Rechargeable Li metal batteries are currently limited by safety concerns, continuous electrolyte decomposition and rapid consumption of Li. These issues are mainly related to reactions occurring at the Li metal–liquid electrolyte interface. The formation of a passivation film (that is, a solid electrolyte interphase) determines ionic diffusion and the structural and morphological evolution of the Li metal electrode upon cycling. In this Review, we discuss spontaneous and operation-induced reactions at the Li metal–electrolyte interface from a corrosion science perspective. We highlight that the instantaneous formation of a thin protective film of corrosion products at the Li surface, which acts as a barrier to further chemical reactions with the electrolyte, precedes film reformation, which occurs during subsequent electrochemical stripping and plating of Li during battery operation. Finally, we discuss solutions to overcoming remaining challenges of Li metal batteries related to Li surface science, electrolyte chemistry, cell engineering and the intrinsic instability of the Li metal–electrolyte interface.
This is a preview of subscription content, access via your institution
Open Access articles citing this article.
Nature Communications Open Access 17 March 2022
Subscribe to Nature+
Get immediate online access to Nature and 55 other Nature journal
Subscribe to Journal
Get full journal access for 1 year
only $9.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Get time limited or full article access on ReadCube.
All prices are NET prices.
Palacín, M. R. Recent advances in rechargeable battery materials: a chemist’s perspective. Chem. Soc. Rev. 38, 2565–2575 (2009).
Meister, P. et al. Best practice: performance and cost evaluation of lithium ion battery active materials with special emphasis on energy efficiency. Chem. Mater. 28, 7203–7217 (2016).
Tarascon, J. M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).
Choi, J. W. & Aurbach, D. Promise and reality of post-lithium-ion batteries with high energy densities. Nat. Rev. Mater. 1, 16013 (2016).
Haregewoin, A. M., Wotango, A. S. & Hwang, B. J. Electrolyte additives for lithium ion battery electrodes: Progress and perspectives. Energy Environ. Sci. 9, 1955–1988 (2016).
Hun, L., Yanilmaz, M., Toprakci, O., Fu, K. & Zhang, X. A review of recent developments in membrane separators for rechargeable lithium-ion batteries. Energy Environ. Sci. 7, 3857–3886 (2014).
Liu, J. et al. Pathways for practical high-energy long-cycling lithium metal batteries lithium metal batteries. Nat. Energy 4, 180–186 (2019).
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. Nanotechnol. 12, 194–206 (2017).
Knapp, H. R. in Proceedings of the 19th Annual Power Sources Conference 94–97 (PSC Publications Committee, 1965).
Whittingham, M. S. Electrical energy storage and intercalation chemistry. Science 192, 1126–1127 (1976).
Yoshino, A. The birth of the lithium-ion battery. Angew. Chem. Int. Ed. 51, 5798–5800 (2012).
Kalhoff, J., Eshetu, G. G., Bresser, D. & Passerini, S. Safer electrolytes for lithium-ion batteries: state of the art and perspectives. ChemSusChem 8, 2154–2175 (2015).
Wang, J. et al. Fire-extinguishing organic electrolytes for safe batteries. Nat. Energy 3, 22–29 (2018).
Zheng, J. et al. Regulating electrodeposition morphology of lithium: towards commercially relevant secondary Li metal batteries. Chem. Soc. Rev. 49, 2701–2750 (2020).
Cheng, X. B. et al. A review of solid electrolyte interphases on lithium metal anode. Adv. Sci. 3, 1500213 (2016).
Shi, P. et al. A review of composite lithium metal anode for practical applications. Adv. Mater. Technol. 5, 1900806 (2020).
Richey, F. W., Mccloskey, B. D. & Luntz, A. C. Mg anode corrosion in aqueous electrolytes and implications for Mg-air batteries. J. Electrochem. Soc. 163, A958–A963 (2016).
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).
Alekseev, V. I., Perkas, M. M., Yusupov, V. S. & Lazarenko, G. Y. The mechanism of metal corrosion passivation. Russ. J. Phys. Chem. A 87, 1380–1385 (2013).
Revie, R. W. & Uhlig, H. H. Corrosion and Corrosion Control 3rd edn (Wiley, 1985).
Ospina-Acevedo, F., Guo, N. & Balbuena, P. B. Lithium oxidation and electrolyte decomposition at Li-metal/liquid electrolyte interfaces. J. Mater. Chem. A 8, 17036–17055 (2020).
Winter, M. The solid electrolyte interphase–the most important and the least understood solid electrolyte in rechargeable Li batteries. Z. Phys. Chem. 223, 1395–1406 (2009).
