Superior Sodium Storage in 3D Interconnected Nitrogen and Oxygen Dual‐Doped Carbon Network

Carbonaceous materials have attracted immense interest as anode materials for Na‐ion batteries (NIBs) because of their good chemical, thermal stabilities, as well as high Na‐storage capacity. However, the carbonaceous materials as anodes for NIBs still suffer from the lower rate capability and poor cycle life. An N,O‐dual doped carbon (denoted as NOC) network is designed and synthesized, which is greatly favorable for sodium storage. It exhibits high specific capacity and ultralong cycling stability, delivering a capacity of 545 mAh g^?1 at 100 mA g^?1 after 100 cycles and retaining a capacity of 240 mAh g^?1 at 2 A g^?1 after 2000 cycles. The NOC composite with 3D well‐defined porosity and N,O‐dual doped induces active sites, contributing to the enhanced sodium storage. In addition, the NOC is synthesized through a facile solution process, which can be easily extended to the preparation of many other N,O‐dual doped carbonaceous materials for wide applications in catalysis, energy storage, and solar cells.     

N‐Doped C@Zn3B2O6 as a Low Cost and Environmentally Friendly Anode Material for Na‐Ion Batteries: High Performance and New Reaction Mechanism

Na‐ion batteries (NIBs) are ideal candidates for solving the problem of large‐scale energy storage, due to the worldwide sodium resource, but the efforts in exploring and synthesizing low‐cost and eco‐friendly anode materials with convenient technologies and low‐cost raw materials are still insufficient. Herein, with the assistance of a simple calcination method and common raw materials, the environmentally friendly and nontoxic N‐doped C@Zn₃B₂O₆ composite is directly synthesized and proved to be a potential anode material for NIBs. The composite demonstrates a high reversible charge capacity of 446.2 mAh g^?1 and a safe and suitable average voltage of 0.69 V, together with application potential in full cells (discharge capacity of 98.4 mAh g^?1 and long cycle performance of 300 cycles at 1000 mA g^?1). In addition, the sodium‐ion storage mechanism of N‐doped C@Zn₃B₂O₆ is subsequently studied through air‐insulated ex situ characterizations of X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), and Fourier‐transform infrared (FT‐IR) spectroscopy, and is found to be rather different from previous reports on borate anode materials for NIBs and lithium‐ion batteries. The reaction mechanism is deduced and proposed as: Zn₃B₂O₆ + 6Na⁺ + 6e^? ? 3Zn + B₂O₃ ? 3Na₂O, which indicates that the generated boracic phase is electrochemically active and participates in the later discharge/charge progress.     

A Flexible Sulfur‐Enriched Nitrogen Doped Multichannel Hollow Carbon Nanofibers Film for High Performance Sodium Storage

Heteroatom doping is regarded as a promising method to enhance the sodium storage performance of carbon materials. In this work, a sulfur‐enriched N‐doped multichannel hollow carbon nanofiber (denoted as S‐NCNF) film is prepared through electrospinning technology and heat treatment with sublimed sulfur as the flexible anode for sodium ion batteries (NIBs). The S‐NCNF film displays outstanding electrochemical performance, particularly with a high rate capacity (132 mA h g^?1 at the current density of 10 A g^?1) and remarkable long cycling stability (reversible specific capacity of 187 mA h g^?1 at 2 A g^?1 over 2000 cycles). The improved sodium storage performance results from the unique 3D structure, abundant defects, and increased interlayer spacing of S‐NCNFs. The density functional theory calculations demonstrate that nitrogenous carbon nanofibers doping with sulfur could not only promote the adsorption of sodium but also favor electrons' transfer. This strategy has been demonstrated as a general process to design free‐standing carbon‐based thin film with other heteroatom doping.     

Na2Ti6O13 Nanorods with Dominant Large Interlayer Spacing Exposed Facet for High‐Performance Na‐Ion Batteries

As the delegate of tunnel structure sodium titanates, Na₂Ti₆O₁₃ nanorods with dominant large interlayer spacing exposed facet are prepared. The exposed large interlayers provide facile channels for Na⁺ insertion and extraction when this material is used as anode for Na‐ion batteries (NIBs). After an activation process, this NIB anode achieves a high specific capacity (a capacity of 172 mAh g^?1 at 0.1 A g^?1) and outstanding cycling stability (a capacity of 109 mAh g^?1 after 2800 cycles at 1 A g^?1), showing its promising application on large‐scale energy storage systems. Furthermore, the electrochemical and structural characterization reveals that the expanded interlayer spacings should be in charge of the activation process, including the enhanced kinetics, the lowered apparent activation energy, and the increased capacity.     

