NH4 + Pre-Intercalation and Mo Doping VS2 to Regulate Nanostructure and Electronic Properties for High Efficiency Sodium Storage.

Sodium-ion hybrid capacitors (SIHCs) have attracted much attention due to integrating the high energy density of battery and high out power of supercapacitors. However, rapid Na+ diffusion kinetics in cathode is counterbalanced with sluggish anode, hindering the further advancement and commercialization of SIHCs. Here, aiming at conversion-type metal sulfide anode, taking typical VS2 as an example, a comprehensive regulation of nanostructure and electronic properties through NH4 + pre-intercalation and Mo-doping VS2 (Mo-NVS2) is reported. It is demonstrated that NH4 + pre-intercalation can enlarge the interplanar spacing and Mo-doping can induce interlayer defects and sulfur vacancies that are favorable to construct new ion transport channels, thus resulting in significantly enhanced Na+ diffusion kinetics and pseudocapacitance. Density functional theory calculations further reveal that the introduction of NH4 + and Mo-doping enhances the electronic conductivity, lowers the diffusion energy barrier of Na+, and produces stronger d-p hybridization to promote conversion kinetics of Na+ intercalation intermediates. Consequently, Mo-NVS2 delivers a record-high reversible capacity of 453 mAh g-1 at 3 A g-1 and an ultra-stable cycle life of over 20 000 cycles. The assembled SIHCs achieve impressive energy density/power density of 98 Wh kg-1/11.84 kW kg-1, ultralong cycling life of over 15000 cycles, and very low self-discharge rate (0.84 mV h-1).

Ultrafast and Durable Sodium-Ion Storage of Pseudocapacitive VN@C Hybrid Nanorods from Metal-Organic Framework.

Vanadium nitride (VN) is a promising electrode material for sodium-ion storage due to its multivalent states and high electrical conductivity. However, its electrochemical performance has not been fully explored and the storage mechanism remains to be clarified up to date. Here, the possibility of VN/carbon hybrid nanorods synthesized from a metal-organic framework for ultrafast and durable sodium-ion storage is demonstrated. The VN/carbon electrode delivers a high specific capacity (352 mA h g-1), fast-charging capability (within 47.5 s), and ultralong cycling stability (10 000 cycles) for sodium-ion storage. In situ XRD characterization and density functional theory (DFT) calculations reveal that surface-redox reactions at vanadium sites are the dominant sodium-ion storage mechanism. An energy-power balanced hybrid capacitor device is verified by assembling the VN/carbon anode and active carbon cathode, and it shows a maximum energy density of 103 Wh kg-1 at a power density of 113 W kg-1.

Nanohybrids of BCN-Fe1-xS for Sodium and Lithium Hybrid Ion Capacitors.

Hybrid ion capacitors (HIC) are receiving a lot of attention due to their potential to achieve high energy and power densities, but they remain insufficient. It is imperative to explore outstanding and environmentally benign electrode materials to achieve high-performing HIC systems. Here, a unique boron carbon nitride (BCN)-based HIC system that comprises a microporous BCN structure and Fe1-xS nanoparticle incorporated BCN nanosheets (BNF) as cathode and anode, respectively is reported. The BNF is prepared through a facile one-pot calcination process using dithiooxamide (DTO), boric acid, and iron source. In situ, crystal growth of Fe1-xS facilitates the formation of BCN structure through the creation of holes/defects in the polymeric structure. The first principle density functional (DFT) theory simulations demonstrate the structural and electronic properties of the hybrid of BCN and Fe1-xS as compelling anode materials for HIC applications. The DFT calculations reveal that both BCN and BNF structures have excellent metallic characters with Li+ storage capacities of 128.4 and 1021.38 mAh g-1 respectively. These findings are confirmed experimentally where the BCN-based HIC system delivers exceptional energy and power densities of 267.5 Wh kg-1/749.5 W kg-1 toward Li+ storage, which outweighs previous HIC performances and demonstrates favorable performance for Li+ and Na+ storages.

Olive Leaves-Derived Hierarchical Porous Carbon as Cathode Material for Anti-Self-Discharge Zinc-Ion Hybrid Capacitor.

