NixMnyCozO Nanowire/CNT Composite Microspheres with 3D Interconnected Conductive Network Structure via Spray‐Drying Method: A High‐Capacity and Long‐Cycle‐Life Anode Material for Lithium‐Ion Batteries

The combination of high‐capacity and long‐term cycling stability is an important factor for practical application of anode materials for lithium‐ion batteries. Herein, Ni_xMn_yCo_zO nanowire (x + y + z = 1)/carbon nanotube (CNT) composite microspheres with a 3D interconnected conductive network structure (3DICN‐NCS) are prepared via a spray‐drying method. The 3D interconnected conductive network structure can facilitate the penetration of electrolyte into the microspheres and provide excellent connectivity for rapid Li⁺ ion/electron transfer in the microspheres, thus greatly reducing the concentration polarization in the electrode. Additionally, the empty spaces among the nanowires in the network accommodate microsphere volume expansion associated with Li⁺ intercalation during the cycling process, which improves the cycling stability of the electrode. The CNTs distribute uniformly in the microspheres, which act as conductive frameworks to greatly improve the electrical conductivity of the microspheres. As expected, the prepared 3DICN‐NCS demonstrates excellent electrochemical performance, showing a high capacity of 1277 mAh g^?1 at 1 A g^?1 after 2000 cycles and 790 mAh g^?1 at 5 A g^?1 after 1000 cycles. This work demonstrates a universal method to construct a 3D interconnected conductive network structure for anode materials     

Hierarchical 3D Cobalt‐Doped Fe3O4 Nanospheres@NG Hybrid as an Advanced Anode Material for High‐Performance Asymmetric Supercapacitors

Hierarchical nanostructure, high electrical conductivity, extraordinary specific surface area, and unique porous architecture are essential properties in energy storage and conversion studies. A new type of hierarchical 3D cobalt encapsulated Fe₃O₄ nanosphere is successfully developed on N‐graphene sheet (Co?Fe₃O₄ NS@NG) hybrid with unique nanostructure by simple, scalable, and efficient solvothermal technique. When applied as an electrode material for supercapacitors, hierarchical Co?Fe₃O₄ NS@NG hybrid shows an ultrahigh specific capacitance (775 F g^?1 at a current density of 1 A g^?1) with exceptional rate capability (475 F g^?1 at current density of 50 A g^?1), and admirable cycling performance (97.1% capacitance retention after 10 000 cycles). Furthermore, the fabricated Co?Fe₃O₄ NS@NG//CoMnO₃@NG asymmetric supercapacitor (ASC) device exhibits a high energy density of 89.1 Wh kg^?1 at power density of 0.901 kW kg^?1, and outstanding cycling performance (89.3% capacitance retention after 10 000 cycles). Such eminent electrochemical properties of the Co?Fe₃O₄ NS@NG are due to the high electrical conductivity, ultrahigh surface area, and unique porous architecture. This research first proposes hierarchical Co?Fe₃O₄ NS@NG hybrid as an ultrafast charge?discharge anode material for the ASC device, that holds great potential for the development of high‐performance energy storage devices.     

Core–Shell Nitrogen‐Doped Carbon Hollow Spheres/Co3O4 Nanosheets as Advanced Electrode for High‐Performance Supercapacitor

Co₃O₄/nitrogen‐doped carbon hollow spheres (Co₃O₄/NHCSs) with hierarchical structures are synthesized by virtue of a hydrothermal method and subsequent calcination treatment. NHCSs, as a hard template, can aid the generation of Co₃O₄ nanosheets on its surface; while SiO₂ spheres, as a sacrificed‐template, can be dissolved in the process. The prepared Co₃O₄/NHCS composites are investigated as the electrode active material. This composite exhibits an enhanced performance than Co₃O₄ itself. A higher specific capacitance of 581 F g^?1 at 1 A g^?1 and a higher rate performance of 91.6% retention at 20 A g^?1 are achieved, better than Co₃O₄ nanorods (318 F g^?1 at 1 A g^?1 and 67.1% retention at 20 A g^?1). In addition, the composite is employed as a positive electrode to fabricate an asymmetric supercapacitor. The device can deliver a high energy density of 34.5 Wh kg^?1 at the power density of 753 W kg^?1 and display a desirable cycling stability. All of these attractive results make the unique hierarchical Co₃O₄/NHCS core–shell structure a promising electrode material for high‐performance supercapacitors.     

