Issue

Vol. 17 (2025)

Aligned Ion Conduction Pathway of Polyrotaxane-Based Electrolyte with Dispersed Hydrophobic Chains for Solid-State Lithium–Oxygen Batteries

https://doi.org/10.1007/s40820-024-01535-w
Bitgaram Kim
Department of Materials Science and Engineering, Korea University, 145 Anam‑Ro, Seongbuk‑Gu, Seoul 02841, Republic of Korea
Myeong‑Chang Sung
School of Civil, Environmental and Architectural Engineering, Korea University, 145 Anam‑Ro, Seongbuk‑Gu, Seoul 02841, Republic of Korea
Gwang‑Hee Lee
Materials Science and Chemical Engineering Center, Institute for Advanced Engineering (IAE), Yongin 17180, Republic of Korea
Byoungjoon Hwang
School of Civil, Environmental and Architectural Engineering, Korea University, 145 Anam‑Ro, Seongbuk‑Gu, Seoul 02841, Republic of Korea
Sojung Seo
Department of Materials Science and Engineering, Korea University, 145 Anam‑Ro, Seongbuk‑Gu, Seoul 02841, Republic of Korea
Ji‑Hun Seo
Department of Materials Science and Engineering, Korea University, 145 Anam‑Ro, Seongbuk‑Gu, Seoul 02841, Republic of Korea
Dong‑Wan Kim
School of Civil, Environmental and Architectural Engineering, Korea University, 145 Anam‑Ro, Seongbuk‑Gu, Seoul 02841, Republic of Korea

Corresponding Author: Dong‑Wan Kim

dwkim1@korea.ac.kr

Nano-Micro Letters, Vol. 17 (2025), Article Number: 31

Abstract

A critical challenge hindering the practical application of lithium–oxygen batteries (LOBs) is the inevitable problems associated with liquid electrolytes, such as evaporation and safety problems. Our study addresses these problems by proposing a modified polyrotaxane (mPR)-based solid polymer electrolyte (SPE) design that simultaneously mitigates solvent-related problems and improves conductivity. mPR-SPE exhibits high ion conductivity (2.8 × 10−3 S cm−1 at 25 °C) through aligned ion conduction pathways and provides electrode protection ability through hydrophobic chain dispersion. Integrating this mPR-SPE into solid-state LOBs resulted in stable potentials over 300 cycles. In situ Raman spectroscopy reveals the presence of an LiO2 intermediate alongside Li2O2 during oxygen reactions. Ex situ X-ray diffraction confirm the ability of the SPE to hinder the permeation of oxygen and moisture, as demonstrated by the air permeability tests. The present study suggests that maintaining a low residual solvent while achieving high ionic conductivity is crucial for restricting the sub-reactions of solid-state LOBs.


Highlights:
1 Strategic materials design of polyrotaxane-based electrolytes was suggested by aligning the ion conduction pathways and dispersing hydrophobic chains for solid-state Li–O2 batteries.
2 Owing to intentional design, solid-state Li–O2 battery resulted in stable potential over 300 cycles at 25 °C.

