Coordinated Solvation and Interphase Regulation by Sodium p-Aminobenzenesulfonate for Long-Life Aqueous Zinc-Ion Batteries

Abstract

Aqueous zinc-ion batteries (AZIBs) have garnered considerable attention due to their superior safety, affordability, and eco-friendliness. However, the uncontrolled growth of zinc dendrites and the parasitic hydrogen evolution reaction (HER) severely limit their cycling stability and practical lifespan. In this study, sodium p-aminobenzenesulfonate (SABS) is introduced into ZnSO₄-based electrolytes as a functional additive. SABS not only reconstructs the Zn²⁺ solvation sheath but also forms stable complexes with Zn²⁺, facilitating the in-situ formation of a robust three-dimensional networked solid electrolyte interphase (SEI) on the zinc anode surface. As a result, Zn||Zn symmetric cells exhibit ultra-stable cycling performance exceeding 2000 h at 1 mA cm⁻², while Zn||Cu asymmetric cells maintain over 2000 cycles at 5 mA cm⁻² with high Coulombic efficiency. The underlying mechanism of interfacial stabilization and SEI-like interphase formation is further elucidated by combining ex situ structural/chemical characterizations with density functional theory (DFT) calculations. Moreover, the Zn||I₂@AC full cell containing SABS additives exhibits excellent specific capacity and long-term cycling performance over a wide range of current densities. This work provides a promising electrolyte additive strategy to enhance the interfacial stability and electrochemical performance of AZIBs through coordinated solvation and interphase regulation.

Keywords

aqueous zinc-ion batteries / electrolyte additive / sodium p-aminobenzenesulfonate / solid-electrolyte interphase / zinc metal anode

References

[1] W. Kou, Y. Gao, S. Zhang, et al., “High Downward Surface Solar Radiation Conducive to Ozone Pollution More Frequent Under Global Warming,” Science Bulletin 68 (2023): 388–392.

[2] M. J. Aziz, D. F. Gayme, K. Johnson, et al., “A Co-Design Framework for Wind Energy Integrated With Storage,” Joule 6 (2022): 1995–2015.

[3] J. Lin, X. Zhang, E. Fan, R. Chen, F. Wu, and L. Li, “Carbon Neutrality Strategies for Sustainable Batteries: From Structure, Recycling, and Properties to Applications,” Energy & Environmental Science 16 (2023): 745–791.

[4] C. A. Rufino Júnior, E. Riva Sanseverino, P. Gallo, et al., “Towards a Business Model for Second-Life Batteries: Barriers, Opportunities, Uncertainties, and Technologies,” Journal of Energy Chemistry 78 (2023): 507–525.

[5] L. E. Blanc, D. Kundu, and L. F. Nazar, “Scientific Challenges for the Implementation of Zn-Ion Batteries,” Joule 4 (2020): 771–799.

[6] N. Liu, X. Wu, Y. Zhang, et al., “Building High Rate Capability and Ultrastable Dendrite-Free Organic Anode for Rechargeable Aqueous Zinc Batteries,” Advanced Science 7 (2020): 2000146.

[7] J. Wang, J.-G. Wang, X. Qin, et al., “Superfine MnO₂ Nanowires With Rich Defects Toward Boosted Zinc Ion Storage Performance,” ACS Applied Materials & Interfaces 12 (2020): 34949–34958.

[8] Y. Tian, Y. An, J. Feng, and Y. Qian, “MXenes and Their Derivatives for Advanced Aqueous Rechargeable Batteries,” Materials Today 52 (2022): 225–249.

[9] T. Xin, R. Zhou, Q. Xu, et al., “15-Crown-5 Ether as Efficient Electrolyte Additive for Performance Enhancement of Aqueous Zn-Ion Batteries,” Chemical Engineering Journal 452 (2023): 139572.

[10] C. Bai, F. Cai, L. Wang, S. Guo, X. Liu, and Z. Yuan, “A Sustainable Aqueous Zn-I2 Battery,” Nano Research 11 (2018): 3548–3554.

[11] B. Li, Y. Ma, J. Ma, L. Chen, Y. Zhao, and M.-C. Tang, “Challenges and Opportunities Facing Zinc Anodes for Aqueous Zinc-Ion Battery,” Energy Materials and Devices 2 (2024): 9370044.

[12] J. Xu, W. Lv, W. Yang, et al., “In Situ Construction of Protective Films on Zn Metal Anodes via Natural Protein Additives Enabling High-Performance Zinc Ion Batteries,” ACS Nano 16 (2022): 11392–11404.

[13] Q. Zhang, Y. Ma, Y. Lu, et al., “Designing Anion-Type Water-Free Zn²⁺ Solvation Structure for Robust Zn Metal Anode,” Angewandte Chemie International Edition 60 (2021): 23357–23364.

