In Situ Construction of Anode–Molecule Interface via Lone‐Pair Electrons in Trace Organic Molecules Additives to Achieve Stable Zinc Metal Anodes

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(22)

Published: April 25, 2023

Abstract The practical application of aqueous zinc batteries (AZBs) is significantly limited by the poor reversibility anodes, including rampant dendrite growth and severe interfacial side‐reactions. Herein, trace hexamethylenetetramine (HMTA) additive with a lone‐pair‐electron containing heterocycle introduced for Zn metal anode protection. Specifically, added HMTA can change solvated structure strong interaction ions, preferentially absorb on surface to in situ establish an unique anode–molecule interface. Such interface not only shows affinity promote dynamic transmission deposition 2+ ions but also displays role suppressing parasitic reactions. Consequently, electrolyte achieves high Coulombic efficiency 99.75%, delivers remarkable lifespan over 4000 h at 5 mA cm −2 1 mAh Zn//Zn symmetric cell. Even under deep plating/stripping condition (5 ), it still run almost 600 h. Additionally, Zn//V 2 O full cell retains capacity retention 61.7% after cycles A g −1 . innovative strategy expected be immediate benefit design low‐cost AZBs ultra‐long lifespan.

Language: Английский

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Manipulating Zn 002 deposition plane with zirconium ion crosslinked hydrogel electrolyte toward dendrite free Zn metal anodes

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(10), P. 4561 - 4571

Published: Jan. 1, 2023

A Zr 4+ crosslinked hydrogel electrolyte is demonstrated on side reaction resistance for high-performance aqueous Zn-based devices.

Language: Английский

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Highly Reversible Zinc Metal Anodes Enabled by Solvation Structure and Interface Chemistry Modulation

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(36)

Published: Aug. 9, 2023

Abstract Aqueous Zn−ion batteries (AZIBs) promise appealing advantages including safety, affordability, and high volumetric energy density. However, rampant parasitic reactions dendrite growth result in inadequate Zn reversibility. Here, a biocompatible additive, L‐asparagine (Asp), low‐cost aqueous electrolyte, is introduced to address these concerns. Combining substantive verification tests theoretical calculations, it demonstrated that an Asp‐containing ZnSO 4 electrolyte can create robust nanostructured solid‐electrolyte interface (SEI) by simultaneously modulating the 2+ solvation structure optimizing metal‐molecule interface, which enables dense deposition. The optimized supports excellent reversibility achieving dendrite‐free plating/stripping over 240 h at utilization of 85.5% symmetrical cell average 99.6% Coulombic efficiency for 1600 cycles asymmetrical cell. Adequate full‐cell performance with poly(3,4‐ethylenedioxythiophene) intercalated vanadium oxide (PEDOT‐V 2 O 5 ) cathode, delivers areal capacity 4.62 mAh cm −2 holds 84.4% retention 200 under practical conditions ultrathin anode (20 µm) low negative/positive ratio (≈2.4). This engineering strategy provides new insights into regulating anode/electrolyte interfacial chemistries toward high‐performance AZIBs.

Language: Английский

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Comprehensive Review of Electrolyte Modification Strategies for Stabilizing Zn Metal Anodes

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(51)

Published: Aug. 24, 2023

Abstract In response to the need of sustainable development, there is an increasing demand for electrical energy storage, leading a stimulated pursuit advanced batteries. Aqueous zinc ion batteries (AZIBs) have attracted much attention due their low cost, high safety, and environmental friendliness. Despite great efforts made by researchers in designing developing high‐performance AZIBs, several challenges remain. Particularly Zn anode, growth dendrites occurance various side reactions significantly hinder advancement AZIBs. This review article aims discuss principles electrolyte's structure properties, faced AZIBs anodesm strategies improve battery performance through electrolyte modification systematic manner. conclusion, potential future directions aimed at enhancing stability anodes cathodes are proposed ensure that research geared toward achieving realistic targets commercializing

Language: Английский

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A Bio‐Inspired Trehalose Additive for Reversible Zinc Anodes with Improved Stability and Kinetics

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(41)

Published: Aug. 14, 2023

The moderate reversibility of Zn anodes, as a long-standing challenge in aqueous zinc-ion batteries, promotes the exploration suitable electrolyte additives continuously. It is crucial to establish absolute predominance smooth deposition within multiple interfacial reactions for stable zinc including suppressing side parasitic and facilitating plating process. Trehalose catches our attention due reported mechanisms sustaining biological stabilization. In this work, inter-disciplinary application trehalose modification first time. pivotal roles suppressed hydrogen evolution accelerated have been investigated based on principles thermodynamics well reaction kinetics. electrodeposit changes from random accumulation flakes dense bulk with (002)-plane exposure unlocked crystal-face oriented addition. As result, highly reversible anode obtained, exhibiting high average CE 99.8 % Zn/Cu cell cycling over 1500 h under 9.0 depth discharge symmetric cell. designing mechanism analysis study could serve source inspiration exploring novel advanced anodes.

Language: Английский

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Facet‐Termination Promoted Uniform Zn (100) Deposition for High‐Stable Zinc‐Ion Batteries

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(31)

Published: June 27, 2023

Abstract Reversibility, usually evaluated by Coulombic efficiency (CE) and limited dendrite growth, has become the major roadblock toward widespread commercialization of zincion batteries. Tailoring Zn deposition behavior is vital to prevent growth. In this work, facet‐terminator serine introduced modulate interface obstruct rampant growth (100) plane. The cation (Ser + ) revealed preferentially adsorb onto electrode/electrolyte interface, suppressing interfacial parasitic reaction. Theoretical analysis postmortem/operando experimental techniques indicate that Ser bestows (100)‐dominated morphology zinc anodes, enabling a highly reversible dendrite‐free anode. These features endow anode with long cyclic life more than 800 h for Zn//Zn batteries high average 99.8% at 5 mA cm −2 mAh Zn//Cu When assembling commercial V 2 O , full battery delivers capacity 345.1 g −1 A retention 74.1% over 2000 cycles.

