Walnut‐Like Multicore–Shell MnO Encapsulated Nitrogen‐Rich Carbon Nanocapsules as Anode Material for Long‐Cycling and Soft‐Packed Lithium‐Ion Batteries

Metal oxide‐based nanomaterials are widely studied because of their high‐energy densities as anode materials in lithium‐ion batteries. However, the fast capacity degradation resulting from the large volume expansion upon lithiation hinders their practical application. In this work, the preparation of walnut‐like multicore–shell MnO encapsulated nitrogen‐rich carbon nanocapsules (MnO@NC) is reported via a facile and eco‐friendly process for long‐cycling Li‐ion batteries. In this hybrid structure, MnO nanoparticles are uniformly dispersed inside carbon nanoshells, which can simultaneously act as a conductive framework and also a protective buffer layer to restrain the volume variation. The MnO@NC nanocapsules show remarkable electrochemical performances for lithium‐ion batteries, exhibiting high reversible capability (762 mAh g^?1 at 100 mA g^?1) and stable cycling life (624 mAh g^?1 after 1000 cycles at 1000 mA g^?1). In addition, the soft‐packed full batteries based on MnO@NC nanocapsules anodes and commercial LiFePO₄ cathodes present good flexibility and cycling stability.     

Silicon‐Based Self‐Assemblies for High Volumetric Capacity Li‐Ion Batteries via Effective Stress Management

Silicon nanoparticles (Si NPs) have been considered as promising anode materials for next‐generation lithium‐ion batteries, but the practical issues such as mechanical structure instability and low volumetric energy density limit their development. At present, the functional energy‐storing architectures based on Si NPs building blocks have been proposed to solve the adverse effects of nanostructures, but designing ideal functional architectures with excellent electrochemical performance is still a significant challenge. This study shows that the effective stress evolution management is applied for self‐assembled functional architectures via cross‐scale simulation and the simulated stress evolution can be a guide to design a scalable self‐assembled hierarchical Si@TiO₂@C (SA‐SiTC) based on core–shell Si@TiO₂ nanoscale building blocks. It is found that the carbon filler and TiO₂ layer can effectively reduce the risk of cracking during (de)lithiation, ensuring the stability of the mechanical structure of SA‐SiTC. The SA‐SiTC electrode shows long cycling stability (842.6 mAh g^?1 after 1000 cycles at 2 A g^?1), high volumetric capacity (174 mAh cm^?3), high initial Coulombic efficiency (80.9%), and stable solid‐electrolyte interphase (SEI) layer. This work provides insight into the development of the structural stable Si‐based anodes with long cycle life and high volumetric energy density for practical energy applications.     

Dual‐Salt Mg‐Based Batteries with Conversion Cathodes

Mg batteries as the most typical multivalent batteries are attracting increasing attention because of resource abundance, high volumetric energy density, and smooth plating/stripping of Mg anodes. However, current limitations for the progress of Mg batteries come from the lack of high voltage electrolytes and fast Mg‐insertable structure prototypes. In order to improve their energy or power density, hybrid systems combining Li‐driven cathode reaction with Mg anode process appear to be a potential solution by bypassing the aforementioned limitations. Here, FeS _x (x = 1 or 2) is employed as conversion cathode with 2–4 electron transfers to achieve a maximum energy density close to 400 Wh kg^?1, which is comparable with that of Li‐ion batteries but without serious dendrite growth and polysulphide dissolution. In situ formation of solid electrolyte interfaces on both sulfide and Mg electrodes is likely responsible for long‐life cycling and suppression of S‐species passivation at Mg anodes. Without any decoration on the cathode, electrolyte additive, or anode protection, a reversible capacity of more than 200 mAh g^?1 is still preserved for Mg/FeS₂ after 200 cycles.     

A Robust Ion‐Conductive Biopolymer as a Binder for Si Anodes of Lithium‐Ion Batteries

Binders have been reported to play a key role in improving the cycle performance of Si anode materials of lithium‐ion batteries. In this study, the biopolymer guar gum (GG) is applied as the binder for a silicon nano­particle (SiNP) anode of a lithium‐ion battery for the first time. Due to the large number of polar hydroxyl groups in the GG molecule, a robust interaction between the GG binder and the SiNPs is achieved, resulting in a stable Si anode during cycling. More specifically, the GG binder can effectively transfer lithium ions to the Si surface, similarly to polyethylene oxide solid electrolytes. When GG is used as a binder, the SiNP anode can deliver an initial discharge capacity as high as 3364 mAh g^?1, with a Coulombic efficiency of 88.3% at the current density of 2100 mA g^?1, and maintain a capacity of 1561 mAh g^?1 after 300 cycles. The study shows that the electrochemical performance of the SiNP anode with GG binder is significantly improved compared to that of a SiNP anode with a sodium alginate binder, and it demonstrates that GG is a promising binder for Si anodes of lithium‐ion batteries.     

