RESUMEN
Anionic chemistry modulation represents a promising avenue to enhance the electrochemical performance and unlock versatile applications in cutting-edge energy storage devices. Herein, we propose a methodology that involves anionic chemistry of carbonate anions to tailor the electrochemical oxidation-reduction reactions of bismuth (Bi) electrodes, where the conversion energy barrier for Bi (0) to Bi (III) has been significantly reduced, endowing anionic full batteries with enhanced electrochemical kinetics and chemical self-charging property. The elaborately designed batteries with an air-switch demonstrate rapid self-recharging capabilities, recovering over 80% of the electrochemical full charging capacity within a remarkably short timeframe of 1 hour and achieving a cumulative self-charging capacity of 5 Ah g-1. The aqueous self-charging battery strategy induced by carbonate anion, as proposed in this study, holds the potential for extending to various anionic systems, including seawater-based Cl- ion batteries. This work offers a universal framework for advancing next-generation multi-functional power sources.
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The catalytic process of Li2S formation is considered a key pathway to enhance the kinetics of lithium-sulfur batteries. Due to the system's complexity, the catalytic behavior is uncertain, posing significant challenges for predicting activity. Herein, we report a novel cascaded dual-cavity nanoreactor (NiCo-B) by controlling reaction kinetics, providing an opportunity for achieving hierarchical catalytic behavior. Through experimental and theoretical analysis, the multilevel structure can effectively suppress polysulfides dissolution and accelerate sulfur conversion. Furthermore, we differentiate the adsorption (B-S) and catalytic effect (Co-S) in NiCo-B, avoiding catalyst deactivation caused by excessive adsorption. As a result, the as-prepared battery displays high reversible capacity, even with sulfur loading of 13.2â mg cm-2 (E/S=4â µl mg-1), the areal capacity can reach 18.7â mAh cm-2.
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The advancement of aqueous zinc-ion batteries (AZIBs) is often hampered by the dendritic zinc growth and the parasitic side reactions between the zinc anode and the aqueous electrolyte, especially under extreme temperature conditions. This study unveils the performance decay mechanism of zinc anodes in harsh environments, characterized by "dead zinc" at low temperatures and aggravated hydrogen evolution and adverse by-products at elevated temperatures. To address these issues, a temperature self-adaptive electrolyte (TSAE), founded on the competitive coordination principle of co-solvent and anions, is introduced. This electrolyte exhibits a dynamic solvation capability, engendering an inorganic-rich solid electrolyte interface (SEI) at low temperatures while an organic alkyl ether- and alkyl carbonate-containing SEI at elevated temperatures. The self-adaptability of the electrolyte significantly enhances the performance of the zinc anode across a broad temperature range. A Zn//Zn symmetrical cell, based on the TSAE, showcases reversible plating/stripping exceeding 16 800 h (>700 d) at room temperature under 1 mA cm-2 and 1 mAh cm-2, setting a record of lifespan. Furthermore, the TSAE enables stable operation of the zinc full batteries across an ultrawide temperature range of -35 to 75 °C. This work illuminates a pathway for optimizing AZIBs under extreme temperatures by fine-tuning the interfacial chemistry.
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Low capacity and poor cycle stability greatly inhibit the development of zinc-iodine batteries. Herein, a high-performance Zn-iodine battery has been reached by designing and optimizing both electrode and electrolyte. The Br- is introduced as the activator to trigger I+, and coupled with I+ forming interhalogen to stabilize I+ to achieve a four-electron reaction, which greatly promotes the capacity. And the Ni-Fe-I LDH nanoflowers serve as the confinement host to enable the reactions of I-/I+ occurring in the layer due to the spacious and stable interlayer spacing of Ni-Fe-I LDH, which effectively suppresses the iodine-species shuttle ensuring high cycling stability. As a result, the electrochemical performance is greatly enhanced, especially in specific capacity (as high as 350â mAh g-1 at 1â A g-1 far higher than two-electron transfer Zn-iodine batteries) and cycling performance (94.6 % capacity retention after 10000â cycles). This strategy provides a new way to realize high capacity and long-term stability of Zn-iodine batteries.
