Graphene Caging Silicon Particles for High‐Performance Lithium‐Ion Batteries

Silicon holds great promise as an anode material for lithium‐ion batteries with higher energy density; its implication, however, is limited by rapid capacity fading. A catalytic growth of graphene cages on composite particles of magnesium oxide and silicon, which are made by magnesiothermic reduction reaction of silica particles, is reported herein. Catalyzed by the magnesium oxide, graphene cages can be conformally grown onto the composite particles, leading to the formation of hollow graphene‐encapsulated Si particles. Such materials exhibit excellent lithium storage properties in terms of high specific capacity, remarkable rate capability (890 mAh g^?1 at 5 A g^?1), and good cycling retention over 200 cycles with consistently high coulombic efficiency at a current density of 1 A g^?1. A full battery test using LiCoO₂ as the cathode demonstrates a high energy density of 329 Wh kg^?1.     

Etching‐Assisted Crumpled Graphene Wrapped Spiky Iron Oxide Particles for High‐Performance Li‐Ion Hybrid Supercapacitor

From graphene oxide wrapped iron oxide particles with etching/reduction process, high‐performance anode and cathode materials of lithium‐ion hybrid supercapacitors are obtained in the same process with different etching conditions, which consist of partially etched crumpled graphene (CG) wrapped spiky iron oxide particles (CG@SF) for a battery‐type anode, and fully etched CG for a capacitive‐type cathode. The CG is formed along the shape of spikily etched particles, resulting in high specific surface area and electrical conductivity, thus the CG‐based cathode exhibits remarkable capacitive performance of 210 F g^?1 and excellent rate capabilities. The CG@SF can also be ideal anode materials owing to spiky and porous morphology of the particles and tightly attached crumpled graphene onto the spiky particles, which provides structural stability and low contact resistance during repetitive lithiation/delithiation processes. The CG@SF anode shows a particularly high capacitive performance of 1420 mAh g^?1 after 270 cycles, continuously increases capacity beyond the 270th cycle, and also maintains a high capacity of 170 mAh g^?1 at extremely high speeds of 100 C. The full‐cell exhibits a higher energy density up to 121 Wh kg^?1 and maintains high energy density of 60.1 Wh kg^?1 at 18.0 kW kg^?1. This system could thus be a practical energy storage system to fill the gap between batteries and supercapacitors.     

High Performance of N‐Doped Graphene with Bubble‐like Textures for Supercapacitors

Nitrogen‐doped graphene (NG) with wrinkled and bubble‐like texture is fabricated by a thermal treatment. Especially, a novel sonication‐assisted pretreatment with nitric acid is used to further oxidize graphene oxide and its binding with melamine molecules. There are many bubble‐like nanoflakes with a dimension of about 10 nm appeared on the undulated graphene nanosheets. The bubble‐like texture provides more active sites for effective ion transport and reversible capacitive behavior. The specific surface area of NG (5.03 at% N) can reach up to 438.7 m² g^?1, and the NG electrode demonstrates high specific capacitance (481 F g^?1 at 1 A g^?1, four times higher than reduced graphene oxide electrode (127.5 F g^?1)), superior cycle stability (the capacitance retention of 98.9% in 2 m KOH and 99.2% in 1 m H₂SO₄ after 8000 cycles), and excellent energy density (42.8 Wh kg^?1 at power density of 500 W kg^?1 in 2 m KOH aqueous electrolyte). The results indicate the potential use of NG as graphene‐based electrode material for energy storage devices.     

A Novel Potassium‐Ion‐Based Dual‐Ion Battery

In this work, combining both advantages of potassium‐ion batteries and dual‐ion batteries, a novel potassium‐ion‐based dual‐ion battery (named as K‐DIB) system is developed based on a potassium‐ion electrolyte, using metal foil (Sn, Pb, K, or Na) as anode and expanded graphite as cathode. When using Sn foil as the anode, the K‐DIB presents a high reversible capacity of 66 mAh g^?1 at a current density of 50 mA g^?1 over the voltage window of 3.0–5.0 V, and exhibits excellent long‐term cycling performance with 93% capacity retention for 300 cycles. Moreover, as the Sn foil simultaneously acts as the anode material and the current collector, dead load and dead volume of the battery can be greatly reduced, thus the energy density of the K‐DIB is further improved. It delivers a high energy density of 155 Wh kg^?1 at a power density of 116 W kg^?1, which is comparable with commercial lithium‐ion batteries. Thus, with the advantages of environmentally friendly, cost effective, and high energy density, this K‐DIB shows attractive potential for future energy storage application.     

