Developing a viable metallic lithium anode is a prerequisite for next-generation batteries. However, the low redox potential of lithium metal renders it prone to corrosion, which must be thoroughly understood for it to be used in practical energy-storage devices. Here we report a previously overlooked mechanism by which lithium deposits can corrode on a copper surface. Voids are observed in the corroded deposits and a Kirkendall-type mechanism is validated through electrochemical analysis. Although it is a long-held view that lithium corrosion in electrolytes involves direct charge-transfer through the lithium–electrolyte interphase, the corrosion observed here is found to be governed by a galvanic process between lithium and the copper substrate—a pathway largely neglected by previous battery corrosion studies. The observations are further rationalized by detailed analyses of the solid–electrolyte interphase formed on copper and lithium, where the disparities in electrolyte reduction kinetics on the two surfaces can account for the fast galvanic process.
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Jones, D. A. Principles and Prevention of Corrosion (Macmillan, New York, 1992).
Bard, A. J., Faulkner, L. R., Leddy, J. & Zoski, C. G. Electrochemical Methods: Fundamentals and Applications Vol. 2 (Wiley, New York, 1980).
Winter, M. & Brodd, R. J. What are batteries, fuel cells, and supercapacitors? Chem. Rev. 104, 4245–4270 (2004).
Tarascon, J.-M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).
Goodenough, J. B. & Park, K.-S. The Li-ion rechargeable battery: a perspective. J. Am. Chem. Soc. 135, 1167–1176 (2013).
Park, H. et al. Thermal behavior of solid electrolyte interphase films deposited on graphite electrodes with different states-of-charge. J. Electrochem. Soc. 162, A892–A896 (2015).
Fong, R., von Sacken, U. & Dahn, J. R. Studies of lithium intercalation into carbons using nonaqueous electrochemical cells. J. Electrochem. Soc. 137, 2009–2013 (1990).
Dunn, B., Kamath, H. & Tarascon, J. –M. Electrical energy storage for the grid: a battery of choices. Science 334, 928–935 (2011).
Bruce, P. G., Freunberger, S. A., Hardwick, L. J. & Tarascon, J.-M. Li–O2 and Li–S batteries with high energy storage. Nat. Mater. 11, 19–29 (2012).
Aurbach, D. et al. On the surface chemical aspects of very high energy density, rechargeable Li–sulfur batteries. J. Electrochem. Soc. 156, A694–A702 (2009).
Harrison, K. L. et al. Lithium self-discharge and its prevention: direct visualization through in situ electrochemical scanning transmission electron microscopy. ACS Nano 11, 11194–11205 (2017).
Pei, A., Zheng, G., Shi, F., Li, Y. & Cui, Y. Nanoscale nucleation and growth of electrodeposited lithium metal. Nano Lett. 17, 1132–1139 (2017).
Yang, H., Fey, E. O., Trimm, B. D., Dimitrov, N. & Whittingham, M. S. Effects of pulse plating on lithium electrodeposition, morphology and cycling efficiency. J. Power Sources 272, 900–908 (2014).
Zheng, J. et al. Electrolyte additive enabled fast charging and stable cycling lithium metal batteries. Nat. Energy 2, 17012 (2017).
Chen, S. et al. High-efficiency lithium metal batteries with fire-retardant electrolytes. Joule 2, 1548–1558 (2018).
Fan, X. et al. Non-flammable electrolyte enables Li–metal batteries with aggressive cathode chemistries. Nat. Nanotech. 13, 715–722 (2018).
Kozen, A. C. et al. Next-generation lithium metal anode engineering via atomic layer deposition. ACS Nano 9, 5884–5892 (2015).
Liu, Y. et al. An ultrastrong double-layer nanodiamond interface for stable lithium metal anodes. Joule 2, 1595–1609 (2018).
Xie, J. et al. Stitching h-BN by atomic layer deposition of LiF as a stable interface for lithium metal anode. Sci. Adv. 3, eaao3170 (2017).
Lin, D. et al. Layered reduced graphene oxide with nanoscale interlayer gaps as a stable host for lithium metal anodes. Nat. Nanotech. 11, 626–632 (2016).
Yang, C.-P., Yin, Y.-X., Zhang, S.-F., Li, N.-W. & Guo, Y.-G. Accommodating lithium into 3D current collectors with a submicron skeleton towards long-life lithium metal anodes. Nat. Commun. 6, 8058 (2015).
Xu, W. et al. Lithium metal anodes for rechargeable batteries. Energy Environ. Sci. 7, 513–537 (2014).
Lin, D., Liu, Y. & Cui, Y. Reviving the lithium metal anode for high-energy batteries. Nat. Nanotech. 12, 194–206 (2017).
Qian, J. et al. High rate and stable cycling of lithium metal anode. Nat. Commun. 6, 6362 (2015).
