Issue

Vol. 18 (2026)

Self-Separating Biphasic Electrolyte Enables High-Performance Aqueous Zinc-Ion Batteries via Electron-Enriched Interphase Engineering

https://doi.org/10.1007/s40820-026-02219-3
Chengwu Yang
State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, People’s Republic of China
Pattaraporn Woottapanit
Department of Materials Science, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand
Qizhi Hou
State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, People’s Republic of China
Zhiqiang Dai
State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, People’s Republic of China
Wanwisa Limphirat
Synchrotron Light Research Institute (Public Organization), Nakhon Ratchasima 30000, Thailand
Jiaqian Qin
Department of Materials Science, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand
Xinyu Zhang
State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, People’s Republic of China

Corresponding Author: Xinyu Zhang

xyzhang@ysu.edu.cn

Nano-Micro Letters, Vol. 18 (2026), Article Number: 367

Abstract

Aqueous Zn-ion batteries encounter significant challenges, including unstable electrolyte interfaces and dendrite formation, which curtail their cycle life and metal utilization. Here, we present a self-separating biphasic electrolyte through phase separation of poly (3,4-ethylenedioxythiophene): poly (styrenesulfonic acid) (PEDOT:PSS) conductive polymers in Zn sulfate solution driven by a mechanical shear-ionic crosslinking process. The negatively charged sulfonic groups in PSS disrupt the hydrogen-bonding network of bulk electrolyte and remodel solvation structure of Zn2+ ions, enhancing ionic transfer kinetics and facilitating desolvation. Meanwhile, the insoluble PEDOT fibers with continuous conjugated thiophene ring together with sulfonic groups in PSS spontaneously adhere to the electrode surface, establishing a robust electron-rich interphase that regulates electric double layer thickness, promotes uniform Zn deposition and repels sulfate ions. Consequently, this electrolyte allows Zn anodes to achieve exceptional stability and longevity even at larger depths of discharge (68.4% and 94.1%) and delivers outstanding cyclability exceeding 10,000 cycles in Zn||V2O5 full cells.


Highlights:
1 A self-separating biphasic electrolyte was developed via mechanical shear-ionic crosslinking phase separation of poly(3,4-ethylenedioxythiophene): poly(styrenesulfonic acid) (PEDOT:PSS).
2 The insoluble PEDOT fibers and the soluble PSS establish an electron-rich interphase to improve the Zn anode performance.
3 Zn anodes achieve exceptional stability at large depths of discharge and deliver outstanding cyclability exceeding 10,000 cycles in full cells.

