[go: up one dir, main page]
Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Perspective
  • Published:

Pathways for practical high-energy long-cycling lithium metal batteries

Nature Energy volume 4, pages 180–186 (2019)Cite this article

Subjects

Abstract

State-of-the-art lithium (Li)-ion batteries are approaching their specific energy limits yet are challenged by the ever-increasing demand of today’s energy storage and power applications, especially for electric vehicles. Li metal is considered an ultimate anode material for future high-energy rechargeable batteries when combined with existing or emerging high-capacity cathode materials. However, much current research focuses on the battery materials level, and there have been very few accounts of cell design principles. Here we discuss crucial conditions needed to achieve a specific energy higher than 350 Wh kg−1, up to 500 Wh kg−1, for rechargeable Li metal batteries using high-nickel-content lithium nickel manganese cobalt oxides as cathode materials. We also provide an analysis of key factors such as cathode loading, electrolyte amount and Li foil thickness that impact the cell-level cycle life. Furthermore, we identify several important strategies to reduce electrolyte-Li reaction, protect Li surfaces and stabilize anode architectures for long-cycling high-specific-energy cells.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on SpringerLink
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Calculated cell-level specific energy as a function of cell parameters.
Fig. 2: Relation between cell parameters and cell cycle life and Li anode morphologies.
Fig. 3: Illustration of major failure mechanisms in Li metal anodes.
Fig. 4: Solutions proposed in the literature to characterize and mitigate Li metal problems.

Similar content being viewed by others

References

  1. Whittingham, M. S. Ultimate limits to intercalation reactions for lithium batteries. Chem. Rev. 114, 11414–11443 (2014).

    Article  Google Scholar 

  2. Van Noorden, R. A better battery. Nature 507, 26–28 (2014).

    Article  Google Scholar 

  3. Xia, C., Kwok, C. Y. & Nazar, L. F. A high-energy-density lithium-oxygen battery based on a reversible four-electron conversion to lithium oxide. Science 361, 777–781 (2018).

    Article  Google Scholar 

  4. Fang, R. et al. More reliable lithium-sulfur batteries: status, solutions and prospects. Adv. Mater. 29, 1606823 (2017).

    Article  Google Scholar 

  5. Wu, B. et al. Interfacial behaviours between lithium ion conductors and electrode materials in various battery systems. J. Mater. Chem. A 4, 15266–15280 (2016).

    Article  Google Scholar 

  6. Wu, B., Lochala, J., Taverne, T. & Xiao, J. The interplay between solid electrolyte interface (SEI) and dendritic lithium growth. Nano Energy 40, 34–41 (2017).

    Article  Google Scholar 

  7. 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).

    Article  Google Scholar 

  8. Li, Y. et al. Atomic structure of sensitive battery materials and interfaces revealed by cryo-electron microscopy. Science 358, 506–510 (2017).

    Article  Google Scholar 

  9. 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).

    Article  Google Scholar 

  10. Kim, M. S. et al. Langmuir–Blodgett artificial solid-electrolyte interphases for practical lithium metal batteries. Nat. Energy 3, 889–898 (2018).

    Article  Google Scholar 

  11. Xu, W. et al. Lithium metal anodes for rechargeable batteries. Energy Environ. Sci. 7, 513–537 (2014).

    Article  Google Scholar 

  12. Pohl, A. et al. Development of a water based process for stable conversion cathodes on the basis of FeF3. J. Power Sources 313, 213–222 (2016).

    Article  Google Scholar 

  13. Li, X. et al. Fundamental insight into Zr modification of Li- and Mn-rich cathodes: combined transmission electron microscopy and electrochemical impedance spectroscopy study. Chem. Mater. 30, 2566–2573 (2018).

    Article  Google Scholar 

  14. Zhu, Z. et al. Anion-redox nanolithia cathodes for Li-ion batteries. Nat. Energy 1, 16111 (2016).

    Article  Google Scholar 

  15. Yu, L. et al. A localized high-concentration electrolyte with optimized solvents and lithium difluoro(oxalate)borate additive for stable lithium metal batteries. ACS Energy Lett. 3, 2059–2067 (2018).

    Article  Google Scholar 

  16. Nagpure, S. C. et al. Impacts of lean electrolyte on cycle life for rechargeable Li metal batteries. J. Power Sources 407, 53–62 (2018).

