Citation: Qilin Zhang, Decai Ji, Wenwei Ding, Qian Ni, Wenjuan Zhu, Chuyang Li, Qingqing Zhou, Bin Wang, Yadong Wang, Zhipeng Liu, Xiang Han. Localized surface segregation of lithium salts enabling fast lithium-ion channels and robust interphases toward stable solid-state lithium batteries[J]. Chinese Chemical Letters, ;2026, 37(12): 113223. doi: 10.1016/j.cclet.2026.113223 shu

Localized surface segregation of lithium salts enabling fast lithium-ion channels and robust interphases toward stable solid-state lithium batteries

College of Materials Science and Engineering, Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China

zpliu@njfu.edu.cn

hanxiang@njfu.edu.cn

Received Date: 20 May 2026
Revised Date: 14 July 2026
Accepted Date: 19 July 2026
Available Online: 20 July 2026

Figures(5)

Composite solid-polymer electrolytes (SPEs) integrate the merits of polymer electrolytes and inorganic fillers, demonstrating excellent interfacial wetting with lithium metal and competitive ionic conductivity. However, the formidable interfacial impedance and poor compatibility between the polymer matrix and inorganic fillers often hinder the realization of high-rate capability and long-term cycling stability. Herein, we report a PVDF-HFP-based SPE featuring garnet-type Li₇La₃Zr₂O₁₂ (LLZO) as the inorganic filler and fluoroethylene carbonate (FEC) as a functional additive, that enhancing binding energies with LLZO and induces local lithium salts enrichment at the LLZO surface. This FEC absorbs and wet the surface of LLZO, resulting in lithium salts aggregation at the interface between LLZO and PVDF-HFP. This unique local ion rich characteristic provides additional lithium-ion channels and enables high ionic conductivity. In addition, the replacement of N,N-dimethylformamide (DMF) by FEC, inhibits the DMF with the La sites of LLZO, preventing the subsequent dehydrofluorination of the PVDF-HFP chains and fundamentally securing the intrinsic chemical stability throughout the SPE. Furthermore, FEC introduction induces a dense and LiF-rich solid electrolyte interphase (SEI), effectively curtailing dendrite penetration and establishing a stabilized interfacial contact. Consequently, the engineered electrolyte membrane achieves a remarkable ambient ionic conductivity of 7.4 × 10^–4 S/cm. The SPE enables exceptionally stable Li plating/stripping for 650 h. The assembled Li//LiFePO₄ cells deliver outstanding high-rate (640 cycles at 8C) and high-temperature (400 cycles at 5 C, 50 ℃) lifespans. Furthermore, high-voltage Li//NCM811 cells exhibit superior compatibility with over 250 stable cycles. This work offers a compelling paradigm to overcome the inherent interfacial mismatch among rigid inorganic fillers, polymeric networks, and active electrodes, for next-generation solid-state lithium metal batteries.
- Lithium metal batteries,
- Solid polymer electrolyte,
- Localized surface segregation,
- Interface,
- Fluoroethylene carbonate
1. [1]
  R. Chen, Q. Li, X. Yu, et al., Chem. Rev. 120 (2020) 6820–6877. doi: 10.1021/acs.chemrev.9b00268
2. [2]