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Sluggish sulfur redox kinetics and Li-dendrite growth are the main bottlenecks for lithium-sulfur (Li-S) batteries. Separator modification serves as a dual-purpose approach to address both of these challenges. In this study, the Co/MoN composite is rationally designed and applied as the modifier to modulate the electrochemical kinetics on both sides of the sulfur cathode and lithium anode. Benefiting from its adsorption-catalysis function, the decorated separators (Co/MoN@PP) not only effectively inhibit polysulfides (LiPSs) shuttle and accelerate their electrochemical conversion but also boost Li+ flux, realizing uniform Li plating/stripping. The accelerated LiPSs conversion kinetics and excellent sulfur redox reversibility triggered by Co/MoN modified separators are evidenced by performance, in-situ Raman detection and theoretical calculations. The batteries with Co/MoN@PP achieve a high initial discharge capacity of 1570 mAh g-1 at 0.2 C with a low decay rate of 0.39%, uniform Li+ transportation at 1 mA cm-2 over 800 h. Moreover, the areal capacity of 4.62 mAh cm-2 is achieved under high mass loadings of 4.92 mg cm-2. This study provides a feasible strategy for the rational utilization of the synergistic effect of composite with multifunctional microdomains to solve the problems of Li anode and S cathode toward long-cycling Li-S batteries.
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Aqueous copper-based batteries have many favourable properties and have thus attracted considerable attention, but their application is limited by their low operating voltage originating from the high potential of copper negative electrode (0.34 V vs. standard hydrogen electrode). Herein, we propose a coordination strategy for reducing the intrinsic negative electrode redox potential in aqueous copper-based batteries and thus improving their operating voltage. This is achieved by establishing an appropriate coordination environment through the electrolyte tailoring via Cl- ions. When coordinated with chlorine, the intermediate Cu+ ions in aqueous electrolytes are successfully stabilized and the electrochemical process is decoupled into two separate redox reactions involving Cu2+/Cu+ and Cu+/Cu0; Cu+/Cu0 results in a redox potential approximately 0.3 V lower than that for Cu2+/Cu0. Compared to the coordination with water, the coordination with chlorine also results in higher copper utilization, more rapid redox kinetics, and superior cycle stability. An aqueous copper-chlorine battery, harnessing Cl-/Cl0 redox reaction at the positive electrode, is discovered to have a high discharge voltage of 1.3 V, and retains 77.4% of initial capacity after 10,000 cycles. This work may open up an avenue to boosting the voltage and energy of aqueous copper batteries.
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Ammonium-ion batteries, leveraging non-metallic ammonium ions, have arisen as a promising electrochemical energy storage system; however, their advancement has been hindered by the scarcity of high-performance ammonium-ion storage materials. In this study, an electrochemical phase transformation approach is proposed for the in situ synthesis of layered VOPO4 ·2H2 O (E-VOPO) with predominant growth on the (200) plane, corresponding to the tetragonal channels on the (001) layers. The findings reveal that these tetragonal in-layer channels not only furnish NH4 + storage sites but also enhance transfer kinetics by providing rapid cross-layer migration pathways. This crucial aspect has been largely overlooked in previous studies. The E-VOPO electrode exhibits exceptional ammonium-ion storage performance, including significantly increased specific capacity, enhanced rate capability, and robust cycling stability. The resulting full cell can be stably operated for 12 500 charge-discharge cycles at 2 A g-1 for over 70 days. The proposed approach offers a new strategy for meticulously engineering electrode materials with facilitated ion storage and migration, thereby paving the way for developing more efficient and sustainable energy storage systems.
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Benefiting from the admirable energy density (1086 Wh kg-1 ), overwhelming security, and low environmental impact, rechargeable zinc-air batteries (ZABs) are deemed to be attractive candidates for lithium-ion batteries. The exploration of novel oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) bifunctional catalysts is the key to promoting the development of zinc-air batteries. Transitional metal phosphides (TMPs) especially Fe-based TMPs are deemed to be a rational type of catalyst, however, their catalytic performance still needs to be further improved. Considering Fe (heme) and Cu (copper terminal oxidases) are nature's options for ORR catalysis in many forms of life from bacteria to humans. Herein, a general "in situ etch-adsorption-phosphatization" strategy is designed for the fabrication of hollow FeP/Fe2 P/Cu3 P-N, P codoped carbon (FeP/Cu3 P-NPC) catalyst as the cathode of liquid and flexible ZABs. The liquid ZABs manifest a high peak power density of 158.5 mW cm-2 and outstanding long-term cycling performance (≈1100 cycles at 2 mA cm-2 ). Similarly, the flexible ZABs deliver superior cycling stability of 81 h at 2 mA cm-2 without bending and 26 h with different bending angles.
RESUMEN
Aqueous rechargeable batteries are prospective candidates for large-scale grid energy storage. However, traditional anode materials applied lack acid-alkali co-tolerance. Herein, we report a covalent organic framework containing pyrazine (C=N) and phenylimino (-NH-) groups (HPP-COF) as a long-cycle and high-rate anode for both acidic and alkaline batteries. The HPP-COF's robust covalent linkage and the hydrogen bond network between -NH- and water molecules collectively improve the acid-alkaline co-tolerance. More importantly, the hydrogen bond network promotes the rapid transport of H+ /OH- by the Grotthuss mechanism. As a result, the HPP-COF delivers a superior capacity and cycle stability (66.6â mAh g-1 @ 30â A g-1 , over 40000 cycles in 1â M H2 SO4 electrolyte; 91.7â mAh g-1 @ 100â A g-1 , over 30000 cycles @ 30â A g-1 in 1â M NaOH electrolyte). The work opens a new direction for the structural design and application of COF materials in acidic and alkaline batteries.
