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At least 109 records · Page 6

Transforming nanoscale VO 2 (B) into a scalable sodium-ion electrode

The intermittent nature of renewable energies requires highly reliable grid-level energy storage approaches. A critical consideration in developing this technology is the areal capacity which determines battery performance and influences the cost of battery technology. Of related importance is finding new ways of developing scalable electrodes. In recent years, three-dimensional (3D) printing of conductive scaffolds has emerged as an alternative to overcome the scalability limitations of commercial tape cast electrodes. The research carried out in the current study demonstrates a successful scalability pathway for nanoscale VO 2 (B), a desirable cathode for sodium-ion batteries which has a nano-flower morphology with a crystallite size < 20 nm. By electrodepositing VO 2 (B) onto a graphene aerogel scaffold, we were able to achieve mass loading of over 100 mg·cm −2 and still possess an areal capacity of 10 mAh·cm −2 at a current density of 5 mA·cm −2 . Moreover, after 1000 cycles, these electrodes retained 75% to 80% of their initial capacity. Even at high loading levels, the electrodeposited VO 2 (B) exhibits pseudocapacitive material signatures such as a box-like voltammetry response, linear galvanostatic response, and no phase change upon lithiation. The scalability of the VO 2 (B) electrode is demonstrated in a series of experiments which show the areal capacity to scale upon increase in both mass loading and electrode thickness, with only small changes in specific capacity. Furthermore, this study establishes that nanoscale materials can be scaled up to achieve thick electrodes without compromising their electrochemical properties.

additive manufacturing↗

Keratin-derived functional carbon with superior charge storage and transport for high-performance supercapacitors

In this work, we report a scalable method to synthesize hierarchically porous, hetero-atom doped activated carbon nanosheet from waste biomass-human hair, and demonstrates the use of this carbon as an ultra-high performance electrode material for supercapacitor applications. Microscopic analyses reveal that sheet size ranges from 50 to 200 nm having a thickness of 15–27 nm. As-synthesized, carbon nanosheets possess a hierarchical porous structure having a specific surface area of 1548 m 2 g -1 . Heteroatom concentration (nitrogen, oxygen, and sulfur) of around 25% is confirmed from XPS analysis. Therefore, the novel interconnected hierarchical porous nanosheets structure enables fast adsorption and transportation of ions during electrochemical processes. Also, the abundant chemically available electroactive heteroatom species in the material enhance the wettability of ions and contribute to pseudocapacitance. The electrochemical analyses through cyclic voltammetry and galvanostatic charge-discharge measurements in 6 M KOH reveal the quasi-EDLC behavior of the activated carbons due to the presence of heteroatoms. A reprensentative KOH activated carbon shows an excellent specific capacitance value of 999 F g -1 at a current density of 1 A g -1 . Furthermore, the symmetrically assembled two-electrode device also delivers a maximum energy density of 32 W h Kg -1 at a power density of 325 W Kg -1 . In addition, excellent cyclic stability of 98% capacitance retention is observed after 10,000 continuous GCD cycles even at a high current density of 5 A g -1 . Symmetric flexible supercapacitor device using KOH-PVA-K3FeCN6 as redox gel polymer electrolyte shows a synergistic specific capacitance of 145 mF cm -1 at a current density of 0.8 mA cm -1 exhibiting very less deviation in bending mode. Therefore, this waste biomass derived heteroatom doped hierarchical porous carbon nanosheets can be a promising material for cost-effective high- performance supercapacitor.

42 ENGINEERING↗

Spinel high-entropy oxides (FeNiCrMnZnX) 3 O 4 (X = Al, mg) as anode materials for high-performance lithium-ion batteries

To address the high cost, cobalt dependency, and resource constraints typical of conventional high-entropy oxide (HEO) anodes, this study reports the successful synthesis of two Co-free, six-component spinel-type HEOs(FeNiCrMnZnAl) 3 O 4 (HEO-Al) and (FeNiCrMnZnMg) 3 O 4 (HEO-Mg), via a sol-gel method. The distinct effects of Al 3+ and Mg 2+ incorporation on the electrochemical performance and lithium storage kinetics were systematically investigated. XRD, Raman, and TEM characterizations confirm that both materials possess a pure spinel phase, uniform particle size, and homogeneous elemental distribution. Notably, electrochemical evaluations reveal that HEO-Al delivers a superior reversible capacity of 480.7 mAh g −1 after 100 cycles at 0.1 A g −1 , and maintains 354.5 mAh g −1 after 1000 long-term cycles at 1 A g −1 , significantly outperforming HEO-Mg. Kinetic analysis indicates that HEO-Al exhibits lower charge transfer resistance, a higher Li + diffusion coefficient, and a pseudocapacitive contribution of up to 82%. Furthermore, these findings demonstrate that Al substitution effectively optimizes the structural stability and lithium storage kinetics of Co-free HEOs, providing a viable strategy for designing low-cost, highly stable HEO anode systems.

