Citation: 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[J]. Chinese Chemical Letters, ;2026, 37(5): 110851. doi: 10.1016/j.cclet.2025.110851 shu

Oxygen defect-mediated Li-ion transport for long-cycle solid-state lithium metal batteries

Zi-Hao Zuo ^{a, b} ,
Jiang-Kui Hu ^{a, b} ,
Xi-Long Wang ^{a, b} ,
Shi-Jie Yang ^{a, b} ,
Wei-Qi Mai ^{a, d} ,
Yao-Hui Zhu ^{a, d} ,
Zheng Liao ^{a, b} ,
Jia Liu ^c ,
Hong Yuan ^{a, b, *,} ,
Jia-Qi Huang ^{a, b, *,}

a.
School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, China
b.
Advanced Research Institute of Multidisciplinary Science, Beijing Institute of Technology, Beijing 100081, China
c.
Beijing Key Laboratory of Lignocellulosic Chemistry, College of Materials Science and Technology, Beijing Forestry University, Beijing 100083, China
d.
Advanced Research Institute of Multidisciplinary Science, Beijing Institute of Technology, Zhuhai 519088, China

yuanhong@bit.edu.cn

jqhuang@bit.edu.cn

Received Date: 26 November 2024
Revised Date: 28 December 2024
Accepted Date: 14 January 2025
Available Online: 14 January 2025

Figures(5)

