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Aqueous zinc-ion batteries (AZIBs) have attracted significant attention owing to their inherent security, low cost, abundant zinc (Zn) resources and high energy density. Nevertheless, the growth of zinc dendrites and side reactions on the surface of Zn anodes during repeatedly plating/stripping shorten the cycle life of AZIBs. Herein, a simple organic molecule with abundant polar functional groups, 2,2,2-trifluoroether formate (TF), has been proposed as a high-efficient additive in the ZnSO4 electrolyte to suppress the growth of Zn dendrites and side reaction during cycling. It is found that TF molecules can infiltrate the solvated sheath layer of the hydrated Zn2+ to reduce the number of highly chemically active H2O molecules owing to their strong binding energy with Zn2+. Simultaneously, TF molecules can preferentially adsorb onto the Zn surface, guiding the uniform deposition of Zn2+ along the crystalline surface of Zn(002). This dual action significantly inhibits the formation of Zn dendrites and side reactions, thus greatly extending the cycling life of the batteries. Accordingly, the Zn//Cu asymmetric cell with 2 % TF exhibits stable cycling for more than 3,800 cycles, achieving an excellent average Columbic efficiency (CE) of 99.81 % at 2 mA cm-2/1 mAh cm-2. Meanwhile, the Zn||Zn symmetric cell with 2 % TF demonstrates a superlong cycle life exceeding 3,800 h and 2,400 h at 2 mA cm-2/1 mAh cm-2 and 5 mA cm-2/2.5 mAh cm-2, respectively. Simultaneously, the Zn//VO2 full cell with 2 % TF possesses high initial capacity (276.8 mAh/g) and capacity retention (72.5 %) at 5 A/g after 500 cycles. This investigation provides new insights into stabilizing Zn metal anodes for AZIBs through the co-regulation of Zn2+ solvated structure and surface crystallography.
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Currently, conversion-type transition metal sulfides have been extensively favored as the anodes for sodium-ion batteries due to their excellent redox reversibility and high theoretical capacity; however, they generally suffer from large volume expansion and structural instability during repeatedly Na+ de/intercalation. Herein, spatially dual-confined Ni-doped CoS2@NC@C microrods (Ni-CoS2@NC@C) are developed via structural design, heteroatom doping and carbon confinement to boost sodium storage performance of the material. The morphology of one-dimensional-structured microrods effectively enlarges the electrode/electrolyte contact area, while the confinement of dual-carbon layers greatly alleviates the volume change-induced stress, pulverization, agglomeration of the material during charging and discharging. Moreover, the introduction of Ni improves the electrical conductivity of the material by modulating the electronic structure and enlarges the interlayer distance to accelerate Na+ diffusion. Accordingly, the as-prepared Ni-CoS2@NC@C exhibits superb electrochemical properties, delivering the satisfactory cycling performance of 526.6 mA h g-1 after 250 cycles at 1 A g-1, excellent rate performance of 410.9 mA h g-1 at 5 A g-1 and superior long cycling life of 502.5 mA h g-1 after 1,500 cycles at 5 A g-1. This study provides an innovative idea to improve sodium storage performance of conversion-type transition metal sulfides through the comprehensive strategy of structural design, heteroatom doping and carbon confinement.