Magnesium Anodes with Extended Cycling Stability for Lithium‐Ion Batteries

Magnesium as a promising alloy‐type anode material for lithium‐ion batteries features both high theoretical specific capacity (2150 mAh g^?1) and stack energy density (1032 Wh L^?1). However, the poor cycling performance of Mg‐based anodes severely limits their application, mainly because high‐impedance films can grow easily on the surface of Mg and cause diminished electrochemical activity. As a result, the capacities of reported Mg anodes fade quickly in less than 100 cycles. To improve the stability of Mg anodes, 3D Cu@Mg@C structures are prepared by depositing Mg/C composite on 3D Cu current collectors. The resulting 3D Cu@Mg@C anodes can deliver an initial capacity of 1392 mAh g^?1. With a second‐cycle capacity of 1255 mAh g^?1, 91% can be retained after 1000 cycles at 0.5 C. When cycled at 2 C, the initial capacity can be maintained for 4000 cycles. This remarkably improved cycling performance can be attributed to both the 3D structure and the embedded carbon layers of the 3D Cu@Mg@C electrodes that facilitate electrical contact and prevent the growth of high‐impedance films during cycling. With 3D Cu@Mg@C anodes and LiFePO₄ cathodes, full cells are assembled and charging by a rotating triboelectric nanogenerator that can harvest mechanical energy is demonstrated.     

Lithium Accommodation in a Redox‐Active Covalent Triazine Framework for High Areal Capacity and Fast‐Charging Lithium‐Ion Batteries

The synthesis of a new type of redox‐active covalent triazine framework (rCTF) material, which is promising as an anode for Li‐ion batteries, is reported. After activation, it has a capacity up to ≈1190 mAh g^?1 at 0.5C with a current density of 300 mA g^?1 and a high cycling stability of over 1000 discharge/charge cycles with a stable Coulombic efficiency in an rCTF/Li half‐cell. This rCTF has a high rate performance, and at a charging rate of 20C with a current density of 12 A g^?1 and it functions well for over 1000 discharge/charge cycles with a reversible capacity of over 500 mAh g^?1. By electrochemical analysis and theoretical calculations, it is found that its lithium‐storage mechanism involves multi‐electron redox‐reactions at anthraquinone, triazine, and benzene rings by the accommodation of Li. The structural features and progressively increased structural disorder of the rCTF increase the kinetics of infiltration and significantly shortens the activation period, yielding fast‐charging Li‐ion half and full cells even at a high capacity loading.     

Highly Stretchable Conductive Glue for High‐Performance Silicon Anodes in Advanced Lithium‐Ion Batteries

Binder plays a key role in maintaining the mechanical integrity of electrodes in lithium‐ion batteries. However, the existing binders typically exhibit poor stretchability or low conductivity at large strains, which are not suitable for high‐capacity silicon (Si)‐based anodes undergoing severe volume changes during cycling. Herein, a novel stretchable conductive glue (CG) polymer that possesses inherent high conductivity, excellent stretchablity, and ductility is designed for high‐performance Si anodes. The CG can be stretched up to 400% in volume without conductivity loss and mechanical fracture and thus can accommodate the large volume change of Si nanoparticles to maintain the electrode integrity and stabilize solid electrolyte interface growth during cycling while retaining the high conductivity, even with a high Si mass loading of 90%. The Si‐CG anode has a large reversible capacity of 1500 mA h g^?1 for over 700 cycles at 840 mA g^?1 with a large initial Coulombic efficiency of 80% and high rate capability of 737 mA h g^?1 at 8400 mA g^?1. Moreover, the Si‐CG anode demonstrates the highest achieved areal capacity of 5.13 mA h cm^?2 at a high mass loading of 2 mg cm^?2. The highly stretchable CG provides a new perspective for designing next‐generation high‐capacity and high‐power batteries.     

