles at 600 mA g^?1. A combination of electrochemical profiles, in operando synchrotron X‐ray diffraction analysis, and first‐principles calculations are used to understand the overall Na storage mechanism of P2‐type Na_0.55[Ni_0.1Fe_0.1Mn_0.8]O₂.     

Boosting Sodium Storage in TiF3/Carbon Core/Sheath Nanofibers through an Efficient Mixed‐Conducting Network

Sodium‐ion batteries (SIBs) are considered to be promising energy storage devices for large‐scale grid storage application due to the vast earth‐abundance and low cost of sodium‐containing precursors. Designing and fabricating a highly efficient anode is one of the keys to improve the electrochemical performance of SIBs. Recently, fluoride‐based materials are found to show an exceptional anode function with high theoretical specific capacity, based on open‐framework structure enabling Na insertion and also exhibiting improved safety. However, fluoride‐based materials suffer from sluggish kinetics and poor capacity retention essentially due to low electric conductivity. Here, an efficient mixed‐conducting network offering fast pathways is proposed to address these issues. This network relies on titanium fluoride?carbon (TiF₃?C) core/sheath nanofibers that are prepared via electrospinning. Such highly interconnected electrodes exhibit an enhanced and faster sodium storage performance. Carbon sheath nanofibers are key to an efficient ion‐ and electron‐conducting network that enable Na⁺/e^? transfer to reach the nanosized TiF₃. In addition, in‐situ‐converted Ti and NaF particles embedded in the carbon matrix allow high reversible interfacial storage. As a result, the TiF₃?C core/sheath electrode exhibits a high capacity of 161 mAh g^?1 at a high current density of 1000 mA g^?1 over 2000 cycles.     

Boosting Fast Sodium Storage of a Large‐Scalable Carbon Anode with an Ultralong Cycle Life

Sodium‐ion batteries (SIBs) are considered to be a promising alternative for large‐scale electricity storage. However, it is urgent to develop new anode materials with superior ultralong cycle life performance at high current rates. Herein, a low‐cost and large‐scalable sulfur‐doped carbon anode material that exhibits the best high‐rate cycle performance and the longest cycle life ever reported for carbon anodes is developed. The material delivers a reversible capacity of 142 mA h g^?1 at a current rate up to 10 A g^?1. After 10 000 cycles the capacity is remained at 126.5 mA h g^?1; 89.1% of the initial value. Density functional theory computations demonstrate that the sulfur‐doped carbon has a strong binding affinity for sodium which promotes sodium storage. Meanwhile, the kinetics analysis identifies the capacitive charge storage as a large contributor to sodium storage, which favors ultrafast storage of sodium ions. These results demonstrate a new way to design carbon‐based SIBs anodes for next‐generation large‐scale electricity storage.     

Mn‐Rich P′2‐Na0.67[Ni0.1Fe0.1Mn0.8]O2 as High‐Energy‐Density and Long‐Life Cathode Material for Sodium‐Ion Batteries

Herein, P′2‐type Na_0.67[Ni_0.1Fe_0.1Mn_0.8]O₂ is introduced as a promising new cathode material for sodium‐ion batteries (SIBs) that exhibits remarkable structural stability during repetitive Na⁺ de/intercalation. The O? Ni? O? Mn? O? Fe? O bond in the octahedra of transition‐metal layers is used to suppress the elongation of the Mn? O bond and to improve the electrochemical activity, leading to the highly reversible Na storage mechanism. A high discharge capacity of ≈220 mAh g^?1 (≈605 Wh kg^?1) is delivered at 0.05 C (13 mAg^?1) with a high reversible capacity of ≈140 mAh g^?1 at 3 C and excellent capacity retention of 80% over 200 cycles. This performance is associated with the reversible P′2–OP4 phase transition and small volume change upon charge and discharge (≈3%). The nature of the sodium storage mechanism in a full cell paired with a hard carbon anode reveals an unexpectedly high energy density of ≈542 Wh kg^?1 at 0.2 C and good capacity retention of ≈81% for 500 cycles at 1 C (260 mAg^?1).     

