Synergistic Manipulation of Hydrogen Evolution and Zinc Ion Flux in Metal‐Covalent Organic Frameworks for Dendrite‐free Zn‐based Aqueous Batteries

Guo, Can; Zhou, Jie; Chen, Yuting; Zhuang, Huifen; Li, Qi; Li, Jie; Tian, Xi; Zhang, Yuluan; Yao, Xiaoman; Chen, Yifa; Li, Shun-Li; Lan, Ya‐Qian

doi:10.1002/anie.202210871

Cited by 99 publications

(58 citation statements)

References 53 publications

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“…Impressively, a better redox reaction kinetic behaviors were gained in DE electrolyte due to less polarization reflecting as relatively small potential differences between two pairs of redox peaks (Fig. 5 a) [ 53 , 54 ]. The rate performance of full cells using different electrolytes were illustrated in Fig.…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2023

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

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Section: Resultsmentioning

confidence: 99%

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

et al. 2023

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“…However, F-BG-4 showed the strongest improvement at 10 A g –1 , which is 6.6 mAh g –1 higher than the device using the bare zinc anode. The reason for this is that the F-BG structure is broken down at high current densities, the rapid generation of zinc dendrites and side reactions will accelerate the collapse of the anode surface, and the thicker buffer layer can effectively regulate the exfoliation and nucleation of zinc, demonstrating excellent rate capability while stabilizing the zinc anode. − Cycle stability was evaluated by measuring the retention of discharge capacity after 500 cycles at 10 A g –1 . The AZHC using the F-BG@Zn anode retained 81.1% of its original capacity, while the retention rate of Zn//AC using bare zinc was only 37.5%, indicating the unique advantages of the F-BG protective layer in inhibiting dendrites and side reactions.…”

Section: Resultsmentioning

confidence: 99%

Strategically Constructing a Hydrophilic Interface toward Ultrastable Zinc Metal Anodes

Wang

Huang

Wang

et al. 2023

ACS Appl. Mater. Interfaces

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Aqueous zinc-ion storage devices have received increasing attention due to their inherent safety, high capacity, and cost-effectiveness. However, problems such as uneven Zn deposition, limited diffusion kinetics, and corrosion greatly reduce the cycling performance of zinc anodes. Here, a sulfonate-functionalized boron nitride/graphene oxide (F-BG) buffer layer is designed and utilized to modulate the plating/stripping behavior and mitigate the side reactions with the electrolyte. Benefiting from the synergistic effect of high electronegativity and abundant surface functional groups, the F-BG protective layer accelerates the ordered migration of Zn2+, homogenizes the Zn2+ flux, and effectively improves the reversibility of plating and nucleation with strong zincphilicity and dendrite-inhibiting capabilities. Further, electrochemical measurements and cryo-EM observations reveal the mechanism by which the interfacial wettability of the zinc negative electrode acts on capacity and cycling stability. Our work provides deeper insight into the influence of wettability on the energy storage properties and brings forward a facile and instructive way to construct stable zinc anodes for zinc-ion hybrid capacitors.

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“…Lan et al [40] designed COFs (i. e., Zn-AAn-COF, Zn-DAAQ-COF, Zn-DAA-COF) with structures rationally selected to have structural pillars with polar groups or zincophilic groups that provide a high degree of interaction with Zn 2 + , water molecules, and zinc surfaces, thus promoting the generation of zincophilic layers, electrolyte/electrode wetting and Zn 2 + jumping/deposition. To address these issues, Li et al [31] prepared covalent triazine frameworks (CTFs) with rich zinc ion transfer channels and strong chemical stability as zinc anode coatings.…”

Section: Organic Interfacial Layermentioning

confidence: 99%

Zincophilic Design and the Electrode/Electrolyte Interface for Aqueous Zinc‐Ion Batteries: A Review

Zhao

Gao²,

Guo

et al. 2023

Batteries & Supercaps

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Aqueous zinc‐ion batteries (ZIBs) are limited in energy storage by the persistent Zn dendrites, which is a major bottleneck preventing the commercial application of rechargeable aqueous zinc‐ion batteries. The dendritic problems associated with Zn metal anodes can lead to rapid performance degradation, failure and even safety risks of the battery. Zincophilicity of the electrode/electrolyte interface is critical to the stable and safe operation for aqueous ZIBs. In this review, we discuss that zincophilicity can be regulated by tuning the chemical interactions of material surface energy with zinc metal, emphasizing the importance of zincophilic design for improving the electrochemical performance of zinc electrodes. Advances in optimization strategies for the zincophilic zinc metal anode/electrolyte interface are summarized. Challenges and prospects for further exploration and balance of zincophilicity of the anode/electrolyte interface are presented, which are expected to promote in‐depth research and practical applications of advanced aqueous zinc ions.

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Synergistic Manipulation of Hydrogen Evolution and Zinc Ion Flux in Metal‐Covalent Organic Frameworks for Dendrite‐free Zn‐based Aqueous Batteries

Cited by 99 publications

References 53 publications

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

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

Strategically Constructing a Hydrophilic Interface toward Ultrastable Zinc Metal Anodes

Zincophilic Design and the Electrode/Electrolyte Interface for Aqueous Zinc‐Ion Batteries: A Review

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