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Introducing N atoms in vanadium oxides (VOx) of aqueous Zn-ion batteries (ZIBs) can reduce their bandgap energy and enhance their electronic conductivity, thereby promoting the diffusion of Zn2+. The close-packed vanadium oxynitride (VON) generated often necessitates the intercalation of water molecules for restructuring, rendering it more conducive for zinc ion intercalation. However, its dense structure often causes structural strain and the formation of by-products during this process, resulting in decreased electrochemical performance. Herein, carbon-coated porous V2O3/VN nanosheets (p-VON@C) are constructed by annealing vanadium metal-organic framework in an ammonia-contained environment. The designed p-VON@C nanosheets are efficiently converted to low-crystalline hydrated N-doped VOx during subsequent activation while maintaining structural stability. This is because the V2O3/VN heterojunction and abundant oxygen vacancies in p-VON@C alleviate the structural strain during water molecule intercalation, and accelerate the intercalation rate. Carbon coating is beneficial to prevent p-VON@C from sliding or falling off during the activation and cycling process. Profiting from these advantages, the activated p-VON@C cathode delivers a high specific capacity of 518 mAh g-1 at 0.2 A g-1 and maintains a capacity retention rate of 80.9% after 2000 cycles at 10 A g-1. This work provides a pathway to designing high-quality aqueous ZIB cathodes.
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Aqueous Zn-ion batteries (ZIBs) are promising next-generation energy storage devices, yet suffer from the issues of hydrogen evolution reaction (HER) and intricate side reactions on the Zn anode surface. The hydrogen (H)-bond networks play a critical role in interfacial proton transport that may closely relate to HER but are rarely investigated. Herein, we report a self-assembled monolayer (SAM) strategy which is constructed by anchoring ionic liquid cations on Ti3C2Tx substrate for HER-free Zn anode. Molecule dynamics simulations reveal that the rationally designed SAM with a high coordination number of water molecules (25-27, 4-6 for Zn2+) largely reduces the interfacial densities of H2O molecules, therefore breaking the connectivity of H-bond networks and blocking proton transport on the interface, by which the HER is suppressed. Then, a series of in situ characterizations demonstrate that negligible amounts of H2 gas are collected from the Zn@SAM-MXene anode. Consequently, the symmetric cell enables a long-cycling life of 3000â h at 1â mA cm-2 and 1000â h at 5â mA cm-2. More significantly, the stable Zn@SAM-MXene films are successfully used for coin full cells showing high-capacity retention of over 94 % after 1000 cycles and large-area (10×5â cm2) pouch cells with desired performance.
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Developing a facile strategy to activate the inert crystal face of an electrocatalyst is critical to full-facet utilization, yet still challenging. Herein, the electrocatalytic activity of the inert crystal face is activated by quenching Co3O4 cubes and hexagonal plates with different crystal faces in Fe(NO3)3 solution, and the regulation mechanism of facet-dependent quench-engineering is further revealed. Compared to the Co3O4 cube with exposed {100} facet, the Co3O4 hexagonal plate with exposed {111} facet is more responsive to quenching, accompanied by a rougher surface, richer defect, and more Fe doping. Theoretical calculations indicate that the {111} facet has a more open structure with lower defect formation energy and Fe doping energy, ensuring its electronic and coordination structure is easier to optimize. Therefore, quench-engineering largely increases the catalytic activity of {111) facet for oxygen evolution reaction by 13.2% (the overpotential at 10 mA cm-2 decreases from 380 to 330 mV), while {100} facet only increases by 7.6% (from 393 to 363 mV). The quenched Co3O4 hexagonal plate exhibits excellent electrocatalytic activity and stability in both zinc-air battery and water-splitting. The work reveals the influence mechanism of crystal face on quench-engineering and inspires the activation of the inert crystal face.
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Atomically dispersed single-atom catalysts are intriguing catalysts in the field of electrocatalysis for nearly 100% exploitation of metal atoms. However, they are still far from practical usage due to the scaling relationship limit and metal loading limit. Generation of a diatomic complex would offer superior catalytic performance through the cooperation of two neighboring atoms as active sites. Herein, Fe/Co dual atomic sites embedded in a tube-on-plate hollow structure are designed and fabricated for an efficient electrochemical oxygen reduction reaction (ORR). The unique structure composed of ultrathin nanotube building blocks dramatically maximizes the surface area for copious active site exposure. Thanks to the synergetic interaction between Fe/Co pairs, the obtained FeCo/NC exhibits outstanding ORR activity and stability in alkaline media. Furthermore, density functional theory calculations have revealed that the remarkable activity is attributed to the electron-deficient Fe sites in FeCoN6. This work may pave the way for the innovative design of highly dispersed dual-site catalysts for broader applications in the realm of electrochemical catalysis.