[14] W. Chen, S. Guo, L. Qin, et al., “Hydrogen Bond-Functionalized Massive Solvation Modules Stabilizing Bilateral Interfaces,” Advanced Functional Materials 32 (2022): 2112609.

[15] M. Wang, Y. Meng, K. Li, et al., “Toward Dendrite-Free and Anti-Corrosion Zn Anodes by Regulating a Bismuth-Based Energizer,” eScience 2 (2022): 509–517.

[16] Z. Yi, G. Chen, F. Hou, L. Wang, and J. Liang, “Strategies for the Stabilization of Zn Metal Anodes for Zn-Ion Batteries,” Advanced Energy Materials 11 (2021): 2003065.

[17] Y.-H. Wang, S. Zheng, W.-M. Yang, et al., “In Situ Raman Spectroscopy Reveals the Structure and Dissociation of Interfacial Water,” Nature 600 (2021): 81–85.

[18] Y. Tian, S. Chen, Y. He, Q. Chen, L. Zhang, and J. Zhang, “A Highly Reversible Dendrite-Free Zn Anode via Spontaneous Galvanic Replacement Reaction for Advanced Zinc-Iodine Batteries,” Nano Research Energy 1 (2022): e9120025.

[19] Y. Zhang, X. Zheng, N. Wang, et al., “Anode Optimization Strategies for Aqueous Zinc-Ion Batteries,” Chemical Science 13 (2022): 14246–14263.

[20] Q. Wen, H. Fu, R. Cui, et al., “Recent Advances in Interfacial Modification of Zinc Anode for Aqueous Rechargeable Zinc Ion Batteries,” Journal of Energy Chemistry 83 (2023): 287–303.

[21] D. Zhu, J. Li, F. Ren, Y. Liu, J. Ren, and Y. Xiong, “Towards a High-Performance Anode for Zinc Metal Batteries: A Tri-Functional Nitrogen-Defective Graphitic Carbon Nitride Material for Anode Protection,” Journal of Colloid and Interface Science 651 (2023): 504–513.

[22] H. Yan, S. Li, Y. Nan, S. Yang, and B. Li, “Ultrafast Zinc–Ion–Conductor Interface Toward High-Rate and Stable Zinc Metal Batteries,” Advanced Energy Materials 11 (2021): 2100186.

[23] Y. Wang, Y. Fan, D. Liao, Y. Wu, Y. Yu, and C. Hu, “Highly Zn²⁺-conductive and Robust Modified Montmorillonite Protective Layer of Electrodes Toward High-Performance Rechargeable Zinc-Ion Batteries,” Energy Storage Materials 51 (2022): 212–222.

[24] Z. Guo, L. Fan, C. Zhao, et al., “A Dynamic and Self-Adapting Interface Coating for Stable Zn-Metal Anodes,” Advanced Materials 34 (2022): 2105133.

[25] Y. Jiao, F. Li, X. Jin, et al., “Engineering Polymer Glue Towards 90% Zinc Utilization for 1000 Hours to Make High-Performance Zn-Ion Batteries,” Advanced Functional Materials 31 (2021): 2107652.

[26] J. Han, H. Euchner, M. Kuenzel, et al., “A Thin and Uniform Fluoride-Based Artificial Interphase for the Zinc Metal Anode Enabling Reversible Zn/MnO₂ Batteries,” ACS Energy Letters 6 (2021): 3063–3071.

[27] 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.

[28] D. Zhu, Y. Zheng, Y. Xiong, C. Cui, F. Ren, and Y. Liu, “In Situ Growth of S-Doped Zno Thin Film Enabling Dendrite-Free Zinc Anode for High-Performance Aqueous Zinc-Ion Batteries,” Journal of Alloys and Compounds 918 (2022): 165486.

[29] Y. Yang, C. Liu, Z. Lv, et al., “Synergistic Manipulation of Zn²⁺ Ion Flux and Desolvation Effect Enabled by Anodic Growth of a 3D ZnF₂ Matrix for Long-Lifespan and Dendrite-Free Zn Metal Anodes,” Advanced Materials 33 (2021): 2007388.

[30] 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 (2019): 3364–3371.

[31] Y. An, Y. Tian, S. Xiong, J. Feng, and Y. Qian, “Scalable and Controllable Synthesis of Interface-Engineered Nanoporous Host for Dendrite-Free and High Rate Zinc Metal Batteries,” ACS Nano 15 (2021): 11828–11842.

[32] Y. Tian, Y. An, C. Wei, et al., “Flexible and Free-Standing Ti₃C₂T_x MXene@Zn Paper for Dendrite-Free Aqueous Zinc Metal Batteries and Nonaqueous Lithium Metal Batteries,” ACS Nano 13 (2019): 11676–11685.

