Direct Growth of Leopard-Patterned Graphene on Zinc Anodes via Sonochemistry for High-Performance Aqueous Zinc-Ion Batteries

Abstract

Aqueous zinc-ion batteries encounter issues with the formation of Zn dendrites and parasitic reactions at Zn anodes. To address these issues, coating Zn anodes with two-dimensional (2D) nanocarbon materials, such as graphene, has proven effective in ensuring uniform current distribution and facilitating charge transfer. While direct growth of 2D nanocarbon on Zn substrates offers significant advantages, it remains challenging due to Zn's low melting point (420°C). In this study, as a first proof-of-concept, a unique sonochemical route was developed to directly grow crystalline-amorphous mixed 2D nanocarbon films, named “Leopard-patterned graphene,” on Zn substrates. This unique structure provides uniform nucleation sites while maintaining high Zn²⁺ ion permeability, mitigating dendrite formation. In Zn symmetric coin cell tests, the Zn electrodes coated with Leopard-patterned graphene maintained stable cycling for over 2000 h at a constant current density of 3 mA cm⁻². This study introduces an innovative approach for bottom-up synthesis of 2D nanocarbon on Zn substrates under ambient conditions and demonstrates its potential to address critical challenges in Zn-ion battery performance. The findings provide insights into advanced electrode design strategies for next-generation energy storage devices.

Keywords

aqueous zinc ion batteries / graphene synthesis methods / sonochemistry / Zn metal anodes

References

[1] F. Wang, O. Borodin, T. Gao, et al., “Highly Reversible Zinc Metal Anode for Aqueous Batteries,” Nature Materials 17, no. 6 (2018): 543–549.

[2] C. Xu, B. Li, H. Du, and F. Kang, “Energetic Zinc Ion Chemistry: The Rechargeable Zinc Ion Battery,” Angewandte Chemie International Edition 51, no. 4 (2012): 933–935.

[3] C. Han, W. Li, H. K. Liu, S. Dou, and J. Wang, “Principals and Strategies for Constructing a Highly Reversible Zinc Metal Anode in Aqueous Batteries,” Nano Energy 74 (2020): 104880.

[4] F. Zhang, J. W. Qian, W. X. Dong, et al., “Integration of Confinement Crosslinking and In Situ Grafting for Constructing Artificial Interphases Toward Stabilized Zinc Anodes,” Energy & Environmental Science 17, no. 19 (2024): 7258–7270.

[5] Y. F. Qu, J. W. Qian, F. Zhang, et al., “Constructing 3D Crosslinked Macromolecular Networks as a Highly Efficient Interface Layer for Ultra-Stable Zn Metal Anodes,” Advanced Materials 37, no. 1 (2025): 2413370.

[6] F. Zhang, Q. Meng, J. W. Qian, et al., “Selective Interface Engineering With Large π-Conjugated Molecules Enables Durable Zn Anodes,” Angewandte Chemie 137, no. 15 (2025): e202425487.

[7] 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.

[8] Q. Zhang, J. Luan, X. Huang, et al., “Simultaneously Regulating the Ion Distribution and Electric Field to Achieve Dendrite-Free Zn Anode,” Small 16, no. 35 (2020): 2000929.

[9] H. B. Jeong, D. I. Kim, G. Yoo, et al., “Selective Control of Sharp-Edge Zinc Electrodes With (002) Plane for High-Performance Aqueous Zinc-Ion Batteries,” Journal of Materials Chemistry A 12, no. 25 (2024): 15265–15277.

[10] X. Liu, J. W. Qian, J. W. Chen, et al., “A Sustainable and Scalable Approach for In Situ Induction of Gradient Nucleation Sites in Biomass-Derived Interface Layers for Ultra-Stable Aqueous Zinc Metal Batteries,” Angewandte Chemie International Edition 64, no. 26 (2025): e202504613.

[11] J. H. Wang, L. F. Chen, W. X. Dong, et al., “Three-Dimensional Zinc-Seeded Carbon Nanofiber Architectures as Lightweight and Flexible Hosts for a Highly Reversible Zinc Metal Anode,” ACS Nano 17, no. 19 (2023): 19087–19097.

[12] F. Tao, Y. Liu, X. Ren, et al., “Different Surface Modification Methods and Coating Materials of Zinc Metal Anode,” Journal of Energy Chemistry 66 (2022): 397–412.

[13] A. Yu, W. Zhang, N. Joshi, and Y. Yang, “Recent Advances in Anode Design for Mild Aqueous Zn-Ion Batteries,” Energy Storage Materials 64 (2024): 103075.

[14] H. S. Jeong, D. I. Kim, J. Lim, et al., “A Practical Zinc Metal Anode Coating Strategy Utilizing Bulk h-BN and Improved Hydrogen Redox Kinetics,” Energy & Environmental Materials 8, no. 2 (2025): e12826.

[15] W. Nie, H. Cheng, Q. Sun, et al., “Design Strategies Toward High-Performance Zn Metal Anode,” Small Methods 8, no. 6 (2024): 2201572.

[16] X. Fan, L. Chen, Y. Wang, et al., “Selection of Negative Charged Acidic Polar Additives to Regulate Electric Double Layer for Stable Zinc Ion Battery,” Nano-Micro Letters 16, no. 1 (2024): 270.

[17] M. Chen, Y. Gong, Y. Zhao, et al., “Spontaneous Grain Refinement Effect of Rare Earth Zinc Alloy Anodes Enables Stable Zinc Batteries,” National Science Review 11, no. 7 (2024): nwae205.

[18] H. Wong, Y. Li, J. Wang, et al., “Two-Dimensional Materials for High Density, Safe and Robust Metal Anodes Batteries,” Nano Convergence 10, no. 1 (2023): 37.

[19] Y. Su, X. Yang, Q. Zhang, J. Sun, and Z. Liu, “Carbon Nanomaterials for Highly Stable Zn Anode: Recent Progress and Future Outlook,” Journal of Electroanalytical Chemistry 904 (2022): 115883.

[20] X. Zhang, L. Zhang, X. Jia, W. Song, and Y. Liu, “Design Strategies for Aqueous Zinc Metal Batteries With High Zinc Utilization: From Metal Anodes to Anode-Free Structures,” Nano-Micro Letters 16, no. 1 (2024): 75.

[21] N. Li, Z. Chen, W. Ren, F. Li, and H. M. Cheng, “Flexible Graphene-Based Lithium Ion Batteries With Ultrafast Charge and Discharge Rates,” Proceedings of the National Academy of Sciences 109, no. 43 (2012): 17360–17365.

[22] J. Zheng, Q. Zhao, T. Tang, et al., “Reversible Epitaxial Electrodeposition of Metals in Battery Anodes,” Science 366, no. 6465 (2019): 645–648.

[23] Z. Zhou, Y. Zhang, P. Chen, et al., “Graphene Oxide-Modified Zinc Anode for Rechargeable Aqueous Batteries,” Chemical Engineering Science 194 (2019): 142–147.

[24] J. Zhou, M. Xie, F. Wu, et al., “Ultrathin Surface Coating of Nitrogen-Doped Graphene Enables Stable Zinc Anodes for Aqueous Zinc-Ion Batteries,” Advanced Materials 33, no. 33 (2021): 2101649.

[25] Y. Zou, Y. Wu, W. Wei, et al., “Establishing Pinhole Deposition Mode of Zn via Scalable Monolayer Graphene Film,” Advanced Materials 36, no. 19 (2024): 2313775.

[26] F. Zhang and L. Qi, “Recent Progress in Self-Supported Metal Oxide Nanoarray Electrodes for Advanced Lithium-Ion Batteries,” Advanced Science 3, no. 9 (2016): 1600049.

[27] P. Liu, K. Zhu, Y. Gao, H. Luo, and L. Lu, “Recent Progress in the Applications of Vanadium-Based Oxides on Energy Storage: From Low-Dimensional Nanomaterials Synthesis to 3D Micro/Nano-Structures and Free-Standing Electrodes Fabrication,” Advanced Energy Materials 7, no. 23 (2017): 1700547.