Keywords

Solid polymer electrolyte Lithium-oxygen batteries Polyrotaxane ion conductivity Hydrophobic chain
Kim, Bitgaram, Myeong‑Chang Sung, Gwang‑Hee Lee, Byoungjoon Hwang, Sojung Seo, Ji‑Hun Seo, and Dong‑Wan Kim. 2024. “Aligned Ion Conduction Pathway of Polyrotaxane-Based Electrolyte With Dispersed Hydrophobic Chains for Solid-State Lithium–Oxygen Batteries”. Nano-Micro Letters 17 (October):31. https://doi.org/10.1007/s40820-024-01535-w.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. C. Shu, J. Long, S.-X. Dou, J. Wang, Component-interaction reinforced quasi-solid electrolyte with multifunctionality for flexible Li–O2 battery with superior safety under extreme conditions. Small 15, e1804701 (2019). https://doi.org/10.1002/smll.201804701
  2. P. Tan, M. Liu, Z. Shao, M. Ni, Recent advances in perovskite oxides as electrode materials for nonaqueous lithium–oxygen batteries. Adv. Energy Mater. 7, 1602674 (2017). https://doi.org/10.1002/aenm.201602674
  3. T. Liu, J.P. Vivek, E.W. Zhao, J. Lei, N. Garcia-Araez et al., Current challenges and routes forward for nonaqueous lithium-air batteries. Chem. Rev. 120, 6558–6625 (2020). https://doi.org/10.1021/acs.chemrev.9b00545
  4. C.H. Kim, M.-C. Sung, B. Hwang, D.-W. Kim, Cu3P nanoarrays derived from 7, 7, 8, 8-tetracyanoquinodimethane for high-rate electrocatalytic oxygen reactions of lithium-oxygen batteries. Int. J. Energy Res. 2024, 1756429 (2024). https://doi.org/10.1155/2024/1756429
  5. X. Chen, Y. Zhang, C. Chen, H. Li, Y. Lin et al., Atomically dispersed ruthenium catalysts with open hollow structure for lithium–oxygen batteries. Nano-Micro Lett. 16, 27 (2023). https://doi.org/10.1007/s40820-023-01240-0
  6. W.-J. Kwak, D. Rosy, C. Sharon, H.K. Xia et al., Lithium-oxygen batteries and related systems: potential, status, and future. Chem. Rev. 120, 6626–6683 (2020). https://doi.org/10.1021/acs.chemrev.9b00609
  7. Z. Zhang, W.-Q. Han, From liquid to solid-state lithium metal batteries: fundamental issues and recent developments. Nano-Micro Lett. 16, 24 (2023). https://doi.org/10.1007/s40820-023-01234-y
  8. Z. Huang, J. Ren, W. Zhang, M. Xie, Y. Li et al., Protecting the Li-metal anode in a Li–O2 battery by using boric acid as an SEI-forming additive. Adv. Mater. 30, e1803270 (2018). https://doi.org/10.1002/adma.201803270
  9. G.-H. Lee, M.-C. Sung, D.-W. Kim, Synergistic coupling of a self-defense redox mediator and anti-superoxide disproportionator in lithium-oxygen batteries for high stability. Chem. Eng. J. 453, 139878 (2023). https://doi.org/10.1016/j.cej.2022.139878
  10. H. Liang, L. Wang, A. Wang, Y. Song, Y. Wu et al., Tailoring practically accessible polymer/inorganic composite electrolytes for all-solid-state lithium metal batteries: a review. Nano-Micro Lett. 15, 42 (2023). https://doi.org/10.1007/s40820-022-00996-1
  11. D. Zhou, D. Shanmukaraj, A. Tkacheva, M. Armand, G. Wang, Polymer electrolytes for lithium-based batteries: advances and prospects. Chem 5, 2326–2352 (2019). https://doi.org/10.1016/j.chempr.2019.05.009
  12. B. Kim, S.H. Yang, J.-H. Seo, Y.C. Kang, Inducing an amorphous phase in polymer plastic crystal electrolyte for effective ion transportation in lithium metal batteries. Adv. Funct. Mater. 34, 2310957 (2024). https://doi.org/10.1002/adfm.202310957
  13. K. Kimura, J. Motomatsu, Y. Tominaga, Correlation between solvation structure and ion-conductive behavior of concentrated poly(ethylene carbonate)-based electrolytes. J. Phys. Chem. C 120, 12385–12391 (2016). https://doi.org/10.1021/acs.jpcc.6b03277