(Ni,Co)Se2/NiCo‐LDH Core/Shell Structural Electrode with the Cactus‐Like (Ni,Co)Se2 Core for Asymmetric Supercapacitors

Supercapacitors (SCs) have been widely studied as a class of promising energy‐storage systems for powering next‐generation E‐vehicles and wearable electronics. Fabricating hybrid‐types of electrode materials and designing smart nanoarchitectures are effective approaches to developing high‐performance SCs. Herein, first, a Ni‐Co selenide material (Ni,Co)Se₂ with special cactus‐like structure as the core, to scaffold the NiCo‐layered double hydroxides (LDHs) shell, is designed and fabricated. The cactus‐like structural (Ni,Co)Se₂ core, as a highly conductive and robust support, promotes the electron transport as well as hinders the agglomeration of LDHs. The synergistic contributions from the two types of active materials together with the superior properties of the cactus‐like nanostructure enable the (Ni,Co)Se₂/NiCo‐LDH hybrid electrode to exhibit a high capacity of ≈170 mA h g^?1 (≈1224 F g^?1), good rate performance, and long durability. The as‐assembled (Ni,Co)Se₂/NiCo‐LDH//PC (porous carbon) asymmetric supercapacitor (ASC) with an operating voltage of 1.65 V delivers a high energy density of 39 W h kg^?1 at a power density of 1650 W kg^?1. Therefore, the cactus‐like core/shell structure offers an effective pathway to engineer advanced electrodes. The assembled flexible ASC is demonstrated to effectively power electronic devices.     

One‐Pot Synthesis of Tunable Crystalline Ni3S4@Amorphous MoS2 Core/Shell Nanospheres for High‐Performance Supercapacitors

Transition metal sulfides gain much attention as electrode materials for supercapacitors due to their rich redox chemistry and high electrical conductivity. Designing hierarchical nanostructures is an efficient approach to fully utilize merits of each component. In this work, amorphous MoS₂ is firstly demonstrated to show specific capacitance 1.6 times as that of the crystalline counterpart. Then, crystalline core@amorphous shell (Ni₃S₄@MoS₂) is prepared by a facile one‐pot process. The diameter of the core and the thickness of the shell can be independently tuned. Taking advantages of flexible protection of amorphous shell and high capacitance of the conductive core, Ni₃S₄@amorphous MoS₂ nanospheres are tested as supercapacitor electrodes, which exhibit high specific capacitance of 1440.9 F g^?1 at 2 A g^?1 and a good capacitance retention of 90.7% after 3000 cycles at 10 A g^?1. This design of crystalline core@amorphous shell architecture may open up new strategies for synthesizing promising electrode materials for supercapacitors.     

Interface‐Engineered Nickel Cobaltite Nanowires through NiO Atomic Layer Deposition and Nitrogen Plasma for High‐Energy,Long‐Cycle‐Life Foldable All‐Solid‐State Supercapacitors

The large‐scale application of supercapacitors (SCs) for portable electronics is restricted by low energy density and cycling stability. To alleviate the limitations, a unique interface engineering strategy is suggested through atomic layer deposition (ALD) and nitrogen plasma. First, commercial carbon cloth (CC) is treated with nitrogen plasma and later inorganic NiCo₂O₄ (NCO)/NiO core–shell nanowire arrays are deposited on nitrogen plasma–treated CC (NCC) to fabricate the ultrahigh stable SC. An ultrathin layer of NiO deposited on the NCO nanowire arrays via conformal ALD plays a vital role in stabilizing the NCO nanowires for thousands of electrochemical cycles. The optimized NCC/NCO/NiO core–shell electrode exhibits a high specific capacitance of 2439 F g^?1 with a remarkable cycling stability (94.2% over 20 000 cycles). Benefiting from these integrated merits, the foldable solid‐state SCs are fabricated with excellent NCC/NCO/NiO core–shell nanowire array electrodes. The fabricated SC device delivers a high energy density of 72.32 Wh kg^?1 at a specific capacitance of 578 F g^?1, with ultrasmall capacitance decline rate of 0.0003% per cycle over 10 000 charge–discharge cycles. Overall, this strategy offers a new avenue for developing a new‐generation high‐energy, ultrahigh stable supercapacitor for real‐life applications.     