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Transition metal selenides (TMSs) stand out as a promising anode material for sodium-ion batteries (SIBs) owing to their natural resources and exceptional sodium storage capacity. Despite these advantages, their practical application faces challenges, such as poor electronic conductivity, sluggish reaction kinetics and severe agglomeration during electrochemical reactions, hindering their effective utilization. Herein, the dual-carbon-confined CoSe2/FeSe2@NC@C nanocubes with heterogeneous structure are synthesized using ZIF-67 as the template by ion exchange, resorcin-formaldehyde (RF) coating, and subsequent in situ carbonization and selenidation. The N-doped porous carbon promotes rapid electrolyte penetration and minimizes the agglomeration of active materials during charging and discharging, while the RF-derived carbon framework reduces the cycling stress and keeps the integrity of the material structure. More importantly, the built-in electric field at the heterogeneous boundary layer drives electron redistribution, optimizing the electronic structure and enhancing the reaction kinetics of the anode material. Based on this, the nanocubes of CoSe2/FeSe2@NC@C exhibits superb sodium storage performance, delivering a high discharge capacity of 512.6 mA h g-1 at 0.5 A g-1 after 150 cycles and giving a discharge capacity of 298.2 mA h g-1 at 10 A g-1 with a CE close to 100.0 % even after 1000 cycles. This study proposes a viable method to synthesize advanced anodes for SIBs by a synergy effect of heterogeneous interfacial engineering and a carbon confinement strategy.
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Vanadium dioxide-based materials have been proved to be promising cathodes for aqueous zinc ion batteries (AZIBs) due to their cost-effectiveness and high theoretical specific capacity; nevertheless, the low electronic conductivity and poor cycle stability restrict their application. Herein, hollow VO2 microspheres anchored on graphene oxide (H-VO2@GO) are synthesized via a facile simple hydrothermal reaction as high-performance cathodes for AZIBs. The hollow micromorphology of the material provides a large specific surface area and effectively alleviates the volume changes during cycling, while the anchoring of VO2 on graphene oxide greatly improves the electronic conductivity and inhibits the agglomeration and pulverization of the material. Resulting from the combination of unique micromorphology and graphene oxide anchoring, the as-prepared H-VO2@GO exhibits the impressive specific capacity of 400.1 mAh/g at 0.5 A/g and excellent cycling performance with 96.1 % of capacity retention after 1500 cycles at 10 A/g. This investigation provides a use reference for designing high-performance cathodes materials for AZIBs by optimizing the microstructure of electrode materials.
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Ammonium vanadates, featuring an NâH···O hydrogen bond network structure between NH4 + and VâO layers, have become popular cathode materials for aqueous zinc-ion batteries (AZIBs). Their appeal lies in their multi-electron transfer, high specific capacity, and facile synthesis. However, a major drawback arises as Zn2+ ions tend to form bonds with electronegative oxygen atoms between VâO layers during cycling, leading to irreversible structural collapse. Herein, Li+ pre-insertion into the intermediate layer of NH4V4O10 is proposed to enhance the electrochemical activity of ammonium vanadate cathodes for AZIBs, which extends the interlayer distance of NH4V4O10 to 9.8 Å and offers large interlaminar channels for Zn2+ (de)intercalation. Moreover, Li+ intercalation weakens the crystallinity, transforms the micromorphology from non-nanostructured strips to ultrathin nanosheets, and increases the level of oxygen defects, thus exposing more active sites for ion and electron transport, facilitating electrolyte penetration, and improving electrochemical kinetics of electrode. In addition, the introduction of Li+ significantly reduces the bandgap by 0.18 eV, enhancing electron transfer in redox reactions. Leveraging these unique advantages, the Li+ pre-intercalated NH4V4O10 cathode exhibits a high reversible capacity of 486.1 mAh g-1 at 0.5 A g-1 and an impressive capacity retention rate of 72% after 5,000 cycles at 5 A g-1.
