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Porous carbon is a pivotal material for electrochemical applications. The manufacture of porous carbon has relied on chemical treatments (etching or template) that require processing in all areas of the carbon/carbon precursor. We present a unique approach to preparing porous carbon nanospheres by inhibiting the pyrolytic condensation of polymers. Specifically, the porous carbon nanospheres are obtained by coating a thin film of ZnO on polystyrene spheres. The porosity of the porous carbon nanospheres is controlled by the thickness of the ZnO shell, achieving a BET-specific area of 1,124 m2/g with a specific volume of 1.09 cm3/g. We confirm that under the support force by the ZnO shell, a hierarchical pore structure in which small mesopores are connected by large mesopores is formed and that the pore-associated sp3 defects are enriched. These features allow full utilization of the surface area of the carbon pores. The electrochemical capacitive performance of porous carbon nanospheres was evaluated, achieving a high capacitance of 389 F/g at 1 A/g, capacitance retention of 71% at a 20-fold increase in current density, and stability up to 30,000 cycles. In particular, we achieve a specific area-normalized capacitance of 34.6 µF/cm2, which overcomes the limitations of conventional carbon materials.
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Metal-sulfur batteries have received great attention for electrochemical energy storage due to high theoretical capacity and low cost, but their further development is impeded by low sulfur utilization, poor electrochemical kinetics, and serious shuttle effect of the sulfur cathode. To avoid these problems, herein, a triple-synergistic small-molecule sulfur cathode is designed by employing N, S co-doped hierarchical porous bamboo charcoal as a sulfur host in an aqueous Cu-S battery. Expect the enhanced conductivity and chemisorption induced by N, S synergistic co-doping, the intrinsic synergy of macro-/meso-/microporous triple structure also ensures space-confined small-molecule sulfur as high utilization reactant and effectively alleviates the volume expansion during conversion reaction. Under a further joint synergy between hierarchical structure and heteroatom doping, the resulting sulfur cathode endows the Cu-S battery with outstanding electrochemical performance. Cycled at 5 A g-1, it can deliver a high reversible capacity of 2,509.8 mAh g-1 with a good capacity retention of 97.9% after 800 cycles. In addition, a flexible hybrid pouch cell built by a small-molecule sulfur cathode, Zn anode, and gel electrolytes can firmly deliver high average operating voltage of about 1.3 V with a reversible capacity of over 2,500 mAh g-1 under various destructive conditions, suggesting that the triple-synergistic small-molecule sulfur cathode promises energetic metal-sulfur batteries.
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Electroactive artificial muscles with deformability have attracted widespread interest in the field of soft robotics. However, the design of artificial muscles with low-driven voltage and operational durability remains challenging. Herein, novel biomass porous carbon (BPC) electrodes are proposed. The nanoporous BPC enables the electrode to provide exposed active surfaces for charge transfer and unimpeded channels for ion migration, thus decreasing the driving voltage, enhancing time durability, and maintaining the actuation performances simultaneously. The proposed actuator exhibits a high displacement of 13.6 mm (bending strain of 0.54%) under 0.5 V and long-term durability of 99.3% retention after 550,000 cycles (â¼13 days) without breaks. Further, the actuators are integrated to perform soft touch on a smartphone and demonstrated as bioinspired robots, including a bionic butterfly and a crawling robot (moving speed = 0.08 BL s-1). This strategy provides new insight into the design and fabrication of high-performance electroactive soft actuators with great application potential.
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Porous carbon is widely used in energy storage-conversion systems, and the question of how to explore an efficient strategy for preparation is very significant. Herein, the flame retardant capability of (NH4 )2 SO4 /Mg(OH)2 that contains gas phase-heat absorption-condensate phase components is assisted to carbonize coal tar pitch in air and obtain the porous carbon. The mechanism of stepwise inflaming retarding is systematically investigated. In the carbonization process in a muffle furnace, (NH4 )2 SO4 decomposes releasing gases at below 400 °C to act as the role of gas phase flame retardant. Mg(OH)2 starts to decompose at ≥ 400 °C, and it has the effect of heat absorption and condensed phase flame retardation (MgSO4 and MgO). What's more, the flame retardant also serves as an N, S source and template. The obtained porous carbon possesses an ultrahigh carbon yield of 56.9 wt.%, hierarchical pore structure, and multi-heteroatoms doping. It can still reach up to 244.7 F g-1 even loaded 20 mg of active material. In addition, the (NH4 )2 SO4 /agar gel electrolyte is synthesized, and the fabricated flexible ammonium ion capacitor exhibits a superior energy density of 40.8 Wh kg-1 . This work uncovers a new way to construct porous carbon, which is expected to synthesize more carbon materials using other carbon sources.
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Biomass-derived materials generally exhibit uniform and highly-stable hierarchical porous structures that can hardly be achieved by conventional chemical synthesis and artificial design. When used as electrodes for rechargeable batteries, these structural and compositional advantages often endow the batteries with superior electrochemical performances. This review systematically introduces the innate merits of biomass-derived materials and their applications as the electrode for advanced rechargeable batteries, including lithium-ion batteries, sodium-ion batteries, potassium-ion batteries, and metal-sulfur batteries. In addition, biomass-derived materials as catalyst supports for metal-air batteries, fuel cells, and redox-flow batteries are also included. The major challenges for specific batteries and the strategies for utilizing biomass-derived materials are detailly introduced. Finally, the future development of biomass-derived materials for advanced rechargeable batteries is prospected. This review aims to promote the development of biomass-derived materials in the field of energy storage and provides effective suggestions for building advanced rechargeable batteries.
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Active compounds based on LDH (ternary layered double hydroxide) are considered the perfect supercapacitor electrode materials on account of their superior electrochemical qualities and distinct structural characteristics, and flexible supercapacitors are an ideal option as an energy source for wearable electronics. However, the prevalent aggregation effect of LDH materials results in significantly compromised actual specific capacitance, which limits its broad practical applications. In this research, a 3D eggshell-like interconnected porous carbon (IPC) framework with confinement and isolation capability is designed and synthesized by using glucose as the carbon source to disperse the LDH active material and enhance the conductivity of the composite material. Second, by constructing NiCoMn-LDH nanocage structure based on ZIF-67 (zeolitic imidazolate framework-67) at the nanometer scale the obtained IPC/NiCoMn-LDH electrode material can expose more active sites, which allows to achieve excellent specific capacitance (2236 F g-1/ 310.6 mAh g-1 at 1 A g-1), good rate as well as the desired cycle stability (85.9% of the initial capacitance upon 5000 cycles test). The constructed IPC/NiCoMn-LDH//IPC ASC (asymmetric supercapacitor) exhibits superior capacitive property (135 F g-1/60.1 mAh g-1 at 0.5 A g-1) as well as desired energy density (40 Wh kg-1 at 800 W kg-1).
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Hierarchical porous materials have attracted the attention of researchers due to their enormous specific surface area, maximized active site utilization efficiency, and unique structure and properties. In this context, metal-organic frameworks (MOFs) offer a unique mix of properties that make them particularly appealing as tunable porous substrates containing highly active sites. This review focuses on recent advances in the types and synthetic strategies of hierarchical porous MOFs and their derived materials. Furthermore, it highlights the relationship between the mass diffusion and transport of hierarchical porous structures and the pore size with examples and simulations, while identifying their potential and limitations. On this basis, how the synthesis conditions affect the structure and electrochemical properties of MOFs based hierarchical porous materials with different structures is discussed, highlighting the prospects and challenges for the synthetization, as well as further scientific research and practical applications. Finally, some insights into current research and future design ideas for advanced MOFs based hierarchical porous materials are presented.
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N-doped carbon (NC)-encapsulated transition metal (TM) nanocomposites are considered as alternatives to Pt-based hydrogen evolution reaction (HER) electrocatalysts; however, their poor electron transfer and mass diffusion capability at high current densities hinder their practical application. Herein, an oriented coupling strategy for the in situ grafting of ultrafine Co nanoparticle-embedded hollow porous C polyhedra onto Si nanowires (Co/NC-HP@Si-NWs) is proposed to address this concern. Experimental investigations reveal that the intimate coupling between the Si-NW and Co/NC nanocage forms a multithreaded conductive network, lowering the energy barrier for internal electron transfer. When functionalized as an HER electrocatalyst in 0.5 m H2 SO4 , Co/NC-HP@Si-NWs deliver overpotentials as low as 57 and 440 mV at 10 and 500 mA cm-2 , respectively, which are much better than those of the pristine Co/NC-HP. Moreover, Co/NC-HP@Si-NWs show an outstanding cycle durability of 24 h at 10 and 500 mA cm-2 . The findings of this study are expected to inspire revolutionary work on the development of Si-mediated TM-based electrocatalysts for the HER.
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Solid proton electrolytes play a crucial role in various electrochemical energy storage and conversion devices. However, the development of fast proton conducting solid proton electrolytes at ambient conditions remains a significant challenge. In this study, a novel acidified nitrogen self-doped porous carbon material is presented that demonstrates exceptional superprotonic conduction for applications in solid-state proton battery. The material, designated as MSA@ZIF-8-C, is synthesized through the acidification of nitrogen-doped porous carbon, specifically by integrating methanesulfonic acid (MSA) into zeolitic imidazolate framework-derived nitrogen self-doped porous carbons (ZIF-8-C). This study reveals that MSA@ZIF-8-C achieves a record-high proton conductivity beyond 10-2 S cm-1 at ambient condition, along with good long-term stability, positioning it as a cutting-edge alternative solid proton electrolyte to the default aqueous H2 SO4 electrolyte in proton batteries.
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Precise control of pore volume and size of carbon nanoscale materials is crucial for achieving high capacity and rate performances of charge/discharge. In this paper, starting from the unique mechanism of the role of In, Zn combination, and carboxyl functional groups in the formation of the lumen and pore size, the composition of InZn-MIL-68 is regulated to precisely tune the diameter and wall pore size of the hollow carbon tubes. The hollow carbon nanotubes (CNT) with high-capacity storage and fast exchange of Na+ ions and charges are prepared. The CNT possess ultra-high specific capacitance and ultra-long cycle life and also offer several times higher Na+ ion storage capacity and rate performance than the existing CNTs. Density functional theory calculations and tests reveal that these superior characteristics are attributed to the spacious hollow structure, which provides sufficient space for Na+ storage and the tube wall's distinctive porosity of tube wall as well as open ends for facilitating Na+ rapid desorption. It is believed that precise control of sub-nanopore volume and pore size by tuning the composition of the carbon materials derived from bimetallic metal-organic frameworks (MOFs) will establish the basis for the future development of high-energy density and high-power density supercapacitors and batteries.
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Aqueous zinc-ion hybrid capacitors (ZIHCs), as ideal candidates for high energy-power supply systems, are restricted by unsatisfied energy density and poor cycling durability for further applications. The construction of a surface-functionalized carbon cathode is an effective strategy for improving the performance of ZIHCs. Herein, a high-performance ZIHC is achieved using oxygen-rich hierarchically porous carbon rods (MDPC-X) prepared by the pyrolysis of a metal-organic framework (MOF) assisted by KOH activation. The MDPC-X samples displayed high electric double-layer capacitance (EDLC) and pseudocapacitance owing to their oxygen-rich surfaces, abundant electroactive sites, and short ions/electron transfer lengths. The surface oxygen functional groups for the reversible chemical adsorption/desorption of Zn2+ are identified using ex situ X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Consequently, the as-assembled ZIHC exhibited a high capacity of 323.4 F g-1 (161.7 mA h g-1) at 0.5 A g-1 and a retention of 147 F g-1 (73.5 mA h g-1) at an ultrahigh current density of 50 A g-1, corresponding to high energy and power densities of 145.5 W h kg-1 and 45 kW kg-1, respectively. Furthermore, an excellent cycling life with 96.5% of capacity retention is also maintained after 10 000 cycles at 10 A g-1, demonstrating its promising potential for applications.
