MoS2/NiS Yolk–Shell Microsphere‐Based Electrodes for Overall Water Splitting and Asymmetric Supercapacitor

Rational designing of the composition and structure of electrode material is of great significance for achieving highly efficient energy storage and conversion in electrochemical energy devices. Herein, MoS₂/NiS yolk–shell microspheres are successfully synthesized via a facile ionic liquid‐assisted one‐step hydrothermal method. With the favorable interface effect and hollow structure, the electrodes assembled with MoS₂/NiS hybrid microspheres present remarkably enhanced electrochemical performance for both overall water splitting and asymmetric supercapacitors. In particular, to deliver a current density of 10 mA cm^?2, the MoS₂/NiS‐based electrolysis cell for overall water splitting only needs an output voltage of 1.64 V in the alkaline medium, lower than that of Pt/C–IrO₂‐based electrolysis cells (1.70 V). As an electrode for supercapacitors, the MoS₂/NiS hybrid microspheres exhibit a specific capacitance of 1493 F g^?1 at current density of 0.2 A g^?1, and remain 1165 F g^?1 even at a large current density of 2 A g^?1, implying outstanding charge storage capacity and excellent rate performance. The MoS₂/NiS‐ and active carbon‐based asymmetric supercapacitor manifests a maximum energy density of 31 Wh kg^?1 at a power density of 155.7 W kg^?1, and remarkable cycling stability with a capacitance retention of approximately 100% after 10 000 cycles.     

Robust Electrodes Based on Coaxial TiC/C–MnO2 Core/Shell Nanofiber Arrays with Excellent Cycling Stability for High‐Performance Supercapacitors

A coaxial electrode structure composed of manganese oxide‐decorated TiC/C core/shell nanofiber arrays is produced hydrothermally in a KMnO₄ solution. The pristine TiC/C core/shell structure prepared on the Ti alloy substrate provides the self‐sacrificing carbon shell and highly conductive TiC core, thus greatly simplifying the fabrication process without requiring an additional reduction source and conductive additive. The as‐prepared electrode exhibits a high specific capacitance of 645 F g^?1 at a discharging current density of 1 A g^?1 attributable to the highly conductive TiC/C and amorphous MnO₂ shell with fast ion diffusion. In the charging/discharging cycling test, the as‐prepared electrode shows high stability and 99% capacity retention after 5000 cycles. Although the thermal treatment conducted on the as‐prepared electrode decreases the initial capacitance, the electrode undergoes capacitance recovery through structural transformation from the crystalline cluster to layered birnessite type MnO₂ nanosheets as a result of dissolution and further electrodeposition in the cycling. 96.5% of the initial capacitance is retained after 1000 cycles at high charging/discharging current density of 25 A g^?1. This study demonstrates a novel scaffold to construct MnO₂ based SCs with high specific capacitance as well as excellent mechanical and cycling stability boding well for future design of high‐performance MnO₂‐based SCs.     

Hierarchical α‐MnO2 Nanowires@Ni1‐xMnxOy Nanoflakes Core–Shell Nanostructures for Supercapacitors

A facile two‐step solution‐phase method has been developed for the preparation of hierarchical α‐MnO₂ nanowires@Ni_1‐xMn_xO_y nanoflakes core–shell nanostructures. Ultralong α‐MnO₂ nanowires were synthesized by a hydrothermal method in the first step. Subsequently, Ni_1‐xMn_xO_y nanoflakes were grown on α‐MnO₂ nanowires to form core–shell nanostructures using chemical bath deposition followed by thermal annealing. Both solution‐phase methods can be easily scaled up for mass production. We have evaluated their application in supercapacitors. The ultralong one‐dimensional (1D) α‐MnO₂ nanowires in hierarchical core–shell nanostructures offer a stable and efficient backbone for charge transport; while the two‐dimensional (2D) Ni_1‐xMn_xO_y nanoflakes on α‐MnO₂ nanowires provide high accessible surface to ions in the electrolyte. These beneficial features enable the electrode with high capacitance and reliable stability. The capacitance of the core–shell α‐MnO₂@Ni_1‐xMn_xO_y nanostructures (x = 0.75) is as high as 657 F g^?1 at a current density of 250 mA g^?1, and stable charging‐discharging cycling over 1000 times at a current density of 2000 mA g^?1 has been realized.     