As a promising low-cost and high-safety energy storage candidate, zinc-ion hybrid capacitors (ZIHCs) have received extensive attention. For maximizing the advantages of ZIHC with high energy density and high power density, the structural engineering of the porous carbon materials is the crucial and effective strategy. Herein, an oxygen-enriched hierarchical porous carbon has been fabricated from the pyrolysis of olive leaves combing the chemical activation. The abundant interfacial active sites and short ions/electrons transfer length endow the hierarchical porous carbon cathode with high ions adsorption capacity and fast kinetic behaviors. Meanwhile, the oxygen-rich functional groups can provide extra pseudocapacitance and improve the wettability and conductivity of porous carbon. Benefiting from these advantages, an anti-self-discharge ZIHC device with a high energy-power feature has been assembled. The electrochemical process is studied by ex situ X-ray diffraction (XRD) and scanning electron microscope (SEM) methods. Finally, an excellent energy density of 136.3 W h kg-1 , and high power output of 20 kW kg-1 , as well as long cycle life with 91% capacity retention over 20 000 cycles at 10 A g-1 are realized by as-assembled ZIHC.

Understanding the Predominant Potassium-Ion Intercalation Mechanism of Single-Phased Bimetal Oxides by in Situ Magnetometry.

The electrochemical performance of electrode materials is largely dependent on the structural and chemical evolutions during the charge-discharge processes. Hence, revealing ion storage chemistry could enlighten mechanistic understanding and offer guidance for rational design for energy storage materials. Here, we investigate the mechanisms of potassium (K)-ion storage in the promising bimetal oxide materials by in situ magnetometry. We focus on a single-phased hollow FeTiO3 (SPH-FTO) hexagonal prism synthesized through a complexing-reagent assisted approach and find that the K-ion storage in this compound occurs predominantly with an intercalation mechanism and fractionally a conversion mechanism. We also demonstrate a K-ion hybrid capacitor assembled with the prepared SPH-FTO hexagonal prism anode and activated carbon cathode, delivering a high energy density and high power density as well as extraordinary cycling stability. This new understanding is used to showcase the inherently high K-ion storage properties from the earth-abundant FeTiO3.

Improved Interfacial Ion Migration and Deposition through the Chain-Liquid Synergistic Effect by a Carboxylated Hydrogel Electrolyte for Stable Zinc Metal Anodes.

The large-scale applicability of Zn-metal anodes is severely impeded by the issues such as the dendrite growth, complicated hydrogen evolution, and uncontrollable passivation reaction. Herein, a negatively charged carboxylated double-network hydrogel electrolyte (Gelatin/Sodium alginate-acetate, denoted as Gel/SA-acetate) has been developed to stabilize the interfacial electrochemistry, which restructures a type of Zn2+ ion solvent sheath optimized via a chain-liquid synergistic effect. New hydrogen bonds are reconstructed with water molecules by the zincophilic functional groups, and directional migration of hydrated Zn2+ ions is therefore induced. Concomitantly, the robust chemical bonding of such hydrogel layers to the Zn slab exhibits a desirable anti-catalytic effect, thereby greatly diminishing the water activity and eliminating side reactions. Subsequently, a symmetric cell using the Gel/SA-acetate electrolyte demonstrates a reversible plating/stripping performance for 1580 h, and an asymmetric cell reaches a state-of-the-art runtime of 5600 h with a high average Coulombic efficiency of 99.9 %. The resultant zinc ion hybrid capacitors deliver exceptional properties including the capacity retention of 98.5 % over 15000 cycles, energy density of 236.8 Wh kg-1 , and high mechanical adaptability. This work is expected to pave a new avenue for the development of novel hydrogel electrolytes towards safe and stable Zn anodes.

Toward Flexible Zinc-Ion Hybrid Capacitors with Superhigh Energy Density and Ultralong Cycling Life: The Pivotal Role of ZnCl2 Salt-Based Electrolytes.

Zinc ion hybrid capacitors (ZIHCs) are promising energy storage devices for emerging flexible electronics, but they still suffer from trade-off in energy density and cycling life. Herein, we show that such a dilemma can be well-addressed by deploying ZnCl2 based electrolytes. Combining experimental studies and density functional theory (DFT) calculations, for the first time, we demonstrate an intriguing chloride ion (Cl- ) facilitated desolvation mechanism in hydrated [ZnCl]+ (H2 O)n-1 (with n=1-6) clusters. Based on this mechanism, a water-in-salt type hydrogel electrolyte filled with ZnCl2 was developed to concurrently improve the energy storage capacity of porous carbon materials and the reversibility of Zn metal electrode. The resulting ZIHCs deliver a battery-level energy density up to 217 Wh kg-1 at a power density of 450 W kg-1 , an unprecedented cycling life of 100 000 cycles, together with excellent low-temperature adaptability and mechanical flexibility.