Growth of cobalt–nickel layered double hydroxide on nitrogen-doped graphene by simple co-precipitation method for supercapacitor electrodes

Nitrogen-doped graphene/Co–Ni layered double hydroxide (RGN/Co–Ni LDH) is synthesized by a facile co-precipitation method. Transmission electron microscopy images indicated that the formation of Co–Ni(OH)₂ nanoflakes with the good dispersion anchored on the surfaces of the nitrogen-doped graphene sheets. The nitrogen-doped graphene composites delivered the enhanced electrochemical performances compared to the pure Co–Ni LDH due to the improved electronic conductivity and its hierarchical layer structures. The high specific capacitance of 2092 F g^?1 at current density of 5 mA cm^?2 and the rate retention of 86.5% at current density of 5–50 mA cm^?2 are achieved by RGN/Co–Ni LDH, higher than that of pure Co–Ni LDH (1479 F g^?1 and 76.5%). Moreover, the two-electrode asymmetric supercapacitor, with the RGN/Co–Ni LDH composites as the positive electrode and active carbon as the negative electrode material, exhibits energy density of 49.4 Wh kg^?1 and power density of 101.97 W kg^?1 at the current density of 5 mA cm^?2, indicating the composite has better capacitive behavior.     

Biomass‐Derived Nitrogen‐Doped Carbon Nanofiber Network: A Facile Template for Decoration of Ultrathin Nickel‐Cobalt Layered Double Hydroxide Nanosheets as High‐Performance Asymmetric Supercapacitor Electrode

The development of biomass‐based energy storage devices is an emerging trend to reduce the ever‐increasing consumption of non‐renewable resources. Here, nitrogen‐doped carbonized bacterial cellulose (CBC‐N) nanofibers are obtained by one‐step carbonization of polyaniline coated bacterial cellulose (BC) nanofibers, which not only display excellent capacitive performance as the supercapacitor electrode, but also act as 3D bio‐template for further deposition of ultrathin nickel‐cobalt layered double hydroxide (Ni‐Co LDH) nanosheets. The as‐obtained CBC‐N@LDH composite electrodes exhibit significantly enhanced specific capacitance (1949.5 F g^?1 at a discharge current density of 1 A g^?1, based on active materials), high capacitance retention of 54.7% even at a high discharge current density of 10 A g^?1 and excellent cycling stability of 74.4% retention after 5000 cycles. Furthermore, asymmetric supercapacitors (ASCs) are constructed using CBC‐N@LDH composites as positive electrode materials and CBC‐N nanofibers as negative electrode materials. By virtue of the intrinsic pseudocapacitive characteristics of CBC‐N@LDH composites and 3D nitrogen‐doped carbon nanofiber networks, the developed ASC exhibits high energy density of 36.3 Wh kg^?1 at the power density of 800.2 W kg^?1. Therefore, this work presents a novel protocol for the large‐scale production of biomass‐derived high‐performance electrode materials in practical supercapacitor applications.     

(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.     

