Highly Reversible Zinc Metal Anode in a Dilute Aqueous Electrolyte Enabled by a pH Buffer Additive

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(5)

Published: Nov. 14, 2022

Aqueous zinc-ion batteries have drawn increasing attention due to the intrinsic safety, cost-effectiveness and high energy density. However, parasitic reactions non-uniform dendrite growth on Zn anode side impede their application. Herein, a multifunctional additive, ammonium dihydrogen phosphate (NHP), is introduced regulate uniform zinc deposition suppress reactions. The results show that NH

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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Reversible Zn Metal Anodes Enabled by Trace Amounts of Underpotential Deposition Initiators

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(18)

Published: March 3, 2023

Abstract Routine electrolyte additives are not effective enough for uniform zinc (Zn) deposition, because they hard to proactively guide atomic‐level Zn deposition. Here, based on underpotential deposition (UPD), we propose an “escort effect” of at the atomic level. With nickel ion (Ni 2+ ) additives, found that metallic Ni deposits preferentially and triggers UPD Ni. This facilitates firm nucleation growth while suppressing side reactions. Besides, dissolves back into after stripping with no influence interfacial charge transfer resistance. Consequently, optimized cell operates over 900 h 1 mA cm −2 (more than 4 times longer blank one). Moreover, universality is identified by using Cr 3+ Co additives. work would inspire a wide range principles controlling electrochemistry various metal batteries.

Language: Английский

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Construct Robust Epitaxial Growth of (101) Textured Zinc Metal Anode for Long Life and High Capacity in Mild Aqueous Zinc‐Ion Batteries

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(5)

Published: Nov. 23, 2023

Abstract Aqueous zinc‐metal batteries are considered to have the potential for energy storage due their high safety and low cost. However, practical applications of zinc limited by dendrite growth side reactions. Epitaxial is an effective method stabilizing Zn anode, especially manipulating (002) plane deposited zinc. texture difficult achieve stable cycle at capacity its large lattice distortion uneven electric field distribution. Here, a novel anode with highly (101) (denoted as (101)‐Zn) constructed. Due unique directional guidance strong bonding effect, (101)‐Zn can dense vertical electroepitaxy in near‐neutral electrolytes. In addition, grain boundary area inhibits occurrence The resultant symmetric cells exhibit excellent stability over 5300 h (4 mA cm −2 2 mAh ) 330 (15 10 ). Meanwhile, life Zn//MnO full cell meaningfully improved 1000 cycles.

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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Challenges and perspectives of hydrogen evolution-free aqueous Zn-Ion batteries

Energy storage materials, Journal Year: 2023, Volume and Issue: 59, P. 102767 - 102767

Published: April 6, 2023

Language: Английский

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Polyhydroxylated Organic Molecular Additives for Durable Aqueous Zinc Battery

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(4)

Published: Sept. 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.

Language: Английский

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Realizing Textured Zinc Metal Anodes through Regulating Electrodeposition Current for Aqueous Zinc Batteries

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(10)

Published: Jan. 13, 2023

Crystallography modulation of zinc (Zn) metal anode is promising to promote Zn reversibility in aqueous electrolytes, but efficiently constructing with specific crystallographic texture remains challenging. Herein, we report a current-controlled electrodeposition strategy the electrodeposits conventional electrolytes. Using electrolytic cell low-cost Zn(CH3 COO)2 electrolyte and Cu substrate as model system, as-deposited gradually transforms from (101) (002) crystal plane increasing current density 20 80 mA cm-2 . Moreover, high accelerates nucleation rate abundant nuclei, enabling uniform deposition. The permits stronger resistance dendrite growth interfacial side reactions than texture. resultant (002)-textured electrode achieves deep cycling stability supports stable operation full batteries V/Mn-based oxide cathodes.

Language: Английский

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Low‐Cost Multi‐Function Electrolyte Additive Enabling Highly Stable Interfacial Chemical Environment for Highly Reversible Aqueous Zinc Ion Batteries

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(49)

Published: Sept. 1, 2023

Abstract The practicality of aqueous zinc ion batteries (AZIBs) for large‐scale energy storage is hindered by challenges associated with anodes. In this study, a low‐cost and multi‐function electrolyte additive, cetyltrimethyl ammonium bromide (CTAB), presented to address these issues. CTAB adsorbs onto the anode surface, regulating Zn 2+ deposition orientation inhibiting dendrite formation. It also modifies solvation structure reduce water reactivity minimize side reactions. Additionally, optimizes key physicochemical parameters electrolyte, enhancing stability electrode/electrolyte interface promoting reversibility in AZIBs. Theoretical simulations combined operando synchrotron radiation‐based situ Fourier transform infrared spectra electrochemical impedance further confirm modified coordination environment adsorption effect cations at anode/electrolyte interface. As result, assembled Zn‐MnO 2 battery demonstrates remarkable specific capacity 126.56 mAh g −1 high current density 4 A after 1000 cycles. This work highlights potential as promising solution improving performance AZIBs applications.

Language: Английский

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Trace Amounts of Triple-Functional Additives Enable Reversible Aqueous Zinc-Ion Batteries from a Comprehensive Perspective

Nano-Micro Letters, Journal Year: 2023, Volume and Issue: 15(1)

Published: March 31, 2023

Although their cost-effectiveness and intrinsic safety, aqueous zinc-ion batteries suffer from notorious side reactions including hydrogen evolution reaction, Zn corrosion passivation, dendrite formation on the anode. Despite numerous strategies to alleviate these have been demonstrated, they can only provide limited performance improvement a single aspect. Herein, triple-functional additive with trace amounts, ammonium hydroxide, was demonstrated comprehensively protect zinc anodes. The results show that shift of electrolyte pH 4.1 5.2 lowers HER potential encourages in situ uniform ZHS-based solid interphase Moreover, cationic NH4+ preferentially adsorb anode surface shield "tip effect" homogenize electric field. Benefitting this comprehensive protection, dendrite-free deposition highly reversible plating/stripping behaviors were realized. Besides, improved electrochemical performances also be achieved Zn//MnO2 full cells by taking advantages additive. This work provides new strategy for stabilizing anodes perspective.

Language: Английский

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