  14. J. Zheng, W. Li, X. Liu, J. Zhang, X. Feng et al., Progress in gel polymer electrolytes for sodium-ion batteries. Energy Environ. Mater. 6, 12422 (2023). https://doi.org/10.1002/eem2.12422
  15. Y. Liu, P. He, H. Zhou, Rechargeable solid-state Li–air and Li–S batteries: materials, construction, and challenges. Adv. Energy Mater. 8, 1701602 (2018). https://doi.org/10.1002/aenm.201701602
  16. W. Yu, C. Xue, B. Hu, B. Xu, L. Li et al., Oxygen- and dendrite-resistant ultra-dry polymer electrolytes for solid-state Li–O2 batteries. Energy Storage Mater. 27, 244–251 (2020). https://doi.org/10.1016/j.ensm.2020.02.001
  17. C. Yang, Q. Wu, W. Xie, X. Zhang, A. Brozena et al., Copper-coordinated cellulose ion conductors for solid-state batteries. Nature 598, 590–596 (2021). https://doi.org/10.1038/s41586-021-03885-6
  18. L.F. Hart, J.E. Hertzog, P.M. Rauscher, B.W. Rawe, M.M. Tranquilli et al., Material properties and applications of mechanically interlocked polymers. Nat. Rev. Mater. 6, 508–530 (2021). https://doi.org/10.1038/s41578-021-00278-z
  19. J. Seo, G.-H. Lee, J. Hur, M.-C. Sung, J.-H. Seo et al., Mechanically interlocked polymer electrolyte with built-In fast molecular shuttles for all-solid-state lithium batteries. Adv. Energy Mater. 11, 2170173 (2021). https://doi.org/10.1002/aenm.202170173
  20. M. Inutsuka, K. Inoue, Y. Hayashi, A. Inomata, Y. Sakai et al., Highly dielectric and flexible polyrotaxane elastomer by introduction of cyano groups. Polymer 59, 10–15 (2015). https://doi.org/10.1016/j.polymer.2014.12.055
  21. J. Seo, B. Kim, M.-S. Kim, J.-H. Seo, Optimization of anisotropic crystalline structure of molecular necklace-like polyrotaxane for tough piezoelectric elastomer. ACS Macro Lett. 10, 1371–1376 (2021). https://doi.org/10.1021/acsmacrolett.1c00567
  22. K. Kato, T. Mizusawa, H. Yokoyama, K. Ito, Effect of topological constraint and confined motions on the viscoelasticity of polyrotaxane glass with different interactions between rings. J. Phys. Chem. C 121, 1861–1869 (2017). https://doi.org/10.1021/acs.jpcc.6b11362
  23. Q. Lin, L. Li, M. Tang, S. Uenuma, J. Samanta et al., Kinetic trapping of 3D-printable cyclodextrin-based poly(pseudo)rotaxane networks. Chem 7, 2442–2459 (2021). https://doi.org/10.1016/j.chempr.2021.06.004
  24. J. Seo, J. Hur, M.-S. Kim, T.-G. Lee, S.J. Seo et al., All-organic piezoelectric elastomer formed through the optimal cross-linking of semi-crystalline polyrotaxanes. Chem. Eng. J. 426, 130792 (2021). https://doi.org/10.1016/j.cej.2021.130792
  25. R. Baskaran, S. Selvasekarapandian, N. Kuwata, J. Kawamura, T. Hattori, Structure, thermal and transport properties of PVAc–LiClO4 solid polymer electrolytes. J. Phys. Chem. Solids 68, 407–412 (2007). https://doi.org/10.1016/j.jpcs.2006.12.001
  26. Y. Deng, Q. Zhang, B.L. Feringa, H. Tian, D.-H. Qu, Toughening a self-healable supramolecular polymer by ionic cluster-enhanced iron-carboxylate complexes. Angew. Chem. Int. Ed. 59, 5278–5283 (2020). https://doi.org/10.1002/anie.201913893
  27. B. Kim, M. Jang, S. Heo, M.-S. Kim, J.-H. Seo, Mechanically robust cellulose-based piezoelectric elastomer formed by slidable polyrotaxane cross-linker. ACS Macro Lett. 12, 1705–1710 (2023). https://doi.org/10.1021/acsmacrolett.3c00576
  28. L. Stolz, S. Röser, G. Homann, M. Winter, J. Kasnatscheew, Pragmatic approaches to correlate between the physicochemical properties of a linear poly(ethylene oxide)-based solid polymer electrolyte and the performance in a high-voltage Li-metal battery. J. Phys. Chem. C 125, 18089–18097 (2021). https://doi.org/10.1021/acs.jpcc.1c03614