Solid‐State Plastic Crystal Electrolytes: Effective Protection Interlayers for Sulfide‐Based All‐Solid‐State Lithium Metal Batteries

All‐solid‐state lithium metal batteries (ASSLMBs) have attracted significant attention due to their superior safety and high energy density. However, little success has been made in adopting Li metal anodes in sulfide electrolyte (SE)‐based ASSLMBs. The main challenges are the remarkable interfacial reactions and Li dendrite formation between Li metal and SEs. In this work, a solid‐state plastic crystal electrolyte (PCE) is engineered as an interlayer in SE‐based ASSLMBs. It is demonstrated that the PCE interlayer can prevent the interfacial reactions and lithium dendrite formation between SEs and Li metal. As a result, ASSLMBs with LiFePO₄ exhibit a high initial capacity of 148 mAh g^?1 at 0.1 C and 131 mAh g^?1 at 0.5 C (1 C = 170 mA g^?1), which remains at 122 mAh g^?1 after 120 cycles at 0.5 C. All‐solid‐state Li‐S batteries based on the polyacrylonitrile‐sulfur composite are also demonstrated, showing an initial capacity of 1682 mAh g^?1. The second discharge capacity of 890 mAh g^?1 keeps at 775 mAh g^?1 after 100 cycles. This work provides a new avenue to address the interfacial challenges between Li metal and SEs, enabling the successful adoption of Li metal in SE‐based ASSLMBs with high energy density.     

Multicore–Shell Bi@N‐doped Carbon Nanospheres for High Power Density and Long Cycle Life Sodium‐ and Potassium‐Ion Anodes

Bismuth (Bi) is an attractive material as anodes for both sodium‐ion batteries (NIBs) and potassium‐ion batteries (KIBs), because it has a high theoretical gravimetric capacity (386 mAh g^?1) and high volumetric capacity (3800 mAh L^?1). The main challenges associated with Bi anodes are structural degradation and instability of the solid electrolyte interphase (SEI) resulting from the huge volume change during charge/discharge. Here, a multicore–shell structured Bi@N‐doped carbon (Bi@N‐C) anode is designed that addresses these issues. The nanosized Bi spheres are encapsulated by a conductive porous N‐doped carbon shell that not only prevents the volume expansion during charge/discharge but also constructs a stable SEI during cycling. The Bi@N‐C exhibits unprecedented rate capability and long cycle life for both NIBs (235 mAh g^?1 after 2000 cycles at 10 A g^?1) and KIBs (152 mAh g^?1 at 100 A g^?1). The kinetic analysis reveals the outstanding electrochemical performance can be attributed to significant pseudocapacitance behavior upon cycling.     

Temperature‐Mediated Engineering of Graphdiyne Framework Enabling High‐Performance Potassium Storage

Graphdiyne (GDY), an emerging type of carbon allotropes, possesses fascinating electrical, chemical, and mechanical properties to readily spark energy applications in the realm of Li‐ion and Na‐ion batteries. Nevertheless, rational design of GDY architectures targeting advanced K‐ion storage has rarely been reported to date. Herein, the first example of synthesizing GDY frameworks in a scalable fashion to realize superb potassium storage for high‐performance K‐ion battery (KIB) anodes is showcased. To begin with, first principles calculations provide theoretical guidances for analyzing the intrinsic potassium storage capability of GDY. Meanwhile, the specific capacity is predicted to be as high as 620 mAh g^?1, which is considerably augmented as compared with graphite (278 mAh g^?1). Experimental tests then reveal that prepared GDY framework indeed harvests excellent electrochemical performance as a KIB anode, achieving high specific capacity (≈505 mAh g^?1 at 50 mA g^?1), outstanding rate performance (150 mAh g^?1 at 5000 mA g^?1) and favorable cycling stability (a high capacity retention of over 90% after 2000 cycles at 1000 mA g^?1). Furthermore, kinetic analysis reveals that capacitive effect mainly accounts for the K‐ion storage, with operando Raman spectroscopy/ex situ X‐ray photoelectron spectroscopy identifying good electrochemical reversibility of GDY.     