Solid-state lithium (Li) metal batteries have attracted significant attention due to their high energy density and improved safety performance. However, sluggish Li-ion transport and rapid anion migration in solid-state electrolytes often result in heterogeneous Li-ion flux distribution and thus Li dendrite growth. Herein, we developed a highly conductive composite solid electrolyte with an elevated Li-ion transference number through incorporating Gd-doped CeO₂ (GDC) nanofillers with abundant surface oxygen defects into poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrices. The defect concentrations were effectively controlled by regulating the Gd doping ratio in CeO₂. As a result, the highest oxygen concentration of 12.2% is achieved for the GDC with 10% Gd doping (GDC-10). The GDC-10 electrolyte demonstrated a high Li-ion transference number of 0.59 and an improved ionic conductivity of 0.40 mS/cm at room temperature, attributed to anion immobilization and enhanced Li-salt dissociation. This was due to the strong interactions between positively charged oxygen vacancies and anions, which effectively reduces surface concentration polarization and homogenizes Li-ion flux. Therefore, LiLi symmetric cells exhibited exceptional cycling stability of 1500 h without noticeable Li dendrite growth at 1 mA/cm² and 1 mAh/cm². Furthermore, LiLiFePO₄ full cell also stably cycles for 500 cycles with a capacity retention of 90.44% at 1 C. This work provides new insights into the design of composite solid electrolytes through the defect regulation of fillers.
- Solid-state batteries,
- Composite solid-state electrolytes,
- Li-ion transport,
- Anion immobilization,
- Li-ion transference number
1. [1]
  J. Liu, M. Yue, S. Wang, Y. Zhao, J. Zhang, Adv. Funct. Mater. 32 (2022) 2107769. doi: 10.1002/adfm.202107769
2. [2]
  J. Liu, X.W. Mei, F. Peng, Chin. Chem. Lett. 34 (2023) 108187. doi: 10.1016/j.cclet.2023.108187
3. [3]
  L.J. He, J. Liu, T.T. Lv, A.C. Wei, T.Q. Yuan, J. Colloid Interf. Sci. 671 (2024) 175–183. doi: 10.1016/j.jcis.2024.05.140
4. [4]
  Y. Wei, H. Wang, X. Lin, et al., Energy Environ. Sci. 18 (2025) 786–798. doi: 10.1039/D4EE03192J
5. [5]
  J. Xiang, Y. Wei, Y. Zhong, et al., Adv. Mater. 34 (2022) 2200912. doi: 10.1002/adma.202200912
6. [6]
  A. Kwade, W. Haselrieder, R. Leithoff, et al., Nat. Energy 3 (2018) 290–300. doi: 10.1038/s41560-018-0130-3
7. [7]
  S.J. Yang, J.K. Hu, F.N. Jiang, et al., InfoMat 6 (2024) e12512. doi: 10.1002/inf2.12512
8. [8]
  S.J. Yang, J.K. Hu, F.N. Jiang, et al., eTransportation 18 (2023) 100279. doi: 10.1016/j.etran.2023.100279
9. [9]
  J.K. Hu, S.J. Yang, Y.Y. Pei, et al., Particuology 86 (2024) 55–66. doi: 10.1016/j.partic.2023.04.005
10. [10]
  T.Q. Yang, C. Wang, W.K. Zhang, et al., J. Energy Chem. 84 (2023) 189–209. doi: 10.1016/j.jechem.2023.05.011
11. [11]
  X. Yu, A. Manthiram, Energy Storage Mater. 34 (2021) 282–300. doi: 10.1016/j.ensm.2020.10.006
12. [12]
  R.S. Chen, Q.H. Li, X.Q. Yu, L.Q. Chen, H. Li, Chem. Rev. 120 (2020) 6820– 6877. doi: 10.1021/acs.chemrev.9b00268
13. [13]
  J.K. Hu, H. Yuan, S.J. Yang, et al., J. Energy Chem. 71 (2022) 612–618. doi: 10.1016/j.jechem.2022.04.048
14. [14]
  G. Yan, S.C. Yu, J.F. Nonemacher, et al., Ceram. Int. 45 (2019) 14697–14703. doi: 10.1016/j.ceramint.2019.04.191
15. [15]
  Y. Lu, C.Z. Zhao, J.K. Hu, et al., Sci. Adv. 8 (2022) eadd0510. doi: 10.1126/sciadv.add0510
16. [16]
  S.F. Wang, H.H. Xu, W.D. Li, A. Dolocan, A. Manthiram, J. Am. Chem. Soc. 140 (2018) 250–257. doi: 10.1021/jacs.7b09531
