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Silicon has gained significant attention as a lithium-ion battery anode material due to its high theoretical capacity compared to conventional graphite. Unfortunately, silicon anodes suffer from poor cycling performance caused by their extreme volume change during lithiation and de-lithiation. Compositing silicon particles with 2D carbon materials, such as graphene, can help mitigate this problem. However, an unaddressed challenge remains: a simple, inexpensive synthesis of Si/graphene composites. Here, a one-step laser-scribing method is proposed as a straightforward, rapid (≈3 min), scalable, and less-energy-consuming (≈5 W for a few minutes under air) process to prepare Si/laser-scribed graphene (LSG) composites. In this research, two types of Si particles, Si nanoparticles (SiNPs) and Si microparticles (SiMPs), are used. The rate performance is improved after laser scribing: SiNP/LSG retains 827.6 mAh g-1 at 2.0 A gSi+C -1, while SiNP/GO (before laser scribing) retains only 463.8 mAh g-1. This can be attributed to the fast ion transport within the well-exfoliated 3D graphene network formed by laser scribing. The cyclability is also improved: SiNP/LSG retains 88.3% capacity after 100 cycles at 2.0 A gSi+C -1, while SiNP/GO retains only 57.0%. The same trend is found for SiMPs: the SiMP/LSG shows better rate and cycling performance than SiMP/GO composites.
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Conducting polymers like polyaniline (PANI) are promising pseudocapacitive electrode materials, yet experience instability in cycling performance. Since polymers often degrade into oligomers, short chain length anilines have been developed to improve the cycling stability of PANI-based supercapacitors. However, the capacitance degradation mechanisms of aniline oligomer-based materials have not been systematically investigated and are little understood. Herein, two composite electrodes based on aniline trimers (AT) and carbon nanotubes (CNTs) are studied as model systems and evaluated at both pre-cycling and post-cycling states through physicochemical and electrochemical characterizations. The favorable effect of covalent bonding between AT and CNTs is confirmed to enhance cycling stability by preventing the detachment of aniline trimer and preserving the electrode microstructure throughout the charge/discharge cycling process. In addition, higher porosity has a positive effect on electron/ion transfer and the adaptation to volumetric changes, resulting in higher conductivity and extended cycle life. This work provides insights into the mechanism of enhanced cycling stability of aniline oligomers, indicating design features for aniline oligomer electrode materials to improve their electrochemical performance.
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Nanotubos de Carbono , Polímeros , Polímeros/química , Nanotubos de Carbono/química , Compostos de Anilina/químicaRESUMO
Long cycle life and high energy/power density are imperative to energy storage systems. Polyaniline (PANI) has shown great potential as an electrode material but is limited by poor cycling and rate performance. We present a molecular design approach of binding short-chain aniline trimers (ATs) and carbon nanotubes (CNTs) through the formation of amide covalent linkages enabled by a simple laser scribing technique. The covalently coupled AT/CNT (cc-AT/CNT) composite retains 80% of its original capacitance after 20â¯000 charge/discharge cycles, which readily outperforms long-chain PANI/CNT composites without covalent connections. The compact AT/CNT heterointerfaces produce fast charge/discharge kinetics and excellent rate capability. The flexible symmetric quasi-solid-state devices can be stably cycled beyond 50â¯000 cycles, at least 5 times longer than most PANI/CNT-based symmetric supercapacitors reported to date. This molecular design of durable conducting polymer-based electrode materials enabled by laser irradiation presents a feasible approach toward robust advanced energy storage devices.
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The interfacial properties within a composite structure of membranes play a vital role in the separation properties and application performances. Building an interlayer can facilitate the formation of a highly selective layer as well as improve the interfacial properties of the composite membrane. However, it is difficult for a nanomaterial-based interlayer to increase the flux and retention of nanofiltration membranes simultaneously. Here, we report a nanofiltration membrane with a hybrid dimensional titania interlayer that exhibits excellent separation performance. The interlayer, composed of Fe-doped titania nanosheets and titania nanoparticles, helps the formation of an ultrathin (â¼30 nm thick) and defect-free polyamide selective layer with an ideal nanostructure. The hybrid dimensional interlayer endows the membrane with a superior permeability and alleviates flux decline. In addition, the rigid interlayer framework on a PVDF support drastically improves the pressure resistance of nanofiltration membranes and shows negligible flux loss up to 1.5 MPa of pressure.