Ryou, M. H., Lee, Y. M., Lee, Y., Winter, M. & Bieker, P. Mechanical surface modification of lithium metal: towards improved Li metal anode performance by directed Li plating. Adv. Funct. Mater. 25, 834–841 (2015).
Peled, E. The electrochemical behavior of alkali and alkaline earth metals in nonaqueous battery systems—the solid electrolyte interphase model. J. Electrochem. Soc. 126, 2047–2051 (1979).
Aurbach, D., Gofer, Y. & Langzam, J. The correlation between surface chemistry, surface morphology, and cycling efficiency of lithium electrodes in a few polar aprotic systems. J. Electrochem. Soc. 136, 3198–3205 (1989).
Aurbach, D., Youngman, O. & Dan, P. The electrochemical behavior of 1, 3-dioxolane–LiClO4 solutions—II. Contaminated solutions. Electrochim. Acta 35, 639–655 (1990).
Odziemkowski, M. & Irish, D. E. An electrochemical study of the reactivity at the lithium electrolyte/bare lithium metal interface: I. Purified electrolytes. J. Electrochem. Soc. 139, 3063–3074 (1992).
Aurbach, D., Ein‐Ely, Y. & Zaban, A. The surface chemistry of lithium electrodes in alkyl carbonate solutions. J. Electrochem. Soc. 141, L1–L3 (1994).
Peled, E., Golodnitsky, D. & Ardel, G. Advanced model for solid electrolyte interphase electrodes in liquid and polymer electrolytes. J. Electrochem. Soc. 144, L208–L210 (1997).
Aurbach, D., Zinigrad, E., Cohen, Y. & Teller, H. A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions. Solid State Ionics 148, 405–416 (2002).
Aurbach, D. Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries. J. Power Sources 89, 206–218 (2000).
Cheng, X. B. et al. A review of solid electrolyte interphases on lithium metal anode. Adv. Sci. 3, 1500213 (2016).
Keil, P. et al. Calendar aging of lithium-ion batteries: I. Impact of the graphite anode on capacity fade. J. Electrochem. Soc. 163, A1872–A1880 (2016).
Smigelskas, A. & Kirkendall, E. Zinc diffusion in alpha brass. Trans. Metall. Soc. AIME 171, 130–142 (1947).
Yin, Y. et al. Formation of hollow nanocrystals through the nanoscale Kirkendall effect. Science 304, 711–714 (2004).
Chee, S. W., Tan, S. F., Baraissov, Z., Bosman, M. & Mirsaidov, U. Direct observation of the nanoscale Kirkendall effect during galvanic replacement reactions. Nat. Commun. 8, 1224 (2017).
Oldfield, J. W. in Galvanic Corrosion (ed. Hack, H. P.) 5–22 (ASTM International, Philadelphia, 1988).
Li, W. et al. The synergetic effect of lithium polysulfide and lithium nitrate to prevent lithium dendrite growth. Nat. Commun. 6, 7436 (2015).
Li, Y. et al. Atomic structure of sensitive battery materials and interfaces revealed by cryo-electron microscopy. Science 358, 506–510 (2017).
Peled, E. & Menkin, S. SEI: past, present and future. J. Electrochem. Soc. 164, A1703–A1719 (2017).
Chen, K. -H. et al. Dead lithium: mass transport effects on voltage, capacity, and failure of lithium metal anodes. J. Mater. Chem. A 5, 11671–11681 (2017).
Soto, F. A., Ma, Y., Martinez de la Hoz, J. M., Seminario, J. M. & Balbuena, P. B. Formation and growth mechanisms of solid–electrolyte interphase layers in rechargeable batteries. Chem. Mater. 27, 7990–8000 (2015).
Anderson, B. D. & Tracy, J. B. Nanoparticle conversion chemistry: Kirkendall effect, galvanic exchange, and anion exchange. Nanoscale 6, 12195–12216 (2014).
Xu, K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chem. Rev. 104, 4303–4418 (2004).
Xu, K. Electrolytes and interphases in Li-ion batteries and beyond. Chem. Rev. 114, 11503–11618 (2014).
Thevenin, J. & Muller, R. Impedance of lithium electrodes in a propylene carbonate electrolyte. J. Electrochem. Soc. 134, 273–280 (1987).
Peled, E. et al. The role of SEI in lithium and lithium ion batteries. Mater. Res. Soc. Symp. 393, 209 (1995).
Y.C. acknowledges support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy under the Battery Materials Research (BMR) program and Battery500 consortium.
The authors declare no competing interests.
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Supplementary Fig. 1–40, Supplementary Methods, and Supplementary Movie Captions
Movie of FIB millings of 10 representative Li deposits without rest in the electrolyte
Movie of FIB millings of 10 representative Li deposits after rest in the electrolyte for 100 hours
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Lin, D., Liu, Y., Li, Y. et al. Fast galvanic lithium corrosion involving a Kirkendall-type mechanism. Nat. Chem. 11, 382–389 (2019) doi:10.1038/s41557-018-0203-8
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