Direct Ink Writing of Adjustable Electrochemical Energy Storage Device with High Gravimetric Energy Densities

3D printing graphene aerogel with periodic microlattices has great prospects for various practical applications due to their low density, large surface area, high porosity, excellent electrical conductivity, good elasticity, and designed lattice structures. However, the low specific capacitance limits their development in energy storage fields due to the stacking of graphene. Therefore, constructing a graphene‐based 2D materials hybridization aerogel that consists of the pseduocapacitive substance and graphene material is necessary for enhancing electrochemical performance. Herein, 3D printing periodic graphene‐based composite hybrid aerogel microlattices (HAMs) are reported via 3D printing direct ink writing technology. The rich porous structure, high electrical conductivity, and highly interconnected networks of the HAMs aid electron and ion transport, further enabling excellent capacitive performance for supercapacitors. An asymmetric supercapacitor device is assembled by two different 4‐mm‐thick electrodes, which can yield high gravimetric specific capacitance (C_g) of 149.71 F g^?1 at a current density of 0.5 A g^?1 and gravimetric energy density (E_g) of 52.64 Wh kg^?1, and retains a capacitance retention of 95.5% after 10 000 cycles. This work provides a general strategy for designing the graphene‐based mixed‐dimensional hybrid architectures, which can be utilized in energy storage fields.     

Engineering 3D Ion Transport Channels for Flexible MXene Films with Superior Capacitive Performance

2D MXene materials are of considerable interest for future energy storage. A MXene film could be used as an effective flexible supercapacitor electrode due to its flexibility and, more importantly, its high specific capacitance. However, although it has excellent electronic conductivity, sluggish ionic kinetics within the MXene film becomes a fundamental limitation to the electrochemical performance. To compensate for the relative deficiency, MXene films are frequently reduced to several micrometer dimensions with low mass loading (<1 mg cm^?2), to the point of detriment of areal performance and commercial value. Herein, for the first time, the design of a 3D porous MXene/bacterial cellulose (BC) self‐supporting film is reported for ultrahigh capacitance performance (416 F g^?1, 2084 mF cm^?2) with outstanding mechanical properties and high flexibility, even when the MXene loading reaches 5 mg cm^?2. The highly interconnected MXene/BC network enables both excellent electron and ion transport channel. Additionally, a maximum energy density of 252 µWh cm^?2 is achieved in an asymmetric supercapacitor, higher than that of all ever‐reported MXene‐based supercapacitors. This work exploits a simple route for assembling 2D MXene materials into 3D porous films as state‐of‐the‐art electrodes for high performance energy storage devices.     

Prolifera‐Green‐Tide as Sustainable Source for Carbonaceous Aerogels with Hierarchical Pore to Achieve Multiple Energy Storage

The increasing demand for efficient energy storage and conversion devices has aroused great interest in designing advanced materials with high specific surface areas, multiple holes, and good conductivity. Here, we report a new method for fabricating a hierarchical porous carbonaceous aerogel (HPCA) from renewable seaweed aerogel. The HPCA possesses high specific surface area of 2200 m² g^?1 and multilevel micro/meso/macropore structures. These important features make HPCA exhibit a reversible lithium storage capacity of 827.1 mAh g^?1 at the current density of 0.1 A g^?1, which is the highest capacity for all the previously reported nonheteroatom‐doped carbon nanomaterials. It also shows high specific capacitance and excellent rate performance for electric double layer capacitors (260.6 F g^?1 at 1 A g^?1 and 190.0 F g^?1 at 50 A g^?1), and long cycle life with 91.7% capacitance retention after 10 000 cycles at 10 A g^?1. The HPCA also can be used as support to assemble Co₃O₄ nanowires (Co₃O₄@HPCA) for constructing a high performance pseudocapacitor with the maximum specific capacitance of 1167.6 F g^?1 at the current density of 1 A g^?1. The present work highlights the first example in using prolifera‐green‐tide as a sustainable source for developing advanced carbon porous aerogels to achieve multiple energy storage.     

Advanced Asymmetric Supercapacitors Based on Ni(OH)2/Graphene and Porous Graphene Electrodes with High Energy Density

Hierarchical flowerlike nickel hydroxide decorated on graphene sheets has been prepared by a facile and cost‐effective microwave‐assisted method. In order to achieve high energy and power densities, a high‐voltage asymmetric supercapacitor is successfully fabricated using Ni(OH)₂/graphene and porous graphene as the positive and negative electrodes, respectively. Because of their unique structure, both of these materials exhibit excellent electrochemical performances. The optimized asymmetric supercapacitor could be cycled reversibly in the high‐voltage region of 0–1.6 V and displays intriguing performances with a maximum specific capacitance of 218.4 F g^?1 and high energy density of 77.8 Wh kg^?1. Furthermore, the Ni(OH)₂/graphene//porous graphene supercapacitor device exhibits an excellent long cycle life along with 94.3% specific capacitance retained after 3000 cycles. These fascinating performances can be attributed to the high capacitance and the positive synergistic effects of the two electrodes. The impressive results presented here may pave the way for promising applications in high energy density storage systems.     

Flexible Solid‐State Supercapacitor Based on Graphene‐based Hybrid Films

A flexible solid‐state asymmetric supercapacitor based on bendable film electrodes with 3D expressway‐like architecture of graphenes and “hard nano‐spacer” is fabricated via an extended filtration assisted method. In the designed structure of the positive electrode, graphene sheets are densely packed, and Ni(OH)₂ nanoplates are intercalated in between the densely stacked graphenes. The 3D expressway‐like electrodes exhibit superior supercapacitive performance including high gravimetric capacitance (≈573 F g^‐1), high volumetric capacitance (≈655 F cm^‐3), excellent rate capability, and superior cycling stability. In addition, another hybrid film of graphene and carbon nanotubes (CNT) is fabricated as the negative electrodes for the designed asymmetric device. In the obtained graphene@CNT films, CNTs served as the hard spacer to prevent restacking of graphene sheets but also as a conductive and robust network to facilitate the electrons collection/transport in order to fulfill the demand of high‐rate performance of the asymmetric supercapacitor. Based on these two hybrid electrode films, a solid‐state flexible asymmetric supercapacitor device is assembled, which is able to deliver competitive volumetric capacitance of 58.5 F cm^‐3 and good rate capacity. There is no obvious degradation of the supercapacitor performance when the device is in bending configuration, suggesting the excellent flexibility of the device.     

Controllable Patterning of Porous MXene (Ti3C2) by Metal-Assisted Electro-Gelation Method

Since discovered in 2011, transition metal carbides or nitrides (MXenes) have attracted enormous attention due to their unique properties. Morphology regulation strategies assembling 2D MXene sheets into 3D architecture have endowed the as-formed porous MXene with a better performance in various fields. However, the direct patterning strategy for the porous MXene into integration with multifunctional and multichannel electronic devices still needs to be investigated. The metal-assisted electro-gelation method the authors propose can directly generate porous-structured MXene hydrogel with a tunable feature. By electrolyzing the sacrificial metal, the released metal cations initiate the electro-gelation process during which electrostatic interactions occur between cations and the MXene sheets. A high spatial resolution down to micro-meter level is achieved utilizing the method, enabling high-performance hydrogels with more complex architectures. Electronics prepared through this metal-assisted electro-gelation process have shown promising applications of the porous MXene in energy and biochemical sensing fields. Energy storage devices with a capacitance at 33.3 mF cm⁻² and biochemical sensors show prominent current responses towards metabolites (sensitivity of H₂O₂: 165.6  µ A mm ⁻¹ cm⁻²; sensitivity of DA: 212 nA  µ m ⁻¹ cm⁻²), suggesting that the metal-assisted electro-gelation method will become a prospective technique for advanced fabrication of MXene-based devices.     

Direct 3D Printing of Ultralight Graphene Oxide Aerogel Microlattices

Graphene aerogel microlattices (GAMs) hold great prospects for many multifunctional applications due to their low density, high porosity, designed lattice structures, good elasticity, and tunable electrical conductivity. Previous 3D printing approaches to fabricate GAMs require either high content of additives or complex processes, limiting their wide applications. Here, a facile ion‐induced gelation method is demonstrated to directly print GAMs from graphene oxide (GO) based ink. With trace addition of Ca²⁺ ions as gelators, aqueous GO sol converts to printable gel ink. Self‐standing 3D structures with programmable microlattices are directly printed just in air at room temperature. The rich hierarchical pores and high electrical conductivity of GAMs bring admirable capacitive performance for supercapacitors. The gravimetric capacitance (C_s) of GAMs is 213 F g^?1 at 0.5 A g^?1 and 183 F g^?1 at 100 A g^?1, and retains over 90% after 50 000 cycles. The facile, direct 3D printing of neat graphene oxide can promote wide applications of GAMs from energy storage to tissue engineering scaffolds.     

Flexible MXene/Graphene Films for Ultrafast Supercapacitors with Outstanding Volumetric Capacitance

A strategy to prepare flexible and conductive MXene/graphene (reduced graphene oxide, rGO) supercapacitor electrodes by using electrostatic self‐assembly between positively charged rGO modified with poly(diallyldimethylammonium chloride) and negatively charged titanium carbide MXene nanosheets is presented. After electrostatic assembly, rGO nanosheets are inserted in‐between MXene layers. As a result, the self‐restacking of MXene nanosheets is effectively prevented, leading to a considerably increased interlayer spacing. Accelerated diffusion of electrolyte ions enables more electroactive sites to become accessible. The freestanding MXene/rGO‐5 wt% electrode displays a volumetric capacitance of 1040 F cm^?3 at a scan rate of 2 mV s^?1 , an impressive rate capability with 61% capacitance retention at 1 V s^?1 and long cycle life. Moreover, the fabricated binder‐free symmetric supercapacitor shows an ultrahigh volumetric energy density of 32.6 Wh L^?1, which is among the highest values reported for carbon and MXene based materials in aqueous electrolytes. This work provides fundamental insight into the effect of interlayer spacing on the electrochemical performance of 2D hybrid materials and sheds light on the design of next‐generation flexible, portable and highly integrated supercapacitors with high volumetric and rate performances.     

Dual Support System Ensuring Porous Co–Al Hydroxide Nanosheets with Ultrahigh Rate Performance and High Energy Density for Supercapacitors

Layered double hydroxides (LDHs) are promising supercapacitor electrode materials due to their high specific capacitances. However, their electrochemical performances such as rate performance and energy density at a high current density, are rather poor. Accordingly, a facile strategy is demonstrated for the synthesis of the integrated porous Co–Al hydroxide nanosheets (named as GSP‐LDH) with dual support system using dodecyl sulfate anions and graphene sheets as structural and conductive supports, respectively. Owing to fast ion/electron transport, porous and integrated structure, the GSP‐LDH electrode exhibits remarkably improved electrochemical characteristics such as high specific capacitance (1043 F g^?1 at 1 A g^?1) and ultra‐high rate performance capability (912 F g^?1 at 20 A g^?1). Moreover, the assembled sandwiched graphene/porous carbon (SGC)//GSP‐LDH asymmetric supercapacitor delivers a high energy density up to 20.4 Wh kg^?1 at a very high power density of 9.3 kW kg^?1, higher than those of previously reported asymmetric supercapacitors. The strategy provides a facile and effective method to achieve high rate performance LDH based electrode materials for supercapacitors.     

Hierarchical Composite Electrodes of Nickel Oxide Nanoflake 3D Graphene for High‐Performance Pseudocapacitors

NiO nanoflakes are created with a simple hydrothermal method on 3D (three‐dimensional) graphene scaffolds grown on Ni foams by microwave plasma enhanced chemical vapor deposition (MPCVD). Such as‐grown NiO‐3D graphene hierarchical composites are then applied as monolithic electrodes for a pseudo‐supercapacitor application without needing binders or metal‐based current collectors. Electrochemical measurements impart that the hierarchical NiO‐3D graphene composite delivers a high specific capacitance of ≈1829 F g^?1 at a current density of 3 A g^?1 (the theoretical capacitance of NiO is 2584 F g^?1). Furthermore, a full‐cell is realized with an energy density of 138 Wh kg^?1 at a power density of 5.25 kW kg^?1, which is much superior to commercial ones as well as reported devices in asymmetric capacitors of NiO. More attractively, this asymmetric supercapacitor exhibits capacitance retention of 85% after 5000 cycles relative to the initial value of the 1^st cycle.     

3D Porous Oxidation-Resistant MXene/Graphene Architectures Induced by In Situ Zinc Template toward High-Performance Supercapacitors

2D MXene materials have attracted intensive attention in energy storage application. However, MXene usually undergoes serious face-to-face restacking and inferior stability, significantly preventing its further commercial application. Herein, to suppress the oxidation and self-restacking of MXene, an efficient and fast self-assembly route to prepare a 3D porous oxidation-resistant MXene/graphene (PMG) composite with the assistance of an in situ sacrificial metallic zinc template is demonstrated. The self-assembled 3D porous architecture can effectively prevent the oxidation of MXene layers with no evident variation in electrical conductivity in air at room temperature after two months, guaranteeing outstanding electrical conductivity and abundant electrochemical active sites accessible to electrolyte ions. Consequently, the PMG-5 electrode possesses a striking specific capacitance of 393 F g⁻¹, superb rate performance (32.7% at 10 V s⁻¹), and outstanding cycling stability. Furthermore, the as-assembled asymmetric supercapacitor possesses a pronounced energy density of 50.8 Wh kg⁻¹ and remarkable cycling stability with a 4.3% deterioration of specific capacitance after 10 000 cycles. This work paves a new avenue to solve the two long-standing significant challenges of MXene in the future.     

Flexible Solid‐State Supercapacitors with Enhanced Performance from Hierarchically Graphene Nanocomposite Electrodes and Ionic Liquid Incorporated Gel Polymer Electrolyte

High energy density, durability, and flexibility of supercapacitors are required urgently for the next generation of wearable and portable electronic devices. Herein, a novel strategy is introduced to boost the energy density of flexible soild‐state supercapacitors via rational design of hierarchically graphene nanocomposite (GNC) electrode material and employing an ionic liquid gel polymer electrolyte. The hierarchical graphene nanocomposite consisting of graphene and polyaniline‐derived carbon is synthesized as an electrode material via a scalable process. The meso/microporous graphene nanocomposites exhibit a high specific capacitance of 176 F g^?1 at 0.5 A g^?1 in the ionic liquid 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIBF₄) with a wide voltage window of 3.5 V, good rate capability of 80.7% in the range of 0.5–10 A g^?1 and excellent stability over 10 000 cycles, which is attributed to the superior conductivity (7246 S m^?1), and quite large specific surface area (2416 m² g^?1) as well as hierarchical meso/micropores distribution of the electrode materials. Furthermore, flexible solid‐state supercapacitor devices based on the GNC electrodes and gel polymer electrolyte film are assembled, which offer high specific capacitance of 180 F g^?1 at 1 A g^?1, large energy density of 75 Wh Kg^?1, and remarkable flexible performance under consecutive bending conditions.     

High‐Performance Ultrathin Flexible Solid‐State Supercapacitors Based on Solution Processable Mo1.33C MXene and PEDOT:PSS

MXenes, a young family of 2D transition metal carbides/nitrides, show great potential in electrochemical energy storage applications. Herein, a high performance ultrathin flexible solid‐state supercapacitor is demonstrated based on a Mo_1.33C MXene with vacancy ordering in an aligned layer structure MXene/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) composite film posttreated with concentrated H₂SO₄. The flexible solid‐state supercapacitor delivers a maximum capacitance of 568 F cm^?3, an ultrahigh energy density of 33.2 mWh cm^?3 and a power density of 19 470 mW cm^?3. The Mo_1.33C MXene/PEDOT:PSS composite film shows a reduction in resistance upon H₂SO₄ treatment, a higher capacitance (1310 F cm^?3) and improved rate capabilities than both pristine Mo_1.33C MXene and the nontreated Mo_1.33C/PEDOT:PSS composite films. The enhanced capacitance and stability are attributed to the synergistic effect of increased interlayer spacing between Mo_1.33C MXene layers due to insertion of conductive PEDOT, and surface redox processes of the PEDOT and the MXene.     

An Ultrafast,High-Loading,and Durable Poly(p-aminoazobenzene)/Reduced Graphene Oxide Composite Electrode for Supercapacitors

Although challenging, the fabricated supercapacitor electrodes with excellent rate capability, long cycling stability, and high mass-loading are crucial for practical applications. Herein, a novel 3D porous poly(p-aminoazobenzene)/reduced graphene oxide hydrogel is designed and prepared as an ultrafast, high-loading, and durable pseudocapacitive electrode through a facile two-step self-assembly approach. Owing to abundant stable redox-active sites, fast electrolyte diffusion, and efficient charge conduction, the PRH electrode (5 mg cm⁻²) shows a high specific capacitance (701 F g⁻¹ at 2 A g⁻¹) and ultrafast rate (97% capacitance retention at 100 A g⁻¹). Furthermore, even with a mass-loading of 10 mg cm⁻², the electrode still exhibits comparable high performance and excellent long-term cycling life (only 6.7% capacitance loss after 10 000 cycles). This work demonstrates novel polyaniline analog composites for constructing novel electrodes, promising to open an avenue toward practical applications.     

