Citation: Linfeng Peng, Cong Liao, Jiayue Peng, Shuai Chen, Tianyu Lei, Shijie Cheng, Jia Xie. Effect of oxygen doping sources on enhancing air stability and lithium metal compatibility of Li_5.5PS_4.5Cl_1.5 electrolyte[J]. Chinese Chemical Letters, ;2026, 37(6): 111015. doi: 10.1016/j.cclet.2025.111015 shu

Effect of oxygen doping sources on enhancing air stability and lithium metal compatibility of Li_5.5PS_4.5Cl_1.5 electrolyte

State Key Laboratory of Advanced Electromagnetic Technology, School of Electrical and Electronic Engineering, Huazhong University of Science and Technology, Wuhan 430074, China

xiejia@hust.edu.cn

Received Date: 21 November 2024
Revised Date: 25 February 2025
Accepted Date: 27 February 2025
Available Online: 27 February 2025

Figures(4)

Oxygen (O) doping is a promising strategy for enhancing the air stability and lithium metal compatibility of sulfide solid electrolytes (SSEs). However, the impact of various O sources on the structure and properties of SSEs remains unclear. In this study, we synthesized a series of O-doped electrolytes, Li_5.5PS_4.5-xO_xCl_1.5 (LPSCO_x, 0.1 ≤ x ≤ 0.5), using Li₂O and P₂O₅ as O sources, and systematically investigated their differences in structure, air stability, and electrochemical properties. O preferentially substitutes sulfur (S) at the 16e site and begins to replace S at the 4d site once a certain O concentration is reached. Notably, the P₂O₅-doped electrolytes (P-LPSCO_x) exhibit a greater oxygen tolerance content (0.24) at the 16e site, along with better air stability, higher ionic conductivity, and superior lithium metal compatibility. XRD, SEM, and XPS analyses reveal that the P₂O₅-doped electrolytes exhibit larger cell parameters, higher densification, and fewer side reactions with lithium metal compared to the Li₂O-doped counterparts. This study provides valuable insights into the development of high-performance O-doped sulfide electrolytes.
- All-solid-state battery,
- Sulfide solid electrolyte,
- Oxygen substitution,
- Air stability,
- Lithium metal compatibility
1. [1]
  K. Kim, M. Balaish, M. Wadaguchi, L. Kong, J. Rupp, Adv. Energy Mater. 11 (2021) 2002689. doi: 10.1002/aenm.202002689
2. [2]
  H. Yuan, J. Liu, Y. Lu, et al., Chem. Res. Chin. U. 36 (2020) 377–385. doi: 10.1007/s40242-020-0103-5
3. [3]
  C. Wei, X. Liu, C. Yu, et al., Chin. Chem. Lett. 34 (2023) 107859. doi: 10.1016/j.cclet.2022.107859
4. [4]
  S. Chen, C. Yu, C. Wei, et al., Chin. Chem. Lett. 34 (2023) 107544. doi: 10.1016/j.cclet.2022.05.058
5. [5]
  Y. Wang, P. Yuan, Z. Xu, et al., Chin. Chem. Lett. 35 (2024) 108776. doi: 10.1016/j.cclet.2023.108776
6. [6]
  S.J. Chen, D.J. Xie, G.Z. Liu, et al., Energy Storage Mater. 14 (2018) 58–74. doi: 10.1016/j.ensm.2018.02.020
7. [7]
  Z. Zhang, Y. Sun, X. Duan, et al., J. Mater. Chem. A 7 (2019) 2717–2722. doi: 10.1039/c8ta10790d
8. [8]
  L. Peng, H. Ren, J. Zhang, et al., Energy Storage Mater. 43 (2021) 53–61. doi: 10.1016/j.ensm.2021.08.028
9. [9]
  Y. Morino, H. Sano, K. Kawamoto, et al., Solid State Ionics 392 (2023) 116162. doi: 10.1016/j.ssi.2023.116162
10. [10]
  W. Yang, M.K. Tufail, L. Zhou, et al., Sci. Sin. Chim. 50 (2020) 1031–1044. doi: 10.1360/ssc-2020-0089
11. [11]
  F. Ren, Y. Wu, W. Zuo, et al., Energ. Environ Sci. 17 (2024) 2743–2752. doi: 10.1039/d3ee03536k
12. [12]
  B.D. Dandena, D.S. Tsai, S.H. Wu, et al., Energy Storage Mater. 69 (2024) 103305. doi: 10.1016/j.ensm.2024.103305
13. [13]
  S. Chen, C. Yu, S. Chen, et al., Chin. Chem. Lett. 33 (2022) 4635–4639. doi: 10.1016/j.cclet.2021.12.048