Rapid Pseudocapacitive Sodium‐Ion Response Induced by 2D Ultrathin Tin Monoxide Nanoarrays

Nanostructured tin‐based anodes are promising for both lithium and sodium ion batteries (LIBs and SIBs), but their performances are limited by the rate capability and long‐term cycling stability. Here, ultrathin SnO nanoflakes arrays are in situ grown on highly conductive graphene foam/carbon nanotubes substrate, forming a unique, flexible, and binder‐free 3D hybrid structure electrode. This electrode exhibits an excellent Na⁺ storage capacity of 580 mAh g^?1 at 0.1 A g^?1, and to the best of our knowledge, has the longest‐reported high‐rate cycling (1000 cycles at 1 A g^?1) among tin‐based SIB anodes. Compared with its LIB performance, the enhanced pseudocapacitive contribution in SIB is proved to be the origin of fast kinetics and long durability of the electrode. Moreover, Raman peaks from the full sodiation product Na₁₅Sn₄ at 75 and 105 cm^?1 are successfully detected and also proved by density functional theory calculations, which could be a promising clue for structure evolution analysis of other tin‐based electrodes.     

Carbon Nanotubes Rooted in Porous Ternary Metal Sulfide@N/S‐Doped Carbon Dodecahedron: Bimetal‐Organic‐Frameworks Derivation and Electrochemical Application for High‐Capacity and Long‐Life Lithium‐Ion Batteries

Lithium ion battery is the predominant power source for portable electronic devices, electrical vehicles, and back‐up electricity storage units for clean and renewable energies. High‐capacity and long‐life electrode materials are essential for the next‐generation Li‐ion battery with high energy density. Here bimetal‐organic‐frameworks synthesis of Co_0.4Zn_0.19S@N and S codoped carbon dodecahedron is shown with rooted carbon nanotubes (Co‐Zn‐S@N‐S‐C‐CNT) for high‐performance Li‐ion battery application. Benefiting from the synergetic effect of two metal sulfide species for Li‐storage at different voltages, mesoporous dodecahedron structure, N and S codoped carbon overlayer and deep‐rooted CNTs network, the product exhibits a larger‐than‐theoretical reversible Li‐storage capacity of 941 mAh g^?1 after 250 cycles at 100 mA g^?1 and excellent high‐rate capability (734, 591, 505 mAh g^?1 after 500 cycles at large current densities of 1, 2, and 5 A g^?1 , respectively).     

Graphitic Nanocarbon with Engineered Defects for High‐Performance Potassium‐Ion Battery Anodes

The application of graphite anodes in potassium‐ion batteries (KIB) is limited by the large variation in lattice volume and the low diffusion coefficient of potassium ions during (de)potassiation. This study demonstrates nitrogen‐doped, defect‐rich graphitic nanocarbons (GNCs) as high‐performance KIB anodes. The GNCs with controllable defect densities are synthesized by annealing an ethylenediaminetetraacetic acid nickel coordination compound. The GNCs show better performance than the previously reported thin‐walled graphitic carbonaceous materials such as carbon nanocages and nanotubes. In particular, the GNC prepared at 600 °C shows a stabilized capacity of 280 mAh g^?1 at 50 mA g^?1, robust rate capability, and long cycling life due to its high‐nitrogen‐doping, short‐range‐ordered, defect‐rich graphitic structure. A high capacity of 189 mAh g^?1 with a long cycle life over 200 cycles is demonstrated at a current density of 200 mA g^?1. Further, it is confirmed that the potassium ion storage mechanism of GNCs is different from that of graphite using multiple characterization methods. Specifically, the GNCs with numerous defects provide more active sites for the potassiation process, which results in a final discharge product with short‐range order. This study opens a new pathway for designing graphitic carbonaceous materials for KIB anodes.     

A High‐Energy Li‐Ion Battery Using a Silicon‐Based Anode and a Nano‐Structured Layered Composite Cathode

High capacity electrodes based on a Si composite anode and a layered composite oxide cathode, Ni‐rich Li[Ni_0.75Co_0.1Mn_0.15]O₂, are evaluated and combined to fabricate a high energy lithium ion battery. The Si composite anode, Si/C‐IWGS (internally wired with graphene sheets), is prepared by a scalable sol–gel process. The Si/C‐IWGS anode delivers a high capacity of >800 mAh g^?1 with an excellent cycling stability of up to 200 cycles, mainly due to the small amount of graphene (～6 wt%). The cathode (Li[Ni_0.75Co_0.1Mn_0.15]O₂) is structurally optimized (Ni‐rich core and a Ni‐depleted shell with a continuous concentration gradient between the core and shell, i.e., a full concentration gradient, FCG, cathode) so as to deliver a high capacity (>200 mAh g^?1) with excellent stability at high voltage (～4.3 V). A novel lithium ion battery system based on the Si/C‐IWGS anode and FCG cathode successfully demonstrates a high energy density (240 Wh kg^?1 at least) as well as an unprecedented excellent cycling stability of up to 750 cycles between 2.7 and 4.2 V at 1C. As a result, the novel battery system is an attractive candidate for energy storage applications demanding a high energy density and long cycle life.     

