Disrupting Hydrogen Bond Network Connectivity With a Double-Site Additive for Long-Life Aqueous Zinc Metal Batteries

Abstract

Irregular dendrite growth and complex side reactions pose critical challenges that significantly impede the further industrialization of aqueous zinc-ion batteries (AZIBs). The “competitive co-solvents” strategy could introduce hydrogen bond (H-bond) accepting sites to effectively alleviate the free water molecules. however, it suffers from low conductivity, high cost, and safety risks. Herein, we selected N, N'-methylenebisacrylamide (MBA) as a trace additive with amide groups to decrease the activity of water by disrupting the H-bond. The MBA additive, which incorporates both hydrogen bond donor and acceptor functionalities, successfully restricts H₂O molecules within a double-site anchoring configuration. This configuration enhances hydrogen-bonding interactions and breaks part of the original hydrogen bond network among H₂O molecules, thereby significantly restraining parasitic side reactions due to the decomposition of active water. Additionally, MBA molecules adsorbed on the surface of the Zn anode could regulate the desolvation and nucleation processes of zinc ions, achieving dense and flat zinc deposition. A high Zn reversibility with Coulombic efficiency (CE) of 99.74% and ultra-long lifespan of 2800 cycles at 1 and 0.5 mAh cm⁻² was demonstrated. Besides, a highly reversible Zn electrode significantly boosted the overall performance of Zn//Zn symmetric cells of 1500 h at 5 mA cm⁻² and Zn//V₂O₅ full cell of 2000 cycles at 5 A g⁻¹.

Keywords

aqueous zinc-ion batteries / electrolyte additives / hydrogen bond network

References

[1] a) M. Li, X. Wang, J. Meng, et al., “Comprehensive Understandings of Hydrogen Bond Chemistry in Aqueous Batteries,” Advanced Materials36 (2024): 2308628. b) Y. Li, Y. Li, Q. Liu, et al., “Revealing the Dominance of the Dissolution-Deposition Mechanism in Aqueous Zn−MnO₂ Batteries,” Angewandte Chemie International Edition63 (2024): e202318444.

[2] a) G. Liu, Y. Tang, Y. Wei, et al., “Hydrophobic Ion Barrier-Enabled Ultradurable Zn (002) Plane Orientation Towards Long-Life Anode-Less Zn Batteries,” Angewandte Chemie International Edition63 (2024): e202407639. b) L. Ni, G. Xu, C. Li, and G. Cui, “Electrolyte Formulation Strategies for Potassium-Based Batteries,” Exploration2 (2022): 20210239. c) C.-Y. Park, J. Kim, W.-G. Lim, and J. Lee, “Toward Maximum Energy Density Enabled by Anode-Free Lithium Metal Batteries: Recent Progress and Perspective,” Exploration4 (2024): 20210255.

[3] a) Z. Liu, S. Peng, P. Xiaokaiti, et al., “Electrothermal Model of all-Solid-State Lithium Battery With Composite Solid-State Electrolyte,” EcoEnergy1 (2023): 414-424. b) F. Jing, Y. Liu, Y. Shang, et al., “Dual Ions Intercalation Drives High-performance Aqueous Zn-Ion Storage on Birnessite-Type Manganese Oxides Cathode,” Energy Storage Mater49 (2022): 164-171. c) S. Z. Huang, K. Li, Z. Y. He, et al., “Rolling Strategy for Highly Efficient Preparation of Phosphating Interface Enabled the Stable Lithium Anode,” Journal of Alloys and Compounds1005 (2024): 176193. d) F. K. Zuo, H. Zhang, M. H. Liu, et al., “Insight Into the Ion-Dependent Capacity Mismatch in Alkali Metal Ion Batteries by In Situ Magnetometry,” Energy Storage Materials58 (2023): 299-310. e) D. Li, Y. He, B. Chen, et al., “Self-Smoothing Lithium Metal Anode Based on Screen-Printed Cu-Mesh Current Collector for Long-Term Safety of Lithium Metal Batteries,” EcoEnergy2 (2024): 311-321.

