Cells with lithium-metal anodes are viewed as the most viable future technology, with higher energy density than existing lithium-ion batteries. Many researchers believe that for lithium-metal cells, the typical liquid electrolyte used in lithium-ion batteries must be replaced with a solid-state electrolyte to maintain the flat, dendrite-free lithium morphologies necessary for long-term stable cycling. Here, we show that anode-free lithium-metal pouch cells with a dual-salt LiDFOB/LiBF4 liquid electrolyte have 80% capacity remaining after 90 charge–discharge cycles, which is the longest life demonstrated to date for cells with zero excess lithium. The liquid electrolyte enables smooth dendrite-free lithium morphology comprised of densely packed columns even after 50 charge–discharge cycles. NMR measurements reveal that the electrolyte salts responsible for the excellent lithium morphology are slowly consumed during cycling.
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The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.
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 (2018).
Betz, J. et al. Theoretical versus practical energy: a plea for more transparency in the energy calculation of different rechargeable battery systems. Adv. Energy Mater. 9, 1803170 (2019).
Genovese, M., Louli, A. J., Weber, R., Hames, S. & Dahn, J. R. Measuring the coulombic efficiency of lithium metal cycling in anode-free lithium metal batteries. J. Electrochem. Soc. 165, A3321–A3325 (2018).
Liu, J. et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nat. Energy 4, 180 (2019).
Ding, F. et al. Effects of carbonate solvents and lithium salts on morphology and coulombic efficiency of lithium electrode. J. Electrochem. Soc. 160, A1894–A1901 (2013).
Aurbach, D., Zinigrad, E., Teller, H. & Dan, P. Factors which limit the cycle life of rechargeable lithium (metal) batteries. J. Electrochem. Soc. 147, 1274–1279 (2000).
Lin, D., Liu, Y. & Cui, Y. Reviving the lithium metal anode for high-energy batteries. Nat. Nanotechnol. 12, 194–206 (2017).
Neudecker, B. J., Dudney, N. J. & Bates, J. B. “Lithium-free” thin-film battery with in situ plated Li anode. J. Electrochem. Soc. 147, 517–523 (2000).
Qian, J. et al. Anode-free rechargeable lithium metal batteries. Adv. Funct. Mater. 26, 7094–7102 (2016).
Cohn, A. P., Muralidharan, N., Carter, R., Share, K. & Pint, C. L. Anode-free sodium battery through in situ plating of sodium metal. Nano Lett. 17, 1296–1301 (2017).
Assegie, A. A., Cheng, J.-H., Kuo, L.-M., Su, W.-N. & Hwang, B.-J. Polyethylene oxide film coating enhances lithium cycling efficiency of an anode-free lithium-metal battery. Nanoscale 10, 6125–6138 (2018).
Zhang, S. S., Fan, X. & Wang, C. A tin-plated copper substrate for efficient cycling of lithium metal in an anode-free rechargeable lithium battery. Electrochim. Acta 258, 1201–1207 (2017).
Woo, J.-J. et al. Symmetrical impedance study on inactivation induced degradation of lithium electrodes for batteries beyond lithium-ion. J. Electrochem. Soc. 161, A827–A830 (2014).
Fan, X. et al. Highly fluorinated interphases enable high-voltage Li-metal batteries. Chem 4, 174–185 (2018).
Jiao, S. et al. Stable cycling of high-voltage lithium metal batteries in ether electrolytes. Nat. Energy 3, 1–8 (2018).
Kanamura, K., Shiraishi, S. & Takehara, Z. Electrochemical deposition of very smooth lithium using nonaqueous electrolytes containing HF. J. Electrochem. Soc. 143, 2187–2197 (1996).
Kanamura, K., Shiraishi, S. & Takehara, Z. Electrochemical deposition of lithium metal in nonaqueous electrolyte containing (C2H5)4NF(HF)4 additive. J. Fluor. Chem. 87, 235–243 (1998).
Yan, K. et al. Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth. Nat. Energy 1, 16010 (2016).
Nagpure, S. C., Dufek, E. J., Wood, S. M., Dickerson, C. C. & Liaw, B. Effects of external pressure on the performance of lithium anode. Cells Meet. Abstr. MA2018-02, 305–305 (2018).