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The proposal of hybrid ion batteries, which can integrate the advantages of the single ion battery, opens up a new route for developing high-performance secondary batteries. Herein, we successfully constructed an aqueous hybrid battery comprised of polyanionic-type cathode material (Na3V2(PO4)3, NVP), Zn metal anode, and aqueous Ca2+/Zn2+ hybrid electrolyte. This exciting combination gives full play to not only the excellent diffusion dynamics of Ca2+ in the NASICON (sodium super ion conductors) structure but also the electrostatic shielding effect of Ca2+ with low reduction potential that inhibits the formation of zinc dendrites. As results, the NVP//Zn Zn/Ca hybrid battery delivers favorable specific capacity with outstanding rate performance (85.3 mAh g-1 capacity at 1 C, 60.5 mAh g-1 capacity at 20 C), and excellent cycle stability (74 % capacity retention after 1300 cycles).
Asunto(s)
Calcinosis , Zinc , Humanos , Calcificación Fisiológica , Electrodos , DifusiónRESUMEN
Aqueous zinc ion batteries (AZIBs) have broad prospects in many fields because of their high theoretical capacity, high hydrogen overpotential, low equilibrium potential, low cost and high safety. However, the surface chemical reactivity of cathode is usually limited by the utilization of active materials, resulting in insensitive edge position and unsatisfactory capacity. In this paper, a simple and convenient strategy is reported, in which the bimetallic phosphide nano-interfaces are constructed only by electrochemical high-voltage activation, so as to increase the electrode capacity of about 150 % (compared to the original NiCoP electrode). Under the combined action of water and oxygen, a coating of NiCo-OH nanosheet is formed on the NiCoP nano-wall, and the surfaces are rich in low-priced mixed state with remarkable reactivity and structural stability, which is theoretically confirmed by density functional theory (DFT). As a result, the 3D cathode has an ultra-high capacity of 544.9 mAh g-1 and excellent rate performance (still about 69.5 % at 30 A g-1). The assembled NCPOH//Zn battery has excellent reversibility and long life (maintained 97 % of initial capacity after 2000 cycles) and achieves a remarkable energy density of 933.5 Wh kg-1. Our work explores the relationship between interface corrosion mechanism and corrosion surface activity, which is a powerful strategy to build metal phosphides with high surface electrochemical activity as advanced energy storage devices.
RESUMEN
High-performance aqueous zinc batteries are expected to be realized, rooting from component synergistic effects of the hierarchical composite electrode materials. Herein, hierarchical crystalline Ni-Co phosphide coated with amorphous phosphate nanoarrays (C-NiCoP@A-NiCoPO4) self-supporting on the Ni foam are constructed as cathode material of an aqueous zinc battery. In this unique core-shell structure, the hexagonal phosphide with high conductivity offers ultra-fast electronic transmission and amorphous phosphate with high stability, and open-framework provides more favorable ion diffusivity and a stable protective barrier. The synergistic effects of this intriguing core-shell structure endow the electrode material with outstanding reaction kinetics and structural stability, which is theoretically confirmed by density functional theory (DFT) calculations. As a result, the C-NiCoP@A-NiCoPO4 electrode exhibits a higher specific capacity of 350.6 mA h g-1 and excellent cyclic stability with 92.6% retention after 10 000 cycles. Moreover, the C-NiCoP@A-NiCoPO4 is coupled with Zn anode to assemble an aqueous pouch battery that delivers ultra-high energy density (626.33 W h kg-1 at 1.72 kW kg-1) with extraordinary rate performance (452.05 W h kg-1 at 33.56 kW kg-1). Moreover, the corresponding quasi-solid flexible battery with polyacrylamide hydrogel electrolyte exhibits favorable durability under frequent mechanical strains, which indicates the great promise of crystalline/amorphous hierarchical electrodes in the field of energy storage.
