Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Extreme lithium-metal cycling enabled by a mixed ion- and electron-conducting garnet three-dimensional architecture

Nature Materials volume 22, pages 1136–1143 (2023)Cite this article

Subjects

Abstract

The development of solid-state Li-metal batteries has been limited by the Li-metal plating and stripping rates and the tendency for dendrite shorts to form at commercially relevant current densities. To address this, we developed a single-phase mixed ion- and electron-conducting (MIEC) garnet with comparable Li-ion and electronic conductivities. We demonstrate that in a trilayer architecture with a porous MIEC framework supporting a thin, dense, garnet electrolyte, the critical current density can be increased to a previously unheard of 100 mA cm−2, with no dendrite-shorting. Additionally, we demonstrate that symmetric Li cells can be continuously cycled at a current density of 60 mA cm−2 with a maximum per-cycle Li plating and stripping capacity of 30 mAh cm−2, which is 6× the capacity of state-of-the-art cathodes. Moreover, a cumulative Li plating capacity of 18.5 Ah cm−2 was achieved with the MIEC/electrolyte/MIEC architecture, which if paired with a state-of-the-art cathode areal capacity of 5 mAh cm−2 would yield a projected 3,700 cycles, significantly surpassing requirements for commercial electric vehicle battery lifetimes.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Schematic diagram of Li-metal plating and stripping inside a non-MIEC garnet structure and a MIEC garnet structure.
Fig. 2: Characterization of prepared MIEC garnet.
Fig. 3: Schematic diagrams and cross-sectional SEM images of trilayers with and without Li-metal infiltration inside the porous MIEC structure.
Fig. 4: Electrochemical performance of symmetric Li-metal cells with thin, dense Ta-LLZ supported by a porous MIEC garnet network.
Fig. 5: Electrochemical performance of cells with an NMC cathode, MIEC(P)–Ta-LLZ(D)–MIEC(P) trilayer architecture and an Li-metal anode at room temperature.

Similar content being viewed by others

Data availability

Data presented in this study are available from the corresponding author on reasonable request.

References

  1. Tarascon, J. M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).

    CAS  Google Scholar 

  2. Lin, D., Liu, Y. & Cui, Y. Reviving the lithium metal anode for high-energy batteries. Nat. Nanotechnol. 12, 194–206 (2017).

    CAS  Google Scholar 

  3. Lee, H. G., Kim, S. Y. & Lee, J. S. Dynamic observation of dendrite growth on lithium metal anode during battery charging/discharging cycles. npj Comput. Mater. 8, 1–13 (2022).

    Google Scholar 

  4. Jana, A. & García, R. E. Lithium dendrite growth mechanisms in liquid electrolytes. Nano Energy 41, 552–565 (2017).

    CAS  Google Scholar 

  5. Qian, J. et al. High rate and stable cycling of lithium metal anode. Nat. Commun. 6, 6362 (2015).

    CAS  Google Scholar 

  6. Subramanian, K. et al. A brief review of recent advances in garnet structured solid electrolyte based lithium metal batteries. J. Energy Storage 33, 102157 (2021).

    Google Scholar 

  7. Wang, C. et al. Garnet-type solid-state electrolytes: materials, interfaces, and batteries. Chem. Rev. 120, 4257–4300 (2020).

    CAS  Google Scholar 

  8. Ramakumar, S., Deviannapoorani, C., Dhivya, L., Shankar, L. S. & Murugan, R. Lithium garnets: synthesis, structure, Li+ conductivity, Li+ dynamics and applications. Prog. Mater. Sci. 88, 325–411 (2017).

    CAS  Google Scholar 

  9. Murugan, R., Thangadurai, V. & Weppner, W. Fast lithium ion conduction in garnet-type Li7La3Zr2O12. Angew. Chem. Int. Ed. 46, 7778–7781 (2007).

    CAS  Google Scholar 

  10. Albertus, P., Babinec, S., Litzelman, S. & Newman, A. Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries. Nat. Energy 3, 16–21 (2017).

    Google Scholar 

  11. Huo, H. et al. In-situ formed Li2CO3-free garnet/Li interface by rapid acid treatment for dendrite-free solid-state batteries. Nano Energy 61, 119–125 (2019).

    CAS  Google Scholar 

  12. Fu, K. et al. Three-dimensional bilayer garnet solid electrolyte based high energy density lithium metal–sulfur batteries. Energy Environ. Sci. 10, 1568–1575 (2017).

    CAS  Google Scholar 

  13. Lee, S. et al. Design of a lithiophilic and electron-blocking interlayer for dendrite-free lithium-metal solid-state batteries. Sci. Adv. 8, 153 (2022).

    CAS  Google Scholar 

  14. Samson, A. J., Hofstetter, K., Bag, S. & Thangadurai, V. A bird’s-eye view of Li-stuffed garnet-type Li7La3Zr2O12 ceramic electrolytes for advanced all-solid-state Li batteries. Energy Environ. Sci. 12, 2957–2975 (2019).