Amorphous Red Phosphorus Embedded in Sandwiched Porous Carbon Enabling Superior Sodium Storage Performances

The red P anode for sodium ion batteries has attracted great attention recently due to the high theoretical capacity, but the poor intrinsic electronic conductivity and large volume expansion restrain its widespread applications. Herein, the red P is successfully encapsulated into the cube shaped sandwich‐like interconnected porous carbon building (denoted as P@C‐GO/MOF‐5) via the vaporization–condensation method. Superior cycling stability (high capacity retention of about 93% at 2 A g^?1 after 100 cycles) and excellent rate performance (502 mAh g^?1 at 10 A g^?1) can be obtained for the P@C‐GO/MOF‐5 electrode. The superior electrochemical performance can be ascribed to the successful incorporation of red P into the unique carbon matrix with large surface area and pore volume, interconnected porous structure, excellent electronic conductivity and superior structural stability.     

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.     

Controllable Interlayer Spacing of Sulfur‐Doped Graphitic Carbon Nanosheets for Fast Sodium‐Ion Batteries

The electrochemical behaviors of current graphitic carbons are seriously restricted by its low surface area and insufficient interlayer spacing for sodium‐ion batteries. Here, sulfur‐doped graphitic carbon nanosheets are reported by utilizing sodium dodecyl sulfate as sulfur resource and graphitization additive, showing a controllable interlayer spacing range from 0.38 to 0.41 nm and a high specific surface area up to 898.8 m² g^?1. The obtained carbon exhibits an extraordinary electrochemical activity for sodium‐ion storage with a large reversible capacity of 321.8 mAh g^?1 at 100 mA g^?1, which can be mainly attributed to the expanded interlayer spacing of the carbon materials resulted from the S‐doping. Impressively, superior rate capability of 161.8 mAh g^?1 is reserved at a high current density of 5 A g^?1 within 5000 cycles, which should be ascribed to the fast surface‐induced capacitive behavior derived from its high surface area. Furthermore, the storage processes are also quantitatively evaluated, confirming a mixed storage mechanism of diffusion‐controlled intercalation behavior and surface‐induced capacitive behavior. This study provides a novel route for rationally designing various carbon‐based anodes with enhanced rate capability.     

3D Graphene Networks Encapsulated with Ultrathin SnS Nanosheets@Hollow Mesoporous Carbon Spheres Nanocomposite with Pseudocapacitance‐Enhanced Lithium and Sodium Storage Kinetics

The lithium and sodium storage performances of SnS anode often undergo rapid capacity decay and poor rate capability owing to its huge volume fluctuation and structural instability upon the repeated charge/discharge processes. Herein, a novel and versatile method is described for in situ synthesis of ultrathin SnS nanosheets inside and outside hollow mesoporous carbon spheres crosslinked reduced graphene oxide networks. Thus, 3D honeycomb‐like network architecture is formed. Systematic electrochemical studies manifest that this nanocomposite as anode material for lithium‐ion batteries delivers a high charge capacity of 1027 mAh g^?1 at 0.2 A g^?1 after 100 cycles. Meanwhile, the as‐developed nanocomposite still retains a charge capacity of 524 mAh g^?1 at 0.1 A g^?1 after 100 cycles for sodium‐ion batteries. In addition, the electrochemical kinetics analysis verifies the basic principles of enhanced rate capacity. The appealing electrochemical performance for both lithium‐ion batteries and sodium‐ion batteries can be mainly related to the porous 3D interconnected architecture, in which the nanoscale SnS nanosheets not only offer decreased ion diffusion pathways and fast Li⁺/Na⁺ transport kinetics, but also the 3D interconnected conductive networks constructed from the hollow mesoporous carbon spheres and reduced graphene oxide enhance the conductivity and ensure the structural integrity.     

ZIF‐8@ZIF‐67‐Derived Nitrogen‐Doped Porous Carbon Confined CoP Polyhedron Targeting Superior Potassium‐Ion Storage

Potassium ion batteries (KIB) have become a compelling energy‐storage system owing to their cost effectiveness and the high abundance of potassium in comparison with lithium. However, its practical applications have been thwarted by a series of challenges, including marked volume expansion and sluggish reaction kinetics caused by the large radius of potassium ions. In line with this, the exploration of reliable anode materials affording high electrical conductivity, sufficient active sites, and structural robustness is the key. The synthesis of ZIF‐8@ZIF‐67 derived nitrogen‐doped porous carbon confined CoP polyhedron architectures (NC@CoP/NC) to function as innovative KIB anode materials is reported. Such composites enable an outstanding rate performance to harvest a capacity of ≈200 mAh g^?1 at 2000 mA g^?1. Additionally, a high cycling stability can be gained by maintaining a high capacity retention of 93% after 100 cycles at 100 mA g^?1. Furthermore, the potassium ion storage mechanism of the NC@CoP/NC anode is systematically probed through theoretical simulations and experimental characterization. This contribution may offer an innovative and feasible route of emerging anode design toward high performance KIBs.     

Ultra‐High Pyridinic N‐Doped Porous Carbon Monolith Enabling High‐Capacity K‐Ion Battery Anodes for Both Half‐Cell and Full‐Cell Applications

An ultrahigh pyridinic N‐content‐doped porous carbon monolith is reported, and the content of pyridinic N reaches up to 10.1% in overall material (53.4 ± 0.9% out of 18.9 ± 0.4% N content), being higher than most of previously reported N‐doping carbonaceous materials, which exhibit greatly improved electrochemical performance for potassium storage, especially in term of the high reversible capacity. Remarkably, the pyridinic N‐doped porous carbon monolith (PNCM) electrode exhibits high initial charge capacity of 487 mAh g^?1 at a current density of 20 mA g^?1, which is one of the highest reversible capacities among all carbonaceous anodes for K‐ion batteries. Moreover, the K‐ion full cell is successfully assembled, demonstrating a high practical energy density of 153.5 Wh kg^?1. These results make PNCM promising for practical application in energy storage devices and encourage more investigations on a similar potassium storage system.     

Design Nitrogen (N) and Sulfur (S) Co‐Doped 3D Graphene Network Architectures for High‐Performance Sodium Storage

To develop high‐performance sodium‐ion batteries (NIBs), electrodes should possess well‐defined pathways for efficient electronic/ionic transport. In this work, high‐performance NIBs are demonstrated by designing a 3D interconnected porous structure that consists of N, S co‐doped 3D porous graphene frameworks (3DPGFs‐NS). The most typical electrode materials (i.e., Na₃V₂(PO₄)₃ (NVP), MoS₂, and TiO₂) are anchored onto the 3DPGFs‐NS matrix (denoted as NVP@C@3DPGFs‐NS; MoS₂@C@3DPGFs‐NS and TiO₂@C@3DPGFs‐NS) to demonstrate its general process to boost the energy density of NIBs. The N, S co‐doped porous graphene structure with a large surface area offers fast ionic transport within the electrode and facilitates efficient electron transport, and thus endows the 3DPGFs‐NS‐based composite electrodes with excellent sodium storage performance. The resulting NVP@C@3DPGFs‐NS displays excellent electrochemical performance as both cathode and anode for NIBs. The MoS₂@C@3DPGFs‐NS and TiO₂@C@3DPGFs‐NS deliver capacities of 317 mAhg^?1 at 5 Ag^?1 after 1000 cycles and 185 mAhg^?1 at 1 Ag^?1 after 2000 cycles, respectively. The excellent long cycle life is attributed to the 3D porous structure that could greatly release mechanical stress from repeated Na⁺ extraction/insertion. The novel structure 3D PGFs‐NS provides a general approach to modify electrodes of NIBs and holds great potential applications in other energy storage fields.     

Enhancing the Sequential Conversion‐Alloying Reaction of Mixed Sn–S Hybrid Anode for Efficient Sodium Storage by a Carbon Healed Graphene Oxide

To date, the possible depletion of lithium resources has become relevant, giving rise to the interest in Na‐ion batteries (NIBs) as promising alternatives to Li‐ion batteries. While extensive investigations have examined various transition metal oxides and chalcogenides as anode materials for NIBs, few of these have been able to utilize their high specific capacity in sodium‐based systems because of their irreversibility in a charge/discharge process. Here, the mixed Sn–S nanocomposites uniformly distributed on reduced graphene oxide are prepared via a facile hydrothermal synthesis and a unique carbothermal reduction process, producing ultrafine nanoparticle with the size of 2 nm. These nanocomposites are experimentally confirmed to overcome the intrinsic drawbacks of tin sulfides such as large volume change and sluggish diffusion kinetics, demonstrating an outstanding electrochemical performance: an excellent specific capacity of 1230 mAh g^?1, and an impressive rate capability (445 mAh g^?1 at 5000 mA g^?1). The electrochemical behavior of a sequential conversion‐alloying reaction for the anode materials is investigated, revealing both the structural transition and the chemical state in the discharge/charge process. Comprehension of the reaction mechanism for the mixed Sn–S/rGO hybrid nanocomposites makes it a promising electrode material and provides a new approach for the Na‐ion battery anodes.     

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.     

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.     

Mild‐Temperature Solution‐Assisted Encapsulation of Phosphorus into ZIF‐8 Derived Porous Carbon as Lithium‐Ion Battery Anode

The high theoretical capacity of red phosphorus (RP) makes it a promising anode material for lithium‐ion batteries. However, the large volume change of RP during charging/discharging imposes an adverse effect on the cyclability and the rate performance suffers from its low conductivity. Herein, a facile solution‐based strategy is exploited to incorporate phosphorus into the pores of zeolitic imidazole framework (ZIF‐8) derived carbon hosts under a mild temperature. With this method, the blocky RP is etched into the form of polyphosphides anions (PP, mainly P₅^?) so that it can easily diffuse into the pores of porous carbon hosts. Especially, the indelible crystalline surface phosphorus can be effectively avoided, which usually generates in the conventional vapor‐condensation encapsulation method. Moreover, highly‐conductive ZIF‐8 derived carbon hosts with any pore smaller than 3 nm are efficient for loading PP and these pores can alleviate the volume change well. Finally, the composite of phosphorus encapsulated into ZIF‐8 derived porous carbon exhibits a significantly improved electrochemical performance as lithium‐ion battery anode with a high capacity of 786 mAh g^?1 after 100 cycles at 0.1 A g^?1, a good stability within 700 cycles at 1 A g^?1, and an excellent rate performance.     

SnS2/Co3S4 Hollow Nanocubes Anchored on S‐Doped Graphene for Ultrafast and Stable Na‐Ion Storage

SnS₂ has been widely studied as an anode material for sodium‐ion batteries (SIBs) based on the high theoretical capacity and layered structure. Unfortunately, rapid capacity decay associated with volume variation during cycling limits practical application. Herein, SnS₂/Co₃S₄ hollow nanocubes anchored on S‐doped graphene are synthesized for the first time via coprecipitation and hydrothermal methods. When applied as the anode for SIBs, the sample delivers a distinguished charge specific capacity of 1141.8 mAh g^?1 and there is no significant capacity decay (0.1 A g^?1 for 50 cycles). When the rate is increased to 0.5 A g^?1, it presents 845.7 mAh g^?1 after cycling 100 times. Furthermore, the composite also exhibits an ultrafast sodium storage capability where 392.9 mAh g^?1 can be obtained at 10 A g^?1 and the charging time is less than 3 min. The outstanding electrochemical properties can be ascribed to the enhancement of conductivity for the addition of S‐doped graphene and the existence of p–n junctions in the SnS₂/Co₃S₄ heterostructure. Moreover, the presence of mesopores between nanosheets can alleviate volume expansion during cycling as well as being beneficial for the migration of Na⁺.     

Plasma Treatment for Nitrogen‐Doped 3D Graphene Framework by a Conductive Matrix with Sulfur for High‐Performance Li–S Batteries

Carbon materials have received considerable attention as host cathode materials for sulfur in lithium–sulfur batteries; N‐doped carbon materials show particularly high electrocatalytic activity. Efforts are made to synthesize N‐doped carbon materials by introducing nitrogen‐rich sources followed by sintering or hydrothermal processes. In the present work, an in situ hollow cathode discharge plasma treatment method is used to prepare 3D porous frameworks based on N‐doped graphene as a potential conductive matrix material. The resulting N‐doped graphene is used to prepare a 3D porous framework with a S content of 90 wt% as a cathode in lithium–sulfur cells, which delivers a specific discharge capacity of 1186 mAh g^?1 at 0.1 C, a coulombic efficiency of 96% after 200 cycles, and a capacity retention of 578 mAh g^?1 at 1.0 C after 1000 cycles. The performance is attributed to the flexible 3D structure and clustering of pyridinic N‐dopants in graphene. The N‐doped graphene shows high electrochemical performance and the flexible 3D porous stable structure accommodates the considerable volume change of the active material during lithium insertion and extraction processes, improving the long‐term electrochemical performance.     

