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

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(27)

Опубликована: Май 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.

Язык: 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, Год журнала: 2023, Номер 62(21)

Опубликована: Март 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.

Язык: Английский

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Polyhydroxylated Organic Molecular Additives for Durable Aqueous Zinc Battery

Advanced Functional Materials, Год журнала: 2023, Номер 34(4)

Опубликована: Сен. 27, 2023

Abstract The large‐scale deployment of aqueous Zn‐ion batteries is hindered by Zn anode instability including surface corrosion, hydrogen gas evolution, and irregular deposition. To tackle these challenges, a polyhydroxylated organic molecular additive, trehalose, incorporated to refine the solvation structure promote planar Within regions involving hydroxy groups participate in reconstruction bond networks, which increases overpotential for water decomposition reaction. Moreover, at metal–molecule interface, chemisorption trehalose onto zinc enhances corrosion resistance facilitates deposition manner. optimized electrolyte significantly improves striping/plating reversibility maintains stable potentials over 1600 h 5 mA cm −2 with cutoff capacity 1 symmetric cells. When combined MnO 2 cathode, assembled coin cell retains ≈89% its after 1000 cycles. This molecule emphasizing role molecules fine‐tuning structures anode/electrolyte interfaces, holds promise enhancing various metal batteries.

Язык: Английский

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Reunderstanding aqueous Zn electrochemistry from interfacial specific adsorption of solvation structures

Energy & Environmental Science, Год журнала: 2023, Номер 16(7), С. 2910 - 2923

Опубликована: Янв. 1, 2023

Reunderstanding the faradaic reaction mechanism at electrode/electrolyte interface from specific adsorption of solvation structures towards advanced aqueous Zn–Mn batteries.

Язык: Английский

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Design Strategies for Aqueous Zinc Metal Batteries with High Zinc Utilization: From Metal Anodes to Anode-Free Structures

Nano-Micro Letters, Год журнала: 2024, Номер 16(1)

Опубликована: Янв. 4, 2024

Aqueous zinc metal batteries (AZMBs) are promising candidates for next-generation energy storage due to the excellent safety, environmental friendliness, natural abundance, high theoretical specific capacity, and low redox potential of (Zn) metal. However, several issues such as dendrite formation, hydrogen evolution, corrosion, passivation Zn anodes cause irreversible loss active materials. To solve these issues, researchers often use large amounts excess ensure a continuous supply materials anodes. This leads ultralow utilization squanders density AZMBs. Herein, design strategies AZMBs with discussed in depth, from utilizing thinner foils constructing anode-free structures 100%, which provides comprehensive guidelines further research. Representative methods calculating depth discharge different first summarized. The reasonable modification foil anodes, current collectors pre-deposited Zn, aqueous (AF-AZMBs) improve then detailed. In particular, working mechanism AF-AZMBs is systematically introduced. Finally, challenges perspectives high-utilization presented.

Язык: Английский

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An Aqueous Electrolyte Regulator for Highly Stable Zinc Anode Under −35 to 65 °C

Advanced Energy Materials, Год журнала: 2023, Номер 13(40)

Опубликована: Сен. 13, 2023

Abstract The reversibility and long‐term cycling stability of aqueous zinc‐ion batteries (AZIBs) in a wide temperature range have rarely been explored. Herein, diethylene glycol monoethyl ether (DG) is introduced as an electrolyte additive to enhance Zn performance within −35 65 °C. Operando synchrotron Fourier transform infrared spectroscopy analysis combined with molecular dynamics simulations reveal that the introduction DG disrupts initial hydrogen bonding network electrolyte, restructuring solvation structure surrounding 2+ ions mitigating water‐induced parasitic reactions. Adding reduces freezing point without compromising its incombustibility. Moreover, operando electrochemical quartz crystal microbalance dissipation monitoring (EQCM‐D) X‐ray photoelectron demonstrated coordinated OTF − undergo reductive decomposition, forming self‐healing solid interphase comprising inorganic/organic ZnF 2 ‐ZnS, which can effectively suppress notorious side reactions guide uniform deposition. Consequently, symmetric Zn/Zn cells demonstrate excellent for 3500 h under 1 mA cm −2 at 25 °C, 1000 both Full DG‐containing exhibit long lifespan 5000 cycles A g −1 .

Язык: 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, Год журнала: 2023, Номер 62(31)

Опубликована: Июнь 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.

Язык: Английский

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Synergistic Modulation of In‐Situ Hybrid Interface Construction and pH Buffering Enabled Ultra‐Stable Zinc Anode at High Current Density and Areal Capacity

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(45)

Опубликована: Сен. 25, 2023

In aqueous electrolytes, the uncontrollable interfacial evolution caused by a series of factors such as pH variation and unregulated Zn2+ diffusion would usually result in rapid failure metallic Zn anode. Considering high correlation among various triggers that induce anode deterioration, synergistic modulation strategy based on electrolyte modification is developed. Benefitting from unique buffer mechanism additive its capability to situ construct zincophilic solid interface, this effect can comprehensively manage thermodynamic kinetic properties inhibiting parasitic side reactions, accelerating de-solvation hydrated , regulating behavior realize uniform deposition. Thus, modified achieve an impressive lifespan at ultra-high current density areal capacity, operating stably for 609 209 hours 20 mA cm-2 mAh 40 respectively. Based exceptional performance, loading Zn||NH4 V4 O10 batteries excellent cycle stability rate performance. Compared with those previously reported single strategies, concept expected provide new approach highly stable zinc-ion batteries.

Язык: 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, Год журнала: 2023, Номер 135(21)

Опубликована: Март 24, 2023

Abstract 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 H 2 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‐H volume ratio), for regulating molecule distribution Density functional theory (DFT) calculations molecular dynamics (MD) simulation verify that incorporated Py could tailor 2+ 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.

Язык: Английский

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Periodically Alternating Electric Field Layers Induces the Preferential Growth of Zn (002) Plane for Ultralow Overpotential Zinc‐Ion Batteries

Advanced Energy Materials, Год журнала: 2023, Номер 13(21)

Опубликована: Апрель 23, 2023

Abstract The sluggish de‐solvation kinetics and uneven Zn 2+ transport behavior at the anode are undesirable for commercialization of zinc ion batteries. To address these issues, a periodically alternating electric field is introduced on by constructing laponite nano‐clay layer with unique separation properties. This exhibits negative positive fields together in same space but different directions (negative normal direction while radial direction); thus, achieving both homogeneous an effective effect. film (LAP@Zn) as multifunctional artificial can induce nucleation preferential orientation growth along (002) planes, thereby suppressing dendrite anode. Consequently, LAP@Zn symmetric cells exhibit ultralow overpotential (12 mV) cycle smoothly over 1100 h 0.5 mA cm −2 . Even ultrahigh current density 40 , cell still operates stably 500 h. More encouragingly, effectiveness also convincing MnO 2 ‐based full excellent rate performance stability. strategy provides path toward high‐performance dendrite‐free Zn‐based storage systems.

Язык: Английский

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