Designed Formation of Hybrid Nanobox Composed of Carbon Sheathed CoSe2 Anchored on Nitrogen‐Doped Carbon Skeleton as Ultrastable Anode for Sodium‐Ion Batteries

Research on sodium‐ion batteries (SIBs) has recently been revitalized due to the unique features of much lower costs and comparable energy/power density to lithium‐ion batteries (LIBs), which holds great potential for grid‐level energy storage systems. Transition metal dichalcogenides (TMDCs) are considered as promising anode candidates for SIBs with high theoretical capacity, while their intrinsic low electrical conductivity and large volume expansion upon Na⁺ intercalation raise the challenging issues of poor cycle stability and inferior rate performance. Herein, the designed formation of hybrid nanoboxes composed of carbon‐protected CoSe₂ nanoparticles anchored on nitrogen‐doped carbon hollow skeletons (denoted as CoSe₂@C∩NC) via a template‐assisted refluxing process followed by conventional selenization treatment is reported, which exhibits tremendously enhanced electrochemical performance when applied as the anode for SIBs. Specifically, it can deliver a high reversible specific capacity of 324 mAh g^?1 at current density of 0.1 A g^?1 after 200 cycles and exhibit outstanding high rate cycling stability at the rate of 5 A g^?1 over 2000 cycles. This work provides a rational strategy for the design of advanced hybrid nanostructures as anode candidates for SIBs, which could push forward the development of high energy and low cost energy storage devices.     

High‐Performance Flexible Freestanding Anode with Hierarchical 3D Carbon‐Networks/Fe7S8/Graphene for Applicable Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) have gained tremendous interest for grid scale energy storage system and power energy batteries. However, the current researches of anode for SIBs still face the critical issues of low areal capacity, limited cycle life, and low initial coulombic efficiency for practical application perspective. To solve this issue, a kind of hierarchical 3D carbon‐networks/Fe₇S₈/graphene (CFG) is designed and synthesized as freestanding anode, which is constructed with Fe₇S₈ microparticles well‐welded on 3D‐crosslinked carbon‐networks and embedded in highly conductive graphene film, via a facile and scalable synthetic method. The as‐prepared freestanding electrode CFG represents high areal capacity (2.12 mAh cm^?2 at 0.25 mA cm^?2) and excellent cycle stability of 5000 cycles (0.0095% capacity decay per cycle). The assembled all‐flexible sodium‐ion battery delivers remarkable performance (high areal capacity of 1.42 mAh cm^?2 at 0.3 mA cm^?2 and superior energy density of 144 Wh kg^?1), which are very close to the requirement of practical application. This work not only enlightens the material design and electrode engineering, but also provides a new kind of freestanding high energy density anode with great potential application prospective for SIBs.     

S‐Doped Carbon Fibers Uniformly Embedded with Ultrasmall TiO2 for Na+/Li+ Storage with High Capacity and Long‐Time Stability

Building a rechargeable battery with high capacity, high energy density, and long lifetime contributes to the development of novel energy storage devices in the future. Although carbon materials are very attractive anode materials for lithium‐ion batteries (LIBs), they present several deficiencies when used in sodium‐ion batteries (SIBs). The choice of an appropriate structural design and heteroatom doping are critical steps to improve the capacity and stability. Here, carbon‐based nanofibers are produced by sulfur doping and via the introduction of ultrasmall TiO₂ nanoparticles into the carbon fibers (CNF‐S@TiO₂). It is discovered that the introduction of TiO₂ into carbon nanofibers can significantly improve the specific surface area and microporous volume for carbon materials. The TiO₂ content is controlled to obtain CNF‐S@TiO₂‐5 to use as the anode material for SIBs/LIBs with enhanced electrochemical performance in Na⁺/Li⁺ storage. During the charge/discharge process, the S‐doping and the incorporation of TiO₂ nanoparticles into carbon fibers promote the insertion/extraction of the ions and enhance the capacity and cycle life. The capacity of CNF‐S@TiO₂‐5 can be maintained at ≈300 mAh g^?1 over 600 cycles at 2 A g^?1 in SIBs. Moreover, the capacity retention of such devices is 94%, showing high capacity and good stability.     