Enhanced Li‐Storage of Ni3S2 Nanowire Arrays with N‐Doped Carbon Coating Synthesized by One‐Step CVD Process and Investigated Via Ex Situ TEM

In this work, a facile strategy for the construction of single crystalline Ni₃S₂ nanowires coated with N‐doped carbon shell (NC) forming Ni₃S₂@NC core/shell arrays by one‐step chemical vapor deposition process is reported. In addition to the good electronic conductivity from the NC shell, the nanowire structure also ensures the accommodation of large volume expansion during cycling, leading to pre‐eminent high‐rate capacities (470 mAh g^?1 at 0.05 A g^?1 and 385 mAh g^?1 at 2 A g^?1) and outstanding cycling stability with a capacity retention of 91% after 100 cycles at 1 A g^?1. Furthermore, ex situ transmission electron microscopy combined with X‐ray diffraction and Raman spectra are used to investigate the reaction mechanism of Ni₃S₂@NC during the charge/discharge process. The product after delithiation consists of Ni₃S₂ and sulfur, suggesting that the capacity of the electrode comes from the conversion reaction of both Ni₃S₂ and sulfur with Li₂S.     

Scalable Synthesis of Triple‐Core–Shell Nanostructures of TiO2@MnO2@C for High Performance Supercapacitors Using Structure‐Guided Combustion Waves

Core–shell nanostructures of metal oxides and carbon‐based materials have emerged as outstanding electrode materials for supercapacitors and batteries. However, their synthesis requires complex procedures that incur high costs and long processing times. Herein, a new route is proposed for synthesizing triple‐core–shell nanoparticles of TiO₂@MnO₂@C using structure‐guided combustion waves (SGCWs), which originate from incomplete combustion inside chemical‐fuel‐wrapped nanostructures, and their application in supercapacitor electrodes. SGCWs transform TiO₂ to TiO₂@C and TiO₂@MnO₂ to TiO₂@MnO₂@C via the incompletely combusted carbonaceous fuels under an open‐air atmosphere, in seconds. The synthesized carbon layers act as templates for MnO₂ shells in TiO₂@C and organic shells of TiO₂@MnO₂@C. The TiO₂@MnO₂@C‐based electrodes exhibit a greater specific capacitance (488 F g^?1 at 5 mV s^?1) and capacitance retention (97.4% after 10 000 cycles at 1.0 V s^?1), while the absence of MnO₂ and carbon shells reveals a severe degradation in the specific capacitance and capacitance retention. Because the core‐TiO₂ nanoparticles and carbon shell prevent the deformation of the inner and outer sides of the MnO₂ shell, the nanostructures of the TiO₂@MnO₂@C are preserved despite the long‐term cycling, giving the superior performance. This SGCW‐driven fabrication enables the scalable synthesis of multiple‐core–shell structures applicable to diverse electrochemical applications.     

Phosphorus‐Mediated MoS2 Nanowires as a High‐Performance Electrode Material for Quasi‐Solid‐State Sodium‐Ion Intercalation Supercapacitors

Molybdenum disulfide (MoS₂) is a promising electrode material for electrochemical energy storage owing to its high theoretical specific capacity and fascinating 2D layered structure. However, its sluggish kinetics for ionic diffusion and charge transfer limits its practical applications. Here, a promising strategy is reported for enhancing the Na⁺‐ion charge storage kinetics of MoS₂ for supercapacitors. In this strategy, electrical conductivity is enhanced and the diffusion barrier of Na⁺ ion is lowered by a facile phosphorus‐doping treatment. Density functional theory results reveal that the lowest energy barrier of dilute Na‐vacancy diffusion on P‐doped MoS₂ (0.11 eV) is considerably lower than that on pure MoS₂ (0.19 eV), thereby signifying a prominent rate performance at high Na intercalation stages upon P‐doping. Moreover, the Na‐vacancy diffusion coefficient of the P‐doped MoS₂ at room temperatures can be enhanced substantially by approximately two orders of magnitude (10^?6–10^?4 cm² s^?1) compared with pure MoS₂. Finally, the quasi‐solid‐state asymmetrical supercapacitor assembled with P‐doped MoS₂ and MnO₂, as the positive and negative electrode materials, respectively, exhibits an ultrahigh energy density of 67.4 W h kg^?1 at 850 W kg^?1 and excellent cycling stability with 93.4% capacitance retention after 5000 cycles at 8 A g^?1.     

Cost‐effective Atomic Layer Deposition Synthesis of Pt Nanotube Arrays: Application for High Performance Supercapacitor

Due to the unique advantages of Pt, it plays an important role in fuel cells and microelectronics. Considering the fact that Pt is an expensive metal, a major challenging point nowadays is how to realize efficient utilization of Pt. In this paper, a cost‐effective atomic layer deposition (ALD) process with a low N₂ filling step is introduced for realizing well‐defined Pt nanotube arrays in anodic alumina nano‐porous templates. Compared to the conventional ALD growth of Pt, much fewer ALD cycles and a shorter precursor pulsing time are required, which originates from the low N₂ filling step. To achieve similar Pt nanotubes, about half cycles and 10% Pt precursor pulsing time is needed using our ALD process. Meanwhile, the Pt nanotube array is explored as a current collector for supercapacitors based on core/shell Pt/MnO₂ nanotubes. This nanotube‐based electrode exhibits high gravimetric and areal specific capacitance (810 Fg^?1 and 75 mF cm^?2 at a scan rate of 5 mV s^?1) as well as an excellent rate capability (68% capacitance retention from 2 to 100 Ag^?1). Additionally, a negligible capacitance loss is observed after 8000 cycles of random charging‐discharging from 2 to 100 Ag^?1.     

Fabrication of a 3D Hierarchical Sandwich Co9S8/α‐MnS@N–C@MoS2 Nanowire Architectures as Advanced Electrode Material for High Performance Hybrid Supercapacitors

Supercapacitors suffer from lack of energy density and impulse the energy density limit, so a new class of hybrid electrode materials with promising architectures is strongly desirable. Here, the rational design of a 3D hierarchical sandwich Co₉S₈/α‐MnS@N–C@MoS₂ nanowire architecture is achieved during the hydrothermal sulphurization reaction by the conversion of binary mesoporous metal oxide core to corresponding individual metal sulphides core along with the formation of outer metal sulphide shell at the same time. Benefiting from the 3D hierarchical sandwich architecture, Co₉S₈/α‐MnS@N–C@MoS₂ electrode exhibits enhanced electrochemical performance with high specific capacity/capacitance of 306 mA h g^?1/1938 F g^?1 at 1 A g^?1, and excellent cycling stability with a specific capacity retention of 86.9% after 10 000 cycles at 10 A g^?1. Moreover, the fabricated asymmetric supercapacitor device using Co₉S₈/α‐MnS@N–C@MoS₂ as the positive electrode and nitrogen doped graphene as the negative electrode demonstrates high energy density of 64.2 Wh kg^?1 at 729.2 W kg^?1, and a promising energy density of 23.5 Wh kg^?1 is still attained at a high power density of 11 300 W kg^?1. The hybrid electrode with 3D hierarchical sandwich architecture promotes enhanced energy density with excellent cyclic stability for energy storage.     

Rational Design of Hierarchically Core–Shell Structured Ni3S2@NiMoO4 Nanowires for Electrochemical Energy Storage

Rational design and controllable synthesis of nanostructured materials with unique microstructure and excellent electrochemical performance for energy storage are crucially desired. In this paper, a facile method is reported for general synthesis of hierarchically core–shell structured Ni₃S₂@NiMoO₄ nanowires (NWs) as a binder‐free electrode for asymmetric supercapacitors. Due to the intimate contact between Ni₃S₂ and NiMoO₄, the hierarchical structured electrodes provide a promising unique structure for asymmetric supercapacitors. The as‐prepared binder‐free Ni₃S₂@NiMoO₄ electrode can significantly improve the electrical conductivity between Ni₃S₂ and NiMoO₄, and effectively avoid the aggregation of NiMoO₄ nanosheets, which provide more active space for storing charge. The Ni₃S₂@NiMoO₄ electrode presents a high areal capacity of 1327.3 µAh cm⁻² and 67.8% retention of its initial capacity when current density increases from 2 to 40 mA cm⁻². In a two‐electrode Ni₃S₂@NiMoO₄ // active carbon cell, the active materials deliver a high energy density of 121.5 Wh kg⁻¹ at a power density of 2.285 kW kg⁻¹ with excellent cycling stability.     

