Functional Ultrathin Separators Proactively Stabilizing Zinc Anodes for Zinc‐Based Energy Storage

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(18)

Published: Feb. 14, 2023

Ultrathin separators are indispensable to high-energy-density zinc-ion batteries (ZIBs), but their easy failure caused by zinc dendrites poses a great challenge. Herein, 23 µm-thick functional ultrathin (FUSs), realizing superb electrochemical stability of anodes and outstanding long-term durability separators, reported. In the FUSs, an mechanically strong nanoporous membrane substrate benefits fast flux-homogenized Zn2+ transport, while metal-organic framework (MOF)-derived C/Cu nanocomposite decoration layer provides rich low-barrier nucleation sites, thereby synergistically stabilizing inhibit dendrite-caused separator failure. Investigation affinity MOF-derived nanocomposites unravels high zincophilicity heteroatom-containing interfaces. Zinc coupled with FUSs present superior stability, whose operation lifetime exceeds 2000 h at 1 mA cm-2 600 10 , 40-50 times longer than that using glass-fiber separators. The reliability in ZIBs hybrid supercapacitors is also validated. This work proposes new strategy stabilize theoretical guidance developing for zinc-based energy storage.

Language: Английский

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Polycation‐Regulated Electrolyte and Interfacial Electric Fields for Stable Zinc Metal Batteries

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(27)

Published: May 8, 2023

Zn metal as one of promising anode materials for aqueous batteries but suffers from disreputable dendrite growth, grievous hydrogen evolution and corrosion. Here, a polycation additive, polydiallyl dimethylammonium chloride (PDD), is introduced to achieve long-term highly reversible plating/stripping. Specifically, the PDD can simultaneously regulate electric fields electrolyte Zn/electrolyte interface improve Zn2+ migration behaviors guide dominant (002) deposition, which veritably detected by Zeta potential, Kelvin probe force microscopy scanning electrochemical microscopy. Moreover, also creates positive charge-rich protective outer layer N-rich hybrid inner layer, accelerates desolvation during plating process blocks direct contact between water molecules anode. Thereby, reversibility stability anodes are substantially improved, certified higher average coulombic efficiency 99.7 % Zn||Cu cells 22 times longer life Zn||Zn compared with that PDD-free electrolyte.

Language: Английский

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Organic pH Buffer for Dendrite‐Free and Shuttle‐Free Zn‐I₂ Batteries

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(21)

Published: March 23, 2023

Aqueous Zn-Iodine (I2 ) batteries are attractive for large-scale energy storage. However, drawbacks include, Zn dendrites, hydrogen evolution reaction (HER), corrosion and, cathode "shuttle" of polyiodines. Here we report a class N-containing heterocyclic compounds as organic pH buffers to obviate these. We evidence that addition pyridine /imidazole regulates electrolyte pH, and inhibits HER anode corrosion. In addition, imidazole preferentially absorb on metal, regulating non-dendritic plating /stripping, achieving high Coulombic efficiency 99.6 % long-term cycling stability 3200 h at 2 mA cm-2 , mAh . It is also confirmed polyiodines shuttling boosts conversion kinetics I- /I2 As result, the Zn-I2 full battery exhibits long cycle >25 000 cycles specific capacity 105.5 g-1 10 A conclude buffer engineering practical dendrite-free shuttle-free batteries.

Language: Английский

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Fluoride-Rich, Organic–Inorganic Gradient Interphase Enabled by Sacrificial Solvation Shells for Reversible Zinc Metal Batteries

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(41), P. 22456 - 22465

Published: Oct. 6, 2023

Zinc metal batteries are strongly hindered by water corrosion, as solvated zinc ions would bring the active molecules to electrode/electrolyte interface constantly. Herein, we report a sacrificial solvation shell repel from and assist in forming fluoride-rich, organic-inorganic gradient solid electrolyte (SEI) layer. The simultaneous process of methanol Zn(CF3SO3)2 results SEI layer with an organic-rich surface (CH2OC- C5 product) inorganic-rich (ZnF2) bottom, which combines merits fast ion diffusion high flexibility. As result, additive enables corrosion-free stripping/plating on copper foils for 300 cycles average coulombic efficiency 99.5%, record cumulative plating capacity 10 A h/cm2 at 40 mA/cm2 Zn/Zn symmetrical batteries. More importantly, ultralow N/P ratio 2, practical VO2//20 μm thick Zn plate full areal 4.7 mAh/cm2 stably operate over 250 cycles, establishing their promising application grid-scale energy storage devices. Furthermore, directly utilizing 20 commercial-level (4.7 mAh/cm2) battery our work simplify manufacturing boost development commercial stationary storage.

Language: Английский

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Selection criteria for electrical double layer structure regulators enabling stable Zn metal anodes

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(4), P. 1721 - 1731

Published: Jan. 1, 2023

Combined with experimental and theoretical studies, we revealed a critical criterion that gives priority to the SEI-forming capability of additives for developing effective EDL structure regulators.

Language: Английский

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A eutectic electrolyte for an ultralong-lived Zn//V₂O₅cell: anin situgenerated gradient solid-electrolyte interphase

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(8), P. 3587 - 3599

Published: Jan. 1, 2023

This study achieved dendrite-free Zn metal anodes for Zn-ion batteries via an in situ generated gradient organic/inorganic hybrid solid–electrolyte interphase enabled by a eutectic electrolyte.

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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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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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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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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