Bimetallic Modification Strategy: Ultra-Thin Ni-Ag Coating Prepared via One-Step Method Enables Highly Reversible Zn Anode

Abstract

For aqueous zinc ion batteries (AZIBs), Zn dendritic growth and hydrogen evolution reaction (HER) usually result in the severe degradation of bare Zn anodes. Although the alloy-modified anodes can improve the reversibility of the Zn plating/stripping process, the regulation of alloy components is too complex to meet the requirements for large-scale fabrication. Herein, a Ni-Ag bimetallic coating on Zn foils (Ni-Ag@Zn) is prepared by magnetron co-sputtering. Owing to this bimetallic coating with the ultrathin thickness of 200 nm, the cycling life of Ni-Ag@Zn-based symmetric cells attains more than 5000 h at current density of 1 mA/cm² and areal capacity of 1 mA h/cm², exceeding most of the reported binary/ternary-alloy-based symmetric cells. To the suppression of dendrite growth and HER, the regulation mechanism of the bimetallic coating on Zn deposition is assigned to the synergistic effect, the suppressed HER by the strong adsorption of Ag with H ions and the flatted Zn deposition via the strong adsorption of Ni/Ag with Zn ions. To our knowledge, both the bimetallic and ultrathin features have not been reported to optimize the anodes for AZIBs. The present bimetallic coating strategy renders the diversification of anode modification for the commercialization of high-performance AZIBs.

Keywords

aqueous zinc-ion batteries / bimetallic synergies / electrode coatings / magnetron co-sputtering / zinc anodes

References

[1] T. Li, X. Peng, P. Cui, et al., “Recent Progress and Future Perspectives of Flexible Metal-Air Batteries,” SmartMat 2, no. 4 (2021): 519–553.

[2] G. Fang, J. Zhou, A. Pan, and S. Liang, “Recent Advances in Aqueous Zinc-Ion Batteries,” ACS Energy Letters 3, no. 10 (2018): 2480–2501.

[3] C. Nie, G. Wang, D. Wang, et al., “Recent Progress on Zn Anodes for Advanced Aqueous Zinc-Ion Batteries,” Advanced Energy Materials 13, no. 28 (2023): 2300606.

[4] Z.-H. Huang, J.-S. Wei, T.-B. Song, J.-W. Ni, F. Wang, and H.-M. Xiong, “Carbon Dots Crosslinked Gel Polymer Electrolytes for Dendrite-Free and Long-Cycle Lithium Metal Batteries,” SmartMat 3, no. 2 (2022): 323–336.

[5] Z. Yang, C. Lv, W. Li, et al., “Revealing the Two-Dimensional Surface Diffusion Mechanism for Zinc Dendrite Formation on Zinc Anode,” Small 18, no. 43 (2022): 2104148.

[6] J. Ming, J. Guo, C. Xia, W. Wang, and H. N. Alshareef, “Zinc-Ion Batteries: Materials, Mechanisms, and Applications,” Materials Science and Engineering: R: Reports 135 (2019): 58–84.

[7] D. Chao, W. Zhou, F. Xie, et al., “Roadmap for Advanced Aqueous Batteries: From Design of Materials to Applications,” Science Advances 6, no. 21 (2020): eaba4098.

[8] Z. Yuan, L. Liang, Q. Dai, et al., “Low-Cost Hydrocarbon Membrane Enables Commercial-Scale Flow Batteries for Long-Duration Energy Storage,” Joule 6, no. 4 (2022): 884–905.

[9] B. Sun, P. Wang, L. Yang, X. Wei, Y. Jin, and H. Wu, “Rational Design of an Interfacial Bilayer for Aqueous Dendrite-Free Zinc Anodes,” ACS Applied Materials & Interfaces 14, no. 1 (2022): 954–960.

[10] P. Lu, Z. Fan, C. Guo, and J. Liang, “Recent Progresses of Aqueous Zinc-Ion Batteries and Their Prospects in the Field of Smart City,” Advanced Sustainable Systems 8, no. 6 (2024): 2300545.

[11] J. L. Yang, H. H. Liu, X. X. Zhao, et al., “Janus Binder Chemistry for Synchronous Enhancement of Iodine Species Adsorption and Redox Kinetics Toward Sustainable Aqueous Zn–I₂ Batteries,” Journal of the American Chemical Society 146, no. 10 (2024): 6628–6637.

