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:

Negating interfacial impedance in garnet-based solid-state Li metal batteries

Nature Materials volume 16, pages 572–579 (2017)Cite this article

Subjects

Abstract

Garnet-type solid-state electrolytes have attracted extensive attention due to their high ionic conductivity, approaching 1 mS cm−1, excellent environmental stability, and wide electrochemical stability window, from lithium metal to ∼6 V. However, to date, there has been little success in the development of high-performance solid-state batteries using these exceptional materials, the major challenge being the high solid–solid interfacial impedance between the garnet electrolyte and electrode materials. In this work, we effectively address the large interfacial impedance between a lithium metal anode and the garnet electrolyte using ultrathin aluminium oxide (Al2O3) by atomic layer deposition. Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZN) is the garnet composition of choice in this work due to its reduced sintering temperature and increased lithium ion conductivity. A significant decrease of interfacial impedance, from 1,710 Ω cm2 to 1 Ω cm2, was observed at room temperature, effectively negating the lithium metal/garnet interfacial impedance. Experimental and computational results reveal that the oxide coating enables wetting of metallic lithium in contact with the garnet electrolyte surface and the lithiated-alumina interface allows effective lithium ion transport between the lithium metal anode and garnet electrolyte. We also demonstrate a working cell with a lithium metal anode, garnet electrolyte and a high-voltage cathode by applying the newly developed interface chemistry.

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

Figure 1: Characterization of as-prepared LLCZN garnet electrolyte.
Figure 2: Characterizations of garnet solid-state electrolyte/Li metal interface.
Figure 3: Characterization for the interface of ALD-Al2O3-coated garnet solid electrolyte.
Figure 4: First-principles calculations of Li metal and garnet interface with and without ALD-Al2O3.
Figure 5: High-voltage cell with Li metal anode and LLZCN electrolyte.

Similar content being viewed by others

References

  1. Xu, X. et al. Self-organized core–shell structure for high-power electrode in solid-state lithium batteries. Chem. Mater. 23, 3798–3804 (2011).

    CAS  Google Scholar 

  2. Inada, T. et al. All solid-state sheet battery using lithium inorganic solid electrolyte, thio-LISICON. J. Power Sources 194, 1085–1088 (2009).

    CAS  Google Scholar 

  3. Feng, J. K., Yan, B. G., Liu, J. C., Lai, M. O. & Li, L. All solid state lithium ion rechargeable batteries using NASICON structured electrolyte. Mater. Technol. 28, 276–279 (2013).

    CAS  Google Scholar 

  4. Noguchi, Y., Kobayashi, E., Plashnitsa, L. S., Okada, S. & Yamaki, J.-I. Fabrication and performances of all solid-state symmetric sodium battery based on NASICON-related compounds. Electrochim. Acta 101, 59–65 (2013).

    CAS  Google Scholar 

  5. Ihlefeld, J. F. et al. Fast lithium-ion conducting thin-film electrolytes integrated directly on flexible substrates for high-power solid-state batteries. Adv. Mater. 23, 5663–5667 (2011).

    CAS  Google Scholar 

  6. Lü, X. et al. Antiperovskite Li3OCl superionic conductor films for solid-state Li-ion batteries. Adv. Sci. 3, 1500359 (2016).

    Google Scholar 

  7. Takahashi, K. et al. All-solid-state lithium battery with LiBH4 solid electrolyte. J. Power Sources 226, 61–64 (2013).

    CAS  Google Scholar 

  8. Trevey, J. E., Jung, Y. S. & Lee, S.-H. High lithium ion conducting Li2S–GeS2–P2S5 glass–ceramic solid electrolyte with sulfur additive for all solid-state lithium secondary batteries. Electrochim. Acta 56, 4243–4247 (2011).

    CAS  Google Scholar 

  9. Yersak, T. A. et al. An all-solid-state Li-ion battery with a pre-lithiated Si–Ti–Ni alloy anode. J. Electrochem. Soc. 160, A1497–A1501 (2013).

    CAS  Google Scholar 

  10. Buschmann, H. et al. Structure and dynamics of the fast lithium ion conductor “Li7La3Zr2O12”. Phys. Chem. Chem. Phys. 13, 19378–19392 (2011).