17. [17]
  Y.T. Li, B.Y. Xu, H.H. Xu, et al., Angew. Chem. Int. Ed. 56 (2017) 753–756. doi: 10.1002/anie.201608924
18. [18]
  B.W. Shao, Y.L. Huang, F.D. Han, Adv. Energy Mater. 13 (2023) 2204098. doi: 10.1002/aenm.202204098
19. [19]
  Y.L. Liao, J.K. Hu, Z.H. Fu, et al., J. Energy Chem. 80 (2023) 458–465. doi: 10.1016/j.jechem.2023.02.012
20. [20]
  S. Li, S.J. Yang, G.X. Liu, et al., Adv. Mater. 36 (2024) 2307768. doi: 10.1002/adma.202307768
21. [21]
  Z.X. Wang, Y. Lu, C.Z. Zhao, et al., Joule 8 (2024) 2794–2810. doi: 10.1016/j.joule.2024.07.007
22. [22]
  X.B. Cheng, S.J. Yang, Z. Liu, et al., Adv. Mater. 36 (2024) 2307370. doi: 10.1002/adma.202307370
23. [23]
  J. Liu, H. Yuan, H. Liu, et al., Adv. Energy Mater. 12 (2022) 2100748. doi: 10.1002/aenm.202100748
24. [24]
  M.H. Yang, Y.S. Liu, Y.F. Mo, Nat. Commun. 14 (2023) 2986. doi: 10.1038/s41467-023-38757-2
25. [25]
  M.H. Yang, Y.S. Liu, A.M. Nolan, Y.F. Mo, Adv. Mater. 33 (2021) 2008081. doi: 10.1002/adma.202008081
26. [26]
  D.R. Dong, B. Zhou, Y.F. Sun, et al., Nano Lett. 19 (2019) 2343–2349. doi: 10.1021/acs.nanolett.8b05019
27. [27]
  F.Z. Liu, J.Y. Wang, W.Y. Chen, et al., Adv. Mater. 36 (2024) 2409838. doi: 10.1002/adma.202409838
28. [28]
  G. Feng, Q.Y. Ma, D. Luo, et al., Angew. Chem. Int. Ed. 63 (2024) e202413306.
29. [29]
  G.Q. Tan, F. Wu, C. Zhan, et al., Nano Lett. 16 (2016) 1960–1968. doi: 10.1021/acs.nanolett.5b05234
30. [30]
  J.K. Hu, Y.C. Gao, S.J. Yang, et al., Adv. Funct. Mater. 34 (2024) 2311633. doi: 10.1002/adfm.202311633
31. [31]
  N.W. Utomo, S.F. Hong, R. Sinha, et al., Sci. Adv. 10 (2024) eado4719. doi: 10.1126/sciadv.ado4719
32. [32]
  Y.F. Zhu, Z.J. Lao, M.T. Zhang, et al., Nat. Commun. 15 (2024) 3914. doi: 10.1038/s41467-024-48078-7
33. [33]
  Z.X. Wang, Z.H. Sun, J. Li, et al., Chem. Soc. Rev. 50 (2021) 3178–3210. doi: 10.1039/D0CS01017K
34. [34]
  J.N. Chazalviel, Phys. Rev. A 42 (1990) 7355–7367. doi: 10.1103/PhysRevA.42.7355
35. [35]
  W. Xu, J.L. Wang, F. Ding, et al., Energy Environ. Sci. 7 (2014) 513–537. doi: 10.1039/C3EE40795K
36. [36]
  M.Y. Cui, Y.Y. Qin, Z.C. Li, et al., Sci. Bull. 69 (2024) 1706–1715. doi: 10.1016/j.scib.2024.03.048
37. [37]
  Y. Zhai, W. Hou, M. Tao, et al., Adv. Mater. 34 (2022) 2205560. doi: 10.1002/adma.202205560
38. [38]
  T.T. Lv, J. Liu, L.J. He, H. Yuan, T.Q. Yuan, J. Energy Chem. 98 (2024) 414–421. doi: 10.1016/j.jechem.2024.07.003
39. [39]
  Q. Ma, H. Zhang, C.W. Zhou, et al., Angew. Chem. Int. Ed. 55 (2016) 2521–2525. doi: 10.1002/anie.201509299
40. [40]
  Y. Wang, Q. Sun, J. Zou, et al., Small 19 (2023) 2303344. doi: 10.1002/smll.202303344
41. [41]
  H.M. Liang, L. Wang, A.P. Wang, et al., Nano-Micro Lett. 15 (2023) 42. doi: 10.1007/s40820-022-00996-1
42. [42]
  T. Duan, H.W. Cheng, Y.B. Liu, et al., Energy Storage Mater. 65 (2024) 103091. doi: 10.1016/j.ensm.2023.103091
43. [43]
  X. Zhang, T. Liu, S.F. Zhang, et al., J. Am. Chem. Soc. 139 (2017) 13779–13785. doi: 10.1021/jacs.7b06364
44. [44]
  J. Janek, W.G. Zeier, Nat. Energy 1 (2016) 16141. doi: 10.1038/nenergy.2016.141
45. [45]
  B. Luo, W.G. Wang, Q. Wang, et al., Chem. Eng. J. 460 (2023) 141329. doi: 10.1016/j.cej.2023.141329
46. [46]
  H. Yun, J. Cho, S. Ryu, et al., Small 19 (2023) 2207223. doi: 10.1002/smll.202207223
47. [47]
  W. Liu, D.C. Lin, J. Sun, G.M. Zhou, Y. Cui, ACS Nano 10 (2016) 11407–11413. doi: 10.1021/acsnano.6b06797
48. [48]
  N. Wu, P.H. Chien, Y.M. Qian, et al., Angew. Chem. Int. Ed. 59 (2020) 4131–4137. doi: 10.1002/anie.201914478
49. [49]