[28] J. Kang, D. Shin, S. Bae, and B. H. Hong, “Graphene Transfer: Key for Applications,” Nanoscale 4, no. 18 (2012): 5527–5537.

[29] S. Chaitoglou and E. Bertran, “Effect of Temperature on Graphene Grown by Chemical Vapor Deposition,” Journal of Materials Science 52, no. 13 (2017): 8348–8356.

[30] X. Zhang, S. Wan, J. Pu, L. Wang, and X. Liu, “Highly Hydrophobic and Adhesive Performance of Graphene Films,” Journal of Materials Chemistry 21, no. 33 (2011): 12251–12258.

[31] J. S. Bunch, S. S. Verbridge, J. S. Alden, et al., “Impermeable Atomic Membranes From Graphene Sheets,” Nano Letters 8, no. 8 (2008): 2458–2462.

[32] K. S. Suslick, “Sonochemistry,” Science 247, no. 4949 (1990): 1439–1445.

[33] Z. Qin and H. Alehossein, “Heat Transfer During Cavitation Bubble Collapse,” Applied Thermal Engineering 105 (2016): 1067–1075.

[34] P. Wu, L. Bai, and W. Lin, “On the Definition of Cavitation Intensity,” Ultrasonics Sonochemistry 67 (2020): 105141.

[35] S. Lin, J. Tang, K. Zhang, et al., “Tuning Oxygen-Containing Functional Groups of Graphene for Supercapacitors With High Stability,” Nanoscale Advances 5, no. 4 (2023): 1163–1171.

[36] C. Mattevi, G. Eda, S. Agnoli, et al., “Evolution of Electrical, Chemical, and Structural Properties of Transparent and Conducting Chemically Derived Graphene Thin Films,” Advanced Functional Materials 19, no. 16 (2009): 2577–2583.

[37] T. Malis, S. C. Cheng, and R. F. Egerton, “EELS Log-Ratio Technique for Specimen-Thickness Measurement in the TEM,” Journal of Electron Microscopy Technique 8, no. 2 (1988): 193–200.

[38] N. Li, R. J. Zhang, Z. Zhen, Z. H. Xu, R. D. Mu, and L. M. He, “The Effect of Catalytic Copper Pretreatments on CVD Graphene Growth at Different Stages,” Nanotechnology 32, no. 9 (2020): 095607.

[39] R. Saito, M. Hofmann, G. Dresselhaus, A. Jorio, and M. S. Dresselhaus, “Raman Spectroscopy of Graphene and Carbon Nanotubes,” Advances in Physics 60, no. 3 (2011): 413–550.

[40] S. Naghdi, K. Nešović, G. Sánchez-Arriaga, et al., “The Effect of Cesium Dopant on APCVD Graphene Coating on Copper,” Journal of Materials Research and Technology 9, no. 5 (2020): 9798–9812.

[41] S. Perumbilavil, P. Sankar, T. Priya Rose, and R. Philip, “White Light Z-Scan Measurements of Ultrafast Optical Nonlinearity in Reduced Graphene Oxide Nanosheets in the 400–700 nm Region,” Applied Physics Letters 107, no. 5 (2015): 051104.

[42] T. Milenov and I. Avramova, “Deposition of Graphene by Sublimation of Pyrolytic Carbon,” Optical and Quantum Electronics 47, no. 4 (2015): 851–863.

[43] A. Abliz, X. Xue, X. Liu, G. Li, and L. Tang, “Rational Design of Hydrogen and Nitrogen Co-Doped ZnO for High Performance Thin-Film Transistors,” Applied Physics Letters 118, no. 12 (2021): 123504.

[44] K. A. Moltved and K. P. Kepp, “The Chemical Bond Between Transition Metals and Oxygen: Electronegativity, d-Orbital Effects, and Oxophilicity as Descriptors of Metal-Oxygen Interactions,” Journal of Physical Chemistry C 123, no. 30 (2019): 18432–18444.

[45] 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.

[46] L. Li, Y. Zhang, C. Du, et al., “Achieving Stable Zn Metal Anode via a Hydrophobic and Zn²⁺-Conductive Amorphous Carbon Interface,” Journal of Colloid and Interface Science 657 (2024): 644–652.