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With the pursuit of high energy and power density, the fast-charging capability of lithium-metal batteries has progressively been the primary focus of attention. To prevent the formation of lithium dendrites during fast charging, the ideal solid electrolyte interphase should be capable of concurrent fast Li+ transport and uniform nucleation sites; however, its construction in a facile manner remains a challenge. Here, as Al3+ has a higher charge and Al metal is lithiophilic, we tuned the Li+ solvation structure by introducing LiNO3 and aluminum ethoxide together, resulting in the dissolution of LiNO3 and the simultaneous generation of fast ionic conductor and lithiophilic sites. Consequently, our approach facilitated the deposition of lithium metal in a uniform and chunky way, even at a high current density. As a result, the Coulombic efficiency of the Li||Cu cell increased to over 99%. Moreover, the Li||LiFePO4 full cell demonstrated significantly enhanced cycling performance with a remarkable capacity retention of 94.5% at 4 C, far superior to the 46.1% capacity retention observed with the base electrolyte.
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Protein channels on the biofilm conditionally manipulate ion transport via regulating the distribution of charge residues, making analogous processes on artificial membranes a hot spot and challenge. Here, we employ metal-organic frameworks (MOFs) membrane with charge-adjustable subnano-channel to selectively govern ion transport. Various valent ions are binded with crown ethers embedded in the MOF cavity, which act as charged guest to regulate the channels' charge state from the negativity to positivity. Compared with the negatively charged channel, the positive counterpart obviously enhances Li+ /Mg2+ selectivity, which benefit from the reinforcement of the electrostatic repulsion between ions and the channel. Meanwhile, theoretical calculations reveal that Mg2+ transport through the more positively charged channel needed to overcome higher entrance energy barrier than that of Li+ . This work provides a subtle strategy for ion-selective transport upon regulating the charge state of insulating membrane, which paves the way for the application like seawater desalination and lithium extraction from salt lakes.
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The constructing of artificial channels with gating functions is an important undertaking for gaining insight into biological process and achieving efficient bionic functions. Typically, controllable transport within such channels relies on either electrostatic or specific interactions between the transporting species and the channel. However, for molecules with weak interactions with the channel, achieving precise gating of the transport remains a significant challenge. In this regard, this study proposes a voltage gating membrane of two-dimensional channels that selectively transport of neutral molecules glucose with a dimension of 0.60â nm. The permeation of glucose is switched on/off by electrochemically manipulating the water dynamics in the nanochannel. Voltage driven-intercalation of ion into the two-dimensional channel causes water to stratify and move closer to the channel walls, thereby resulting in the channel center being emptier for glucose diffusion. Due to the sub-nanometer size dimension of the channel, selective permeation of glucose over sucrose is also achieved in this approach.
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Rechargeable magnesium batteries (RMBs) are seriously plagued by the direct exposure of the Mg anode to the electrolyte components, leading to spontaneous and electrochemical side reactions and interfacial passivation. Herein, a benign coordination layer is constructed at the Mg/electrolyte interface where aniline with a strong magnesiophilic amine group and high stability to Mg is chosen as representative, which has higher adsorption energy than DME (1,2-dimethoxyethane) and trace water. This Mg coordination environment mitigates side reactions, forming a non-passivating interface consisting of aniline and much fewer by-products after several cycles. Therefore, the Mg symmetrical cell operates with a low overpotential and uniform Mg0 deposition. This interfacial coordination can also be adopted for Mg anode protection in various electrolyte cases of Mg(TFSI)2 electrolyte systems.
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Compuestos de Anilina , Magnesio , Adsorción , ElectrodosRESUMEN
Multifunctional electrochromic-induced rechargeable aqueous batteries (MERABs) integrate electrochromism and aqueous ion batteries into one platform, which is able to deliver the conversion and storage of photo-thermal-electrochemical sources. Aqueous ion batteries compensate for the drawbacks of slow kinetic reactions and unsatisfied storage capacities of electrochromic devices. On the other hand, electrochromic technology can enable dynamically regulation of solar light and heat radiation. However, MERABs still face several technical issues, including a trade-off between electrochromic and electrochemical performance, low conversion efficiency and poor service life. In this connection, novel device configuration and electrode materials, and an optimized compatibility need to be considered for multidisciplinary applications. In this review, the unique advantages, key challenges and advanced applications are elucidated in a timely and comprehensive manner. Firstly, the prerequisites for effective integration of the working mechanism and device configuration, as well as the choice of electrode materials are examined. Secondly, the latest advances in the applications of MERABs are discussed, including wearable, self-powered, integrated systems and multisystem conversion. Finally, perspectives on the current challenges and future development are outlined, highlighting the giant leap required from laboratory prototypes to large-scale production and eventual commercialization.