Maximization of Spatial Charge Density: An Approach to Ultrahigh Energy Density of Capacitive Charge Storage.

Capacitive energy storage has advantages of high power density, long lifespan, and good safety, but is restricted by low energy density. Inspired by the charge storage mechanism of batteries, a spatial charge density (SCD) maximization strategy is developed to compensate this shortage by densely and neatly packing ionic charges in capacitive materials. A record high SCD (ca. 550 C cm-3 ) was achieved by balancing the valance and size of charge-carrier ions and matching the ion sizes with the pore structure of electrode materials, nearly five times higher than those of conventional ones (ca. 120 C cm-3 ). The maximization of SCD was confirmed by Monte Carlo calculations, molecular dynamics simulations, and in situ electrochemical Raman spectroscopy. A full-cell supercapacitor was further constructed; it delivers an ultrahigh energy density of 165 Wh L-1 at a power density of 150 WL-1 and retains 120 Wh L-1 even at 36 kW L-1 , opening a pathway towards high-energy-density capacitive energy storage.

Zinc Ion Hybrid Capacitors: Four Essential Parameters Determining Device Energy Density.

Zinc ion hybrid capacitors (ZIHCs) with Zn metal faradic and carbon capacitive electrodes have potential applications in grid-scale energy storage systems and wearable devices. However, the high specific energy density reported in many recent studies is based on the mass of active carbon materials alone, with deficient device energy density. This perspective article discusses how four crucial parameters influence the device energy density of ZIHCs, including areal mass loading (mc) and specific capacity (Qg,c) of active carbon materials in cathodes, negative-to-positive electrode capacity ratio (N/P), and electrolyte-to-active carbon materials mass ratio (E/C). Using a representative device model, how the device energy density varies when these four parameters change is shown. Detailed analysis indicates that specific parameter windows with the four parameters within narrow ranges (e.g., mc = 10-20 mg cm-2, Qg,c > 100 mAh g-1, N/P < 20, and E/C < 5) need to be achieved simultaneously to deliver application-relevant energy density (e.g., >30 Wh kg-1) in ZIHCs. It is hoped that these findings assist in objectively evaluating reported performance data and identifying essential issues for future research development to realize practical applications.

Synthesis of Porous Carbon Honeycomb Structures Derived from Hemp for Hybrid Supercapacitors with Improved Electrochemistry.

Energy storage in electrochemical hybrid capacitors involves fast faradaic reactions such as an intercalation, or redox process occurring at a solid electrode surface at an appropriate potential. Hybrid sodium-ion electrochemical capacitors bring the advantages of both the high specific power of capacitors and the high specific energy of batteries, where activated carbon serves as a critical electrode material. The charge storage in activated carbon arises from an adsorption process rather than a redox reaction and is an electrical double-layer capacitor. Advanced carbon materials with interconnecting porous structures possessing high surface area and high conductivity are the prerequisites 1128to qualify for efficient energy storage. Herein, we have demonstrated that a porous honeycomb structure activated carbon derived from Australian hemp hurd (Cannabis sativa L.) in aqueous Na2SO4 electrolyte showed a specific capacitance of 240 F/g at 1 A/g. The mass ratio of biochar to KOH during the chemical activation associated with the synthesis temperature influences the change in morphologies, and distribution of pore sizes on the adsorption of ions. At higher synthesis temperatures, the tubular form of the honeycomb starts to disintegrate. The hybrid sodium-ion device employing hemp-derived activated carbon (HAC) coupled with electrolytic manganese dioxide (EMD) in an aqueous Na2SO4 electrolyte showed a specific capacitance of 95 F/g at 1 A/g having a capacitance retention of 90 %. The hybrid device (HAC||EMD) can possess excellent electrochemical performance metrics, having a high energy density of 38 Wh/kg at a power density of 761 W/kg. Overall, this study provides insights into the influence of the activation temperature and the KOH impregnation ratio on morphology, porosity distribution, and the activated carbon's electrochemical properties with faster kinetics. The high cell voltage for the device is devoted to the EMD electrode.