14. [14]
  A. Morscher, B.B. Duff, G. Han, et al., J. Am. Chem. Soc. 144 (2022) 22178–22192. doi: 10.1021/jacs.2c09863
15. [15]
  Y.Z. Zhu, Y.F. Mo, Angew. Chem. Int. Ed. 59 (2020) 17472–17476. doi: 10.1002/anie.202007621
16. [16]
  D. Wang, H. Shi, W. Cui, et al., J. Mater. Chem. A 12 (2024) 10863–10874. doi: 10.1039/d3ta07453f
17. [17]
  N. Ahmad, S. Sun, P. Yu, W. Yang, Adv. Funct. Mater. 32 (2022) 2201528. doi: 10.1002/adfm.202201528
18. [18]
  M. Wu, G. Liu, X. Yao, Appl. Phys. Lett. 121 (2022) 0114275.
19. [19]
  H. Xu, G. Cao, Y. Shen, et al., Energy Environ. Mater. 5 (2021) 852.
20. [20]
  T. Chen, L. Zhang, Z.X. Zhang, et al., ACS Appl. Mater. Interfaces 11 (2019) 40808–40816. doi: 10.1021/acsami.9b13313
21. [21]
  T. Chen, D. Zeng, L. Zhang, et al., J. Energy Chem. 59 (2021) 530–537. doi: 10.1016/j.jechem.2020.11.031
22. [22]
  S. Shim, W.B. Park, J. Han, et al., Adv. Sci. 9 (2022) e2201648. doi: 10.1002/advs.202201648
23. [23]
  T. Hwang, Y.J. Lee, S.R. Lee, et al., J. Mater. Chem. A 10 (2022) 16908–16919. doi: 10.1039/d2ta03649e
24. [24]
  L. Peng, S. Chen, C. Yu, et al., ACS Appl. Mater. Interfaces 14 (2022) 4179–4185. doi: 10.1021/acsami.1c21561
25. [25]
  Z. Sun, Y. Lai, N. lv, et al., ACS Appl. Mater. Interfaces 13 (2021) 54924–54935. doi: 10.1021/acsami.1c14573
26. [26]
  M.J. Deck, P.H. Chien, T.P. Poudel, et al., Adv. Energy Mater. 14 (2024) 2302785. doi: 10.1002/aenm.202302785
27. [27]
  Z. Zhang, L. Zhang, X. Yan, et al., J. Power Sources 410-411 (2019) 162–170. doi: 10.22323/1.345.0162
28. [28]
  T. Ohtomo, A. Hayashi, M. Tatsumisago, et al., J. Solid State Electr. 17 (2013) 2551–2557. doi: 10.1007/s10008-013-2149-5
29. [29]
  T. Ohtomo, A. Hayashi, M. Tatsumisago, et al., Electrochemistry 81 (2013) 428–431. doi: 10.5796/electrochemistry.81.428
30. [30]
  A. Kato, M. Nagao, A. Sakuda, et al., J. Ceram. Soc. Jpn. 122 (2014) 552–555. doi: 10.2109/jcersj2.122.552
31. [31]
  Y. Tao, S. Chen, D. Liu, et al., J. Electrochem. Soc. 163 (2015) A96–A101.
32. [32]
  A. Hayashi, H. Muramatsu, T. Ohtomo, et al., J. Alloy. Compd. 591 (2014) 247–250. doi: 10.1016/j.jallcom.2013.12.191
33. [33]
  Y. Sun, K. Suzuki, K. Hara, et al., J. Power Sources 324 (2016) 798–803. doi: 10.1016/j.jpowsour.2016.05.100
34. [34]
  H. Li, Q. Lin, J. Wang, et al., Angew. Chem. Int. Ed. 63 (2024) e202407892. doi: 10.1002/anie.202407892
35. [35]
  P. Adeli, J.D. Bazak, K.H. Park, et al., Angew. Chem. Int. Ed. 58 (2019) 8681–8686. doi: 10.1002/anie.201814222
36. [36]
  L. Peng, C. Yu, Z. Zhang, et al., Chem. Eng. J. 430 (2022) 132896.
37. [37]
  T. Lei, L. Peng, C. Liao, et al., Chem. Commun. 59 (2023) 14285–14288. doi: 10.1039/d3cc05099h
38. [38]
  S. Li, J. Lin, M. Schaller, et al., Angew. Chem. Int. Ed. 62 (2023) e202314155. doi: 10.1002/anie.202314155
39. [39]
  J.E. Trevey, J.R. Gilsdorf, S.W. Miller, et al., Solid State Ionics 214 (2012) 25–30.
40. [40]
  G. Liu, W. Weng, Z. Zhang, et al., Nano Lett. 20 (2020) 6660–6665. doi: 10.1021/acs.nanolett.0c02489
41. [41]
  Y. Nikodimos, S.K. Jiang, S.J. Huang, et al., ACS Energy Lett. 9 (2024) 1844–1852. doi: 10.1021/acsenergylett.4c00500
42. [42]
  J. Auvergniot, A. Cassel, D. Foix, et al., Solid State Ionics 300 (2017) 78–85.
1. [1]
  Zhangran Ye , Zhixuan Yu , Jingming Yao , Lei Deng , Yunna Guo , Hantao Cui , Chongchong Ma , Chao Tai , Liqiang Zhang , Lingyun Zhu , Peng Jia . An ionically conductive and compressible sulfochloride solid-state electrolyte for stable all-solid-state lithium-based batteries. Chinese Chemical Letters, 2025, 36(8): 110272-. doi: 10.1016/j.cclet.2024.110272
