Skip to main content
SpringerLink
Log in

Fast Li+-conducting Zr4+-based oxychloride electrolyte with good thermal and solvent stability

具有优异热稳定性和溶剂稳定性的快锂离子导体—锆基氧氯化物固态电解质

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

Li2ZrCl6 with a trigonal structure is a low-cost Li+-conducting chloride electrolyte, which is stable at high voltages up to 4.2 V and is compatible with high-voltage cathodes. However, its relatively low room-temperature ionic conductivity, poor stability in different solvents and at high temperatures limit its application for next-generation all-solid-state batteries. Herein, we prepared new oxychloride electrolytes with different molar ratios of Li2O, ZrCl4, and LiCl, replacing Cl− with O2− anion to optimize the electrolyte performance. The results showed that increasing the Li2O content reduced the crystallization degree of trigonal Li2ZrCl6 and induced a monoclinic structure in the prepared oxychloride electrolyte. The oxychloride with the general formula Li2.22Zr1.11Cl5.33O0.67 had a high room-temperature ionic conductivity above 10−3 S cm−1. Moreover, introducing Li2O considerably increased the thermal and solvent stability of the electrolyte. Good ionic conductivity and stability of the electrolyte enable the stable cycling of all-solid-state Li-In/LiCoO2 batteries.

摘要

成本低廉的锂离子导体氯化物固态电解质Li2ZrCl6, 属于三方晶系, 可在4.2 V下保持稳定, 与高压正极材料具有良好的兼容性. 然而,相对较低的室温离子电导率、较差的化学稳定性和热稳定性等缺点阻碍了它在全固态电池中的进一步发展. 基于此, 我们利用Li2O, ZrCl 4 和LiCl合成了新型氧氯化物固态电解质, 并通过O2−对Cl−的取代来优化固态电解质的性能. 结果表明增加Li2O的含量会降低三方相Li2ZrCl 6 的结晶度, 且诱导单斜结构的产生. 新合成的Li2.22Zr1.11Cl5.33O0.67 室温电导率可到10−3S cm−1. 此外, Li2O的加入能够提高固态电解质的热稳定性和溶剂稳定性. 固态电解质Li2.22Zr1.11Cl5.33O0.67 良好的离子电导率及稳定性使得Li-In/LiCoO2 全固态电池具有稳定的循环性能.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Banerjee A, Wang X, Fang C, et al. Interfaces and interphases in all-solid-state batteries with inorganic solid electrolytes. Chem Rev, 2020, 120: 6878–6933

    Article  CAS  Google Scholar 

  2. Li X, Liang J, Yang X, et al. Progress and perspectives on halide lithium conductors for all-solid-state lithium batteries. Energy Environ Sci, 2020, 13: 1429–1461

    Article  CAS  Google Scholar 

  3. Wang C, Liang J, Kim JT, et al. Prospects of halide-based all-solid-state batteries: From material design to practical application. Sci Adv, 2022, 8: eadc9516

    Article  CAS  Google Scholar 

  4. Kwak H, Wang S, Park J, et al. Emerging halide superionic conductors for all-solid-state batteries: Design, synthesis, and practical applications. ACS Energy Lett, 2022, 7: 1776–1805

    Article  CAS  Google Scholar 

  5. Miao X, Guan S, Ma C, et al. Role of interfaces in solid-state batteries. Adv Mater, 2023, 2206402

  6. Wang C, Fu K, Kammampata SP, et al. Garnet-type solid-state electrolytes: Materials, interfaces, and batteries. Chem Rev, 2020, 120: 4257–4300

    Article  CAS  Google Scholar 

  7. Li Y, Xu B, Xu H, et al. Hybrid polymer/garnet electrolyte with a small interfacial resistance for lithium-ion batteries. Angew Chem Int Ed, 2017, 56: 753–756

    Article  CAS  Google Scholar 

  8. Li Y, Han JT, Wang CA, et al. Optimizing Li+ conductivity in a garnet framework. J Mater Chem, 2012, 22: 15357–15361

    Article  CAS  Google Scholar 

  9. Zhao Q, Stalin S, Zhao CZ, et al. Designing solid-state electrolytes for safe, energy-dense batteries. Nat Rev Mater, 2020, 5: 229–252

    Article  CAS  Google Scholar 

  10. Schlem R, Muy S, Prinz N, et al. Mechanochemical synthesis: A tool to tune cation site disorder and ionic transport properties of Li3MCl6 (M = Y, Er) superionic conductors. Adv Energy Mater, 2020, 10: 1903719

    Article  CAS  Google Scholar 

  11. Wang S, Bai Q, Nolan AM, et al. Lithium chlorides and bromides as promising solid-state chemistries for fast ion conductors with good electrochemical stability. Angew Chem Int Ed, 2019, 58: 8039–8043

    Article  CAS  Google Scholar 

  12. Sebti E, Evans HA, Chen H, et al. Stacking faults assist lithium-ion conduction in a halide-based superionic conductor. J Am Chem Soc, 2022, 144: 5795–5811

    Article  CAS  Google Scholar 

  13. Asano T, Sakai A, Ouchi S, et al. Solid halide electrolytes with high lithium-ion conductivity for application in 4 V class bulk-type all-solidstate batteries. Adv Mater, 2018, 30: 1803075

    Article  Google Scholar 

  14. Kageyama H, Hayashi K, Maeda K, et al. Expanding frontiers in materials chemistry and physics with multiple anions. Nat Commun, 2018, 9: 772

    Article  Google Scholar 

  15. Li X, Liang J, Chen N, et al. Water-mediated synthesis of a superionic halide solid electrolyte. Angew Chem Int Ed, 2019, 58: 16427–16432

    Article  CAS  Google Scholar 

  16. Wang K, Ren Q, Gu Z, et al. A cost-effective and humidity-tolerant chloride solid electrolyte for lithium batteries. Nat Commun, 2021, 12: 4410

    Article  CAS  Google Scholar 

  17. Kwak H, Han D, Lyoo J, et al. New cost-effective halide solid electrolytes for all-solid-state batteries: Mechanochemically prepared Fe3+-substituted Li2ZrCl6. Adv Energy Mater, 2021, 11: 2003190

    Article  CAS  Google Scholar 

  18. Gautam A, Sadowski M, Prinz N, et al. Rapid crystallization and kinetic freezing of site-disorder in the lithium superionic argyrodite Li6PS5Br. Chem Mater, 2019, 31: 10178–10185

    Article  CAS  Google Scholar 

  19. Wang S, Fang R, Li Y, et al. Interfacial challenges for all-solid-state batteries based on sulfide solid electrolytes. J Materiomics, 2021, 7: 209–218

    Article  CAS  Google Scholar 

  20. Schlem R, Banik A, Ohno S, et al. Insights into the lithium substructure of superionic conductors Li3YCl6 and Li3YBr6. Chem Mater, 2021, 33: 327–337

    Article  CAS  Google Scholar 

  21. Zhou L, Zuo TT, Kwok CY, et al. High areal capacity, long cycle life 4 V ceramic all-solid-state Li-ion batteries enabled by chloride solid electrolytes. Nat Energy, 2022, 7: 83–93

    Article  CAS  Google Scholar 

  22. Shao Q, Yan C, Gao M, et al. New insights into the effects of Zr substitution and carbon additive on Li3−xEr1−xZrxCl6 halide solid electrolytes. ACS Appl Mater Interfaces, 2022, 14: 8095–8105

    Article  CAS  Google Scholar 

  23. Zhou L, Kwok CY, Shyamsunder A, et al. A new halospinel superionic conductor for high-voltage all solid state lithium batteries. Energy Environ Sci, 2020, 13: 2056–2063

    Article  CAS  Google Scholar 

  24. Nikodimos Y, Huang CJ, Taklu BW, et al. Chemical stability of sulfide solid-state electrolytes: Stability toward humid air and compatibility with solvents and binders. Energy Environ Sci, 2022, 15: 991–1033

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (22025507 and 21931012), the Key Research Program of Frontier Sciences, Chinese Academy of Sciences (ZDBS-LYSLH020), and Beijing National Laboratory for Molecular Sciences (BNLMS-CXXM-202010).

Author information

Authors and Affiliations

  1. CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Bing Li  (李冰), Hong-Shen Zhang  (张洪申), Sijie Guo  (郭思杰) & An-Min Cao  (曹安民)

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Bing Li  (李冰), Yutao Li  (李玉涛), Hong-Shen Zhang  (张洪申) & An-Min Cao  (曹安民)

  3. Beijing Frontier Research Center on Clean Energy, Huairou Division, Institute of Physics, Chinese Academy of Sciences, Beijing, 101400, China

    Yutao Li  (李玉涛)

  4. National Engineering Research Center for Advanced Polymer Processing Technology, Key Laboratory of Advanced Material Processing & Mold (Ministry of Education), Zhengzhou University, Zhengzhou, 450002, China

    Ting-Ting Wu  (仵亭亭)

Authors
  1. Bing Li  (李冰)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yutao Li  (李玉涛)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hong-Shen Zhang  (张洪申)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Ting-Ting Wu  (仵亭亭)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Sijie Guo  (郭思杰)
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. An-Min Cao  (曹安民)
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Cao AM and Li Y designed the samples; Li B and Wu TT performed the experiments; Li B, Zhang HS and Guo S performed the data analysis; Li B and Li Y wrote the paper with support from Cao AM. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Yutao Li  (李玉涛) or An-Min Cao  (曹安民).

Additional information

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Experimental details and supporting data are available in the online version of the paper.

Bing Li is pursuing her doctor degree at the Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences (ICCAS). She received her Master degree from Zhengzhou University. Her research interest focuses on designing solid-state oxychloride electrolytes and optimizing the interface for all-solid-state batteries.

Yutao Li received his PhD degree in materials science and engineering from Tsinghua University in 2013. He joined Prof. John B. Goodenough’s group to develop new materials for next-generation solid-state batteries at the University of Texas, Austin from 2013 to 2022. He is currently an associate professor at the Institute of Physics, CAS. His research focuses on developing fast ionic conductors and optimizing the interface for all-solid-state batteries.

An-Min Cao earned his PhD degree from the ICCAS in 2006. Thereafter he did postdoctoral research in Prof. Götz Veser’s group on functional nanomaterials for heterogeneous catalytic reactions. In May 2010, he transferred to the University of Texas, Austin to work on clean energy-related materials with Prof. A. Manthiram. He has served as a full professor at the ICCAS since 2012. His current research centers on the surface/interface control of high-energy electrode materials for secondary batteries.

Supplementary Information

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Li, B., Li, Y., Zhang, HS. et al. Fast Li+-conducting Zr4+-based oxychloride electrolyte with good thermal and solvent stability. Sci. China Mater. 66, 3123–3128 (2023). https://doi.org/10.1007/s40843-023-2434-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-023-2434-4

Keywords

Search

Navigation