Generic Synthesis of Carbon Nanotube Branches on Metal Oxide Arrays Exhibiting Stable High‐Rate and Long‐Cycle Sodium‐Ion Storage

A new and generic strategy to construct interwoven carbon nanotube (CNT) branches on various metal oxide nanostructure arrays (exemplified by V₂O₃ nanoflakes, Co₃O₄ nanowires, Co₃O₄–CoTiO₃ composite nanotubes, and ZnO microrods), in order to enhance their electrochemical performance, is demonstrated for the first time. In the second part, the V₂O₃/CNTs core/branch composite arrays as the host for Na⁺ storage are investigated in detail. This V₂O₃/CNTs hybrid electrode achieves a reversible charge storage capacity of 612 mAh g^?1 at 0.1 A g^?1 and outstanding high‐rate cycling stability (a capacity retention of 100% after 6000 cycles at 2 A g^?1, and 70% after 10 000 cycles at 10 A g^?1). Kinetics analysis reveals that the Na⁺ storage is a pseudocapacitive dominating process and the CNTs improve the levels of pseudocapacitive energy by providing a conductive network.     

Co@Co3O4@PPD Core@bishell Nanoparticle‐Based Composite as an Efficient Electrocatalyst for Oxygen Reduction Reaction

Durable electrocatalysts with high catalytic activity toward oxygen reduction reaction (ORR) are crucial to high‐performance primary zinc‐air batteries (ZnABs) and direct methanol fuel cells (DMFCs). An efficient composite electrocatalyst, Co@Co₃O₄ core@shell nanoparticles (NPs) embedded in pyrolyzed polydopamine (PPD) is reported, i.e., in Co@Co₃O₄@PPD core@bishell structure, obtained via a three‐step sequential process involving hydrothermal synthesis, high temperature calcination under nitrogen atmosphere, and gentle heating in air. With Co@Co₃O₄ NPs encapsulated by ultrathin highly graphitized N‐doped carbon, the catalyst exhibits excellent stability in aqueous alkaline solution over extended period and good tolerance to methanol crossover effect. The integration of N‐doped graphitic carbon outer shell and ultrathin nanocrystalline Co₃O₄ inner shell enable high ORR activity of the core@bishell NPs, as evidenced by ZnABs using catalyst of Co@Co₃O₄@PPD in air‐cathode which delivers a stable voltage profile over 40 h at a discharge current density of as high as 20 mA cm^?2.     

Hierarchical α‐MnO2 Nanowires@Ni1‐xMnxOy Nanoflakes Core–Shell Nanostructures for Supercapacitors

A facile two‐step solution‐phase method has been developed for the preparation of hierarchical α‐MnO₂ nanowires@Ni_1‐xMn_xO_y nanoflakes core–shell nanostructures. Ultralong α‐MnO₂ nanowires were synthesized by a hydrothermal method in the first step. Subsequently, Ni_1‐xMn_xO_y nanoflakes were grown on α‐MnO₂ nanowires to form core–shell nanostructures using chemical bath deposition followed by thermal annealing. Both solution‐phase methods can be easily scaled up for mass production. We have evaluated their application in supercapacitors. The ultralong one‐dimensional (1D) α‐MnO₂ nanowires in hierarchical core–shell nanostructures offer a stable and efficient backbone for charge transport; while the two‐dimensional (2D) Ni_1‐xMn_xO_y nanoflakes on α‐MnO₂ nanowires provide high accessible surface to ions in the electrolyte. These beneficial features enable the electrode with high capacitance and reliable stability. The capacitance of the core–shell α‐MnO₂@Ni_1‐xMn_xO_y nanostructures (x = 0.75) is as high as 657 F g^?1 at a current density of 250 mA g^?1, and stable charging‐discharging cycling over 1000 times at a current density of 2000 mA g^?1 has been realized.     