    CAS  Google Scholar 

  15. Alexander, G. V., Indu, M. S. & Murugan, R. Review on the critical issues for the realization of all-solid-state lithium metal batteries with garnet electrolyte: interfacial chemistry, dendrite growth, and critical current densities. Ionics 27, 4105–4126 (2021).

    CAS  Google Scholar 

  16. Basappa, R. H., Ito, T. & Yamada, H. Contact between garnet-type solid electrolyte and lithium metal anode: influence on charge transfer resistance and short circuit prevention. J. Electrochem. Soc. 164, A666–A671 (2017).

    CAS  Google Scholar 

  17. Han, X. et al. Negating interfacial impedance in garnet-based solid-state Li metal batteries. Nat. Mater. 16, 572–579 (2016).

    Google Scholar 

  18. Alexander, G. V. et al. Electrodes-electrolyte interfacial engineering for realizing room temperature lithium metal battery based on garnet structured solid fast Li+ conductors. J. Power Sources 396, 764–773 (2018).

    CAS  Google Scholar 

  19. Alexander, G. V., Indu, M. S., Kamakshy, S. & Murugan, R. Development of stable and conductive interface between garnet structured solid electrolyte and lithium metal anode for high performance solid-state battery. Electrochim. Acta 332, 135511 (2020).

    CAS  Google Scholar 

  20. Feng, W., Dong, X., Li, P., Wang, Y. & Xia, Y. Interfacial modification of Li/Garnet electrolyte by a lithiophilic and breathing interlayer. J. Power Sources 419, 91–98 (2019).

    CAS  Google Scholar 

  21. Lou, J. et al. Achieving efficient and stable interface between metallic lithium and garnet-type solid electrolyte through a thin indium tin oxide interlayer. J. Power Sources 448, 227440 (2020).

    CAS  Google Scholar 

  22. Luo, W. et al. Reducing interfacial resistance between garnet-structured solid-state electrolyte and Li-metal anode by a germanium layer. Adv. Mater. 29, 1606042 (2017).

    Google Scholar 

  23. Li, Y. et al. Garnet electrolyte with an ultralow interfacial resistance for Li-metal batteries. J. Am. Chem. Soc. 140, 6448–6455 (2018).

    CAS  Google Scholar 

  24. Alexander, G. V., Sreejith, O. V., Indu, M. S. & Murugan, R. Interface-compatible and high-cyclability lithiophilic lithium-zinc alloy anodes for garnet-structured solid electrolytes. ACS Appl. Energy Mater. 3, 9010–9017 (2020).

    CAS  Google Scholar 

  25. Huang, Y. et al. Graphitic carbon nitride (g-C3N4): an interface enabler for solid-state lithium metal batteries. Angew. Chem. Int. Ed. 59, 3699–3704 (2020).

    CAS  Google Scholar 

  26. Zhang, X. et al. Long cycling life solid-state Li metal batteries with stress self-adapted Li/garnet interface. Nano Lett. 20, 2871–2878 (2020).

    CAS  Google Scholar 

  27. Fu, K. K. et al. Toward garnet electrolyte–based Li metal batteries: an ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface. Sci. Adv. 3, e1601659 (2017).

    Google Scholar 

  28. Cui, J. et al. Melt-quenching of artificial metallic interlayer enables a resistance-free garnet/lithium interface for all-solid-state lithium-metal batteries. Energy Storage Mater. 53, 899–908(2022).

    Google Scholar 

  29. Wang, C. et al. Conformal, nanoscale ZnO surface modification of garnet-based solid-state electrolyte for lithium metal anodes. Nano Lett. 17, 565–571 (2017).

    CAS  Google Scholar 

  30. Xu, S. et al. Three-dimensional, solid-state mixed electron–ion conductive framework for lithium metal anode. Nano Lett. 18, 3926–3933 (2018).

    CAS  Google Scholar 

  31. Liu, B. et al. 3D lithium metal anodes hosted in asymmetric garnet frameworks toward high energy density batteries. Energy Storage Mater. 14, 376–382 (2018).

    Google Scholar 

  32. Xu, S. et al. All-in-one lithium-sulfur battery enabled by a porous-dense-porous garnet architecture. Energy Storage Mater. 15, 458–464 (2018).

    Google Scholar 

  33. Hitz, G. T. et al. High-rate lithium cycling in a scalable trilayer Li-garnet-electrolyte architecture. Mater. Today 22, 50–57 (2019).

    CAS  Google Scholar 

  34. Yang, C. et al. Continuous plating/stripping behavior of solid-state lithium metal anode in a 3D ion-conductive framework. Proc. Natl Acad. Sci. USA 115, 3770–3775 (2018).

