Citation: Yuxiang Guo, Peiwen Fan, Jiacheng Liu, Qinpeng Qiao, Ahu Shao, Lu Cheng, Jiawen Tang, Yaxin Zhang, Zhiqiao Wang, Yunsong Li, Helin Wang, Chunwei Li, Junyu Zhang, Yue Ma. High-rate Na⁺ diffusion in solid polymer electrolytes enabled by high-concentration Na salt aggregates and size-selective anion immobilization[J]. Chinese Chemical Letters, ;2026, 37(10): 111602. doi: 10.1016/j.cclet.2025.111602 shu

High-rate Na⁺ diffusion in solid polymer electrolytes enabled by high-concentration Na salt aggregates and size-selective anion immobilization

Yuxiang Guo ^{a, 1} ,
Peiwen Fan ^{a, 1} ,
Jiacheng Liu ^a ,
Qinpeng Qiao ^b ,
Ahu Shao ^a ,
Lu Cheng ^a ,
Jiawen Tang ^a ,
Yaxin Zhang ^a ,
Zhiqiao Wang ^a ,
Yunsong Li ^a ,
Helin Wang ^a ,
Chunwei Li ^a ,
Junyu Zhang ^a ,
Yue Ma ^{a, *,}

a.
State Key Laboratory of Solidification Processing, Center for Nano Energy Materials, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi'an 710072, China
b.
Queen Mary University of London Engineering School, Northwestern Polytechnical University, Xi'an 710072, China

mayue04@nwpu.edu.cn

Received Date: 18 June 2025
Revised Date: 8 July 2025
Accepted Date: 17 July 2025
Available Online: 17 July 2025

Figures(7)

