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

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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.

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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.

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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.

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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.

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Correspondence to Eric D. Wachsman or Liangbing Hu.

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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

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