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

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

Self‐Assembled Nickel Pyrophosphate‐Decorated Amorphous Bimetal Hydroxides 2D‐on‐2D Nanostructure for High‐Energy Solid‐State Asymmetric Supercapacitor

To obtain a supercapacitor with a remarkable specific capacitance and rate performance, a cogent design and synthesis of the electrode material containing abundant active sites is necessary. In present work, a scalable strategy is developed for preparing 2D‐on‐2D nanostructures for high‐energy solid‐state asymmetric supercapacitors (ASCs). The self‐assembled vertically aligned microsheet‐structured 2D nickel pyrophosphate (Ni₂P₂O₇) is decorated with amorphous bimetallic nickel cobalt hydroxide (NiCo‐OH) to form a 2D‐on‐2D nanostructure arrays electrode. The resulting Ni₂P₂O₇/NiCo‐OH 2D‐on‐2D array electrode exhibits peak specific capacity of 281 mA hg^?1 (4.3 F cm^?2), excellent rate capacity, and cycling stability over 10 000 charge–discharge cycles in the positive potential range. The excellent electrochemical features can be attributed to the high electrical conductivity and 2D layered structure of Ni₂P₂O₇ along with the Faradic capacitance of the amorphous NiCo‐OH nanosheets. The constructed Ni₂P₂O₇/NiCo‐OH//activated carbon based solid‐state ASC cell operates in a high voltage window of 1.8 V with an energy density of 78 Wh kg^?1 (1.065 mWh cm^?3) and extraordinary cyclic stability over 10 000 charge–discharge cycles with excellent energy efficiency (75%–80%) over all current densities. The excellent electrochemical performance of the prepared electrode and solid‐state ASC device offers a favorable and scalable pathway for developing advanced electrodes.     

Interface‐Engineered Nickel Cobaltite Nanowires through NiO Atomic Layer Deposition and Nitrogen Plasma for High‐Energy,Long‐Cycle‐Life Foldable All‐Solid‐State Supercapacitors

The large‐scale application of supercapacitors (SCs) for portable electronics is restricted by low energy density and cycling stability. To alleviate the limitations, a unique interface engineering strategy is suggested through atomic layer deposition (ALD) and nitrogen plasma. First, commercial carbon cloth (CC) is treated with nitrogen plasma and later inorganic NiCo₂O₄ (NCO)/NiO core–shell nanowire arrays are deposited on nitrogen plasma–treated CC (NCC) to fabricate the ultrahigh stable SC. An ultrathin layer of NiO deposited on the NCO nanowire arrays via conformal ALD plays a vital role in stabilizing the NCO nanowires for thousands of electrochemical cycles. The optimized NCC/NCO/NiO core–shell electrode exhibits a high specific capacitance of 2439 F g^?1 with a remarkable cycling stability (94.2% over 20 000 cycles). Benefiting from these integrated merits, the foldable solid‐state SCs are fabricated with excellent NCC/NCO/NiO core–shell nanowire array electrodes. The fabricated SC device delivers a high energy density of 72.32 Wh kg^?1 at a specific capacitance of 578 F g^?1, with ultrasmall capacitance decline rate of 0.0003% per cycle over 10 000 charge–discharge cycles. Overall, this strategy offers a new avenue for developing a new‐generation high‐energy, ultrahigh stable supercapacitor for real‐life applications.     

(Ni,Co)Se2/NiCo‐LDH Core/Shell Structural Electrode with the Cactus‐Like (Ni,Co)Se2 Core for Asymmetric Supercapacitors

Supercapacitors (SCs) have been widely studied as a class of promising energy‐storage systems for powering next‐generation E‐vehicles and wearable electronics. Fabricating hybrid‐types of electrode materials and designing smart nanoarchitectures are effective approaches to developing high‐performance SCs. Herein, first, a Ni‐Co selenide material (Ni,Co)Se₂ with special cactus‐like structure as the core, to scaffold the NiCo‐layered double hydroxides (LDHs) shell, is designed and fabricated. The cactus‐like structural (Ni,Co)Se₂ core, as a highly conductive and robust support, promotes the electron transport as well as hinders the agglomeration of LDHs. The synergistic contributions from the two types of active materials together with the superior properties of the cactus‐like nanostructure enable the (Ni,Co)Se₂/NiCo‐LDH hybrid electrode to exhibit a high capacity of ≈170 mA h g^?1 (≈1224 F g^?1), good rate performance, and long durability. The as‐assembled (Ni,Co)Se₂/NiCo‐LDH//PC (porous carbon) asymmetric supercapacitor (ASC) with an operating voltage of 1.65 V delivers a high energy density of 39 W h kg^?1 at a power density of 1650 W kg^?1. Therefore, the cactus‐like core/shell structure offers an effective pathway to engineer advanced electrodes. The assembled flexible ASC is demonstrated to effectively power electronic devices.     