    Article  Google Scholar 

  17. Elezgaray, J., Léger, C. & Argoul, F. Linear stability analysis of unsteady galvanostatic electrodeposition in the two-dimensional diffusion-limited regime. J. Electrochem. Soc. 145, 2016–2024 (1998).

    Article  Google Scholar 

  18. 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).

    Article  Google Scholar 

  19. Burns, J. C. et al. Predicting and extending the lifetime of Li-ion batteries. J. Electrochem. Soc. 160, A1451–A1456 (2013).

    Article  Google Scholar 

  20. 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).

    Article  Google Scholar 

  21. 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).

    Article  Google Scholar 

  22. 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).

    Article  Google Scholar 

  23. Li, J., Li, W., You, Y. & Manthiram, A. Extending the service life of high-Ni layered oxides by tuning the electrode–electrolyte interphase. Adv. Energy Mater. 8, 1801957 (2018).

    Article  Google Scholar 

  24. Chen, S. et al. High-voltage lithium-metal batteries enabled by localized high-concentration electrolytes. Adv. Mater. 30, 1706102 (2018).

    Article  Google Scholar 

  25. Liu, B., Zhang, J.-G. & Xu, W. Advancing lithium metal batteries. Joule 2, 833–845 (2018).

    Article  Google Scholar 

  26. Zheng, J. et al. Electrolyte additive enabled fast charging and stable cycling lithium metal batteries. Nat. Energy 2, 17012 (2017).

    Article  Google Scholar 

  27. Ding, F. et al. Dendrite-free lithium deposition via self-healing electrostatic shield mechanism. J. Am. Chem. Soc. 135, 4450–4456 (2013).

    Article  Google Scholar 

  28. Qian, J. et al. Dendrite-free Li deposition using trace-amounts of water as an electrolyte additive. Nano Energy 15, 135–144 (2015).

    Article  Google Scholar 

  29. Ren, X. et al. Guided lithium metal deposition and improved lithium Coulombic efficiency through synergistic effects of LiAsF6 and cyclic carbonate additives. ACS Energy Lett. 3, 14–19 (2018).

    Article  Google Scholar 

  30. Liang, X. et al. A facile surface chemistry route to a stabilized lithium metal anode. Nat. Energy 2, 17119 (2017).

    Article  Google Scholar 

  31. Qian, J. et al. High rate and stable cycling of lithium metal anode. Nat. Commun. 6, 6362 (2015).

    Article  Google Scholar 

  32. Ren, X. et al. Localized high-concentration sulfone electrolytes for high-efficiency lithium-metal batteries. Chem 4, 1877–1892 (2018).

    Article  Google Scholar 

  33. Chen, S. et al. High-efficiency lithium metal batteries with fire-retardant electrolytes. Joule 2, 1548–1558 (2018).

    Article  Google Scholar 

  34. Cheng, L. et al. Accelerating electrolyte discovery for energy storage with high-throughput screening. J. Phys. Chem. Lett. 6, 283–291 (2015).

    Article  Google Scholar 

  35. Khurana, R., Schaefer, J. L., Archer, L. A. & Coates, G. W. Suppression of lithium dendrite growth using cross-linked polyethylene/poly(ethylene oxide) electrolytes: a new approach for practical lithium-metal polymer batteries. J. Am. Chem. Soc. 136, 7395–7402 (2014).

    Article  Google Scholar 

  36. Choudhury, S., Mangal, R., Agrawal, A. & Archer, L. A. A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles. Nat. Commun. 6, 10101 (2015).

    Article  Google Scholar 

  37. Orsini, F. et al. In situ scanning electron microscopy (SEM) observation of interfaces within plastic lithium batteries. J. Power Sources 76, 19–29 (1998).

    Article  Google Scholar 

  38. Han, X. et al. Negating interfacial impedance in garnet-based solid-state Li metal batteries. Nat. Mater. 16, 572–579 (2017).

    Article  Google Scholar 

  39. Monroe, C. & Newman, J. The impact of elastic deformation on deposition kinetics at lithium/polymer interfaces. J. Electrochem. Soc. 152, A396–A404 (2005).

    Article  Google Scholar 

  40. Cheng, E. J., Sharafi, A. & Sakamoto, J. Intergranular Li metal propagation through polycrystalline Li6.25Al0.25La3Zr2O12 ceramic electrolyte. Electrochim. Acta 223, 85–91 (2017).