Anode materials↗

Carbon-encapsulated niobium carbonitride with high volumetric capacitance and wide potential windows in aqueous pseudocapacitors

Electrochemical capacitors deliver high power and have long operational lives; yet, their energy densities are limited. Compared to carbon-based electrical double-layer capacitors, pseudocapacitors with an aqueous electrolyte are predicated to provide both high gravimetric and volumetric capacitance while being cost-effective and eco-friendly. However, their narrow operational potential windows limit the practical delivery of energy. In this study, we synthesized novel NbCxN1-x nanoparticles encapsulated in a uniform carbon layer. This pseudocapacitive material exhibits a high volumetric capacitance, a wide potential window stability (~345 F cm –3 , 2.1 V, in 1 M of Li 2 SO 4 ), and a long cycling life (>10 000 cycles). Moreover, the symmetric cells (2.2 V, in 1 M of Li 2 SO 4 ) exhibit high energy density as well as excellent cyclability and rate performances. These results offer new chances for the design of aqueous energy storage devices having a wide applied potential difference and excellent performance.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Robust hierarchical three dimensional nickel cobalt tungstate-MXene nanocomposite for high performance symmetric coin cell supercapacitors

Design of rational electrode materials with hierarchically structured pseudocapacitive materials has been identified as a successful strategy for revamping the electrochemical characteristics of supercapacitors. However, the simultaneous assurance of strong electrical conductivity and higher specific capacitance via a simple and cost-effective synthesis protocol is of concern today. In this work, Ni-CoWO 4 incorporated MXene nanocomposite has been successfully prepared by a facile hydrothermal process. The structure, morphology, stoichiometry, and chemical characterization of the prepared Ni-CoWO 4 , Ti 3 C 2 T x , and Ni-CoWO4@MXene nanocomposite were explored extensively. MXene demonstrated a layered 2D nanoscale structure whereas pure Ni-CoWO 4 was composed of spherical nanoparticles. The composite Ni-CoWO 4 @MXene revealed the morphology of spherical Ni-CoWO 4 nanoparticles decorated on MXene sheets. Furthermore, a series of electrochemical characterizations illustrated the contribution of the delightful morphology of Ni-CoWO 4 @MXene composite to excellent electrochemistry. The resultant Ni-CoWO 4 @MXene electrode exhibited high specific capacitance of 582 Fg -1 at 1 A g -1 and 93.5 % capacitance retention over the 10,000 cycles., which is higher than that of the individual counterparts Ni-CoWO 4 and MXene. The excellent electrochemical performance of Ni-CoWO 4 @MXene is attributed to the synergistic interaction between Ni-CoWO4 nanoparticles and nanolayered MXene that may create new active sites that enhanced the charge transfer, charge/discharge kinetics and the electrical conductivity. Significantly, the unique Ni-CoWO 4 @MXene supercapacitor prototype delivered a higher energy density of 85.7 Wh kg -1 and power density of 0.85 kW kg -1 establishing its superiority over other Cosingle bondW based supercapacitors. A theoretical study was also performed to correlate the improved charge storage capacity of the prepared Ni-CoWO 4 @MXene composite.

25 ENERGY STORAGE↗

Solvent-free production of carbon materials with developed pore structure from biomass for high-performance supercapacitors

The study aimed at preparing porous carbon materials, with superhydrophilic characteristics and developed micro/mesoporous structure (CSB-800), from corn stover by a solvent-free method including pre-carbonization, ball milling, and activation. The effect of pre-carbonization, ball milling on the detailed structural composition and properties especially the hydrophilicity and porous structures were studied, and the potential application of CSB-800 as electrode in supercapacitors was also investigated. The results revealed that pre-carbonization increased the accessibility of raw materials as well as the efficiency of the ball milling with KOH, leading to small carbon particles with good dispersion behavior. Ball milling promoted the porosity, surface energy, hydrophilicity, crystallinity, and graphitization of the carbon materials. CSB-800 exhibited a high specific surface area of 2440.6 m 2 /g with developed micro and porous structures. The heteroatom nitrogen formed nitrogen-containing groups of N Q and N X, which provided faradaic pseudocapacitance when CSB-800 was used as an electrode material, and this material presented a specific capacitance of 398 F/g at 0.5 A/g in 1 M H 2 SO 4 electrolyte in a three-electrode system, while the value was 243 F/g in a two-electrode system, and the energy density reached 5.01 Wh/kg at a power density of 100 W/kg.