High‐Stacking‐Density,Superior‐Roughness LDH Bridged with Vertically Aligned Graphene for High‐Performance Asymmetric Supercapacitors

The high‐performance electrode materials with tuned surface and interface structure and functionalities are highly demanded for advanced supercapacitors. A novel strategy is presented to conFigure high‐stacking‐density, superior‐roughness nickel manganese layered double hydroxide (LDH) bridged by vertically aligned graphene (VG) with nickel foam (NF) as the conductive collector, yielding the LDH‐NF@VG hybrids for asymmetric supercapacitors. The VG nanosheets provide numerous electron transfer channels for quick redox reactions, and well‐developed open structure for fast mass transport. Moreover, the high‐stacking‐density LDH grown and assembled on VG nanosheets result in a superior hydrophilicity derived from the tuned nano/microstructures, especially microroughness. Such a high stacking density with abundant active sites and superior wettability can be easily accessed by aqueous electrolytes. Benefitting from the above features, the LDH‐NF@VG can deliver a high capacitance of 2920 F g^?1 at a current density of 2 A g^?1, and the asymmetric supercapacitor with the LDH‐NF@VG as positive electrode and activated carbon as negative electrode can deliver a high energy density of 56.8 Wh kg^?1 at a power density of 260 W kg^?1, with a high specific capacitance retention rate of 87% even after 10 000 cycles.     

Coordination Polymers Derived General Synthesis of Multishelled Mixed Metal‐Oxide Particles for Hybrid Supercapacitors

Metal–organic frameworks (MOFs) or coordination polymers (CPs) have been used as precursors for synthesis of materials. Unlike crystalline MOF, amorphous CP is nonspecific to metal cation species, therefore its composition can be tuned easily. Here, it is shown that amorphous CP can be used as general synthesis precursors of highly complex mixed metal oxide shells. As a proof of concept, Ni? Co coordination polymer spheres are first synthesized and subsequently transformed into seven‐layered Ni? Co oxide onions by rapid thermal oxidation. This approach is very versatile and can be applied to produce ternary and quaternary metal oxide onions with tunable size and composition. The Ni? Co oxide onions exhibit exceptional charge storage capability in aqueous electrolyte with high specific capacitance (≈1900 F g^?1 at 2 A g^?1), good rate capability, and ultrahigh cycling stability (93.6% retention over 20 000 cycles). A hybrid supercapacitor against graphene/multishelled mesoporous carbon sphere shows a high energy density of 52.6 Wh kg^?1 at a power density of 1604 W kg^?1 (based on active materials weight), as well as remarkable cycling stability.     

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.     

Redox Tuning in Crystalline and Electronic Structure of Bimetal–Organic Frameworks Derived Cobalt/Nickel Boride/Sulfide for Boosted Faradaic Capacitance

The development of efficient electrode materials is a cutting‐edge approach for high‐performance energy storage devices. Herein, an effective chemical redox approach is reported for tuning the crystalline and electronic structures of bimetallic cobalt/nickel–organic frameworks (Co‐Ni MOFs) to boost faradaic redox reaction for high energy density. The as‐obtained cobalt/nickel boride/sulfide exhibits a high specific capacitance (1281 F g^?1 at 1 A g^?1), remarkable rate performance (802.9 F g^?1 at 20 A g^?1), and outstanding cycling stability (92.1% retention after 10 000 cycles). An energy storage device fabricated with a cobalt/nickel boride/sulfide electrode exhibits a high energy density of 50.0 Wh kg^?1 at a power density of 857.7 W kg^?1, and capacity retention of 87.7% (up to 5000 cycles at 12 A g^?1). Such an effective redox approach realizes the systematic electronic tuning that activates the fast faradaic reactions of the metal species in cobalt/nickel boride/sulfide which may shed substantial light on inspiring MOFs and their derivatives for energy storage devices.     

Few‐Layered Tin Sulfide Nanosheets Supported on Reduced Graphene Oxide as a High‐Performance Anode for Potassium‐Ion Batteries