[33] Q. Zhang, J. Luan, L. Fu, et al., “The Three-Dimensional Dendrite-Free Zinc Anode on a Copper Mesh With a Zinc-Oriented Polyacrylamide Electrolyte Additive,” Angewandte Chemie International Edition 58 (2019): 15841–15847.

[34] X. Li, Q. Li, Y. Hou, et al., “Toward a Practical Zn Powder Anode: Ti₃C₂T_x MXene as a Lattice-Match Electrons/Ions Redistributor,” ACS Nano 15 (2021): 14631–14642.

[35] Z. Yang, Q. Zhang, W. Li, et al., “A Semi-Solid Zinc Powder-Based Slurry Anode for Advanced Aqueous Zinc-Ion Batteries,” Angewandte Chemie International Edition 62 (2023): e202215306.

[36] C. Cao, K. Zhou, W. Du, et al., “Designing Soft Solid-Like Viscoelastic Zinc Powder Anode Toward High-Performance Aqueous Zinc-Ion Batteries,” Advanced Energy Materials 13 (2023): 2301835.

[37] C. Huang, X. Zhao, S. Liu, et al., “Stabilizing Zinc Anodes by Regulating the Electrical Double Layer With Saccharin Anions,” Advanced Materials 33 (2021): 2100445.

[38] P. Sun, L. Ma, W. Zhou, et al., “Simultaneous Regulation on Solvation Shell and Electrode Interface for Dendrite-Free Zn Ion Batteries Achieved by a Low-Cost Glucose Additive,” Angewandte Chemie International Edition 60 (2021): 18247–18255.

[39] X. Feng, P. Li, J. Yin, et al., “Enabling Highly Reversible Zn Anode by Multifunctional Synergistic Effects of Hybrid Solute Additives,” ACS Energy Letters 8 (2023): 1192–1200.

[40] H. Wang, A. Zhou, Z. Hu, et al., “Toward Simultaneous Dense Zinc Deposition and Broken Side-Reaction Loops in the Zn//V₂O₅ System,” Angewandte Chemie International Edition 63 (2024): e202318928.

[41] Y. Wang, Q. Li, J. Xiong, et al., “High-Performance Vanadium Oxide-Based Aqueous Zinc Batteries: Organic Molecule Modification, Challenges, and Future Prospects,” EcoEnergy 2 (2024): 652–678.

[42] W. Kao-ian, M. T. Nguyen, T. Yonezawa, et al., “Highly Stable Rechargeable Zinc-Ion Battery Using Dimethyl Sulfoxide Electrolyte,” Materials Today Energy 21 (2021): 100738.

[43] C. Lu, Z. Yang, Y. Wang, et al., “Ethylene Glycol-Regulated Ammonium Vanadate With Stable Layered Structure and Favorable Interplanar Spacing as High-Performance Cathode for Aqueous Zinc Ion Batteries,” Chinese Chemical Letters 34 (2023): 108572.

[44] A. Naveed, H. Yang, J. Yang, Y. Nuli, and J. Wang, “Highly Reversible and Rechargeable Safe Zn Batteries Based on a Triethyl Phosphate Electrolyte,” Angewandte Chemie International Edition 58 (2019): 2760–2764.

[45] T.-Y. Chen, T.-J. Lin, B. Vedhanarayanan, H.-H. Shen, and T.-W. Lin, “Optimization of Acetamide Based Deep Eutectic Solvents With Dual Cations for High Performance and Low Temperature-Tolerant Aqueous Zinc Ion Batteries via Tuning the Ratio of Co-Solvents,” Journal of Colloid and Interface Science 629 (2023): 166–178.

[46] W. Xu, K. Zhao, W. Huo, et al., “Diethyl Ether as Self-Healing Electrolyte Additive Enabled Long-Life Rechargeable Aqueous Zinc Ion Batteries,” Nano Energy 62 (2019): 275–281.

[47] M. Liu, M. Qin, G. Fang, S. Liang, X. Wang, and Z. Luo, “Realization Restrain Vanadium Dissolution in Aqueous Zinc-Ion Batteries With Amphoteric Ionic Polyacrylamide Gel Electrolyte,” Journal of Alloys and Compounds 959 (2023): 170455.

[48] Y. Zhong, Z. Cheng, H. Zhang, et al., “Monosodium Glutamate, an Effective Electrolyte Additive to Enhance Cycling Performance of Zn Anode in Aqueous Battery,” Nano Energy 98 (2022): 107220.

[49] K. Xie, K. Ren, C. Sun, et al., “Toward Stable Zinc-Ion Batteries: Use of a Chelate Electrolyte Additive for Uniform Zinc Deposition,” ACS Applied Energy Materials 5 (2022): 4170–4178.

