Abstract
Solid-state lithium metal batteries require accommodation of electrochemically generated mechanical stress inside the lithium: this stress can be1,2 up to 1 gigapascal for an overpotential of 135 millivolts. Maintaining the mechanical and electrochemical stability of the solid structure despite physical contact with moving corrosive lithium metal is a demanding requirement. Using in situ transmission electron microscopy, we investigated the deposition and stripping of metallic lithium or sodium held within a large number of parallel hollow tubules made of a mixed ionic-electronic conductor (MIEC). Here we show that these alkali metals—as single crystals—can grow out of and retract inside the tubules via mainly diffusional Coble creep along the MIEC/metal phase boundary. Unlike solid electrolytes, many MIECs are electrochemically stable in contact with lithium (that is, there is a direct tie-line to metallic lithium on the equilibrium phase diagram), so this Coble creep mechanism can effectively relieve stress, maintain electronic and ionic contacts, eliminate solid-electrolyte interphase debris, and allow the reversible deposition/stripping of lithium across a distance of 10 micrometres for 100 cycles. A centimetre-wide full cell—consisting of approximately 1010 MIEC cylinders/solid electrolyte/LiFePO4—shows a high capacity of about 164 milliampere hours per gram of LiFePO4, and almost no degradation for over 50 cycles, starting with a 1× excess of Li. Modelling shows that the design is insensitive to MIEC material choice with channels about 100 nanometres wide and 10–100 micrometres deep. The behaviour of lithium metal within the MIEC channels suggests that the chemical and mechanical stability issues with the metal–electrolyte interface in solid-state lithium metal batteries can be overcome using this architecture.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Data availability
The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.
References
Porz, L. et al. Mechanism of lithium metal penetration through inorganic solid electrolytes. Adv. Energy Mater. 7, 1701003 (2017).
Armstrong, R. D., Dickinson, T. & Turner, J. The breakdown of β-alumina ceramic electrolyte. Electrochim. Acta 19, 187–192 (1974).
Yang, C. et al. Continuous plating/stripping behavior of solid-state lithium metal anode in a 3D ion-conductive framework. Proc. Natl Acad. Sci. USA 115, 3770–3775 (2018).
Liu, Y. et al. Transforming from planar to three-dimensional lithium with flowable interphase for solid lithium metal batteries. Sci. Adv. 3, eaao0713 (2017).
Monroe, C. & Newman, J. The impact of elastic deformation on deposition kinetics at lithium/polymer interfaces. J. Electrochem. Soc. 152, A396–A404 (2005).
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).
Li, Y. et al. Atomic structure of sensitive battery materials and interfaces revealed by cryo-electron microscopy. Science 358, 506–510 (2017).
Lu, J., Chen, Z., Pan, F., Cui, Y. & Amine, K. High-performance anode materials for rechargeable lithium-ion batteries. Electrochem. Energy Rev. 1, 35–53 (2018).
Devaux, D. et al. Failure mode of lithium metal batteries with a block copolymer electrolyte analyzed by X-ray microtomography. J. Electrochem. Soc. 162, A1301–A1309 (2015).
Harry, K. J., Hallinan, D. T., Parkinson, D. Y., MacDowell, A. A. & Balsara, N. P. Detection of subsurface structures underneath dendrites formed on cycled lithium metal electrodes. Nat. Mater. 13, 69 (2014).
Maslyn, J. A. et al. Growth of lithium dendrites and globules through a solid block copolymer electrolyte as a function of current density. J. Phys. Chem. C 122, 26797–26804 (2018).
Harry, K. J., Liao, X., Parkinson, D. Y., Minor, A. M. & Balsara, N. P. Electrochemical deposition and stripping behavior of lithium metal across a rigid block copolymer electrolyte membrane. J. Electrochem. Soc. 162, A2699–A2706 (2015).
Richards, W. D., Miara, L. J., Wang, Y., Kim, J. C. & Ceder, G. Interface stability in solid-state batteries. Chem. Mater. 28, 266–273 (2016).
Kim, S. et al. Electrochemically driven mechanical energy harvesting. Nat. Commun. 7, 10146 (2016).
Jin, C. et al. 3D lithium metal embedded within lithiophilic porous matrix for stable lithium metal batteries. Nano Energy 37, 177–186 (2017).
Zhao, J. et al. Air-stable and freestanding lithium alloy/graphene foil as an alternative to lithium metal anodes. Nat. Nanotechnol. 12, 993–999 (2017).
Yan, K. et al. Selective deposition and stable encapsulation of lithium through heterogeneous seed growth. Nat. Energy 1, 16010 (2016).
Frost, H. & Ashby, M. Deformation-Mechanism Maps (Pergamon, 1982).
Zhu, T. & Li, J. Ultra-strength materials. Prog. Mater. Sci. 55, 710–757 (2010).
Nitta, N. & Yushin, G. High-capacity anode materials for lithium-ion batteries: choice of elements and structures for active particles. Part. Part. Syst. Charact. 31, 317–336 (2014).
Chen, Y. et al. Nitrogen-doped carbon for sodium-ion battery anode by self-etching and graphitization of bimetallic MOF-based composite. Chem 3, 152–163 (2017).
Zheng, H., Liu, Y., Mao, S. X., Wang, J. & Huang, J. Y. Beam-assisted large elongation of in situ formed Li2O nanowires. Sci. Rep. 2, 542 (2012).
Liu, Y. et al. Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode. Nat. Commun. 7, 10992 (2016).