Dual cross-linked cellulose-based hydrogel for dendrites-inhibited flexible zinc-ion energy storage devices with ultra-long cycles and high energy density.

Hydrogel electrolytes, renowned for their mechanical robustness and versatility, are crucial in ensuring stable energy output in flexible energy storage devices. This work presents a dual cross-linked cellulose-based hydrogel electrolyte with chemical cross-linking from covalent bonding and physical cross-linking from hydrogen bonding. This electrolyte demonstrated outstanding mechanical strength and porous structure with abundant hydroxyl groups, which facilitates the migration of Zn2+ and suppresses the formation of undesirable zinc dendrite, thereby enhancing the ion conductivity (18.46 ± 0.39 mS cm-1 at room temperature) and extending electrochemical stability window (0-2.23 V). Zn||Zn symmetric cells based on this electrolyte demonstrated stable stripping/plating cycles of 3000 h at a current density of 1 mA cm-2. Furthermore, the corresponding flexible zinc-ion hybrid capacitor retains a 90.3 % capacity over 100,000 cycles at 10 A g-1, while remaining functional across various folding angles. Hence, this biomass-derived hydrogel electrolyte holds promise for flexible energy storage device applications.

2D heterostructural Mn2O3 quantum dots embedded N-doped carbon nanosheets with strongly stable interface enabling high-performance sodium-ion hybrid capacitors.

The ingenious architectural structural engineering is extensively identified as a cogent means for facilitating the electrochemical properties of conversion-type anode materials for sodium-ion storage. Herein, a delicate, scalable and controllable solvent-free strategy is proposed to synthesize ultrafine Mn2O3 quantum dots embedded into N-doped carbon to generate two-dimensional (2D) composites (MNC) with robust interfacial heterostructural interactions for high sodium ion storage and fast reaction kinetics, which averts the use of solvents and environmental pollution, greatly reduces time and production costs. The introduction of metallic Mn species simultaneously achieves the construction of ultrafine Mn2O3 quantum dots and strong interfacial heterostructural COMn bonds between metal species and 2D N-doped carbon matrix. The synergistic effect of the formation of oxide quantum dots, the combination of 2D N-doped carbon and the construction of robust interfacial interactions provides the stable electrode structure, fast reaction kinetics and high electrochemical storage capability of anode materials. Hence, MNC composites in SIBs convey remarkable reversible rate capability. Its superior capacity reaches 215 mAh g-1 for 50 cycles at 0.2 A g-1 and 155 mAh g-1 for 1000 cycles at a high current density of 5 A g-1, which shows good long-term stability. The assembled sodium-ion hybrid capacitors (SIHCs) device delivers outstanding energy density of 138 Wh kg-1 at a power density of 126 W kg-1 and 98% capacity retention after 2000 cycles at 2 A g-1, and tremendous capability for practical applications (69 LEDs can be easily lighted). This work not merely offers guidance for the rational interfacial engineering design of high-capacity Mn-based electrode materials in a feasible and scalable solvent-free tactics for Na+ storage, but also broadens the routes for projecting a better electrode material for other battery systems.

Hydrogen-bonded micelle assembly directed conjugated microporous polymers for nanospherical carbon frameworks towards dual-ion capacitors.

Well-orchestrated carbon nanostructure with superb stable framework and high surface accessibility is crucial for zinc-ion hybrid capacitors (ZIHCs). Herein, a hydrogen-bonded micelle self-assembly strategy is proposed for morphology-controllable synthesis of conjugated microporous polymers (CMPs) derived carbon to boost zinc ion storage capability. In the strategy, F127 micellar assembly through intermolecular hydrogen bonds serves as structure-directed agents, directing CMPs' oligomers grow into nanospherical assembly. The nanospherical carbon frameworks derived from CMPs (CNS-2) have shown maximized surface accessibility due to their plentiful tunable porosity and hierarchical porous structure with abundant mesoporous interconnected channels, and superb stability originating from CMPs' robust framework, thus the CNS-2-based ZIHCs exhibit ultrahigh energy density of 163 Wh kg-1 and ultralong lifespan with 93 % capacity retention after 200, 000 cycles at 20 A g-1. Charged ion storage efficiency also lies in dual-ion alternate uptake of Zn2+ and CF3SO3- as well as chemical redox of Zn2+ with carbonyl/pyridine motifs forming O-Zn-N bonds. Maximized surface accessibility and dual-ion storage mechanism ensure excellent electrochemical performance. Thus, the hydrogen-bond-guide micelle self-assembly strategy has provided a facile way to design nanoarchitectures of CMPs derived carbon for advanced cathodes of ZIHCs.