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Metal-oxygen bonds significantly affect the oxygen reaction kinetics of metal oxide-based catalysts but still face the bottlenecks of limited cognition and insufficient regulation. Herein, we develop a unique strategy to accurately tailor metal-oxygen bond structure via amorphous/crystalline heterojunction realized by ion-exchange. Compared with pristine amorphous CoSnO3-y, iron ion-exchange induced amorphous/crystalline structure strengthens the Sn-O bond, weakens the Co-O bond strength, and introduces additional Fe-O bond, accompanied by abundant cobalt defects and optimal oxygen defects with larger pore structure and specific surface area. The optimization of metal-oxygen bond structure is dominated by the introduction of crystal structure and further promoted by the introduction of Fe-O bond and rich Co defect. Remarkably, the Fe doped amorphous/crystalline catalyst (Co1-xSnO3-y-Fe0.021-A/C) demonstrates excellent oxygen evolution reaction and oxygen reduction reaction activities with a smaller potential gap (ΔE = 0.687 V), and the Zn-air battery based with Co1-xSnO3-y-Fe0.021-A/C exhibits excellent output power density, cycle performance, and flexibility.
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Aqueous zinc-ion battery (ZIB) featuring with high safety, low cost, environmentally friendly, and high energy density is one of the most promising systems for large-scale energy storage application. Despite extensive research progress made in developing high-performance cathodes, the Zn anode issues, such as Zn dendrites, corrosion, and hydrogen evolution, have been observed to shorten ZIB's lifespan seriously, thus restricting their practical application. Engineering advanced Zn anodes based on two-dimensional (2D) materials are widely investigated to address these issues. With atomic thickness, 2D materials possess ultrahigh specific surface area, much exposed active sites, superior mechanical strength and flexibility, and unique electrical properties, which confirm to be a promising alternative anode material for ZIBs. This review aims to boost rational design strategies of 2D materials for practical application of ZIB by combining the fundamental principle and research progress. Firstly, the fundamental principles of 2D materials against the drawbacks of Zn anode are introduced. Then, the designed strategies of several typical 2D materials for stable Zn anodes are comprehensively summarized. Finally, perspectives on the future development of advanced Zn anodes by taking advantage of these unique properties of 2D materials are proposed.
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The demand for high-energy-density and safe energy storage devices has spurred increasing interest in high-voltage rechargeable magnesium batteries (RMB). As electrolytes are the bridge connecting the cathode and anode materials, the development of high-voltage electrolytes is the key factor in realizing high-voltage RMBs. This concept presents an overview of three chloride-free electrolyte systems with wide electrochemical windows, together with the degradation mechanisms and modification strategies at the anode/electrolyte interphase. Finally, future directions in stabilizing Mg anodes and realizing high-voltage RMBs are highlighted.
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Aqueous zinc-ion batteries (ZIBs) have significant potential for large energy storage systems because of their high energy density, cost-effectiveness and environmental friendliness. However, the limited voltage window, poor reaction kinetics and structural instability of cathode materials are current bottlenecks which contain the further development of ZIBs. In this work, we rationally design a Ni-doped V2O5@3D Ni core/shell composite on a carbon cloth electrode (Ni-V2O5@3D Ni@CC) by growing Ni-V2O5 on free-standing 3D Ni metal nanonets for high-voltage and high-capacity ZIBs. Impressively, embedded Ni doping increases the interlayer spacing of V2O5, extending the working voltage and improving the zinc-ion (Zn302+) reaction kinetics of the cathode materials; at the same time, the 3D structure, with its high specific surface area and superior electronic conductivity, aids in fast Zn302+ transport. Consequently, the as-designed Ni-V2O5@3D Ni@CC cathodes can operate within a wide voltage window from 0.3 to 1.8 V vs. Zn30/Zn302+ and deliver a high capacity of 270 mAh g-1 (~1050 mAh cm-3) at a high current density of 0.8 A g-1. In addition, reversible Zn2+ (de)incorporation reaction mechanisms in the Ni-V2O5@3D Ni@CC cathodes are investigated through multiple characterization methods (SEM, TEM, XRD, XPS, etc.). As a result, we achieved significant progress toward practical applications of ZIBs.