Robust Electrodes Based on Coaxial TiC/C–MnO2 Core/Shell Nanofiber Arrays with Excellent Cycling Stability for High‐Performance Supercapacitors

A coaxial electrode structure composed of manganese oxide‐decorated TiC/C core/shell nanofiber arrays is produced hydrothermally in a KMnO₄ solution. The pristine TiC/C core/shell structure prepared on the Ti alloy substrate provides the self‐sacrificing carbon shell and highly conductive TiC core, thus greatly simplifying the fabrication process without requiring an additional reduction source and conductive additive. The as‐prepared electrode exhibits a high specific capacitance of 645 F g^?1 at a discharging current density of 1 A g^?1 attributable to the highly conductive TiC/C and amorphous MnO₂ shell with fast ion diffusion. In the charging/discharging cycling test, the as‐prepared electrode shows high stability and 99% capacity retention after 5000 cycles. Although the thermal treatment conducted on the as‐prepared electrode decreases the initial capacitance, the electrode undergoes capacitance recovery through structural transformation from the crystalline cluster to layered birnessite type MnO₂ nanosheets as a result of dissolution and further electrodeposition in the cycling. 96.5% of the initial capacitance is retained after 1000 cycles at high charging/discharging current density of 25 A g^?1. This study demonstrates a novel scaffold to construct MnO₂ based SCs with high specific capacitance as well as excellent mechanical and cycling stability boding well for future design of high‐performance MnO₂‐based SCs.     

Pine‐Needle‐Like Cu–Co Skeleton Composited with Li4Ti5O12 Forming Core–Branch Arrays for High‐Rate Lithium Ion Storage

High‐performance of lithium‐ion batteries (LIBs) rely largely on the scrupulous design of nanoarchitectures and smart hybridization of bespoke active materials. In this work, the pine‐needle‐like Cu–Co skeleton is reported to support highly active Li₄Ti₅O₁₂ (LTO) forming Cu–Co/LTO core–branch arrays via a united hydrothermal‐atomic layer deposition (ALD) method. ALD‐formed LTO layer is uniformly anchored on the pine‐needle‐like heterostructured Cu–Co backbone, which consists of branched Co nanowires (diameters in 20 nm) and Cu nanowires (250–300 nm) core. The designed Cu–Co/LTO core–branch arrays show combined advantages of large porosity, high electrical conductivity, and good adhesion. Due to the unique positive features, the Cu–Co/LTO electrodes are demonstrated with enhanced electrochemical performance including excellent high‐rate capacity (155 mAh g^?1 at 20 C) and noticeable long‐term cycles (144 mAh g^?1 at 20 C after 3000 cycles). Additionally, the full cell assembled with activated carbon positive electrode and Cu–Co/LTO negative electrode exhibits high power/energy densities (41.6 Wh kg^?1 at 7.5 kW kg^?1). The design protocol combining binder‐free characteristics and array configuration opens a new door for construction of advanced electrodes for application in high‐rate electrochemical energy storage.     

Oxygen Evolution Assisted Fabrication of Highly Loaded Carbon Nanotube/MnO2 Hybrid Films for High‐Performance Flexible Pseudosupercapacitors