Solid polymer electrolytes present transformative potential for all-solid-state sodium metal batteries (ASSMBs) owing to their molecular tailorability, cost-effectiveness and ease of processability, yet face critical challenges including sluggish Na⁺ diffusion kinetics at room temperature, high-voltage oxidation tendency, and uncontrolled Na dendrite growth. To address these limitations, we propose an anion-regulation strategy through a hierarchically engineered composite polymer electrolyte (CPE) that strategically integrates (1) a high-concentration NaTFSI⁻ optimized polyethylene oxide (PEO) matrix (EO: Na⁺ = 6:1) and (2) a mechanically reinforced polyacrylonitrile (PAN) scaffold embedded with uniformly dispersed UIO-66 metal–organic framework nanoparticles (UIO-66@PAN). High-concentration TFSI⁻ dissociation activates mobile anion-Na⁺ cluster species that form dynamic percolation networks, establishing low-energy-barrier pathways for accelerated Na⁺ migration (1.01 mS/cm at 30 ℃). Meanwhile, the UIO-66@PAN scaffold delivers exceptional tensile resilience (3.46 MPa) for the CPE membrane, meanwhile sub-nanometer precision of porous architecture (7.5–8.1 Å in UIO-66 vs. 7.9 Å for TFSI⁻) enables steric-electronic dual-anchoring effects for TFSI⁻ immobilization, achieving a high Na⁺ transference number (t_Na⁺ = 0.76). In a solvent-free, layer-stacked ASSMB assembly with sodium vanadium phosphate (NVP) cathode (1 mAh/cm²), 25 µm CPE and the Na foil, the prototype achieves 91.3% capacity retention over 200 cycles at room temperature, rate behavior up to 1 C as well as robust cyclability across a wide temperature range (25–80 ℃). This molecular-scale engineering of anion behavior in the CPE design thus establishes a new paradigm for the practical ASSMB prototyping.
- All-solid-state Na metal battery,
- Molecular sieving confinement,
- High-concentration salt,
- Anion immobilization,
- Room-temperature cyclability
1. [1]
  Y. Lu, L. Li, Q. Zhang, Z. Niu, J. Chen, Joule 2 (2018) 1747–1770. doi: 10.1016/j.joule.2018.07.028
2. [2]
  Y. Su, F. Xu, X. Zhang, Y. Qiu, H. Wang, Nano-Micro Lett. 15 (2023) 023–01055-z.
3. [3]
  Z. Bi, S. Mu, N. Zhao, et al., Energy Storage Mater. 35 (2021) 512–519. doi: 10.1016/j.ensm.2020.11.038
4. [4]
  Z. Ye, S. Zhai, R. Liu, et al., Chem. Eng. J. 479 (2024) 147847. doi: 10.1016/j.cej.2023.147847
5. [5]
  Z. Guo, G. Qian, C. Wang, et al., Prog. Nat. Sci. : Mater. Int. 33 (2023) 1–7.
6. [6]
  Q. Yu, K. Jiang, C. Yu, et al., Chin. Chem. Lett. 32 (2021) 2659–2678. doi: 10.1016/j.cclet.2021.03.032
7. [7]
  X. Shan, M. Morey, Z. Li, et al., ACS Energy Lett. 7 (2022) 4342–4351. doi: 10.1021/acsenergylett.2c02349
8. [8]
  H. Liang, L. Wang, A. Wang, et al., Nano-Micro Lett. 15 (2023) 022–00996-00991.
9. [9]
  W. Tang, R. Qi, J. Wu, et al., Electrochem. Energy Rev. 7 (2024) 024-00228-00227.
10. [10]
  C. Zhao, L. Liu, X. Qi, et al., Adv. Energy Mater. 8 (2018) 1703012. doi: 10.1002/aenm.201703012
11. [11]
  X. Huang, R. He, M. Li, et al., Mater. Today 41 (2020) 143–155. doi: 10.1016/j.mattod.2020.07.015
12. [12]
  M. Zhang, H. Wang, A. Shao, et al., Adv. Energy Mater. 14 (2024) 2303932. doi: 10.1002/aenm.202303932
13. [13]
  D. Kim, X. Hu, B. Yu, Y.I. Chen, Adv. Mater. 36 (2024) 2401625. doi: 10.1002/adma.202401625
14. [14]
  H. Xu, S. Yang, B. Li, Adv. Energy Mater. 14 (2024) 2303539. doi: 10.1002/aenm.202303539
15. [15]
  N. Ding, S.W. Chien, T.L.D. Tam, et al., Adv. Energy Mater. 14 (2024) 2402986. doi: 10.1002/aenm.202402986
16. [16]
  C. Yang, Q. Wu, W. Xie, et al., Nature 598 (2021) 590–596. doi: 10.1038/s41586-021-03885-6
17. [17]
  F. He, W. Tang, X. Zhang, L. Deng, J. Luo, Adv. Mater. 33 (2021) 2105329. doi: 10.1002/adma.202105329
