Issue

Vol. 17 (2025)

Integrating Electric Ambipolar Effect for High-Performance Zinc Bromide Batteries

https://doi.org/10.1007/s40820-024-01636-6
Wenda Li
State Key Laboratory of Precision Spectroscopy, Engineering Research Center of Nanophotonics and Advanced Instrument (Ministry of Education), School of Physics and Electronic Science, East China Normal University, Shanghai 200241, People’s Republic of China
Hengyue Xu
Department of Chemistry, Tsinghua University, Haidian District, Beijing 100084, People’s Republic of China
Shanzhe Ke
State Key Laboratory of Precision Spectroscopy, Engineering Research Center of Nanophotonics and Advanced Instrument (Ministry of Education), School of Physics and Electronic Science, East China Normal University, Shanghai 200241, People’s Republic of China
Hongyi Zhang
State Key Laboratory of Precision Spectroscopy, Engineering Research Center of Nanophotonics and Advanced Instrument (Ministry of Education), School of Physics and Electronic Science, East China Normal University, Shanghai 200241, People’s Republic of China
Hao Chen
State Key Laboratory of Precision Spectroscopy, Engineering Research Center of Nanophotonics and Advanced Instrument (Ministry of Education), School of Physics and Electronic Science, East China Normal University, Shanghai 200241, People’s Republic of China
Gaijuan Guo
State Key Laboratory of Precision Spectroscopy, Engineering Research Center of Nanophotonics and Advanced Instrument (Ministry of Education), School of Physics and Electronic Science, East China Normal University, Shanghai 200241, People’s Republic of China
Xuanyi Xiong
State Key Laboratory of Precision Spectroscopy, Engineering Research Center of Nanophotonics and Advanced Instrument (Ministry of Education), School of Physics and Electronic Science, East China Normal University, Shanghai 200241, People’s Republic of China
Shiyao Zhang
State Key Laboratory of Precision Spectroscopy, Engineering Research Center of Nanophotonics and Advanced Instrument (Ministry of Education), School of Physics and Electronic Science, East China Normal University, Shanghai 200241, People’s Republic of China
Jianwei Fu
School of Materials Science and Engineering, Zhengzhou University, 75 Daxue Road, Zhengzhou 450052, People’s Republic of China
Chengbin Jing
State Key Laboratory of Precision Spectroscopy, Engineering Research Center of Nanophotonics and Advanced Instrument (Ministry of Education), School of Physics and Electronic Science, East China Normal University, Shanghai 200241, People’s Republic of China
Jiangong Cheng
State Key Lab of Transducer Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050, People’s Republic of China
Shaohua Liu
State Key Laboratory of Precision Spectroscopy, Engineering Research Center of Nanophotonics and Advanced Instrument (Ministry of Education), School of Physics and Electronic Science, East China Normal University, Shanghai 200241, People’s Republic of China

Corresponding Author: Shaohua Liu

shliu@phy.ecnu.edu.cn

Nano-Micro Letters, Vol. 17 (2025), Article Number: 143

Abstract

The coupling of fast redox kinetics, high-energy density, and prolonged lifespan is a permanent aspiration for aqueous rechargeable zinc batteries, but which has been severely hampered by a narrow voltage range and suboptimal compatibility between the electrolytes and electrodes. Here, we unprecedentedly introduced an electric ambipolar effect for synergistic manipulation on Zn2+ ternary-hydrated eutectic electrolyte (ZTE) enabling high-performance Zn-Br2 batteries. The electric ambipolar effect motivates strong dipole interactions among hydrated perchlorates and bipolar ligands of L-carnitine (L-CN) and sulfamide, which reorganized primary cations solvation sheath in a manner of forming Zn[(L-CN)(SA)(H2O)4]2+ configuration and dynamically restricting desolvated H2O molecules, thus ensuring a broadened electrochemical window of 2.9 V coupled with high ionic conductivity. Noticeably, L-CN affords an electrostatic shielding effect and an in situ construction of organic–inorganic interphase, endowing oriented Zn anode plating/stripping reversibly for over 2400 h. Therefore, with the synergy of electro/nucleophilicity and exceptional compatibility, the ZTE electrolyte dynamically boosts the conversion redox of Zn-Br2 batteries in terms of high specific capacity and stable cycling performance. These findings open a window for designing electrolytes with synergetic chemical stability and compatibility toward advanced zinc-ion batteries.