  29. S. Chen, Y. Li, Y. Wang, Z. Li, C. Peng et al., Cross-linked single-ion solid polymer electrolytes with alternately distributed lithium sources and ion-conducting segments for lithium metal batteries. Macromolecules 54, 9135–9144 (2021). https://doi.org/10.1021/acs.macromol.1c01102
  30. Y. Wei, L. Hu, J. Yao, Z. Shao, X. Chen, Facile dissolution of zein using a common solvent dimethyl sulfoxide. Langmuir 35, 6640–6649 (2019). https://doi.org/10.1021/acs.langmuir.9b00670
  31. X. Zhang, J. Han, X. Niu, C. Xin, C. Xue et al., High cycling stability for solid-state Li metal batteries via regulating solvation effect in poly(vinylidene fluoride)-based electrolytes. Batter. Supercaps 3, 876–883 (2020). https://doi.org/10.1002/batt.202000081
  32. Z. Zhou, R. Zou, Z. Liu, P. Zhang, Deciphering the role of tetrahydrofuran residue in the poly(ethylene oxide)/LiTFSI hybrid used for secondary battery electrolyte. Giant 6, 100056 (2021). https://doi.org/10.1016/j.giant.2021.100056
  33. B. Yiming, Y. Han, Z. Han, X. Zhang, Y. Li et al., A mechanically robust and versatile liquid-free ionic conductive elastomer. Adv. Mater. 33, e2006111 (2021). https://doi.org/10.1002/adma.202006111
  34. B. Kim, Y.J. Cho, D.-G. Kim, J.-H. Seo, Ion conducting elastomer designed from thiourea-based dynamic covalent bonds with reprocessing capability. Mater. Today Chem. 30, 101583 (2023). https://doi.org/10.1016/j.mtchem.2023.101583
  35. Y. Xiao, R. Xu, C. Yan, Y. Liang, J.-F. Ding et al., Waterproof lithium metal anode enabled by cross-linking encapsulation. Sci. Bull. 65, 909–916 (2020). https://doi.org/10.1016/j.scib.2020.02.022
  36. B.G. Kim, J.-S. Kim, J. Min, Y.-H. Lee, J.H. Choi et al., A moisture- and oxygen-impermeable separator for aprotic Li–O2 batteries. Adv. Funct. Mater. 26, 1747–1756 (2016). https://doi.org/10.1002/adfm.201504437
  37. R. Li, Y. Fan, C. Zhao, A. Hu, B. Zhou et al., Air-stable protective layers for lithium anode achieving safe lithium metal batteries. Small Methods 7, e2201177 (2023). https://doi.org/10.1002/smtd.202201177
  38. M. Xia, H. Fu, K. Lin, A.M. Rao, L. Cha et al., Hydrogen-bond regulation in organic/aqueous hybrid electrolyte for safe and high-voltage K-ion batteries. Energy Environ. Sci. 17, 1255–1265 (2024). https://doi.org/10.1039/D3EE03729K
  39. W. Lyu, X. Yu, Y. Lv, A.M. Rao, J. Zhou et al., Building stable solid-state potassium metal batteries. Adv. Mater. 36, e2305795 (2024). https://doi.org/10.1002/adma.202305795
  40. Y. Xia, Y.F. Liang, D. Xie, X.L. Wang, S.Z. Zhang et al., A poly (vinylidene fluoride-hexafluoropropylene) based three-dimensional network gel polymer electrolyte for solid-state lithium-sulfur batteries. Chem. Eng. J. 358, 1047–1053 (2019). https://doi.org/10.1016/j.cej.2018.10.092
  41. H. Xia, G. Xu, X. Cao, C. Miao, H. Zhang et al., Single-ion-conducting hydrogel electrolytes based on slide-ring pseudo-polyrotaxane for ultralong-cycling flexible zinc-ion batteries. Adv. Mater. 35, e2301996 (2023). https://doi.org/10.1002/adma.202301996
  42. C. Piedrahita, V. Kusuma, H.B. Nulwala, T. Kyu, Highly conductive, flexible polymer electrolyte membrane based on poly(ethylene glycol) diacrylate-co-thiosiloxane network. Solid State Ion. 322, 61–68 (2018). https://doi.org/10.1016/j.ssi.2018.05.006
  43. K. Yamada, S. Yuasa, R. Matsuoka, R. Sai, Y. Katayama et al., Improved ionic conductivity for amide-containing electrolytes by tuning intermolecular interaction: the effect of branched side-chains with cyanoethoxy groups. Phys. Chem. Chem. Phys. 23, 10070–10080 (2021). https://doi.org/10.1039/d1cp00852h