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.     

Codoped Holey Graphene Aerogel by Selective Etching for High‐Performance Sodium‐Ion Storage

The pursuit of more efficient carbon‐based anodes for sodium‐ion batteries (SIBs) prepared from facile and economical methods is a very important endeavor. Based on the crystallinity difference within carbon materials, herein, a low‐temperature selective burning method is developed for preparing oxygen and nitrogen codoped holey graphene aerogel as additive‐free anode for SIBs. By selective burning of a mixture of graphene and low‐crystallinity carbon at 450 °C in air, an elastic porous graphene monolith with abundant holes on graphene sheets and optimized crystallinity is obtained. These structural characteristics lead to an additive‐free electrode with fast charge (ions and electrons) transfer and more abundant Na⁺ storage active sites. Moreover, the heteroatom oxygen/nitrogen doping favors large interlayer distance for rapid Na⁺ insertion/extraction and provides more active sites for high capacitive contribution. The optimized sample exhibits superior sodium‐ion storage capability, i.e., high specific capacity (446 mAh g^?1 at 0.1 A g^?1), ultrahigh rate capability (189 mAh g^?1 at 10 A g^?1), and long cycle life (81.0% capacity retention after 2000 cycles at 5 A g^?1). This facile and economic strategy might be extended to fabricating other superior carbon‐based energy storage materials.     

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.     

Nitrogen Doped/Carbon Tuning Yolk‐Like TiO2 and Its Remarkable Impact on Sodium Storage Performances

Yolk‐like TiO₂ are prepared through an asymmetric Ostwald ripening, which is simultaneously doped by nitrogen and wrapped by carbon from core to shell. It presents a high specific surface area (144.9 m² g^?1), well‐defined yolk‐like structure (600–700 nm), covered with interweaved nanosheets (3–5 nm) and tailored porosity (5–10 nm) configuration. When first utilized as anode material for sodium‐ion batteries (SIBs), it delivers a high reversible specific capacity of 242.7 mA h g^?1 at 0.5 C and maintains a considerable capacity of 115.9 mA h g^?1 especially at rate 20 C. Moreover, the reversible capacity can still reach 200.7 mA h g^?1 after 550 cycles with full capacity retention at 1 C. Even cycled at extremely high rate 25 C, the capacity retention of 95.5% after 3000 cycles is acquired. Notably, an ultrahigh initial coulombic efficiency of 59.1% is achieved. The incorporation of nitrogen with narrowing the band gap accompanied with carbon uniformly coating from core to shell make the NC TiO₂‐Y favor a bulk type conductor, resulting in fast electron transfer, which is beneficial to long‐term cycling stability and remarkable rate capability. It is of great significance to improve the energy‐storage properties through development of the bulk type conductor as anode materials in SIBs.     

Nanosheets‐Assembled CuSe Crystal Pillar as a Stable and High‐Power Anode for Sodium‐Ion and Potassium‐Ion Batteries

Thanks to low costs and the abundance of the resources, sodium‐ion (SIBs) and potassium‐ion batteries (PIBs) have emerged as leading candidates for next‐generation energy storage devices. So far, only few materials can serve as the host for both Na⁺ and K⁺ ions. Herein, a cubic phase CuSe with crystal‐pillar‐like morphology (CPL‐CuSe) assembled by the nanosheets are synthesized and its dual functionality in SIBs and PIBs is comprehensively studied. The electrochemical measurements demonstrate that CPL‐CuSe enables fast Na⁺ and K⁺ storage as well as the sufficiently long duration. Specifically, the anode delivers a specific capacity of 295 mA h g^?1 at current density of 10 A g^?1 in SIBs, while 280 mA h g^?1 at 5 A g^?1 in PIBs, as well as the high capacity retention of nearly 100% over 1200 cycles and 340 cycles, respectively. Remarkably, CPL‐CuSe exhibits a high initial coulombic efficiency of 91.0% (SIBs) and 92.4% (PIBs), superior to most existing selenide anodes. A combination of in situ X‐ray diffraction and ex situ transmission electron microscopy tests fundamentally reveal the structural transition and phase evolution of CuSe, which shows a reversible conversion reaction for both cells, while the intermediate products are different due to the sluggish K⁺ insertion reaction.     