[12] R. Qin, Y. Wang, L. Yao, et al., “Progress in Interface Structure and Modification of Zinc Anode for Aqueous Batteries,” Nano Energy 98 (2022): 107333.

[13] L. Li, S. F. Jia, M. H. Cao, Y. Q. Ji, H. W. Qiu, and D. Zhang, “Progress in Research on Metal-Based Materials in Stabilized Zn Anodes,” Rare Metals 43, no. 1 (2024): 20–40.

[14] Y. M. Li, Z. W. Wang, W. H. Li, et al., “Trinary Nanogradients at Electrode/Electrolyte Interface for Lean Zinc Metal Batteries,” Energy Storage Materials 61 (2023): 102873.

[15] B. Li, X. Zhang, T. Wang, et al., “Interfacial Engineering Strategy for High-Performance Zn Metal Anodes,” Nano-Micro Letters 14, no. 1 (2022): 6.

[16] Z. Kang, C. Wu, L. Dong, et al., “3D Porous Copper Skeleton Supported Zinc Anode Toward High Capacity and Long Cycle Life Zinc Ion Batteries,” ACS Sustainable Chemistry & Engineering 7, no. 3 (2019): 3364–3371.

[17] R. Xue, J. Kong, Y. Wu, et al., “Highly Reversible Zinc Metal Anodes Enabled by a Three-Dimensional Silver Host for Aqueous Batteries,” Journal of Materials Chemistry A 10, no. 18 (2022): 10043–10050.

[18] M. Cui, Y. Xiao, L. Kang, et al., “Quasi-Isolated Au Particles as Heterogeneous Seeds to Guide Uniform Zn Deposition for Aqueous Zinc-Ion Batteries,” ACS Applied Energy Materials 2, no. 9 (2019): 6490–6496.

[19] H. Li, W. Jia, P. Chen, L. Wang, X. Yan, and Y. Y. Yang, “Zinc Deposition Characteristics on Different Substrates for Aqueous Zinc Ion Battery,” Applied Surface Science 607 (2023): 155111.

[20] J. Sun, X. Zheng, K. Li, et al., “Scalable Production of Hydrogen Evolution Corrosion Resistant Zn-Al Alloy Anode for Electrolytic MnO₂/Zn Batteries,” Energy Storage Materials 54 (2023): 570–578.

[21] Y. Zhao, S. Guo, M. Chen, et al., “Tailoring Grain Boundary Stability of Zinc-Titanium Alloy for Long-Lasting Aqueous Zinc Batteries,” Nature Communications 14, no. 1 (2023): 7080.

[22] H. Li, C. Xu, C. Han, et al., “Enhancement on Cycle Performance of Zn Anodes by Activated Carbon Modification for Neutral Rechargeable Zinc Ion Batteries,” Journal of the Electrochemical Society 162, no. 8 (2015): A1439–A1444.

[23] X. Gao, K. Liu, C. Su, et al., “From Bibliometric Analysis: 3D Printing Design Strategies and Battery Applications With a Focus on Zinc-Ion Batteries,” SmartMat 5, no. 1 (2024): e1197.

[24] Q. Zhang, Y. Dai, K. Zhao, et al., “Dynamic Reconstruction of Ni-Zn Alloy Solid-Electrolyte Interface for Highly Stable Zn Anode,” Nano Research 16, no. 9 (2023): 11604–11611.

[25] P. Cao, J. Tang, A. Wei, et al., “Manipulating Uniform Nucleation to Achieve Dendrite-Free Zn Anodes for Aqueous Zn-Ion Batteries,” ACS Applied Materials & Interfaces 13, no. 41 (2021): 48855–48864.

[26] C. Zhu, P. Li, G. Xu, H. Cheng, and G. Gao, “Recent Progress and Challenges of Zn Anode Modification Materials in Aqueous Zn-Ion Batteries,” Coordination Chemistry Reviews 485 (2023): 215142.

[27] G. Zhang, X. Zhang, H. Liu, J. Li, Y. Chen, and H. Duan, “3D-Printed Multi-Channel Metal Lattices Enabling Localized Electric-Field Redistribution for Dendrite-Free Aqueous Zn Ion Batteries,” Advanced Energy Materials 11, no. 19 (2021): 2003927.