18. [18]
  R. Li, H. Hua, Y. Zeng, et al., J. Energy Chem. 64 (2022) 395–403. doi: 10.1016/j.jechem.2021.04.037
19. [19]
  Y. Yu, W. Gao, Y. Peng, et al., Chin. Chem. Lett. 37 (2026) 111309. doi: 10.1016/j.cclet.2025.111309111309
20. [20]
  Y. Wei, T.H. Liu, W. Zhou, et al., Adv. Energy Mater. 13 (2023) 2203547. doi: 10.1002/aenm.202203547
21. [21]
  H. Cheng, Z. Ma, P. Kumar, ACS Energy Lett. 9 (2024) 1604–1616. doi: 10.1021/acsenergylett.3c02789
22. [22]
  X. Wang, C. Zhang, M. Sawczyk, et al., Nat. Mater. 21 (2022) 1057–1065. doi: 10.1038/s41563-022-01296-0
23. [23]
  S. Tang, Q. Lan, L. Xu, et al., Nano Energy 71 (2020) 104600. doi: 10.1016/j.nanoen.2020.104600
24. [24]
  M.S.M. Misenan, A.S.A. Khiar, T. Eren, Polym. Int. 71 (2022) 751–769. doi: 10.1002/pi.6395
25. [25]
  H. Kokubo, E. Nakazawa, M. Watanabe, Polym. Adv. Technol. 30 (2018) 736–742.
26. [26]
  X. Zeng, X. Liu, H. Zhu, et al., Adv. Energy Mater. 14 (2024) 2402671. doi: 10.1002/aenm.202402671
27. [27]
  Y.W. Song, S.J. Park, H. Lee, et al., J. Mater. Chem. A 12 (2024) 9594–9605. doi: 10.1039/d4ta00479e
28. [28]
  X. Lin, C. Chu, Z. Li, et al., Nano Energy 89 (2021) 106351. doi: 10.1016/j.nanoen.2021.106351
29. [29]
  J. Ou, G. Li, Z. Chen, J. Electrochem. Soc. 166 (2019) A1785–A1792. doi: 10.1149/2.0401910jes
30. [30]
  E. Kim, H. Jamal, I. Jeon, et al., Adv. Energy Mater. 13 (2023) 2301674. doi: 10.1002/aenm.202301674
31. [31]
  S. Yang, X. He, T. Hu, et al., Adv. Funct. Mater. 33 (2023) 2304727. doi: 10.1002/adfm.202304727
32. [32]
  J. Park, H. Seong, C. Yuk, et al., Adv. Mater. 36 (2024) 2403191. doi: 10.1002/adma.202403191
33. [33]
  Z. Zhang, Q. Zhang, J. Shi, et al., Adv. Energy Mater. 7 (2016) 1601196.
34. [34]
  S. He, Y. Xu, Y. Chen, X. Ma, J. Mater. Chem. A 8 (2020) 12594–12602. doi: 10.1039/c9ta12213c
35. [35]
  J. Naik, R.F. Bhajantri, V. Hebbar, S.G. Rathod, Adv. Compos. Hybrid Mater. 1 (2018) 518–529. doi: 10.1007/s42114-018-0030-9
36. [36]
  P.N. Didwal, Y.N. Singhbabu, R. Verma, et al., Energy Storage Mater. 37 (2021) 476–490. doi: 10.1016/j.ensm.2021.02.034
37. [37]
  X. Li, Y. Pan, Y. Liu, et al., Carbon Neutrality 2 (2023) 34. doi: 10.1007/s43979-023-00074-4
38. [38]
  Y. Yusim, E. Trevisanello, R. Ruess, et al., Angew. Chem. Int. Ed. 62 (2023) e202218316. doi: 10.1002/anie.202218316
39. [39]
  W. Liu, C. Yi, L. Li, et al., Angew. Chem. Int. Ed. 60 (2021) 12931–12940. doi: 10.1002/anie.202101537
40. [40]
  M. Sun, Z. Zeng, W. Zhong, et al., J. Mater. Chem. A 10 (2022) 11732–11741. doi: 10.1039/d2ta00093h
41. [41]
  J. Zhang, Y. Wang, Q. Xia, et al., Angew. Chem. Int. Ed. 63 (2024) 2318822.
42. [42]
  P. Zhai, S. Qu, N. Ahmad, et al., Small 20 (2024) 2310547. doi: 10.1002/smll.202310547
43. [43]
  Y.L. Ni'mah, M.Y. Cheng, J.H. Cheng, J. Rick, B.J. Hwang, J. Power Sources 278 (2015) 375–381. doi: 10.1016/j.jpowsour.2014.11.047
44. [44]
  A.G. Nguyen, R. Verma, G.C. Song, J. Kim, C.J. Park, Adv. Sci. 10 (2023) 2207744. doi: 10.1002/advs.202207744
45. [45]
  J. Lu, J. Zhou, R. Chen, et al., Energy Storage Mater. 32 (2020) 191–198. doi: 10.1016/j.ensm.2020.07.026
46. [46]
  D. Zhou, X. Tang, X. Guo, et al., Angew. Chem. Int. Ed. 59 (2020) 16725–16734. doi: 10.1002/anie.202007008
47. [47]
  J. Wan, J. Xie, X. Kong, et al., Nat. Nanotechnol. 14 (2019) 705–711. doi: 10.1038/s41565-019-0465-3
48. [48]
  M.M. Hassan, X.Y. Wang, A.A. Bristi, et al., Nano Energy 128 (2024) 109971. doi: 10.1016/j.nanoen.2024.109971
49. [49]
  J.H. Yim, B.K. Oh, J.S. Lim, J. Chem. Engin. Data 65 (2020) 4S378–44386. doi: 10.1021/acs.jced.0c00188
50. [50]