[50] J. Chen, W. Zhou, Y. Quan, et al., “Ionic Liquid Additive Enabling Anti-Freezing Aqueous Electrolyte and Dendrite-Free Zn Metal Electrode With Organic/Inorganic Hybrid Solid Electrolyte Interphase Layer,” Energy Storage Materials 53 (2022): 629–637.

[51] X. Zhao, N. Dong, M. Yan, and H. Pan, “Unraveling the Interphasial Chemistry for Highly Reversible Aqueous Zn Ion Batteries,” ACS Applied Materials & Interfaces 15 (2023): 4053–4060.

[52] Y. Lin, Y. Hu, S. Zhang, et al., “Highly Reversible Aqueous Zinc-Ion Battery Using the Chelating Agent Triethanolamine as an Electrolyte Additive,” CrystEngComm 24 (2022): 7950–7961.

[53] L. Jin, Y. Ma, Q. Lu, et al., “Green Synthesis and Characterization of a Zn(Ⅱ) Complex of p-Aminobenzenesulfonate,” University Chemistry 38 (2022): 181–187.

[54] L. Hu, P. Xiao, L. Xue, H. Li, and T. Zhai, “The Rising Zinc Anodes for High-Energy Aqueous Batteries,” EnergyChem 3 (2021): 100052.

[55] K. Leng, G. Li, J. Guo, et al., “A Safe Polyzwitterionic Hydrogel Electrolyte for Long-Life Quasi-Solid State Zinc Metal Batteries,” Advanced Functional Materials 30 (2020): 2001317.

[56] Z. Cai, Y. Ou, J. Wang, et al., “Chemically Resistant Cu–Zn/Zn Composite Anode for Long Cycling Aqueous Batteries,” Energy Storage Materials 27 (2020): 205–211.

[57] R. Zhao, Y. Yang, G. Liu, et al., “Redirected Zn Electrodeposition by an Anti-Corrosion Elastic Constraint for Highly Reversible Zn Anodes,” Advanced Functional Materials 31 (2020): 2001867.

[58] D. Han, Z. Wang, H. Lu, et al., “A Self-Regulated Interface Toward Highly Reversible Aqueous Zinc Batteries,” Advanced Energy Materials 12 (2022): 2102982.

[59] Z. Zhao, J. Zhao, Z. Hu, et al., “Long-Life and Deeply Rechargeable Aqueous Zn Anodes Enabled by a Multifunctional Brightener-Inspired Interphase,” Energy & Environmental Science 12 (2019): 1938–1949.

[60] M. Zhou, S. Guo, J. Li, et al., “Surface-Preferred Crystal Plane for a Stable and Reversible Zinc Anode,” Advanced Materials 33 (2021): 2100187.

[61] Q. Zhang, K. Xia, Y. Ma, et al., “Chaotropic Anion and Fast-Kinetics Cathode Enabling Low-Temperature Aqueous Zn Batteries,” ACS Energy Letters 6 (2021): 2704–2712.

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

[63] J. Yin, H. Liu, P. Li, et al., “Integrated Electrolyte Regulation Strategy: Trace Trifunctional Tranexamic Acid Additive for Highly Reversible Zn Metal Anode and Stable Aqueous Zinc Ion Battery,” Energy Storage Materials 59 (2023): 102800.

[64] H. Peng, X. Wang, F. Yang, et al., “Regulating Solvation Structure and Inducing Zn (002) Plane by a Multifunctional Electrolyte Additive Toward Dendrite Suppression and Long-Life Zinc Ion Hybrid Capacitors,” Chemical Engineering Journal 474 (2023): 145864.

[65] L. Cao, D. Li, E. Hu, et al., “Solvation Structure Design for Aqueous Zn Metal Batteries,” Journal of the American Chemical Society 142 (2020): 21404–21409.

[66] M. Qiu, P. Sun, G. Cui, and W. Mai, “Chaotropic Polymer Additive With Ion Transport Tunnel Enable Dendrite-Free Zinc Battery,” ACS Applied Materials & Interfaces 14 (2022): 40951–40958.

[67] Z. Chen, H. Chen, Y. Che, et al., “Arginine Cations Inhibiting Charge Accumulation of Dendrites and Boosting Zn Metal Reversibility in Aqueous Rechargeable Batteries,” ACS Sustainable Chemistry & Engineering 9 (2021): 6855–6863.

[68] Y. Li, P. Wu, W. Zhong, et al., “A Progressive Nucleation Mechanism Enables Stable Zinc Stripping–Plating Behavior,” Energy & Environmental Science 14 (2021): 5563–5571.

[69] C. Wu, C. Sun, K. Ren, et al., “2-Methyl Imidazole Electrolyte Additive Enabling Ultra-Stable Zn Anode,” Chemical Engineering Journal 452 (2023): 139465.

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