To date, it has been a great challenge to design high‐performance flexible energy storage devices for sufficient loading of redox species in the electrode assemblies, with well‐maintained mechanical robustness and enhanced electron/ionic transport during charge/discharge cycles. An electrochemical activation strategy is demonstrated for the facile regeneration of carbon nanotube (CNT) film prepared via floating catalyst chemical vapor deposition strategy into a flexible, robust, and highly conductive hydrogel‐like film, which is promising as electrode matrix for efficient loading of redox species and the fabrication of high‐performance flexible pseudosupercapacitors. The strong and conductive CNT films can be effectively expanded and activated by electrochemical anodic oxygen evolution reaction, presenting greatly enhanced internal space and surface wettability with well‐maintained strength, flexibility, and conductivity. The as‐formed hydrogel‐like film is quite favorable for electrochemical deposition of manganese dioxide (MnO₂) with loading mass up to 93 wt% and electrode capacitance kept around 300 F g^?1 (areal capacitance of 1.2 F cm^?2). This hybrid film was further used to assemble a flexible symmetric pseudosupercapacitor without using any other current collectors and conductive additives. The assembled flexible supercapacitors exhibited good rate performance, with the areal capacitance of more than 300 mF cm^?2, much superior to other reported MnO₂ based flexible thin‐film supercapacitors.     

Ni2P@Carbon Core–Shell Nanoparticle‐Arched 3D Interconnected Graphene Aerogel Architectures as Anodes for High‐Performance Sodium‐Ion Batteries

To alleviate large volume change and improve poor electrochemical reaction kinetics of metal phosphide anode for sodium‐ion batteries, for the first time, an unique Ni₂P@carbon/graphene aerogel (GA) 3D interconnected porous architecture is synthesized through a solvothermal reaction and in situ phosphorization process, where core–shell Ni₂P@C nanoparticles are homogenously embedded in GA nanosheets. The synergistic effect between components endows Ni₂P@C/GA electrode with high structural stability and electrochemical activity, leading to excellent electrochemical performance, retaining a specific capacity of 124.5 mA h g^?1 at a current density of 1 A g^?1 over 2000 cycles. The robust 3D GA matrix with abundant open pores and large surface area can provide unblocked channels for electrolyte storage and Na⁺ transfer and make fully close contact between the electrode and electrolyte. The carbon layers and 3D GA together build a 3D conductive matrix, which not only tolerates the volume expansion as well as prevents the aggregation and pulverization of Ni₂P nanoparticles during Na⁺ insertion/extraction processes, but also provides a 3D conductive highway for rapid charge transfer processes. The present strategy for phosphides via in situ phosphization route and coupling phosphides with 3D GA can be extended to other novel electrodes for high‐performance energy storage devices.     

Electrostatically Assembling 2D Nanosheets of MXene and MOF‐Derivatives into 3D Hollow Frameworks for Enhanced Lithium Storage

As an essential member of 2D materials, MXene (e.g., Ti₃C₂T_x) is highly preferred for energy storage owing to a high surface‐to‐volume ratio, shortened ion diffusion pathway, superior electronic conductivity, and neglectable volume change, which are beneficial for electrochemical kinetics. However, the low theoretical capacitance and restacking issues of MXene severely limit its practical application in lithium‐ion batteries (LIBs). Herein, a facile and controllable method is developed to engineer 2D nanosheets of negatively charged MXene and positively charged layered double hydroxides derived from ZIF‐67 polyhedrons into 3D hollow frameworks via electrostatic self‐assembling. After thermal annealing, transition metal oxides (TMOs)@MXene (CoO/Co₂Mo₃O₈@MXene) hollow frameworks are obtained and used as anode materials for LIBs. CoO/Co₂Mo₃O₈ nanosheets prevent MXene from aggregation and contribute remarkable lithium storage capacity, while MXene nanosheets provide a 3D conductive network and mechanical robustness to facilitate rapid charge transfer at the interface, and accommodate the volume expansion of the internal CoO/Co₂Mo₃O₈. Such hollow frameworks present a high reversible capacity of 947.4 mAh g^?1 at 0.1 A g^?1, an impressive rate behavior with 435.8 mAh g^?1 retained at 5 A g^?1, and good stability over 1200 cycles (545 mAh g^?1 at 2 A g^?1).     