Anodes involving conversion and alloying reaction mechanisms are attractive for potassium‐ion batteries (PIBs) due to their high theoretical capacities. However, serious volume change and metal aggregation upon potassiation/depotassiation usually cause poor electrochemical performance. Herein, few‐layered SnS₂ nanosheets supported on reduced graphene oxide (SnS₂@rGO) are fabricated and investigated as anode material for PIBs, showing high specific capacity (448 mAh g^?1 at 0.05 A g^?1), high rate capability (247 mAh g^?1 at 1 A g^?1), and improved cycle performance (73% capacity retention after 300 cycles). In this composite electrode, SnS₂ nanosheets undergo sequential conversion (SnS₂ to Sn) and alloying (Sn to K₄Sn₂₃, KSn) reactions during potassiation/depotassiation, giving rise to a high specific capacity. Meanwhile, the hybrid ultrathin nanosheets enable fast K storage kinetics and excellent structure integrity because of fast electron/ionic transportation, surface capacitive‐dominated charge storage mechanism, and effective accommodation for volume variation. This work demonstrates that K storage performance of alloy and conversion‐based anodes can be remarkably promoted by subtle structure engineering.     

Achieving High Capacitance of Paper‐Like Graphene Films by Adsorbing Molecules from Hydrolyzed Polyimide

To date, graphene‐based electric double layer supercapacitors have not shown the remarkable specific capacitance as theoretically predicted. An efficient strategy toward boosting the overall capacitance is to endow graphene with pseudocapacitance. Herein, molecules of hydrolyzed polyimide (HPI) are used to functionalize N‐doped graphene (NG) via π–π interaction and the resulting enhanced electrochemical energy storage is reported. These aromatic molecules in monolayer form on graphene contribute strong pseudocapacitance. Paper‐like NG films with different areal mass loadings ranging from 0.5 to 4.8 mg cm^?2 are prepared for supercapacitor electrodes. It is shown that the gravimetric capacitance can be increased by 50–60% after the surface functionalization by HPI molecules. A high specific capacitance of 553 F g^?1 at 5 mV s^?1 is achieved by the HPI‐NG film with a graphene mass loading of 0.5 mg cm^?2 in H₂SO₄ aqueous electrolyte. For the HPI‐NG film with highest mass loading, the gravimetric specific capacitance drops to 340 F g^?1 while the areal specific capacitance reaches a high value of 1.7 F cm^?2. HPI‐NG films are also tested in Li₂SO₄ aqueous electrolyte, over an extended voltage window of 1.6 V. High specific energy densities up to 40 Wh kg^?1 are achieved with the Li₂SO₄ electrolyte.     

Oxygen‐Vacancy and Surface Modulation of Ultrathin Nickel Cobaltite Nanosheets as a High‐Energy Cathode for Advanced Zn‐Ion Batteries

The development of high‐capacity, Earth‐abundant, and stable cathode materials for robust aqueous Zn‐ion batteries is an ongoing challenge. Herein, ultrathin nickel cobaltite (NiCo₂O₄) nanosheets with enriched oxygen vacancies and surface phosphate ions (P–NiCo₂O_4‐x) are reported as a new high‐energy‐density cathode material for rechargeable Zn‐ion batteries. The oxygen‐vacancy and surface phosphate‐ion modulation are achieved by annealing the pristine NiCo₂O₄ nanosheets using a simple phosphating process. Benefiting from the merits of substantially improved electrical conductivity and increased concentration of active sites, the optimized P–NiCo₂O_4‐x nanosheet electrode delivers remarkable capacity (309.2 mAh g^?1 at 6.0 A g^?1) and extraordinary rate performance (64% capacity retention at 60.4 A g^?1). Moreover, based on the P–NiCo₂O_4‐x cathode, our fabricated P–NiCo₂O_4‐x//Zn battery presents an impressive specific capacity of 361.3 mAh g^?1 at the high current density of 3.0 A g^?1 in an alkaline electrolyte. Furthermore, extremely high energy density (616.5 Wh kg^?1) and power density (30.2 kW kg^?1) are also achieved, which outperforms most of the previously reported aqueous Zn‐ion batteries. This ultrafast and high‐energy aqueous Zn‐ion battery is promising for widespread application to electric vehicles and intelligent devices.     

