Stabling Zinc Metal Anode with Polydopamine Regulation through Dual Effects of Fast Desolvation and Ion Confinement

Advanced Energy Materials, Journal Year: 2022, Volume and Issue: 13(5)

Published: Dec. 13, 2022

Abstract Metal zinc is recognized as a promising anode candidate for aqueous zinc‐ion batteries (AZIBs), however, dendrites and byproducts formation severe deteriorate its reversibility practical lifespan. Herein, polydopamine (PDA) layer, which offers the dual effects of fast desolvation ion confinement, constructed on surface Zn efficient AZIBs. The abundant polar functional groups in PDA significantly enhance interfacial contact media, reduces number water molecules reaching through desolvation, thus lowering energy barrier 2+ migration. Furthermore, porous coating controls flux via ion‐confinement effect, thereby accelerating kinetics surface. Consequently, Zn@PDA exhibits improved deposition (nucleation potential only 32.6 mV vs 50.2 bare Zn) compared with at 2.0 mA cm −2 , dendrite‐free negligible byproduct formation. When paired MnO 2 cathode, Zn@PDA//MnO cell delivers high discharge capacity long cycle stability without significant performance deterioration over 1000 cycles 1.0 A g −1 . Additionally, demonstrates excellent shelving‐restoring performance.

Language: Английский

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Addition of Dioxane in Electrolyte Promotes (002)-Textured Zinc Growth and Suppressed Side Reactions in Zinc-Ion Batteries

ACS Nano, Journal Year: 2023, Volume and Issue: 17(4), P. 3765 - 3775

Published: Feb. 8, 2023

The reversibility and cyclability of aqueous zinc-ion batteries (ZIBs) are largely determined by the stabilization Zn anode. Therefore, a stable anode/electrolyte interface capable inhibiting dendrites side reactions is crucial for high-performing ZIBs. In this study, we investigated adsorption 1,4-dioxane (DX) to promote exposure (002) facets prevent dendrite growth. DX appears reside at suppress detrimental reactions. ZIBs with addition demonstrated long-term cycling stability 1000 h in harsh conditions 10 mA cm–2 an ultrahigh cumulative plated capacity 5 Ah shows good average Coulombic efficiency 99.7%. Zn//NH4V4O10 full battery achieves high specific (202 mAh g–1 A g–1) retention (90.6% after 5000 cycles), much better than that pristine ZnSO4 electrolyte. By selectively adjusting Zn2+ deposition rate on crystal adsorbed molecules, work provides promising modulation strategy molecular level anodes can potentially be applied other metal suffering from instability irreversibility.

Language: Английский

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Reversible adsorption with oriented arrangement of a zwitterionic additive stabilizes electrodes for ultralong-life Zn-ion batteries

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(6), P. 2684 - 2695

Published: Jan. 1, 2023

A zwitterionic additive ( l -CN) with a positively charged quaternary ammonium site and multifunctional polar groups was employed to achieve ultralong-life Zn-ion batteries.

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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Nonepitaxial Electrodeposition of (002)‐Textured Zn Anode on Textureless Substrates for Dendrite‐Free and Hydrogen Evolution‐Suppressed Zn Batteries

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(21)

Published: March 2, 2023

Nontoxic and safe aqueous Zn batteries are largely restricted by the detrimental dendrite growth hydrogen evolution of metal anode. The (002)-textured electrodeposition, demonstrated as an effective approach for solving these issues, is nevertheless achieved mainly epitaxial or hetero-epitaxial deposition on pre-textured substrates. Herein, electrodeposition compact textureless substrates (commercial Zn, Cu, Ti foils) at a medium-high galvanostatic current density reported. According to systematic investigations nucleation behaviors, this ascribed two reasons: i) promoted nonepitaxial fine horizontal (002) nuclei increased overpotential ii) competitive advantages (002)-orientated nuclei. resulting freestanding film exhibits significantly suppressed prolonged plating-stripping cycling life, achieving over 2100 mAh cm-2 cumulative capacity under 10 mA high depth discharge (DOD) 45.5%. Therefore, study provides both fundamental practical insights into long-life batteries.

Language: Английский

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Regulating the Inner Helmholtz Plane with a High Donor Additive for Efficient Anode Reversibility in Aqueous Zn‐Ion Batteries

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

Published: March 24, 2023

The performance of aqueous Zn ion batteries (AZIBs) is highly dependent on inner Helmholtz plane (IHP) chemistry. Notorious parasitic reactions containing hydrogen evolution (HER) and dendrites both originate from abundant free H2 O random deposition inside active IHP. Here, we report a universal high donor number (DN) additive pyridine (Py) with only 1 vol. % addition (Py-to-H2 volume ratio), for regulating molecule distribution Density functional theory (DFT) calculations molecular dynamics (MD) simulation verify that incorporated Py could tailor Zn2+ solvation sheath exclude molecules IHP effectively, which in favor preventing decomposition. Consequently, even at extreme conditions such as depth discharge (DOD) 80 %, the symmetric cell based can sustain approximately 500 h long-term stability. This efficient strategy DN additives furnishes promising direction designing novel electrolytes promoting practical application AZIBs, despite inevitably introducing trace organic additives.

Language: Английский

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Self-assembled multilayers direct a buffer interphase for long-life aqueous zinc-ion batteries

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(8), P. 3381 - 3390

Published: Jan. 1, 2023

A self-assembled multilayer was used to homogenize ion flux and accelerate charge transfer through area-induced deposition effects strong dipole moments. The molecular domains act as a buffer interphase achieve long-term stability.

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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Electric double layer design for Zn-based batteries

Energy storage materials, Journal Year: 2023, Volume and Issue: 62, P. 102932 - 102932

Published: Aug. 16, 2023

Language: Английский

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