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Owing to several advantages of metallic sodium (Na), such as a relatively high theoretical capacity, low redox potential, wide availability, and low cost, Na metal batteries are being extensively studied, which are expected to play a major role in the fields of electric vehicles and grid-scale energy storage. Although considerable efforts have been devoted to utilizing MXene-based materials for suppressing Na dendrites, achieving a stable cycling of Na metal anodes remains extremely challenging due to, for example, the low Coulombic efficiency (CE) caused by the severe side reactions. Herein, a g-C3N4 layer was attached in situ on the Ti3C2 MXene surface, inducing a surface state reconstruction and thus forming a stable hetero-interphase with excellent sodiophilicity between the MXene and g-C3N4 to inhibit side reactions and guide uniform Na ion flux. The 3D construction can not only lower the local current density to facilitate uniform Na plating/stripping but also mitigate volume change to stabilize the electrolyte/electrode interphase. Thus, the 3D Ti3C2 MXene@g-C3N4 nanocomposite enables much enhanced average CEs (99.9% at 1 mA h cm-2, 0.5 mA cm-2) in asymmetric half cells, long-term stability (up to 700 h) for symmetric cells, and stable cycling (up to 800 cycles at 2 C), together with outstanding rate capability (up to 20 C), of full cells. The present study demonstrates an approach in developing practically high performance for Na metal anodes.
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Metal-organic framework (MOF) derivatives promise great potential in energy storage and conversion because of their excellent tunability in both the active metal sites, organic links, and the overall structures down to atomic and up to mesoscale. Nevertheless, a big challenge is to precisely control and thoroughly understand the actual MOF-to-derivative conversion process to realize the template-free synthesis of the MOF-derived ordered mesoporous materials. Here, a class of ordered mesoporous N-doped carbon nanoflakes is presented with slit-shaped pores synthesized by one-step pyrolysis of Zn1 Cux -MOF, where the Cu doping plays a critically important direction-inducing function on the dissociation of organic ligands during the pyrolysis. Benefiting from the uniquely ordered mesoporous structure and large specific surface area (910 m2 g-1 ), the Zn1 Cux -MOF-derived ordered mesoporous carbon nanoflakes present outstanding electrochemical storage performance for multivalent metal ions, such as Mg2+ , Ca2+ , Co2+ , Ni2+ , Al3+ , and Zn2+ , demonstrating the universal nature of the slit-shaped pores in enabling the multivalent metal ions for energy storage. Moreover, the assembled flexible Zn-ion hybrid supercapacitor (ZHSC) delivers a high specific capacity of 134 mAh g-1 at 0.5 A g-1 , excellent cycling and mechanical stability, showing great application potential in the new generation energy storage devices.
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Rechargeable magnesium (Mg) batteries based on conventional electrolytes are seriously plagued by the formation of the ion-blocking passivation layer on the Mg metal anode. By tracking the Mg2+ solvation sheath, this work links the passivation components to the Mg2+ -solvents (1,2-dimethoxyethane, DME) coordination and the consequent thermodynamically unstable DME molecules. On this basis, we propose a methodology to tailor solvation coordination by introducing the additive solvent with extreme electron richness. Oxygen atoms in phosphorus-oxygen groups compete with that in carbon-oxygen groups of DME for the coordination with Mg2+ , thus softening the solvation sheath deformation. Meanwhile, the organophosphorus molecules in the rearranged solvation sheath decompose on the Mg surface, increasing the Mg2+ transport and electrical resistance by three and one orders of magnitude, respectively. Consequently, the symmetric cells exhibit superior cycling performance of over 600â cycles with low polarization.
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Metal-organic frameworks (MOFs) have recently emerged as ideal electrode materials and precursors for electrochemical energy storage and conversion (EESC) owing to their large specific surface areas, highly tunable porosities, abundant active sites, and diversified choices of metal nodes and organic linkers. Both MOF-based and MOF-derived materials in powder form have been widely investigated in relation to their synthesis methods, structure and morphology controls, and performance advantages in targeted applications. However, to engage them for energy applications, both binders and additives would be required to form postprocessed electrodes, fundamentally eliminating some of the active sites and thus degrading the superior effects of the MOF-based/derived materials. The advancement of freestanding electrodes provides a new promising platform for MOF-based/derived materials in EESC thanks to their apparent merits, including fast electron/charge transmission and seamless contact between active materials and current collectors. Benefiting from the synergistic effect of freestanding structures and MOF-based/derived materials, outstanding electrochemical performance in EESC can be achieved, stimulating the increasing enthusiasm in recent years. This review provides a timely and comprehensive overview on the structural features and fabrication techniques of freestanding MOF-based/derived electrodes. Then, the latest advances in freestanding MOF-based/derived electrodes are summarized from electrochemical energy storage devices to electrocatalysis. Finally, insights into the currently faced challenges and further perspectives on these feasible solutions of freestanding MOF-based/derived electrodes for EESC are discussed, aiming at providing a new set of guidance to promote their further development in scale-up production and commercial applications.
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Estructuras Metalorgánicas , Electrodos , Estructuras Metalorgánicas/química , MetalesRESUMEN
Rechargeable batteries of high energy density and overall performance are becoming a critically important technology in the rapidly changing society of the twenty-first century. While lithium-ion batteries have so far been the dominant choice, numerous emerging applications call for higher capacity, better safety and lower costs while maintaining sufficient cyclability. The design space for potentially better alternatives is extremely large, with numerous new chemistries and architectures being simultaneously explored. These include other insertion ions (e.g. sodium and numerous multivalent ions), conversion electrode materials (e.g. silicon, metallic anodes, halides and chalcogens) and aqueous and solid electrolytes. However, each of these potential "beyond lithium-ion" alternatives faces numerous challenges that often lead to very poor cyclability, especially at the commercial cell level, while lithium-ion batteries continue to improve in performance and decrease in cost. This review examines fundamental principles to rationalise these numerous developments, and in each case, a brief overview is given on the advantages, advances, remaining challenges preventing cell-level implementation and the state-of-the-art of the solutions to these challenges. Finally, research and development results obtained in academia are compared to emerging commercial examples, as a commentary on the current and near-future viability of these "beyond lithium-ion" alternatives.
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Graphene-constructed micro-supercapacitors (MSCs) have received considerable attention recently, as part of the prospective wearable and portable electronics, owing to their distinctive merits of well-tunable power output, robust mechanical flexibility, and long cyclability. In the current work, the focus is on the fabrication of high-quality and solution-processible chlorine-doped graphene (Cl-G) nanosheets through a handy yet eco-friendly electrochemical exfoliation process. The Cl-G is characteristic of the large lateral size of ≈10 µm, abundant nanopores with sizes of as small as 2 nm, as well as numerous steps from the rugged surface. Arising from the rich chemical functionalities and structure defects, the all-solid-state MSC built by using Cl-G via a facile mask-assisted method delivers a large reversible capacity and ultrasteady charge/discharge performance, with the capacitance being maintained at 98.1% even after 250 000 cycles. The Cl-G-MSC with EMIMBF4 /PVDF-HFP as the electrolyte displays a large volumetric capacitance up to 160 F cm-3 at the scan rate of 5 mV s-1 and high volumetric energy density of 97.9 mW h cm-3 at the power density of 3.4 W cm-3 . The device can also output a high voltage up to 3.5 V and robust capability with 94.8% of capacitance retention upon 10 000 cycles.
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The electrochemical oxygen evolution reaction (OER) by efficient catalysts is a crucial step for the conversion of renewable energy into hydrogen fuel, in which surface/near-surface engineering has been recognized as an effective strategy for enhancing the intrinsic activities of the OER electrocatalysts. Herein, a facile quenching approach is demonstrated that can simultaneously enable the required surface metal doping and vacancy generation in reconfiguring the desired surface of the NiCo2 O4 catalyst, giving rise to greatly enhanced OER activities in both alkaline freshwater and seawater electrolytes. As a result, the quenched-engineered NiCo2 O4 nanowire electrode achieves a current density of 10 mA cm-2 at a low overpotential of 258 mV in 1 m KOH electrolyte, showing the remarkable catalytic performance towards OER. More impressively, the same electrode also displays extraordinary activity in an alkaline seawater environment and only needs 293 mV to reach 10 mA cm-2 . Density functional theory (DFT) calculations reveal the strong electronic synergies among the metal cations in the quench-derived catalyst, where the metal doping regulates the electronic structure, thereby yielding near-optimal adsorption energies for OER intermediates and giving rise to superior activity. This study provides a new quenching method to obtain high-performance transition metal oxide catalysts for freshwater/seawater electrocatalysis.