Achieving Ultrahigh Energy Density and Long Durability in a Flexible Rechargeable Quasi‐Solid‐State Zn–MnO2 Battery

Advanced flexible batteries with high energy density and long cycle life are an important research target. Herein, the first paradigm of a high‐performance and stable flexible rechargeable quasi‐solid‐state Zn–MnO₂ battery is constructed by engineering MnO₂ electrodes and gel electrolyte. Benefiting from a poly(3,4‐ethylenedioxythiophene) (PEDOT) buffer layer and a Mn²⁺‐based neutral electrolyte, the fabricated Zn–MnO₂@PEDOT battery presents a remarkable capacity of 366.6 mA h g^?1 and good cycling performance (83.7% after 300 cycles) in aqueous electrolyte. More importantly, when using PVA/ZnCl₂/MnSO₄ gel as electrolyte, the as‐fabricated quasi‐solid‐state Zn–MnO₂@PEDOT battery remains highly rechargeable, maintaining more than 77.7% of its initial capacity and nearly 100% Coulombic efficiency after 300 cycles. Moreover, this flexible quasi‐solid‐state Zn–MnO₂ battery achieves an admirable energy density of 504.9 W h kg^?1 (33.95 mW h cm^?3), together with a peak power density of 8.6 kW kg^?1, substantially higher than most recently reported flexible energy‐storage devices. With the merits of impressive energy density and durability, this highly flexible rechargeable Zn–MnO₂ battery opens new opportunities for powering portable and wearable electronics.     

Water‐Lubricated Intercalation in V2O5·nH2O for High‐Capacity and High‐Rate Aqueous Rechargeable Zinc Batteries

Low‐cost, environment‐friendly aqueous Zn batteries have great potential for large‐scale energy storage, but the intercalation of zinc ions in the cathode materials is challenging and complex. Herein, the critical role of structural H₂O on Zn²⁺ intercalation into bilayer V₂O₅·nH₂O is demonstrated. The results suggest that the H₂O‐solvated Zn²⁺ possesses largely reduced effective charge and thus reduced electrostatic interactions with the V₂O₅ framework, effectively promoting its diffusion. Benefited from the “lubricating” effect, the aqueous Zn battery shows a specific energy of ≈144 Wh kg^?1 at 0.3 A g^?1. Meanwhile, it can maintain an energy density of 90 Wh kg^?1 at a high power density of 6.4 kW kg^?1 (based on the cathode and 200% Zn anode), making it a promising candidate for high‐performance, low‐cost, safe, and environment‐friendly energy‐storage devices.     

Graphene Scroll‐Coated α‐MnO2 Nanowires as High‐Performance Cathode Materials for Aqueous Zn‐Ion Battery

The development of manganese dioxide as the cathode for aqueous Zn‐ion battery (ZIB) is limited by the rapid capacity fading and material dissolution. Here, a highly reversible aqueous ZIB using graphene scroll‐coated α‐MnO₂ as the cathode is proposed. The graphene scroll is uniformly coated on the MnO₂ nanowire with an average width of 5 nm, which increases the electrical conductivity of the MnO₂ nanowire and relieves the dissolution of the cathode material during cycling. An energy density of 406.6 Wh kg^?1 (382.2 mA h g^?1) at 0.3 A g^?1 can be reached, which is the highest specific energy value among all the cathode materials for aqueous Zn‐ion battery so far, and good long‐term cycling stability with 94% capacity retention after 3000 cycles at 3 A g^?1 are achieved. Meanwhile, a two‐step intercalation mechanism that Zn ions first insert into the layers and then the tunnels of MnO₂ framework is proved by in situ X‐ray diffraction, galvanostatic intermittent titration technique, and X‐ray photoelectron spectroscopy characterizations. The graphene scroll‐coated metallic oxide strategy can also bring intensive interests for other energy storage systems.     