    Article  Google Scholar 

  41. Long, L., Wang, S., Xiao, M. & Meng, Y. Polymer electrolytes for lithium polymer batteries. J. Mater. Chem. A 4, 10038–10069 (2016).

    Article  Google Scholar 

  42. Gomez, E. D. et al. Effect of ion distribution on conductivity of block copolymer electrolytes. Nano Lett. 9, 1212–1216 (2009).

    Article  Google Scholar 

  43. Liu, K. et al. Lithium metal anodes with an adaptive “solid–liquid” interfacial protective layer. J. Am. Chem. Soc. 139, 4815–4820 (2017).

    Article  Google Scholar 

  44. Wang, Y. & Sokolov, A. P. Design of superionic polymer electrolytes. Curr. Opin. Chem. Eng. 7, 113–119 (2015).

    Article  Google Scholar 

  45. Aetukuri, N. B. et al. Flexible ion-conducting composite membranes for lithium batteries. Adv. Energy Mater. 5, 1500265 (2015).

    Article  Google Scholar 

  46. Ye, H. et al. Stable Li plating/stripping electrochemistry realized by a hybrid Li reservoir in spherical carbon granules with 3D conducting skeletons. J. Am. Chem. Soc. 139, 5916–5922 (2017).

    Article  Google Scholar 

  47. Liang, Z. et al. Composite lithium metal anode by melt infusion of lithium into a 3D conducting scaffold with lithiophilic coating. Proc. Natl Acad. Sci. USA 113, 2862–2867 (2016).

    Article  Google Scholar 

  48. Zhang, Y. et al. High-capacity, low-tortuosity, and channel-guided lithium metal anode. Proc. Natl Acad. Sci. USA 114, 3584–3589 (2017).

    Article  Google Scholar 

  49. Zeng, Z. et al. Non-flammable electrolytes with high salt-to-solvent ratios for Li-ion and Li-metal batteries. Nat. Energy 3, 674–681 (2018).

    Article  Google Scholar 

Download references

Acknowledgements

This research 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 (BMR) Program (Battery500 Consortium) under contract no. DE-AC02-05CH11231. The authors thank H. Pan, H. Lee, C. Niu and B. Liu of Pacific Northwest National Laboratory for their assistance in preparing this manuscript.

Author information

Authors and Affiliations

  1. Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA, USA

    Jun Liu, Qiuyan Li, Venkat R. Subramanian, Vilayanur V. Viswanathan, Jie Xiao, Wu Xu & Ji-Guang Zhang

  2. Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA

    Zhenan Bao & Yi Cui

  3. Clean Energy and Transportation Division, Idaho National Laboratory, Idaho Falls, ID, USA

    Eric J. Dufek & Bor Yann Liaw

  4. Department of Mechanical Engineering, The University of Texas at Austin, Austin, TX, USA

    John B. Goodenough & Arumugam Manthiram

  5. Chemistry Division, Brookhaven National Laboratory, Upton, NY, USA

    Peter Khalifah & Xiao-Qing Yang

  6. Department of NanoEngineering, University of California, San Diego, CA, USA

    Ping Liu & Y. Shirley Meng

  7. College of Engineering, University of Washington, Seattle, WA, USA

    Venkat R. Subramanian & Jihui Yang

  8. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Michael F. Toney

  9. Department of Materials Science and Engineering, Binghamton University, Binghamton, NY, USA

    M. Stanley Whittingham

Authors
  1. Jun Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Zhenan Bao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yi Cui
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Eric J. Dufek
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. John B. Goodenough
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Peter Khalifah
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Qiuyan Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Bor Yann Liaw
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Ping Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Arumugam Manthiram
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Y. Shirley Meng
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Venkat R. Subramanian
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Michael F. Toney
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Vilayanur V. Viswanathan
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. M. Stanley Whittingham
    View author publications

    You can also search for this author in PubMed Google Scholar

  16. Jie Xiao
    View author publications

    You can also search for this author in PubMed Google Scholar

  17. Wu Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  18. Jihui Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  19. Xiao-Qing Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  20. Ji-Guang Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Jun Liu.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liu, J., Bao, Z., Cui, Y. et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nat Energy 4, 180–186 (2019). https://doi.org/10.1038/s41560-019-0338-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41560-019-0338-x

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing