High‐Performance Supercapacitors Based on a Zwitterionic Network of Covalently Functionalized Graphene with Iron Tetraaminophthalocyanine

Graphene derivatives are promising candidates as electrode materials in supercapacitor cells, therefore, functionalization strategies are pursued to improve their performance. A scalable approach is reported for preparing a covalently and homogenously functionalized graphene with iron tetraaminophthalocyanine (FePc‐NH₂) with a high degree of functionalization. This is achieved by exploiting fluorographene's reactivity with the diethyl bromomalonate, producing graphene‐dicarboxylic acid after hydrolysis, which is conjugated with FePc‐NH₂. The material exhibits an ultrahigh gravimetric specific capacitance of 960 F g^?1 at 1 A g^?1 and zero losses upon charging–discharging cycling. The energy density of 59 Wh kg^?1 is eminent among supercapacitors operating in aqueous electrolytes with graphene‐based electrode materials. This is attributed to the structural and functional synergy of the covalently bound components, giving rise to a zwitterionic surface with extensive π–π stacking, but not graphene restacking, all being very beneficial for charge and ionic transport. The safety of the proposed system, owing to the benign Na₂SO₄ aqueous electrolyte, the high capacitance, energy density, and potential of preparing the electrode material on a large‐scale and at low cost make the reported strategy very attractive for development of supercapacitors based on the covalent attachment of suitable molecules onto graphene toward high‐synergy hybrids.     

Asymmetric Supercapacitors Based on Graphene/MnO2 and Activated Carbon Nanofiber Electrodes with High Power and Energy Density

Asymmetric supercapacitor with high energy density has been developed successfully using graphene/MnO₂ composite as positive electrode and activated carbon nanofibers (ACN) as negative electrode in a neutral aqueous Na₂SO₄ electrolyte. Due to the high capacitances and excellent rate performances of graphene/MnO₂ and ACN, as well as the synergistic effects of the two electrodes, such asymmetric cell exhibits superior electrochemical performances. An optimized asymmetric supercapacitor can be cycled reversibly in the voltage range of 0–1.8 V, and exhibits maximum energy density of 51.1 Wh kg^?1, which is much higher than that of MnO₂//DWNT cell (29.1 Wh kg^?1). Additionally, graphene/MnO₂//ACN asymmetric supercapacitor exhibits excellent cycling durability, with 97% specific capacitance retained even after 1000 cycles. These encouraging results show great potential in developing energy storage devices with high energy and power densities for practical applications.     

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.     

Scalable Production of Graphene Inks via Wet‐Jet Milling Exfoliation for Screen‐Printed Micro‐Supercapacitors

The miniaturization of energy storage units is pivotal for the development of next‐generation portable electronic devices. Micro‐supercapacitors (MSCs) hold great potential to work as on‐chip micro‐power sources and energy storage units complementing batteries and energy harvester systems. Scalable production of supercapacitor materials with cost‐effective and high‐throughput processing methods is crucial for the widespread application of MSCs. Here, wet‐jet milling exfoliation of graphite is reported to scale up the production of graphene as a supercapacitor material. The formulation of aqueous/alcohol‐based graphene inks allows metal‐free, flexible MSCs to be screen‐printed. These MSCs exhibit areal capacitance (C_areal) values up to 1.324 mF cm^?2 (5.296 mF cm^?2 for a single electrode), corresponding to an outstanding volumetric capacitance (C_vol) of 0.490 F cm^?3 (1.961 F cm^?3 for a single electrode). The screen‐printed MSCs can operate up to a power density above 20 mW cm^?2 at an energy density of 0.064 µWh cm^?2. The devices exhibit excellent cycling stability over charge–discharge cycling (10 000 cycles), bending cycling (100 cycles at a bending radius of 1 cm) and folding (up to angles of 180°). Moreover, ethylene vinyl acetate‐encapsulated MSCs retain their electrochemical properties after a home‐laundry cycle, providing waterproof and washable properties for prospective application in wearable electronics.     