O’Brien, T. F., Bommaraju, T. V. & Hine, F. in Handbook of Chlor-Alkali Technology 1295–1348 (Springer, 2005).
Pilling, N. B. & Bedworth, R. E. The oxidation of metals in high temperature. J. Inst. Met. 29, 529–591 (1923).
Soltis, J. Passivity breakdown, pit initiation and propagation of pits in metallic materials – Review. Corros. Sci. 90, 5–22 (2015).
Ashby, M., Shercliff, H. & Cebon, D. in Materials: Engineering, Science, Processing and Design Ch. 17 (Elsevier, 2007).
Gomera, L., Spanish, T., Islands, C., Gomera, L. & Spanish, T. Passivation of iron by chromate solutions. Nature 180, 27–28 (1957).
Sato, N. Interfacial ion-selective diffusion layer and passivation of metal anodes. Electrochim. Acta 41, 1525–1532 (1996).
Beleevskii, V. S., Kudelin, Y. I., Lisov, S. F. & Timonin, V. A. Electrochemical and corrosion behavior of metals in solutions of weak acids and salts of weak acids. Sov. Mater. Sci. 26, 622–628 (1991).
Yuan, D., Zhao, J., Manalastas, W., Kumar, S. & Srinivasan, M. Emerging rechargeable aqueous aluminum ion battery: Status, challenges, and outlooks. Nano Mater. Sci. 2, 248–263 (2020).
Yang, H. et al. The rechargeable aluminum battery: opportunities and challenges. Angew. Chem. Int. Ed. 58, 11978–11996 (2019).
Liu, Y. et al. A comprehensive review on recent progress in aluminum–air batteries. Green Energy Environ. 2, 246–277 (2017).
Rahman, M. A., Wang, X. & Wenz, C. High energy density metal-air batteries: a review. J. Electrochem. Soc. 160, A1759–A1771 (2013).
Zhang, T., Tao, Z. & Chen, J. Magnesium–air batteries: from principle to application. Mater. Horiz. 1, 196–206 (2014).
Harris, W. S. Electrochemical Studies in Cyclic Esters. PhD thesis, Univ. California (1958).
Jorne, J. & Tobias, C. W. Electrodeposition of the alkali metals from propylene carbonate. J. Appl. Electrochem. 5, 279–290 (1975).
Geronov, Y., Schwager, F. & Muller, R. H. Film formation on lithium in propylene carbonate solutions under open circuit conditions. J. Electrochem. Soc. (1980).
Lu, Z., Schechter, A., Moshkovich, M. & Aurbach, D. On the electrochemical behavior of magnesium electrodes in polar aprotic electrolyte solutions. J. Electroanal. Chem. 466, 203–217 (1999).
Wang, H. F. & Xu, Q. Materials design for rechargeable metal-air batteries. Matter 1, 565–595 (2019).
Winter, M., Barnett, B. & Xu, K. Before Li ion batteries. Chem. Rev. 118, 11433–11456 (2018).
Odziemkowski, M. & Irish, D. E. An electrochemical study of the reactivity at the lithium electrolyte/bare lithium metal interface. J. Electrochem. Soc. 139, 3063–3074 (1993).
Heiskanen, S. K., Kim, J. & Lucht, B. L. Generation and evolution of the solid electrolyte interphase of lithium-ion batteries. Joule 3, 2322–2333 (2019).
Xiong, S., Diao, Y., Hong, X., Chen, Y. & Xie, K. Characterization of solid electrolyte interphase on lithium electrodes cycled in ether-based electrolytes for lithium batteries. J. Electroanal. Chem. 719, 122–126 (2014).
Lin, C. F., Kozen, A. C., Noked, M., Liu, C. & Rubloff, G. W. ALD protection of Li-metal anode surfaces–quantifying and preventing chemical and electrochemical corrosion in organic solvent. Adv. Mater. Interfaces 3, 1600426 (2016).
Yin, X. et al. Insights into morphological evolution and cycling behaviour of lithium metal anode under mechanical pressure. Nano Energy 50, 659–664 (2018).
Wood, K. N., Noked, M. & Dasgupta, N. P. Lithium metal anodes: toward an improved understanding of coupled morphological, electrochemical, and mechanical behavior. ACS Energy Lett. 2, 664–672 (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).
Wang, A., Kadam, S., Li, H., Shi, S. & Qi, Y. Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries. NPJ Comput. Mater. 4, 1–26 (2018).
Li, Y., Leung, K. & Qi, Y. Computational exploration of the Li-electrode|electrolyte interface in the presence of a nanometer thick solid-electrolyte interphase layer. Acc. Chem. Res. 49, 2363–2370 (2016).