In Situ Encapsulating α‐MnS into N,S‐Codoped Nanotube‐Like Carbon as Advanced Anode Material: α → β Phase Transition Promoted Cycling Stability and Superior Li/Na‐Storage Performance in Half/Full Cells

Incorporation of N,S‐codoped nanotube‐like carbon (N,S‐NTC) can endow electrode materials with superior electrochemical properties owing to the unique nanoarchitecture and improved kinetics. Herein, α‐MnS nanoparticles (NPs) are in situ encapsulated into N,S‐NTC, preparing an advanced anode material (α‐MnS@N,S‐NTC) for lithium‐ion/sodium‐ion batteries (LIBs/SIBs). It is for the first time revealed that electrochemical α → β phase transition of MnS NPs during the 1st cycle effectively promotes Li‐storage properties, which is deduced by the studies of ex situ X‐ray diffraction/high‐resolution transmission electron microscopy and electrode kinetics. As a result, the optimized α‐MnS@N,S‐NTC electrode delivers a high Li‐storage capacity (1415 mA h g^?1 at 50 mA g^?1), excellent rate capability (430 mA h g^?1 at 10 A g^?1), and long‐term cycling stability (no obvious capacity decay over 5000 cycles at 1 A g^?1) with retained morphology. In addition, the N,S‐NTC‐based encapsulation plays the key roles on enhancing the electrochemical properties due to its high conductivity and unique 1D nanoarchitecture with excellent protective effects to active MnS NPs. Furthermore, α‐MnS@N,S‐NTC also delivers high Na‐storage capacity (536 mA h g^?1 at 50 mA g^?1) without the occurrence of such α → β phase transition and excellent full‐cell performances as coupling with commercial LiFePO₄ and LiNi_0.6Co_0.2Mn_0.2O₂ cathodes in LIBs as well as Na₃V₂(PO₄)₂O₂F cathode in SIBs.     

3D Printing of Freestanding MXene Architectures for Current‐Collector‐Free Supercapacitors

Additive manufacturing (AM) technologies appear as a paradigm for scalable manufacture of electrochemical energy storage (EES) devices, where complex 3D architectures are typically required but are hard to achieve using conventional techniques. The combination of these technologies and innovative material formulations that maximize surface area accessibility and ion transport within electrodes while minimizing space are of growing interest. Herein, aqueous inks composed of atomically thin (1–3 nm) 2D Ti₃C₂T_x with large lateral size of about 8 µm possessing ideal viscoelastic properties are formulated for extrusion‐based 3D printing of freestanding, high specific surface area architectures to determine the viability of manufacturing energy storage devices. The 3D‐printed device achieves a high areal capacitance of 2.1 F cm^?2 at 1.7 mA cm^?2 and a gravimetric capacitance of 242.5 F g^?1 at 0.2 A g^?1 with a retention of above 90% capacitance for 10 000 cycles. It also exhibits a high energy density of 0.0244 mWh cm^?2 and a power density of 0.64 mW cm^?2 at 4.3 mA cm^?2. It is anticipated that the sustainable printing and design approach developed in this work can be applied to fabricate high‐performance bespoke multiscale and multidimensional architectures of functional and structural materials for integrated devices in various applications.     

Tungsten Oxide@Polypyrrole Core–Shell Nanowire Arrays as Novel Negative Electrodes for Asymmetric Supercapacitors

Among active pseudocapacitive materials, polypyrrole (PPy) is a promising electrode material in electrochemical capacitors. PPy‐based materials research has thus far focused on its electrochemical performance as a positive electrode rather than as a negative electrode for asymmetric supercapacitors (ASCs). Here high‐performance electrochemical supercapacitors are designed with tungsten oxide@PPy (WO₃@PPy) core–shell nanowire arrays and Co(OH)₂ nanowires grown on carbon fibers. The WO₃@PPy core–shell nanowire electrode exhibits a high capacitance (253 mF/cm²) in negative potentials (–1.0–0.0 V). The ASCs packaged with CF‐Co(OH)₂ as a positive electrode and CF‐WO₃@PPy as a negative electrode display a high volumetric capacitance up to 2.865 F/cm³ based on volume of the device, an energy density of 1.02 mWh/cm³, and very good stability performance. These findings promote the application of PPy‐based nanostructures as advanced negative electrodes for ASCs.     