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The need for enhanced energy storage and improved catalysts has led researchers to explore advanced functional materials for sustainable energy production and storage. Herein, we demonstrate a reductive electrosynthesis approach to prepare a layer-by-layer (LbL) assembled trimetallic Fe-Co-Ni metal-organic framework (MOF) in which the metal cations within each layer or at the interface of the two layers are linked to one another by bridging 2-amino-1,4-benzenedicarboxylic acid linkers. Tailoring catalytically active sites in an LbL fashion affords a highly porous material that exhibits excellent trifunctional electrocatalytic activities toward the hydrogen evolution reaction (ηj=10 = 116 mV), oxygen evolution reaction (ηj=10 = 254 mV), as well as oxygen reduction reaction (half-wave potential = 0.75 V vs reference hydrogen electrode) in alkaline solutions. The dispersion-corrected density functional theory calculations suggest that the prominent catalytic activity of the LbL MOF toward the HER, OER, and ORR is due to the initial negative adsorption energy of water on the metal nodes and the elongated O-H bond length of the H2O molecule. The Fe-Co-Ni MOF-based Zn-air battery exhibits a remarkable energy storage performance and excellent cycling stability of over 700 cycles that outperform the commercial noble metal benchmarks. When assembled in an asymmetric device configuration, the activated carbon||Fe-Co-Ni MOF supercapacitor provides a superb specific energy and a power of up to 56.2 W h kg-1 and 42.2 kW kg-1, respectively. This work offers not only a novel approach to prepare an LbL assembled multimetallic MOF but also provides a benchmark for a multifunctional electrocatalyst for water splitting and Zn-air batteries.
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Increasing mass loadings of battery electrodes critically enhances the energy density of an overall battery by eliminating much of the inactive components, while compacting the battery size and lowering the costs of the ingredients. A hard carbon microlattice, digitally designed and fabricated by stereolithography 3D-printing and pyrolysis, offers enormous potential for high-mass-loading electrodes. In this work, sodium-ion batteries using hard carbon microlattices produced by an inexpensive 3D printer are demonstrated. Controlled periodic carbon microlattices are created with enhanced ion transport through microchannels. Carbon microlattices with a beam width of 32.8 µm reach a record-high areal capacity of 21.3 mAh cm-2 at a loading of 98 mg cm-2 without degrading performance, which is much higher than the conventional monolithic electrodes (≈5.2 mAh cm-2 at 92 mg cm-2 ). Furthermore, binder-free, pure-carbon elements of microlattices enable the tracking of structural changes in hard carbon that support the hypothesized intercalation of ions at plateau regions by temporal ex situ X-ray diffraction measurements. These results will advance the development of high-performance and low-cost anodes for sodium-ion batteries as well as help with understanding the mechanisms of ion intercalations in hard carbon, expanding the utilities of 3D-printed carbon architectures in both applications and fundamental studies.
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Conjugated polyaniline can impact the field of water filtration membranes due to its hydrophilic and antibacterial nature, facile and inexpensive synthesis procedure, heat and acid tolerance, and unique doping/dedoping chemistry. However, the gelation effect, its rigid backbone, and the limited hydrophilicity of polyaniline severely restrict the adaptability to membranes and their antifouling performance. This Mini Review summarizes important works of polyaniline-related ultrafiltration membranes, highlighting solutions to conquer engineering obstacles in processing and challenges in enhancing surface hydrophilicity with an emphasis on chemistry. As a pH-responsive polymer convertible to a conductive salt, this classic material should continue to bring unconventional advances into the realm of water filtration membranes.