KTi2(PO4)3 with Large Ion Diffusion Channel for High‐Efficiency Sodium Storage

To accommodate the decreasing lithium resource and ensure continuous development of energy storage industry, sodium‐based batteries are widely studied to inherit the next generation of energy storage devices. In this work, a novel Na super ionic conductor type KTi₂(PO₄)₃/carbon nanocomposite is designed and fabricated as sodium storage electrode materials, which exhibits considerable reversible capacity (104 mAh g^?1 under the rate of 1 C with flat voltage plateaus at ≈2.1 V), high‐rate cycling stability (74.2% capacity retention after 5000 cycles at 20 C), and ultrahigh rate capability (76 mAh g^?1 at 100 C) in sodium ion batteries. Besides, the maximum ability for sodium storage is deeply excavated by further investigations about different voltage windows in half and full sodium ion cells. Meanwhile, as cathode material in sodium‐magnesium hybrid batteries, the KTi₂(PO₄)₃/carbon nanocomposite also displays good electrochemical performances (63 mAh g^?1 at the 230th cycle under the voltage window of 1.0–1.9 V). The results demonstrate that the KTi₂(PO₄)₃/carbon nanocomposite is a promising electrode material for sodium ion storage, and lay theoretical foundations for the development of new type of batteries.     

Black Phosphorus Quantum Dot/Ti3C2 MXene Nanosheet Composites for Efficient Electrochemical Lithium/Sodium‐Ion Storage

The exploration of new and efficient energy storage mechanisms through nanostructured electrode design is crucial for the development of high‐performance rechargeable batteries. Herein, black phosphorus quantum dots (BPQDs) and Ti₃C₂ nanosheets (TNSs) are employed as battery and pseudocapacitive components, respectively, to construct BPQD/TNS composite anodes with a novel battery‐capacitive dual‐model energy storage (DMES) mechanism for lithium‐ion and sodium‐ion batteries. Specifically, as a battery‐type component, BPQDs anchored on the TNSs are endowed with improved conductivity and relieved stress upon cycling, enabling a high‐capacity and stable energy storage. Meanwhile, the pseudocapacitive TNS component with further atomic charge polarization induced by P? O? Ti interfacial bonds between the two components allows enhanced charge adsorption and efficient interfacial electron transfer, contributing a higher pseudocapacitive value and fast energy storage. The DMES mechanism is evidenced by substantial characterizations of X‐ray photoelectron spectroscopy and X‐ray absorption fine structure spectroscopy, density functional theory calculations, and kinetics analyses. Consequently, the composite electrode exhibits superior battery performance, especially for lithium storage, such as high capacity (910 mAh g^?1 at 100 mA g^?1), long cycling stability (2400 cycles with a capacity retention over 100%), and high rate capability, representing the best comprehensive battery performance in BP‐based anodes to date.     

Ice Templated Free‐Standing Hierarchically WS2/CNT‐rGO Aerogel for High‐Performance Rechargeable Lithium and Sodium Ion Batteries

A hybrid nanoarchitecture aerogel composed of WS₂ nanosheets and carbon nanotube‐reduced graphene oxide (CNT‐rGO) with ordered microchannel three‐dimensional (3D) scaffold structure was synthesized by a simple solvothermal method followed by freeze‐drying and post annealing process. The 3D ordered microchannel structures not only provide good electronic transportation routes, but also provide excellent ionic conductive channels, leading to an enhanced electrochemical performance as anode materials both for lithium‐ion batteries (LIBs) and sodium‐ion batteries (SIBs). Significantly, WS₂/CNT‐rGO aerogel nanostructure can deliver a specific capacity of 749 mA h g^?1 at 100 mA g^?1 and a high first‐cycle coulombic efficiency of 53.4% as the anode material of LIBs. In addition, it also can deliver a capacity of 311.4 mA h g^?1 at 100 mA g^?1, and retain a capacity of 252.9 mA h g^?1 at 200 mA g^?1 after 100 cycles as the anode electrode of SIBs. The excellent electrochemical performance is attributed to the synergistic effect between the WS₂ nanosheets and CNT‐rGO scaffold network and rational design of 3D ordered structure. These results demonstrate the potential applications of ordered CNT‐rGO aerogel platform to support transition‐metal‐dichalcogenides (i.e., WS₂) for energy storage devices and open up a route for material design for future generation energy storage devices.     

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.     

Partially Reduced Holey Graphene Oxide as High Performance Anode for Sodium‐Ion Batteries

The current Na⁺ storage performance of carbon‐based materials is still hindered by the sluggish Na⁺ ion transfer kinetics and low capacity. Graphene and its derivatives have been widely investigated as electrode materials in energy storage and conversion systems. However, as anode materials for sodium‐ion batteries (SIBs), the severe π–π restacking of graphene sheets usually results in compact structure with a small interlayer distance and a long ion transfer distance, thus leading to low capacity and poor rate capability. Herein, partially reduced holey graphene oxide is prepared by simple H₂O₂ treatment and subsequent low temperature reduction of graphene oxide, leading to large interlayer distance (0.434 nm), fast ion transport, and larger Na⁺ storage space. The partially remaining oxygenous groups can also contribute to the capacity by redox reaction. As anode material for SIBs, the optimized electrode delivers high reversible capacity, high rate capability (365 and 131 mAh g^?1 at 0.1 and 10 A g^?1, respectively), and good cycling performance (163 mAh g^?1 after 3000 cycles at a current density of 2 A g^?1), which is among the best reported performances for carbon‐based SIB anodes.     

Electrospun NaVPO4F/C Nanofibers as Self‐Standing Cathode Material for Ultralong Cycle Life Na‐Ion Batteries

NaVPO₄F has received a great deal of attention as cathode material for Na‐ion batteries due to its high theoretical capacity (143 mA h g^?1), high voltage platform, and structural stability. Novel NaVPO₄F/C nanofibers are successfully prepared via a feasible electrospinning method and subsequent heat treatment as self‐standing cathode for Na‐ion batteries. Based on the morphological and microstructural characterization, it can be seen that the NaVPO₄F/C nanofibers are smooth and continuous with NaVPO₄F nanoparticles (≈6 nm) embedded in porous carbon matrix. For Na‐storage, this electrode exhibits extraordinary electrochemical performance: a high capacity (126.3 mA h g^?1 at 1 C), a superior rate capability (61.2 mA h g^?1 at 50 C), and ultralong cyclability (96.5% capacity retention after 1000 cycles at 2 C). 1D NaVPO₄F/C nanofibers that interlink into 3D conductive network improve the conductivity of NaVPO₄F, and effectively restrain the aggregation of NaVPO₄F particles during charge/discharge process, leading to the high performance.     

Chemical Synthesis of 3D Graphene‐Like Cages for Sodium‐Ion Batteries Applications

Sodium (Na) super ion conductor structured Na₃V₂(PO₄)₃ (NVP) is extensively explored as cathode material for sodium‐ion batteries (SIBs) due to its large interstitial channels for Na⁺ migration. The synthesis of 3D graphene‐like structure coated on NVP nanoflakes arrays via a one‐pot, solid‐state reaction in molten hydrocarbon is reported. The NVP nanoflakes are uniformly coated by the in situ generated 3D graphene‐like layers with the thickness of 3 nm. As a cathode material, graphene covered NVP nanoflakes exhibit excellent electrochemical performances, including close to theoretical reversible capacity (115.2 mA h g^?1 at 1 C), superior rate capability (75.9 mA h g^?1 at 200 C), and excellent cyclic stability (62.5% of capacity retention over 30000 cycles at 50 C). Furthermore, the 3D graphene‐like cages after removing NVP also serve as a good anode material and deliver a specific capacity of 242.5 mA h g^?1 at 0.1 A g^?1. The full SIB using these two cathode and anode materials delivers a high specific capacity (109.2 mA h g^?1 at 0.1 A g^?1) and good cycling stability (77.1% capacity retention over 200 cycles at 0.1 A g^?1).     