[28] J. Zheng, X. Liu, Y. Zheng, et al., “Ag_xZn_y Protective Coatings With Selective Zn²⁺/H⁺ Binding Enable Reversible Zn Anodes,” Nano Letters 23, no. 13 (2023): 6156–6163.

[29] H. Tian, Z. Li, G. Feng, et al., “Stable, High-Performance, Dendrite-Free, Seawater-Based Aqueou. Batteries,” Nature Communications 12, no. 1 (2021): 237.

[30] H. Yu, Y. Zeng, N. W. Li, D. Luan, L. Yu, and X. W. Lou, “Confining Sn Nanoparticles in Interconnected N-Doped Hollow Carbon Spheres as Hierarchical Zincophilic Fibers for Dendrite-Free Zn Metal Anodes,” Science Advances 8, no. 10 (2022): eabm5766.

[31] F. Wang, H. Zhao, J. Liang, et al., “Magnetron Sputtering Enabled Synthesis of Nanostructured Materials for Electrochemical Energy Storage,” Journal of Materials Chemistry A 8, no. 39 (2020): 20260–20285.

[32] L. Gan, Z. Zeng, H. Lu, et al., “A Large-Scalable Spraying-Spinning Process for Multifunctional Electronic Yarns,” SmartMat 4, no. 2 (2023): e1151.

[33] D. Zhang, J. Shi, Y. Qi, et al., “Quasi-Amorphous Metallic Nickel Nanopowder as an Efficient and Durable Electrocatalyst for Alkaline Hydrogen Evolution,” Advanced Science 5, no. 12 (2018): 1801216.

[34] G. Zhang, Y. Chen, L. Fu, et al., “Regulating the Solvation Sheath of Zinc Ions by Supramolecular Coordination Chemistry Toward Ultrastable Zinc Anodes,” SmartMat 5, no. 3 (2023): e1216.

[35] Q. Cao, Y. Gao, J. Pu, A. M. Elshahawy, and C. Guan, “Materials and Structural Design for Preferable Zn Deposition Behavior Toward Stable Zn Anodes,” SmartMat 5, no. 1 (2024): e1194.

[36] Y. Dai, R. Lu, C. Zhang, et al., “Zn²⁺-Mediated Catalysis for Fast-Charging Aqueous Zn-Ion Batteries,” Nature Catalysis 7, no. 7 (2024): 776–784.

[37] M. Abdallah, “Ethoxylated Fatty Alcohols as Corrosion Inhibitors for Dissolution of Zinc in Hydrochloric Acid,” Corrosion Science 45, no. 12 (2003): 2705–2716.

[38] L. Hu, K. Yang, Y. Zhang, et al., “Interface Engineering With Porous Graphene as Deposition Regulator of Stable Zn Metal Anode for Long-Life Zn-Ion Capacitor,” Journal of Colloid and Interface Science 631 (2023): 135–146.

[39] X. Li, J. Jiang, Y. Zhao, A. Ma, D. Wen, and Y. Zhu, “Effect of Equal-Channel Angular Pressing and Aging on Corrosion Behavior of ZK60 Mg Alloy,” Transactions of Nonferrous Metals Society of China 25, no. 12 (2015): 3909–3920.

[40] Q. Zhang, J. Luan, X. Huang, et al., “Revealing the Role of Crystal Orientation of Protective Layers for Stable Zinc Anode,” Nature Communications 11, no. 1 (2020): 3961.

[41] Q. Li, D. Wang, B. Yan, Y. Zhao, J. Fan, and C. Zhi, “Dendrite Issues for Zinc Anodes in a Flexible Cell Configuration for Zinc-Based Wearable Energy-Storage Devices,” Angewandte Chemie International Edition 61, no. 25 (2022): e202202780.

[42] R. Zhao, X. Dong, P. Liang, et al., “Prioritizing Hetero-Metallic Interfaces via Thermodynamics Inertia and Kinetics Zincophilia Metrics for Tough Zn-Based Aqueous Batteries,” Advanced Materials 35, no. 17 (2023): 2209288.

[43] X. Yang, C. Li, Z. Sun, et al., “Interfacial Manipulation via in Situ Grown ZnSe Cultivator Toward Highly Reversible Zn Metal Anodes,” Advanced Materials 33, no. 52 (2021): 2105951.