[47] W. J. Joo, J. H. Lee, Y. Jang, et al., “Realization of Continuous Zachariasen Carbon Monolayer,” Science Advances 3, no. 2 (2017): e1601821.

[48] V. G. Akkili, J. Yoon, K. Shin, et al., “Amorphous Carbon Monolayer: A van der Waals Interface for High-Performance Metal Oxide Semiconductor Devices,” ACS Nano 19, no. 1 (2024): 1056–1069.

[49] Y. Chu, S. Zhang, S. Wu, et al., “‘In Situ Built Interphase With High Interface Energy and Fast Kinetics for High Performance Zn Metal Anodes,” Energy & Environmental Science 14, no. 6 (2021): 3609–3620.

[50] X. Xie, S. Liang, J. Gao, et al., “Manipulating the Ion-Transfer Kinetics and Interface Stability for High-Performance Zinc Metal Anodes,” Energy & Environmental Science 13, no. 2 (2020): 503–510.

[51] X. Fan, W. T. Zheng, and J. L. Kuo, “Adsorption and Diffusion of Li on Pristine and Defective Graphene,” ACS Applied Materials & Interfaces 4, no. 5 (2012): 2432–2438.

[52] M. Noor-A-Alam, H. Ullah, and Y.-H. Shin, “Switchable Polarization in Mn Embedded Graphene,” Scientific Reports 8, no. 1 (2018): 4538.

[53] W. Qin, W. C. Lu, X. Y. Xue, K. M. Ho, and C. Z. Wang, “Lithium Diffusion In Silicon Encapsulated With Graphene,” Nanomaterials 11, no. 12 (2021): 3397.

[54] P. Liang, J. Yi, X. Liu, et al., “Highly Reversible Zn Anode Enabled by Controllable Formation of Nucleation Sites for Zn-Based Batteries,” Advanced Functional Materials 30, no. 13 (2020): 1908528.

[55] H. Liu, C. Li, H. P. Zhang, L. J. Fu, Y. P. Wu, and H. Q. Wu, “Kinetic Study on LiFePO₄/C Nanocomposites Synthesized by Solid State Technique,” Journal of Power Sources 159, no. 1 (2006): 717–720.

[56] G. Kresse and J. Hafner, “Ab initio Molecular Dynamics for Liquid Metals,” Physical Review B 47, no. 1 (1993): 558–561.

[57] G. Kresse and J. Hafner, “Ab initio Molecular-Dynamics Simulation of the Liquid-Metal-Amorphous-Semiconductor Transition in Germanium,” Physical Review B 49, no. 20 (1994): 14251–14269.

[58] G. Kresse and J. Furthmüller, “Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set,” Physical Review B 54, no. 16 (1996): 11169–11186.

[59] J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized Gradient Approximation Made Simple,” Physical Review Letters 77, no. 18 (1996): 3865–3868.

[60] S. Grimme, J. Antony, S. Ehrlich, and H. Krieg, “A Consistent and Accurate Ab Initio Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-Pu,” Journal of Chemical Physics 132, no. 15 (2010): 154104.

[61] S. Grimme, S. Ehrlich, and L. Goerigk, “Effect of the Damping Function in Dispersion Corrected Density Functional Theory,” Journal of Computational Chemistry 32, no. 7 (2011): 1456–1465.

[62] P. E. Blöchl, “Projector Augmented-Wave Method,” Physical Review B 50, no. 24 (1994): 17953–17979.

[63] G. Kresse and D. Joubert, “From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method,” Physical Review B 59, no. 3 (1999): 1758–1775.

[64] H. J. Monkhorst and J. D. Pack, “Special Points for Brillouin-Zone Integrations,” Physical Review B 13, no. 12 (1976): 5188–5192.

[65] G. Henkelman, B. P. Uberuaga, and H. Jónsson, “A Climbing Image Nudged Elastic Band Method for Finding Saddle Points and Minimum Energy Paths,” Journal of Chemical Physics 113, no. 22 (2000): 9901–9904.

RIGHTS & PERMISSIONS

2025 The Author(s). Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd.