Fundamental Understanding of Hydrogen Evolution Reaction on Zinc Anode Surface: A First-Principles Study

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

Опубликована: Фев. 6, 2024

Hydrogen evolution reaction (HER) has become a key factor affecting the cycling stability of aqueous Zn-ion batteries, while corresponding fundamental issues involving HER are still unclear. Herein, mechanisms on various crystalline surfaces have been investigated by first-principle calculations based density functional theory. It is found that Volmer step rate-limiting Zn (002) and (100) surfaces, while, rates (101), (102) (103) determined Tafel step. Moreover, correlation between activity generalized coordination number ([Formula: see text]) at revealed. The relatively weaker surface can be attributed to higher [Formula: text] atom. atomically uneven shows significantly than flat as atom lowered. proposed descriptor activity. Tuning would vital strategy inhibit anode presented theoretical studies. Furthermore, this work provides basis for in-depth understanding surface.

Язык: Английский

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Chelating Additive Regulating Zn‐Ion Solvation Chemistry for Highly Efficient Aqueous Zinc‐Metal Battery

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(21)

Опубликована: Март 27, 2024

Abstract Aqueous zinc‐metal batteries (AZMBs) usually suffered from poor reversibility and limited lifespan because of serious water induced side‐reactions, hydrogen evolution reactions (HER) rampant zinc (Zn) dendrite growth. Reducing the content molecules within Zn‐ion solvation sheaths can effectively suppress those inherent defects AZMBs. In this work, we originally discovered that two carbonyl groups N‐Acetyl‐ϵ‐caprolactam (N‐ac) chelating ligand serve as dual sites to coordinate with Zn 2+ , thereby minimizing sheaths, greatly inhibit water‐induced side‐reactions HER. Moreover, N‐ac additive form a unique physical barrier interface on surface, preventing harmful contacting water. addition, preferential adsorption (002) facets promote highly reversible dendrite‐free deposition. As result, Zn//Cu half‐cell added electrolyte delivered ultra‐high 99.89 % Coulombic efficiency during 8000 cycles. Zn//Zn symmetric cells also demonstrated unprecedented long life more than 9800 hours (over one year). Zn//ZnV 6 O 16 ⋅ 8H 2 (Zn//ZVO) full‐cell preserved 78 capacity even after ultra‐long 2000 A practical pouch‐cell was obtained (90.2 100 cycles). This method offers promising strategy for accelerating development efficient

Язык: Английский

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Mapping the design of electrolyte additive for stabilizing zinc anode in aqueous zinc ion batteries

Energy storage materials, Год журнала: 2024, Номер 68, С. 103364 - 103364

Опубликована: Март 24, 2024

Язык: Английский

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Molecular Engineering Enables Hydrogel Electrolyte with Ionic Hopping Migration and Self‐Healability toward Dendrite‐Free Zinc‐Metal Anodes

Advanced Materials, Год журнала: 2024, Номер 36(19)

Опубликована: Янв. 30, 2024

Abstract Hydrogel electrolytes (HEs), characterized by intrinsic safety, mechanical stability, and biocompatibility, can promote the development of flexible aqueous zinc‐ion batteries (FAZIBs). However, current FAZIB technology is severely restricted uncontrollable dendrite growth arising from undesirable reactions between HEs with sluggish ionic conductivity Zn metal. To overcome this challenge, work proposes a molecular engineering strategy, which involves introduction oxygen‐rich poly(urea‐urethane) (OR‐PUU) into polyacrylamide (PAM)‐based HEs. The OR‐PUU/PAM facilitate rapid ion transfer through their hopping migration mechanism, resulting in uniform orderly 2+ deposition. abundant polar groups on OR‐PUU molecules break inherent H‐bond network, tune solvation structure hydrated , inhibit occurrence side reactions. Moreover, interaction hierarchical H‐bonds endows them self‐healability, enabling situ repair cracks induced plating/stripping. Consequently, symmetric cells incorporating novel exhibit long cycling life 2000 h. Zn–MnO 2 battery displays low capacity decay rate 0.009% over cycles at mA g −1 . Overall, provides valuable insights to realization dendrite‐free Zn‐metal anodes

Язык: Английский

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Overcoming challenges of protonation effects induced by high isoelectric point amino acids through a synergistic strategy towards highly stable and reversible zinc electrode-electrolyte interface

Journal of Colloid and Interface Science, Год журнала: 2024, Номер 674, С. 713 - 721

Опубликована: Июнь 24, 2024

Язык: Английский

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For Zinc Metal Batteries, How Many Electrons go to Hydrogen Evolution? An Electrochemical Mass Spectrometry Study

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(11)