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Exploration of innovative strategies aiming to boost energy densities of supercapacitors without sacrificing the power density and long-term stability is of great importance. Herein, highly porous nitrogen-doped carbon spheres (NPCS) are decorated onto the graphite sheets (GSs) through a hydrothermal route, followed by a chemical activation. The capacitive performance of the NPCS is then enhanced by hydroquinone sulfonic acid (HSQA) incorporation in both cathodic electrolyte and electrode materials. Later, NPCS are decorated with polypyrrole (PPY), in which HSQA takes a versatile role as conjugated polymer dopant and cathodic redox additive. The capacitive performance of the negative electrodes is enhanced by incorporating of alizarin red S (ARS) as anodic redox additive. Finally, PPY(HQSA)@NPCS-GS//NPCS-GS asymmetric supercapacitor is assembled and tested in dual redox electrolyte system containing HQSA-cathodic and ARS-anodic electrolytes. This device delivers a remarkable energy density of 60.37 Wh kg-1, which is close or even better than lead acid batteries. Thus, the present work provides a novel pathway to develop high energy supercapacitors using redox active electrolytes for next-generation energy storage applications.
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Nowadays, capacitive deionization (CDI) has emerged as a prominent technology in the desalination field, typically utilizing porous carbons as electrodes. However, the precise significance of electrode properties and operational conditions in shaping desalination performance remains blurry, necessitating numerous time-consuming and resource-intensive CDI experiments. Machine learning (ML) presents an emerging solution, offering the prospect of predicting CDI performance with minimal investment in electrode material synthesis and testing. Herein, four ML models are used for predicting the CDI performance of porous carbons. Among them, the gradient boosting model delivers the best performance on test set with low root mean square error values of 2.13 mg g-1 and 0.073 mg g-1 min-1 for predicting desalination capacity and rate, respectively. Furthermore, SHapley Additive exPlanations is introduced to analyze the significance of electrode properties and operational conditions. It highlights that electrolyte concentration and specific surface area exert a substantially more influential role in determining desalination performance compared to other features. Ultimately, experimental validation employing metal-organic frameworks-derived porous carbons and biomass-derived porous carbons as CDI electrodes is conducted to affirm the prediction accuracy of ML models. This study pioneers ML techniques for predicting CDI performance, offering a compelling strategy for advancing CDI technology.
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Porous carbon has been widely focused to solve the problems of low coulombic efficiency (ICE) and low multiplication capacity of Sodium-ion batteries (SIBs) anodes. The superior energy storage properties of two-dimensional(2D) carbon nanosheets can be realized by modulating the structure, but be limited by the carbon sources, making it challenging to obtain 2D structures with large surface area. In this work, a new method for forming carbon materials with high N/S doping content based on combustion activation using the dual activation effect of K2SO4/KNO3 is proposed. The synthesized carbon material as an anode for SIBs has a high reversible capacity of 344.44 mAh g-1 at 0.05 A g-1. Even at the current density of 5 Ag-1, the capacity remained at 143.08 mAh g-1. And the ICE of sodium-ion in ether electrolytes is ≈2.5 times higher than that in ester electrolytes. The sodium storage mechanism of ether/ester-based electrolytes is further explored through ex-situ characterizations. The disparity in electrochemical performance can be ascribed to the discrepancy in kinetics, wherein ether-based electrolytes exhibit a higher rate of Na+ storage and shedding compared to ester-based electrolytes. This work suggests an effective way to develop doubly doped carbon anode materials for SIBs.