Polyoxometalate‐coupled Graphene via Polymeric Ionic Liquid Linker for Supercapacitors

The integration of electrical double‐layer capacitive and pseudocapacitive materials into novel hybrid materials is crucial to realize supercapacitors with high energy and power densities. Here, high levels of energy and power densities are demonstrated in supercapacitors based on a new type of nanohybrid electrode consisting of polyoxometalate (POM)‐coupled graphene in which a polymeric ionic liquid (henceforth simply PIL) serves as an interfacial linker. The adoption of PIL in the construction of nanohybrids enables a uniform distribution of discrete POM molecules along with a large surface area of graphene sheets. When testing electrochemical characteristics under a two‐electrode system, as‐prepared supercapacitors exhibit a high specific capacitance (408 F g^?1 at 0.5 A g^?1), rapid rate capability (92% retention at 10 A g^?1), a long cycling life (98% retention during 2000 cycles), and high energy (56 Wh kg^?1) and power (52 kW kg^?1) densities. First‐principles calculations and impedance spectroscopy analysis reveal that the PILs enhance the redox reactions of POMs by providing efficient ion transfer channels and facilitating the charge transfer in the nanohybrids.     

Highly Conductive Ordered Mesoporous Carbon Based Electrodes Decorated by 3D Graphene and 1D Silver Nanowire for Flexible Supercapacitor

Ordered mesoporous carbon (OMC) is considered one of the most promising materials for electric double layer capacitors (EDLC) given its low‐cost, high specific surface area, and easily accessed ordered pore channels. However, pristine OMC electrode suffers from poor electrical conductivity and mechanical flexibility, whose specific capacitance and cycling stability is unsatisfactory in flexible devices. In this work, OMC is coated on the surface of highly conductive three‐dimensional graphene foam, serving as both charge collector and flexible substrate. Upon further decoration with silver nanowires (Ag NWs), the novel architecture of Ag NWs/3D‐graphene foam/OMC (Ag‐GF‐OMC) exhibits exceptional electrical conductivity (up to 762 S cm^?1) and mechanical robustness. The Ag‐GF‐OMC electrodes in flexible supercapacitors reach a specific capacitance as high as 213 F g^?1, a value five‐fold higher than that of the pristine OMC electrode. Moreover, these flexible electrodes also exhibit excellent long‐term stability with >90% capacitance retention over 10 000 cycles, as well as high energy and power density (4.5 Wh kg^?1 and 5040 W kg^?1, respectively). This study provides a new procedure to enhance the device performance of OMC based supercapacitors, which is a promising candidate for the application of flexible energy storage devices.     

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.     

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.     

All‐Solid‐State Asymmetric Supercapacitors with Metal Selenides Electrodes and Ionic Conductive Composites Electrolytes

All‐solid‐state flexible asymmetric supercapacitors (ASCs) are developed by utilization of graphene nanoribbon (GNR)/Co_0.85Se composites as the positive electrode, GNR/Bi₂Se₃ composites as the negative electrode, and polymer‐grafted‐graphene oxide membranes as solid‐state electrolytes. Both GNR/Co_0.85Se and GNR/Bi₂Se₃ composite electrodes are developed by a facile one‐step hydrothermal growth method from graphene oxide nanoribbons as the nucleation framework. The GNR/Co_0.85Se composite electrode exhibits a specific capacity of 76.4 mAh g^?1 at a current density of 1 A g^?1 and the GNR/Bi₂Se₃ composite electrode exhibits a specific capacity of 100.2 mAh g^?1 at a current density of 0.5 A g^?1. Moreover, the stretchable membrane solid‐state electrolytes exhibit superior ionic conductivity of 108.7 mS cm^?1. As a result, the flexible ASCs demonstrate an operating voltage of 1.6 V, an energy density of 30.9 Wh kg^?1 at the power density of 559 W kg^?1, and excellent cycling stability with 89% capacitance retention after 5000 cycles. All these results demonstrate that this study provides a simple, scalable, and efficient approach to fabricate high performance flexible all‐solid‐state ASCs for energy storage.     

Nickel–Cobalt Layered Double Hydroxide Nanosheets for High‐performance Supercapacitor Electrode Materials

A facile and novel one‐step method of growing nickel‐cobalt layered double hydroxide (Ni‐Co LDH) hybrid films with ultrathin nanosheets and porous nanostructures on nickel foam is presented using cetyltrimethylammonium bromide as nanostructure growth assisting agent but without any adscititious alkali sources and oxidants. As pseudocapacitors, the as‐obtained Ni‐Co LDH hybrid film‐based electrodes display a significantly enhanced specific capacitance (2682 F g^?1 at 3 A g^?1, based on active materials) and energy density (77.3 Wh kg^?1 at 623 W kg^?1), compared to most previously reported electrodes based on nickel‐cobalt oxides/hydroxides. Moreover, the asymmetric supercapacitor, with the Ni‐Co LDH hybrid film as the positive electrode material and porous freeze‐dried reduced graphene oxide (RGO) as the negative electrode material, exhibits an ultrahigh energy density (188 Wh kg^?1) at an average power density of 1499 W kg^?1 based on the mass of active material, which greatly exceeds the energy densities of most previously reported nickel or cobalt oxide/hydroxide‐based asymmetric supercapacitors.     

Facile Synthesis of Hematite Quantum‐Dot/Functionalized Graphene‐Sheet Composites as Advanced Anode Materials for Asymmetric Supercapacitors

For building high‐energy density asymmetric supercapacitors, developing anode materials with large specific capacitance remains a great challenge. Although Fe₂O₃ has been considered as a promising anode material for asymmetric supercapacitors, the specific capacitance of the Fe₂O₃‐based anodes is still low and cannot match that of cathodes in the full cells. In this work, a composite material with well dispersed Fe₂O₃ quantum dots (QDs, ≈2 nm) decorated on functionalized graphene‐sheets (FGS) is prepared by a facile and scalable method. The Fe₂O₃ QDs/FGS composites exhibit a large specific capacitance up to 347 F g^?1 in 1 m Na₂SO₄ between –1 and 0 V versus Ag/AgCl. An asymmetric supercapacitor operating at 2 V is fabricated using Fe₂O₃/FGS as anode and MnO₂/FGS as cathode in 1 m Na₂SO₄ aqueous electrolyte. The Fe₂O₃/FGS//MnO₂/FGS asymmetric supercapacitor shows a high energy density of 50.7 Wh kg^?1 at a power density of 100 W kg^?1 as well as excellent cycling stability and power capability. The facile synthesis method and superior supercapacitive performance of the Fe₂O₃ QDs/FGS composites make them promising as anode materials for high‐performance asymmetric supercapacitors.     

Amorphous FeOOH Quantum Dots Assembled Mesoporous Film Anchored on Graphene Nanosheets with Superior Electrochemical Performance for Supercapacitors

Previous research on iron oxides/hydroxides has focused on the crystalline rather than the amorphous phase, despite that the latter could have superior electrochemical activity due to the disordered structure. In this work, a simple and scalable synthesis route is developed to prepare amorphous FeOOH quantum dots (QDs) and FeOOH QDs/graphene hybrid nanosheets. The hybrid nanosheets possess a unique heterostructure, comprising a continuous mesoporous FeOOH nanofilm tightly anchored on the graphene surface. The amorphous FeOOH/graphene hybrid nanosheets exhibit superior pseudocapacitive performance, which largely outperforms the crystalline iron oxides/hydroxides‐based materials. In the voltage range between ?0.8 and 0 V versus Ag/AgCl, the amorphous FeOOH/graphene composite electrode exhibits a large specific capacitance of about 365 F g^?1, outstanding cycle performance (89.7% capacitance retention after 20 000 cycles), and excellent rate capability (189 F g^?1 at a current density of 128 A g^?1). When the lower cutoff voltage is extended to ?1.0 and ?1.25 V, the specific capacitance of the amorphous FeOOH/graphene composite electrode can be increased to 403 and 1243 F g^?1, respectively, which, however, compromises the rate capability and cycle performance. This work brings new opportunities to design high‐performance electrode materials for supercapacitors, especially for amorphous oxides/hydroxides‐based materials.     

Superior Micro‐Supercapacitors Based on Graphene Quantum Dots

Graphene quantum dots (GQDs) have attracted tremendous research interest due to the unique properties associated with both graphene and quantum dots. Here, a new application of GQDs as ideal electrode materials for supercapacitors is reported. To this end, a GQDs//GQDs symmetric micro‐supercapacitor is prepared using a simple electro‐deposition approach, and its electrochemical properties in aqueous electrolyte and ionic liquid electrolyte are systematically investigated. The results show that the as‐made GQDs micro‐supercapacitor has superior rate capability up to 1000 V s^?1, excellent power response with very short relaxation time constant (τ₀ = 103.6 μs in aqueous electrolyte and τ₀ = 53.8 μs in ionic liquid electrolyte), and excellent cycle stability. Additionally, another GQDs//MnO₂ asymmetric supercapacitor is also built using MnO₂ nanoneedles as the positive electrode and GQDs as the negative electrode in aqueous electrolyte. Its specific capacitance and energy density are both two times higher than those of GQDs//GQDs symmetric micro‐supercapacitor in the same electrolyte. The results presented here may pave the way for a new promising application of GQDs in micropower suppliers and microenergy storage devices.     

Molecular Design of Mesoporous NiCo2O4 and NiCo2S4 with Sub‐Micrometer‐Polyhedron Architectures for Efficient Pseudocapacitive Energy Storage

Spinel‐type NiCo₂O₄ (NCO) and NiCo₂S₄ (NCS) polyhedron architectures with sizes of 500–600 nm and rich mesopores with diameters of 1–2 nm are prepared facilely by the molecular design of Ni and Co into polyhedron‐shaped zeolitic imidazolate frameworks as solid precursors. Both as‐prepared NCO and NCS nanostructures exhibit excellent pseudocapacitance and stability as electrodes in supercapacitors. In particular, the exchange of O^2? in the lattice of NCO with S^2? obviously improves the electrochemical performance. NCS shows a highly attractive capacitance of 1296 F g^?1 at a current density of 1 A g^?1, ultrahigh rate capability with 93.2% capacitance retention at 10 A g^?1, and excellent cycling stability with a capacitance retention of 94.5% after cycling at 1 A g^?1 for 6000 times. The asymmetric supercapacitor with an NCS negative electrode and an active carbon positive electrode delivers a very attractive energy density of 44.8 Wh kg^?1 at power density 794.5 W kg^?1, and a favorable energy density of 37.7 Wh kg^?1 is still achieved at a high power density of 7981.1 W kg^?1. The specific mesoporous polyhedron architecture contributes significantly to the outstanding electrochemical performances of both NCO and NCS for capacitive energy storage.     

In Situ Preparation of Sandwich MoO3/C Hybrid Nanostructures for High‐Rate and Ultralong‐Life Supercapacitors

This work presents a design of sandwich MoO₃/C hybrid nanostructure via calcination of the dodecylamine‐intercalated layered α‐MoO₃, leading to the in situ production of the interlayered graphene layer. The sample with a high degree of graphitization of graphene layer and more interlayered void region exhibits the most outstanding energy storage performance. The obtained material is capable of delivering a high specific capacitance of 331 F g^?1 at a current density of 1 A g^?1 and retained 71% capacitance at 10 A g^?1. In addition, nearly no discharge capacity decay between 1000 and 10 000 continuous charge–discharge cycles is observed at a high current density of 10 A g^?1, indicating an excellent specific capacitance retention ability. The exceptional rate capability endows the electrode with a high energy density of 41.2 W h kg^?1 and a high power density of 12.0 kW kg^?1 simultaneously. The excellent performance is attributed to the sandwich hybrid nanostructure of MoO₃/C with broad ion diffusion pathway, low charge‐transfer resistance, and robust structure at high current density for long‐time cycling. The present work provides an insight into the fabrication of novel electrode materials with both enhanced rate capability and cyclability for potential use in supercapacitor and other energy storage devices.     