Ultrahigh Rate Performance of Hollow Antimony Nanoparticles Impregnated in Open Carbon Boxes for Sodium‐Ion Battery under Elevated Temperature

Antimony is a competitive and promising anode material for sodium‐ion batteries (SIBs) due to its high theoretical capacity. However, the poor rate capability and fast capacity fading greatly restrict its practical application. To address the above issues, a facile and eco‐friendly sacrificial template method is developed to synthesize hollow Sb nanoparticles impregnated in open carbon boxes (Sb HPs@OCB). The as‐obtained Sb HPs@OCB composite exhibits excellent sodium storage properties even when operated at an elevated temperature of 50 °C, delivering a robust rate capability of 345 mAh g^?1 at 16 A g^?1 and rendering an outstanding reversible capacity of 187 mAh g^?1 at a high rate of 10 A g^?1 after 300 cycles. Such superior electrochemical performance of the Sb HPs@OCB can be attributed to the comprehensive characteristics of improved kinetics derived from hollow Sb nanoparticles impregnated into 2D carbon nanowalls, the existence of robust Sb? O? C bond, and enhanced pseudocapacitive behavior. All those factors enable Sb HPs@OCB great potential and distinct merit for large‐scale energy storage of SIBs.     

In Situ Two‐Step Activation Strategy Boosting Hierarchical Porous Carbon Cathode for an Aqueous Zn‐Based Hybrid Energy Storage Device with High Capacity and Ultra‐Long Cycling Life

Aqueous Zn‐based hybrid energy storage devices (HESDs) exhibit great potential for large‐scale energy storage applications for the merits of environmental friendliness, low redox potential, and high theoretical capacity of Zn anode. However, they are still subjected to low specific capacities since adsorption‐type cathodes (i.e., activated carbon, hard carbon) have limited capability to accommodate active ions. Herein, a hierarchical porous activated carbon cathode (HPAC) is prepared via an in situ two‐step activation strategy, different from the typical one‐step/postmortem activation of fully carbonized precursors. The strategy endows the HPAC with a high specific surface area and a large mesoporous volume, and thus provides abundant active sites and fast kinetics for accommodating active ions. Consequently, pairing the HPAC with Zn anode yields an aqueous Zn‐based HESD, which delivers a high specific capacity of 231 mAh g^?1 at 0.5 A g^?1 and excellent rate performance with a retained capacity of 119 mAh g^?1 at 20 A g^?1, the best result among previously reported lithium‐free HESDs based on carbon cathodes. Further, the aqueous Zn‐based HESD shows ultra‐long cycling stability with a capacity retention of ≈70% after 18 000 cycles at 10 A g^?1, indicating great potential for environmentally friendly, low‐cost, and high‐safety energy storage applications.     

Construction of Bimetallic Selenides Encapsulated in Nitrogen/Sulfur Co‐Doped Hollow Carbon Nanospheres for High‐Performance Sodium/Potassium‐Ion Half/Full Batteries

Metallic selenides have been widely investigated as promising electrode materials for metal‐ion batteries based on their relatively high theoretical capacity. However, rapid capacity decay and structural collapse resulting from the larger‐sized Na⁺/K⁺ greatly hamper their application. Herein, a bimetallic selenide (MoSe₂/CoSe₂) encapsulated in nitrogen, sulfur‐codoped hollow carbon nanospheres interconnected reduced graphene oxide nanosheets (rGO@MCSe) are successfully designed as advanced anode materials for Na/K‐ion batteries. As expected, the significant pseudocapacitive charge storage behavior substantially contributes to superior rate capability. Specifically, it achieves a high reversible specific capacity of 311 mAh g^?1 at 10 A g^?1 in NIBs and 310 mAh g^?1 at 5 A g^?1 in KIBs. A combination of ex situ X‐ray diffraction, Raman spectroscopy, and transmission electron microscopy tests reveals the phase transition of rGO@MCSe in NIBs/KIBs. Unexpectedly, they show quite different Na⁺/K⁺ insertion/extraction reaction mechanisms for both cells, maybe due to more sluggish K⁺ diffusion kinetics than that of Na⁺. More significantly, it shows excellent energy storage properties in Na/K‐ion full cells when coupled with Na₃V₂(PO₄)₂O₂F and PTCDA@450 °C cathodes. This work offers an advanced electrode construction guidance for the development of high‐performance energy storage devices.