Опубликована: Янв. 3, 2024

Abstract Despite the advantages of aqueous zinc (Zn) metal batteries (AZMB) like high specific capacity (820 mAh g −1 and 5,854 cm −3 ), low redox potential (−0.76 V vs. standard hydrogen electrode), cost, water compatibility, safety, development practically relevant is plagued by several issues unwanted evolution reaction (HER), corrosion Zn substrate (insulating ZnO, Zn(OH) 2 , Zn(SO 4 ) x (OH) y Zn(ClO etc. passivation layer), dendrite growth. Controlling suppressing HER activity strongly correlates with long‐term cyclability AZMBs. Therefore, a precise quantitative technique needed to monitor real‐time dynamics during electrodeposition. In this study, we quantify using in situ electrochemical mass spectrometry (ECMS). This methodology enables us determine correction factor for faradaic efficiency system unmatched precision. For instance, electrodeposition on copper at current density 1.5 mA/cm 600 seconds, 0.3 % total charge attributed HER, while rest contributes At first glance, may seem small fraction, but it can be detrimental cycling performance Furthermore, our results provide insights into correlation between porous morphology electrodeposited zinc, unravelling presence trapped H charging process. Overall, study sets platform accurately provides powerful tool evaluating electrolyte additives, salts, electrode modifications aimed enhancing stability batteries.

Язык: Английский

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Improvements and Challenges of Hydrogel Polymer Electrolytes for Advanced Zinc Anodes in Aqueous Zinc-Ion Batteries

ACS Nano, Год журнала: 2024, Номер 18(33), С. 21779 - 21803

Опубликована: Авг. 12, 2024

Aqueous zinc-ion batteries (AZIBs) are widely regarded as desirable energy storage devices due to their inherent safety and low cost. Hydrogel polymer electrolytes (HPEs) cross-linked polymers filled with water zinc salts. They not only used in flexible but also represent an ideal electrolyte candidate for addressing the issues associated Zn anode, including dendrite formation side reactions. In HPEs, abundance of hydrophilic groups can form strong hydrogen bonds molecules, reducing activity inhibiting decomposition. At same time, special

Язык: Английский

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Reconstruction of Electric Double Layer on the Anode Interface by Localized Electronic Structure Engineering for Aqueous Zn Ion Batteries

Advanced Energy Materials, Год журнала: 2024, Номер 14(29)

Опубликована: Май 7, 2024

Abstract The electric double layer (EDL) at the electrode/electrolyte interface plays a crucial role to electrochemical reactions of zinc ion batteries. For Zn anode, EDL consists H 2 O dipoles, which can cause corrosion and passivation. Herein, localized electronic‐rich (LER) structure performing as soild electrolyte interphase (SEI) changes electron distribution, leading rapid capture 2+ , thus promoting desolvation cH shell. Moreover, LER generates an electrostatic repulsion effect SO 4 2− . Consequently, unique O‐poor is reconstructed with distribution ‐H O‐SO inhibits side improves deposition kinetics In situ Raman intuitively confirms that zinc‐ion‐flux uniform during whole electroplating process. regulator for structure, leads smooth fast deposition. performance enhancement demonstrated by LER@Zn//LER@Zn cells, exhibit exceptional lifespan 4800 h. Furthermore, LER@Zn///MnO cell shows improved cycling stability over 1500 cycles, high capacity 124 mAh g −1 5 C.

Язык: Английский

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Construction of Stable Zn Metal Anode by Inorganic Functional Protective Layer Toward Long-Life Aqueous Zn-Ion Battery

Energy storage materials, Год журнала: 2024, Номер 71, С. 103628 - 103628

Опубликована: Июль 8, 2024

Язык: Английский

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Capping Effect on High‐Active Nucleated‐Zn Toward Hydrogen Evolution‐Free Zn Metal Batteries

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 5, 2025

Abstract Aqueous Zn‐ion batteries are promising for large‐scale energy storage due to low cost and high safety. However, aqueous electrolyte induces severe side reactions at Zn anode, especially hydrogen evolution reaction (HER). Herein, it is first revealed that the freshly nucleated‐Zn (FN‐Zn) atoms during plating process show higher reactivity stronger adsorption of proton than metallic anode by X‐ray absorption near edge structure (XANES) corresponding extended fine (EXAFS), density functional theory simulations, promoting decomposition H 2 O. Then, a universal effective capping effect strategy proposed alleviate HER electrostatically shielding FN‐Zn activity. Specifically, sodium benzenesulfonate (SBS) selected as typical example screening comparing series additives, in which sulfonate group with coordination can be preferentially capped on reduce its reactivity. Consequently, symmetrical cell SBS not only generates negligible amounts situ electrochemical‐gas chromatography but also up 2550 h 1 mA cm −2 . More importantly, HER‐free verified coin full cells exhibiting capacity retention of≈87.1% after 1000 cycles large‐area (4 × 6 ) pouch desired performance.

Язык: Английский

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