  E. Fan, L. Li, Z. Wang, et al., Chem. Rev. 120 (2020) 7020–7063. doi: 10.1021/acs.chemrev.9b00535
3. [3]
  J. Pei, X. Bai, P. Xue, et al., Nano Res. Energy 4 (2025) e9120155. doi: 10.26599/nre.2025.9120155
4. [4]
  X. Lu, Y. Wang, X. Xu, et al., Adv. Energy Mater. 13 (2023) 2301746. doi: 10.1002/aenm.202301746
5. [5]
  N. Xu, Y. Zhao, M. Ni, et al., Angew. Chem. Int. Ed. 63 (2024) e202404400. doi: 10.1002/anie.202404400
6. [6]
  L. Xu, S. Tang, Y. Cheng, et al., Joule 2 (2018) 1991–2015. doi: 10.1016/j.joule.2018.07.009
7. [7]
  M. Palmer, V.K. Singh, L. Merola, et al., Energy Environ. Sci. 19 (2026) 3283–3299. doi: 10.1039/d5ee07777j
8. [8]
  T. Xue, W. Wang, X. Guo, et al., Chin. Chem. Lett. 37 (2026) 112535. doi: 10.1016/j.cclet.2026.112535
9. [9]
  X. Han, J. Lu, Q. Zou, et al., Adv. Mater. 37 (2025) 2504419. doi: 10.1002/adma.202504419
10. [10]
  B. Sheng, J. Lu, H. Chen, et al., Adv. Funct. Mater. 36 (2026) e14960. doi: 10.1002/adfm.202514960
11. [11]
  X. Gao, N. Piao, Y. Yan, et al., Chin. Chem. Lett. 37 (2026) 110591. doi: 10.1016/j.cclet.2024.110591
12. [12]
  K. Chen, A. Hu, W. Yang, et al., Adv. Funct. Mater. 36 (2026) e13143. doi: 10.1002/adfm.202513143
13. [13]
  R. Yang, D. Ai, S. Fan, et al., Energy Environ. Sci. 18 (2025) 3718–3729. doi: 10.1039/d5ee00368g
14. [14]
  R. Lin, Y. He, C. Wang, et al., Nat. Nanotechnol. 17 (2022) 768–776. doi: 10.1038/s41565-022-01148-7
15. [15]
  B. Qiu, J. Wen, F. Xu, et al., Angew. Chem. Int. Ed. 65 (2026) e8139928. doi: 10.1002/anie.8139928
16. [16]
  X. Han, L. Gu, Z. Sun, et al., Energy Environ. Sci. 16 (2023) 5395–5408. doi: 10.1039/d3ee01696j
17. [17]
  G. Zheng, Y. Chen, R. Chen, et al., Chem. Eng. J. 518 (2025) 164616. doi: 10.1016/j.cej.2025.164616
18. [18]
  X. Zhang, S. Cheng, C. Fu, et al., Nano-Micro Lett. 17 (2025) 2. doi: 10.1007/s40820-024-01498-y
19. [19]
  P. Shi, J. Ma, M. Liu, et al., Nat. Nanotechnol. 18 (2023) 602–610. doi: 10.1038/s41565-023-01341-2
20. [20]
  J. Mi, J. Yang, L. Chen, et al., Nature 647 (2025) 86–92. doi: 10.1038/s41586-025-09675-8
21. [21]
  J. Wang, Z. Bai, Z. Zhao, et al., Nano Res. Energy 4 (2025) e9120133. doi: 10.26599/nre.2024.9120133
22. [22]
  Z. Huang, T. Yang, M. Jiang, et al., Adv. Funct. Mater. 36 (2026) e75619. doi: 10.1002/adfm.75619
23. [23]
  G. Huang, R. Chen, Y. Yang, et al., J. Energy Chem. 119 (2026) 155–165. doi: 10.1016/j.jechem.2026.04.026
24. [24]
  X. Zhao, Y. Li, C. Wang, et al., Adv. Funct. Mater. 36 (2026) e32132. doi: 10.1002/adfm.202532132
25. [25]
  J. Lu, B. Sheng, M. Chen, et al., Energy Storage Mater. 71 (2024) 103570. doi: 10.1016/j.ensm.2024.103570
26. [26]
  Q. Zhou, C. Li, B. Wang, et al., J. Colloid Interface Sci. 690 (2025) 137302. doi: 10.1016/j.jcis.2025.137302
27. [27]
  R. Li, H. Hua, X. Yang, et al., Energy Environ. Sci. 17 (2024) 5601–5612. doi: 10.1039/d4ee01188k
28. [28]
  Y. Yang, H. Zhu, ACS Appl. Energy Mater. 5 (2022) 15086–15092. doi: 10.1021/acsaem.2c02747
29. [29]
  J. Biao, B. Han, Y. Cao, et al., Adv. Mater. 35 (2023) 2208951. doi: 10.1002/adma.202208951
30. [30]
  A.J. Samson, K. Hofstetter, S. Bag, et al., Energy Environ. Sci. 12 (2019) 2957–2975. doi: 10.1039/c9ee01548e
31. [31]
  N. Zhao, W. Khokhar, Z. Bi, et al., Joule 3 (2019) 1190–1199. doi: 10.1016/j.joule.2019.03.019
32. [32]
  Q. Zhu, K. Yang, L. Chen, et al., Angew. Chem. Int. Ed. 64 (2025) e202425221. doi: 10.1002/anie.202425221
33. [33]
  P. Pan, M. Zhang, Z. Cheng, et al., Energy Storage Mater. 47 (2022) 279–287. doi: 10.1016/j.ensm.2022.02.018
34. [34]
  A.M. Nolan, Y. Zhu, X. He, et al., Joule 2 (2018) 2016–2046. doi: 10.1016/j.joule.2018.08.017
35. [35]
  Y. Huang, G. Rui, Q. Li, et al., Nat. Commun. 12 (2021) 675. doi: 10.1111/jfd.13329
36. [36]
  K. Cheng, S. Tu, B. Zhang, et al., Energy Environ. Sci. 17 (2024) 2631–2641. doi: 10.1039/d4ee00407h
37. [37]
  L. Cheng, Y. Wang, J. Yang, et al., Adv. Funct. Mater. 33 (2023) 2212349. doi: 10.1002/adfm.202212349
38. [38]
  L. Ruan, X. Yao, Y. Chang, et al., Polymers 10 (2018) 228. doi: 10.3390/polym10030228
39. [39]
  Q. Lv, C. Li, Y. Liu, et al., ACS Nano 18 (2024) 23253–23264. doi: 10.1021/acsnano.4c06057
40. [40]
  Y. Jing, S. Liu, C. Li, et al., Chem. Eng. J. 511 (2025) 162149. doi: 10.1016/j.cej.2025.162149
41. [41]
  Z. He, E. Dong, C. Li, et al., J. Energy Chem. 116 (2026) 504–513. doi: 10.1016/j.jechem.2026.01.017
42. [42]
  C. Li, Y. Jing, J. Zhu, et al., Adv. Funct. Mater. 36 (2026) e22002. doi: 10.1002/adfm.202522002
43. [43]
  P. Prakash, B. Fall, J. Aguirre, et al., Nat. Mater. 22 (2023) 627–635. doi: 10.1038/s41563-023-01508-1
44. [44]
  W. Huang, S. Wang, X. Zhang, et al., Adv. Mater. 35 (2023) 2310147. doi: 10.1002/adma.202310147
45. [45]
  C. Zhang, Z. Jiang, X. Yang, et al., Chem. Eng. J. 523 (2025) 168521. doi: 10.1016/j.cej.2025.168521
46. [46]
  X. An, Y. Liu, K. Yang, et al., Adv. Mater. 36 (2024) 2311195. doi: 10.1002/adma.202311195
47. [47]
  C.X. Zhao, Z. Wang, D. Jacobson, et al., Science 390 (2025) 745–750. doi: 10.1126/science.adv1739
48. [48]
  L. Zhang, Y. Dai, C. Li, et al., Energy Storage Mater. 69 (2024) 103378. doi: 10.1016/j.ensm.2024.103378
49. [49]
  M. Liu, A. Song, X. Zhang, et al., Nano Energy 136 (2025) 110749. doi: 10.1016/j.nanoen.2025.110749
50. [50]
  D. Zhang, Y. Liu, D. Li, et al., Energy Environ. Sci. 18 (2025) 227–235. doi: 10.1039/d4ee04078c
51. [51]
  N. Wu, P.H. Chien, Y. Qian, et al., Angew. Chem. Int. Ed. 59 (2020) 4131–4137. doi: 10.1002/anie.201914478
52. [52]
  J. Lu, B. Sheng, Q. Fang, et al., eScience 6 (2026) 100462. doi: 10.1016/j.esci.2025.100462
53. [53]
  H. Huo, Y. Chen, R. Li, et al., Energy Environ. Sci. 13 (2020) 127–134. doi: 10.1039/c9ee01903k
54. [54]
  K. Liu, H. Cheng, Z. Wang, et al., Adv. Energy Mater. 14 (2024) 2303940. doi: 10.1002/aenm.202303940
55. [55]
  H. Zeng, K. Yu, J. Li, et al., ACS Nano 18 (2024) 1969–1981. doi: 10.1021/acsnano.3c07038
56. [56]
  X. Liu, S. Li, C. Yuan, et al., Nature 646 (2025) 102–107. doi: 10.1038/s41586-025-09498-7
57. [57]
  P.G. Kitz, M.J. Lacey, P. Novák, et al., J. Power Sources 477 (2020) 228567. doi: 10.1016/j.jpowsour.2020.228567
58. [58]
  P. Jiang, J. Cao, B. Wei, et al., Energy Storage Mater. 48 (2022) 145–154. doi: 10.1016/j.ensm.2022.03.017
1. [1]