Strehblow, H.-H., Maurice, V. & Marcus, P. in Corrosion Mechanisms in Theory and Practice 3rd edn Ch. 5 (ed. Marcus, P.) (CRC Press, 2011).
Keßler, S. & Sagüés, A. A. A minimalist approach to polarization resistance measurements in a reinforced concrete structure. Mater. Corros. 71, 849–856 (2020).
Popov, B. N. Corrosion Engineering Ch. 3 (Elsevier, 2015).
Littauer, E. L. & Tsai, K. C. Corrosion of lithium in alkaline solution. J. Electrochem. Soc. 124, 850–855 (1977).
Slemnik, M. Activation energies ratio as corrosion indicator for different heat treated stainless steels. Mater. Des. 89, 795–801 (2016).
Gunnarsdóttir, A. B., Vema, S., Menkin, S., Marbella, L. E. & Grey, C. P. Investigating the effect of a fluoroethylene carbonate additive on lithium deposition and the solid electrolyte interphase in lithium metal batteries using in situ NMR spectroscopy. J. Mater. Chem. A 8, 14975–14992 (2020).
Camacho-Forero, L. E. & Balbuena, P. B. Effects of charged interfaces on electrolyte decomposition at the lithium metal anode. J. Power Sources 472, 228449 (2020).
Tikekar, M. D., Choudhury, S., Tu, Z. & Archer, L. A. Design principles for electrolytes and interfaces for stable lithium-metal batteries. Nat. Energy 1, 16114 (2016).
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).
Lafage, M., Windel, D., Russier, V. & Badiali, J. P. Mechanisms of growth and corrosion at the lithium-solvent interface. Electrochim. Acta 42, 2841–2852 (1997).
Jiao, S. et al. Stable cycling of high-voltage lithium metal batteries in ether electrolytes. Nat. Energy 3, 739–746 (2018).
Xu, J. et al. Mechanical and electronic stabilization of solid electrolyte interphase with sulfite additive for lithium metal batteries. J. Electrochem. Soc. 166, A3201–A3206 (2019).
Macdonald, D. D. Fundamental Studies of Passivity and Passivity Breakdown (US Department of Energy, 1993).
Verhallen, T. W., Lv, S. & Wagemaker, M. Operando neutron depth profiling to determine the spatial distribution of Li in Li-ion batteries. Front. Energy Res. 6, 62 (2018).
Yu, S. H., Huang, X., Brock, J. D. & Abruña, H. D. Regulating key variables and visualizing lithium dendrite growth: an operando X-ray study. J. Am. Chem. Soc. 141, 8441–8449 (2019).
Lv, D. et al. Failure mechanism for fast-charged lithium metal batteries with liquid electrolytes. Adv. Energy Mater. 5, 1400993 (2015).
Fang, C. et al. Quantifying inactive lithium in lithium metal batteries. Nature 572, 511–515 (2019).
Xu, S., Chen, K.-H., Dasgupta, N. P., Siegel, J. B. & Stefanopoulou, A. G. Evolution of dead lithium growth in lithium metal batteries: experimentally validated model of the apparent capacity loss. J. Electrochem. Soc. 166, A3456–A3463 (2019).
Nanda, S., Gupta, A. & Manthiram, A. Anode-free full cells: a pathway to high-energy density lithium-metal batteries. Adv. Energy Mater. 11, 2000804 (2021).
Lin, D. et al. Fast galvanic lithium corrosion involving a Kirkendall-type mechanism. Nat. Chem. 11, 382–389 (2019).
Kolesnikov, A. et al. Galvanic corrosion of lithium-powder-based electrodes. Adv. Energy Mater. 10, 2000017 (2020).
Wu, X. et al. Safety issues in lithium ion batteries: materials and cell design. Front. Energy Res. 7, 65 (2019).
Xu, K., Von Cresce, A. & Lee, U. Differentiating contributions to “ion transfer” barrier from interphasial resistance and Li+ desolvation at electrolyte/graphite interface. Langmuir 26, 11538–11543 (2010).
Fujieda, T. et al. Surface of lithium electrodes prepared in Ar + CO2 gas. J. Power Sources 52, 197–200 (1994).
Koch, S. L., Morgan, B. J., Passerini, S. & Teobaldi, G. Density functional theory screening of gas-treatment strategies for stabilization of high energy-density lithium metal anodes. J. Power Sources 296, 150–161 (2015).
Zhao, J. et al. Surface fluorination of reactive battery anode materials for enhanced stability. J. Am. Chem. Soc. 139, 11550–11558 (2017).