Efficient Laser‐Induced Construction of Oxygen‐Vacancy Abundant Nano‐ZnCo2O4/Porous Reduced Graphene Oxide Hybrids toward Exceptional Capacitive Lithium Storage

Recently, binary ZnCo₂O₄ has drawn enormous attention for lithium‐ion batteries (LIBs) as attractive anode owing to its large theoretical capacity and good environmental benignity. However, the modest electrical conductivity and serious volumetric effect/particle agglomeration over cycling hinder its extensive applications. To address the concerns, herein, a rapid laser‐irradiation methodology is firstly devised toward efficient synthesis of oxygen‐vacancy abundant nano‐ZnCo₂O₄/porous reduced graphene oxide (rGO) hybrids as anodes for LIBs. The synergistic contributions from nano‐dimensional ZnCo₂O₄ with rich oxygen vacancies and flexible rGO guarantee abundant active sites, fast electron/ion transport, and robust structural stability, and inhibit the agglomeration of nanoscale ZnCo₂O₄, favoring for superb electrochemical lithium‐storage performance. More encouragingly, the optimal L‐ZCO@rGO‐30 anode exhibits a large reversible capacity of ≈1053 mAh g^?1 at 0.05 A g^?1, excellent cycling stability (≈746 mAh g^?1 at 1.0 A g^?1 after 250 cycles), and preeminent rate capability (≈686 mAh g^?1 at 3.2 A g^?1). Further kinetic analysis corroborates that the capacitive‐controlled process dominates the involved electrochemical reactions of hybrid anodes. More significantly, this rational design holds the promise of being extended for smart fabrication of other oxygen‐vacancy abundant metal oxide/porous rGO hybrids toward advanced LIBs and beyond.     

Necklace‐Like Structures Composed of Fe3N@C Yolk–Shell Particles as an Advanced Anode for Sodium‐Ion Batteries

It is of great importance to develop cost‐effective electrode materials for large‐scale use of Na‐ion batteries. Here, a binder‐free electrode based on necklace‐like structures composed of Fe₃N@C yolk–shell particles as an advanced anode for Na‐ion batteries is reported. In this electrode, every Fe₃N@C unit has a novel yolk–shell structure, which can accommodate the volumetric changes of Fe₃N during the (de)sodiation processes for superior structural integrity. Moreover, all reaction units are threaded along the carbon fibers, guaranteeing excellent kinetics for the electrochemical reactions. As a result, when evaluated as an anode material for Na‐ion batteries, the Fe₃N@C nano‐necklace electrode delivers a prolonged cycle life over 300 cycles, and achieves a high C‐rate capacity of 248 mAh g^?1 at 2 A g^?1.     

Aluminum‐Ion‐Intercalation Supercapacitors with Ultrahigh Areal Capacitance and Highly Enhanced Cycling Stability: Power Supply for Flexible Electrochromic Devices

Electrochemical capacitor systems based on Al ions can offer the possibilities of low cost and high safety, together with a three‐electron redox‐mechanism‐based high capacity, and thus are expected to provide a feasible solution to meet ever‐increasing energy demands. Here, highly efficient Al‐ion intercalation into W₁₈O₄₉ nanowires (W₁₈O₄₉NWs) with wide lattice spacing and layered single‐crystal structure for electrochemical storage is demonstrated. Moreover, a freestanding composite film with a hierarchical porous structure is prepared through vacuum‐assisted filtration of a mixed dispersion containing W₁₈O₄₉NWs and single‐walled carbon nanotubes. The as‐prepared composite electrode exhibits extremely high areal capacitances of 1.11–2.92 F cm^?2 and 459 F cm^?3 at 2 mA cm^?2, enhanced electrochemical stability in the Al³⁺ electrolyte, as well as excellent mechanical properties. An Al‐ion‐based, flexible, asymmetric electrochemical capacitor is assembled that displays a high volumetric energy density of 19.0 mWh cm^?3 at a high power density of 295 mW cm^?3. Finally, the Al‐ion‐based asymmetric supercapacitor is used as the power source for poly(3‐hexylthiophene)‐based electrochromic devices, demonstrating their promising capability in flexible electronic devices.