  Mengwen Wang , Qintao Sun , Yue Liu , Zhengan Yan , Qiyu Xu , Yuchen Wu , Tao Cheng . Impact of lithium nitrate additives on the solid electrolyte interphase in lithium metal batteries. Chinese Journal of Structural Chemistry, 2024, 43(2): 100203-100203. doi: 10.1016/j.cjsc.2023.100203
2. [2]
  Guihuang Fang , Wei Chen , Hongwei Yang , Haisheng Fang , Chuang Yu , Maoxiang Wu . Improved performance of LiMn_0.8Fe_0.2PO₄ by addition of fluoroethylene carbonate electrolyte additive. Chinese Chemical Letters, 2024, 35(6): 108799-. doi: 10.1016/j.cclet.2023.108799
3. [3]
  Yuhao Xiong , Jian Zhang , Yue Sun , Boyuan Hu , Wei Wang , Yuanyuan Yin , Debin Xia , Kaifeng Lin , Yulin Yang , Evgeny Tretyakov . Metal-organic frameworks in perovskite solar cells: Harnessing structural diversity for enhanced photovoltaic performance. Chinese Journal of Structural Chemistry, 2026, 45(3): 100842-100842. doi: 10.1016/j.cjsc.2025.100842
4. [4]
  Zhaojun Chen , Yongqi Wang , Yongshun Liang , Liang Shan , Ying Wang , Jiyue Hou , Ziyi Zhu , Xue Li , Yiyong Zhang . In-situ polymerization technology for all-solid state lithium batteries: Current status and future development. Chinese Chemical Letters, 2026, 37(6): 112020-. doi: 10.1016/j.cclet.2025.112020
5. [5]
  Qian Wang , Ting Gao , Xiwen Lu , Hangchao Wang , Minggui Xu , Longtao Ren , Zheng Chang , Wen Liu . Nanophase separated, grafted alternate copolymer styrene-maleic anhydride as an efficient room temperature solid state lithium ion conductor. Chinese Chemical Letters, 2024, 35(7): 108887-. doi: 10.1016/j.cclet.2023.108887
6. [6]
  Weijie Cai , Xinxin Han , Min Chen , Haoyuan Chen , Hao Wang , Zhixiang Chen , Mengmeng Shao , Ke Zheng , Wenlong Wang , Rui Hong , Xiaodong Shi . Stabilizing the dual electrode interface via a crosslinked gelatin nonwoven separator for durable lithium metal batteries. Chinese Chemical Letters, 2025, 36(12): 111809-. doi: 10.1016/j.cclet.2025.111809
7. [7]
  Haining Peng , Huijun Liu , Chengzong Li , Yingfu Li , Qizhi Chen , Tao Li . Diluent modified weakly solvating electrolyte for fast-charging high-voltage lithium metal batteries. Chinese Chemical Letters, 2025, 36(1): 109556-. doi: 10.1016/j.cclet.2024.109556
8. [8]
  Xin Xia , Zhong-Qi Zhang , Qing Wen , Pei-Yao Li , Ding-Hao Le , Zhen-Yu Wang , Pan-Pan Dong , Guo-Dong Ren , Jun-Chao Zheng . Metal-organic-framework-based solid-state electrolytes for high-performance lithium metal batteries: Recent advances and prospects. Chinese Chemical Letters, 2026, 37(10): 111653-. doi: 10.1016/j.cclet.2025.111653
9. [9]
  Xiaohan Wang , Xue Guo , Zhuo Song , Chen Guan , Chengyu Yang , Tianyang Li , Yukun Zhu , Yan Xu . Interface engineering of Co9S8/Ni3S2 heterojunction with robust stability for boosting peroxymonosulfate activation. Chinese Journal of Structural Chemistry, 2026, 45(2): 100771-100771. doi: 10.1016/j.cjsc.2025.100771
10. [10]
  Hongfei Li , Hao Chen , Qi Kang , Lihe Guo , Xingyi Huang , Haiping Xu . Gel polymer electrolyte for flexible and stretchable lithium metal battery: Advances and prospects. Chinese Chemical Letters, 2025, 36(9): 110325-. doi: 10.1016/j.cclet.2024.110325
11. [11]