Becking, J. et al. Lithium-metal foil surface modification: an effective method to improve the cycling performance of lithium-metal batteries. Adv. Mater. Interfaces 4, 1700166 (2017).
Xu, K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chem. Rev. 104, 4303–4417 (2004).
Leung, K., Soto, F., Hankins, K., Balbuena, P. B. & Harrison, K. L. Stability of solid electrolyte interphase components on lithium metal and reactive anode material surfaces. J. Phys. Chem. C 120, 6302–6313 (2016).
Peled, E. & Menkin, S. Review — SEI: past, present and future. J. Electrochem. Soc. 164, A1703–A1719 (2017).
Aurbach, D., Youngman, O. & Dan, P. The electrochemical behaviour of 1,3-dioxolane — LiClO4 solutions — I. Uncontaminated solutions. Electrochim. Acta 35, 639–655 (1990).
Zhang, H. et al. Electrolyte additives for lithium metal anodes and rechargeable lithium metal batteries: progress and perspectives angewandte. Angew. Chem. Int. Ed. 57, 15002–15027 (2018).
Peljo, P. & Girault, H. H. Electrochemical potential window of battery electrolytes: the HOMO–LUMO misconception. Energy Environ. Sci. 11, 2306–2309 (2018).
Goodenough, J. B. & Kim, Y. Challenges for rechargeable Li batteries. Chem. Mater. 22, 587–603 (2010).
Gauthier, M. et al. Electrode–electrolyte interface in Li-Ion batteries: current understanding and new insights. J. Phys. Chem. Lett. 6, 4653–4672 (2015).
Zheng, J. et al. Electrolyte additive enabled fast charging and stable cycling lithium metal batteries. Nat. Energy 2, 17012 (2017).
Beyene, T. T. et al. Concentrated dual-salt electrolyte to stabilize Li metal and increase cycle life of anode free li-metal batteries. J. Electrochem. Soc. 166, A1501–A1509 (2019).
Borodin, O., Olguin, M., Spear, C. E., Leiter, K. W. & Knap, J. Towards high throughput screening of electrochemical stability of battery electrolytes. Nanotechnology 26, 354003 (2015).
Borodin, O. et al. Modeling insight into battery electrolyte electrochemical stability and interfacial structure. Acc. Chem. Res. 50, 2886–2894 (2017).
Chen, X., Li, H., Shen, X. & Zhang, Q. The origin of the reduced reductive stability of ion–solvent complexes on alkali and alkaline earth metal anodes. Angew. Chem. 130, 16885–16889 (2018).
Xiong, S., Xie, K., Diao, Y. & Hong, X. Properties of surface film on lithium anode with LiNO3 as lithium salt in electrolyte solution for lithium–sulfur batteries. Electrochim. Acta 83, 78–86 (2012).
Aurbach, D. et al. On the surface chemical aspects of very high energy density, rechargeable Li–sulfur batteries. J. Electrochem. Soc. 156, 694–702 (2009).
Xu, K. Electrolytes and interphases in Li-ion batteries and beyond. Chem. Rev. 114, 11503–11618 (2014).
Zhang, X., Cheng, X., Chen, X., Yan, C. & Zhang, Q. Fluoroethylene carbonate additives to render uniform Li deposits in lithium metal batteries. Adv. Funct. Mater. 27, 1605989 (2017).
Suo, L. et al. Fluorine-donating electrolytes enable highly reversible 5-V-class Li metal batteries. Proc. Natl Acad. Sci. USA 115, 1156–1161 (2018).
Shi, Q., Zhong, Y., Wu, M., Wang, H. & Wang, H. High-capacity rechargeable batteries based on deeply cyclable lithium metal anodes. Proc. Natl Acad. Sci. USA 115, 5676–5680 (2018).
Budi, A. et al. Study of the initial stage of solid electrolyte interphase formation upon chemical reaction of lithium metal and N-methyl-N-propyl-pyrrolidinium-bis(fluorosulfonyl)imide. J. Phys. Chem. C 116, 19789–19797 (2012).
Zhou, H., Yu, S., Liu, H. & Liu, P. Protective coatings for lithium metal anodes: Recent progress and future perspectives. J. Power Sources 450, 227632 (2020).
Lin, D. et al. Layered reduced graphene oxide with nanoscale interlayer gaps as a stable host for lithium metal anodes. Nat. Nanotechnol. 11, 626–632 (2016).
Foroozan, T. et al. Synergistic effect of graphene oxide for impeding the dendritic plating of Li. Adv. Funct. Mater. 28, 1705917 (2018).