Co@Co3O4 Core–Shell Three‐Dimensional Nano‐Network for High‐Performance Electrochemical Energy Storage

An alternative routine is presented by constructing a novel architecture, conductive metal/transition oxide (Co@Co₃O₄) core–shell three‐dimensional nano‐network (3DN) by surface oxidating Co 3DN in situ, for high‐performance electrochemical capacitors. It is found that the Co@Co₃O₄ core–shell 3DN consists of petal‐like nanosheets with thickness of <10 nm interconnected forming a 3D porous nanostructure, which preserves the original morphology of Co 3DN well. X‐ray photoelectron spectroscopy by polishing the specimen layer by layer reveals that the Co@Co₃O₄ nano‐network is core–shell‐like structure. In the application of electrochemical capacitors, the electrodes exhibit a high specific capacitance of 1049 F g^?1 at scan rate of 2 mV/s with capacitance retention of ～52.05% (546 F g^?1 at scan rate of 100 mV) and relative high areal mass density of 850 F g^?1 at areal mass of 3.52 mg/cm². It is believed that the good electrochemical behaviors mainly originate from its extremely high specific surface area and underneath core‐Co “conductive network”. The high specific surface area enables more electroactive sites for efficient Faradaic redox reactions and thus enhances ion and electron diffusion. The underneath core‐Co “conductive network” enables an ultrafast electron transport.     

Ni2P@Carbon Core–Shell Nanoparticle‐Arched 3D Interconnected Graphene Aerogel Architectures as Anodes for High‐Performance Sodium‐Ion Batteries

To alleviate large volume change and improve poor electrochemical reaction kinetics of metal phosphide anode for sodium‐ion batteries, for the first time, an unique Ni₂P@carbon/graphene aerogel (GA) 3D interconnected porous architecture is synthesized through a solvothermal reaction and in situ phosphorization process, where core–shell Ni₂P@C nanoparticles are homogenously embedded in GA nanosheets. The synergistic effect between components endows Ni₂P@C/GA electrode with high structural stability and electrochemical activity, leading to excellent electrochemical performance, retaining a specific capacity of 124.5 mA h g^?1 at a current density of 1 A g^?1 over 2000 cycles. The robust 3D GA matrix with abundant open pores and large surface area can provide unblocked channels for electrolyte storage and Na⁺ transfer and make fully close contact between the electrode and electrolyte. The carbon layers and 3D GA together build a 3D conductive matrix, which not only tolerates the volume expansion as well as prevents the aggregation and pulverization of Ni₂P nanoparticles during Na⁺ insertion/extraction processes, but also provides a 3D conductive highway for rapid charge transfer processes. The present strategy for phosphides via in situ phosphization route and coupling phosphides with 3D GA can be extended to other novel electrodes for high‐performance energy storage devices.     

“HOT” Alkaline Hydrolysis of Amorphous MOF Microspheres to Produce Ultrastable Bimetal Hydroxide Electrode with Boosted Cycling Stability

Nickel/cobalt hydroxide is a promising battery‐type electrode material for supercapacitors. However, its low cycle stability hinders further applications. Herein, Ni_0.7Co_0.3(OH)₂ core–shell microspheres exhibiting extreme‐prolonged cycling life are successfully synthesized, employing Ni‐Co‐metal–organic framework (MOF) as the precursor/template and a specific hydrolysis strategy. The Ni‐Co‐MOF and KOH aqueous solution are separated and heated to 120 °C before mixing, rather than mixing before heating. Through this hydrolysis strategy, no MOF residual exists in the product, contributing to close stacking of the hydroxide nanoflakes to generate Ni_0.7Co_0.3(OH)₂ microspheres with a robust core–shell structure. The electrode material exhibits high specific capacity (945 C g^?1 at 0.5 A g^?1) and unprecedented cycling performance (100% after 10 000 cycles). The fabricated asymmetric supercapacitor delivers an energy density of 40.14 Wh kg^?1 at a power density of 400.56 W kg^?1 and excellent cycling stability (100% after 20 000 cycles). As far as is known, it is the best cycling performance for pure Ni/Co(OH)₂.     