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Transition metal sulfides (TMS) have been considered as a promising group of electrode materials for supercapacitors as a result of their strong redox activity, but high volumetric strain of the materials during electrochemical reactions causes rapid structural collapse and severe capacity loss. Herein, we have synthesized phosphorus-doped (P-doped) Ni2S3/Co3S4/ZnS battery-type nanowire/nanosheet arrays as an advanced cathode for supercapacitor through a two-step process of hydrothermal and annealing treatments. The material has a one-dimensional nanowire/two-dimensional nanosheet-like coexisting microscopic morphology, which facilitates the exposure of abundant active centers and promotes the transport and migration of ions in the electrolyte, while the doping of P significantly enhances the conductivity of the electrode material. Simultaneously, the element phosphorus with similar atomic radii and electronegativity to sulfur may act as electron donors to regulate the electron distribution, thus providing more effective electrochemically active sites. In gratitude to the synergistic effect of microstructure optimization and electronic structure regulation induced by the doing of P, the P-Ni2S3/Co3S4/ZnS nanoarrays provide a superior capacity of 2716 F g-1 at 1 A/g, while the assembled P-Ni2S3/Co3S4/ZnS//AC asymmetric supercapacitor exhibits a high energy density of 48.2 Wh kg-1 at a power density of 800 W kg-1 with the capacity retention of 89 % after 9000 cycles. This work reveals a possible method for developing high-performance transition metal sulfide-based battery-like electrode materials for supercapacitors through microstructure optimization and electronic structure regulation.
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Sodium superionic conductor (NASICON)-type Na3 V2 (PO4 )3 has attracted considerable interest owing to its stable three-dimensional framework and high operating voltage; however, it suffers from a low-energy density due to the poor intrinsic electronic conductivity and limited redox couples. Herein, the partial substitution of Mn3+ for V3+ in Na3 V2 (PO4 )3 is proposed to activate V4+ /V5+ redox couple for boosting energy density of the cathodes (Na3 V2- x Mnx (PO4 )3 ). With the introduction of Mn3+ into Na3 V2 (PO4 )3 , the band gap is significantly reduced by 1.406 eV and thus the electronic conductivity is greatly enhanced. The successive conversions of four stable oxidation states (V2+ /V3+ , V3+ /V4+ , and V4+ /V5+ ) are also successfully achieved in the voltage window of 1.4-4.0 V, corresponding to three electrons involved in the reversible reaction. Consequently, the cathode with x = 0.5 exhibits a high reversible discharge capacity of 170.9 mAh g-1 at 0.5 C with an ultrahigh energy density of 577 Wh kg-1 . Ex-situ x-ray diffraction (XRD) analysis reveals that the sodium-storage mechanism for Mn-doped Na3 V2 (PO4 )3 consists of single-phase and bi-phase reactions. This work deepens the understanding of the activation of reversible three-electron reaction in NASICON-structured polyanionic phosphates and provides a feasible strategy to develop high-energy-density cathodes for sodium-ion batteries.
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Recently, vanadium dioxide (VO2) has been recognized as one of the most prospective cathodes for aqueous zinc ion batteries (AZIBs) for its high reversible specific capacity; nevertheless, its Zn2+ diffusion kinetics and cycling stability have not yet met expectations. Herein, Mo ions are introduced into VO2 to optimize the intrinsic electronic structure and micromorphology of VO2, achieving significantly enhanced zinc-ion storage. It is found that the substitution of Mo for V narrows the band gap of VO2 and thus enhances the conductivity of the material, while VO2 nanorods are transformed into VO2 nanoflowers which are self-assembled from ultra-thin nanosheets after the introduction of Mo, exposing much more active sites to enhance the migration kinetics of Zn2+. Consequently, the Mo-substituted VO2 (0.5-Mo-VO2) exhibits excellent electrochemical properties, presenting a high initial capacity of 494.5 mAh/g at 0.5 A/g, excellent rate capability of 336 mA h g-1 at 10 A/g and brilliant cycling stability with the capacity retention of 82% over 2000 cycles at 10 A/g. This work provides significant guidance for the design of advanced cathodes for AZIBs by optimizing the electronic structure and tailoring morphology of V-based materials.