Cristian, M. et al. Sputter coating of lithium metal electrodes with lithiophilic metals for homogeneous and reversible lithium electrodeposition and electrodissolution. Mater. Today 39, 137–145 (2020).
Liang, X. et al. A facile surface chemistry route to a stabilized lithium metal anode. Nat. Energy 2, 17119 (2017).
Gao, Y. et al. Interfacial chemistry regulation via a skin-grafting strategy enables high-performance lithium-metal batteries. J. Am. Chem. Soc. 139, 15288–15291 (2017).
Li, N. W. et al. A flexible solid electrolyte interphase layer for long-life lithium metal anodes. Angew. Chem. Int. Ed. 57, 1505–1509 (2018).
Liu, Y. et al. An artificial solid electrolyte interphase with high Li-ion conductivity, mechanical strength, and flexibility for stable lithium metal anodes. Adv. Mater. 29, 1605531 (2017).
Bresser, D., Buchholz, D., Moretti, A., Varzi, A. & Passerini, S. Alternative binders for sustainable electrochemical energy storage–the transition to aqueous electrode processing and bio-derived polymers. Energy Environ. Sci. 11, 3096–3127 (2018).
Gao, Y. et al. Polymer–inorganic solid–electrolyte interphase for stable lithium metal batteries under lean electrolyte conditions. Nat. Mater. 18, 384–389 (2019).
Betz, J. et al. Cross talk between transition metal cathode and Li metal anode: unraveling its influence on the deposition/dissolution behavior and morphology of lithium. Adv. Energy Mater. 9, 1900574 (2019).
Zhang, X. Q. et al. Crosstalk shielding of transition metal ions for long cycling lithium-metal batteries. J. Mater. Chem. A 8, 4283–4289 (2020).
Moore, K. L., Sykes, J. M., Hogg, S. C. & Grant, P. S. Pitting corrosion of spray formed Al–Li–Mg alloys. Corros. Sci. 50, 3221–3226 (2008).
Koo, D., Kwon, B., Lee, J. & Lee, K. T. Asymmetric behaviour of Li/Li symmetric cells for Li metal batteries. Chem. Commun. 55, 9637–9640 (2019).
Hou, C. et al. Operando observations of SEI film evolution by mass-sensitive scanning transmission electron microscopy. Adv. Energy Mater. 9, 1902675 (2019).
Bieker, G., Winter, M. & Bieker, P. Electrochemical in situ investigations of SEI and dendrite formation on the lithium metal anode. Phys. Chem. Chem. Phys. 17, 8670–8679 (2015).
Selis, L. A. & Seminario, J. M. Dendrite formation in Li-metal anodes: an atomistic molecular dynamics study. RSC Adv. 9, 27835–27848 (2019).
Gireaud, L., Grugeon, S., Laruelle, S., Yrieix, B. & Tarascon, J.-M. Lithium metal stripping/plating mechanisms studies: A metallurgical approach. Electrochem. Commun. 8, 1639–1649 (2006).
Jurng, S., Brown, Z. L., Kim, J. & Lucht, B. L. Effect of electrolyte on the nanostructure of the solid electrolyte interphase (SEI) and performance of lithium metal anodes. Energy Environ. Sci. 11, 2600–2608 (2018).
Li, Y. et al. Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy. Science 358, 506–510 (2017).
Zachman, M. J., Tu, Z., Choudhury, S., Archer, L. A. & Kourkoutis, L. F. Cryo-STEM mapping of solid–liquid interfaces and dendrites in lithium-metal batteries. Nature 560, 345–349 (2018).
Zhuang, G. V., Xu, K., Yang, H., Jow, T. R. & Ross, P. N. Lithium ethylene dicarbonate identified as the primary product of chemical and electrochemical reduction of EC in 1.2 M LiPF6/EC:EMC electrolyte. J. Phys. Chem. B 560, 17567–17573 (2005).
Muralidharan, A., Chaudhari, M., Rempe, S. & Pratt, L. R. Molecular dynamics simulations of lithium ion transport through a model solid electrolyte interphase (SEI) layer. ECS Trans. 77, 1155–1162 (2017).
Benitez, L. & Seminario, J. M. Ion diffusivity through the solid electrolyte interphase in lithium-ion batteries. J. Electrochem. Soc. 164, E3159–E3170 (2017).
Shi, S. et al. Direct calculation of Li-ion transport in the solid electrolyte interphase. J. Am. Chem. Soc. 134, 15476–15487 (2012).
Ramasubramanian, A. et al. Lithium diffusion mechanism through solid–electrolyte interphase in rechargeable lithium batteries. J. Phys. Chem. C 123, 10237–10245 (2019).