  44. Q. Qiu, Z.-Z. Pan, P. Yao, J. Yuan, C. Xia et al., A 98.2% energy efficiency Li–O2 battery using a LaNi−0.5Co0.5O3 perovskite cathode with extremely fast oxygen reduction and evolution kinetics. Chem. Eng. J. 452, 139608 (2023). https://doi.org/10.1016/j.cej.2022.139608
  45. X. Zou, Q. Lu, Y. Zhong, K. Liao, W. Zhou et al., Flexible, flame-resistant, and dendrite-impermeable gel-polymer electrolyte for Li–O2/air batteries workable under hurdle conditions. Small 14, e1801798 (2018). https://doi.org/10.1002/smll.201801798
  46. L. Johnson, C. Li, Z. Liu, Y. Chen, S.A. Freunberger et al., The role of LiO2 solubility in O2 reduction in aprotic solvents and its consequences for Li–O2 batteries. Nat. Chem. 6, 1091–1099 (2014). https://doi.org/10.1038/nchem.2101
  47. Z. Rao, P. Lyu, P. Du, D. He, Y. Huo et al., Thermal safety and thermal management of batteries. Battery Energy 1, 210019 (2022). https://doi.org/10.1002/bte2.20210019
  48. S.G. Mohamed, Y.Q. Tsai, C.J. Chen, Y.T. Tsai, T.F. Hung et al., Ternary spinel MCo2O4 (M=Mn, Fe, Ni, and Zn) porous nanorods as bifunctional cathode materials for lithium–O2 batteries. ACS Appl. Mater. Interfaces 7, 12038–12046 (2015). https://doi.org/10.1021/acsami.5b02180
  49. Y.-G. Wu, X.-B. Zhu, W.-H. Wan, Z.-N. Man, Y. Wang et al., Advanced engineering for cathode in lithium–oxygen batteries: flexible 3D hierarchical porous architecture design and its functional modification. Adv. Funct. Mater. 31, 2105664 (2021). https://doi.org/10.1002/adfm.202105664
  50. A. Kondori, M. Esmaeilirad, A.M. Harzandi, R. Amine, M.T. Saray et al., A room temperature rechargeable Li2O-based lithium-air battery enabled by a solid electrolyte. Science 379, 499–505 (2023). https://doi.org/10.1126/science.abq1347
  51. H. Gong, T. Wang, K. Chang, P. Li, L. Liu et al., Revealing the illumination effect on the discharge products in high-performance Li–O2 batteries with heterostructured photocatalysts. Carbon Energy 4, 1169–1181 (2022). https://doi.org/10.1002/cey2.208
  52. Y. Rao, J. Yang, S. Chu, S. Guo, H. Zhou, Solid-state Li–air batteries: fundamentals, challenges, and strategies. SmartMat 4, e1205 (2023). https://doi.org/10.1002/smm2.1205
  53. L. Luo, B. Liu, S. Song, W. Xu, J.-G. Zhang et al., Revealing the reaction mechanisms of Li–O2 batteries using environmental transmission electron microscopy. Nat. Nanotechnol. 12, 535–539 (2017). https://doi.org/10.1038/nnano.2017.27
  54. K.R. Yoon, J.-W. Jung, P.I.-D. Kim, Recent progress in 1D air electrode nanomaterials for enhancing the performance of nonaqueous lithium–oxygen batteries. ChemNanoMat 2, 616–634 (2016). https://doi.org/10.1002/cnma.201600137
  55. D. Zhai, H.H. Wang, K.C. Lau, J. Gao, P.C. Redfern et al., Raman evidence for late stage disproportionation in a Li–O2 battery. J. Phys. Chem. Lett. 5, 2705–2710 (2014). https://doi.org/10.1021/jz501323n
  56. J.F. Leal Silva, M.C. Policano, G.C. Tonon, C.G. Anchieta, G. Doubek et al., The potential of hydrophobic membranes in enabling the operation of lithium-air batteries with ambient air. Chem. Eng. J. Adv. 11, 100336 (2022). https://doi.org/10.1016/j.ceja.2022.100336
  57. M.-C. Sung, G.-H. Lee, D.-W. Kim, Kinetic insight into perovskite La0.8Sr0.2VO3 nanofibers as an efficient electrocatalytic cathode for high-ratehigh-rate Li-O2 batteries. InfoMat 3, 1295–1310 (2021). https://doi.org/10.1002/inf2.12243
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY FILE
Statistic
Read Counter : 2061 Download : 1535