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Sulfur-based aqueous batteries (SABs) are promising for safe, low-cost, and high-capacity energy storage. However, the low output voltage of sulfur cannot meet the demands of high-energy cathode applications due to its intrinsic negative potential (E0 = -0.51 V vs SHE) of low-valent polysulfide redox (S2-/S0). Here, instead of relying on traditional aqueous polysulfide redox, for the first time, we demonstrate a high-valent thiosulfate redox (S2O32-/S4O62-) electrochemistry, exhibiting positive redox potential (E0 > 0 V vs SHE) and reversible cation storage in aqueous environment. Operando X-ray absorption fine structure spectroscopy, in situ Raman spectroscopy, and density functional theory calculations reveal the high reversibility and dynamic charge transfer process of high-valent thiosulfate redox. Significantly, the aqueous thiosulfate redox exhibits a high operating voltage of approximately 1.4 V, a reversible capacity of 193 Ah L-1, and a long cycling life of over 1000 cycles (99.6% capacity retention). This work provides new insights into the high-valent S-based electrochemistry and opens a new pathway to achieve energetic aqueous batteries.
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The virtues of electrolytic MnO2 aqueous batteries are high theoretical energy density, affordability and safety. However, the continuous dead MnO2 and unstable Mn2+/MnO2 electrolysis pose challenges to the practical output energy and lifespan. Herein, we demonstrate bifunctional cationic redox mediation and catalysis kinetics metrics to rescue dead MnO2 and construct a stable and fast electrolytic Zn-Mn redox-flow battery (eZMRFB). Spectroscopic characterizations and electrochemical evaluation reveal the superior mediation kinetics of a cationic Fe2+ redox mediator compared with the anionic ones (e.g. I- and Br-), thus eliminating dead MnO2 effectively. With intensified oxygen vacancies, density functional theory simulations of the reaction pathways further verify the concomitant Fe-catalysed Mn2+/MnO2 electrolysis kinetics via charge delocalization and activated O 2p electron states, boosting its rate capability. As a result, the elaborated eZMRFB achieves a coulombic efficiency of nearly 100%, ultra-high areal capacity of 80 mAh cm-2, rate capability of 20 C and a long lifespan of 2500 cycles. This work may advance high-energy aqueous batteries to next-generation scalable energy storage.
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Zinc-based aqueous batteries (ZABs) are attracting extensive attention due to the low cost, high capacity, and environmental benignity of the zinc anode. However, their application is still hindered by the undesired zinc dendrites. Despite Zn-surface modification being promising in relieving dendrites, a thick separator (i.e. glass fiber, 250-700â µm) is still required to resist the dendrite puncture, which limits volumetric energy density of battery. Here, we pivot from the traditional interphase plus extra separator categories, proposing an all-in-one ligand buffer layer (ca. 20â µm) to effectively modulate the Zn2+ transfer and deposition behaviors proved by in situ electrochemical digital holography. Experimental characterizations and density functional theory simulations further reveal that the catechol groups in the buffer layer can accelerate the Zn2+ reduction reaction (ZRR) through the electron-donating p-π conjugation effect, decreasing the negative charge in the coordination environment. Without extra separators, the elaborated system endows low polarization below 28.2â mV, long lifespan of 4950â h at 5â mA cm-2 in symmetric batteries, and an unprecedented volumetric energy density of 99.2â Wh L-1 based on the whole pouch cells. The concomitantly "separator-free" and "dendrite-free" conjugation effect with an accelerated ZRR process could foster the progression of metallic anodes and benefit energetic aqueous batteries.