Keywords

Zn-ion batteries Biphasic electrolyte PEDOT:PSS Hydrogen-bonding network Electrode interphase
Yang, Chengwu, Pattaraporn Woottapanit, Qizhi Hou, Zhiqiang Dai, Wanwisa Limphirat, Jiaqian Qin, and Xinyu Zhang. 2026. “Self-Separating Biphasic Electrolyte Enables High-Performance Aqueous Zinc-Ion Batteries via Electron-Enriched Interphase Engineering”. Nano-Micro Letters 18 (May):367. https://doi.org/10.1007/s40820-026-02219-3.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. B. Yang, Q. Zhang, H. Huang, H. Pan, W. Zhu et al., Engineering relaxors by entropy for high energy storage performance. Nat. Energy 8(9), 956–964 (2023). https://doi.org/10.1038/s41560-023-01300-0
  2. K. Liu, Y. Liu, D. Lin, A. Pei, Y. Cui, Materials for lithium-ion battery safety. Sci. Adv. 4(6), eaas9820 (2018). https://doi.org/10.1126/sciadv.aas9820
  3. J. Wei, P. Zhang, J. Sun, Y. Liu, F. Li et al., Advanced electrolytes for high-performance aqueous Zinc-ion batteries. Chem. Soc. Rev. 53(20), 10335–10369 (2024). https://doi.org/10.1039/d4cs00584h
  4. C. Yang, P. Woottapanit, S. Geng, K. Lolupiman, X. Zhang et al., Highly reversible Zn anode design through oriented ZnO(002) facets. Adv. Mater. 36(49), 2408908 (2024). https://doi.org/10.1002/adma.202408908
  5. Y.-F. Qu, J.-W. Qian, F. Zhang, Z. Zhu, Y. Zhu et al., Constructing 3D crosslinked macromolecular networks as a highly efficient interface layer for ultra-stable Zn metal anodes. Adv. Mater. 37(1), 2413370 (2025). https://doi.org/10.1002/adma.202413370
  6. Y. He, Z. Chen, Q. Gao, J. Feng, Z. Hao, Dynamic interface modulation of aqueous Zinc–ion batteries by rational design of organic additives. Small 21(40), e06244 (2025). https://doi.org/10.1002/smll.202506244
  7. C. Yang, P. Woottapanit, Y. Yue, S. Geng, J. Cao et al., Industrial waste derived separators for Zn-ion batteries achieve homogeneous Zn(002) deposition through low chemical affinity effects. Small 20(26), 2311203 (2024). https://doi.org/10.1002/smll.202311203
  8. R. Pan, Y. Xie, B. Jiang, T. Liu, Y. Han et al., Flexible and dynamic interfacial desolvation in high-entropy electrolyte for dendrite-free aqueous Zinc-ion batteries. Adv. Mater. 38(2), e12633 (2026). https://doi.org/10.1002/adma.202512633
  9. H. Wu, S.-J. Zhang, Y. Jiang, M. Jaroniec, J. Hao et al., Self-discharge behaviors in aqueous batteries. Angew. Chem. Int. Ed. 65(7), e20601 (2026). https://doi.org/10.1002/anie.202520601
  10. L. Wu, H. Yuan, Y. An, J. Sun, Y. Liu et al., Sulfurized composite interphase enables a highly reversible Zn anode. Angew. Chem. Int. Ed. 64(7), e202419495 (2025). https://doi.org/10.1002/anie.202419495
  11. J. Wang, Y. Ochiai, N. Wu, K. Adachi, D. Inoue et al., Intrinsically stretchable organic photovoltaics by redistributing strain to PEDOT: PSS with enhanced stretchability and interfacial adhesion. Nat. Commun. 15(1), 4902 (2024). https://doi.org/10.1038/s41467-024-49352-4
  12. M. Gu, L. Travaglini, D. Ta, J. Hopkins, A. Lauto et al., A PEDOT based graft copolymer with enhanced electronic stability. Mater. Horiz. 11(19), 4809–4818 (2024)
  13. B. Chen, D. Xu, S. Chai, Z. Chang, A. Pan, Enhanced silicon anodes with robust SEI formation enabled by functional conductive binder. Adv. Funct. Mater. 34(34), 2401794 (2024). https://doi.org/10.1002/adfm.202401794
  14. G. Kresse, J. Hafner, Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47(1), 558–561 (1993). https://doi.org/10.1103/physrevb.47.558