Direct Laser‐Patterned Micro‐Supercapacitors from Paintable MoS2 Films

Micrometer‐sized electrochemical capacitors have recently attracted attention due to their possible applications in micro‐electronic devices. Here, a new approach to large‐scale fabrication of high‐capacitance, two‐dimensional MoS₂ film‐based micro‐supercapacitors is demonstrated via simple and low‐cost spray painting of MoS₂ nanosheets on Si/SiO₂ chip and subsequent laser patterning. The obtained micro‐supercapacitors are well defined by ten interdigitated electrodes (five electrodes per polarity) with 4.5 mm length, 820 μm wide for each electrode, 200 μm spacing between two electrodes and the thickness of electrode is ～0.45 μm. The optimum MoS₂‐based micro‐supercapacitor exhibits excellent electrochemical performance for energy storage with aqueous electrolytes, with a high area capacitance of 8 mF cm^?2 (volumetric capacitance of 178 F cm^?3) and excellent cyclic performance, superior to reported graphene‐based micro‐supercapacitors. This strategy could provide a good opportunity to develop various micro‐/nanosized energy storage devices to satisfy the requirements of portable, flexible, and transparent micro‐electronic devices.     

Tungsten Oxide@Polypyrrole Core–Shell Nanowire Arrays as Novel Negative Electrodes for Asymmetric Supercapacitors

Among active pseudocapacitive materials, polypyrrole (PPy) is a promising electrode material in electrochemical capacitors. PPy‐based materials research has thus far focused on its electrochemical performance as a positive electrode rather than as a negative electrode for asymmetric supercapacitors (ASCs). Here high‐performance electrochemical supercapacitors are designed with tungsten oxide@PPy (WO₃@PPy) core–shell nanowire arrays and Co(OH)₂ nanowires grown on carbon fibers. The WO₃@PPy core–shell nanowire electrode exhibits a high capacitance (253 mF/cm²) in negative potentials (–1.0–0.0 V). The ASCs packaged with CF‐Co(OH)₂ as a positive electrode and CF‐WO₃@PPy as a negative electrode display a high volumetric capacitance up to 2.865 F/cm³ based on volume of the device, an energy density of 1.02 mWh/cm³, and very good stability performance. These findings promote the application of PPy‐based nanostructures as advanced negative electrodes for ASCs.     

Efficient Supercapacitor Energy Storage Using Conjugated Microporous Polymer Networks Synthesized from Buchwald–Hartwig Coupling

Supercapacitors have received increasing interest as energy storage devices due to their rapid charge–discharge rates, high power densities, and high durability. In this work, novel conjugated microporous polymer (CMP) networks are presented for supercapacitor energy storage, namely 3D polyaminoanthraquinone (PAQ) networks synthesized via Buchwald–Hartwig coupling between 2,6‐diaminoanthraquinone and aryl bromides. PAQs exhibit surface areas up to 600 m² g^?1, good dispersibility in polar solvents, and can be processed to flexible electrodes. The PAQs exhibit a three‐electrode specific capacitance of 576 F g^?1 in 0.5 m H₂SO₄ at a current of 1 A g^?1 retaining 80–85% capacitances and nearly 100% Coulombic efficiencies (95–98%) upon 6000 cycles at a current density of 2 A g^?1. Asymmetric two‐electrode supercapacitors assembled by PAQs show a capacitance of 168 F g^?1 of total electrode materials, an energy density of 60 Wh kg^?1 at a power density of 1300 W kg^?1, and a wide working potential window (0–1.6 V). The asymmetric supercapacitors show Coulombic efficiencies up to 97% and can retain 95.5% of initial capacitance undergo 2000 cycles. This work thus presents novel promising CMP networks for charge energy storage.     

Preparation of MnO<Subscript>2</Subscript>/porous carbon material with core–shell structure and its application in supercapacitor

Tubular manganese dioxide (MnO₂) is synthesized by hydrothermal method, and a silicon dioxide (SiO₂) used as template is wrapped on the as-synthesized MnO₂. Then poly(styrene-co-divinylbenzene) (PS) as heteropolymeric carbon precursor was wrapped on as-prepared MnO₂/SiO₂ to form intermediate product MnO₂@SiO₂@PS. The intermediate products were treated by carbon tetrachloride, stripped template and carbonized, thus the final product MnO₂/porous carbon composite (MnO₂@PC) with core–shell structure was obtained. The core–shell structural composite is used as an electrode of supercapacitors, which combines high conductivity and high surface specific area of porous carbon material and high electrochemical activity of MnO₂. The resulting core–shell MnO₂@PC exhibits a maximum specific capacitance of 196.2 F g^?1 at a discharge density of 1 A g^?1 with capacitance retention of 78.52% over 5000 discharge/charge cycles.