High‐Energy/Power and Low‐Temperature Cathode for Sodium‐Ion Batteries: In Situ XRD Study and Superior Full‐Cell Performance

Sodium‐ion batteries (SIBs) are still confronted with several major challenges, including low energy and power densities, short‐term cycle life, and poor low‐temperature performance, which severely hinder their practical applications. Here, a high‐voltage cathode composed of Na₃V₂(PO₄)₂O₂F nano‐tetraprisms (NVPF‐NTP) is proposed to enhance the energy density of SIBs. The prepared NVPF‐NTP exhibits two high working plateaux at about 4.01 and 3.60 V versus the Na⁺/Na with a specific capacity of 127.8 mA h g^?1. The energy density of NVPF‐NTP reaches up to 486 W h kg^?1, which is higher than the majority of other cathode materials previously reported for SIBs. Moreover, due to the low strain (≈2.56% volumetric variation) and superior Na transport kinetics in Na intercalation/extraction processes, as demonstrated by in situ X‐ray diffraction, galvanostatic intermittent titration technique, and cyclic voltammetry at varied scan rates, the NVPF‐NTP shows long‐term cycle life, superior low‐temperature performance, and outstanding high‐rate capabilities. The comparison of Ragone plots further discloses that NVPF‐NTP presents the best power performance among the state‐of‐the‐art cathode materials for SIBs. More importantly, when coupled with an Sb‐based anode, the fabricated sodium‐ion full‐cells also exhibit excellent rate and cycling performances, thus providing a preview of their practical application.     

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.     

N‐Doped Carbon Nanofibers with Interweaved Nanochannels for High‐Performance Sodium‐Ion Storage

Although graphite materials have been applied as commercial anodes in lithium‐ion batteries (LIBs), there still remain abundant spaces in the development of carbon‐based anode materials for sodium‐ion batteries (SIBs). Herein, an electrospinning route is reported to fabricate nitrogen‐doped carbon nanofibers with interweaved nanochannels (NCNFs‐IWNC) that contain robust interconnected 1D porous channels, produced by removal of a Te nanowire template that is coelectrospun within carbon nanofibers during the electrospinning process. The NCNFs‐IWNC features favorable properties, including a conductive 1D interconnected porous structure, a large specific surface area, expanded interlayer graphite‐like spacing, enriched N‐doped defects and active sites, toward rapid access and transport of electrolyte and electron/sodium ions. Systematic electrochemical studies indicate that the NCNFs‐IWNC exhibits an impressively high rate capability, delivering a capacity of 148 mA h g^?1 at current density of as high as 10 A g^?1, and has an attractively stable performance over 5000 cycles. The practical application of the as‐designed NCNFs‐IWNC for a full SIBs cell is further verified by coupling the NCNFs‐IWNC anode with a FeFe(CN)₆ cathode, which displays a desirable cycle performance, maintaining acapacity of 97 mA h g^?1 over 100 cycles.     

Bulk Bismuth as a High‐Capacity and Ultralong Cycle‐Life Anode for Sodium‐Ion Batteries by Coupling with Glyme‐Based Electrolytes

Sodium‐ion batteries (SIBs) have attracted great interest for large‐scale electric energy storage in recent years. However, anodes with long cycle life and large reversible capacities are still lacking and therefore limiting the development of SIBs. Here, a bulk Bi anode with surprisingly high Na storage performance in combination with glyme‐based electrolytes is reported. This study shows that the bulk Bi electrode is gradually developed into a porous integrity during initial cycling, which is totally different from that in carbonate‐based electrolytes and ensures facile Na⁺ transport and structural stability. The achievable capacity of bulk Bi in the NaPF₆‐diglyme electrolyte is high up to 400 mAh g^?1, and the capacity retention is 94.4% after 2000 cycles, corresponding to a capacity loss of 0.0028% per cycle. It exhibits two flat discharge/charge plateaus at 0.67/0.77 and 0.46/0.64 V, ascribed to the typical two‐phase reactions of Bi ? NaBi and NaBi ? Na₃Bi, respectively. The excellent performance is attributed to the unique porous integrity, stable solid electrolyte interface, and good electrode wettability of glymes. This interplay between electrolyte and electrode to boost Na storage performance will pave a new pathway for high‐performance SIBs.     