Effect of Sodium Phosphate Coating on Cu and Mg-Substituted P2-Na0.67Ni0.33Mn0.67O2 for Improving the Cycling Performance of Sodium-Ion Capacitors.

Sodium-ion capacitors (SICs) bridge the performance gaps between batteries and supercapacitors by providing a high energy and power density in a single configuration. As battery-type active materials, sodium preintercalated layered metal oxides are desirable owing to their unique crystal structure, simple synthesis process, and high working voltage. However, their poor cyclic stability and low kinetics limit their application. Herein, we report increased rate capability and cycle stability achieved by introducing transition metal substitution and surface coating strategies. By substituting a portion of Ni and Mn with Cu and Mg (the sample name was denoted as NMCM), the P2-O2 transition which occurs at high voltages was alleviated. Additionally, a thin and uniform sodium phosphate coating layer suppressed surface side reactions occurring during charge-discharge processes, as observed through ex-situ X-ray photoelectron spectroscopy and ex-situ transmission electron microscopy. Compared to the pristine sample, the capacity improved by 48% at a high current density of 4 A g-1. After 100 cycles, the sodium-phosphate-coated sample (NMCM@P) retained about 90% of its capacity, whereas NMCM had a capacity retention of 63%. When evaluating the longer stability of SIC full cells, NMCM@P exhibited an outstanding stability of 71% after 5000 cycles. This was higher than that of NMCM, which retained only 17% of its initial capacity.

Rational design of activated graphitic carbon spheres with optimized ion and electron transfer channels for zinc-ion hybrid capacitors.

Herein, three-dimensional activated graphitic carbon spheres (AGCS) were constructed by simultaneous activation-graphitization of Fe-tannic acid coordination spheres with the assistance of KOH. Nanosheets-assembled AGCS with complex intersecting channel system can expose more active sites for charge storage. Simultaneous activation-graphitization can relieve trade-off relationship between porosity and conductivity of carbon materials. Benefiting from multiple synergistic effects of large specific surface area (2069 m2 g-1), abundant ion-accessible micropores (>0.78 nm), good electronic conductivity (IG/ID = 1.11), and moderate amount of oxygen doping, the optimized AGCS-2 has favored ion and electron transfer channels. AGCS-2 based zinc-ion hybrid capacitor (ZIHC) displays a high specific capacity of 148.6 mA h g-1 (334 F g-1) at 0.5 A g-1, a remarkable energy density of 119.0 W h kg-1 at 1440 W kg-1, and superior cycling life with 96% capacity retention after 10,000 cycles. This simultaneous activation-graphitization strategy may open up a new avenue to design novel carbon spheres linking optimal pores and graphitic carbon structure for ZIHC application.

Molten Salt-Assisted Construction of Hollow Carbon Spheres with Outer-Order and Inner-Disorder Heterostructure for Ultra-Stable Potassium Ion Storage.

The central goal of high-performance potassium ion storage is to control the function of the anode material via rational structural design. Herein, N- and S-doped hollow carbon spheres with outer-short-range-order and inner-disorder structures are constructed to achieve highly efficient and ultra-stable potassium ion storage using a low-temperature molten salt system. The ultrathin carbon walls and uniform mesoporous as well as unique heterostructure synergistically realize significant potassium storage performance via facilitating rapid diffusion of potassium ions and alleviating substantial volume expansion. Furthermore, as the anode of a potassium ion battery, the as-prepared MSTC electrode demonstrates a state-of-the-art cycling capability of 221.3 mAh g-1 at 1 A g-1 after 20,000 cycles. The assembled potassium ion hybrid capacitor device demonstrates a high energy of 157 Wh kg-1 at 956 W kg-1 and excellent reversibility at a current density of 5.0 A g-1 after 20,000 cycles with 82.7% capacity retention. Accordingly, our work provides new ideas for designing advanced carbon anode materials and understanding the charge storage mechanism in potassium ion battery, as well as constructing high energy-power density potassium-ion hybrid capacitors (PIHCs).

Agricultural waste to real worth biochar as a sustainable material for supercapacitor.