Highlights:
1 Electric ambipolar effect motivates strong dipole interactions reorganized primary cations solvation sheath.
2 Electrostatic shielding homogenized the distribution for nucleated Zn and facilized the orientated Zn deposition.
3 The eutectic network of Zn2+ ternary hydrated eutectic electrolytes enables highly reversible and noteworthy Br2/Br− reaction kinetics.

Keywords

Electric ambipolar effect Hydrated eutectic electrolyte Electrostatic shielding Zinc bromide batteries
Li, Wenda, Hengyue Xu, Shanzhe Ke, Hongyi Zhang, Hao Chen, Gaijuan Guo, Xuanyi Xiong, Shiyao Zhang, Jianwei Fu, Chengbin Jing, Jiangong Cheng, and Shaohua Liu. 2025. “Integrating Electric Ambipolar Effect for High-Performance Zinc Bromide Batteries”. Nano-Micro Letters 17 (February):143. https://doi.org/10.1007/s40820-024-01636-6.
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References
  1. C. Yang, J. Chen, X. Ji, T.P. Pollard, X. Lü et al., Aqueous Li-ion battery enabled by halogen conversion–intercalation chemistry in graphite. Nature 569, 245–250 (2019). https://doi.org/10.1038/s41586-019-1175-6
  2. T. Chen, H. Banda, L. Yang, J. Li, Y. Zhang et al., High-rate, high-capacity electrochemical energy storage in hydrogen-bonded fused aromatics. Joule 7, 986–1002 (2023). https://doi.org/10.1016/j.joule.2023.03.011
  3. J. Zheng, D.C. Bock, T. Tang, Q. Zhao, J. Yin et al., Regulating electrodeposition morphology in high-capacity aluminium and zinc battery anodes using interfacial metal–substrate bonding. Nat. Energy 6, 398–406 (2021). https://doi.org/10.1038/s41560-021-00797-7
  4. J. Liu, C. Ye, H. Wu, M. Jaroniec, S.-Z. Qiao, 2D mesoporous zincophilic sieve for high-rate sulfur-based aqueous zinc batteries. J. Am. Chem. Soc. 145, 5384–5392 (2023). https://doi.org/10.1021/jacs.2c13540
  5. W. Li, H. Xu, H. Zhang, F. Wei, L. Huang et al., Tuning electron delocalization of hydrogen-bonded organic framework cathode for high-performance zinc-organic batteries. Nat. Commun. 14, 5235 (2023). https://doi.org/10.1038/s41467-023-40969-5
  6. M. Kim, S.J. Shin, J. Lee, Y. Park, Y. Kim et al., Cationic additive with a rigid solvation shell for high-performance zinc ion batteries. Angew. Chem. Int. Ed. 61, e202211589 (2022). https://doi.org/10.1002/anie.202211589
  7. X. Zheng, Z. Liu, J. Sun, R. Luo, K. Xu et al., Constructing robust heterostructured interface for anode-free zinc batteries with ultrahigh capacities. Nat. Commun. 14, 76 (2023). https://doi.org/10.1038/s41467-022-35630-6
  8. S. Chen, D. Ji, Q. Chen, J. Ma, S. Hou et al., Coordination modulation of hydrated zinc ions to enhance redox reversibility of zinc batteries. Nat. Commun. 14, 3526 (2023). https://doi.org/10.1038/s41467-023-39237-3
  9. D. Lin, Y. Li, Recent advances of aqueous rechargeable zinc-iodine batteries: challenges, solutions, and prospects. Adv. Mater. 34, e2108856 (2022). https://doi.org/10.1002/adma.202108856
  10. S. Huang, L. Hou, T. Li, Y. Jiao, P. Wu, Antifreezing hydrogel electrolyte with ternary hydrogen bonding for high-performance zinc-ion batteries. Adv. Mater. 34, e2110140 (2022). https://doi.org/10.1002/adma.202110140
  11. H. Dou, X. Wu, M. Xu, R. Feng, Q. Ma et al., Steric-hindrance effect tuned ion solvation enabling high performance aqueous zinc ion batteries. Angew. Chem. Int. Ed. 63, e202401974 (2024). https://doi.org/10.1002/anie.202401974
  12. C. Dai, L. Hu, X. Jin, Y. Wang, R. Wang et al., Fast constructing polarity-switchable zinc-bromine microbatteries with high areal energy density. Sci. Adv. 8, eabo6688 (2022). https://doi.org/10.1126/sciadv.abo6688