    CAS  Google Scholar 

  35. Xie, H. et al. Amorphous-carbon-coated 3D solid electrolyte for an electro-chemomechanically stable lithium metal anode in solid-state batteries. Nano Lett. 21, 6163–6170 (2021).

    CAS  Google Scholar 

  36. Xu, S. et al. Three-dimensional, solid-state mixed electron-ion conductive framework for lithium metal anode. Nano Lett. 18, 3926–3933 (2018).

    CAS  Google Scholar 

  37. Chen, Y. et al. Li metal deposition and stripping in a solid-state battery via Coble creep. Nature 578, 251–255 (2020).

    CAS  Google Scholar 

  38. Gao, J. et al. Rational design of mixed electronic-ionic conducting Ti-doping Li7La3Zr2O12 for lithium dendrites suppression. Adv. Funct. Mater. 31, 2001918 (2021).

    CAS  Google Scholar 

  39. Cheng, X., Huang, J., Qiang, W. & Huang, B. Synthesis of mixed ionic and electronic conducting garnet with doping of transition elements (Fe, Co, Ni). Ceram. Int. 46, 3731–3737 (2020).

    CAS  Google Scholar 

  40. Samson, A. J., Hofstetter, K., Wachsman, E. & Thangadurai, V. Towards mixed ionic and electronic conducting Li-stuffed garnets. J. Electrochem. Soc. 165, A2303–A2311 (2018).

    CAS  Google Scholar 

  41. Thangadurai, V. & Weppner, W. Li6ALa2Nb2O12 (A=Ca, Sr, Ba): a new class of fast lithium ion conductors with garnet-like structure. J. Am. Ceram. Soc. 88, 411–418 (2005).

    CAS  Google Scholar 

  42. Stockham, M. P., Dong, B., Ding, Y., Li, Y. & Slater, P. R. Evaluation of the effect of site substitution of Pr doping in the lithium garnet system Li5La3Nb2O12. Dalton Trans. 49, 10349–10359 (2020).

    CAS  Google Scholar 

  43. Wagner, R. et al. Crystal structure of garnet-related Li-ion conductor Li7−3xGaxLa3Zr2O12: fast Li-ion conduction caused by a different cubic modification? Chem. Mater. 28, 1861–1871 (2016).

    CAS  Google Scholar 

  44. Flatscher, F., Philipp, M., Ganschow, S., Wilkening, H. M. R. & Rettenwander, D. The natural critical current density limit for Li7La3Zr2O12 garnets. J. Mater. Chem. A 8, 15782–15788 (2020).

    CAS  Google Scholar 

  45. Duan, J. et al. Lithium–graphite paste: an interface compatible anode for solid-state batteries. Adv. Mater. 31, 1807243 (2019).

    Google Scholar 

  46. Raj, V. et al. Direct correlation between void formation and lithium dendrite growth in solid-state electrolytes with interlayers. Nat. Mater. 21, 1050–1056 (2022).

    CAS  Google Scholar 

Download references

Acknowledgements

We thank the Army Research Laboratory under Cooperative Agreement number W911NF-22-2-0021 (E.D.W.) for financial support and acknowledge the X-ray Crystallography Center and Maryland Nanocenter and its AIMLab for support with the characterization. We thank K. Duncan for his suggestions, which improved the manuscript, and thank P. W. Jaschin, G. Scissco and C. Tang for their help in analysing the data.

Author information

Authors and Affiliations

  1. Department of Materials Science and Engineering, University of Maryland, College Park, MD, USA

    George V. Alexander, Changmin Shi, Jon O’Neill & Eric D. Wachsman

  2. Maryland Energy Innovation Institute, University of Maryland, College Park, MD, USA

    George V. Alexander, Changmin Shi, Jon O’Neill & Eric D. Wachsman

Authors
  1. George V. Alexander
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Changmin Shi
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jon O’Neill
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Eric D. Wachsman
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

E.D.W. conceived and supervised the research. G.V.A. performed the experiments. C.S. carried out the characterization via SEM. J.O'N. designed the schematics for the paper. G.V.A. and E.D.W. collectively wrote the paper with assistance from all other authors.

Corresponding author

Correspondence to Eric D. Wachsman.

Ethics declarations

Competing interests

E.D.W. founded Ion Storage Systems to commercialize solid-state batteries. However, all results reported herein were performed at the University of Maryland under federal sponsorship. The remaining authors declare no competing interests.

Peer review

Peer review information

Nature Materials thanks Marca Doeff and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–15 and Tables 1 and 2.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Alexander, G.V., Shi, C., O’Neill, J. et al. Extreme lithium-metal cycling enabled by a mixed ion- and electron-conducting garnet three-dimensional architecture. Nat. Mater. 22, 1136–1143 (2023). https://doi.org/10.1038/s41563-023-01627-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41563-023-01627-9

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing