Dendrites issues and advances in Zn anode for aqueous rechargeable Zn‐based batteries

Li, Qing; Zhao, Yuwei; Mo, Funian; Wang, Donghong; Yang, Qi; Huang, Zhaodong; Liang, Guojin; Chen, Ao; Chen, Zhi

doi:10.1002/eom2.12035

Cited by 146 publications

(106 citation statements)

References 86 publications

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“…However, most artificial solid Zn 2+ ‐ion conductor interlayer suffers from low Zn 2+ conductivity due to a large energy barrier of ion diffusion caused by a much high electric charge density of Zn 2+ ion. [ 31–34 ]…”

Section: Figurementioning

confidence: 99%

“…However, most artificial solid Zn 2+ion conductor interlayer suffers from low Zn 2+ conductivity due to a large energy barrier of ion diffusion caused by a much high electric charge density of Zn 2+ ion. [31][32][33][34] In this work, we demonstrate a compact and homogeneous zinc fluoride (ZnF 2 ) layer with high Zn 2+ conductivity, utilizing an in situ ion metathesis method. At the Zn/ZnF 2 interface, the F atoms of ZnF 2 layer are tightly bound with Zn atoms of Zn metal by electrovalent bonds, giving the credit to the charge migration between Zn and F atoms and charge redistribution.…”

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confidence: 99%

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Toward Practical High‐Areal‐Capacity Aqueous Zinc‐Metal Batteries: Quantifying Hydrogen Evolution and a Solid‐Ion Conductor for Stable Zinc Anodes

et al. 2021

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environments, [7-12] where Zn deposition even during shelf time is continuously interfered by competitive hydrogen evolution through H 2 O decomposition (Zn + 2H 2 O → Zn(OH) 2 + H 2) and by consuming both the electrolyte and active Zn metal. This long-neglected problem will remarkably affect calendar life of batteries, which is equivalently important with the intensively studied cycling life of batteries. As revealed in our preliminary quantitative study shown in Figure 1a, immersing Zn in 2 m ZnSO 4 electrolyte will induce an ≈0.25 mmol h-1 cm-2 hydrogen flux. The continuous hydrogen evolution will cause local pH changes, which further induce the formation of loose and brittle Zn 4 SO 4 (OH) 6 •xH 2 O (3Zn(OH) 2 + ZnSO 4 •xH 2 O → Zn 4 SO 4 (OH) 6 •xH 2 O), as revealed in Figure 1b. [13-18] It is generally assumed that these by-products augment the tortuosity and irregularity at the electrode/electrolyte interface with physical contact surface being increased (Figure 1c-h), which will further accelerate hydrogen evolution reaction. The above issues necessitate an effective method to detect hydrogen evolution. Nevertheless, for a Zn-based battery, these assumption and hypotheses are only based on oversimplified observations of battery swelling, gas bubbles, or conducting polarization curve in the absence of Zn 2+ condition, not reflecting physical truth of battery. [19-21] Hydrogen production during electrochemical procedure and even shelf time has not been precisely quantified. Consequently, efforts to make Zn metal a valid anode material may be misdirected. Quantifying the hydrogen production on the electrode during Zn deposition is key to understanding the mechanisms leading to capacity loss and battery failure. On the other hand, these Zn protrusions caused by hydrogen evolution reaction will attract more Zn 2+ flux ("tip" effect) [22] under concentrated electric field during electrochemical cycling, thus accelerating the vertical growth of Zn dendrites instead of planar growth and hydrogen production further flourish (Figure 1g). Up to now, various strategies have been evolved to prohibit the Zn dendrite growth, such as electrolyte optimization, [8,23-25] Zn surface coating, [9,21,26-29] and alloying. [30] To some extent, these strategies stabilize Zn metal, but they do The hydrogen evolution in Zn metal battery is accurately quantified by in situ battery-gas chromatography-mass analysis. The hydrogen fluxes reach 3.76 mmol h −1 cm −2 in a Zn//Zn symmetric cell in each segment, and 7.70 mmol h −1 cm −2 in a Zn//MnO 2 full cell. Then, a highly electronically insulating (0.11 mS cm −1) but highly Zn 2+ ion conductive (80.2 mS cm −1) ZnF 2 solid ion conductor with high Zn 2+ transfer number (0.65) is constructed to isolate Zn metal from liquid electrolyte, which not only prohibits over 99.2% parasitic hydrogen evolution but also guides uniform Zn electrodeposition. Precisely quantitated, the Zn@ZnF 2 //Zn@ZnF 2 cell only produces 0.02 mmol h −1 cm −2 of hydrogen (0.53% of the Zn//Zn cell). Encouragingly, a hig...

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Section: Figurementioning

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Toward Practical High‐Areal‐Capacity Aqueous Zinc‐Metal Batteries: Quantifying Hydrogen Evolution and a Solid‐Ion Conductor for Stable Zinc Anodes

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“…When these Zn(OH) 4 2− ions reach supersaturation, they spontaneously decompose to form insoluble zinc oxide (ZnO); these reaction pathways are reversible in the subsequent charging process, i.e., ZnO is reduced to the final metallic Zn. [ 116,117 ] The reaction equations are shown below

\begin{matrix} Zn + 4 {OH}^{-} \leftrightarrow Zn {(OH)}_{4}^{2 -} + 2 {normale}^{-} \end{matrix}

\begin{matrix} Zn {(OH)}_{4}^{2 -} \leftrightarrow ZnO + 2 {OH}^{-} + {normalH}_{2} O \end{matrix}

…”

Section: In Situ Characterization Techniques and Xas Analyses In Azmbsmentioning

confidence: 99%

Comprehensive Analyses of Aqueous Zn Metal Batteries: Characterization Methods, Simulations, and Theoretical Calculations

Zhang

Hou

2021

Advanced Energy Materials

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Aqueous zinc metal batteries (AZMBs) are regarded as competitive candidates for next‐generation energy storage owing to their low cost, high performance, high safety, and high environmental friendliness. However, serious issues, including Zn dendrites, chemical corrosion, H2 evolution, and sluggish Zn2+ diffusion kinetics, have largely impeded the commercial application of AZMBs. To understand these issues in depth and identify countermeasures, comprehensive analyses of AZMBs have continuously been developed. In this review, a detailed overview of the analytical techniques used to study AZMBs, including characterization methods, simulations, and theoretical calculations is presented, which provides a comprehensive toolbox for further research. Conventional characterization methods that provide preliminary information are first summarized. Various in situ techniques, including visualization and spectral characterization, are then discussed. These advanced real‐time monitoring techniques contribute to a deeper understanding of the battery failure mechanism. Simulations and theoretical calculations are then presented in detail, enabling an in‐depth investigation of the mechanism at the atomic level. Theoretical analyses can not only explore the mechanism in more detail, but also play a key role in guiding research and predicting future directions. Finally, the challenges and perspective of comprehensive analyses of AZMBs are discussed.

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“…The above finding implies that the storage process is of exceptional importance in RZB performance, which has long been neglected in RZB studies. [ 37 ] Storage is associated with hydrogen evolution, extra capacity fading, and even battery failure. The adverse effects of the storage process are usually covered up using lab‐level loading masses, cell configurations, and sequential cycling conditions.…”

Section: Introductionmentioning

confidence: 99%

Calendar Life of Zn Batteries Based on Zn Anode with Zn Powder/Current Collector Structure

et al. 2021

Advanced Energy Materials

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Zn foil is widely used for studying the stability and dendrite formation behavior of Zn anodes. The reported long cycling life of rechargeable Zn batteries (RZBs) is obtained by testing a battery immediately after its fabrication neglecting the aging effects. The cycling performance demonstrated cannot, however, have practical applications. Using Zn foil as both the working electrode and current collector will cause many problems when the battery is scaled up. A Zn powder (Zn‐P)/current collector configuration is more practical. In this work, the corrosion of the Zn‐P@Cu anode‐induced cell swelling is first quantitatively studied. During the aging process of the Zn‐P@Cu electrode, hydrogen forms on the surface of Cu and the Zn‐P dissolves resulting in morphological changes. These phenomena can be attributed to galvanic corrosion between Cu and Zn. To address this issue, tin with a higher overpotential for hydrogen generation is plated on Cu surface. The results indicate that hydrogen evolution is ameliorated. With a low NP ratio (mass) of 10:7, considerably better storage and cycling performance are achieved for Zn‐P@Cu//MnO2. These results highlight the need to focus on the calendar life of RZBs and corrosion of the Zn anode.

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Dendrites issues and advances in Zn anode for aqueous rechargeable Zn‐based batteries

Cited by 146 publications

References 86 publications

Toward Practical High‐Areal‐Capacity Aqueous Zinc‐Metal Batteries: Quantifying Hydrogen Evolution and a Solid‐Ion Conductor for Stable Zinc Anodes

Toward Practical High‐Areal‐Capacity Aqueous Zinc‐Metal Batteries: Quantifying Hydrogen Evolution and a Solid‐Ion Conductor for Stable Zinc Anodes

Comprehensive Analyses of Aqueous Zn Metal Batteries: Characterization Methods, Simulations, and Theoretical Calculations

Calendar Life of Zn Batteries Based on Zn Anode with Zn Powder/Current Collector Structure

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