  13. C. Xu, C. Lei, P. Jiang, W. Yang, W. Ma et al., Practical high-energy aqueous zinc-bromine static batteries enabled by synergistic exclusion-complexation chemistry. Joule 8, 461–481 (2024). https://doi.org/10.1016/j.joule.2023.12.023
  14. X. Li, N. Li, Z. Huang, Z. Chen, Y. Zhao et al., Confining aqueous Zn-Br halide redox chemistry by Ti3C2TX MXene. ACS Nano 15, 1718–1726 (2021). https://doi.org/10.1021/acsnano.0c09380
  15. J.H. Lee, Y. Byun, G.H. Jeong, C. Choi, J. Kwen et al., High-energy efficiency membraneless flowless Zn-Br battery: utilizing the electrochemical-chemical growth of polybromides. Adv. Mater. 31, e1904524 (2019). https://doi.org/10.1002/adma.201904524
  16. S. Biswas, A. Senju, R. Mohr, T. Hodson, N. Karthikeyan et al., Minimal architecture zinc–bromine battery for low cost electrochemical energy storage. Energy Environ. Sci. 10, 114–120 (2017). https://doi.org/10.1039/c6ee02782b
  17. J. Heo, K. Shin, H.-T. Kim, A zinc-bromine battery with deep eutectic electrolytes. Adv. Sci. 9, e2204908 (2022). https://doi.org/10.1002/advs.202204908
  18. L.E. Blanc, D. Kundu, L.F. Nazar, Scientific challenges for the implementation of Zn-ion batteries. Joule 4, 771–799 (2020). https://doi.org/10.1016/j.joule.2020.03.002
  19. X. Song, Y. Ge, H. Xu, S. Bao, L. Wang et al., Ternary eutectic electrolyte-assisted formation and dynamic breathing effect of the solid-electrolyte interphase for high-stability aqueous magnesium-ion full batteries. J. Am. Chem. Soc. 146, 7018–7028 (2024). https://doi.org/10.1021/jacs.4c00227
  20. H. Qiu, R. Hu, X. Du, Z. Chen, J. Zhao et al., Eutectic crystallization activates solid-state zinc-ion conduction. Angew. Chem. Int. Ed. 61, e202113086 (2022). https://doi.org/10.1002/anie.202113086
  21. W. Yang, X. Du, J. Zhao, Z. Chen, J. Li et al., Hydrated eutectic electrolytes with ligand-oriented solvation shells for long-cycling zinc-organic batteries. Joule 4, 1557–1574 (2020). https://doi.org/10.1016/j.joule.2020.05.018
  22. J. Wu, Q. Liang, X. Yu, Q.-F. Lü, L. Ma et al., Deep eutectic solvents for boosting electrochemical energy storage and conversion: a review and perspective. Adv. Funct. Mater. 31, 2011102 (2021). https://doi.org/10.1002/adfm.202011102
  23. G.A. Kaminski, R.A. Friesner, J. Tirado-Rives, W.L. Jorgensen, Evaluation and reparametrization of the OPLS-AA force field for proteins via comparison with accurate quantum chemical calculations on peptides. J. Phys. Chem. B 105, 6474–6487 (2001). https://doi.org/10.1021/jp003919d
  24. W. Humphrey, A. Dalke, K. Schulten, VMD: visual molecular dynamics. J. Mol. Graph. 14, 33–38 (1996). https://doi.org/10.1016/0263-7855(96)00018-5
  25. C. Zhao, Y. Gong, L. Zheng, M. Zhao, Untargeted metabolomic reveals the changes in muscle metabolites of mice during exercise recovery and the mechanisms of whey protein and whey protein hydrolysate in promoting muscle repair. Food Res. Int. 184, 114261 (2024). https://doi.org/10.1016/j.foodres.2024.114261
  26. L. Liu, H. Lu, C. Han, X. Chen, S. Liu et al., Salt anion amphiphilicity-activated electrolyte cosolvent selection strategy toward durable Zn metal anode. ACS Nano 17, 23065–23078 (2023). https://doi.org/10.1021/acsnano.3c08716
  27. F. Zhang, T. Liao, H. Peng, S. Xi, D.-C. Qi et al., Outer sphere electron transfer enabling high-voltage aqueous electrolytes. J. Am. Chem. Soc. 146, 10812–10821 (2024). https://doi.org/10.1021/jacs.4c01188