  C. Luo, Q. Li, D. Shen, et al., Energy Storage Mater. 43 (2021) 463–470. doi: 10.1016/j.ensm.2021.09.031
51. [51]
  H. Ye, C. Zhang, Y. Li, et al., Prog. Nat. Sci. Mater. Int. 33 (2023) 754–766. doi: 10.1016/j.pnsc.2023.12.018
52. [52]
  J.H. Cavka, S. Jakobsen, U. Olsbye, et al., J. Am. Chem. Soc. 130 (2008) 13850–13851. doi: 10.1021/ja8057953
53. [53]
  Z. Li, S. Wang, J. Shi, et al., Energy Storage Mater. 47 (2022) 262–270. doi: 10.1016/j.ensm.2022.02.014
54. [54]
  G.E. Decker, Z. Stillman, L. Attia, C.A. Fromen, E.D. Bloch, Chem. Mater. 31 (2019) 4831–4839. doi: 10.1021/acs.chemmater.9b01383
1. [1]
  Zi-Hao Zuo , Jiang-Kui Hu , Xi-Long Wang , Shi-Jie Yang , Wei-Qi Mai , Yao-Hui Zhu , Zheng Liao , Jia Liu , Hong Yuan , Jia-Qi Huang . Oxygen defect-mediated Li-ion transport for long-cycle solid-state lithium metal batteries. Chinese Chemical Letters, 2026, 37(5): 110851-. doi: 10.1016/j.cclet.2025.110851
2. [2]
  Hengying Xiang , Nanping Deng , Lu Gao , Wen Yu , Bowen Cheng , Weimin Kang . 3D core-shell nanofibers framework and functional ceramic nanoparticles synergistically reinforced composite polymer electrolytes for high-performance all-solid-state lithium metal battery. Chinese Chemical Letters, 2024, 35(8): 109182-. doi: 10.1016/j.cclet.2023.109182
3. [3]
  Zhe Wang , Li-Peng Hou , Qian-Kui Zhang , Nan Yao , Aibing Chen , Jia-Qi Huang , Xue-Qiang Zhang . High-performance localized high-concentration electrolytes by diluent design for long-cycling lithium metal batteries. Chinese Chemical Letters, 2024, 35(4): 108570-. doi: 10.1016/j.cclet.2023.108570
4. [4]
  Sheng Zhao , Junjie Lu , Bifu Sheng , Siying Zhang , Hao Li , Jizhang Chen , Xiang Han . High-performance room temperature solid-state lithium battery enabled by PP-PVDF multilayer composite electrolyte. Chinese Chemical Letters, 2025, 36(6): 110008-. doi: 10.1016/j.cclet.2024.110008
5. [5]
  Cheng-Jin Liu , Jia-Xiang Wan , Chang Miao , Zhi-Yan Wang , Wei Xiao . Facile ammonium salt-mediated double-deck stacking strategy of Li₃YCl₆ halide solid electrolytes for all-solid-state lithium-metal batteries. Chinese Chemical Letters, 2026, 37(10): 111603-. doi: 10.1016/j.cclet.2025.111603
6. [6]
  Jialiang Zhu , Yuan Zhong , Bingqing Xu , Gen Zhang . Multiscale interfacial engineering of halide electrolytes for high-performance all-solid-state lithium batteries. Chinese Journal of Structural Chemistry, 2026, 45(4): 100850-100850. doi: 10.1016/j.cjsc.2025.100850
7. [7]
  Qiyue Luo , Chen Liu , Siwu Li , Chaochao Wei , Zhongkai Wu , Lin Li , Ziling Jiang , Liping Li , Guangshe Li , Shijie Cheng , Chuang Yu . Charge carrier distribution enabling superior electrochemical performance for all-solid-state lithium batteries over wide temperature range. Chinese Chemical Letters, 2026, 37(7): 111113-. doi: 10.1016/j.cclet.2025.111113
8. [8]
  Xin Li , Ling Zhang , Yunyan Fan , Shaojing Lin , Yong Lin , Yongsheng Ying , Meijiao Hu , Haiying Gao , Xianri Xu , Zhongbiao Xia , Xinchuan Lin , Junjie Lu , Xiang Han . Carbon interconnected microsized Si film toward high energy room temperature solid-state lithium-ion batteries. Chinese Chemical Letters, 2025, 36(2): 109776-. doi: 10.1016/j.cclet.2024.109776
9. [9]
  Yu-Yao Li , Xiao-Hui Li , Zhi-Xuan An , Yang Chu , Xiu-Li Wang . Room-temperature olefin epoxidation reaction by two 2D cobalt metal-organic complexes under O₂ atmosphere: Coordination and structural regulation. Chinese Chemical Letters, 2025, 36(4): 109716-. doi: 10.1016/j.cclet.2024.109716
10. [10]
  Ying Li , Ze-Chen Lv , Peng-Fei Wang , Jie Shu , Ping He , Ting-Feng Yi . Constructing stable cathode by g-C₃N₄ nanosheets for high-energy all-solid-state lithium-sulfur batteries. Chinese Chemical Letters, 2026, 37(7): 111110-. doi: 10.1016/j.cclet.2025.111110
