Engineering interfacial layers to enable Zn metal anodes for aqueous zinc-ion batteries

He, Huibing; Qin, Hongyu; Wu, Jia; Chen, Xingfa; Huang, Renshu; Shen, Fang; Wu, Zhenrui; Chen, Guoning; Yin, Shibin; Liu, Jian

doi:10.1016/j.ensm.2021.09.012

Cited by 216 publications

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“…[1,3,6] These dendritic structures, either rarefied needle, or non-planar platelet deposits, preferentially form at irregular or defective areas of the electrode where the localized current density is highest and the initial nucleation event is most likely, [7] and is exacerbated by cycling at high current densities and capacities. [8,9] Strategies for controlling and suppressing dendritic growth have revolved around manipulating the electrolyte, typically by inclusion of additives, [10][11][12][13][14][15] or by engineering the electrode into a high-surface-area sponge, [16][17][18] or with a protective surface coating, [19] in order to suppress dendrite formation.Despite being one of the most promising candidates for grid-level energy storage, practical aqueous zinc batteries are limited by dendrite formation, which leads to significantly compromised safety and cycling performance. In this study, by using single-crystal Zn-metal anodes, reversible electrodeposition of planar Zn with a high capacity of 8 mAh cm −2 can be achieved at an unprecedentedly high current density of 200 mA cm −2 .…”

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confidence: 99%

Achieving Ultrahigh‐Rate Planar and Dendrite‐Free Zinc Electroplating for Aqueous Zinc Battery Anodes

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attractive for future grid-level energy storage applications. Metallic Zn, as the ideal anode for AZBs, has the highest theoretical capacity (5851 mAh mL −1 ). It is also non-toxic, non-flammable, abundant, and has good electrical conductivity and water stability. [1][2][3][4][5] However, conventional metallic Zn anodes suffer from severe dendrite formation during cycling, causing serious problems like poor reversibility, voltage hysteresis, increased parasitic reactions, shorting-induced battery failures, and other issues. [1,3,6] These dendritic structures, either rarefied needle, or non-planar platelet deposits, preferentially form at irregular or defective areas of the electrode where the localized current density is highest and the initial nucleation event is most likely, [7] and is exacerbated by cycling at high current densities and capacities. [8,9] Strategies for controlling and suppressing dendritic growth have revolved around manipulating the electrolyte, typically by inclusion of additives, [10][11][12][13][14][15] or by engineering the electrode into a high-surface-area sponge, [16][17][18] or with a protective surface coating, [19] in order to suppress dendrite formation.Despite being one of the most promising candidates for grid-level energy storage, practical aqueous zinc batteries are limited by dendrite formation, which leads to significantly compromised safety and cycling performance. In this study, by using single-crystal Zn-metal anodes, reversible electrodeposition of planar Zn with a high capacity of 8 mAh cm −2 can be achieved at an unprecedentedly high current density of 200 mA cm −2 . This dendrite-free electrode is well maintained even after prolonged cycling (>1200 cycles at 50 mA cm −2 ). Such excellent electrochemical performance is due to single-crystal Zn suppressing the major sources of defect generation during electroplating and heavily favoring planar deposition morphologies. As so few defect sites form, including those that would normally be found along grain boundaries or to accommodate lattice mismatch, there is little opportunity for dendritic structures to nucleate, even under extreme plating rates. This scarcity of defects is in part due to perfect atomic-stitching between merging Zn islands, ensuring no defective shallow-angle grain boundaries are formed and thus removing a significant source of non-planar Zn nucleation. It is demonstrated that an ideal high-rate Zn anode should offer perfect lattice matching as this facilitates planar epitaxial Zn growth and minimizes the formation of any defective regions.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adma.202202552.

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Achieving Ultrahigh‐Rate Planar and Dendrite‐Free Zinc Electroplating for Aqueous Zinc Battery Anodes

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“…[11] To solve this problem, various kinds of coatings have been made, which mainly include inorganic coating, polymer coating, organic, and inorganic composite coating. [12] They could block water molecules from reaching the Zn surface, and then improve the stability and reversibility of Zn metal anode. [13] However, thicker coatings were usually chosen to guarantee long-acting anticorrosion effect and retard the growth of dendrites, which meant the long route of ionic Some new insights into traditional metal pretreatment of anticorrosion for high stable Zn metal anodes are provided.…”

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Crystal Plane Reconstruction and Thin Protective Coatings Formation for Superior Stable Zn Anodes Cycling 1300 h

