Issue

Vol. 18 (2026)

Electrically Insulating Rigid Multi-Channel Electrolyte Container for Customizable Electron Transfer in Zn-Halogen Batteries

https://doi.org/10.1007/s40820-025-02007-5
Yifan Zhou
School of Materials Science and Engineering, Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan Province, Central South University, Changsha 410083, People’s Republic of China
Yicai Pan
Department of Materials Science and Engineering and Center of Super‑Diamond and Advanced Films (COSDAF), City University of Hong Kong, Hong Kong SAR 999077, People’s Republic of China
Yongqiang Yang
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong SAR 999077, People’s Republic of China
Taghreed F. Altamimi
Department of Physics, College of Science, University of Hail, P.O. Box 2440, Hail, Saudi Arabia
Yunpeng Zhong
Christopher Ingold Laboratory, Department of Chemistry, University College London, London WC1H0AJ, UK
Dalal A. Alshammari
Department of Chemistry, College of Science, University of Hafr Al Batin, P.O. Box 39524, Hafr Al Batin, Saudi Arabia
Zeinhom M. El‑Bahy
Department of Chemistry, Faculty of Science, Al-Azhar University, Nasr City 11884, Cairo, Egypt
Shuquan Liang
School of Materials Science and Engineering, Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan Province, Central South University, Changsha 410083, People’s Republic of China
Jiang Zhou
School of Materials Science and Engineering, Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan Province, Central South University, Changsha 410083, People’s Republic of China
Xinxin Cao
School of Materials Science and Engineering, Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan Province, Central South University, Changsha 410083, People’s Republic of China

Corresponding Author: Xinxin Cao

caoxinxin@csu.edu.cn

Nano-Micro Letters, Vol. 18 (2026), Article Number: 168

Abstract

Recent advancements in Zn-halogen batteries have focused on enhancing the adsorptive or catalytic capability of host materials and stabilizing complex intermediates with electrolyte additives, while the halogen-ion electrolyte modifications exhibit strong potential for integrated interfacial regulation. Herein, we design an electrically insulating rigid electrolyte container to immobilize a liquid halogen-ion electrolyte for separator-free Zn-halogen batteries with customizable electron transfer. Robust hydrogen bonding of hydroxyl groups in SiO2 with fluorinated moieties in PVDF-hfp regulates Zn2+ solvation and suppresses H2O activity, while multi-channels formed by microcracks and interparticle gaps not only enhance mass transfer but also buffer interfacial electric field, jointly enabling a durable Zn plating/stripping. Effective confinement of intermediates also ensures the high reversibility across single-(I−/I0), double-(I−/I0/I⁺), and triple-(I−/I0/I⁺, Cl−/Cl0) electron transfer mechanisms at cathode, as evidenced by the double-electron transfer systems exhibiting a low capacity decay rate of 0.02‰ over 4500 cycles at 10 mA cm−2 and a high areal capacity of 11.9 mAh cm−2 at 2 mA cm−2. This work presents a novel “container engineering” approach to halogen-ion electrolyte design and provides fundamental insights into the relationships between redox reversibility and reaction kinetics.


Highlights:
1 A rigid electrolyte container (SiO2@PVDF-hfp) was designed to immobilize the liquid halogen-ion electrolyte, enabling separator-free Zn-halogen batteries.
2 The container regulates Zn2+ solvation via hydrogen bonding regulation, while providing multi-channel structure for enhanced mass transfer, jointly enabling durable Zn plating/stripping.
3 Effective confinement of intermediates ensures high reversibility across multi-electron transfer mechanisms, achieving an exceptionally low-capacity decay of 0.02‰ over 4500 cycles and a high areal capacity of 11.9 mAh cm−2.