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Incrustação Biológica , Ultrafiltração , Compostos de Anilina , Incrustação Biológica/prevenção & controle , Membranas ArtificiaisRESUMO
Because of increasing interest in environmentally benign supercapacitors, earth-abundant biopolymers have found their way into value-added applications. Herein, a promising nanocomposite based on an interpenetrating network of polyaniline and sulfonated lignin (lignosulfonate, LS) is presented. On the basis of an appropriate regulation of the nucleation kinetics and growth behavior via applying a series of rationally designed potential pulse patterns, a uniform PANI-LS film is achieved. On the basis of the fast rate of H+ insertion-deinsertion kinetics, rather than the slow SO42- doping-dedoping process, the PANI-LS nanocomposite delivers specific capacitance of 1200 F g-1 at 1 A g-1 surpassing the best conducting polymer-lignin supercapacitors known. A symmetric PANI-LS||PANI-LS device delivers a high specific energy of 21.2 W h kg-1, an outstanding specific power of 26.0 kW kg-1, along with superb flexibility and excellent cycling stability. Thus, combining charge storage attributes of polyaniline and lignosulfonate enables a waste-to-wealth approach to improve the supercapacitive performance of polyaniline.
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Lignina , Nanocompostos , Compostos de Anilina , Capacitância ElétricaRESUMO
Technological breakthroughs in energy storage are being driven by the development of next-generation supercapacitors with favorable features besides high-power density and cycling stability. In this innovation, graphene and its derived materials play an active role. Here, the research status of graphene supercapacitors is analyzed. Recent progress is outlined in graphene assembly, exfoliation, and processing techniques. In addition, electrochemical and electrical attributes that are increasingly valued in next-generation supercapacitors are highlighted along with a summary of the latest research addressing chemical modification of graphene and its derivatives for future supercapacitors. The challenges and solutions discussed in the review hopefully will shed light on the commercialization of graphene and a broader genre of 2D materials in energy storage applications.
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Grafite , EletricidadeRESUMO
Graphene oxide (GO) membranes have great potential for separation applications due to their low-friction water permeation combined with unique molecular sieving ability. However, the practical use of deposited GO membranes is limited by the inferior mechanical robustness of the membrane composite structure derived from conventional deposition methods. Here, we report a nanostructured GO membrane that possesses great permeability and mechanical robustness. This composite membrane consists of an ultrathin selective GO nanofilm (as low as 32 nm thick) and a postsynthesized macroporous support layer that exhibits excellent stability in water and under practical permeability testing. By utilizing thin-film lift off (T-FLO) to fabricate membranes with precise optimizations in both selective and support layers, unprecedented water permeability (47 L·m-2·hr-1·bar-1) and high retention (>98% of solutes with hydrated radii larger than 4.9 Å) were obtained.
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The synthesis of graphene nanoribbons (GNRs) that contain site-specifically substituted backbone heteroatoms is one of the essential goals that must be achieved in order to control the electronic properties of these next generation organic materials. We have exploited our recently reported solid-state topochemical polymerization/cyclization-aromatization strategy to convert the simple 1,4-bis(3-pyridyl)butadiynes 3a,b into the fjord-edge nitrogen-doped graphene nanoribbon structures 1a,b (fjord-edge N2[8]GNRs). Structural assignments are confirmed by CP/MAS 13C NMR, Raman, and XPS spectroscopy. The fjord-edge N2[8]GNRs 1a,b are promising precursors for the novel backbone nitrogen-substituted N2[8]AGNRs 2a,b. Geometry and band calculations on N2[8]AGNR 2c indicate that this class of nanoribbons should have unusual bonding topology and metallicity.
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Grafite/química , Nanotubos de Carbono/química , Nitrogênio/química , Modelos Moleculares , Estrutura MolecularRESUMO
The surging interest in high performance, low-cost, and safe energy storage devices has spurred tremendous research efforts in the development of advanced electrode active materials. Herein, the in situ growth of zinc-iron layered double hydroxide (Zn-Fe LDH) on graphene aerogel (GA) substrates through a facile, one-pot hydrothermal method is reported. The strong interaction and efficient electronic coupling between LDH and graphene substantially improve interfacial charge transport properties of the resulting nanocomposite and provide more available redox active sites for faradaic reactions. An LDH-GA||Ni(OH)2 device is also fabricated that results in greatly enhanced specific capacity (187 mAh g-1 at 0.1 A g-1 ), outstanding specific energy (147 Wh kg-1 ), excellent specific power (16.7 kW kg-1 ), along with 88% capacity retention after >10 000 cycles. This approach is further extended to Ni-MH and Ni-Cd batteries to demonstrate the feasibility of compositing with graphene for boosting the energy storage performance of other well-known Ni-based batteries. In contrast to conventional Ni-based batteries, the nearly flat voltage plateau followed by a sloping potential profile of the integrated supercapacitor-battery enables it to be discharged down to 0 V without being damaged. These findings provide new prospects for the design of high-performance and affordable superbatteries based on earth-abundant elements.
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Ongoing technological advances in diverse fields including portable electronics, transportation, and green energy are often hindered by the insufficient capability of energy-storage devices. By taking advantage of two different electrode materials, asymmetric supercapacitors can extend their operating voltage window beyond the thermodynamic decomposition voltage of electrolytes while enabling a solution to the energy storage limitations of symmetric supercapacitors. This review provides comprehensive knowledge to this field. We first look at the essential energy-storage mechanisms and performance evaluation criteria for asymmetric supercapacitors to understand the wide-ranging research conducted in this area. Then we move to the recent progress made for the design and fabrication of electrode materials and the overall structure of asymmetric supercapacitors in different categories. We also highlight several key scientific challenges and present our perspectives on enhancing the electrochemical performance of future asymmetric supercapacitors.
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Over the past decade, electrochemical energy storage (EES) devices have greatly improved, as a wide variety of advanced electrode active materials and new device architectures have been developed. These new materials and devices should be evaluated against clear and rigorous metrics, primarily based on the evidence of real performances. A series of criteria are commonly used to characterize and report performance of EES systems in the literature. However, as advanced EES systems are becoming more and more sophisticated, the methodologies to reliably evaluate the performance of the electrode active materials and EES devices need to be refined to realize the true promise as well as the limitations of these fast-moving technologies, and target areas for further development. In the absence of a commonly accepted core group of metrics, inconsistencies may arise between the values attributed to the materials or devices and their real performances. Herein, we provide an overview of the energy storage devices from conventional capacitors to supercapacitors to hybrid systems and ultimately to batteries. The metrics for evaluation of energy storage systems are described, although the focus is kept on capacitive and hybrid energy storage systems. In addition, we discuss the challenges that still need to be addressed for establishing more sophisticated criteria for evaluating EES systems. We hope this effort will foster ongoing dialog and promote greater understanding of these metrics to develop an international protocol for accurate assessment of EES systems.
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For the past 30 years, thin-film membrane composites have been the state-of-the-art technology for reverse osmosis, nanofiltration, ultrafiltration, and gas separation. However, traditional membrane casting techniques, such as phase inversion and interfacial polymerization, limit the types of material that are used for the membrane separation layer. Here, we describe a novel thin-film liftoff (T-FLO) technique that enables the fabrication of thin-film composite membranes with new materials for desalination, organic solvent nanofiltration, and gas separation. The active layer is cast separately from the porous support layer, allowing for the tuning of the thickness and chemistry of the active layer. A fiber-reinforced, epoxy-based resin is then cured on top of the active layer to form a covalently bound support layer. Upon submersion in water, the cured membrane lifts off from the substrate to produce a robust, freestanding, asymmetric membrane composite. We demonstrate the fabrication of three novel T-FLO membranes for chlorine-tolerant reverse osmosis, organic solvent nanofiltration, and gas separation. The isolable nature of support and active-layer formation paves the way for the discovery of the transport and selectivity properties of new polymeric materials. This work introduces the foundation for T-FLO membranes and enables exciting new materials to be implemented as the active layers of thin-film membranes, including high-performance polymers, two-dimensional materials, and metal-organic frameworks.