Language: Английский

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Suppressed Water Reactivity by Zincophilic‐Hydrophobic Electrolyte Additive for Superior Aqueous Zn Metal Batteries

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(43)

Published: Oct. 2, 2023

Abstract As one of the most promising anodes aqueous batteries, Zn metal faces uncontrollable side reactions and deleterious dendrite growth, which drastically compromise its cycle life Coulombic efficiency (CE). To tackle these issues, a versatile electrolyte additive is reported that can regulate solvation structure, adsorb on surface, in situ generate novel zincophilic‐microhydrophobic interphase to isolate anode from reactive water molecules. Benefiting triple effects reactivity modulation, exhibits excellent reversibility with an ultra‐high average CE value 99.92% at 5 mA cm −2 ZnSO 4 system, Zn||Zn symmetric cell ethanesulfonamide achieves long lifespan over 6000 h. The merits ESA additives are further displayed Zn//MnO 2 full cells ion hybrid capacitors, exhibiting capacity retention 81.60% C 1000 cycles, 92.25% 50 000 cycles A g −1 , respectively. What's more, exhibit outstanding stability 100% after 120 0.1 C. This strategy shows alternative for development batteries low‐cost ‐based electrolytes.

Language: Английский

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A Double‐Charged Organic Molecule Additive to Customize Electric Double Layer for Super‐Stable and Deep‐Rechargeable Zn Metal Pouch Batteries

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(8)

Published: Nov. 12, 2023

Abstract The electrochemical performance of aqueous zinc metal batteries (AZMBs) is highly dependent on the electric double layer (EDL) properties at Zn electrode/electrolyte interface. Herein, a novel reconfigured EDL constructed via double‐charged theanine (TN) additive for super‐stable and deep‐rechargeable AZMBs. Experiments theoretical computations unravel that positively charged TN not only serves as preferential anchor to form water‐poor Helmholtz plane onto anode, but also its anionic end could coordinate with 2+ tailor solvation structure in diffusion further reconstruct inner H‐bonds networks, thus effectively guiding uniform deposition suppressing water‐induced side reactions. Consequently, Zn//Zn cells acquire outstanding cycling stabilities nearly 800 h high depth discharge 80%. Moreover, Zn//VOX full deliver substantial capacity retention (94.12% after 1400 cycles 2 A g −1 ) under practical conditions. Importantly, designed 2.7 Ah pouch cell harvests recorded energy density 42.3 Wh Kg 79.5 L –1 , remarkable 85.93% 220 50 mA . This innovative design concept reshape chemistry would inject fresh vitality into developing advanced AZMBs beyond.

Language: Английский

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Alleviating Side Reactions on Zn Anodes for Aqueous Batteries by a Cell Membrane Derived Phosphorylcholine Zwitterionic Protective Layer

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(31)

Published: June 19, 2023

Aqueous zinc (Zn) ion batteries are attractive for next generation with high safety, yet their applications still hindered by the uncontrollable dendrite formation and side reactions on Zn anode. Here, a polyzwitterion protective layer (PZIL) was engineered polymerizing 2-methacryloyloxyethyl phosphorylcholine (MPC) in carboxymethyl chitosan (CMCS), which renders following merits: choline groups of MPC can preferentially adsorb onto metal to avoid reactions; charged phosphate chelate Zn2+ regulate solvation structure, further improving reaction inhibition; Hofmeister effect between ZnSO4 CMCS enhance interfacial contact during electrochemical characterization. Consequently, symmetrical battery PZIL keep stable more than 1000 hours under ultra-high current density 40 mA cm-2 . The confers Zn/MnO2 full Zn/active carbon (AC) capacitor cycling performance density.

Language: Английский

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Engineering Fluorine‐rich Double Protective Layer on Zn Anode for Highly Reversible Aqueous Zinc‐ion Batteries

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(51)

Published: Nov. 4, 2023

Abstract The high thermodynamic instability and side reactions of Zn‐metal anode (ZMA), especially at current densities, greatly impede the commercialization aqueous zinc‐ion batteries (AZIBs). Herein, a fluorine‐rich double protective layer strategy is proposed to obtain reversibility AZIBs through introduction versatile tetradecafluorononane‐1,9‐diol (TDFND) additive in electrolyte. TDFND molecule with large adsorption energy (−1.51 eV) preferentially absorbs on Zn surface form Zn(OR) 2 − (R=−CH −(CF ) 7 −CH −) cross‐linking complex network, which balances space electric field controls 2+ ion flux, thus enabling uniform compact deposition (002) crystal planes. Meanwhile, low Lowest unoccupied molecular orbital (LUMO, 0.10 level priorly decomposed regulate interfacial chemistry ZMA by building ZnF ‐rich solid electrode/electrolyte interface (SEI) layer. It found that 14 nm‐thick SEI delivers excellent structural integrity suppress parasitic blocking direct contact active water ZMA. Consequently, electrode exhibits superior cycling life over 430 h 10 mA cm −2 average Coulombic efficiency 99.8 % 5 . Furthermore, 68 mAh pouch cell 80.3 capacity retention for 1000 cycles.

Language: Английский

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