Recent Progress in Rechargeable Sodium‐Ion Batteries: toward High‐Power Applications

The increasing demands for renewable energy to substitute traditional fossil fuels and related large‐scale energy storage systems (EES) drive developments in battery technology and applications today. The lithium‐ion battery (LIB), the trendsetter of rechargeable batteries, has dominated the market for portable electronics and electric vehicles and is seeking a participant opportunity in the grid‐scale battery market. However, there has been a growing concern regarding the cost and resource availability of lithium. The sodium‐ion battery (SIB) is regarded as an ideal battery choice for grid‐scale EES owing to its similar electrochemistry to the LIB and the crust abundance of Na resources. Because of the participation in frequency regulation, high pulse‐power capability is essential for the implanted SIBs in EES. Herein, a comprehensive overview of the recent advances in the exploration of high‐power cathode and anode materials for SIB is presented, and deep understanding of the inherent host structure, sodium storage mechanism, Na⁺ diffusion kinetics, together with promising strategies to promote the rate performance is provided. This work may shed light on the classification and screening of alternative high rate electrode materials and provide guidance for the design and application of high power SIBs in the future.     

Confinement Growth of Layered WS2 in Hollow Beaded Carbon Nanofibers with Synergistic Anchoring Effect to Reinforce Li+/Na+ Storage Performance

Novel nitrogen doped (N‐doped) hollow beaded structural composite carbon nanofibers are successfully applied for lithium‐ion batteries (LIBs) and sodium‐ion batteries (SIBs). Tungsten disulfide (WS₂) nanosheets are confined, through synergistic anchoring, on the surface and inside of hollow beaded carbon nanofibers (HB CNFs) via a hydrothermal reaction method to construct the hierarchical structure HB WS₂@CNFs. Benefiting from this unique advantage, HB WS₂@CNFs exhibits remarkable lithium‐storage performance in terms of high rate capability (≈351 mAh g^?1 at 2 A g^?1) and stable long‐term cycle (≈446 mAh g^?1 at 1 A g^?1 after 100 cycles). Moreover, as an anode material for SIBs, HB WS₂@CNFs obtains excellent long cycle life and rate performance. During the charging/discharging process, the evolution of morphology and composition of the composite are analyzed by a set of ex situ methods. This synergistic anchoring effect between WS₂ nanosheets and HB CNFs is capable of effectively restraining volume expansion from the metal ions intercalation/deintercalation process and improving the cycling stability and rate performance in LIBs and SIBs.     

In Situ Carbon‐Doped Mo(Se0.85S0.15)2 Hierarchical Nanotubes as Stable Anodes for High‐Performance Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) are promising energy storage devices, but suffer from poor cycling stability and low rate capability. In this work, carbon doped Mo(Se_0.85S_0.15)₂ (i.e., Mo(Se_0.85S_0.15)₂:C) hierarchical nanotubes have been synthesized for the first time and serve as a robust and high‐performance anode material. The hierarchical nanotubes with diameters of 300 nm and wall thicknesses of 50 nm consist of numerous 2D layered nanosheets, and can act as a robust host for sodiation/desodiation cycling. The Mo(Se_0.85S_0.15)₂:C hierarchical nanotubes deliver a discharge capacity of 360 mAh g⁻¹ at a high current density of 2000 mA g⁻¹ and keep a 81.8% capacity retention compared to that at a current density of 50 mA g⁻¹, showing superior rate capability. Comparing with the second cycle discharge capacities, the nanotube anode can maintain capacities of 102.2%, 101.9%, and 97.8% after 100 cycles at current densities of 200, 500, and 1000 mA g⁻¹, respectively. This work demonstrates the best cycling performance and high‐rate sodium storage capabilities of MoSe₂ for SIBs to date. The hollow interior, hierarchical organization, layered structure, and carbon doping are beneficial for fast Na⁺‐ion and electron kinetics and are responsible for the stable cycling performance and high rate capabilities.     