[4] a) L. Zhou, S. Tian, X. Du, et al., “Suppressing Hydrogen Evolution in Aqueous Lithium-Ion Batteries With Double-Site Hydrogen Bonding,” ACS Energy Letters8 (2023): 40-47. b) Y. He, L. Wang, A. Wang, et al., “Insight Into Uniform Filming of LiF-Rich Interphase via Synergistic Adsorption for High-Performance Lithium Metal Anode,” Exploration4 (2024): 20230114.

[5] a) L. Wang, H. M. Yu, D. P. Chen, et al., “Steric Hindrance and Orientation Polarization by a Zwitterionic Additive to Stabilize Zinc Metal Anodes,” Carbon Neutralization (2024). b) M. H. Zhang, H. M. Hua, P. P. Dai, et al., “Dynamically Interfacial pH-Buffering Effect Enabled by N-Methylimidazole Molecules as Spontaneous Proton Pumps Toward Highly Reversible Zinc-Metal Anodes,” Advanced Materials35 (2023): 2208630.

[6] a) S. Liu, R. Zhang, C. Wang, et al., “Zinc Ion Batteries: Bridging the Gap From Academia to Industry for Grid-Scale Energy Storage,” Angewandte Chemie International Edition63 (2024): e202400045. b) Z. Liu, G. Li, M. Xi, et al., “Interfacial Engineering of Zn Metal via a Localized Conjugated Layer for Highly Reversible Aqueous Zinc Ion Battery,” Angewandte Chemie International Edition63 (2024): e202319091.

[7] a) Q. Meng, Q. Bai, R. Zhao, et al., “Attenuating Water Activity through Impeded Proton Transfer Resulting From Hydrogen Bond Enhancement Effect for Fast and Ultra-Stable Zn Metal Anode,” Advanced Energy Materials13 (2023): 2302828. b) K. Xie, K. Ren, Q. Wang, et al., “In Situ Construction of Zinc-rich Polymeric Solid-Electrolyte Interface for High-Performance Zinc Anode,” Escience3 (2023): 100153.

[8] H. Yu, Z. He, D. Chen, et al., “Zwitterionic Materials for Aqueous Zn-based Energy Storage Devices: Current Developments and Perspective,” Energy Reviews4 (2025): 100107.

[9] a) T. Huang, K. Xu, N. Jia, et al., “Intrinsic Interfacial Dynamic Engineering of Zincophilic Microbrushes via Regulating Zn Deposition for Highly Reversible Aqueous Zinc Ion Battery,” Advanced Materials35 (2023): 2205206. b) D. Yuan, X. Li, H. Yao, et al., “A Liquid Crystal Ionomer-Type Electrolyte Toward Ordering-Induced Regulation for Highly Reversible Zinc Ion Battery,” Advancement of Science10 (2023): 2206469. c) H. Yu, C. Lv, C. Yan, and G. Yu, “Interface Engineering for Aqueous Aluminum Metal Batteries: Current Progresses and Future Prospects,” Small Methods8 (2023): 2300758.

[10] a) K. Lu, C. Chen, Y. Wu, et al., “Versatile 1, 3-Dimethyl-2-Imidazolidinone Electrolyte Additive: Enables Extremely Long Life Zinc Metal Batteries With Different Substrates,” Chemical Engineering Journal457 (2023): 141287. b) X. Ma, H. Yu, C. Yan, et al., “Nitroxyl Radical Triggered the Construction of a Molecular Protective Layer for Achieving Durable Zn Metal Anodes,” Journal of Colloid & Interface Science664 (2024): 539-548.