  H. Chen, D. Adekoya, L. Hencz, et al., Adv. Energy Mater. 10 (2020) 2000049. doi: 10.1002/aenm.202000049
50. [50]
  Y.H. Zhang, S. Zhang, N.F. Hu, et al., Chem. Soc. Rev. 53 (2024) 3302–3326. doi: 10.1039/D3CS00872J
51. [51]
  L. Gao, N. Wu, N.P. Deng, et al., Energy Environ. Mater. 6 (2023) e12272. doi: 10.1002/eem2.12272
52. [52]
  Y.Z. Hu, L.G. Li, H.F. Tu, et al., Adv. Funct. Mater. 32 (2022) 2203336. doi: 10.1002/adfm.202203336
53. [53]
  Y. Lin, X. Wang, J. Liu, J.D. Miller, Nano Energy 31 (2017) 478–485. doi: 10.1016/j.nanoen.2016.11.045
54. [54]
  X. Chen, Y.K. Bai, C.Z. Zhao, X. Shen, Q. Zhang, Angew. Chem. Int. Ed. 59 (2020) 11192–11195. doi: 10.1002/anie.201915623
55. [55]
  S.J. Yang, H. Yuan, N. Yao, et al., Adv. Mater. 36 (2024) 2405086. doi: 10.1002/adma.202405086
56. [56]
  Q.K. Zhang, S.Y. Sun, M.Y. Zhou, et al., Angew. Chem. Int. Ed. 62 (2023) e202306889. doi: 10.1002/anie.202306889
57. [57]
  F.L. Chu, R.Y. Deng, F.X. Wu, Energy Storage Mater. 56 (2023) 141–154. doi: 10.1016/j.ensm.2023.01.001
58. [58]
  Z. Wang, L.P. Hou, Q.K. Zhang, et al., Chin. Chem. Lett. 35 (2024) 108570. doi: 10.1016/j.cclet.2023.108570
1. [1]
  Shanyan Huang , Bi Luo , Zixun Zhang , Qi Wang , Guihui Yu , Xudong Bu , Zheng Huang , Xiaowei Wang , Wei-Li Song , Jiafeng Zhang , Shuqiang Jiao . Effect of crystal morphology of nickel-rich cathode materials on electrochemical stability and ion transport kinetics of sulfide-based all-solid-state batteries. Chinese Chemical Letters, 2026, 37(3): 110729-. doi: 10.1016/j.cclet.2024.110729
2. [2]
  Ziling Jiang , Chen Liu , Jie Yang , Xia Li , Chaochao Wei , Qiyue Luo , Zhongkai Wu , Lin Li , Liping Li , Shijie Cheng , Chuang Yu . Designing F-doped Li₃InCl₆ electrolyte with enhanced stability for all-solid-state lithium batteries in a wide voltage window. Chinese Chemical Letters, 2025, 36(6): 109741-. doi: 10.1016/j.cclet.2024.109741
3. [3]
  Ruofan Qi , Jing Zhang , Wang Sun , Bai Yu , Zhenhua Wang , Kening Sun . Solid-acid-Lewis-base interaction accelerates lithium ion transport for uniform lithium deposition. Chinese Chemical Letters, 2025, 36(6): 110009-. doi: 10.1016/j.cclet.2024.110009
4. [4]
  Shanyan Huang , Shijie Li , Zheng Huang , Kailun Zhang , Wei-Li Song , Shuqiang Jiao . A review of multiscale characterization methods of ion transport in solid-state electrolytes. Chinese Chemical Letters, 2026, 37(5): 110973-. doi: 10.1016/j.cclet.2025.110973
5. [5]
  Yue Zheng , Tianpeng Huang , Pengxian Han , Jun Ma , Guanglei Cui . Cathodal Li-ion interfacial transport in sulfide-based all-solid-state batteries: Challenges and improvement strategies. Chinese Journal of Structural Chemistry, 2024, 43(10): 100390-100390. doi: 10.1016/j.cjsc.2024.100390
6. [6]
  Tianyi Hou , Yunhui Huang , Henghui Xu . Interfacial engineering for advanced solid-state Li-metal batteries. Chinese Journal of Structural Chemistry, 2024, 43(7): 100313-100313. doi: 10.1016/j.cjsc.2024.100313
7. [7]
  Dixing Ni , Jiarui Qi , Zhi Deng , Dong Ding , Rui Wang , Wenjie Zhou , Sisi Zhou , Yang Sun , Shuai Li , Zhaoxiang Wang . Voltage design and transport channel optimization of anti-perovskite cathode materials: A density functional theory study. Chinese Chemical Letters, 2025, 36(12): 110683-. doi: 10.1016/j.cclet.2024.110683
8. [8]
  Qiao Wang , Ziling Jiang , Chuang Yu , Liping Li , Guangshe Li . Research progress of inorganic sodium ion conductors for solid-state batteries. Chinese Chemical Letters, 2025, 36(6): 110006-. doi: 10.1016/j.cclet.2024.110006
9. [9]