Recent Progress in Iron‐Based Electrode Materials for Grid‐Scale Sodium‐Ion Batteries

Grid‐scale energy storage batteries with electrode materials made from low‐cost, earth‐abundant elements are needed to meet the requirements of sustainable energy systems. Sodium‐ion batteries (SIBs) with iron‐based electrodes offer an attractive combination of low cost, plentiful structural diversity and high stability, making them ideal candidates for grid‐scale energy storage systems. Although various iron‐based cathode and anode materials have been synthesized and evaluated for sodium storage, further improvements are still required in terms of energy/power density and long cyclic stability for commercialization. In this Review, progress in iron‐based electrode materials for SIBs, including oxides, polyanions, ferrocyanides, and sulfides, is briefly summarized. In addition, the reaction mechanisms, electrochemical performance enhancements, structure–composition–performance relationships, merits and drawbacks of iron‐based electrode materials for SIBs are discussed. Such iron‐based electrode materials will be competitive and attractive electrodes for next‐generation energy storage devices.     

Mesoporous NiS2 Nanospheres Anode with Pseudocapacitance for High‐Rate and Long‐Life Sodium‐Ion Battery

It is of great importance to exploit electrode materials for sodium‐ion batteries (SIBs) with low cost, long life, and high‐rate capability. However, achieving quick charge and high power density is still a major challenge for most SIBs electrodes because of the sluggish sodiation kinetics. Herein, uniform and mesoporous NiS₂ nanospheres are synthesized via a facile one‐step polyvinylpyrrolidone assisted method. By controlling the voltage window, the mesoporous NiS₂ nanospheres present excellent electrochemical performance in SIBs. It delivers a high reversible specific capacity of 692 mA h g^?1. The NiS₂ anode also exhibits excellent high‐rate capability (253 mA h g^?1 at 5 A g^?1) and long‐term cycling performance (319 mA h g^?1 capacity remained even after 1000 cycles at 0.5 A g^?1). A dominant pseudocapacitance contribution is identified and verified by kinetics analysis. In addition, the amorphization and conversion reactions during the electrochemical process of the mesoporous NiS₂ nanospheres is also investigated by in situ X‐ray diffraction. The impressive electrochemical performance reveals that the NiS₂ offers great potential toward the development of next generation large scale energy storage.     

Bismuth Nanoparticle@Carbon Composite Anodes for Ultralong Cycle Life and High‐Rate Sodium‐Ion Batteries

Bismuth has emerged as a promising anode material for sodium‐ion batteries (SIBs), owing to its high capacity and suitable operating potential. However, large volume changes during alloying/dealloying processes lead to poor cycling performance. Herein, bismuth nanoparticle@carbon (Bi@C) composite is prepared via a facile annealing method using a commercial coordination compound precursor of bismuth citrate. The composite has a uniform structure with Bi nanoparticles embedded within a carbon framework. The nanosized structure ensures a fast kinetics and efficient alleviation of stress/strain caused by the volume change, and the resilient and conductive carbon matrix provides an interconnected electron transportation pathway. The Bi@C composite delivers outstanding sodium‐storage performance with an ultralong cycle life of 30 000 cycles at a high current density of 8 A g^?1 and an excellent rate capability of 71% capacity retention at an ultrahigh current rate of 60 A g^?1. Even at a high mass loading of 11.5 mg cm^?2, a stable reversible capacity of 280 mA h g^?1 can be obtained after 200 cycles. More importantly, full SIBs by pairing with a Na₃V₂(PO₄)₃ cathode demonstrates superior performance. Combining the facile synthesis and the commercial precursor, the exceptional performance makes the Bi@C composite very promising for practical large‐scale applications.     