Keywords

Electrolyte container Interfacial reaction regulation Customizable electron transfer Zn-halogen batteries
Zhou, Yifan, Yicai Pan, Yongqiang Yang, Taghreed F. Altamimi, Yunpeng Zhong, Dalal A. Alshammari, Zeinhom M. El‑Bahy, Shuquan Liang, Jiang Zhou, and Xinxin Cao. 2026. “Electrically Insulating Rigid Multi-Channel Electrolyte Container for Customizable Electron Transfer in Zn-Halogen Batteries”. Nano-Micro Letters 18 (January):168. https://doi.org/10.1007/s40820-025-02007-5.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. B. Tang, L. Shan, S. Liang, J. Zhou, Issues and opportunities facing aqueous zinc-ion batteries. Energy Environ. Sci. 12(11), 3288–3304 (2019). https://doi.org/10.1039/c9ee02526j
  2. X. Jia, C. Liu, Z.G. Neale, J. Yang, G. Cao, Active materials for aqueous zinc ion batteries: synthesis, crystal structure, morphology, and electrochemistry. Chem. Rev. 120(15), 7795–7866 (2020). https://doi.org/10.1021/acs.chemrev.9b00628
  3. D. Lin, Y. Li, Recent advances of aqueous rechargeable zinc-iodine batteries: challenges, solutions, and prospects. Adv. Mater. 34(23), 2108856 (2022). https://doi.org/10.1002/adma.202108856
  4. C. Zhou, Z. Ding, S. Ying, H. Jiang, Y. Wang et al., Electrode/electrolyte optimization-induced double-layered architecture for high-performance aqueous zinc-(dual) halogen batteries. Nano-Micro Lett. 17(1), 58 (2024). https://doi.org/10.1007/s40820-024-01551-w
  5. Y. Yang, S. Liang, J. Zhou, Progress and prospect of the zinc–iodine battery. Curr. Opin. Electrochem. 30, 100761 (2021). https://doi.org/10.1016/j.coelec.2021.100761
  6. S. Wang, Z. Wei, H. Hong, X. Guo, Y. Wang et al., A tellurium iodide perovskite structure enabling eleven-electron transfer in zinc ion batteries. Nat. Commun. 16(1), 511 (2025). https://doi.org/10.1038/s41467-024-55385-6
  7. Y. Zou, T. Liu, Q. Du, Y. Li, H. Yi et al., A four-electron Zn-I2 aqueous battery enabled by reversible I-/I2/I+ conversion. Nat. Commun. 12(1), 170 (2021). https://doi.org/10.1038/s41467-020-20331-9
  8. L. She, H. Cheng, Z. Yuan, Z. Shen, Q. Wu et al., Rechargeable aqueous zinc–halogen batteries: fundamental mechanisms, research issues, and future perspectives. Adv. Sci. 11(8), 2305061 (2024). https://doi.org/10.1002/advs.202305061
  9. Y. Yin, S. Wang, Q. Zhang, Y. Song, N. Chang et al., Dendrite-free zinc deposition induced by tin-modified multifunctional 3D host for stable zinc-based flow battery. Adv. Mater. 32(6), 1906803 (2020). https://doi.org/10.1002/adma.201906803
  10. M. Liu, Q. Chen, X. Cao, D. Tan, J. Ma et al., Physicochemical confinement effect enables high-performing zinc-iodine batteries. J. Am. Chem. Soc. 144(47), 21683–21691 (2022). https://doi.org/10.1021/jacs.2c09445
  11. J. Zhao, Y. Qi, Y. Chen, M. Zhang, Z. An et al., High-performance zinc halogen aqueous battery exploiting [BrCl2]- storage in ketjenblack by reconstructing electrolyte structure. Angew. Chem. Int. Ed. 64(17), e202421905 (2025). https://doi.org/10.1002/anie.202421905
  12. W. Ma, T. Liu, C. Xu, C. Lei, P. Jiang et al., A twelve-electron conversion iodine cathode enabled by interhalogen chemistry in aqueous solution. Nat. Commun. 14(1), 5508 (2023). https://doi.org/10.1038/s41467-023-41071-6
  13. F. Wang, J. Tseng, Z. Liu, P. Zhang, G. Wang et al., A stimulus-responsive zinc-iodine battery with smart overcharge self-protection function. Adv. Mater. 32(16), e2000287 (2020). https://doi.org/10.1002/adma.202000287
  14. 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(10), 4502–4510 (2023). https://doi.org/10.1039/d3ee01567j