Ultra‐High Surface Area Nitrogen‐Doped Carbon Aerogels Derived From a Schiff‐Base Porous Organic Polymer Aerogel for CO2 Storage and Supercapacitors

Nitrogen‐doped carbon aerogels (NCAs) have received great attention for a wide range of applications, from thermal electronics to waste water purification, heavy metal or gas adsorption, energy storage, and catalyst supports. Herein NCAs are developed via the synthesis of a Schiff‐base porous organic polymer aerogel followed by pyrolysis. By controlling the pyrolysis temperature, the polymer aerogel can be simply converted into porous NCAs with a low bulk density (5 mg cm^?3), high surface area (2356 m² g^?1), and high bulk porosity (70%). The NCAs containing 1.8–5.3 wt% N atoms exhibit remarkable CO₂ uptake capacities (6.1 mmol g^?1 at 273 K and 1 bar, 33.1 mmol g^?1 at 323 K and 30 bar) and high ideal adsorption solution theory selectivity (47.8) at ambient pressure. Supercapacitors fabricated with NCAs display high specific capacitance (300 F g^?1 at 0.5 A g^?1), fast rate (charge to 221 F g^?1 within only 17 s), and high stability (retained >98% capacity after 5000 cycles). Asymmetric supercapacitors assembled with NCAs also show high energy density and power density with maximal values of 30.5 Wh kg^?1 and 7088 W kg^?1, respectively. The outstanding CO₂ uptake and energy storage abilities are attributed to the ultra‐high surface area, N‐doping, conductivity, and rigidity of NCA frameworks.     

3D Porous N‐Doped Graphene Frameworks Made of Interconnected Nanocages for Ultrahigh‐Rate and Long‐Life Li–O2 Batteries

The inferior rate capability and poor cycle stability of the present Li–O₂ batteries are still critical obstacles for practice applications. Configuring novel and integrated air electrode materials with unique structure and tunable chemical compositions is one of the efficient strategies to solve these bottleneck problems. Herein, a novel strategy for synthesis of 3D porous N‐doped graphene aerogels (NPGAs) with frameworks constructed by interconnected nanocages with the aid of polystyrene sphere@polydopamine is reported. The interconnected nanocages as the basic building unit of graphene sheets are assembled inside the skeletons of 3D graphene aerogels, leading to the 3D NPGA with well‐developed interconnected channels and the full exposure of electrochemically active sites. Benefiting from such an unique structure, the as‐made NPGA delivers a high specific capacity, an excellent rate capacity of 5978 mA h g^?1 at 3.2 A g^?1, and long cycle stability, especially at a large current density (54 cycles at 1 A g^?1), indicative of boosted rate capability and cycle life as air electrodes for Li–O₂ batteries. More importantly, based on the total mass of C+Li₂O₂, a gravimetric energy density of 2400 W h kg^?1 for the NPGA–O₂//Li cell is delivered at a power density of 1300 W kg^?1.     

Boosting the Electrical Double‐Layer Capacitance of Graphene by Self‐Doped Defects through Ball‐Milling

Improving the capacitance of carbon materials for supercapacitors without sacrificing their rate performance, especially volumetric capacitance at high mass loadings, is a big challenge because of the limited assessable surface area and sluggish electrochemical kinetics of the pseudocapacitive reactions. Here, it is demonstrated that “self‐doping” defects in carbon materials can contribute to additional capacitance with an electrical double‐layer behavior, thus promoting a significant increase in the specific capacitance. As an exemplification, a novel defect‐enriched graphene block with a low specific surface area of 29.7 m² g^?1 and high packing density of 0.917 g cm^?3 performs high gravimetric, volumetric, and areal capacitances of 235 F g^?1, 215 F cm^?3, and 3.95 F cm^?2 (mass loading of 22 mg cm^?2) at 1 A g^?1, respectively, as well as outstanding rate performance. The resulting specific areal capacitance reaches an ultrahigh value of 7.91 F m^?2 including a “self‐doping” defect contribution of 4.81 F m^?2, which is dramatically higher than the theoretical capacitance of graphene (0.21 F m^?2) and most of the reported carbon‐based materials. Therefore, the defect engineering route broadens the avenue to further improve the capacitive performance of carbon materials, especially for compact energy storage under limited surface areas.     