    CAS  Google Scholar 

  11. Djenadic, R. et al. Nebulized spray pyrolysis of Al-doped Li7La3Zr2O12 solid electrolyte for battery applications. Solid State Ion. 263, 49–56 (2014).

    CAS  Google Scholar 

  12. 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 

  13. Ren, Y. et al. Effects of Li source on microstructure and ionic conductivity of Al-contained Li6.75La3Zr1.75Ta0.25O12 ceramics. J. Eur. Ceram. Soc. 35, 561–572 (2015).

    CAS  Google Scholar 

  14. Thangadurai, V., Schwenzel, J. & Weppner, W. Tailoring ceramics for specific applications: a case study of the development of all-solid-state lithium batteries. Ionics 11, 11–23 (2005).

    CAS  Google Scholar 

  15. Kamaya, N. et al. A lithium superionic conductor. Nat. Mater. 10, 682–686 (2011).

    CAS  Google Scholar 

  16. Yada, C. et al. Dielectric modification of 5 V-class cathodes for high-voltage all-solid-state lithium batteries. Adv. Energy Mater. 4, 1301416 (2014).

    Google Scholar 

  17. Takada, K. et al. Interfacial phenomena in solid-state lithium battery with sulfide solid electrolyte. Solid State Ion. 225, 594–597 (2012).

    CAS  Google Scholar 

  18. Sakuda, A. et al. All-solid-state lithium secondary batteries with metal-sulfide-coated LiCoO2 prepared by thermal decomposition of dithiocarbamato complexes. J. Mater. Chem. 22, 15247–15254 (2012).

    CAS  Google Scholar 

  19. Sakuda, A. et al. All-solid-state lithium secondary batteries using Li2S-P2S5 solid electrolytes and LiFePO4 electrode particles with amorphous surface layer. Chem. Lett. 41, 260–261 (2012).

    CAS  Google Scholar 

  20. Seino, Y., Ota, T. & Takada, K. High rate capabilities of all-solid-state lithium secondary batteries using Li4Ti5O12-coated LiNi0.8Co0.15Al0.05O2 and a sulfide-based solid electrolyte. J. Power Sources 196, 6488–6492 (2011).

    CAS  Google Scholar 

  21. Ohta, N. et al. LiNbO3-coated LiCoO2 as cathode material for all solid-state lithium secondary batteries. Electrochem. Commun. 9, 1486–1490 (2007).

    CAS  Google Scholar 

  22. Kato, T. et al. In-situ Li7La3Zr2O12/LiCoO2 interface modification for advanced all-solid-state battery. J. Power Sources 260, 292–298 (2014).

    CAS  Google Scholar 

  23. Ohta, S. et al. All-solid-state lithium ion battery using garnet-type oxide and Li3BO3 solid electrolytes fabricated by screen-printing. J. Power Sources 238, 53–56 (2013).

    CAS  Google Scholar 

  24. Van den Broek, J., Afyon, S. & Rupp, J. L. M. Interface-engineered all-solid-state Li-ion batteries based on garnet-type fast Li + conductors. Adv. Energy Mater. 6, 1600736 (2016).

    Google Scholar 

  25. Thangadurai, V., Pinzaru, D., Narayanan, S. & Baral, A. K. Fast solid-state Li ion conducting garnet-type structure metal oxides for energy storage. J. Phys. Chem. Lett. 6, 292–299 (2015).

    CAS  Google Scholar 

  26. Sudo, R. et al. Interface behavior between garnet-type lithium-conducting solid electrolyte and lithium metal. Solid State Ion. 262, 151–154 (2014).

    CAS  Google Scholar 

  27. Ohta, S. et al. Co-sinterable lithium garnet-type oxide electrolyte with cathode for all-solid-state lithium ion battery. J. Power Sources 265, 40–44 (2014).

    CAS  Google Scholar 

  28. Jin, Y. & McGinn, P. J. Bulk solid state rechargeable lithium ion battery fabrication with Al-doped Li7La3Zr2O12 electrolyte and Cu0.1V2O5 cathode. Electrochim. Acta 89, 407–412 (2013).