  15. X. Yang, Y. Lu, Z. Liu, H. Ji, Z. Chen et al., Facet-governed Zn homoepitaxy via lattice potential regulation. Energy Environ. Sci. 17(15), 5563–5575 (2024). https://doi.org/10.1039/d4ee00881b
  16. Z. Dong, C. Zhong, H. Chai, G. Weng, J. Chen et al., Emerging in situ thermal treatment strategies for tailoring uniform Zn deposition toward stable Zn anodes. Adv. Funct. Mater. 35(39), 2503502 (2025). https://doi.org/10.1002/adfm.202503502
  17. T. Wang, Q. Xi, K. Yao, Y. Liu, H. Fu et al., Surface patterning of metal zinc electrode with an in-region zincophilic interface for high-rate and long-cycle-life zinc metal anode. Nano-Micro Lett. 16(1), 112 (2024). https://doi.org/10.1007/s40820-024-01327-2
  18. 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(28), eabo6688 (2022). https://doi.org/10.1126/sciadv.abo6688
  19. P. Blöchl, O. Jepsen, O. Andersen, Improved tetrahedron method for Brillouin-zone integrations. Phys. Rev. B 49(23), 16223–16233 (1994). https://doi.org/10.1103/physrevb.49.16223
  20. J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple. Phys. Rev. Lett. 77(18), 3865–3868 (1996). https://doi.org/10.1103/physrevlett.77.3865
  21. T. Nishiyama, T. Sumihara, E. Sato, H. Horibe, Effect of solvents on the crystal formation of poly(vinylidene fluoride) film prepared by a spin-coating process. Polym. J. 49(3), 319–325 (2017). https://doi.org/10.1038/pj.2016.116
  22. E. Kabir, M. Khatun, L. Nasrin, M.J. Raihan, M. Rahman, Pureβ-phase formation in polyvinylidene fluoride (PVDF)-carbon nanotube composites. J. Phys. D Appl. Phys. 50(16), 163002 (2017). https://doi.org/10.1088/1361-6463/aa5f85
  23. D. Yuan, Z. Li, W. Thitsartarn, X. Fan, J. Sun et al., β phase PVDF-hfp induced by mesoporous SiO2 nanorods: synthesis and formation mechanism. J. Mater. Chem. C 3(15), 3708–3713 (2015). https://doi.org/10.1039/C5TC00005J
  24. X. Meng, Y. Liu, M. Guan, J. Qiu, Z. Wang, A high-energy and safe lithium battery enabled by solid-state redox chemistry in a fireproof gel electrolyte. Adv. Mater. 34(28), 2201981 (2022). https://doi.org/10.1002/adma.202201981
  25. Q. Liu, G. Yang, X. Li, S. Zhang, R. Chen et al., Polymer electrolytes based on interactions between [solvent-Li+] complex and solvent-modified polymer. Energy Storage Mater. 51, 443–452 (2022). https://doi.org/10.1016/j.ensm.2022.06.040
  26. 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(7), 1557–1574 (2020). https://doi.org/10.1016/j.joule.2020.05.018
  27. R. Chen, C. Zhang, J. Li, Z. Du, F. Guo et al., A hydrated deep eutectic electrolyte with finely-tuned solvation chemistry for high-performance zinc-ion batteries. Energy Environ. Sci. 16(6), 2540–2549 (2023). https://doi.org/10.1039/D3EE00462G
  28. X. Hu, Z. Zhao, Y. Yang, H. Zhang, G. Lai et al., Bifunctional self-segregated electrolyte realizing high-performance zinc-iodine batteries. InfoMat 6(12), e12620 (2024). https://doi.org/10.1002/inf2.12620
  29. Y. Yang, S. Liang, B. Lu, J. Zhou, Eutectic electrolyte based on N-methylacetamide for highly reversible zinc–iodine battery. Energy Environ. Sci. 15(3), 1192–1200 (2022). https://doi.org/10.1039/d1ee03268b
  30. L. Zhu, J. Chen, Y. Wang, W. Feng, Y. Zhu et al., Tunneling interpenetrative lithium ion conduction channels in polymer-in-ceramic composite solid electrolytes. J. Am. Chem. Soc. 146(10), 6591–6603 (2024). https://doi.org/10.1021/jacs.3c11988
  31. H. Qiu, X. Du, J. Zhao, Y. Wang, J. Ju et al., Zinc anode-compatible in situ solid electrolyte interphase via cation solvation modulation. Nat. Commun. 10(1), 5374 (2019). https://doi.org/10.1038/s41467-019-13436-3