Lithium Titanate Cuboid Arrays Grown on Carbon Fiber Cloth for High‐Rate Flexible Lithium‐Ion Batteries

High‐rate performance flexible lithium‐ion batteries are desirable for the realization of wearable electronics. The flexibility of the electrode in the battery is a key requirement for this technology. In the present work, spinel lithium titanate (Li₄Ti₅O₁₂, LTO) cuboid arrays are grown on flexible carbon fiber cloth (CFC) to fabricate a binder‐free composite electrode (LTO@CFC) for flexible lithium‐ion batteries. Experimental results show that the LTO@CFC electrode exhibits a remarkably high‐rate performance with a capacity of 105.8 mAh g^?1 at 50C and an excellent electrochemical stability against cycling (only 2.2% capacity loss after 1000 cycles at 10C). A flexible full cell fabricated with the LTO@CFC as the anode and LiNi_0.5Mn_1.5O₄ coated on Al foil as the cathode displays a reversible capacity of 109.1 mAh g^?1 at 10C, an excellent stability against cycling and a great mechanical stability against bending. The observed high‐rate performance of the LTO@CFC electrode is due to its unique corn‐like architecture with LTO cuboid arrays (corn kernels) grown on CFC (corn cob). This work presents a new approach to preparing LTO‐based composite electrodes with an architecture favorable for ion and electron transport for flexible energy storage devices.     

Efficient Sodium Storage in Rolled‐Up Amorphous Si Nanomembranes

Alloying‐type materials are promising anodes for high‐performance sodium‐ion batteries (SIBs) because of their high capacities and low Na‐ion insertion potentials. However, the typical candidates, such as P, Sn, Sb, and Pb, suffer from severe volume changes (≈293–487%) during the electrochemical reactions, leading to inferior cycling performances. Here, a high‐rate and ultrastable alloying‐type anode based on the rolled‐up amorphous Si nanomembranes is demonstrated. The rolled‐up amorphous Si nanomembranes show a very small volume change during the sodiation/desodiation processes and deliver an excellent rate capability and ultralong cycle life up to 2000 cycles with 85% capacity retention. The structural evolution and pseudocapacitance contribution are investigated by using the ex situ characterization techniques combined with kinetics analysis. Furthermore, the mechanism of efficient sodium‐ion storage in amorphous Si is kinetically analyzed through an illustrative atomic structure with dangling bonds, offering a new perspective on understanding the sodium storage behavior. These results suggest that nanostructured amorphous Si is a promising anode material for high‐performance SIBs.     

Reactive Oxygen‐Doped 3D Interdigital Carbonaceous Materials for Li and Na Ion Batteries

Carbonaceous materials as anodes usually exhibit low capacity for lithium ion batteries (LIBs) and sodium ion batteries (SIBs). Oxygen‐doped carbonaceous materials have the potential of high capacity and super rate performance. However, up to now, the reported oxygen‐doped carbonaceous materials usually exhibit inferior electrochemical performance. To overcome this problem, a high reactive oxygen‐doped 3D interdigital porous carbonaceous material is designed and synthesized through epitaxial growth method and used as anodes for LIBs and SIBs. It delivers high reversible capacity, super rate performance, and long cycling stability (473 mA h g^?1after 500 cycles for LIBs and 223 mA h g^?1 after 1200 cycles for SIBs, respectively, at the current density of 1000 mA g^?1), with a capacity decay of 0.0214% per cycle for LIBs and 0.0155% per cycle for SIBs. The results demonstrate that constructing 3D interdigital porous structure with reactive oxygen functional groups can significantly enhance the electrochemical performance of oxygen‐doped carbonaceous material.     

Metal Cation‐Assisted Synthesis of Amorphous B,N Co‐Doped Carbon Nanotubes for Superior Sodium Storage

Nearly inexhaustible sodium sources on earth make sodium ion batteries (SIBs) the best candidate for large‐scale energy storage. However, the main obstacles faced by SIBs are the low rate performance and poor cycle stability caused by the large size of Na⁺ ions. Herein, a universal strategy for synthesizing amorphous metals encapsulated into amorphous B, N co‐doped carbon (a‐M@a‐BCN; M = Co, Ni, Mn) nanotubes by metal cation‐assisted carbonization is explored. The methodology allows tailoring the structures (e.g., length, wall thickness, and metals doping) of a‐M@a‐BCN nannotubes at the molecular level. Furthermore, the amorphous metal sulfide encapsulated into a‐BCN (a‐MS_x@a‐BCN; MS_x: CoS, Ni₃S₂, MnS) nanotubes are obtained by one‐step sulfidation process. The a‐M@a‐BCN and a‐MS_x@a‐BCN possess the larger interlayer spacing (0.40 nm) amorphous carbon nanotube rich in heteroatoms active sites, making them exhibit excellent Na⁺ ions diffusion kinetics and capacitive storage behavior. As SIBs anodes, they show high capacity, excellent rate performance, and long cycle stability.     

