Flexible Carbon Dots-Intercalated MXene Film Electrode with Outstanding Volumetric Performance for Supercapacitors

2D MXenes have emerged as promising supercapacitor electrode materials due to their metallic conductivity, pseudo-capacitive mechanism, and high density. However, layer-restacking is a bottleneck that restrains their ionic kinetics and active site exposure. Herein, a carbon dots-intercalated strategy is proposed to fabricate flexible MXene film electrodes with both large ion-accessible active surfaces and high density through gelation of calcium alginate (CA) within the MXene nanosheets followed by carbonization. The formation of CA hydrogel within the MXene nanosheets accompanied by evaporative drying endow the MXene/CA film with high density. In the carbonization process, the CA-derived carbon dots can intercalate into the MXene nanosheets, increasing the interlayer spacing and promoting the electrolytic diffusion inside the MXene film. Consequently, the carbon dots-intercalated MXene films exhibit high volumetric capacitance (1244.6 F cm⁻³ at 1 A g⁻¹), superior rate capability (662.5 F cm⁻³ at 1000 A g⁻¹), and excellent cycling stability (93.5% capacitance retention after 30 000 cycles) in 3 m H₂SO₄. Additionally, an all-solid-state symmetric supercapacitor based on the carbon dots-intercalated MXene film achieves a high volumetric energy density of 27.2 Wh L⁻¹. This study provides a simple yet efficient strategy to construct high-volumetric performance MXene film electrodes for advanced supercapacitors.     

3D Printed Nanocarbon Frameworks for Li-Ion Battery Cathodes

The use of conductive carbon materials in 3D-printing is attracting growing academic and industrial attention in electrochemical energy storage due to the high customization and on-demand capabilities of the additive manufacturing. However, typical polymers used in conductive filaments for 3D printing show high resistivity and low compatibility with electrochemical energy applications. Removal of insulating thermoplastics in as-printed materials is a common post-printing strategy, however, excessive loss of thermoplastics can weaken the structural integrity. This work reports a two-step surface engineering methodology for fabrication of 3D-printed carbon materials for electrochemical applications, incorporating conductive poly(ortho-phenylenediamine) (PoPD) via electrodeposition. A conductive PoPD effectively enhances the electrochemical activities of 3D-printed frameworks. When PoPD-refilled frameworks casted with LiMn₂O₄ (LMO) composite materials used as battery cathode, it delivers a capacity of 69.1 mAh g⁻¹ at a current density of 0.036 mA cm⁻² ( ≈ 1.2 C discharge rate) and good cyclability with a retained capacity of 84.4% after 200 cycles at 0.36 mA cm⁻². This work provides a pathway for developing electroactive 3D-printed electrodes particularly with cost-efficient low-dimensional carbon materials for aqueous rechargeable Li-ion batteries.     

Layered Double Hydroxide with Interlayer Quantum Dots and Laminate Defects for High-Performance Supercapacitor

Owing to the flexible adjustability of laminates, layered double hydroxides (LDHs) can achieve enhanced conductivity and capacitance. However, the regulation of interlayer activity is a great challenge because of the unconquerable charge repulsion between laminates. Herein, a dual-activity design of LDHs is uniquely realized, including laminate defects and interlayer ZnS quantum dots (QDs). Via pre-embedding Zn2+ and controllable vulcanization, ZnS-QDs interpenetrate between CuCo-LDH layers, exposing abundant active sites and widening the layer spacing. Meanwhile, sulfur replaces part of the oxygen on the laminates to form rich oxygen vacancies (CuCo-LDH-S), which does not damage the layered spatial structure and ensures the fast ions/electron transport. Theoretical calculations indicate that the new active centers exhibit higher charge density as compared to CuCo-LDH. Moreover, the copper foam directly provides copper source to ensure that CuCo-LDH-S/ZnS-QDs present a 3D self-supporting structure with ultrastability. Hence, it delivers an ultrahigh capacitance of 7.82 F cm⁻² at 2 mA cm⁻² and 4.43 F cm⁻² at 20 mA cm⁻². The hybrid supercapacitors display an outstanding energy density of 299 µWh cm⁻² at power density of 1600 µW cm⁻², with outstanding capacitance retention of 102.3% and coulomb efficiency of 96.2% after 10 000 cycles.     