Li, Y. et al. Correlating structure and function of battery interphases at atomic resolution using cryoelectron microscopy. Joule 2, 2167–2177 (2018).
Cao, X. et al. Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization. Nat. Energy 4, 796–805 (2019).
Fan, X. et al. Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries. Nat. Nanotechnol. 13, 715–722 (2018).
Heine, J. et al. Fluoroethylene carbonate as electrolyte additive in tetraethylene glycol dimethyl ether based electrolytes for application in lithium ion and lithium metal batteries. J. Electrochem. Soc. 162, A1094–A1101 (2015).
Lin, Y. et al. Connecting the irreversible capacity loss in Li-ion batteries with the electronic insulating properties of solid electrolyte interphase (SEI) components. J. Power Sources 309, 221–230 (2016).
Liu, Z. et al. Interfacial study on solid electrolyte interphase at Li metal anode: implication for Li dendrite growth. J. Electrochem. Soc. 163, A592–A598 (2016).
Fan, X. et al. Fluorinated solid electrolyte interphase enables highly reversible solid-state Li metal battery. Sci. Adv. 4, eaau9245 (2018).
Xu, R. et al. Interface engineering of sulfide electrolytes for all-solid-state lithium batteries. Nano Energy 53, 958–966 (2018).
Bard, A. J. & Faulkner, L. R. Electrochemical Methods: Fundamentals and Applications 2nd edn (Wiley, 2000).
Bae, J. et al. Polar polymer–solvent interaction derived favorable interphase for stable lithium metal batteries. Energy Environ. Sci. 12, 3319–3327 (2019).
Yu, Z. et al. A dynamic, electrolyte-blocking, and single-ion-conductive network for stable lithium-metal anodes. Joule 3, 2761–2776 (2019).
Lopez, J. et al. Effects of polymer coatings on electrodeposited lithium metal. J. Am. Chem. Soc. 140, 11735–11744 (2018).
Zheng, G. et al. Interconnected hollow carbon nanospheres for stable lithium metal anodes. Nat. Nanotechnol. 9, 618–623 (2014).
Zhang, Y. et al. High-capacity, low-tortuosity, and channel-guided lithium metal anode. Proc. Natl Acad. Sci. USA 114, 3584–3589 (2017).
Li, Y. & Qi, Y. Energy landscape of the charge transfer reaction at the complex Li/SEI/electrolyte interface. Energy Environ. Sci. 12, 1286–1295 (2019).
Xiao, J. et al. Understanding and applying coulombic efficiency in lithium metal batteries. Nat. Energy 6, 561–568 (2020).
Genovese, M. et al. Combinatorial methods for improving lithium metal cycling efficiency. J. Electrochem. Soc. 165, A3000–A3013 (2018).
Wang, M. et al. Effect of LiFSI concentrations to form thickness- and modulus-controlled SEI layers on lithium metal anodes. J. Phys. Chem. C 122, 9825–9834 (2018).
Liu, Y. et al. Solubility-mediated sustained release enabling nitrate additive in carbonate electrolytes for stable lithium metal anode. Nat. Commun. 9, 3656 (2018).
Lin, H., Chen, K. H., Shuai, Y., He, X. & Ge, K. Influence of CsNO3 as electrolyte additive on electrochemical property of lithium anode in rechargeable battery. J. Cent. South Univ. 25, 719–728 (2018).
Xie, J. et al. Engineering stable interfaces for three-dimensional lithium metal anodes. Sci. Adv. 4, eaat5168 (2018).
Hao, F., Verma, A. & Mukherjee, P. P. Mechanistic insight into dendrite-SEI interactions for lithium metal electrodes. J. Mater. Chem. A 6, 19664–19671 (2018).
Thenuwara, A. C. et al. Efficient low-temperature cycling of lithium metal anodes by tailoring the solid-electrolyte interphase. ACS Energy Lett. 5, 2411–2420 (2020).
Gao, Y. et al. Low-temperature and high-rate-charging lithium metal batteries enabled by an electrochemically active monolayer-regulated interface. Nat. Energy 5, 534–542 (2020).
Yan, K. et al. Temperature-dependent nucleation and growth of dendrite-free lithium metal anodes. Angew. Chem. Int. Ed. 131, 11486–11490 (2019).
Wang, J. et al. Improving cyclability of Li metal batteries at elevated temperatures and its origin revealed by cryo-electron microscopy. Nat. Energy 4, 664–670 (2019).
Li, P. et al. Synergistic effects of salt concentration and working temperature towards dendrite-free lithium deposition. Research https://doi.org/10.34133/2019/7481319 (2019).