[44] H. Tian, G. Feng, Q. Wang, et al., “Three-Dimensional Zn-Based Alloys for Dendrite-Free Aqueous Zn Battery in Dual-Cation Electrolytes,” Nature Communications 13, no. 1 (2022): 7922.

[45] M. Zhou, C. Fu, L. Qin, et al., “Intrinsic Structural Optimization of Zinc Anode With Uniform Second Phase for Stable Zinc Metal Batteries,” Energy Storage Materials 52 (2022): 161–168.

[46] H. Tao, Z. Hou, L. Zhang, X. Yang, and L. Z. Fan, “Manipulating Alloying Reaction to Achieve the Stable and Dendrite-Free Zinc Metal Anodes,” Chemical Engineering Journal 450 (2022): 138048.

[47] H. Zhao, Z. Chi, Q. Zhang, et al., “Dendrite-Free Zn Anodes Enabled by Sn-Cu Bimetal/rGo Functional Protective Layer for Aqueous Zn-Based Batteries,” Applied Surface Science 613 (2023): 156129.

[48] Y. Guo, H. Jiang, B. Liu, et al., “Better Engineering Layered Vanadium Oxides for Aqueous Zinc-Ion Batteries: Going Beyond Widening the Interlayer Spacing,” SmartMat 5, no. 1 (2024): e1231.

[49] Q. Zhang, Y. Ma, Y. Lu, et al., “Halogenated Zn²⁺ Solvation Structure for Reversible Zn Metal Batteries,” Journal of the American Chemical Society 144, no. 40 (2022): 18435–18443.

[50] Y. Zhu, G. Liang, X. Cui, et al., “Engineering Hosts for Zn Anodes in Aqueous Zn-Ion Batteries,” Energy & Environmental Science 17, no. 2 (2024): 369–385.

[51] S. Li, J. Fu, G. Miao, et al., “Toward Planar and Dendrite-Free Zn Electrodepositions by Regulating Sn-Crystal Textured Surface,” Advanced Materials 33, no. 21 (2021): 2008424.

[52] C. Meng, W. He, L. Jiang, et al., “Ultra-Stable Aqueous Zinc Batteries Enabled by β-Cyclodextrin: Preferred Zinc Deposition and Suppressed Parasitic Reactions,” Advanced Functional Materials 32, no. 47 (2022): 2207732.

[53] X. Zhang, C. Li, G. Qu, et al., “Highly Robust Zinc Metal Anode Directed by Organic–Inorganic Synergistic Interfaces for Wearable Aqueous Zinc Battery,” SmartMat 5, no. 1 (2024): e1212.

[54] C. Tian, H. Wang, L. Xie, Y. Zhong, and Y. Hu, “Arrays of Hierarchical Zincophilic Nanorods With Trapping-and-Leveling Deposition for Ultrastable Zn Metal Anodes,” Advanced Energy Materials 14, no. 21 (2024): 2400276.

[55] Q. Hu, J. Hu, F. Ma, et al., “Redistributing Zinc-Ion Flux by Work Function Chemistry Toward Stabilized and Durable Zn Metal Batteries,” Energy & Environmental Science 17, no. 7 (2024): 2554–2565.

[56] W. Yu, R. Ding, Z. Jia, et al., “Pseudocapacitive Co-Free Trimetallic Ni-Zn-Mn Perovskite Fluorides Enable Fast-Rechargeable Zn-Based Aqueous Batteries,” Advanced Functional Materials 32, no. 19 (2022): 2112469.

[57] F. Yue, Z. Tie, Y. Zhang, S. Bi, Y. Wang, and Z. Niu, “Proton Chemistry Induced Long-Cycle Air Self-Charging Aqueous Batteries,” Angewandte Chemie International Edition 61, no. 40 (2022): e202208513.

[58] Z. H. Huang, Y. Song, D. Y. Feng, Z. Sun, X. Sun, and X. X. Liu, “High Mass Loading MnO₂ With Hierarchical Nanostructures for Supercapacitors,” ACS Nano 12, no. 4 (2018): 3557–3567.

RIGHTS & PERMISSIONS

2025 The Author(s). SmartMat published by Tianjin University and John Wiley & Sons Australia, Ltd.