Interface Engineering of Biomass-Derived Carbon used as Ultrahigh-Energy-Density and Practical Mass-Loading Supercapacitor Electrodes

The development of flexible electrodes with high mass loading and efficient electron/ion transport is of great significance but still remains the challenge of innovating suitable electrode structures for high energy density application. Herein, for the first time, lignosulfonate-derived N/S-co-doped graphene-like carbon is in situ formed within an interface engineered cellulose textile through a sacrificial template method. Both experimental and theoretical calculations disclose that the formed pomegranate-like structure with continuous conductive pathways and porous characteristics allows sufficient ion/electron transport throughout the entire structures. As a result, the obtained flexible electrode delivers a remarkable integrated capacitance of 6534 mF cm⁻² (335.1 F g⁻¹) and a superior stability at an industrially applicable mass loading of 19.5 mg cm⁻². A pseudocapacitive cathode with ultrahigh capacitance of 7000 mF cm⁻² can also be obtained based on the same electrode structure engineering. The as-assembled asymmetric supercapacitor achieves a high areal capacitance of 3625 mF cm⁻², and a maximum energy density of 1.06 mWh cm⁻², outperforms most of other reported high-loading supercapacitors. This synthesis method and structural engineering strategy can provide materials design concepts and a wide range of applications in the fields of energy storage beyond supercapacitors.     

High Power and Energy Density Aqueous Proton Battery Operated at −90 °C

Freezing electrolyte and sluggish ionic migration kinetics limited the low-temperature performance of rechargeable batteries. Here, an aqueous proton battery is developed, which achieves both high power density and energy density at the ultralow temperature conditions. Electrolyte including 2 m HBF₄  +  2 m Mn(BF₄)₂ is used for the ultralow freezing point of below − 160  ° C and high ionic conductivity of 0.21 mS cm⁻¹ at − 70  ° C. Spectroscopic and nuclear magnetic resonance analysis demonstrate the introduction of BF₄⁻ anions efficiently break the hydrogen-bond networks of original water molecules, resulting in ultralow freezing point. Based on H⁺ uptake/removal reaction in alloxazine (ALO) anode and MnO₂/Mn²⁺ conversion in carbon felt cathode, the aqueous proton battery can operate regularly even at − 90  ° C and obtain a high specific discharge capacity of 85 mA h g⁻¹. Benefiting from the rapid diffusion of proton and the pseudocapacitive character of ALO electrolyte, this battery shows a high specific energy density of 110 Wh kg⁻¹ at a specific power density of 1650 W kg⁻¹ at − 60  ° C. This work presents a new way of developing low-temperature batteries.     

Hierarchical Integrated Hybrid Structural Electrodes Based on Co-N/C and Mo-doped NiCo-LDH@Co-N/C Anchored on MX/CF for High Energy Density Fiber-Shaped Supercapacitor

The judicious design of highly electrochemically active materials on 1D fiber substrate to form a hierarchical integrated hybrid structure is an efficient technique to improve the limited cylindrical space and volumetric energy density of fiber-shaped supercapacitors (FSCs). Herein, a 3D negative electrode, consisting of vertically aligned interconnected mesoporous Co-N/C leaf-like structure on 1D MXene-carbon fiber (Co-N/C@MX/CF) is prepared by controlling the composition and morphology. At the same time, a 3D positive electrode is also prepared by introducing Mo in NiCo-LDH anchored on Co-N/C@MX/CF (Mo-NiCo-LDH@Co-N/C@MX/CF) by electrodeposition method. Benefitting from the systematic hierarchical structures with highly accessible surface area, adequate pore size and easy permeation of electrolyte, both positive and negative electrodes demonstrate highly improved electrochemical performance with areal capacity/capacitance of 0.96 mAh cm⁻²/4.55 mF cm⁻² at a current density of 3.86 mA cm⁻², respectively. Furthermore, the fiber-shaped solid-state hybrid supercapacitor (FSHSC) based on Mo_1.5NiCo-LDH@Co-N/C@MX/CF(+)//Co-N/C_0.5@MX/CF(−) is fabricated, exhibiting compelling energy density of 86.72 mWh cm⁻³ at a power density of 480.30 mW cm⁻³ with an outstanding capacitance retention of 80.2% after 20000 galvanostatic-charge-discharge cycles. This study puts forward a new perspective on the development of highly efficient FSCs for practical application.     

Mo-/Co-N-C Hybrid Nanosheets Oriented on Hierarchical Nanoporous Cu as Versatile Electrocatalysts for Efficient Water Splitting

Designing robust and cost-effective electrocatalysts based on Earth-abundant elements is crucial for large-scale hydrogen production through electrochemical water splitting. Here, nitrogen-doped carbon engrafted Mo₂N/CoN hybrid nanosheets that are seamlessly oriented on hierarchical nanoporous Cu scaffold (Mo-/Co-N-C/Cu), as highly efficient electrocatalysts for alkaline hydrogen evolution reaction are reported. The constituent heterostructured Mo₂N/CoN nanosheets work as bifunctional electroactive sites for both water dissociation and adsorption/desorption of hydrogen intermediates while the nitrogen-doped carbon bridges electron transfers between electroactive sites and interconnective Cu current collectors by making use of Mo-/Co-N-C bonds and intimate C/Cu contacts at interfaces. As a consequence of unique architecture having electroactive sites to be sufficiently accessible, self-supported nanoporous Mo-/Co-N-C/Cu hybrid electrodes exhibit outstanding electrocatalysis in 1 m KOH, with a negligible onset overpotential and a low Tafel slope of 47 mV dec⁻¹. They only take overpotential of as low as 230 mV to reach current density of 1000 mA cm⁻². When coupled with their electro-oxidized derivatives that mediate efficiently the oxygen evolution reaction, the alkaline water electrolyzer can achieve ≈100 mA cm⁻² at 1.622 V in 1 m KOH electrolyte, ≈0.343 V lower than the device constructed with commercially available Pt/C and Ir/C nanocatalysts immobilized on nanoporous Cu electrodes.     

Pyrolysis of Enzymolysis-Treated Wood: Hierarchically Assembled Porous Carbon Electrode for Advanced Energy Storage Devices

Designing energy storage devices from thick carbon electrodes with high areal/volumetric energy density via a simple and green way is very attractive but still challenging. Cellulose, as an excellent precursor for thick carbon electrodes with abundant sources and low cost, is usually activated by a chemical activator and pyrolysis route to achieve high electrochemical performance. However, there are still some problems to be addressed, such as the harsh activation conditions, easy collapse of porous structures, and the high cost. Herein, a 3D self-supporting thick carbon electrode derived from wood-based cellulose is proposed for high areal and volumetric energy density of supercapacitor from a mild, simple, and green enzymolysis treatment. Benefiting from the high specific surface area (1418 m² g⁻¹) and abundant active sites on the surface of wood-derived hierarchically porous structures and enzymolysis-induced micropores and mesopores, the assembled symmetry supercapacitor from the thick carbon electrode can realize the high areal/volumetric energy density of 0.21 mWh cm⁻²/0.99 mWh cm⁻³ with excellent stability of 86.58% after 15 000 long-term cycles at 20 mA cm⁻². Significantly, the simple and universal strategy to design material with high specific surface area, provides a new research idea for realizing multi-functional application.     

Ultrahigh-Areal Capacitance Flexible Supercapacitors Based on Laser Assisted Construction of Hierarchical Aligned Carbon Nanotubes

Electrochemical energy storage is a key technology for a clean and sustainable energy supply. In this respect, supercapacitors (SC) have recently received considerable attention due to their excellent performance, including high-power density and long-cycle life. However, the poor binding strength between the active materials and substrate, the low active material loading, and small specific capacitance hinder the overall performance improvement of the device. In this study, an ultrahigh-areal capacitance flexible SC based on the Al micro grid-based hierarchical vertically aligned carbon nanotubes (VACNTs) is studied. Interestingly, the Al micro grid-based VACNTs exhibit ultrahigh loading (13 mg cm⁻²), and the as-fabricated VACNTs electrode display outstanding electrochemical performance, including an impressive areal capacitance of 1,300 mF cm⁻² at the current density of 13 mA cm⁻² and excellent stability with a retention ratio of 90% after 20,000 cycles at the current density of 130 mA cm⁻². Furthermore, the hierarchical VACNT electrodes show excellent mechanical flexibility when assembled into quasi-solid-state SC using Na₂SO₄-PVA gel as the electrolyte. The capacitance of this device is hardly changed bending different angles, even 180°. This study demonstrates the tremendous potential of Al micro grid-based hierarchical VACNTs as electrodes for high-performance flexible and wearable energy storage devices.     

A highly flexible solid-state supercapacitor based on the carbon nanotube doped graphene oxide/polypyrrole composites with superior electrochemical performances

Flexible electrodes of ternary composites, in which highly conductive carbon nanotube films (CNFs) are coated with carbon nanotube-doped graphene oxide/polypyrrole (CNT-GO/PPy), have been fabricated via facile electrochemical synthesis. Long and short CNTs are separately doped into the composites (lCNT-GO/PPy and sCNT-GO/PPy) and their electrochemical performances are compared. Electrochemical measurements indicate that the doping of CNTs in the composites significantly improves the electrochemical behaviors of the GO/PPy electrodes. Notably, the lCNT-GO/PPy electrodes show superior electrochemical properties with respect to the sCNT-GO/PPy electrodes, which is related to the introduction of abundant CNTs in the former electrodes and their special microstructures. Two symmetric electrodes with the lCNT-GO/PPy composites coated on CNFs are assembled to fabricate a solid-state supercapacitor device, which features lightweight, ultrathinness, and high flexibility. The device achieves a high areal and volumetric specific capacitance of 70.0 mF cm⁻² at 10 mV s⁻¹ and 6.3 F cm⁻³ at 0.043 A cm⁻³, respectively. It also shows superior rate performance and cycle stability, with a capacitance retention rate of 87.7% for 10,000 cycles. The supercapacitor device fabricated is promising for the use in lightweight and flexible integrated electronics.     

A Kinetic Control Strategy for One-Pot Synthesis of Efficient Bimetallic Metal-Organic Framework/Layered Double Hydroxide Heterojunction Oxygen Evolution Electrocatalysts

Heterojunction materials are promising candidates for oxygen evolution reaction (OER) electrocatalysts to break the linear scaling relationship and lower the reaction barrier. However, the application of heterojunction materials is always hindered by the complicated multistep synthetic procedures which bring cost, complexity, and reproducibility issues. Herein, a strategy of kinetic controlled synthesis is developed to achieve the one-pot formation of bimetallic metal-organic framework (MOF)/layered double hydroxide (LDH) heterojunction electrodes as highly efficient OER electrocatalysts. The heterojunction electrodes present hierarchical structures with highly porous NiFe-LDH nanosheet networks vertically grown on the surface of NiFe-MOF-74 microprisms, promoting fast mass transport and high exposure of active sites. The strong interactions at the MOF/LDH heterojunction interfaces contribute to the outstanding OER activity surpassing the state-of-art RuO₂ OER catalysts. The MOF/LDH heterojunction electrode exhibits an ultralow overpotential of only 159.7 mV to reach the current density of 10 mA cm⁻², and yields large current densities at small overpotential (100 mA cm⁻² at 230.2 mV and 1000 mA cm⁻² at 284.3 mV) with long-term durability. This study presents an innovative approach to construct heterojunction materials with simple one-step synthesis, offering a promising pathway for high-efficiency electrocatalyst development.     

Floating Catalyst Chemical Vapor Deposition Patterning Nitrogen-Doped Single-Walled Carbon Nanotubes for Shape Tailorable and Flexible Micro-Supercapacitors

Micro-supercapacitors (MSCs) as high-power density energy storage units are designed to meet the booming development of flexible electronics, requiring simple and fast fabrication technology. Herein, a fast and direct solvent-free patterning method is reported to fabricate shape-tailorable and flexible MSCs by floating catalyst chemical vapor deposition (FCCVD). The nitrogen-doped single-walled carbon nanotubes (N-SWCNTs) are directly deposited on a patterned filter by FCCVD with designable patterns and facilely dry-transferred on versatile substrates. The obtained MSCs deliver an excellent areal capacitance of 3.6 mF cm⁻² and volumetric capacitance of 98.6 F cm⁻³ at a scan rate of 5 mV s⁻¹ along with excellent long-term cycle stability over 125 000 circles. Furthermore, the MSCs show good performance uniformity, which can be readily integrated via connection in parallel or series to deliver a stable high voltage (4 V with five serially connected devices) and large capacitance (5.1 mF with five parallel devices) at a scan rate of 100 mV s⁻¹, enabling powering the light emitting displays. Therefore, this method blazes the trail of directly preparing flexible, shape-customizable, and high-performance MSCs.     

Efficient Water Splitting System Enabled by Multifunctional Platinum-Free Electrocatalysts

Tremendous research efforts have been focused on the development of a water splitting system (WSS) to harvest hydrogen fuels, but currently available WSSs are complicated and cost-ineffective mainly due to the applications of noble platinum or different electrocatalysts. Herein, a novel WSS comprising electricity generation from solar panels, electricity storage in rechargeable zinc–air batteries (ZABs), and water splitting in electrolyzers, enabled by hybrid cobalt nanoparticles/N-doped carbon embellished on carbon cloth (Co–NC@CC) as multifunctional platinum-free electrocatalysts is reported. Consequently, the Co–NC@CC electrode presents excellent trifunctional electrocatalytic activity with an onset potential of 0.94 V for oxygen reduction reaction, and an overpotential of 240 and 73 mV to achieve a current density of 10 mA cm⁻² for oxygen and hydrogen evolution reactions, respectively. For a proof-of-concept application, a rechargeable ZAB assembled from the high-performance Co–NC@CC air cathode exhibits a high open circuit potential of 1.63 V and a superior energy density of 1051 Wh kg⁻¹_Zn. Furthermore, an overall water splitting electrolyzer constructed by the symmetrical Co–NC@CC electrodes delivers a current density of 10 mA cm⁻² at a low cell voltage of 1.57 V. Such a solar-powered WSS can harvest hydrogen day and night, demonstrating a potential for application in sustainable renewable energy.     

Tandem Carbon Hollow Spheres with Tailored Inner Structure as Sulfur Immobilization for Superior Lithium–Sulfur Batteries

The construction of lithium–sulfur battery cathode materials while simultaneously achieving high areal sulfur-loading, adequate sulfur utilization, efficient polysulfides inhibition, rapid ion diffusion, etc. remains a major challenge. Herein, an internal regulatory strategy to fabricate the unique walnut-like yolk–shell carbon flower@carbon nanospheres is presented (WSYCS) as sulfur hosts. The internal carbon flower, suitable cavity, and external carbon layer effectively disperse the insulate sulfur, accommodate volumetric expansion, and confine polysulfides, thus improving the performance of lithium–sulfur batteries. The finite element simulation method also deduces the enhanced Li⁺ diffusion and lithium–sulfur reaction kinetics. More importantly, WSYCS2 is grafted onto carbon fiber (CF) by electro-spinning method to form a tandem WSYCS2@CF 3D film as a sulfur host for the free-standing electrode. The corresponding battery exhibits an extremely high areal capacity of 15.5 mAh cm⁻² with a sulfur loading of 13.4 mg cm⁻². Particularly, the flexible lithium–sulfur pouch cell delivers a high capacity of 8.1 mAh cm⁻² and excellent capacity retention of 65% over 800 cycles at a relatively high rate of 1C, corresponding to a calculated energy density of 539 Wh kg⁻¹ and 591 Wh L⁻¹. This work not only provides guidance for tailoring thick carbon/sulfur electrodes but also boosts the development of practical lithium–sulfur batteries.     

Modifying Electronic Structure of Cation-Exchanged Bimetallic Sulfide/Metal Oxide Heterostructure through In Situ Inclusion of Silver (Ag) Nanoparticles for Extrinsic Pseudocapacitor

The inferior electrical conductivity of conventional electrodes and their slow charge transport impose limitations on the electrochemical performance of supercapacitors (SCs) using those electrodes, necessitating strategies to overcome the limitations. An in situ Ag ion-incorporated cation-exchanged bimetallic sulfide/metal oxide heterostructure (Ag-Co_9-xFe_xS₈@α-Fe_xO_y) is synthesized using a two-step hydrothermal method. The coordination bond formation and Ag nanoparticle (NP) incorporation improve the electrical conductivity and adhesion of the heterostructure and reduce its interface resistance and volume expansion throughout the charge/discharge cycles. Density functional theory investigations indicate that the remarkable interlayer and interparticle conductivities of the heterostructure resulting from Ag doping have changed its electronic states, leading to an enhanced electrical conductivity. The optimized electrode has an excellent specific capacity (213.6 mA h g⁻¹ at 1 A g⁻¹) and can maintain 93.2% capacity retention with excellent Coulombic efficiency over 20 000 charge/discharge cycles. A flexible solid-state extrinsic pseudocapacitor (EPSC) is fabricated using Ag-Co_9-xFe_xS₈@α-Fe_xO_y and Ti₃C₂T_X electrodes. The EPSC has specific and volumetric capacitances of 259 F g⁻¹ and 2.7 F cm⁻³ at 0.7 A g⁻¹, respectively, an energy density of 80.9 Wh kg⁻¹ at 525 W kg⁻¹, and a capacity retention of 92.8% over 5000 charge/discharge cycles.     

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.     

Reconciling Mass Loading and Gravimetric Performance of MnO2 Cathodes by 3D-Printed Carbon Structures for Zinc-Ion Batteries

To promote the real application of zinc-ion batteries (ZIBs), reconciling the high mass loading and gravimetric performance of MnO₂ electrodes is of paramount importance. Herein, the rational regulation of 3D-printed carbon microlattices (3DP CMs) enabling an ultrathick MnO₂ electrode with well-maintained gravimetric capacities is demonstrated. The 3DP CMs made of graphene and carbon nanotubes (CNTs) are fabricated by direct ink 3D printing and subsequent high-temperature annealing. 3D printing enables a periodic structure of 3DP CMs, while the thermal annealing contributes to high conductivity and defective surfaces. Due to these structural merits, uniform electrical field distribution and facilitated MnO₂ deposition over the 3DP CMs are permitted. The optimal electrode with MnO₂ loaded on the 3DP CMs can achieve a record-high specific capacity of 282.8 mAh g⁻¹ even at a high mass loading of 28.4 mg cm⁻² and high ion transfer dynamics, which reconciles the loading mass and gravimetric performance. As a result, the aqueous ZIBs based on the 3DP CMs loaded MnO₂ afford an outstanding performance superior to most of the previous reports. This study reveals the essential role of interaction between active materials and current collectors, providing an alternative strategy for designing high-performance energy storage devices.     

Aqueous Ammonium-Ion Supercapacitors with Unprecedented Energy Density and Stability Enabled by Oxygen Vacancy-Enriched MoO3@C

The use of non-metal charge carriers such as ammonium (NH₄⁺) in electrochemical energy storage devices offers advantages in terms of weight, element abundance, and compatibility with aqueous electrolytes. However, the development of suitable electrodes for such carriers lags behind other technologies. Herein, we present a high-performance anode material for ammonium-ion supercapacitors based on a MoO₃/carbon (MoO₃@C) composite. The NH₄⁺ storage performance of such composites and their practical application prospects are evaluated both in a three-electrode configuration and as symmetric supercapacitors. The optimized material reaches an unprecedented specific capacitance of 473 F·g⁻¹ (158 mAh·g⁻¹; 1592 mF·cm⁻²) at a current density of 1 A·g⁻¹, and 92.7% capacitance retention after 5000 cycles in a three-electrode set-up. This outstanding performance is related to the presence of oxygen vacancies that enhance the composites’ ionic/electronic transportation and electrochemical reaction site, while at the same time facilitating the formation of hydrogen bonds between NH₄⁺ and the host material. Using the optimized composite, symmetric supercapacitors based on an (NH₄)₂SO₄ gel electrolyte are fabricated and demonstrated to provide unmatched energy densities above 78 Wh·kg⁻¹ at a power density of 929 W·kg⁻¹. Besides, such devices are characterized by extraordinary capacitance retention of 97.6% after 10,000 cycles.     

Redox Poly-Counterion Doped Conducting Polymers for Pseudocapacitive Energy Storage

Conducting polymers (CPs) have been widely studied for electrochemical energy storage. However, the dopants in CPs are often electrochemically inactive, introducing “dead-weight” to the materials. Moreover, commercial-level electrode materials with high mass loadings (e.g., >10 mg cm⁻²) often encounter the problems of inferior electrical and ionic conductivity. Here, a redox-active poly-counterion doping concept is proposed to improve the electrochemical performance of CPs with ultra-high mass loadings. As a study prototype, heptamolybdate anion (Mo₇O₂₄⁶⁻) doped polypyrrole (PPy) is synthesized by electro-polymerization. A 2 mm thick PPy electrode with mass loading of ≈192 mg cm⁻² reaches a record-high areal capacitance of ≈47 F cm⁻², competitive gravimetric capacitance of 235 F g⁻¹, and volumetric capacitance of 235 F cm⁻³. With poly-counterion doping, the dopants also undergo redox reactions during charge/discharge processes, providing additional capacitance to the electrode. The interaction between polymer chains and the poly-counterions enhances the electrical conductivity of CPs. Besides, the poly-counterions with large steric hindrance could act as structural pillars and endow CPs with open structures for facile ion transport. The concept proposed in this work enriches the electrochemistry of CPs and promotes their practical applications.     

Robust Single-Walled Carbon Nanotube-Infiltrated Carbon Fiber Electrodes for Structural Supercapacitors: from Reductive Dissolution to High Performance Devices

Multifunctional electrodes for structural supercapacitors are prepared by vacuum infiltration of single-walled carbon nanotubes (SWCNTs) into woven carbon fibers (CFs); the use of reductive charging chemistry to form nanotubide solutions ensured a high degree of individualization. The route is highly versatile, as shown by comparing four different commercial nanotube feedstocks. In film form, the pure nanotubide networks (“buckypapers”) are highly conductive (up to 2000 S cm⁻¹) with high surface area (>1000 m² g⁻¹) and great electrochemical performance (capacitance of 101 F g⁻¹, energy density of 27.5 Wh kg⁻¹ and power density of 135 kW kg⁻¹). Uniformly integrating these SWCNT networks throughout the CF fabrics significantly increased electrical conductivity (up to 318 S cm⁻¹), surface area (up to 196 m² g⁻¹), and in-plane shear properties, all simultaneously. The CNT-infiltrated CFs electrodes exhibited intrinsically high specific energy (2.6–4.2 Wh kg⁻¹) and power (6.0–8.7 kW kg⁻¹) densities in pure 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM TFSI) electrolyte. Multifunctional structural supercapacitors based on CNT-coated CFs offer a substantial increase in capacitive performance while maintaining the tensile mechanical properties of the as-received CF-based composite. This non-damaging approach to modify CFs with highly graphitic, high surface area nanocarbons provides a new route to structural energy storage systems.