11. [11]
  Yaping Wang , Pengcheng Yuan , Zeyuan Xu , Xiong-Xiong Liu , Shengfa Feng , Mufan Cao , Chen Cao , Xiaoqiang Wang , Long Pan , Zheng-Ming Sun . Ti₃C₂T_x MXene in-situ transformed Li₂TiO₃ interface layer enabling 4.5 V-LiCoO₂/sulfide all-solid-state lithium batteries with superior rate capability and cyclability. Chinese Chemical Letters, 2024, 35(6): 108776-. doi: 10.1016/j.cclet.2023.108776
12. [12]
  Mufan Cao , Long Pan , Yaping Wang , Xianwei Sui , Xiong Xiong Liu , Shengfa Feng , Pengcheng Yuan , Min Gao , Jiacheng Liu , Song-Zhu Kure-Chu , Takehiko Hihara , Yang Zhou , Zheng-Ming Sun . Mechanical-durable and humidity-resistant dry-processed halide solid-state electrolyte films for all-solid-state battery. Chinese Chemical Letters, 2025, 36(6): 110391-. doi: 10.1016/j.cclet.2024.110391
13. [13]
  Dian-Xue Ma , Yu-Wu Zhong . Achieving highly-efficient room-temperature phosphorescence with a nylon matrix. Chinese Journal of Structural Chemistry, 2024, 43(9): 100391-100391. doi: 10.1016/j.cjsc.2024.100391
14. [14]
  Bosen Zhang , Yecheng Yan , Zhiyuan Chen , Shuo Yang , Zhi Yang . Ga₂O₃-doped argyrodite sulfide solid electrolyte enhances interface stability of all-solid-state lithium metal batteries. Chinese Chemical Letters, 2026, 37(10): 111952-. doi: 10.1016/j.cclet.2025.111952
15. [15]
  Jiao Wang , Shuang-Yan Lang , Zhen-Zhen Shen , Gui-Xian Liu , Jian-Xin Tian , Yuan Li , Rui-Zhi Liu , Rui Wen . In situ imaging of the interfacial processes manipulated by salt concentration on zinc anodes in zinc metal batteries. Chinese Chemical Letters, 2025, 36(4): 109815-. doi: 10.1016/j.cclet.2024.109815
16. [16]
  Jiayin Zhou , Depeng Liu , Longqiang Li , Min Qi , Guangqiang Yin , Tao Chen . Responsive organic room-temperature phosphorescence materials for spatial-time-resolved anti-counterfeiting. Chinese Chemical Letters, 2024, 35(11): 109929-. doi: 10.1016/j.cclet.2024.109929
17. [17]
  Zeyin Chen , Jiaju Shi , Yusheng Zhou , Peng Zhang , Guodong Liang . Polymer microparticles with ultralong room-temperature phosphorescence for visual and quantitative detection of oxygen through phosphorescence image and lifetime analysis. Chinese Chemical Letters, 2025, 36(5): 110629-. doi: 10.1016/j.cclet.2024.110629
18. [18]
  Xinhui Fan , Yonghao Fan , Yuli Dang , Puhui Xie , Xin Li , Zhanqi Cao , Song Jiang , Lijie Liu , Xin Zheng , Lixia Xie , Caoyuan Niu , Guoxing Liu , Yong Chen . Logically ordered control of organic room-temperature long-lived supramolecular luminophors. Chinese Chemical Letters, 2025, 36(8): 110648-. doi: 10.1016/j.cclet.2024.110648
19. [19]
  Bo Yang , Suqiong Yan , Shirong Ban , Wei Huang . New horizons in phosphorus-based emitters: From circularly polarized fluorescence to room-temperature phosphorescence. Chinese Chemical Letters, 2025, 36(11): 110837-. doi: 10.1016/j.cclet.2025.110837
20. [20]
  Zi-Yi Yu , Gen-Feng Li , Zhe-Kun Xu , Lipeng Long , Yan Qin , Zi-Yi Du , Zhong-Xia Wang . Enantiomeric organic amine-borane adduct crystals with room-temperature multi-channel switches. Chinese Journal of Structural Chemistry, 2025, 44(11): 100715-100715. doi: 10.1016/j.cjsc.2025.100715

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(3)
HTML views(0)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

High-rate Na+ diffusion in solid polymer electrolytes enabled by high-concentration Na salt aggregates and size-selective anion immobilization

Metrics

通讯作者: 陈斌, bchen63@163.com

High-rate Na⁺ diffusion in solid polymer electrolytes enabled by high-concentration Na salt aggregates and size-selective anion immobilization