Fan, X. et al. Highly fluorinated interphases enable high-voltage Li-metal batteries. Chem 4, 174–185 (2018).
Markevich, E., Salitra, G., Chesneau, F., Schmidt, M. & Aurbach, D. Very stable lithium metal stripping-plating at a high rate and high areal capacity in fluoroethylene carbonate-based organic electrolyte solution. ACS Energy Lett. 2, 1321–1326 (2017).
Qian, J. et al. High rate and stable cycling of lithium metal anode. Nat. Commun. 6, 6362 (2015).
Shi, F. et al. Lithium metal stripping beneath the solid electrolyte interphase. Proc. Natl Acad. Sci. USA 115, 8529–8534 (2018).
Adams, B. D., Zheng, J., Ren, X., Xu, W. & Zhang, J. G. Accurate determination of Coulombic efficiency for lithium metal anodes and lithium metal batteries. Adv. Energy Mater. 8, 1702097 (2018).
Bai, P., Li, J., Brushett, F. R. & Bazant, M. Z. Transition of lithium growth mechanisms in liquid electrolytes. Energy Environ. Sci. 9, 3221–3229 (2016).
Fu, C. et al. Universal chemomechanical design rules for solid-ion conductors to prevent dendrite formation in lithium metal batteries. Nat. Mater. 19, 758–766 (2020).
United States Council for Automotive Research LLC. USABC goals for advanced high-performance batteries for electric vehicle (EV) applications. USCAR http://www.uscar.org/guest/article_view.php?articles_id=85 (2020).
Wang, Z. et al. Efficient potential-tuning strategy through p-type doping for designing cathodes with ultrahigh energy density. Natl Sci. Rev. 7, 1768–1775 (2020).
Jung, H. G., Hassoun, J., Park, J. B., Sun, Y. K. & Scrosati, B. An improved high-performance lithium–air battery. Nat. Chem. 4, 579–585 (2012).
Mohtadi, R. & Mizuno, F. Magnesium batteries: Current state of the art, issues and future perspectives. Beilstein J. Nanotechnol. 5, 1291–1311 (2014).
Mori, M. Modification of the lithium metal surface by nonionic polyether surfactants: quartz crystal microbalance studies. J. Electrochem. Soc. 145, 2340 (1998).
Morita, M., Aoki, S. & Matsuda, Y. AC imepedance behaviour of lithium electrode in organic electrolyte solutions containing additives. Electrochim. Acta 37, 119–123 (1992).
Schmuch, R., Wagner, R., Hörpel, G., Placke, T. & Winter, M. Performance and cost of materials for lithium-based rechargeable automotive batteries. Nat. Energy 3, 267–278 (2018).
Cheng, X. B. et al. Implantable solid electrolyte interphase in lithium-metal batteries. Chem 2, 258–270 (2017).
Haruna, H., Takahashi, S. & Tanaka, Y. Accurate consumption analysis of vinylene carbonate as an electrolyte additive in an 18650 lithium-ion battery at the first charge-discharge cycle. J. Electrochem. Soc. 164, A6278–A6280 (2017).
Hausbrand, R. et al. Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials: Methodology, insights and novel approaches. Mater. Sci. Eng. B Solid State Mater. Adv. Technol. 192, 3–25 (2015).
Hoh, Y. C., Chiu, T. M. & Chung, Z. J. in Production and Electrolysis of Light Metals (ed. Closset, B.) 223–234 (Elsevier, 1989).
Wang, L., Chen, B., Ma, J., Cui, G. & Chen, L. Reviving lithium cobalt oxide-based lithium secondary batteries-toward a higher energy density. Chem. Soc. Rev. 47, 6505–6602 (2018).
Jiao, S. et al. Behavior of lithium metal anodes under various capacity utilization and high current density in lithium metal batteries. Joule 2, 110–124 (2018).
Alvarado, J. et al. Bisalt ether electrolytes: A pathway towards lithium metal batteries with Ni-rich cathodes. Energy Environ. Sci. 12, 780–794 (2019).
Oh, P. et al. Superior long-term energy retention and volumetric energy density for Li-rich cathode materials. Nano Lett. 14, 5965–5972 (2014).
Wang, J. et al. Lithium- and manganese-rich oxide cathode materials for high-energy lithium ion batteries. Adv. Energy Mater. 6, 1600906 (2016).
Aurbach, D. et al. Recent studies on the correlation between surface chemistry, morphology, three-dimensional structures and performance of Li and Li-C intercalation anodes in several important electrolyte systems. J. Power Sources 68, 91–98 (1997).