Intercalated Electrolyte with High Transference Number for Dendrite‐Free Solid‐State Lithium Batteries

Solid‐state lithium (Li) batteries using solid electrolytes and Li anodes are highly desirable because of their high energy densities and intrinsic safety. However, low ambient‐temperature conductivity and poor interface compatibility of solid electrolytes as well as Li dendrite formation cause large polarization and poor cycling stability. Herein, a high transference number intercalated composite solid electrolyte (CSE) is prepared by the combination of a solution‐casting and hot‐pressing method using layered lithium montmorillonite, poly(ethylene carbonate), lithium bis(fluorosulfonyl)imide, high‐voltage fluoroethylene carbonate additive, and poly(tetrafluoroethylene) binder. The electrolyte presents high ionic conductivity (3.5 × 10^?4 S cm^?1), a wide electrochemical window (4.6 V vs Li⁺/Li), and high ionic transference number (0.83) at 25 °C. In addition, a 3D Li anode is also fabricated via a facile thermal infusion strategy. The synergistic effect of high transference number intercalated electrolyte and 3D Li anode is more favorable to suppress Li dendrites in a working battery. The solid‐state batteries based on LiFePO₄ (Al₂O₃ @ LiNi_0.5Co_0.2Mn_0.3O₂), CSE, and 3D Li deliver admirable cycling stability with discharge capacity 145.9 mAh g^?1 (150.7 mAh g^?1) and capacity retention 91.9% after 200 cycles at 0.5 C (92.0% after 100 cycles at 0.2 C) at 25 °C. This work affords a splendid strategy for high‐performance solid‐state battery.     

Watermelon‐Like Structured SiOx–TiO2@C Nanocomposite as a High‐Performance Lithium‐Ion Battery Anode

A unique watermelon‐like structured SiO_x–TiO₂@C nanocomposite is synthesized by a scalable sol–gel method combined with carbon coating process. Ultrafine TiO₂ nanocrystals are uniformly embedded inside SiO_x particles, forming SiO_x–TiO₂ dual‐phase cores, which are coated with outer carbon shells. The incorporation of TiO₂ component can effectively enhance the electronic and lithium ionic conductivities inside the SiO_x particles, release the structure stress caused by alloying/dealloying of Si component and maximize the capacity utilization by modifying the Si–O bond feature and decreasing the O/Si ratio (x‐value). The synergetic combination of these advantages enables the synthesized SiO_x–TiO₂@C nanocomposite to have excellent electrochemical performances, including high specific capacity, excellent rate capability, and stable long‐term cycleability. A stable specific capacity of ≈910 mAh g^?1 is achieved after 200 cycles at the current density of 0.1 A g^?1 and ≈700 mAh g^?1 at 1 A g^?1 for over 600 cycles. These results suggest a great promise of the proposed particle architecture, which may have potential applications in the improvement of various energy storage materials.     

Facile Synthesis of Blocky SiOx/C with Graphite‐Like Structure for High‐Performance Lithium‐Ion Battery Anodes

SiO_x‐containing graphite composites have aroused great interests as the most promising alternatives for practical application in high‐performance lithium‐ion batteries. However, limited loading amount of SiO_x on the surface of graphite and some inherent disadvantages of SiO_x such as huge volume variation and poor electronic conductivity result in unsatisfactory electrochemical performance. Herein, a novel and facile fabrication approach is developed to synthesize high‐performance SiO_x/C composites with graphite‐like structure in which SiO_x particles are dispersed and anchored in the carbon materials by restoring original structure of artificial graphite. The multicomponent carbon materials are favorable for addressing the disadvantages of SiO_x‐based anodes, especially for the formation of stable solid electrolyte interphase, maintaining structural integrity of electrode materials and improving electrical conductivity of electrode. The resultant SiO_x/C anodes demonstrate high reversible capacities (645 mA h g^?1), excellent cycling stability (≈90% capacity retention for 500 cycles), and superior rate capabilities. Even at high pressing density (1.3 g cm^?3), SiO_x/C anodes still present superior cycling performance due to the high tap density and structural integrity of electrode materials. The proposed synthetic method can also be developed to address other anode materials with inferior electronic conductivity and huge volume variation.     