Recent Progress of Layered Transition Metal Oxide Cathodes for Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) are attracting increasing attention and considered to be a low‐cost complement or an alternative to lithium‐ion batteries (LIBs), especially for large‐scale energy storage. Their application, however, is limited because of the lack of suitable host materials to reversibly intercalate Na⁺ ions. Layered transition metal oxides (Na_xMO₂, M = Fe, Mn, Ni, Co, Cr, Ti, V, and their combinations) appear to be promising cathode candidates for SIBs due to their simple structure, ease of synthesis, high operating potential, and feasibility for commercial production. In the present work, the structural evolution, electrochemical performance, and recent progress of Na_xMO₂ as cathode materials for SIBs are reviewed and summarized. Moreover, the existing drawbacks are discussed and several strategies are proposed to help alleviate these issues. In addition, the exploration of full cells based on Na_xMO₂ cathodes and future perspectives are discussed to provide guidance for the future commercialization of such systems.     

Unique Cobalt Sulfide/Reduced Graphene Oxide Composite as an Anode for Sodium‐Ion Batteries with Superior Rate Capability and Long Cycling Stability

Exploitation of high‐performance anode materials is essential but challenging to the development of sodium‐ion batteries (SIBs). Among all proposed anode materials for SIBs, sulfides have been proved promising candidates due to their unique chemical and physical properties. In this work, a facile solvothermal method to in situ decorate cobalt sulfide (CoS) nanoplates on reduced graphene oxide (rGO) to build CoS@rGO composite is described. When evaluated as anode for SIBs, an impressive high specific capacity (540 mAh g^?1 at 1 A g^?1), excellent rate capability (636 mAh g^?1 at 0.1 A g^?1 and 306 mAh g^?1 at 10 A g^?1), and extraordinarily cycle stability (420 mAh g^?1 at 1 A g^?1 after 1000 cycles) have been demonstrated by CoS@rGO composite for sodium storage. The synergetic effect between the CoS nanoplates and rGO matrix contributes to the enhanced electrochemical performance of the hybrid composite. The results provide a facile approach to fabricate promising anode materials for high‐performance SIBs.     

Nitrogen Doped γ‐Graphyne: A Novel Anode for High‐Capacity Rechargeable Alkali‐Ion Batteries

High energy density is the major demand for next‐generation rechargeable batteries, while the intrinsic low alkali metal adsorption of traditional carbon–based electrode remains the main challenge. Here, the mechanochemical route is proposed to prepare nitrogen doped γ‐graphyne (NGY) and its high capacity is demonstrated in lithium (LIBs)/sodium (SIBs) ion batteries. The sample delivers large reversible Li (1037 mAh g^?1) and Na (570.4 mAh g^?1) storage capacities at 100 mA g^?1 and presents excellent rate capabilities (526 mAh g^?1 for LIBs and 180.2 mAh g^?1 for SIBs) at 5 A g^?1. The superior Li/Na storage mechanisms of NGY are revealed by its 2D morphology evolution, quantitative kinetics, and theoretical calculations. The effects on the diffusion barriers (E_b) and adsorption energies (E_ad) of Li/Na atoms in NGY are also studied and imine‐N is demonstrated to be the ideal doping format to enhance the Li/Na storage performance. Besides, the Li/Na adsorption routes in NGY are optimized according to the experimental and the first‐principles calculation results. This work provides a facile way to fabricate high capacity electrodes in LIBs/SIBs, which is also instructive for the design of other heteroatomic doped electrodes.