  Ying Li , Yanjun Xu , Xingqi Han , Di Han , Xuesong Wu , Xinlong Wang , Zhongmin Su . A new metal–organic rotaxane framework for enhanced ion conductivity of solid-state electrolyte in lithium-metal batteries. Chinese Chemical Letters, 2024, 35(9): 109189-. doi: 10.1016/j.cclet.2023.109189
10. [10]
  Haowen Li , Hongying Hou , Dai-Huo Liu , Bao Li , Dongmei Dai , Bao Wang , Mengmin Jia , Zhuangzhuang Zhang , Liang Wang , Yaru Qiao , Canhui Wu , Huihui Zhu , Pengyao Yan . A designed flexible solid-state electrolyte with rich hydrogen-bonded networks from TPU-PEGDA/LLZTO for Li metal batteries. Chinese Chemical Letters, 2026, 37(2): 111020-. doi: 10.1016/j.cclet.2025.111020
11. [11]
  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
12. [12]
  Qianqian Song , Yunting Zhang , Jianli Liang , Si Liu , Jian Zhu , Xingbin Yan . Boron nitride nanofibers enhanced composite PEO-based solid-state polymer electrolytes for lithium metal batteries. Chinese Chemical Letters, 2024, 35(6): 108797-. doi: 10.1016/j.cclet.2023.108797
13. [13]
  Peng Jia , Yunna Guo , Dongliang Chen , Xuedong Zhang , Jingming Yao , Jianguo Lu , Liqiang Zhang . In-situ imaging electrocatalysis in a solid-state Li-O₂ battery with CuSe nanosheets as air cathode. Chinese Chemical Letters, 2024, 35(5): 108624-. doi: 10.1016/j.cclet.2023.108624
14. [14]
  Ziling Jiang , Shaoqing Chen , Chaochao Wei , Ziqi Zhang , Zhongkai Wu , Qiyue Luo , Liang Ming , Long Zhang , Chuang Yu . Enabling superior electrochemical performance of NCA cathode in Li_5.5PS_4.5Cl_1.5-based solid-state batteries with a dual-electrolyte layer. Chinese Chemical Letters, 2024, 35(4): 108561-. doi: 10.1016/j.cclet.2023.108561
15. [15]
  Yongjian Li , Xinyu Zhu , Chenxi Wei , Youyou Fang , Xinyu Wang , Yizhi Zhai , Wenlong Kang , Lai Chen , Duanyun Cao , Meng Wang , Yun Lu , Qing Huang , Yuefeng Su , Hong Yuan , Ning Li , Feng Wu . Unraveling the chemical and structural evolution of novel Li-rich layered/rocksalt intergrown cathode for Li-ion batteries. Chinese Chemical Letters, 2024, 35(12): 109536-. doi: 10.1016/j.cclet.2024.109536
16. [16]
  Linhui Liu , Wuwan Xiong , Mingli Fu , Junliang Wu , Zhenguo Li , Daiqi Ye , Peirong Chen . Efficient NO_x abatement by passive adsorption over a Pd-SAPO-34 catalyst prepared by solid-state ion exchange. Chinese Chemical Letters, 2024, 35(4): 108870-. doi: 10.1016/j.cclet.2023.108870
17. [17]
  Jing Guo . Stacking solid-state electrolyte and aluminum pellets for anode-free solid-state batteries. Chinese Chemical Letters, 2025, 36(5): 110764-. doi: 10.1016/j.cclet.2024.110764
18. [18]
  Yue Wang , Caixia Xu , Xingtao Tian , Siyu Wang , Yan Zhao . Challenges and Modification Strategies of High-Voltage Cathode Materials for Li-ion Batteries. Chinese Journal of Structural Chemistry, 2023, 42(10): 100167-100167. doi: 10.1016/j.cjsc.2023.100167
19. [19]
  Qingyan JIANG , Yanyong SHA , Chen CHEN , Xiaojuan CHEN , Wenlong LIU , Hao HUANG , Hongjiang LIU , Qi LIU . Constructing a one-dimensional Cu-coordination polymer-based cathode material for Li-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 657-668. doi: 10.11862/CJIC.20240004
20. [20]
  Peining Zhu , Xi Guo , Qinqin Yu , Zuyong Wang , Xiangxiao Lei , Zhiwei Zhu , Juan Du , Xiaojia Zhang , Yuan-Li Ding . Design strategies of Si-based anode for solid-state batteries. Chinese Chemical Letters, 2025, 36(9): 111383-. doi: 10.1016/j.cclet.2025.111383

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(7)
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