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A reliable solid electrolyte interphase (SEI) on the metallic Zn anode is imperative for stable Zn-based aqueous batteries. However, the incompatible Zn-ion reduction processes, scilicet simultaneous adsorption (capture) and desolvation (repulsion) of Zn2+(H2O)6, raise kinetics and stability challenges for the design of SEI. Here, we demonstrate a tandem chemistry strategy to decouple and accelerate the concurrent adsorption and desolvation processes of the Zn2+ cluster at the inner Helmholtz layer. An electrochemically assembled perforative mesopore SiO2 interphase with tandem hydrophilic -OH and hydrophobic -F groups serves as a Janus mesopores accelerator to boost a fast and stable Zn2+ reduction reaction. Combining in situ electrochemical digital holography, molecular dynamics simulations, and spectroscopic characterizations reveals that -OH groups capture Zn2+ clusters from the bulk electrolyte and then -F groups repulse coordinated H2O molecules in the solvation shell to achieve the tandem ion reduction process. The resultant symmetric batteries exhibit reversible cycles over 8000 and 2000 h under high current densities of 4 and 10 mA cm-2, respectively. The feasibility of the tandem chemistry is further evidenced in both Zn//VO2 and Zn//I2 batteries, and it might be universal to other aqueous metal-ion batteries.
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2D transition metal carbides (2D TMCs and MXenes) are promising candidates for applications of energy storage and catalysis. However, producing high-quality, large 2D flakes of Mo2C MXene has been challenging. Here, a new salt-assisted templating approach is reported that enables the direct synthesis of 2D Mo2 C with low defect concentrations. KCl acts as a template to form an intermediate 2D product, facilitating Mo2 C formation without coarsening upon melting. The thickness of the flakes produced can range from monolayer (0.36 nm) to 10 layers (4.55 nm), and the electrocatalytical hydrogen evolution reaction (HER) activity of 2D Mo2 C is inversely proportional to its thickness. The monolayer Mo2 C shows remarkable HER performance with a current density of ≈6800 mA cm- 2 at 470 mV versus reversible hydrogen electrode and an ultrahigh turnover frequency of ≈17 500 s- 1 . This salt-assisted synthesis approach can also produce WC and V8 C7 nanosheets, expanding the family of 2D carbides. The new pathway eliminates the need for layered ceramic precursors, making it a versatile approach to direct synthesis of MXene-like 2D carbides.
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The modification of metallic Zn anode contributes to solving the cycling issue of Zn-ion batteries (ZIBs) by restraining the dendrite growth and side reactions. In this regard, modulating (002) Zn is an effective way to prolong the lifespan of ZIBs with a parallel arrangement of Zn deposition. Herein, the authors propose to add trace amounts of Zn(BF4 )2 additive in 3 M ZnSO4 to promote in-plane Zn deposition by forming a BF4 - -[Zn(H2 O)6 ]2+ -[Zn(BF4 )3 ]- transfer process and specifically functioning on (002) facets. In this way, the optimized electrolyte highly boosts the cycling stability of Zn anodes with a long lifespan at 34.2% Zn utilization (500 h/10 mA cm-2 ) and 51.3% Zn utilization (360 h/10 mA cm-2 ; 834 h/1 mA cm-2 ). Moreover, the electroplated Zn on Cu substrate exhibits a competitive cumulative plating capacity (CPC) of 2.87 Ah cm-2 under harsh conditions. The assembled Zn|(NH4 )2 V6 O16 ·3H2 O full cells with a high cathode loading of 29.12 mg cm-2 also realizes almost no capacity degradation even after 2000 cycles at 2 A g-1 . With this cost-effective strategy, it is promising to push the development of aqueous ZIBs as well as provide inspiration for metal anode optimization in other energy storage systems.
Asunto(s)
Suministros de Energía Eléctrica , Zinc , Iones , ElectrodosRESUMEN
Two-dimensional (2D) oxides have unique electrical, optical, magnetic, and catalytic properties, which are promising for a wide range of applications in different fields. However, it is difficult to fabricate most oxides as 2D materials unless they have a layered structure. Here, we present a facile strategy for the synthesis of ultrathin oxide nanosheets using a self-formed sacrificial template of carbon layers by taking advantage of the Maillard reaction and violent redox reaction between glucose and ammonium nitrate. To date, 36 large-area ultrathin oxides (with thickness ranging from ~1.5 to ~4 nm) have been fabricated using this method, including rare-earth oxides, transition metal oxides, III-main group oxides, II-main group oxides, complex perovskite oxides, and high-entropy oxides. In particular, the as-obtained perovskite oxides exhibit great electrocatalytic activity for oxygen evolution reaction in an alkaline solution. This facile, universal, and scalable strategy provides opportunities to study the properties and applications of atomically thin oxide nanomaterials.