Liu

Cai

et al. 2022

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820 mAh g −1 ), which is attractive as the anode for aqueous batteries. [1] Based on these advantages, various zinc-metal batteries employing aqueous electrolyte with high safety (such as Zn-ion batteries, Zn-air batteries, and Zn-redox-flow batteries) have been intensively investigated. [2] Unfortunately, the poor chemical stability and electrochemical irreversibility of the Zn metal anode limit the practical applications of Zn rechargeable batteries. [3] Undesired side reactions and dendrite growth are two main challenges for aqueous Zn metal batteries.The nonuniform Zn 2+ flux of the interfacial layer on Zn can cause variations in the localized current density and ion depletion during cycling, thus resulting in large overpotentials and dendrite growth. [4] Continued dendrite growth can lead to penetration of the separator and cause short circuiting of cells. Moreover, nonuniform Zn plating/stripping may lead to further undesired side reactions between Zn and aqueous electrolytes. [5] To solve this problem, the interfacial coatings on the Zn surface are used to regulate Zn 2+ flux and suppress Zn dendrite growth, which finally avoids the well-known "tip effect." [6] In addition, the texture designs of the Zn metal surface play an important role in the orientation of the zinc crystal by plating. [7] Due to the smooth equipotential surface of Zn-(001) planes and the stronger adsorption energy of parallel direction between the (001) plane surface and Zn atom, the (001) crystal plane can guide plating sequentially parallel to it. [8] For example, Archer's group and Liang's group reported that the Zn foil exhibiting a preferred (001) texture by plastic deformation could suppress the rough plating/stripping landscape and promote uniform deposition along (001) planes. [9] Undesirable side reactions including chemical corrosion and hydrogen evolution mainly occurred at the interface between the Zn metal surface and electrolytes. [10] They would block the utilization of Zn, and then lead to electrolytes consumption and low Coulombic efficiency. [11] To solve this problem, various kinds of coatings have been made, which mainly include inorganic coating, polymer coating, organic, and inorganic composite coating. [12] They could block water molecules from reaching the Zn surface, and then improve the stability and reversibility of Zn metal anode. [13] However, thicker coatings were usually chosen to guarantee long-acting anticorrosion effect and retard the growth of dendrites, which meant the long route of ionic Some new insights into traditional metal pretreatment of anticorrosion for high stable Zn metal anodes are provided. A developed pretreatment methodology is employed to prefer the crystal plane of polycrystalline Zn and create 3.26 µm protective coatings mainly consisting of organic polymers and zinc salts on Zn foils (ROZ@Zn). In this process, Zn metal exhibits a surface-preferred (001) crystal plane proved by electron backscattered diffraction. Preferred (001) crystal planes and ROZ coatings can regulate ...

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“…The H 2 evolution leads to the accumulation of OH – ions on the Zn anode surface and thus promotes the formation of irreversible byproducts, such as ZnSO 4 (OH) 6 · x H 2 O (ZHS). [ 28 ] Whereas in alkaline electrolytes, Zn 2+ ions tend to react with OH – and form insoluble byproducts (Zn(OH) 2 , ZnO or other Zn composites, Figure 2B), which increase the battery's internal resistance and lead to rapid battery failure. Therefore, most alkaline Zn batteries with alkaline electrolytes are primary batteries since their rechargeability is still a big issue.…”

Section: Main Challenges Facing Zn Anodesmentioning

confidence: 99%

Surface and Interface Engineering of Zn Anodes in Aqueous Rechargeable Zn‐Ion Batteries

Zheng

Huang

Ming

et al. 2022

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Rechargeable zinc-ion batteries (ZIBs) have shown great potential as an alternative to lithium-ion batteries. The ZIBs utilize Zn metal as the anode, which possesses many advantages such as low cost, high safety, eco-friendliness, and high capacity. However, on the other hand, the Zn anode also suffers from many issues, including dendritic growth, corrosion, and passivation. These issues are largely related to the surface and interface properties of the Zn anode. Many efforts have therefore been devoted to the modification of the Zn anode, aiming to eliminate the above-mentioned problems. This review gives a comprehensive summary on the mechanism behind these issues as well as the recent progress on Zn anode modification with focus on the strategies of surface and interface engineering, covering the design and application of both the Zn anode supports and surface protective layers, along with abundant examples. In addition, the promising research directions and perspective on these strategies are also presented.

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Engineering interfacial layers to enable Zn metal anodes for aqueous zinc-ion batteries

Cited by 216 publications

References 168 publications

Achieving Ultrahigh‐Rate Planar and Dendrite‐Free Zinc Electroplating for Aqueous Zinc Battery Anodes

Achieving Ultrahigh‐Rate Planar and Dendrite‐Free Zinc Electroplating for Aqueous Zinc Battery Anodes

Crystal Plane Reconstruction and Thin Protective Coatings Formation for Superior Stable Zn Anodes Cycling 1300 h

Surface and Interface Engineering of Zn Anodes in Aqueous Rechargeable Zn‐Ion Batteries

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