  15. P. Blöchl, Projector augmented-wave method. Phys. Rev. B 50(24), 17953–17979 (1994). https://doi.org/10.1103/physrevb.50.17953
  16. 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
  17. G. Henkelman, H. Jónsson, Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. J. Chem. Phys. 113(22), 9978–9985 (2000). https://doi.org/10.1063/1.1323224
  18. I.T. Todorov, W. Smith, K. Trachenko, M.T. Dove, DL_POLY3: new dimensions in molecular dynamics simulations via massive parallelism. J. Mater. Chem. 16(20), 1911–1918 (2006). https://doi.org/10.1039/b517931a
  19. S. Nosé, A molecular dynamics method for simulations in the canonical ensemble. Mol. Phys. 52(2), 255–268 (1984). https://doi.org/10.1080/00268978400101201
  20. P.P. Ewald, Die berechnung optischer und elektrostatischer gitterpotentiale. Ann. Phys. (Leipz) 369(3), 253–287 (1921). https://doi.org/10.1002/andp.19213690304
  21. H.J.C. Berendsen, J.R. Grigera, T.P. Straatsma, The missing term in effective pair potentials. J. Phys. Chem. 91(24), 6269–6271 (1987). https://doi.org/10.1021/j100308a038
  22. M.P. Allen, D.J. Tildesley, Computer Simulation of Liquids (Oxford university press, 2017)
  23. S.L. Mayo, B.D. Olafson, W.A. Goddard, DREIDING: a generic force field for molecular simulations. J. Phys. Chem. 94(26), 8897–8909 (1990). https://doi.org/10.1021/j100389a010
  24. H.A. Lorentz, Ueber die Anwendung des Satzes vom Virial in der kinetischen Theorie der Gase. Ann. Phys. 248(1), 127–136 (1881). https://doi.org/10.1002/andp.18812480110
  25. C.M. Breneman, K.B. Wiberg, Determining atom-centered monopoles from molecular electrostatic potentials. The need for high sampling density in formamide conformational analysis. J. Comput. Chem. 11(3), 361–373 (1990). https://doi.org/10.1002/jcc.540110311
  26. M. Karabacak, Z. Cinar, M. Kurt, S. Sudha, N. Sundaraganesan, FT-IR, FT-Raman, NMR and UV-vis spectra, vibrational assignments and DFT calculations of 4-butyl benzoic acid. Spectrochim. Acta A Mol. Biomol. Spectrosc. 85(1), 179–189 (2012). https://doi.org/10.1016/j.saa.2011.09.058
  27. D. Zheng, X.-A. Yuan, H. Ma, X. Li, X. Wang et al., Unexpected solvent effects on the UV/Vis absorption spectra of o-cresol in toluene and benzene: in contrast with non-aromatic solvents. R. Soc. Open Sci. 5(3), 171928 (2018). https://doi.org/10.1098/rsos.171928
  28. F.H. Cristovan, C.M. Nascimento, M.J.V. Bell, E. Laureto, J.L. Duarte et al., Synthesis and optical characterization of poly(styrene sulfonate) films doped with Nd(III). Chem. Phys. 326(2–3), 514–520 (2006). https://doi.org/10.1016/j.chemphys.2006.03.014
  29. H.S.O. Chan, S.C. Ng, Synthesis, characterization and applications of thiophene-based functional polymers. Prog. Polym. Sci. 23(7), 1167–1231 (1998). https://doi.org/10.1016/S0079-6700(97)00032-4
  30. A. Tamanai, S. Beck, A. Pucci, Mid-infrared characterization of thiophene-based thin polymer films. Displays 34(5), 399–405 (2013). https://doi.org/10.1016/j.displa.2013.08.005
  31. Y. Deng, H. Wang, M. Fan, B. Zhan, L.-J. Zuo et al., Nanomicellar electrolyte to control release ions and reconstruct hydrogen bonding network for ultrastable high-energy-density Zn-Mn battery. J. Am. Chem. Soc. 145(36), 20109–20120 (2023). https://doi.org/10.1021/jacs.3c07764
  32. H. Jiang, L. Tang, Y. Fu, S. Wang, S.K. Sandstrom et al., Chloride electrolyte enabled practical zinc metal battery with a near-unity coulombic efficiency. Nat. Sustain. 6(7), 806–815 (2023). https://doi.org/10.1038/s41893-023-01092-x
  33. Y. Chen, Z. Deng, Y. Sun, Y. Li, H. Zhang et al., Ultrathin zincophilic interphase regulated electric double layer enabling highly stable aqueous zinc-ion batteries. Nano-Micro. Lett. 16(1), 96 (2024). https://doi.org/10.1007/s40820-023-01312-1
  34. P. Woottapanit, C. Yang, S. Geng, K. Lolupiman, W. Limphirat et al., Electron donation effect of α-boron nanosheet enables highly stable zinc metal anode. Adv. Funct. Mater. 35(46), e2507725 (2025). https://doi.org/10.1002/adfm.202507725
  35. P. Xu, F. Huang, Z. Liu, S. Guo, S. Liang et al., In situ construction of NaF-rich solid electrolyte interphase with metallic Ce sites for stable anode-free sodium metal batteries. Angew. Chem. Int. Ed. Engl. 64(49), e202515566 (2025). https://doi.org/10.1002/anie.202515566
  36. M. Li, Z. Liu, Y. Zhang, S. Liang, X. Wang et al., Anchored Zn(002) orientation with rapid interfacial response guiding high-utilization alloy anode and ah-scale aqueous zinc metal batteries. Angew. Chem. Int. Ed. 65(2), e17845 (2026). https://doi.org/10.1002/anie.202517845
  37. X. Wei, J. Guan, Y. Mu, Y. Zou, X. Wei et al., Decoding hydrogen-bond network of electrolyte for cryogenic durable aqueous zinc-ion batteries. Nano-Micro Lett. 18(1), 127 (2026). https://doi.org/10.1007/s40820-025-01970-3
  38. K. Yang, H. Fu, Y. Duan, Z. Ma, D. Wang et al., Poloxamer pre-solvation sheath ion encapsulation strategy for zinc anode–electrolyte interfaces. ACS Energy Lett. 9(1), 209–217 (2024). https://doi.org/10.1021/acsenergylett.3c02337
  39. C. Huang, J. Mao, S. Li, W. Zhang, X. Wang et al., Amphoteric polymer strategy with buffer-adsorption mechanism for long-life aqueous zinc ion batteries. Adv. Funct. Mater. 34(26), 2315855 (2024). https://doi.org/10.1002/adfm.202315855
  40. N. Wang, X. Chen, H. Wan, B. Zhang, K. Guan et al., Zincophobic electrolyte achieves highly reversible zinc-ion batteries. Adv. Funct. Mater. 33(27), 2300795 (2023). https://doi.org/10.1002/adfm.202300795
  41. K. Guan, W. Chen, Y. Yang, F. Ye, Y. Hong et al., A dual salt/dual solvent electrolyte enables ultrahigh utilization of zinc metal anode for aqueous batteries. Adv. Mater. 36(38), 2405889 (2024). https://doi.org/10.1002/adma.202405889
  42. J. Zhu, M. Yang, Y. Hu, M. Yao, J. Chen et al., The construction of binary phase electrolyte interface for highly stable zinc anodes. Adv. Mater. 36(3), 2304426 (2024). https://doi.org/10.1002/adma.202304426
  43. H. Peng, C. Wang, D. Wang, X. Song, C. Zhang et al., Dynamic Zn/electrolyte interphase and enhanced cation transfer of sol electrolyte for all-climate aqueous zinc metal batteries. Angew. Chem. Int. Ed. 62(34), e202308068 (2023). https://doi.org/10.1002/anie.202308068
  44. M. Yang, J. Zhu, S. Bi, R. Wang, H. Wang et al., The construction of anion-induced solvation structures in low-concentration electrolyte for stable zinc anodes. Angew. Chem. Int. Ed. 63(15), e202400337 (2024). https://doi.org/10.1002/anie.202400337
  45. P. Cui, T. Wang, Z. Wang, H. Geng, P. Song et al., Co-solvent electrolyte-induced zinc anode surface reconstruction for high performance zinc ion batteries. Chem. Eng. J. 500, 156971 (2024). https://doi.org/10.1016/j.cej.2024.156971
  46. 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
  47. W. Deng, Z. Xu, X. Wang, High-donor electrolyte additive enabling stable aqueous zinc-ion batteries. Energy. Storage. Mater. 52, 52–60 (2022). https://doi.org/10.1016/j.ensm.2022.07.032