  32. G.M. Pharr, W.C. Oliver, Measurement of thin film mechanical properties using nanoindentation. MRS Bull. 17(7), 28–33 (1992). https://doi.org/10.1557/S0883769400041634
  33. T. Zhang, J. Li, X. Li, R. Wang, C. Wang et al., A silica-reinforced composite electrolyte with greatly enhanced interfacial lithium-ion transfer kinetics for high-performance lithium metal batteries. Adv. Mater. 34(41), 2205575 (2022). https://doi.org/10.1002/adma.202205575
  34. H. Chen, P. Ruan, H. Zhang, Z.M. El-Bahy, M.M. Ibrahim et al., Achieving highly reversible Mn2+/MnO2 conversion reaction in electrolytic Zn-MnO2 batteries via electrochemical-chemical process regulation. Angew. Chem. Int. Ed. 64(18), e202423999 (2025). https://doi.org/10.1002/anie.202423999
  35. R. Deng, J. Chen, F. Chu, M. Qian, Z. He et al., Soggy-sand” chemistry for high-voltage aqueous zinc-ion batteries. Adv. Mater. 36(11), e2311153 (2024). https://doi.org/10.1002/adma.202311153
  36. P. Shi, J. Ma, M. Liu, S. Guo, Y. Huang et al., A dielectric electrolyte composite with high lithium-ion conductivity for high-voltage solid-state lithium metal batteries. Nat. Nanotechnol. 18(6), 602–610 (2023). https://doi.org/10.1038/s41565-023-01341-2
  37. H. Ge, X. Xie, X. Xie, B. Zhang, S. Li et al., Critical challenges and solutions: quasi-solid-state electrolytes for zinc-based batteries. Energy Environ. Sci. 17(10), 3270–3306 (2024). https://doi.org/10.1039/d4ee00357h
  38. Y. Han, Y. Liu, Y. Zhang, X. He, X. Fu et al., Functionalized quasi-solid-state electrolytes in aqueous Zn-ion batteries for flexible devices: challenges and strategies. Adv. Mater. 37(1), 2412447 (2025). https://doi.org/10.1002/adma.202412447
  39. Y. Guo, L. Shan, Y. Yang, J. Zhou, Z. Zheng, Current-dependent coupling behaviors inspired wide-current cyclable Zn metal anode. EcoMat 7(5), e70013 (2025). https://doi.org/10.1002/eom2.70013
  40. G. Liang, B. Liang, A. Chen, J. Zhu, Q. Li et al., Development of rechargeable high-energy hybrid zinc-iodine aqueous batteries exploiting reversible chlorine-based redox reaction. Nat. Commun. 14(1), 1856 (2023). https://doi.org/10.1038/s41467-023-37565-y
  41. C.L. Bentley, A.M. Bond, A.F. Hollenkamp, P.J. Mahon, J. Zhang, Electrochemistry of iodide, iodine, and iodine monochloride in chloride containing nonhaloaluminate ionic liquids. Anal. Chem. 88(3), 1915–1921 (2016). https://doi.org/10.1021/acs.analchem.5b04332
  42. H. Wu, J. Hao, S. Zhang, Y. Jiang, Y. Zhu et al., Aqueous zinc–iodine pouch cells with long cycling life and low self-discharge. J. Am. Chem. Soc. 146(24), 16601–16608 (2024). https://doi.org/10.1021/jacs.4c03518
  43. T.H. Wan, M. Saccoccio, C. Chen, F. Ciucci, Influence of the discretization methods on the distribution of relaxation times deconvolution: implementing radial basis functions with DRTtools. Electrochim. Acta 184, 483–499 (2015). https://doi.org/10.1016/j.electacta.2015.09.097
  44. Y. Lu, C.-Z. Zhao, J.-Q. Huang, Q. Zhang, The timescale identification decoupling complicated kinetic processes in lithium batteries. Joule 6(6), 1172–1198 (2022). https://doi.org/10.1016/j.joule.2022.05.005
  45. D.-Q. Cai, H. Xu, T. Xue, J.-L. Yang, H.J. Fan, A synchronous strategy to Zn-iodine battery by polycationic long-chain molecules. Nano-Micro Lett. 18(1), 3 (2025). https://doi.org/10.1007/s40820-025-01854-6
  46. X. Li, Y. Wang, J. Lu, S. Li, P. Li et al., Three-electron transfer-based high-capacity organic lithium-iodine (chlorine) batteries. Angew. Chem. Int. Ed. 62(42), e202310168 (2023). https://doi.org/10.1002/anie.202310168
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY FILE

Most read articles by the same author(s)

1 2 > >>