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With the increasing attention to energy and environmental issues, the high value-added utilization of biomass and pitch to functional carbon materials has become an important topic in science and technology. In this work, the soft-hard heterostructure porous carbon (NRP-HPC) is prepared by bio-template method, in which biomass and pitch are used as hard carbon and soft carbon precursors, respectively. The prepared NRP-HPC-4 shows high specific surface area (2293 m2 g-1), suitable pore size distribution, good conductivity (0.25 Ω cm-1), and strong wettability. The synergistic effect of soft carbon and hard carbon ensures the composite material exhibiting excellent electrochemical performance for high mass loading (12.0 mg cm-2) aqueous supercapacitor, i.e., high specific capacitance (304.69 F g-1 at 0.1 A g-1), high area capacitance (3.67 F cm-2 at 0.1 A g-1), high volumetric specific capacitance (202.74 F cm-3 at 0.1 A g-1), low open-circuit voltage attenuation rate (21.04 mV h-1), good voltage retention (79.12%), and excellent cyclic stability (92.04% capacitance retention and 100% coulombic efficiency after 20 000 cycles). The composite technology of soft carbon and hard carbon not only ensures the prepared porous carbon electrode materials with enhanced electrochemical performance, but also realizes the high value-added coupling utilization of biomass and pitch.
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Porous carbon nanomaterials are widely applied in the electromagnetic wave absorption (EMWA) field. Among them, an emerging flower-like carbon nanomaterial, termed carbon nanoflowers (CNFs), has attracted tremendous research attention due to their unique hierarchical flower-like structure. However, the design of flower-like carbon nanomaterials with different magnetic cores for EMWA has rarely been reported. Herein, a general template method is proposed to achieve a set of high-quality magnetic CNFs, namely Co@Void@CNFs, CoNi@CNFs, and Ni@CNFs. The prepared magnetic CNFs have highly accessible surface area and internal space, rich heteroatom content, multi-scale pore system, and uniform and highly dispersed magnetic nanoparticles, as a result, deliver superior EMWA performance. Specifically, when the thickness is 2.6 mm, the Co@Void@CNFs exhibit a maximum refection loss (RLmax) of -56.6 dB and an effective absorption bandwidth (EAB) from 8.0 to 12.1 GHz covering the whole X band. The CoNi@CNFs have an RLmax of up to -57.6 dB and a wide EAB of 5.6 GHz at just 1.9 mm. For the Ni@CNFs, possess an ultra-broad EAB of 6.1 GHz, covering the entire Ku band at 2.0 mm. Overall, the hierarchical magnetic carbon nanoflowers proposed here offer new insights toward realizing multifunctional integrated carbon nanomaterials for EMWA.
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The practical implementation of lithium-sulfur batteries is severely hindered by the rapid capacity fading due to the solubility of the intermediate lithium polysulfides (LiPSs) and the sluggish redox kinetics. Herein, high-entropy metal nitride nanocrystals (HEMN) embedded within nitrogen-doped concave porous carbon (N-CPC) polyhedra are rationally designed as a sulfur host via a facile zeolitic imidazolate framework (ZIF)-driven adsorption-nitridation process toward this challenge. The configuration of high-entropy with incorporated metal manganese (Mn) and chromium (Cr) will optimize the d-band center of active sites with more electrons occupied in antibonding orbitals, thus promoting the adsorption and catalytic conversion of LiPSs. While the concave porous carbon not only accommodates the volume change upon the cycling processes but also physically confines and exposes active sites for accelerated sulfur redox reactions. As a result, the resultant HEMN/N-CPC composites-based sulfur cathode can deliver a high specific capacity of 1274 mAh g-1 at 0.2 C and a low capacity decay rate of 0.044% after 1000 cycles at 1 C. Moreover, upon sulfur loading of 5.0 mg cm-2, the areal capacity of 5.0 mAh cm-2 can still be achieved. The present work may provide a new avenue for the design of high-performance cathodes in Li-S batteries.