09 BIOMASS FUELS↗

Construction of Ni-Co-Mn layered double hydroxide nanoflakes assembled hollow nanocages from bimetallic imidazolate frameworks for supercapacitors

Highlights: • Bimetallic Co-Mn ZIF is successfully prepared. • N-Co-Mn LDH nanoflakes assembled hollow nanocage is constructed by a MOF templating method. • The N-Co-Mn LDH exhibits excellent pseudocapacitive performance. - Abstract: Layered double hydroxides (LDHs) with 3-dimentional (3D) hollow nanoarchitetures are highly desirable for energy related applications. In this study, Ni-Co-Mn LDH nanoflakes assembled hollow nanocages are constructed from bimetallic imidazolate framworks precursors. Benefiting from the 3D hierarchical porous strcuture and composition, the as-synthesized ternary Ni-Co-Mn LDH hollow nanocage, as a electrode for supercapacitor, demonstrates a remarkable electrochemical performance with a high specific capacitance of 2012.5 F g{sup −1} at 1 A g{sup −1} and a good rate capacity of 75.0% retention at 10 A g{sup −1}, significantly outperforming binary Ni-Co LDH (1266.2 F g{sup −1} at 1 A g{sup −1}, 41.8% retention at 10 A g{sup −1}). This work demonstrates the construction of 3D hollow nanostructured LDH with multicomponent compositions for the first time, and can be simply extended to construct other hollow structured electrode materials for energy storage devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Morphological behaviour, electronic bond formation and electrochemical performance study of V2O5-polyaniline composite and its application in asymmetric supercapacitor

Highlights: • Interlinked V{sub 2}O{sub 5}-PANI composites are synthesized by chemical polymerization. • V{sub 2}O{sub 5}-PANI exhibits the highest capacitance of 529.56 F g{sup −1} with wide window of 1.6 V. • Correlation between electrochemical performances with IR peak shifts is studied. • Inorganic-organic synergistic effect plays crucial role for wide working window. • Asymmetric supercapacitor exhibits high energy and power in wide potential windows. - Abstract: To meet the demand of high-energy density supercapacitors, development of suitable electrode material with a wide potential window and high specific capacitance is most important. In this report, we have synthesized V{sub 2}O{sub 5}-PANI nanocomposite through in-situ intercalation and polymerization reaction of aniline with V{sub 2}O{sub 5}, which shows a wide potential window as well as high specific capacitance. XRD, SEM and FTIR have been used to characterize the electrode materials. Their electrochemical activity and pseudocapacitive performances were investigated. The correlation between morphology and electrochemical performances were investigated which is a vital way for the selection of electrode materials. Due to the organic-inorganic compatibility, V{sub 2}O{sub 5}-PANI exhibits good electrochemical charge storage in a wide potential window of 1.6 V (ranging between −0.4 V to 1.2 V) with excellent stability of 84.2% capacitance retention after 5000 GCD cycles. Moreover, asymmetric supercapacitor was assembled V{sub 2}O{sub 5}-PANI composite and NiMn{sub 2}O{sub 4} electrodes which yield remarkable energy and power density.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Role of structural hydroxyl groups in enhancing performance of electrochemically-synthesized bilayer V 2 O 5