  Liang Wang , Weitao Li , Lei Zheng , Mengmin Jia , Dai-Huo Liu , Dongmei Dai , Zhuangzhuang Zhang , Chunyu Ma , Bao Wang , Shengli Zhang , Li Su , Bao Li . Hemin with strong adsorption on zinc anode as a multi-functional interface layer for highly reversible Zn-ion batteries. Chinese Chemical Letters, 2026, 37(1): 111458-. doi: 10.1016/j.cclet.2025.111458
12. [12]
  Xi Tang , Shihan Qi , Jian He , Jiandong Liu , Xiu Li , Jiu Lin , Abdullah N. Alodhayb , Lihua Wang , Jianmin Ma . Electrolyte additive strategy to eliminate hydrofluoric acid and construct robust cathode electrolyte interphase for 4.6 V Li||LiCoO₂ batteries. Chinese Chemical Letters, 2026, 37(2): 110622-. doi: 10.1016/j.cclet.2024.110622
13. [13]
  Xi Tang , Chunlei Zhu , Yulu Yang , Shihan Qi , Mengqiu Cai , Abdullah N. Alodhayb , Jianmin Ma . Additive regulating Li⁺ solvation structure to construct dual LiF−rich electrode electrolyte interphases for sustaining 4.6 V Li||LiCoO₂ batteries. Chinese Chemical Letters, 2024, 35(12): 110014-. doi: 10.1016/j.cclet.2024.110014
14. [14]
  Pu Guo , Dandan Yu , Yuzhen Zhao , Hua Wang . Reactivation of inactive lithium in rechargeable lithium batteries: From fundamental research to industrial applications. Chinese Chemical Letters, 2026, 37(11): 111696-. doi: 10.1016/j.cclet.2025.111696
15. [15]
  Bin Wang , Qingqing Zhou , Junjie Lu , Chuyang Li , Mengmeng Fan , Wenwei Ding , Bifu Sheng , Wenjuan Zhu , Qian Ni , Huixin Chen , Xiang Han . Fluorinate localized solvation PVDF-HFP-based polymer electrolyte producing LiF-rich interface for solid-state lithium metal batteries. Chinese Chemical Letters, 2026, 37(10): 111557-. doi: 10.1016/j.cclet.2025.111557
16. [16]
  Shangda Qu , Yiming Yuan , Xu Ye , Wentao Xu . High sensitivity artificial synapses using printed high-transmittance ITO fibers for neuromorphic computing. Chinese Chemical Letters, 2024, 35(12): 110030-. doi: 10.1016/j.cclet.2024.110030
17. [17]
  Juhong Lian , Deng Li , Yongmei Ma , Hui Bian , Yifan Shao , Zitong Wang , Junqing Yan , Ruibin Jiang , Shengzhong (Frank) Liu , Fuxiang Zhang . Decorating CsPbBr₃ with In₂O₃ seeds to build intimate direct Z-scheme heterojunction for promoted photocatalytic CO₂ reduction. Chinese Chemical Letters, 2025, 36(11): 111394-. doi: 10.1016/j.cclet.2025.111394
18. [18]
  Hua Peng , Dong Hou , Jing-Hua Guo , Yuan Yu , Wei Qin . Interfacial spin polarization improving photovoltaic performance in perovskite solar cells. Chinese Chemical Letters, 2026, 37(7): 111081-. doi: 10.1016/j.cclet.2025.111081
19. [19]
  Longmei Liang , Cong Luo , Lingting Ye , Chaoyang Tu , Kui Xie . Porous magnesium oxide single crystal with Pt-loaded nanoparticles to boost ethane dehydrogenation. Chinese Chemical Letters, 2026, 37(8): 111327-. doi: 10.1016/j.cclet.2025.111327
20. [20]
  Lisi Xu , Maosheng Li , Anqi He , Haijiao Xie , Kuirong Deng . F/N interface engineering of nonflammable polymer electrolyte for wide-temperature quasi-solid-state Li metal batteries. Chinese Chemical Letters, 2026, 37(2): 111815-. doi: 10.1016/j.cclet.2025.111815

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