Self-Supported Ni<Subscript>0.85</Subscript>Se Nanosheets Array on Carbon Fiber Cloth for a High-Performance Asymmetric Supercapacitor

In this work, Ni_0.85Se nanosheets array electrode material was prepared with carbon fiber cloth (CFC) as a substrate. Owing to their special structure, the Ni_0.85Se nanosheets array exhibits an outstanding energy storage property with a superior specific capacitance (820 F/g) and great rate capability (83.17%). Moreover, the Ni_0.85Se electrode presents an great cycling performance with 82.63% retention after 10,000 cycles. The asymmetric supercapacitor (ASC) was fabricated based on Ni_0.85Se positive and activated carbon (AC) negative electrode materials, with KOH/PVA gel as the electrolyte, respectively. A highest energy density of 29 W h kg^?1 was achieved at a power density of 779 W kg^?1 under the optimal potential range of 1.6 V. Furthermore, the Ni_0.85Se//AC ASC devices demonstrate a great cycling performance of 81.25% capacitance retention after 5000 charge–discharge cycles. These excellent performance provide strong evidence to confirm the conclusion that Ni_0.85Se nanosheets array used as electrode materials in supercapacitors and Ni_0.85Se//AC asymmetric supercapacitors hold significant potential in the field of energy storage.     

Anchoring Hydrous RuO2 on Graphene Sheets for High‐Performance Electrochemical Capacitors

Hydrous ruthenium oxide (RuO₂)/graphene sheet composites (ROGSCs) with different loadings of Ru are prepared by combining sol–gel and low‐temperature annealing processes. The graphene sheets (GSs) are well‐separated by fine RuO₂ particles (5–20 nm) and, simultaneously, the RuO₂ particles are anchored by the richly oxygen‐containing functional groups of reduced, chemically exfoliated GSs onto their surface. Benefits from the combined advantages of GSs and RuO₂ in such a unique structure are that the ROGSC‐based supercapacitors exhibit high specific capacitance (～570 F g^?1 for 38.3 wt% Ru loading), enhanced rate capability, excellent electrochemical stability (～97.9% retention after 1000 cycles), and high energy density (20.1 Wh kg^?1) at low operation rate (100 mA g^?1) or high power density (10000 W kg^?1) at a reasonable energy density (4.3 Wh kg^?1). Interestingly, the total specific capacitance of ROGSCs is higher than the sum of specific capacitances of pure GSs and pure RuO₂ in their relative ratios, which is indicative of a positive synergistic effect of GSs and RuO₂ on the improvement of electrochemical performance. These findings demonstrate the importance and great potential of graphene‐based composites in the development of high‐performance energy‐storage systems.     

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.     

Fabrication of Highly Flexible,Scalable, and High‐Performance Supercapacitors Using Polyaniline/Reduced Graphene Oxide Film with Enhanced Electrical Conductivity and Crystallinity

With developments in technology, tremendous effort has been devoted to produce flexible, scalable, and high‐performance supercapacitor electrode materials. This report presents a novel fabrication method of highly flexible and scalable electrode material for high‐performance supercapacitors using solution‐processed polyaniline (PANI)/reduced graphene oxide (RGO) hybrid film. SEM, TEM, Raman, and XPS analyses show that the PANI/RGO film is successfully synthesized. The percentages of the PANI component in the film are controlled (88, 76, and 60%), and the maximum electrical conductivity (906 S cm^?1) is observed at the PANI percentage of 76%. Notably, electrical conductivity of the PANI/RGO film (906 S cm^?1) is larger than both PANI (580 S cm^?1) and RGO (46.5 S cm^?1) components. XRD analysis demonstrates that the strong π–π interaction between the RGO and the PANI cause more compact packing of the PANI chains by inducing more fully expanded conformation of the PANI chains in the solution, leading to increase in the electrical conductivity and crystallinity of the film. The PANI/RGO film also displays diverse advantages as a scalable and flexible electrode material (e.g., controllable size and great flexibility). During the electrochemical tests, the film exhibits high capacitance of 431 F g^?1 with enhanced cycling stability.     

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.