An Ultrastable Presodiated Titanium Disulfide Anode for Aqueous “Rocking‐Chair” Zinc Ion Battery

Rechargeable aqueous Zn‐based batteries are attractive candidates as energy storage technology, but the uncontrollable Zn dendrites, low stripping/plating coulombic efficiency, and inefficient utilization of Zn metal limit the battery reliability and energy density. Herein, for the first time, a novel presodiated TiS₂ (Na_0.14TiS₂) is proposed and investigated as an intercalated anode for aqueous Zn‐ion batteries, showing a capacity of 140 mAh g^?1 with a suitable potential of 0.3 V (vs Zn²⁺/Zn) at 0.05 A g^?1 and superior cyclability of 77% retention over 5000 cycles at 0.5 A g^?1. The remarkable performance originates from the buffer phase formation of Na_0.14TiS₂ after chemically presodiating TiS₂, which not only improves the structural reversibility and stability but also enhances the diffusion coefficient and electronic conductivity, and lowers cation migration barrier, as evidenced by a series of experimental and theoretical studies. Moreover, an aqueous “rocking‐chair” Zn‐ion full battery is successfully demonstrated by this Na_0.14TiS₂ anode and ZnMn₂O₄ cathode, which delivers a capacity of 105 mAh g^?1 (for anode) with an average voltage of 0.95 V at 0.05 A g^?1 and preserves 74% retention after 100 cycles at 0.2 A g^?1, demonstrating the feasibility of Zn‐ion full batteries for energy storage applications.     

Sodium‐Ion Batteries: From Academic Research to Practical Commercialization

Sodium‐ion batteries (SIBs) have been considered as the most promising candidate for large‐scale energy storage system owing to the economic efficiency resulting from abundant sodium resources, superior safety, and similar chemical properties to the commercial lithium‐ion battery. Despite the long period of academic research, how to realize sodium‐ion battery commercialization for market applications is still a great challenge. Thus, from the perspective of future practical application, this review will identify the factors that are restricting commercialization, and evaluate the existing active materials and sodium‐ion‐based full‐cell system. The design and development trends that are needed for SIBs to meet the requirements of practical applications in large‐scale energy storage will also be discussed in detail.     

High Energy Density Sodium‐Ion Battery with Industrially Feasible and Air‐Stable O3‐Type Layered Oxide Cathode

Extensive effort is being made into cathode materials for sodium‐ion battery to address several fatal issues, which restrict their future application in practical sodium‐ion full cell system, such as their unsatisfactory initial Coulombic efficiency, inherent deficiency of cyclable sodium content, and poor industrial feasibility. A novel air‐stable O3‐type Na[Li_0.05Mn_0.50Ni_0.30Cu_0.10Mg_0.05]O₂ is synthesized by a coprecipitation method suitable for mass production followed by high‐temperature annealing. The microscale secondary particle, consisting of numerous primary nanocrystals, can efficiently facilitate sodium‐ion transport due to the short diffusion distance, and this cathode material also has inherent advantages for practical application because of its superior physical properties. It exhibits a reversible capacity of 172 mA h g^?1 at 0.1 C and remarkable capacity retention of 70.4% after 1000 cycles at 20 C. More importantly, it offers good compatibility with pristine hard carbon as anode in the sodium‐ion full cell system, delivering a high energy density of up to 215 W h kg^?1 at 0.1 C and good rate performance. Owing to the high industrial feasibility of the synthesis process, good compatibility with pristine hard carbon anode, and excellent electrochemical performance, it can be considered as a promising active material to promote progress toward sodium‐ion battery commercialization.