A Metal‐Free,Free‐Standing,Macroporous Graphene@g‐C3N4 Composite Air Electrode for High‐Energy Lithium Oxygen Batteries

The nonaqueous lithium oxygen battery is a promising candidate as a next‐generation energy storage system because of its potentially high energy density (up to 2–3 kW kg^?1), exceeding that of any other existing energy storage system for storing sustainable and clean energy to reduce greenhouse gas emissions and the consumption of nonrenewable fossil fuels. To achieve high energy density, long cycling stability, and low cost, the air electrode structure and the electrocatalysts play important roles. Here, a metal‐free, free‐standing macroporous graphene@graphitic carbon nitride (g‐C₃N₄) composite air cathode is first reported, in which the g‐C₃N₄ nanosheets can act as efficient electrocatalysts, and the macroporous graphene nanosheets can provide space for Li₂O₂ to deposit and also promote the electron transfer. The electrochemical results on the graphene@g‐C₃N₄ composite air electrode show a 0.48 V lower charging plateau and a 0.13 V higher discharging plateau than those of pure graphene air electrode, with a discharge capacity of nearly 17300 mA h g^?1 _(composite). Excellent cycling performance, with terminal voltage higher than 2.4 V after 105 cycles at 1000 mA h g^?1 _(composite) capacity, can also be achieved. Therefore, this hybrid material is a promising candidate for use as a high energy, long‐cycle‐life, and low‐cost cathode material for lithium oxygen batteries.     

Hierarchical 3D All‐Carbon Composite Structure Modified with N‐Doped Graphene Quantum Dots for High‐Performance Flexible Supercapacitors

Flexible supercapacitors have shown enormous potential for portable electronic devices. Herein, hierarchical 3D all‐carbon electrode materials are prepared by assembling N‐doped graphene quantum dots (N‐GQDs) on carbonized MOF materials (cZIF‐8) interweaved with carbon nanotubes (CNTs) for flexible all‐solid‐state supercapacitors. In this ternary electrode, cZIF‐8 provides a large accessible surface area, CNTs act as the electrical conductive network, and N‐GQDs serve as highly pseudocapactive materials. Due to the synergistic effect and hierarchical assembly of these components, N‐GQD@cZIF‐8/CNT electrodes exhibit a high specific capacitance of 540 F g^?1 at 0.5 A g^?1 in a 1 m H₂SO₄ electrolyte and excellent cycle stability with 90.9% capacity retention over 8000 cycles. The assembled supercapacitor possesses an energy density of 18.75 Wh kg^?1 with a power density of 108.7 W kg^?1. Meanwhile, three supercapacitors connected in series can power light‐emitting diodes for 20 min. All‐solid‐state N‐GQD@cZIF‐8/CNT flexible supercapacitor exhibits an energy density of 14 Wh kg^?1 with a power density of 89.3 W kg^?1, while the capacitance retention after 5000 cycles reaches 82%. This work provides an effective way to construct novel electrode materials with high energy storage density as well as good cycling performance and power density for high‐performance energy storage devices via the rational design.     

An Ultrastable and High‐Performance Flexible Fiber‐Shaped Ni–Zn Battery based on a Ni–NiO Heterostructured Nanosheet Cathode

Currently, the main bottleneck for the widespread application of Ni–Zn batteries is their poor cycling stability as a result of the irreversibility of the Ni‐based cathode and dendrite formation of the Zn anode during the charging–discharging processes. Herein, a highly rechargeable, flexible, fiber‐shaped Ni–Zn battery with impressive electrochemical performance is rationally demonstrated by employing Ni–NiO heterostructured nanosheets as the cathode. Benefiting from the improved conductivity and enhanced electroactivity of the Ni–NiO heterojunction nanosheet cathode, the as‐fabricated fiber‐shaped Ni–NiO//Zn battery displays high capacity and admirable rate capability. More importantly, this Ni–NiO//Zn battery shows unprecedented cyclic durability both in aqueous (96.6% capacity retention after 10 000 cycles) and polymer (almost no capacity attenuation after 10 000 cycles at 22.2 A g^?1) electrolytes. Moreover, a peak energy density of 6.6 µWh cm^?2, together with a remarkable power density of 20.2 mW cm^?2, is achieved by the flexible quasi‐solid‐state fiber‐shaped Ni–NiO//Zn battery, outperforming most reported fiber‐shaped energy‐storage devices. Such a novel concept of a fiber‐shaped Ni–Zn battery with impressive stability will greatly enrich the flexible energy‐storage technologies for future portable/wearable electronic applications.