Abstract
Extending the lifespan of lithium (Li) batteries involves managing reactions at the Li anode and stabilizing the solid–electrolyte interphase (SEI) through strategic regulation of the electrolyte composition. Here we synthesized a fluorinated cyclic ether with minimized Li-ion coordination capability and enhanced electrochemical stability. We demonstrated its crucial role in manipulating the SEI formation process by differentiating the contribution of dual anions to the SEI layer. Consequently, a bilayer SEI is formed, featuring a Li2O-rich inner layer and a LiF-rich outer layer, enabling improved stability and reversibility of Li-metal anodes. The developed electrolyte shows remarkable improvement in calendar life and cycling stability of Li (50 µm)||NMC811 (4 mAh cm−2) cells, maintaining 80% capacity after 568 and 218 cycles at room temperature and 60 °C, respectively. Furthermore, our 410 Wh kg−1 prototype pouch cells demonstrate 80% capacity retention for 470 cycles.
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References
Liu, J. et al. Pathways for practical high-energy long-cycling 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).
Albertus, P., Babinec, S., Lizelman, 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).
Wang, Q. et al. Confronting the challenges in lithium anodes for lithium metal batteries. Adv. Sci. 8, 2101111 (2021).
Qian, J. et al. High rate and stable cycling of lithium metal anode. Nat. Commun. 6, 6362 (2015).
Wang, J. et al. Superconcentrated electrolytes for a high-voltage lithium-ion battery. Nat. Commun. 7, 12032 (2016).
Jiao, S. et al. Stable cycling of high-voltage lithium metal batteries in ether electrolytes. Nat. Energy 3, 739–746 (2018).
Weber, R. et al. Long cycle life and dendrite-free lithium morphology in anode-free lithium pouch cells enabled by a dual-salt liquid electrolyte. Nat. Energy 4, 683–689 (2019).
Lin, Y.-H. et al. Self-assembly formation of solid–electrolyte interphase in gel polymer electrolytes for high performance lithium metal batteries. Energy Storage Mater. 61, 102868 (2023).
Ren, X. et al. Enabling high-voltage lithium-metal batteries under practical conditions. Joule 3, 1662–1676 (2019).
Yu, Z. et al. Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries. Nat. Energy 5, 526–533 (2020).
Yu, Z. et al. Rational solvent molecule tuning for high-performance lithium metal battery electrolytes. Nat. Energy 7, 94–106 (2022).
Gordin, M. L. et al. Bis(2,2,2-trifluoroethyl) ether as an electrolyte co-solvent for mitigating self-discharge in lithium–sulfur batteries. ACS Appl. Mater. Interfaces 6, 8006–8010 (2014).
Azimi, N. et al. Fluorinated electrolytes for Li–S battery: suppressing the self-discharge with an electrolyte containing fluoroether solvent. J. Electrochem. Soc. 162, A64–A68 (2015).
Chen, S. et al. High-voltage lithium-metal batteries enabled by localized high-concentration electrolytes. Adv. Mater. 30, 1706102 (2018).
Cao, X. et al. Effects of fluorinated solvents on electrolyte solvation structures and electrode/electrolyte interphases for lithium metal batteries. Proc. Natl Acad. Sci. USA 118, e2020357118 (2021).
Guo, R. & Gallant, B. M. Li2O Solid electrolyte interphase: probing transport properties at the chemical potential of lithium. Chem. Mater. 32, 5525–5533 (2020).
Lu, Y., Tu, Z. & Archer, L. A. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes. Nat. Mater. 13, 961–969 (2014).
Von Aspern, N., Roschenthaler, G.-V., Winer, M. & Cekic-Laskovic, I. Fluorine and lithium: ideal partners for high-performance rechargeable battery electrolytes. Angew. Chem. Int. Ed. 58, 15978–16000 (2019).
Li, T., Zhang, X.-Q., Shi, P. & Zhang, Q. Fluorinated solid–electrolyte interphase in high-voltage lithium metal batteries. Joule 3, 2647–2661 (2019).
Xu, K. ‘Charge-transfer’ process at graphite/electrolyte interface and the solvation sheath structure of Li+ in nonaqueous electrolytes. J. Electrochem. Soc. 154, A162–A167 (2007).
Hubble, D. et al. Liquid electrolyte development for low-temperature lithium-ion batteries. Energy Environ. Sci. 15, 550–578 (2022).
Han, S.-D. et al. Solvate structures and computational/spectroscopic characterization of lithium difluoro(oxalato)borate (LiDFOB) electrolytes. J. Phys. Chem. C 117, 5521–5531 (2013).
Li, S. et al. High-efficacy and polymeric solid–electrolyte interphase for closely packed Li electrodeposition. Adv. Sci. 8, 2003240 (2021).
Parimalam, B. S. & Lucht, B. L. Reduction reactions of electrolyte salts for lithium ion batteries: LiPF6, LiBF4, LiDFOB, LiBOB, and LiTFSI. J. Electrochem. Soc. 164, A251–A255 (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).
Li, G.-X. et al. A superior carbonate electrolyte for stable cycling Li metal batteries using high Ni cathode. ACS Energy Lett. 7, 2282–2288 (2022).
Jorgenson, W. L. & Tirado-Rives, J. The OPLS potential functions for proteins. Energy minimizations for crystals of cyclic peptides and crambin. J. Am. Chem. Soc. 110, 1657–1666 (1988).
Jorgenson, W. L., Maxwell, D. S. & Tirado-Rives, J. Development and testing of the OPLS all-atom force field on conformational energetics and properties of organic liquids. J. Am. Chem. Soc. 118, 11225–11236 (1996).
Breneman, C. M. & Wiberg, K. B. Determining atom-centered monopoles from molecular electrostatic potentials. The need for high sampling density in frmamide conformational analysis. J. Comput. Chem. 11, 361–373 (1990).
Martinez, L., Andrade, R., Birgin, E. G. & Martinez, J. M. Software news and update Packmol: a package for building initial configurations for molecular dynamics simulations. J. Comput. Chem. 30, 2157–2164 (2009).
Darden, T., York, D. & Pedersen, L. Particle mesh Ewald: an N⋅log(N) method for Ewald sums in large systems. J. Chem. Phys. 98, 10089–10092 (1993).
Bussi, G., Donadio, D. & Parrinello, M. Canonical sampling through velocity rescaling. J. Chem. Phys. 126, 014101 (2007).
Parrinello, M. & Rahman, A. Polymorphic transitions in single crystals: a new molecular dynamics method. J. Appl. Phys. 52, 7182–7190 (1981).
Acknowledgements
This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy, through the Advanced Battery Materials Research Program (Battery500 Consortium) and Battelle-Pacific Northwest National Laboratory Subcontract Award 614551. We gratefully acknowledge the computing resources provided on Bebop, a high-performance computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory.
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G.-X.L. and D.W. conceived and designed the idea. G.-X.L., R.K. and H.J. conducted the electrochemical tests and 1H, 13C, 17O and 19F NMR characterizations. A.N. and M.L. conducted and analysed the XPS depth-profiling characterization. V.K., M.N., H.G., J.C. and N.D. performed molecular dynamics and DFT simulations. A.T.N. supervised the molecular modelling. K.W. conducted the cryo-TEM experiments. G.-X.L. and D.W. wrote and revised the paper.
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Li, GX., Koverga, V., Nguyen, A. et al. Enhancing lithium-metal battery longevity through minimized coordinating diluent. Nat Energy (2024). https://doi.org/10.1038/s41560-024-01519-5
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DOI: https://doi.org/10.1038/s41560-024-01519-5
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