Wilkinson, D. P., Blom, H., Brandt, K. & Wainwright, D. Effects of physical constraints on Li cyclability. J. Power Sources 36, 517–527 (1991).
Fan, X. et al. Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries. Nat. Nanotechnol. 13, 715 (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).
Hagos, T. T. et al. Locally concentrated LiPF6 in a carbonate-based electrolyte with fluoroethylene carbonate as a diluent for anode-free lithium metal batteries. ACS Appl. Mater. Interfaces 11, 9955–9963 (2019).
Kerman, K., Luntz, A., Viswanathan, V., Chiang, Y.-M. & Chen, Z. Review—practical challenges hindering the development of solid state Li ion batteries. J. Electrochem. Soc. 164, A1731–A1744 (2017).
Porz, L. et al. Mechanism of lithium metal penetration through inorganic solid electrolytes. Adv. Energy Mater. 7, 1701003 (2017).
Aguesse, F. et al. Investigating the dendritic growth during full cell cycling of garnet electrolyte in direct contact with Li metal. ACS Appl. Mater. Interfaces 9, 3808–3816 (2017).
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).
Brown, Z. L. & Lucht, B. L. Synergistic performance of lithium difluoro(oxalato)borate and fluoroethylene carbonate in carbonate electrolytes for lithium metal anodes. J. Electrochem. Soc. 166, A5117–A5121 (2019).
Schedlbauer, T. et al. Lithium difluoro(oxalato)borate: a promising salt for lithium metal based secondary batteries? Electrochim. Acta 92, 102–107 (2013).
Brown, Z. L., Jurng, S., Nguyen, C. C. & Lucht, B. L. Effect of fluoroethylene carbonate electrolytes on the nanostructure of the solid electrolyte interphase and performance of lithium metal anodes. ACS Appl. Energy Mater. 1, 3057–3062 (2018).
Zhu, Y., Li, Y., Bettge, M. & Abraham, D. P. Positive electrode passivation by LiDFOB electrolyte additive in high-capacity lithium-ion cells. J. Electrochem. Soc. 159, A2109–A2117 (2012).
Wilkinson, D. P. & Wainwright, D. In-situ study of electrode stack growth in rechargeable cells at constant pressure. J. Electroanal. Chem. 355, 193–203 (1993).
Hirai, T., Yoshimatsu, I. & Yamaki, J. Influence of electrolyte on lithium cycling efficiency with pressurized electrode stack. J. Electrochem. Soc. 141, 611–614 (1994).
Louli, A. J. et al. Exploring the impact of mechanical pressure on the performance of anode-free lithium metal cells. J. Electrochem. Soc. 166, A1291–A1299 (2019).
Naumkin, A. V., Kraut-Vass, A., Gaarenstroom, S. W. & Powell, C. J. NIST X-ray Photoelectron Spectroscopy Database Version 4.1. (National Institute of Standards and Technology, 2012); https://doi.org/10.18434/T4T88K
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).
Li, J. et al. Comparison of single crystal and polycrystalline LiNi0.5Mn0.3Co0.2O2 positive electrode materials for high voltage Li-ion cells. J. Electrochem. Soc. 164, A1534–A1544 (2017).
Madec, L. et al. Effect of sulfate electrolyte additives on LiNi1/3Mn1/3Co1/3O2/graphite pouch cell lifetime: correlation between XPS surface studies and electrochemical test results. J. Phys. Chem. C 118, 29608–29622 (2014).
This research was financially supported by Tesla Canada and NSERC under the Industrial Research Chairs Program. A.J.L. thanks the Nova Scotia Graduate Scholarship programme and the Walter C. Sumner Memorial fellowship for support. M.G. thanks the NSERC PDF Program. The authors acknowledge Dr J. Li (formerly of BASF) and Dr D. J. Xiong (formerly of Capchem) for providing chemicals used in the electrolytes, as well as S. Trussler for expert fabrication of the parts used in this work.
Rochelle Weber is employed by Tesla Canada R&D.
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Supplementary Figs. 1–14, Supplementary Table 1 and Supplementary refs.
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Nature Energy (2019)