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A highly viable alternative to lithium-ion batteries for stationary electrochemical energy-storage systems is the potassium dual-ion hybrid capacitor (PIHC), especially toward fast-charging capability. However, the sluggish reaction kinetics of negative electrode materials seriously impedes their practical implementation. In this paper, a new negative electrode Bi@RPC (Nano-bismuth confined in nitrogen- and oxygen-doped carbon with rationally designed pores, evidenced by advanced characterization) is developed, leading to a remarkable electrochemical performance. PIHCs building with the active carbon YP50F positive electrode result in a high operation voltage (0.1-4 V), and remarkably well-retained energy density at a high-power density (11107 W kg-1 at 98 Wh kg-1). After 5000 cycles the proposed PHICs still show a superior capacity retention of 92.6%. Moreover, a reversible mechanism of "absorption-alloying" of the Bi@RPC nanocomposite is revealed by operando synchrotron X-ray diffraction and Raman spectroscopy. With the synergistic potassium ions storage mechanism arising from the presence of well-structured pores and nano-sized bismuth, the Bi@RPC electrode exhibits an astonishingly rapid kinetics and high energy density. The results demonstrate that PIHCs with Bi@RPC-based negative electrode is the promising option for simultaneously high-capacity and fast-charging energy storage devices.
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The notorious shuttle effect and sluggish conversion kinetics of intermediate polysulfides (Li2S4, Li2S6, Li2S8) are severely hindered the large-scale development of Lithium-sulfur (Li-S) batteries. Rectifying interface effect has been a solution to regulate the electron distribution of catalysts via interfacial charge exchange. Herein, a ZnTe-ZnO heterojunction encapsulated in nitrogen-doped hierarchical porous carbon (ZnTe-O@NC) derived from metal-organic framework is fabricated. Theoretical calculations and experiments prove that the built-in electric field constructed at ZnTe-ZnO heterojunction via the rectifying interface contact, thus promoting the charge transfer as well as enhancing adsorption and conversion kinetics toward polysulfides, thereby stimulating the catalytic activity of the ZnTe. Meanwhile, the nitrogen-doped hierarchical porous carbon acts as confinement substrate also enables fast electrons/ions transport, combining with ZnTe-ZnO heterojunction realize a synergistic confinement-adsorption-catalysis toward polysulfides. As a result, the Li-S batteries with S/ZnTe-O@NC electrodes exhibit an impressive rate capability (639.7 mAh g-1 at 3 C) and cycling performance (70% capacity retention at 1 C over 500 cycles). Even with a high sulfur loading, it still delivers a superior electrochemical performance. This work provides a novel perspective on designing highly catalytic materials to achieve synergistic confinement-adsorption-catalysis for high-performance Li-S batteries.
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With the extensive use of fossil fuels, the ever-increasing greenhouse gas of mainly carbon dioxide emissions will result in global climate change. It is of utmost importance to reduce carbon dioxide emissions and its utilization. Li-CO2 batteries can convert carbon dioxide into electrochemical energy. However, developing efficient catalysts for the decomposition of Li2 CO3 as the discharge product represents a challenge in Li-CO2 batteries. Herein, we demonstrate a carbon foam composite with growing carbon nanotube by using cobalt as the catalyst, showing the ability to enhance the decomposition rate of Li2 CO3 , and thus improve the electrochemical performance of Li-CO2 batteries. Benefiting from its abundant pore structure and catalytic sites, the as-assembled Li-CO2 battery exhibits a desirable overpotential of 1.67â V after 50â cycles. Moreover, the overpotentials are 1.05 and 2.38â V at current densities of 0.02 and 0.20â mA cm-2 , respectively. These results provide a new avenue for the development of efficient catalysts for Li-CO2 batteries.