  48. T. Yan, M. Tao, J. Liang, G. Zheng, B. Wu et al., Refining the inner Helmholtz plane adsorption for achieving a stable solid-electrolyte interphase in reversible aqueous Zn-ion pouch cells. Energy. Storage. Mater. 65, 103190 (2024). https://doi.org/10.1016/j.ensm.2024.103190
  49. M. Wu, Y. Zhang, L. Xu, C. Yang, M. Hong et al., A sustainable chitosan-zinc electrolyte for high-rate zinc-metal batteries. Matter 5(10), 3402–3416 (2022). https://doi.org/10.1016/j.matt.2022.07.015
  50. Y. Wang, Q. Li, H. Hong, S. Yang, R. Zhang et al., Lean-water hydrogel electrolyte for zinc ion batteries. Nat. Commun. 14(1), 3890 (2023). https://doi.org/10.1038/s41467-023-39634-8
  51. S. Wang, Y. Zhao, H. Lv, X. Hu, J. He et al., Low-concentration redox-electrolytes for high-rate and long-life zinc metal batteries. Small 20(50), 2207664 (2024). https://doi.org/10.1002/smll.202207664
  52. L. Yao, L. Jiang, Y. Wang, X. Chi, Y. Liu, A 1000 wh kg-1 cathode facilitated by in situ mineralized electrolyte with electron potential well for high-energy aqueous zinc batteries. Adv. Mater. 37(41), e05342 (2025). https://doi.org/10.1002/adma.202505342
  53. 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
  54. Q. Li, D. Luo, Q. Ma, Z. Zheng, S. Li et al., Designing a bridging solvation structure using recessive solvents for high energy density aqueous zinc-ion batteries with 88% depth of discharge zinc rechargeability. Energy Environ. Sci. 18(3), 1489–1501 (2025). https://doi.org/10.1039/D4EE04847D
  55. N. Hu, W. Lv, W. Chen, H. Tang, X. Zhang et al., A double-charged organic molecule additive to customize electric double layer for super-stable and deep-rechargeable Zn metal pouch batteries. Adv. Funct. Mater. 34(8), 2311773 (2024). https://doi.org/10.1002/adfm.202311773
  56. J. Heo, D. Dong, Z. Wang, F. Chen, C. Wang, Electrolyte design for aqueous Zn batteries. Joule 9(4), 101844 (2025). https://doi.org/10.1016/j.joule.2025.101844
  57. J. Li, J. Ba, C. Zhao, F. Duan, X. Yin et al., A hydrophobic and high surface charge phosphate interphase for high areal capacity zinc metal batteries. Adv. Mater. 37(34), 2501956 (2025). https://doi.org/10.1002/adma.202501956
  58. Y. Wang, B. Liang, J. Zhu, G. Li, Q. Li et al., Manipulating electric double layer adsorption for stable solid-electrolyte interphase in 2.3 Ah Zn-pouch cells. Angew. Chem. Int. Ed. 62(23), e202302583 (2023). https://doi.org/10.1002/anie.202302583
  59. R. Xue, Z. Wang, N. Yao, Y. Liu, H. Wang et al., Multiscale interfacial regulation of Zn-V2O5 pouch cell via ultrathin molecular-engineered separator. Adv. Funct. Mater. 34(30), 2400959 (2024). https://doi.org/10.1002/adfm.202400959
  60. X. Zheng, R. Luo, Z. Liu, M. Wang, M. Sajid et al., A practical zinc-bromine pouch cell enabled by electrolyte dynamic stabilizer. Mater. Today 80, 353–364 (2024). https://doi.org/10.1016/j.mattod.2024.09.015
  61. H. Yang, R. Zhu, Y. Yang, Z. Lu, Z. Chang et al., Sustainable high-energy aqueous zinc–manganese dioxide batteries enabled by stress-governed metal electrodeposition and fast zinc diffusivity. Energy Environ. Sci. 16(5), 2133–2141 (2023). https://doi.org/10.1039/D2EE03777G
  62. J. Ji, H. Du, Z. Zhu, X. Qi, F. Zhou et al., Thin zinc electrodes stabilized with organobromine-partnered H2O−Zn−MeOH cluster ions for practical zinc-metal pouch cells. Angew. Chem. Int. Ed. 64(2), e202414562 (2025). https://doi.org/10.1002/anie.202414562
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY FILE

Most read articles by the same author(s)