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Aqueous zinc-ion batteries (AZIBs) have attracted considerable attention due to their low cost and environmental friendliness. However, the rampant dendrite growth and severe side reactions during plating/stripping on the surface of zinc (Zn) anode hinder the practicability of AZIBs. Herein, an effective and non-toxic cationic electrolyte additive of Rb2 SO4 is proposed to address the issues. The large cation of Rb+ is preferentially adsorbed on the surface of Zn metal to induce a strong shielding effect for realizing the lateral deposition of Zn2+ ions along the Zn surface and isolating water from Zn metal to effectively inhibit side reactions. Consequently, the Zn||Zn symmetric cell with the addition of 1.5 mm Rb2 SO4 can cycle more than 6000 h at 0.5 mA cm-2 /0.25 mAh cm-2 , which is 20 times longer than that without Rb2 SO4 . Besides, the Zn||Cu asymmetric cell with Rb2 SO4 achieves a very high average Coulombic efficiency of 99.16% up to 500 cycles. Moreover, the electrolyte with Rb2 SO4 well matches with the VO2 cathode, achieving high initial capacity of 412.7 mAh g-1 at 5 A g-1 and excellent cycling stability with a capacity retention of 71.6% at 5 A g-1 after 500 cycles for the Zn//VO2 full cell.
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Aqueous rechargeable Zn-ion batteries (ARZIBs) are promising for energy storage. However, the Zn dendrite and corrosive reactions on the surface of Zn anode limit the practical uses of ARZIBs. Herein, we present a valid electrolyte additive of NaI, in which I- can modulate the morphology of Zn crystal growth by adsorbing on specific crystal surfaces (002), and guide Zn deposition by inducing a negative charge on the Zn anode. Simultaneously, it enhances the reduction stability of water molecules by participating in the solvation structure of Zn(H2O)62+ by forming ZnI(H2O)5+. At 10 mA cm-2, the assembled Zn symmetrical batteries can run stably over 1,100 h, and the depth of discharge (DOD) can reach 51.3 %. At 1 A g-1, the VO2||Zn full-cell in 2 M ZnCl2 electrolyte with 0.4 M NaI (2 M ZnCl2-0.4 M NaI) maintains of the capacity retention of 75.7 % over 300 cycles. This work offers an insight into inorganic anions as electrolyte additives for achieving stable zinc anodes of ARZIBs.
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Nickel sulfides with high theoretical capacity are considered as promising anode materials for sodium-ion batteries (SIBs); however, their intrinsic poor electric conductivity, large volume change during charging/discharging, and easy sulfur dissolution result in inferior electrochemical performance for sodium storage. Herein, a hierarchical hollow microsphere is assembled from heterostructured NiS/NiS2 nanoparticles confined by in situ carbon layer (H-NiS/NiS2 @C) via regulating the sulfidation temperature of the precursor Ni-MOFs. The morphology of ultrathin hollow spherical shells and confinement of in situ carbon layer to active materials provide rich channels for ion/electron transfer and alleviate the effects of volume change and agglomeration of the material. Consequently, the as-prepared H-NiS/NiS2 @C exhibit superb electrochemical properties, satisfactory initial specific capacity of 953.0 mA h g-1 at 0.1 A g-1 , excellent rate capability of 509.9 mA h g-1 at 2 A g-1 , and superior longtime cycling life with 433.4 mA h g-1 after 4500 cycles at 10 A g-1 . Density functional theory calculation shows that heterogenous interfaces with electron redistribution lead to charge transfer from NiS to NiS2 , and thus favor interfacial electron transport and reduce ion-diffusion barrier. This work provides an innovative idea for the synthesis of homologous heterostructures for high-efficiency SIB electrode materials.