  28. G. Ma, L. Miao, Y. Dong, W. Yuan, X. Nie et al., Reshaping the electrolyte structure and interface chemistry for stable aqueous zinc batteries. Energy Storage Mater. 47, 203–210 (2022). https://doi.org/10.1016/j.ensm.2022.02.019
  29. M. Qiu, P. Sun, K. Han, Z. Pang, J. Du et al., Tailoring water structure with high-tetrahedral-entropy for antifreezing electrolytes and energy storage at -80 °C. Nat. Commun. 14, 601 (2023). https://doi.org/10.1038/s41467-023-36198-5
  30. W. Li, H. Xu, H. Zhang, F. Wei, T. Zhang et al., Designing ternary hydrated eutectic electrolyte capable of four-electron conversion for advanced Zn–I2 full batteries. Energy Environ. Sci. 16, 4502–4510 (2023). https://doi.org/10.1039/d3ee01567j
  31. C. Chang, S. Hu, T. Li, F. Zeng, D. Wang et al., A robust gradient solid electrolyte interphase enables fast Zn dissolution and deposition dynamics. Energy Environ. Sci. 17, 680–694 (2024). https://doi.org/10.1039/d3ee03422d
  32. X. Liao, S. Chen, J. Chen, Y. Li, W. Wang et al., Suppressing Zn pulverization with three-dimensional inert-cation diversion dam for long-life Zn metal batteries. Proc. Natl. Acad. Sci. U.S.A. 121, e2317796121 (2024). https://doi.org/10.1073/pnas.2317796121
  33. H. Lu, J. Hu, X. Wei, K. Zhang, X. Xiao et al., A recyclable biomass electrolyte towards green zinc-ion batteries. Nat. Commun. 14, 4435 (2023). https://doi.org/10.1038/s41467-023-40178-0
  34. M. Li, X. Wang, J. Hu, J. Zhu, C. Niu et al., Comprehensive H2O molecules regulation via deep eutectic solvents for ultra-stable zinc metal anode. Angew. Chem. Int. Ed. 62, e202215552 (2023). https://doi.org/10.1002/anie.202215552
  35. P. Xiong, Y. Kang, N. Yao, X. Chen, H. Mao et al., Zn-ion transporting, in situ formed robust solid electrolyte interphase for stable zinc metal anodes over a wide temperature range. ACS Energy Lett. 8, 1613–1625 (2023). https://doi.org/10.1021/acsenergylett.3c00154
  36. X. Zhao, Y. Wang, C. Huang, Y. Gao, M. Huang et al., Tetraphenylporphyrin-based chelating ligand additive as a molecular sieving interfacial barrier toward durable aqueous zinc metal batteries. Angew. Chem. Int. Ed. 62, e202312193 (2023). https://doi.org/10.1002/anie.202312193
  37. J. Zheng, B. Zhang, X. Chen, W. Hao, J. Yao et al., Critical solvation structures arrested active molecules for reversible Zn electrochemistry. Nano-Micro Lett. 16, 145 (2024). https://doi.org/10.1007/s40820-024-01361-0
  38. W. Xu, J. Li, X. Liao, L. Zhang, X. Zhang et al., Fluoride-rich, organic-inorganic gradient interphase enabled by sacrificial solvation shells for reversible zinc metal batteries. J. Am. Chem. Soc. 145, 22456–22465 (2023). https://doi.org/10.1021/jacs.3c06523
  39. H. Yu, D. Chen, X. Ni, P. Qing, C. Yan et al., Reversible adsorption with oriented arrangement of a zwitterionic additive stabilizes electrodes for ultralong-life Zn-ion batteries. Energy Environ. Sci. 16, 2684–2695 (2023). https://doi.org/10.1039/d3ee00982c
  40. D. Xu, B. Chen, X. Ren, C. Han, Z. Chang et al., Selectively etching-off the highly reactive (002) Zn facet enables highly efficient aqueous zinc-metal batteries. Energy Environ. Sci. 17, 642–654 (2024). https://doi.org/10.1039/d3ee02522e
  41. S.J. Yoo, B. Evanko, X. Wang, M. Romelczyk, A. Taylor et al., Fundamentally addressing bromine storage through reversible solid-state confinement in porous carbon electrodes: design of a high-performance dual-redox electrochemical capacitor. J. Am. Chem. Soc. 139, 9985–9993 (2017). https://doi.org/10.1021/jacs.7b04603
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