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Single-phase metal dodecaboride solid solutions, Zr0.5Y0.5B12 and Zr0.5U0.5B12, were prepared by arc melting from pure elements. The phase purity and composition were established by powder X-ray diffraction (PXRD), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and 10B and 11B solid-state nuclear magnetic resonance (NMR) spectroscopy. The effects of carbon addition to Zr1- xY xB12 were studied and it was found that carbon causes fast cooling and as a result rapid nucleation of grains, as well as "templating" and patterning effects of the surface morphology. The hardness of the Zr0.5Y0.5B12 phase is 47.6 ± 1.7 GPa at 0.49 N load, which is â¼17% higher than that of its parent compounds, ZrB12 and YB12, with hardness values of 41.6 ± 2.6 and 37.5 ± 4.3 GPa, respectively. The hardness of Zr0.5U0.5B12 is â¼54% higher than that of its UB12 parent. The dodecaborides were confirmed to be metallic by band structure calculations, diffuse reflectance UV-vis, and solid-state NMR spectroscopies. The nature of the dodecaboride colors-violet for ZrB12 and blue for YB12-can be attributed to charge-transfer. XPS indicates that the metals are in the following oxidation states: Y3+, Zr4+, and U5+/6+. The superconducting transition temperatures ( Tc) of the dodecaborides were determined to be 4.5 and 6.0 K for YB12 and ZrB12, respectively, as shown by resistivity and superconducting quantum interference device (SQUID) measurements. The Tc of the Zr0.5Y0.5B12 solid solution was suppressed to 2.5 K.
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Producing highly oriented graphene is a major challenge that constrains graphene from fulfilling its full potential in technological applications. The exciting properties of graphene are impeded in practical bulk materials due to lattice imperfections that hinder charge mobility. A simple method to improve the structural integrity of graphene by utilizing laser irradiation on a composite of carbon nanodots (CNDs) and 3D graphene is presented. The CNDs attach themselves to defect sites in the graphene sheets and, upon laser-assisted reduction, patch defects in the carbon lattice. Spectroscopic experiments reveal graphitic structural recovery of up to 43% and electrical conductivity four times larger than the original graphene. The composites are tested as electrodes in electrochemical capacitors and demonstrate extremely fast RC time constant as low as 0.57 ms. Due to their low defect concentrations, the reduced graphene oxide-carbon nanodot (rGO-CND) composites frequency response is sufficiently fast to operate as AC line filters, potentially replacing today's electrolytic capacitors. Using this methodology, demonstrated is a novel line filter with one of the fastest capacitive responses ever reported, and an aerial capacitance of 68.8 mF cm-2 . This result emphasizes the decisive role of structural integrity for optimizing graphene in electronic applications.
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There is significant interest in the development of methods to create hybrid materials that transform capabilities, in particular for Earth-abundant metal oxides, such as TiO2, to give improved or new properties relevant to a broad spectrum of applications. Here we introduce an approach we refer to as 'molecular cross-linking', whereby a hybrid molecular boron oxide material is formed from polyhedral boron-cluster precursors of the type [B12(OH)12]2-. This new approach is enabled by the inherent robustness of the boron-cluster molecular building block, which is compatible with the harsh thermal and oxidizing conditions that are necessary for the synthesis of many metal oxides. In this work, using a battery of experimental techniques and materials simulation, we show how this material can be interfaced successfully with TiO2 and other metal oxides to give boron-rich hybrid materials with intriguing photophysical and electrochemical properties.
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In the version of this Article originally published, Liban M. A. Saleh was incorrectly listed as Liban A. M. Saleh due to a technical error. This has now been amended in all online versions of the Article.
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High degrees of dispersion are a prerequisite for functional composite materials for applications in electronics such as sensors, charge and data storage, and catalysis. The use of small precursor materials can be a decisive factor in achieving a high degree of dispersion. In this study, carbon nanodots are used to fabricate a homogeneous, finely dispersed Fe2 O3 -graphene composite aerogel in a one-step conversion process from a precursor mixture. The laser-assisted conversion of small size carbon nanodots enables a uniform distribution of 6.5 nm Fe2 O3 nanoparticles during the formation of a highly conductive carbon matrix. Structural and electrochemical characterization shows that the features of both material entities are maintained and successfully integrated. The presence of Fe2 O3 nanoparticles has a positive effect on the active surface area of the carbon aerogel and thus on the capacitance of the material. This is demonstrated by testing the performance of the composite in supercapacitors. Faradaic reactions are exploited in an aqueous electrolyte through the high accessible surface of the incorporated small Fe2 O3 nanoparticles boosting the specific capacitance of the 3D turbostratic graphene network significantly.