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Recently, potassium-ion batteries (PIBs) have been considered as one of the most promising energy storage systems; however, the slow kinetics and large volume variation induced by the large radius of potassium ions (K+) during chemical reactions lead to inferior structural stability and weak electrochemical activity for most potassium storage anodes. Herein, a multilevel space confinement strategy is proposed for developing zinc-cobalt bimetallic selenide (ZnSe/Co0.85Se@NC@C@rGO) as high-efficient anodes for PIBs by in-situ carbonizing and subsequently selenizing the resorcinol-formaldehyde (RF)-coated zeolitic imidazolate framework-8/zeolitic imidazolate framework-67 (ZIF-8/ZIF-67) encapsulated into 2D graphene. The highly porous carbon microcubes derived from ZIF-8/ZIF-67 and carbon shell arising from RF provide rich channels for ion/electron transfer, present a rigid skeleton to ensure the structural stability, offer space for accommodating the volume change, and minimize the agglomeration of active material during the insertion/extraction of large-radius K+. In addition, the three-dimensional (3D) carbon network composed of graphene and RF-derived carbon-coated microcubes accelerates the electron/ion transfer rate and improves the electrochemical reaction kinetics of the material. As a result, the as-synthesized ZnSe/Co0.85Se@NC@C@rGO as the anode of PIBs possesses the excellent rate capability of 203.9 mA h g-1 at 5 A g-1 and brilliant long-term cycling performance of 234 mA h g-1 after 2,000 cycles at 2 A g-1. Ex-situ X-ray diffraction (Ex-situ XRD) diffraction reveals that the intercalation/de-intercalation of K+ proceeds through the conversion-alloying reaction. The proposed strategy based on the spatial confinement engineering is highly effective to construct high-performance anodes for PIBs.
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Two series of lanthanoid (Ln)-containing polyoxometalates (POMs) {[Ln6(ampH)4(H2O)24-n(ampH2)n(PW11O39)2]·21H2O (Ln = Tb, n = 0 (1), Ln = Er, n = 1 (2)) and K2[Ln6(ampH)4(H2O)22(SiW11O39)2]·23H2O (Ln = Tb (3), Er (4)) (ampH2 = (aminomethyl) phosphonic acid)} have been synthesized with tri-lacunary Keggin-type POMs containing different types of heteroatoms. Compounds 1 and 2 display neutral organic-inorganic hybrid POM molecules containing {Ln6(ampH)4} ({Ln6}) cores sandwiched by two {PW11O39} units. By changing the heteroatoms from PV to SiIV, the extended 2D networks of 3 and 4 were successfully isolated where the adjacent {Ln6} clusters were connected by {SiW11O39} moieties. Luminescence performances and magnetic properties of 1-4 have been systematically surveyed. The solid-state fluorescence spectra of 1-4 display characteristic emissions of Ln components resulting from the 4f-4f transitions, and energy transfer from the POM segments to Ln3+ centers in 1 and 3 has been observed based on the lifetime decay behaviors. Furthermore, all compounds can be utilized as electrocatalysts toward reduction of nitrite with high stability.
RESUMO
Designing an earth-abundant and cost-effective electrocatalyst for oxygen evolution reaction (OER) is the crux to the hydrogen production by water electrolysis on industrial scale. Herein, we developed a trimetallic sulfide hybrid of CoS1.097/Fe1-xS/Ni3S2/NF nanoarrays by the combination of morphology optimization and interface modulation. The unique morphology of ultrathin nanosheets significantly enriches the reaction sites of the catalyst, while the abundant heterogeneous interfaces effectively regulate the local electron structure and thus intrinsically enhances the catalytic activity of the material. As a result, the catalyst delivers the superior OER performance with the ultralow overpotential of 229 mV at the current density of 50 mA cm-2 and Tafel slope of 30.2 mV dec-1. Furthermore, the current density of the material keeps constant for 50 h in 1.0 M KOH. This work proposes a strategy for the synthesis of polymetallic sulfide catalysts with composite structure as an efficient OER catalyst by morphology optimization and interface modulation.