Nanostructured electrode materials represent a promising path forward to dramatically improving the performance of both Li-ion and beyond Li-ion battery systems; however, difficulties in characterizing the structural and electrochemical changes that take place in nanoscale systems, which are often poorly crystalline or amorphous, make it difficult to develop design rules for synthesizing new materials with optimal performance. Bilayered vanadium oxide-based materials (BL-V 2 O 5 ) are an ideal platform for understanding the underlying physicochemical properties that determine capacity in nanomaterials, with electrochemically-synthesized V 2 O 5 (EC-V 2 O 5 ) exhibiting particularly high capacities. In this work we provide evidence that the source of high practical capacity in EC-V 2 O 5 is the presence of “structural hydroxyl groups” that are an intrinsic feature of the electrochemical synthesis method. Using both in situ and ex situ characterization methods, we demonstrate that structural OH species are highly stable and persist in the structure during reversible cycling. We hypothesize three important roles for structural OH groups: they maintain a sufficient interlayer spacing to allow the physical diffusion of cations over multiple cycles; they maintain a consistent solvating environment in the bilayer regardless of structural H 2 O content; and they reduce the symmetry of vanadium polyhedra to favor electron transfer over pseudocapacitive adsorption, making it possible to access close to theoretical capacity. Furthermore, these insights have broad implications for understanding the performance of a variety of hydrated oxide systems, and indicate that the formation of covalently-bound hydroxyoxide species can lead to further improvements in the performance of nanoscale materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Boosting the sodium storage behaviors of carbon materials in ether-based electrolyte through the artificial manipulation of microstructure

The porous carbon blacks rationally designed by a facile yet efficient NH 3 thermal etching route have been investigated as anode materials in an ether-based electrolyte for sodium-ion batteries. The as-synthesized CBN35 carbon black with a 35% weight loss after NH3 thermal etching exhibited a large specific charge capacity of 352 mAh g -1 at 50 mA g -1 and a superior rate capability of 101 mAh g -1 at 16000 mA g -1 , due to its highest microporosity, an appropriate surface area, a desirable microstructure, and a promising hybrid intercalation mechanism. Impressively, even cycled at 1600 mA g -1 over 3200 cycles, an outstanding reversible capacity of 103 mAh g -1 with a negligible 0.0162% capacity loss per cycle can still be achieved. Based on the multimodal characterizations including the structural probes of phase evolution for carbon materials, the electrochemical techniques, and the surface-sensitive XAS measurements, the exceptional electrochemical properties should stem from several merits of modified carbon black system. While the particular microporous structure provides relatively more accessible sodium storage sites, a novel hybrid intercalation mechanism in ether-based electrolyte would incorporate the sodium ion insertion into the disordered structure with the solvated sodium ion species co-intercalation into the graphitic phase. In addition to the diffusion-controlled redox reactions, the noticeable surface-induced pseudocapacitive reactions also significantly contribute to the charge storage upon sodiation and guarantee the rapid migrations of sodium ions/solvated compounds. In conclusion, this system further features a controlled emergence of a robust but thin solid electrolyte interphase layer, which could suppress the side reactions of active electrode with reactive electrolyte, maintain the fragile porous structure upon cycling, and facilitate the migrations of sodium ions and solvated sodium ion compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mesoporous MoO 2 thin films for high rate Li + storage: Effect of crystallinity and porous structure

MoO 2 has attracted much recent attention as a high capacity energy storage material. While much of the current work on MoO 2 has been focused on the high capacity four-electron reduction, this reaction is limited to slow charging process due to the large volume change and phase transitions involved. In this study we focus on one-electron insertion reactions and demonstrate that ordered mesoporous thin films of MoO 2 can show signatures of pseudocapacitive charge storage. Mesoporous MoO 2 (mp-MoO 2 ) thin films were treated at different temperatures between 350 and 700 °C to explore the role of crystallinity and nanoscale structure on charging dynamics. The porosity and pore size decreased while the crystallinity and grain size increased as the calcination temperature increased. Materials processed at 600 °C showed the best electrochemical performance due to an optimized combination of high crystallinity and small grain size. These materials could be charged and discharged in 24 s while still achieving a Li + storage capacity of 158 mAh/g. While such thin film systems do not constitute a practical energy storage device, the work here provides structural design parameters for the production of future bulk nanoporous materials.

25 ENERGY STORAGE↗

Optimal Linear Water Density for Proton Transport in Tunnel Oxides

Proton intercalation and transport is key to pseudocapacitive energy storage of oxide electrodes in acidic electrolytes. Although proton transport in water confined in layered or 2D materials is attracting great interest, much less is known about how the proton is transported in the 1D channels of tunnel oxides such as hexagonal WO 3 (h-WO 3 ). Here, we use first-principles molecular dynamics to reveal an optimal linear density of four water molecules per nanometer that yields the highest proton diffusivity. The volcano shape of proton diffusivity versus linear water density is a result of balancing the linear hydrogen-bond chain and the rotation of the water molecules to enable the Grotthuss mechanism. Furthermore, this insight provides a unifying view of proton transport along a single file of water molecules confined in hydrophilic 1D channels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Correlation of the Salt-Reduced Diffusivities of Organic Solvents with the Solvent’s Mole Fraction