Biochar made from agricultural waste is gaining more attention in energy field due to its sustainability, low cost, apart from having high supercapacitance performance. Also, it has a wide range of environmental applications, including wastewater treatment, upgrading soil fertility, contaminant immobilization, and in situ carbon sequestration. The existing thermo-chemical methodologies for converting agricultural waste into a sustainable material i.e. biochar and the role of activation agents in enhancing the performance of these materials were critically analyzed and discussed. An overview of recent trends in agricultural waste-derived biochar for supercapacitor electrodes is highlighted in this review that emphasizes green circular economy for encouraging net-zero utility of agriculture waste biomass. The roles of various newly prepared "green" electrolytes in reducing the negative consequences of supercapacitor is also reviewed. The trashing of agricultural waste and the depletion of energy supplies has become a global concern, hurting the world's ecosystem and economy through pollution and a fuel crisis and hence the concept of a green circular economic model is also highlighted.

Concave Ni(OH)2 Nanocube Synthesis and Its Application in High-Performance Hybrid Capacitors.

The controlled synthesis of hollow structure transition metal compounds has long been a very interesting and significant research topic in the energy storage and conversion fields. Herein, an ultrasound-assisted chemical etching strategy is proposed for fabricating concave Ni(OH)2 nanocubes. The morphology and composition evolution of the concave Ni(OH)2 nanocubes suggest a possible formation mechanism. The as-synthesized Ni(OH)2 nanostructures used as supercapacitor electrode materials exhibit high specific capacitance (1624 F g-1 at 2 A g-1) and excellent cycling stability (77% retention after 4000 cycles) due to their large specific surface area and open pathway. In addition, the corresponding hybrid capacitor (Ni(OH)2//graphene) demonstrates high energy density (42.9 Wh kg-1 at a power density of 800 W kg-1) and long cycle life (78% retention after 4000 cycles at 5 A g-1). This work offers a simple and economic approach for obtaining concave Ni(OH)2 nanocubes for energy storage and conversion.

Homogeneous activation induced by bacterial cellulose nanofibers to construct interconnected microporous carbons for enhanced capacitive storage.

Porous carbons have been widely applied for capacitive energy storage, yet usually suffer from insufficient rate performance because of the sluggish ion transport kinetics in deep and multi-branched pores. Herein, we fabricated an interconnected microporous capacitive carbon (IMCC) by growing D (+)-glucosamine on bacterial cellulose (BC) nanofibers scaffold, followed by carbonization and activation. The BC nanofibers acted as a sacrificial template during pre-carbonization, facilitating the subsequent KOH permeation and homogeneous activation. By taking advantage of the interconnected microporous structure, the IMCC delivers a high capacitance of 302 F g-1 at 1 A g-1 and an excellent rate capability of 165 F g-1 at 100 A g-1 for aqueous supercapacitor, demonstrating its fast ion transport capability. Impressively, it also shows a superior gravimetric capacity of 177 mAh g-1 at 0.5 A g-1 and remains a high value of 72 mAh g-1 at 20 A g-1 as a cathode material for Zn-ion hybrid capacitor. This facile and cost-effective design strategy exhibits a great potential to construct carbohydrates-derived interconnected microporous carbon materials for high-rate energy storage.

Solvent-Free Synthesis of Polymer Spheres and the Activation to Porous Carbon Spheres for Advanced Aluminum-Ion Hybrid Capacitors.

Porous carbon spheres (PCSs) characteristic of perfect symmetry and ideal rheological property have great potential in electrochemical energy storage (EES). However, conventional synthesis of PCSs heavily relies on solution-based methods that may lead to environmental issues. Herein, an environment-friendly solvent-free method toward the facile and mass production of m-phenylenediamine-formaldehyde (MPF) resin spheres, which can be converted into PCSs after carbonization and activation is reported. An ultrahigh productivity of 25.89 g in a 100-mL container and an impressive percent yield of 98.89% can be achieved for the MPF resin spheres, which are further converted into carbon spheres with a reasonable yield of 14.5% after carbonization. When employed as the cathode material for aluminum-ion hybrid capacitors, the obtained PCSs afford a double-layer capacity of ≈200 mAh g-1 , the highest value among reported porous carbon materials for Al-based EES devices. It is anticipated that the solvent-free synthesis method for PCSs developed here may play a significant role in other EES devices, such as magnesium-ion and calcium-ion hybrid capacitors.