Li, S. et al. Developing high-performance lithium metal anode in liquid electrolytes: challenges and progress. Adv. Mater. 30, 1706375 (2018).
Zhang, Y. et al. High-capacity, low-tortuosity, and channel-guided lithium metal anode. Proc. Natl Acad. Sci. USA 114, 3584–3589 (2017).
Sun, J. et al. Liquid-like pseudoelasticity of sub-10-nm crystalline silver particles. Nat. Mater. 13, 1007–1012 (2014).
Yang, Y., Kushima, A., Han, W., Xin, H. & Li, J. Liquid-like, self-healing aluminum oxide during deformation at room temperature. Nano Lett. 18, 2492–2497 (2018).
Kushima, A. et al. Liquid cell transmission electron microscopy observation of lithium metal growth and dissolution: root growth, dead lithium and lithium flotsams. Nano Energy 32, 271–279 (2017).
Moon, S. et al. Encapsulated monoclinic sulfur for stable cycling of Li-S rechargeable batteries. Adv. Mater. 25, 6547–6553 (2013).
Cao, G. & Gao, H. Mechanical properties characterization of two-dimensional materials via nanoindentation experiments. Prog. Mater. Sci. 103, 558–595 (2019).
Yuan, Y., Amine, K., Lu, J. & Shahbazian-Yassar, R. Understanding materials challenges for rechargeable ion batteries with in situ transmission electron microscopy. Nat. Commun. 8, 15806 (2017).
Egerton, R. F., Li, P. & Malac, M. Radiation damage in the TEM and SEM. Micron 35, 399–409 (2004).
Wang, X. et al. New insights on the structure of electrochemically deposited lithium metal and its solid electrolyte interphases via cryogenic TEM. Nano Lett. 17, 7606–7612 (2017).
Malis, T., Cheng, S. C. & Egerton, R. F. EELS log-ratio technique for specimen-thickness measurement in the TEM. J. Electron Microsc. Tech. 8, 193–200 (1988).
Mali, M., Roos, J., Sonderegger, M., Brinkmann, D. & Heitjans, P. 6Li and 7Li diffusion coefficients in solid lithium measured by the NMR pulsed field gradient technique. J. Phys. F 18, 403 (1988).
Xie, D.-G. et al. In situ study of the initiation of hydrogen bubbles at the aluminium metal/oxide interface. Nat. Mater. 14, 899–903 (2015).
Tian, L., Li, J., Sun, J., Ma, E. & Shan, Z-W. Visualizing size-dependent deformation mechanism transition in Sn. Sci. Rep. 3, 2113 (2013).
Gjostein, N. A. Diffusion (ASM, 1973).
Acknowledgements
We acknowledge support by the Department of Energy, Basic Energy Sciences under award number DE-SC0002633 (‘Chemomechanics of far-from-equilibrium interfaces’), and by NSF ECCS-1610806. We thank KISCO Ltd for providing the PEO-based/LiTFSI solid electrolyte film.
Author information
Authors and Affiliations
Contributions
The experiments were conceived and designed by Y.C., Z.W. and J.L.; Y.C. and Z.W. performed the in situ TEM experiments, TEM imaging analysis, materials characterization, and the electrochemical performance assessments; Y.C., Z.W., X.L. and X.Y. synthesized the materials; Y. L., N.W. and J.B.G. helped with the electrochemical characterization; S.Y.K. and Y.-W.M. performed the nanoindentations; Y.C., Z.W. and J.L. wrote the paper; Y.-W.M., Z.W., X.L., X.Y., C.W., W.X., D.Y., F.Y., A.K., G.Z., H.H., J.B.G. and J. L. analysed the data, discussed the results and commented on the manuscript.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Peer review information Nature thanks Werner Sitte and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Supplementary Information
This file contains Supplementary Figures 1–29, a list of the Supplementary Videos and Supplementary References.
Video 1
An in situ TEM video showing Li plating inside the carbon hollow tubule with ZnOx (Fig. 2b–d).
Video 2
An in situ SAED video showing the changes of SAED on tubule region for the carbon tubule with ZnOx when Li plating occurs (Fig. 2e, f).
Video 3
An in situ TEM video showing the HRTEM imaging of Li plating inside the carbon tubule when the fresh Li crystal first forms inside the field of camera (Fig. 2g–i).
Video 4
A speeded-up in situ TEM video showing the Li stripping process inside the carbon tubule when there is a void plug between Li metal and the solid electrolyte (Fig. 2j–l and Supplementary Fig. 17).
Video 5
A speeded-up in situ TEM video showing some typical plating/stripping cycles including the 1st and 30th in the double aligned carbon tubules (Supplementary Fig. 8).
Video 6
A speeded-up in situ TEM video showing Li plating/stripping for 100 cycles in the single carbon tubules (Supplementary Fig. 10).
Video 7
A speeded-up in situ TEM video showing Na plating inside the carbon tubules (Supplementary Fig. 15).
Video 8
A speeded-up in situ TEM video showing Na stripping inside the carbon tubules (Supplementary Fig. 15).
Video 9
An in situ TEM video showing the dark-field imaging of the complete wetting of Li, spreading along the tubule outer surface with zero contact angle (Fig. 3b–f).
Rights and permissions
About this article
Cite this article
Chen, Y., Wang, Z., Li, X. et al. Li metal deposition and stripping in a solid-state battery via Coble creep. Nature 578, 251–255 (2020). https://doi.org/10.1038/s41586-020-1972-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41586-020-1972-y
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.