Morphology Reshaping Enabling Self‐Densification of Manganese Oxide Hybrid Materials for High‐Density Lithium Storage Anodes

Morphology reshaping or reconfiguration, a concept widely used in plastic surgery, energy harvesting, and reconfigurable robots, is introduced for the first time to construct densified electrodes and realize compact Li‐ion storage desirable for high specific energy storage field. Hausmannite‐based hybrid materials, as a proof‐of‐concept prototype, engineered by 1‐methyl‐2‐pyrrolidinone‐soluble surface/interface organic encapsulation, which is crucial in reshaping, exhibit a remarkable increase in the volumetric capacity of more than five times after this process (≈1889 Ah L^?1 vs ≈322 Ah L^?1). With the simultaneous maintenance of the intrinsic nature, good contact, and no collapsed/agglomerated unit structures of the materials in electrodes, the design affords a maximal increase in the packing compactness and manifests no sacrifice of the reversible ion storage capability (1150 mAh g^?1 at 40 mA g^?1), stable cycling (≈100% capacity retention), high rate performance (185 mAh g^?1 at 10 A g^?1), and long lifespan (1000 cycles with 108% capacity retention, ≈455 mAh g^?1 at 3 A g^?1) for relatively highly loaded electrodes (active materials: 1.20–5.34 mg cm^?2). The concept may not only shed new light on fabricating advanced Si‐based and other high capacity–related densified Li storage electrodes but also inject fresh vitality into the field of high‐density power sources.     

Toward High Performance Thiophene‐Containing Conjugated Microporous Polymer Anodes for Lithium‐Ion Batteries through Structure Design

Poly(thiophene) as a kind of n‐doped conjugated polymer with reversible redox behavior can be employed as anode material for lithium‐ion batteries (LIBs). However, the low redox activity and poor rate performance for the poly(thiophene)‐based anodes limit its further development. Herein, a structure‐design strategy is reported for thiophene‐containing conjugated microporous polymers (CMPs) with extraordinary electrochemical performance as anode materials in LIBs. The comparative study on the electrochemical performance of the structure‐designed thiophene‐containing CMPs reveals that high redox‐active thiophene content, highly crosslinked porous structure, and improved surface area play significant roles for enhancing electrochemical performances of the resulting CMPs. The all‐thiophene‐based polymer of poly(3,3′‐bithiophene) with crosslinked structure and a high surface area of 696 m² g^?1 exhibits a discharge capacity of as high as 1215 mAh g^?1 at 45 mA g^?1, excellent rate capability, and outstanding cycling stability with a capacity retention of 663 mAh g^?1 at 500 mA g^?1 after 1000 cycles. The structure–performance relationships revealed in this work offer a fundamental understanding in the rational design of CMPs anode materials for high performance LIBs.     

In Situ Formation of Copper‐Based Hosts Embedded within 3D N‐Doped Hierarchically Porous Carbon Networks for Ultralong Cycle Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries are promising energy storage systems due to their large theoretical energy density of 2600 Wh kg^?1 and cost effectiveness. However, the severe shuttle effect of soluble lithium polysulfide intermediates (LiPSs) and sluggish redox kinetics during the cycling process cause low sulfur utilization, rapid capacity fading, and a low coulombic efficiency. Here, a 3D copper, nitrogen co‐doped hierarchically porous graphitic carbon network developed through a freeze‐drying method (denoted as 3D Cu@NC‐F) is prepared, and it possesses strong chemical absorption and electrocatalytic conversion activity for LiPSs as highly efficient sulfur host materials in Li–S batteries. The porous carbon network consisting of 2D cross‐linked ultrathin carbon nanosheets provides void space to accommodate volumetric expansion upon lithiation, while the Cu, N‐doping effect plays a critical role for the confinement of polysulfides through chemical bonding. In addition, after sulfuration of Cu@NC‐F network, the in situ grown copper sulfide (Cu_xS) embedded within Cu_xS@NC/S‐F composite catalyzes LiPSs conversion during reversible cycling, resulting in low polarization and fast redox reaction kinetics. At a current density of 0.1 C, the Cu_xS@NC/S‐F composites' electrode exhibits an initial capacity of 1432 mAh g^?1 and maintains 1169 mAh g^?1 after 120 cycles, with a coulombic efficiency of nearly 100%.