[11] a) L. Chen, J. Zhang, Q. Li, et al., “A 63 M Superconcentrated Aqueous Electrolyte for High-Energy Li-Ion Batteries,” ACS Energy Letters5 (2020): 968-974. b) L. Suo, O. Borodin, T. Gao, et al., ““Water-in-salt” Electrolyte Enables High-Voltage Aqueous Lithium-Ion Chemistries,” Science350 (2015): 938-943. c) H. Peng, K. Xiao, S. Tian, et al., “Solvation Modulation and Reversible SiO₂-Enriched Interphase Enabled by Deep Eutectic Sol Electrolytes for Low-Temperature Zinc Metal Batteries,” Advanced Energy Materials14 (2024): 2303411. d) C. Meng, W. He, H. Tan, X. Wu, H. Liu, and J. Wang, “A Eutectic Electrolyte for an Ultralong-Lived Zn//V₂ O₅ Cell: An In Situ Generated Gradient Solid-Electrolyte Interphase,” Energy & Environmental Science16 (2023): 3587-3599. e) Z. He, H. Yu, M. Fu, et al., “Competitive Solvation With Regulated Ion-Coordination Chemistry Toward Dendrite-Free and Long-Life Zn Metal Anodes,” Energy Storage Mater70 (2024): 103469.

[12] T. Li, Y. Lim, X. Li, et al., “A Universal Additive Strategy to Reshape Electrolyte Solvation Structure Toward Reversible Zn Storage,” Advanced Energy Materials12 (2022): 2103231.

[13] Y. Zeng, A. Li, and T. Yan, “Hydrogen Bond Dynamics in the Solvation Shell on Proton Transfer in Aqueous Solution,” Journal of Physical Chemistry B124 (2020): 1817-1823.

[14] a) J. Ingenmey, S. Gehrke, and B. Kirchner, “How to Harvest Grotthuss Diffusion in Protic Ionic Liquid Electrolyte Systems,” Chemsuschem11 (2018): 1900-1910. b) C. Wolke, J. Fournier, L. Dzugan, et al., “Spectroscopic Snapshots of the Proton-Transfer Mechanism in Water,” Science354 (2016): 1131-1135.

[15] Y. Zhong, X. Xie, Z. Zeng, B. Lu, G. Chen, and J. Zhou, “Triple-Function Hydrated Eutectic Electrolyte for Enhanced Aqueous Zinc Batteries,” Angewandte Chemie International Edition62 (2023): e202310577.

[16] M. Xia, H. Fu, K. Lin, et al., “Hydrogen-Bond Regulation in Organic/Aqueous Hybrid Electrolyte for Safe and High-Voltage K-Ion Batteries,” Energy & Environmental Science17 (2024): 1255-1265.

[17] a) Y. Liang, M. Qiu, P. Sun, and W. Mai, “Janus Interface Enables Reversible Zn-Ion Battery by Regulating Interfacial Water Structure and Crystal-orientation,” Chemical Science15 (2024): 1488-1497. b) C. You, R. Wu, X. Yuan, et al., “An Inexpensive Electrolyte With Double-Site Hydrogen Bonding and a Regulated Zn²⁺ Solvation Structure for Aqueous Zn-Ion Batteries Capable of High-Rate and Ultra-Long Low-Temperature Operation,” Energy & Environmental Science16 (2023): 5096-5107.

[18] Q. Hu, J. Hu, L. Li, et al., “In-Depth Study on the Regulation of Electrode Interface and Solvation Structure by Hydroxyl Chemistry,” Energy Storage Materials54 (2023): 374-381.

[19] a) T. Petit, L. Puskar, T. Dolenko, et al., “Unusual Water Hydrogen Bond Network Around Hydrogenated Nanodiamonds,” Journal of Physical Chemistry C121 (2017): 5185-5194. b) D. S. Liu, Z. Y. Zhang, Y. F. Zhang, et al., “Manipulating OH⁻-Mediated Anode-Cathode Cross-Communication Toward Long-Life Aqueous Zinc-Vanadium Batteries,” Angewandte Chemie International Edition62 (2023): e202215385.