2. [2]
  Xingjie Li , Chengjun Yi , Weifei Hu , Huishan Zhang , Jiale Xia , Yuanyuan Li , Jinping Liu . Emerging sulfide-polymer composite solid electrolyte membranes. Chinese Chemical Letters, 2025, 36(6): 110215-. doi: 10.1016/j.cclet.2024.110215
3. [3]
  Jie Chen , Hannan Chen , Bingbing Tian . Enhancing moisture and electrochemical stability of the Li_5.7PS_4.7Cl_1.3 electrolyte by boron nitride coating for all-solid-state lithium metal batteries. Chinese Chemical Letters, 2025, 36(7): 109775-. doi: 10.1016/j.cclet.2024.109775
4. [4]
  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
5. [5]
  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
6. [6]
  Mingyang Men , Jinghua Wu , Gaozhan Liu , Jing Zhang , Nini Zhang , Xiayin Yao . Sulfide Solid Electrolyte Synthesized by Liquid Phase Approach and Application in All-Solid-State Lithium Batteries. Acta Physico-Chimica Sinica, 2025, 41(1): 100004-0. doi: 10.3866/PKU.WHXB202309019
7. [7]
  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
8. [8]
  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
9. [9]
  Xiaodong Wang , Miaomiao Zhou , Yirui Deng , Zijun Liu , Huiyou Dong , Peng Yan , Ruiping Liu . Dual functional Ti₃(PO₄)₄-coated NCM811 cathode enables highly stable sulfide-based all-solid-state lithium batteries. Chinese Chemical Letters, 2025, 36(9): 110307-. doi: 10.1016/j.cclet.2024.110307
10. [10]
  Liang Ming , Dan Liu , Qiyue Luo , Chaochao Wei , Chen Liu , Ziling Jiang , Zhongkai Wu , Lin Li , Long Zhang , Shijie Cheng , Chuang Yu . Si-doped Li₆PS₅I with enhanced conductivity enables superior performance for all-solid-state lithium batteries. Chinese Chemical Letters, 2024, 35(10): 109387-. doi: 10.1016/j.cclet.2023.109387
11. [11]
  Xuejie Gao , Xinyang Chen , Ming Jiang , Hanyan Wu , Wenfeng Ren , Xiaofei Yang , Runcang Sun . Long-lifespan thin Li anode achieved by dead Li rejuvenation and Li dendrite suppression for all-solid-state lithium batteries. Chinese Chemical Letters, 2024, 35(10): 109448-. doi: 10.1016/j.cclet.2023.109448
12. [12]
  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
13. [13]
  Dong Sui , Jiayi Liu . Constriction-susceptible lithium support for fast cycling of solid-state lithium metal battery. Chinese Chemical Letters, 2025, 36(2): 110417-. doi: 10.1016/j.cclet.2024.110417
14. [14]
  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
15. [15]
  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
16. [16]
  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
17. [17]
  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
18. [18]
  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
19. [19]
  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
20. [20]
  Jingyu Shi , Xiaofeng Wu , Yutong Chen , Yi Zhang , Xiangyan Hou , Ruike Lv , Junwei Liu , Mengpei Jiang , Keke Huang , Shouhua Feng . Structure factors dictate the ionic conductivity and chemical stability for cubic garnet-based solid-state electrolyte. Chinese Chemical Letters, 2025, 36(5): 109938-. doi: 10.1016/j.cclet.2024.109938

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(17)
HTML views(2)

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

Effect of oxygen doping sources on enhancing air stability and lithium metal compatibility of Li5.5PS4.5Cl1.5 electrolyte

Metrics

通讯作者: 陈斌, bchen63@163.com

Effect of oxygen doping sources on enhancing air stability and lithium metal compatibility of Li_5.5PS_4.5Cl_1.5 electrolyte