    CAS  Google Scholar 

  29. Thangadurai, V., Kaack, H. & Weppner, W. J. F. Novel fast lithium ion conduction in garnet-type Li5La3M2O12 (M = Nb, Ta). J. Am. Ceram. Soc. 86, 437–440 (2003).

    CAS  Google Scholar 

  30. O’Callaghan, M. P., Powell, A. S., Titman, J. J., Chen, G. Z. & Cussen, E. J. Switching on fast lithium ion conductivity in garnets: the structure and transport properties of Li3+xNd3Te2−xSbxO12 . Chem. Mater. 20, 2360–2369 (2008).

    Google Scholar 

  31. Jalem, R. et al. Concerted migration mechanism in the Li ion dynamics of garnet-type Li7La3Zr2O12 . Chem. Mater. 25, 425–430 (2013).

    CAS  Google Scholar 

  32. Thompson, T. et al. A tale of two sites: on defining the carrier concentration in garnet-based ionic conductors for advanced Li batteries. Adv. Energy Mater. 5, 150096 (2015).

    Google Scholar 

  33. Cheng, L. et al. The origin of high electrolyte-electrode interfacial resistances in lithium cells containing garnet type solid electrolytes. Phys. Chem. Chem. Phys. 16, 18294–18300 (2014).

    CAS  Google Scholar 

  34. Kihira, Y., Ohta, S., Imagawa, H. & Asaoka, T. Effect of simultaneous substitution of alkali earth metals and Nb in Li7La3Zr2O12 on lithium-ion conductivity. ECS Electrochem. Lett. 2, A56–A59 (2013).

    CAS  Google Scholar 

  35. Wolfenstine, J., Allen, J. L., Read, J. & Sakamoto, J. Chemical stability of cubic Li7La3Zr2O12 with molten lithium at elevated temperature. J. Mater. Sci. 48, 5846–5851 (2013).

    CAS  Google Scholar 

  36. Jung, S. C. & Han, Y.-K. How do Li atoms pass through the Al2O3 coating layer during lithiation in Li-ion batteries? J. Phys. Chem. Lett. 4, 2681–2685 (2013).

    CAS  Google Scholar 

  37. Jung, S. C., Kim, H.-J., Choi, J. W. & Han, Y.-K. Sodium ion diffusion in Al2O3: a distinct perspective compared with lithium ion diffusion. Nano Lett. 14, 6559–6563 (2014).

    CAS  Google Scholar 

  38. Han, X. et al. Atomic-layer-deposition oxide nanoglue for sodium ion batteries. Nano Lett. 14, 139–147 (2013).

    Google Scholar 

  39. Wang, D. N. et al. Atomic layer deposited coatings to significantly stabilize anodes for Li ion batteries: effects of coating thickness and the size of anode particles. J. Mater. Chem. A 2, 2306–2312 (2014).

    CAS  Google Scholar 

  40. Lotfabad, E. M. et al. Si nanotubes ALD coated with TiO2, TiN or Al2O3 as high performance lithium ion battery anodes. J. Mater. Chem. A 2, 2504–2516 (2014).

    CAS  Google Scholar 

  41. Kohandehghan, A. et al. Silicon nanowire lithium-ion battery anodes with ALD deposited TiN coatings demonstrate a major improvement in cycling performance. J. Mater. Chem. A 1, 12850–12861 (2013).

    CAS  Google Scholar 

  42. Li, Y. et al. Tuning electrochemical performance of Si-based anodes for lithium-ion batteries by employing atomic layer deposition alumina coating. J. Mater. Chem. A 2, 11417–11425 (2014).

    CAS  Google Scholar 

  43. Liu, T. et al. Achieving high capacity in bulk-type solid-state lithium ion battery based on Li6.75La3Zr1.75Ta0.25O12 electrolyte: interfacial resistance. J. Power Sources 324, 349–357 (2016).

    CAS  Google Scholar 

  44. Sharafi, A., Meyer, H. M., Nanda, J., Wolfenstine, J. & Sakamoto, J. Characterizing the Li–Li7La3Zr2O12 interface stability and kinetics as a function of temperature and current density. J. Power Sources 302, 135–139 (2016).