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Rechargeable aqueous zinc ion batteries (ZIBs) represent a promising technology for large-scale energy storage due to their high capacity, intrinsic safety and low cost. However, Zn anodes suffer from poor reversibility and cycling stability caused by the side-reactions and dendrite issues, which limit the Zn utilization in the ZIBs. Herein, to improve the durability of Zn under high utilization, an aluminum-doped zinc oxide (AZO) interphase is presented. The AZO interphase inhibits side reactions by isolating active Zn from the bulk electrolyte, and enables facile and uniform Zn deposition kinetics by accelerating the desolvation of hydrated Zn2+ and homogenizing the electric field distribution. Accordingly, the AZO-coated Zn (AZO@Zn) anode exhibits a long lifespan of 600 h with Zn utilization of 34.1% at the current density of 10 mA cm-2 . Notably, even under ultrahigh Zn utilization of 80%, the AZO@Zn remains stable cycling over 200 h. Meanwhile, the V2 O5 /AZO@Zn full cell with limited Zn excess displays high capacity retention of 86.8% over 500 cycles at 2 A g-1 . This work provides a simple and efficient strategy to ensure the reversibility and durability of Zn anodes under high utilization conditions, holding a great promise for commercially available ZIBs with competitive energy density.
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The printed electronics technology can be used to efficiently construct smart devices and is dependent on functional inks containing well-dispersed active materials. Two-dimensional (2D) materials are promising functional ink candidates due to their superior properties. However, the majority 2D materials can disperse well only in organic solvents or in surfactant-assisted water solutions, which limits their applications. Herein, we report a lithium (Li)-ion exchange method to improve the dispersity of the Na2W4O13 nanosheets in pure water. The Li-ion-exchanged Na2W4O13 (LixNa2-xW4O13) nanosheets show highly stable dispersity in water with a zeta potential of -55 mV. Moreover, this aqueous ink can be sprayed on various substrates to obtain a uniform LixNa2-xW4O13 nanosheet film, exhibiting an excellent electrochromic performance. A complementary electrochromic device containing a LixNa2-xW4O13 nanosheet film as an electrochromic layer and Prussian white (PW) as an ion storage layer exhibits a large optical modulation of 75% at 700 nm, a fast switching response of less than 2 s, and outstanding cyclic stability. This Na2W4O13-based aqueous ink exhibits considerable potential for fabricating large-scale and flexible electrochromic devices, which would meet the practical application requirements.
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Direct conversion of the tremendous and ubiquitous low-grade thermal energy into electricity by thermogalvanic cells is a promising strategy for energy harvesting. The environment is one of the richest and renewable low-grade thermal source. However, critical challenges remain for all-day electricity generation from environmental thermal energy due to the low frequency and small amplitude of temperature fluctuations in the environment. In this work, we report a tandem device consisting of a polypyrrole (PPy) broadband absorber/radiator, thermogalvanic cell, and thermal storage material (Cu foam/PEG1000) that integrates multiple functions of heating, cooling, and recycling of thermal energy. The thermogalvanic cell enables continuous utilization of environmental thermal energy at both daytime and nighttime, yielding maximum outputs as high as 0.6 W m-2 and 53 mW m-2, respectively. As demonstrated outdoors by a large-scale prototype module, this design offers a feasible and promising approach to all-day electricity generation from environmental thermal energy.
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Transition-metal phosphides (TMPs) are considered as promising non-noble electrochemical catalysts for hydrogen evolution reaction (HER). Their highly active sites are located on certain facets, and single crystalline two-dimensional (2D) structures enable them to expose the most active facets for HER. However, the synthesis of single crystalline 2D TMPs is still a challenge owing to their intrinsically non-layered structures. Herein, we demonstrate the synthesis of various single crystalline 2D TMPs (Co2P, MoP2, Ni12P5 and WP2) by a salt-templating method. The as-synthesized 2D Co2P exhibited efficient electrocatalytic ability for HER with an overpotential of 41 mV at 10 mA cm-2 and a Tafel slope of 35 mV dec-1 in 0.5 M H2SO4 solution. We expect that the synthesis of 2D TMPs reported here will open the way to expand the family of 2D materials for electrocatalysis and beyond.