We report that lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in organic solvents (especially propylene carbonate) has demonstrated extraordinary pseudocapacitive performance as an electrolyte in the supercapacitor configuration. However, the influence of the solvated ions on the diffusivity of the solvent molecules is yet to be understood. We examine the impact of LiTFSI on the diffusivity in five organic solvents: acetonitrile (ACN), tetrahydrofuran (THF), methanol (MeOH), dimethyl sulfoxide (DMSO), and propylene carbonate (PC) using a combination of neutron scattering, conductivity measurements, and molecular dynamics simulations. The extent of the diffusivity reduction in the concentration regime of ≤1 M directly correlates with the solvent mole fraction at which the solvation shells around Li + ions are of similar size in all the solvents, resulting in a universal ~50% reduction in the solvent diffusivity. These results provide guidance for formulation of the new electrolytes to enhance the performance of energy storage devices.

conductivity↗

Ionic Tunability of Conjugated Polyelectrolyte Solutions

Conjugated polyelectrolytes (CPEs), which combine a π-conjugated polymer backbone with pendant ionic functionalities, offer an opportunity for electrostatic control of materials properties. In this work, the mesoscale morphology and physical properties of a high-mobility conjugated polyelectrolyte are tuned by the addition of salt, variation of the charge-compensating counterion, and complexation with an oppositely charged polyelectrolyte containing the same π-conjugated backbone. In systems with a single polyelectrolyte species, added ions screen the electrostatic repulsions stabilizing the gel-phase, resulting in the dissolution of ionic cross-links and hydrophobic collapse. Further, exchanging the charge compensating counterion is found to enable finer structural control of the solution behavior and modulation of the self-doping behavior. Finally, novel CPE–CPE complexes resulting in dense solutions and gels of semiconductive material are produced by combination of oppositely charged polyelectrolytes. Such concentrated CPE formulations should be useful materials for mixed electronic–ionic conduction and pseudocapacitative energy storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Covalent Organic Framework for Fast-Charge and Durable Rechargeable Mg Storage

High safety, low cost and high volumetric capacity rechargeable magnesium batteries (RMBs) are promising alternatives to lithium ion batteries. However, lack of high power, high energy and stable cathodes for RMBs hinders their commercialization. Herein, an environmentally benign, low cost and sustainable covalent organic framework (COF) cathode for Mg storage is reported for the first time. It delivers a high power density of 2.8 kW kg -1 , a high specific energy density of 146 Wh kg -1 , and ultra-long cycle life of 3000 cycles with very slow capacity decay rate of 0.0196% per cycle, representing one of the best cathodes to date. The comprehensive electrochemical analysis proves that triazine ring sites in COF are redox centers for reversible reaction with magnesium ions, and the ultra-fast reaction kinetic is mainly attributed to pseudocapacitive behavior. The high-rate Mg storage of COF offers new opportunities for the development of ultra-stable and fast charge RMBs.

36 MATERIALS SCIENCE↗

Electrolyte Effect on the Electrochemical Performance of Mild Aqueous Zinc-Electrolytic Manganese Dioxide Batteries

Recently, mild aqueous rechargeable Zn-MnO 2 batteries have attracted increasing interest for energy storage due to the appealing attributes of low cost of Zn and Mn resource and high safety and environmental benignity. Despite extensive types of MnO 2 have been proposed for cathodes, the different reported performance, complex synthesis methods and lacking a thorough understanding of reactions in MnO 2 cathodes greatly hinder their practical applications for long life energy storage. Here we demonstrate the low cost and commercially available electrolytic manganese dioxide (EMD) as a promising and reversible cathode for mild aqueous rechargeable Zn-MnO 2 batteries through a rational manipulation of redox reactions in EMD cathode. In optimal Zn(TFSI)2-based electrolyte, the EMD cathode exhibits a mixed diffusion controlled conversation relation between EMD and H + and diffusion-free pseudocapacitance-like reactions without phase change. This mechanism enables EMD cathode with excellent cycling stability over 5000 cycles with a capacity retention of 94%. This study provides new opportunity to develop mild aqueous Zn-MnO 2 batteries with low cost and high-performance cathode materials by a rational control of the reaction mechanisms.

25 ENERGY STORAGE↗