    CAS  Google Scholar 

  45. Tsai, C. L. et al. Li7La3Zr2O12 interface modification for Li dendrite prevention. ACS Appl. Mater. Interfaces 8, 10617–10626 (2016).

    CAS  Google Scholar 

  46. Mo, Y., Ong, S. P. & Ceder, G. First principles study of the Li10GeP2S12 lithium super ionic conductor material. Chem. Mater. 24, 15–17 (2012).

    CAS  Google Scholar 

  47. Zhang, Z. et al. Fluorinated electrolytes for 5 V lithium-ion battery chemistry. Energy Environ. Sci. 6, 1806–1810 (2013).

    CAS  Google Scholar 

  48. Kawai, H., Nagata, M., Tabuchi, M., Tukamoto, H. & West, A. R. Novel 5 V spinel cathode Li2FeMn3O8 for lithium ion batteries. Chem. Mater. 10, 3266–3268 (1998).

    CAS  Google Scholar 

  49. Jain, A. et al. Commentary: the Materials Project: a materials genome approach to accelerating materials innovation. APL Mater. 1, 011002 (2013).

    Google Scholar 

Download references

Acknowledgements

This work was supported by the US Department of Energy ARPA-E (Contract No. DE-AR0000384) and EERE (Contract No. DE-EE0006860). We acknowledge S.-C. Liou for TEM and EELS characterization and data analysis, and the support of the Maryland NanoCenter and its FabLab and AIMLab. We acknowledge K. Xu from the US Army Research Laboratory for supplying the liquid electrolyte. We acknowledge computational facilities from the University of Maryland supercomputing resources, the Maryland Advanced Research Computing Center (MARCC), and the Extreme Science and Engineering Discovery Environment (XSEDE) supported by National Science Foundation Award No. DMR150038. The XPS measurements were supported by Nanostructures for Electrical Energy Storage (NEES), an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award Number DESC0001160.

Author information

Author notes

  1. Xiaogang Han, Yunhui Gong and Kun (Kelvin) Fu: These authors contributed equally to this work.

Authors and Affiliations

  1. and Department of Materials Science and Engineering, University of Maryland Energy Research Center, University of Maryland, College Park, Maryland 20742, USA

    Xiaogang Han, Yunhui Gong, Kun (Kelvin) Fu, Xingfeng He, Gregory T. Hitz, Jiaqi Dai, Alex Pearse, Boyang Liu, Howard Wang, Gary Rubloff, Yifei Mo, Eric D. Wachsman & Liangbing Hu

  2. Institute for Systems Research, University of Maryland, College Park, Maryland 20742, USA

    Alex Pearse & Gary Rubloff

  3. Department of Chemistry, University of Calgary, 2500 University Drive Northwest, Calgary, Alberta T2N 1N4, Canada

    Venkataraman Thangadurai

Authors
  1. Xiaogang Han
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yunhui Gong
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Kun (Kelvin) Fu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xingfeng He
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Gregory T. Hitz
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Jiaqi Dai
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Alex Pearse
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Boyang Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Howard Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Gary Rubloff
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Yifei Mo
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Venkataraman Thangadurai
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Eric D. Wachsman
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Liangbing Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

X.H., Y.G. and K.F. fabricated the samples and carried out the experiments, characterizations, data analysis, and manuscript preparation. X.H. and Y.M. conducted the theoretical analysis. G.T.H. helped prepare samples and analysed the experimental results. J.D. drew the schematics and prepared FIB samples. A.P. and G.R. carried out the XPS and XPS data analysis. B.L. prepared samples and conducted ALD. H.W. carried out NDP and NDP data analysis. V.T. helped review the results, and E.D.W. and L.H. managed the project and reviewed the results, data analysis, and manuscript preparation.

Corresponding authors

Correspondence to Eric D. Wachsman or Liangbing Hu.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 910 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Han, X., Gong, Y., Fu, K. et al. Negating interfacial impedance in garnet-based solid-state Li metal batteries. Nature Mater 16, 572–579 (2017). https://doi.org/10.1038/nmat4821

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat4821

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