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Aqueous rechargeable Zn-ion batteries (ARZIBs) have attracted much attention owing to their safety, high energy density and environmental friendliness. However, dendrite formation and corrosive reactions on Zn anode surface limit the development of ARZIBs. Here, Ga3+-doped NaV2(PO4)3 with Na superionic conductor (NASICON) structure [NVP-Ga(x), x = 0, 0.25, 0.5, 0.75] have been exploited as the high-efficiency artificial layer to stabilize Zn anode. The optimal NVP-Ga(0.5) layer can homogenize ion flux and promote uniform deposition of zinc, the dendrite growth and the parasitic reactions can be greatly inhibited. The symmetric cell based on this unique protection layer can stably operate over 1,300 h at 0.5 mA cm-2 with 0.5 mAh cm-2. Benefitting from the high-performance Zn metal anode, the full batteries paired with MnO2 cathode deliver a high discharge capacity of 106 mAh/g with the capacity retention rate of 85 % after 8,000 cycles. This work provides an advanced strategy to stabilize Zn anode for the industrialization of ARZIBs in the near future.
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Layered double hydroxides (LDHs) with high theoretical capacity have broad prospectsin energy storage applications. However, their slow charge transfer kinetics and easy agglomerate hinder their applications in high-performance supercapacitors. Herein, Co2+-doped nickel aluminum layered double hydroxides (NiAl-LDH-Co2+-x, x = 0, 0.3, 0.6, 0.9, 1.2, 1.5) have been designed and prepared by a convenient hydrothermal process. The multicomponent layer structure formed by cobalt doping facilitates sufficient penetration of the electrolyte and accelerates the charge transfer kinetics. Furthermore, the more open layer spacing and electronic interactions induced by Co2+ doping are conducive to accelerating ion de-intercalation, thereby further improving the kinetic behavior of charge storage. Benefiting from the unique microstructure and Co2+ doping effect, the prepared NiAl-LDH-Co2+-0.9 provides a superior specific capacity of 985 C g-1 at 1 A g-1. In addition, the assembled hybrid supercapacitor with the NiAl-LDH-Co2+-0.9 as the positive electrode provides a remarkable energy density of 22.51 Wh kg-1 at a power density of 800 W kg-1 and exhibits an excellent cycle life with 80 % capacity retention after 20,000 cycles. This study demonstrates the great potential of efficient microstructure design and doping strategy in enhancing the charge storage of electrode materials.
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Zinc (Zn) metal possesses broad prospects as an anode for aqueous zinc-ion batteries (AZIBs) due to its considerable theoretical capacity of 820 mAh g-1 . However, the Zn anode suffers from dendrite growth and side reactions during Zn stripping/plating. Herein, a Prussian blue analog of copper hexacyanoferrate (CuHCF) with a 3D open structure and rich polar groups (CN) is coated on Zn foil as a solid-state electrolyte (SSE) protection layer to protect the Zn anode. The CuHCF protection layer possesses low activation energy of 26.49 kJ mol-1 , the high ionic conductivity of 7.6 mS cm-1 , and a large Zn2+ transference number of 0.74. Hence, the Zn@CuHCF||Zn@CuHCF symmetric cell delivers high cycling stability over 1800 h at 5 mA cm-2 , an excellent depth of discharge of 51.3%, and the accumulative discharge capacity over 3000 mAh cm-2 . In addition, the Zn//Ti@CuHCF asymmetric cell achieves the coulombic efficiency (CE) of 99.87% after 2000 cycles. More importantly, the Zn@CuHCF//V2 O5 full cell presents outstanding capacity retention of 87.6% at 10 A g-1 after 3000 cycles. This work develops a type of material to form an artificial protection layer for high-performance AZIBs.
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Energy storage ceramics are widely favored for their rapid charging/discharging speed, good temperature stability and large power density. Nevertheless, most lead-free energy storage ceramics can achieve excellent energy storage density (Wt) only under extremely high breakdown electric field and usually possess inferior efficiency (η). In this research, neoteric (1 - x)(Na0.5Bi0.5)0.7Sr0.3TiO3-xLa1/3(Ta0.5Nb0.5)O3 (NBST-xLTN) ceramics were designed by grain inhibition and dielectric peak flattening engineering to enhance Wt and η simultaneously under a low electric field (≤150 kV cm-1). In particular, in one aspect, multiple co-doping of the elements La3+, Ta5+ and Nb5+ as excellent grain growth inhibitors reduces the concentration of oxygen vacancies and refines the grain size to increase the breakdown strength. In another aspect, partial ion substitution in the A/B sites of BNST ceramics breaks the ferroelectric long-range order to generate polar nanoregions, resulting in a remarkable decrease in remanent polarization. Moreover, the incorporation of LTN distorts the lattice, causing a shift towards room temperature and flattening of dielectric peaks to promote the temperature/frequency stabilities significantly. Ultimately, the ultrahigh η of 92.49%, promising Wt of 2.09 J cm-3 and large Wrec of 1.94 J cm-3 under 148 kV cm-1 are achieved concurrently accompanied by the optimistic temperature, frequency and cyclic stabilities in the BNST-0.025LTN ceramic. Besides, outstanding power and current densities (PD and CD) of 67.86 MW cm-3 and 848.29 A cm-2 are procured in the BNST-0.025LTZ ceramic under a low electric field of 160 kV cm-1. The present strategies of grain inhibition and dielectric peak flattening engineering provide an effective approach to exploit novel lead-free ceramics with excellent energy storage properties.
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High-performance supercapacitors have attracted considerable interests due to their high-power density, fast charge/discharge process and long cycle life. However, the wide application of supercapacitors is limited by their low energy density. Herein, the hierarchical core-shell structured NiCoP@NiS nanoarrays have been successfully synthesized by using the vertically grown nickel-cobalt bimetallic phosphide (NiCoP) nanowire as the core and the nickel sulfide (NiS) by electrodeposition as the shell. As the "super channel" for electron transfer, the NiCoP core is coupled with the NiS shell to promote rapid diffusion of electrons and improve cycle stability of the electrode. Consequently, the optimized NiCoP@NiS nanoarrays display an extremely good specific capacitance (2128F g-1 at 1 A g-1) and a superior long cycle life (the capacitance retention of 90.36 % after 10,000 cycles). A hybrid supercapacitor (HSC) has been assembled using the NiCoP@NiS as the positive and the activated carbon (AC) as the negative, which displays a superior energy density of 30.47 Wh kg-1 at a remarkable power energy of 800 W kg-1. This study shows that the prepared hierarchical core-shell structured nanoarrays have great prospects as a novel electrode material in energy storage.
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Transition-metal sulfides boast a high theoretical capacity and have been regarded as a kind of prospective electrodes for supercapacitors; nevertheless, their inherent poor conductivity and low electrochemical active sites limit the practical applications of the materials.Herein, flower-like zinc cobalt sulfide (ZCS) microspheres with rich sulfur vacancies (ZCSδ) have been synthesized by a three-step procedure of hydrothermal, post-annealing and room-temperaturesulfuration treatments. The flower-like microspheres self-assembled by ultrathin nanosheets bring the active material fully contact with electrolyte, facilitating ion diffusion during charging and discharging. Furthermore, defect engineering of sulfur vacancies at the atomic level raises the intrinsic conductivity and increases active sites for electrochemical reactions. As a result, the obtained sulfur-deficient ZCS microspheres possess an excellent specific capacitance of 2709 F g-1 at 1 A g-1 and an exceptional cycling lifespan of maintaining 90.9% of the initial capacitance over 3000 cycles. In addition, the hybrid supercapacitor employing (HSC) sulfur-deficient flower-like ZCS microspheres as the positive electrode present a high energy density of 28 Wh kg-1 at the power density of 800 W kg-1. This investigation proposes an efficient strategy to significantly and synergistically enhance the electrochemical performance of the electrodes for hybrid supercapacitor by the comprehensive engineering of defect and morphology.