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Hybrid supercapacitors have the advantages of fast charging and discharging and long service life, which are an efficient and practical energy storage device. Therefore, the design of hybrid supercapacitors is the focus of current research. In this paper, the silver modified spinel NiCo2S4 nanorods (Ag2S-NiCo2S4/CF) are synthesized by an efficient and economical method, which has excellent electrochemical performance. The Ag2S-NiCo2S4/CF shows a high specific capacity of 179.7 mAh g-1 at current density of 1 A g-1, and excellent rate capability (capacitance retention of ~87% at 20 A g-1). The corresponding Ag2S-NiCo2S4/CF//AC/CF hybrid supercapacitor is assembled by Ag2S-NiCo2S4/CF as the positive electrode, which can provide an energy density of 35.978 Wh kg-1 at a high-power density of 800 W kg-1 and has significant cyclic stability (~80% of the initial capacitor after ~9600 cycles). Therefore, Ag2S-NiCo2S4/CF material is a promising electrode material that can be applied to hybrid supercapacitors.
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High-performance energy storage systems are becoming essential to cope with the possible energy crisis in the future. Herein, unique hierarchical B-Co4N have been reasonably designed and synthesized on Ni foam (NF) via a typical chemical reduction strategy. The successful realization of B-doping engineering effectively facilitates ion and electron transport, adding the electrochemically reactive sites, which endow the B-Co4N-20/NF electrode with high specific capacity (817.9 C g-1 at 1 A g-1), excellent rate capability (maintained about 90.9% at 10 A g-1) and cycling stability (about 93.06% retention of the initial capacity after 5000 cycles). The corresponding hybrid supercapacitor assembled with B-Co4N-20/NF electrodes has an energy density of 25.85 W h kg-1 at the power density of 800.2 W kg-1 and a long cycle life (98.59% retention ratio after 5000 cycles). These remarkable properties indicate that the doping of heteroatom and the construction of hierarchical structure will provide a favorable reference for the performance promotion of next-generation energy storage devices.
RESUMEN
Nickel-cobalt-based molybdates have been intensively investigated because of their high theoretical specific capacitance and multifarious oxidation states. Here, we have successfully synthesized hierarchical structures (Ni3B/Ni(BO2)2@NixCoyMoO4) by boronizing NixCoyMoO4 nanosheets on flexible carbon cloth substrates. Benefitting from the synergistic effect among Ni3B, Ni(BO2)2 and NixCoyMoO4 in hybrid architectures, the electrode material possesses higher capacity of 394.7 mA h g-1 at 1 A g-1 and a good rate performance (309.5 mA h g-1 maintained at 20 A g-1). Then, a hybrid supercapacitor assembled with Ni3B/Ni(BO2)2@NixCoyMoO4 and activated carbon as the positive and the negative electrode, displays a high specific capacitance of 370.7 F g-1 at 1 A g-1 (210 F g-1 at 10 A g-1), a high voltage of 1.7 V, and a high energy density of 131.8 W h kg-1 at the power density of 800 W kg-1 (still 74.7 W h kg-1 maintained at 8000 W kg-1). This study widens the research scope of boronizing pseudocapacitance materials and reveals a high application potential of Ni3B/Ni(BO2)2@NixCoyMoO4 for energy storage devices in the future.
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Hierarchical nanostructures with outstanding electrochemical properties and mechanical stability are ideal for constructing flexible hybrid supercapacitors. Herein, hierarchically hollow NiCo2S4@NiS nanostructures were designed and synthesized by sulfurizing the hierarchical NiCo double hydroxides (DHs) coated with nickel hydroxide nanostructures on carbon fabrics (NiCo-DHs@Ni(OH)2/CF), which trigger excellent electrochemical performances. The NiCo2S4@NiS/CF exhibits a high specific capacity of 1314.0 C g-1 at a current density of 1 A g-1, and maintains the rate performance at about 79.2% of the initial capacity at 30 A g-1. The hybrid supercapacitors of NiCo2S4@NiS//AC display a high energy density of 62.4 W h kg-1 at a power density of 800 W kg-1 with a remarkable cycling stability (96.2% of initial capacitance after 5000 cycles) and robust mechanical flexibility (no obvious decay of specific capacitance during various deformations). Consequently, NiCo2S4@NiS electrodes are expected to be a promising candidate for new smart energy storage devices with high security, stability and flexibility.
RESUMEN
Dual-functional NiCo2S4 polyhedral architectures with outstanding electrochemical performance for supercapacitors and lithium-ion batteries (LIBs) have been rationally designed and successfully synthesized by a hydrothermal method. The as-synthesized NiCo2S4 electrode for supercapacitor exhibits an outstanding specific capacitance of 1298Fg-1 at 1Ag-1 and an excellent rate capability of ~80.4% at 20Ag-1. Besides, capacitance retention of 90.44% is realized after 8000 cycles. In addition, the NiCo2S4 as anode in LIBs delivers high initial charge/discharge capacities of 807.6 and 972.8mAhg-1 at 0.5C as well as good rate capability. In view of these points, this work provides a feasible pathway for assembling electrodes and devices with excellent electrochemical properties in the next generation energy storage applications.