Multilayer‐Folded Graphene Ribbon Film with Ultrahigh Areal Capacitance and High Rate Performance for Compressible Supercapacitors

Limited by 2D geometric morphology and low bulk packing density, developing graphene‐based flexible/compressible supercapacitors with high specific capacitances (gravimetric/volumetric/areal), especially at high rates, is an outstanding challenge. Here, a strategy for the synthesis of free‐standing graphene ribbon films (GRFs) for high‐performance flexible and compressible supercapacitors through blade‐coating of interconnected graphene oxide ribbons and a subsequent thermal treatment process is reported. With an ultrahigh mass loading of 21 mg cm^?2, large ion‐accessible surface area, efficient electron and ion transport pathways as well as high packing density, the compressed multilayer‐folded GRF films (F‐GRF) exhibit ultrahigh areal capacitance of 6.7 F cm^?2 at 5 mA cm^?2, high gravimetric/volumetric capacitances (318 F g^?1, 293 F cm^?3), and high rate performance (3.9 F cm^?2 at 105 mA cm^?2), as well as excellent cycling stability (109% of capacitance retention after 40 000 cycles). Furthermore, the assembled F‐GRF symmetric supercapacitor with compressible and flexible characteristics, can deliver an ultrahigh areal energy density of 0.52 mWh cm^?2 in aqueous electrolyte, almost two times higher than the values obtained from symmetric supercapacitors with comparable dimensions.     

Oxygen Clusters Distributed in Graphene with “Paddy Land” Structure: Ultrahigh Capacitance and Rate Performance for Supercapacitors

The introduction of surface functional groups onto graphene can provide additional pseudocapacitance for supercapacitors. However, the compensation for the loss of electrical conductivity arising from the disruption of the conjugated system remains a big challenge. Here, a novel strategy is reported for the design of oxygen clusters distributed in graphene with “paddy land” structure via a low‐temperature annealing process. Moreover, the distribution, content, and variety of oxygen groups and the conductivity of reduced graphene oxide (RGO) can be easily adjusted by annealing temperature and time. First‐principles calculations demonstrate that “paddy land” structure exhibits conjugated carbon network, ultralow HOMO–LUMO gap, and long span of atomic charge values, which are beneficial for the enhanced pseudocapacitance and rate performance. As a result, the functionalized graphene (GO‐160‐8D) exhibits high specific capacitance of 436 F g^?1 at 0.5 A g^?1, exceeding the values of previously reported RGO materials, as well as excellent rate performance (261 F g^?1 at 50 A g^?1) and cycling stability (94% of capacitance retention after 10 000 cycles). The findings may open a door for finely controlling the location and density of functionalities on graphene for applications in energy storage and conversion fields via a green and energy‐efficient process.     

Novel Core–Shell FeOF/Ni(OH)2 Hierarchical Nanostructure for All‐Solid‐State Flexible Supercapacitors with Enhanced Performance

Well‐controlled core–shell hierarchical nanostructures based on oxyfluoride and hydroxide are for the first time rationally designed and synthesized via a simple solvothermal and chemical precipitation route, in which FeOF nanorod acts as core and porous Ni(OH)₂ nanosheets as shell. When evaluated as electrodes for supercapacitors, a high specific capacitance of 1452 F g^?1 can be obtained at a current density of 1 A g^?1. Even as the current density increases to 10 A g^?1, the core–shell hybrid still reserves a noticeable capacitance of 1060 F g^?1, showing an excellent rate capacity. Furthermore, all‐solid‐state flexible asymmetric supercapacitor based on the FeOF/Ni(OH)₂ hybrid as a positive electrode and activated carbon as a negative electrode shows high power density, high energy density, and long cycling lifespan. The excellent electrochemical performance of the FeOF/Ni(OH)₂ core–shell hybrid is ascribed to the unique microstructure and synergistic effects. FeOF nanorod from FeF₃ by partial substitution of fluorine with oxygen behaves as a low intrinsic resistance, thus facilitating charge transfer processes. While the hierarchical Ni(OH)₂ nanosheets with large surface area provide enough active sites for redox chemical reactions, leading to greatly enhanced electrochemical activity. The well‐controllable oxyfluoride/hydroxide hybrid is inspiring, opening up a new way to design new electrodes for next‐generation all‐solid‐state supercapacitors.