Wang, Y., Nakamura, S., Ue, M. & Balbuena, P. B. Theoretical studies to understand surface chemistry on carbon anodes for lithium-ion batteries: reduction mechanisms of ethylene carbonate. J. Am. Chem. Soc. 123, 11708–11718 (2001).
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 Ion. 148, 405–416 (2002).
Michan, A. L. et al. Fluoroethylene carbonate and vinylene carbonate reduction: Understanding lithium-ion battery electrolyte additives and solid electrolyte interphase formation. Chem. Mater. 28, 8149–8159 (2016).
Shkrob, I. A., Wishart, J. F. & Abraham, D. P. What makes fluoroethylene carbonate different? J. Phys. Chem. C 119, 14954–14964 (2015).
Nowak, S. & Winter, M. Review — chemical analysis for a better understanding of aging and degradation mechanisms of non-aqueous electrolytes for lithium ion batteries: method development, application and lessons learned. J. Electrochem. Soc. 162, A2500–A2508 (2015).
Aurbach, D. The study of electrolyte solutions based on ethylene and diethyl carbonates for rechargeable Li batteries I. Li metal anodes. J. Electrochem. Soc. 142, 2882 (1995).
Osaka, T. Enhancement of lithium anode cyclability in propylene carbonate electrolyte by CO2 addition and its protective effect against H2O impurity. J. Electrochem. Soc. 142, 1057 (1995).
Aurbach, D. A comparative study of synthetic graphite and Li electrodes in electrolyte solutions based on ethylene carbonate-dimethyl carbonate mixtures. J. Electrochem. Soc. 143, 3809 (1996).
Chang, W., Park, J. H. & Steingart, D. A. Poor man’s atomic layer deposition of LiF for additive-free growth of lithium columns. Nano Lett. 18, 7066–7074 (2018).
Shen, C. et al. Li2O-reinforced solid electrolyte interphase on three-dimensional sponges for dendrite-free lithium deposition. Front. Chem. 6, 517 (2018).
Shiraishi, S., Kanamura, K. & Takehara, Z. I. Influence of initial surface condition of lithium metal anodes on surface modification with HF. J. Appl. Electrochem. 29, 869–881 (1999).
This Review article is the result of a concerted approach within the LILLINT research project, jointly funded by the US Department of Energy (DOE) and the German Federal Ministry of Education and Research (BMBF). X.H. and R.K. kindly acknowledge the financial support of Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office (VTO), under the Advanced Battery Materials Research (BMR) Program, of the US DOE under contract no. DE-AC02-05CH11231. R.A., C.-C.S., J.S. and K.A. acknowledge US DOE, VTO. Argonne National Laboratory is operated by DOE Office of Science by UChicago Argonne, LLC, under contract no. DE-AC02-06CH11357. P.B.B., F.A.S., V.P. and J.M.S. acknowledge the financial support from the US DOE DE-AC02-06CH11357 through a subcontract to Argonne National Lab. W.X., H.J., C.W. and Y.X. at Pacific Northwest National Laboratory (PNNL) acknowledge the support of the Assistant Secretary for Energy Efficiency and Renewable Energy, VTO of the US DOE under contract no. DE-AC05-76RL01830 under the BMR Program and the US–Germany Cooperation on Energy Storage. PNNL is operated by Battelle for the DOE under contract DE-AC05-76RL01830. J.L. acknowledges support by an appointment to the Intelligence Community Postdoctoral Research Fellowship Program at the Massachusetts Institute of Technology, administered by Oak Ridge Institute for Science and Education through an inter-agency agreement between the US DOE and the Office of the Director of National Intelligence. Y.S.-H. and C.T.M. acknowledge the financial support of the Assistant Secretary for Energy Efficiency and Renewable Energy, VTO, under the BMR Program, of the US DOE under contract no. DE-AC02-06CH11357, subcontract no. 9F-60231. F.B. and U.K. acknowledge the BMBF in the framework of LILLINT (project number 03XP0225F). D.B. and S.P. thank the BMBF for financial support within the LILLINT project (03XP0225D). I.C.-L., S.W.-M. and M.W. acknowledge the financial support within the LILLINT project (13XP0225B).
The authors declare no competing interests.
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
He, X., Bresser, D., Passerini, S. et al. The passivity of lithium electrodes in liquid electrolytes for secondary batteries. Nat Rev Mater 6, 1036–1052 (2021). https://doi.org/10.1038/s41578-021-00345-5
This article is cited by
Nature Communications (2022)
Focus on the Electroplating Chemistry of Li Ions in Nonaqueous Liquid Electrolytes: Toward Stable Lithium Metal Batteries
Electrochemical Energy Reviews (2022)