[20] a) M. Yang, J. Zhu, S. Bi, et al., “The Construction of Anion-Induced Solvation Structures in Low-Concentration Electrolyte for Stable Zinc Anodes,” Angewandte Chemie International Edition63 (2024): e202400337. b) C. Huang, X. Zhao, Y. Hao, et al., “Selection Criteria for Electrical Double Layer Structure Regulators Enabling Stable Zn Metal Anodes,” Energy & Environmental Science16 (2023): 1721-1731.

[21] J. Luo, L. Xu, Y. Zhou, et al., “Regulating the Inner Helmholtz Plane With a High Donor Additive for Efficient Anode Reversibility in Aqueous Zn-Ion Batteries,” Angewandte Chemie International Edition62 (2023): e202302302.

[22] J. Zhou, H. M. Yu, P. Qing, et al., “Interfacial Double-coordination Effect Reconstructing Anode/Electrolyte Interface for Long-Term and Highly Reversible Zn Metal Anodes,” Journal of Colloid & Interface Science678 (2025): 772-782.

[23] Y. Wang, B. Liang, J. Zhu, et al., “Manipulating Electric Double Layer Adsorption for Stable Solid-Electrolyte Interphase in 2.3 Ah Zn-Pouch Cells,” Angewandte Chemie International Edition62 (2023): e202302583.

[24] Z. He, H. Yu, D. Chen, et al., “Achieving Dendrite-Free Zinc Metal Anodes via Molecule Anchoring and Ion-Transport Pumping,” Chemistry European Journal30 (2024): e202400567.

[25] a) J. Cao, H. Wu, D. Zhang, et al., “In-Situ Ultrafast Construction of Zinc Tungstate Interface Layer for Highly Reversible Zinc Anodes,” Angewandte Chemie International Edition63 (2024): e202319661. b) S. Huang, R. Tang, X. Q. Liu, et al., “Ion-Dipole Interaction Motivated Zn²⁺ Pump and Anion Repulsion Interface Enable Ultrahigh-Rate Zn Metal Anodes,” Energy & Environmental Science17 (2024): 591-601.

[26] H. Tang, N. Hu, L. Ma, et al., “Interfacial Dual-Modulation via Cationic Electrostatic Shielding and Anionic Preferential Adsorption Toward Planar and Reversible Zinc Electrodeposition,” Advanced Functional Materials34 (2024): 2402484.

[27] Y. Z. Wang, J. Y. Chen, Z. B. Chen, et al., “Flat Zn Deposition at Battery Anode via an Ultrathin Robust Interlayer,” Nano Research17 (2024): 8104-8111.

[28] a) Q. He, T. Hu, Q. Wu, et al., “Tunnel-Oriented VO₂ (B) Cathode for High-Rate Aqueous Zinc-Ion Batteries,” Advanced Materials36 (2024): 2400888. b) C. Li, T. Liao, D. Chen, et al. Chinese Chemical Letters36 (2025): 110557.

[29] Y. D. Li, Y. H. Li, Q. S. Liu, et al., “Revealing the Dominance of the Dissolution-Deposition Mechanism in Aqueous Zn−MnO₂ Batteries,” Angewandte Chemie International Edition63 (2024): e202318444.

[30] M. Frisch, G. W. Trucks, H. B. Schlegel, et al., Fox Gaussian 09 Rev. D.01, (Gaussian, Inc. 2016).

[31] 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 Physics132 (2010): 154104.

[32] P. E. Blöchl, “Projector Augmented-Wave Method,” Physical Review B50 (1994): 17953.

[33] G. Kresse and J. Furthmüller, “Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set,” Physical Review B54 (1996): 11169-11186.

[34] J. Perdew, K. Burke, and M. Ernzerhof, “Generalized Gradient Approximation Made Simple,” Physical Review Letters77 (1996): 3865-3868.

[35] S. Meng, D. Liu, J. Feng, et al., “Prussian Blue Analogs for Zinc Hybrid Ion Batteries: A Promising and Competitive Alternative to Aqueous Zinc-Ion Batteries,” Exploration Portico (2025), https://doi.org/10.1002/exp.20240180.

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