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Tuning the solvation structure with salts for stable sodium-metal batteries

Nature Energy volume 9, pages 446–456 (2024)Cite this article

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Abstract

Sodium-metal batteries are an appealing, sustainable, low-cost alternative to lithium metal batteries due to the high abundance and theoretical specific capacity (1,165 mA h g−1) of sodium. However, the poor compatibility of the electrolyte with the cathode and anode leads to unstable electrode–electrolyte interphases. Here we introduce the concept of using a salt as a diluent, which enables the use of a single non-flammable solvent, such as trimethyl phosphate. By using sodium nitrate (NaNO3) salt as a model diluent, we report a 1.1 M NaFSI–NaNO3–trimethyl phosphate electrolyte that forms a stable interface with sodium-metal anode. In addition, the formation of robust cathode–electrolyte interphases on Na(Ni0.3Fe0.4Mn0.3)O2 cathode facilitates smooth phase transitions, thus leading to stable cycle life with a capacity retention of 80% over 500 cycles at C/5 rate in Na||Na(Ni0.3Fe0.4Mn0.3)O2 cells. The work demonstrates a promising approach towards the development of safe, low-cost, sustainable high-performance sodium-metal batteries.

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Fig. 1: Electrolyte design strategy.
Fig. 2: Behaviour of different electrolyte formulations.
Fig. 3: Electrochemical behaviour of NFM in Na||NFM cells in different electrolytes.
Fig. 4: Characterization of NFM cathode in Na||NFM cells with different electrolytes.
Fig. 5: Na plating and stripping behaviours in different electrolytes.
Fig. 6: Characterization of cycled Na in Na||NFM cells in different electrolytes.

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All data are available in the article and its Supplementary Information files.

References

  1. Yu, Z. et al. Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries. Nat. Energy 5, 526–533 (2020).

    Article  Google Scholar 

  2. Yan, P. et al. Tailoring grain boundary structures and chemistry of Ni-rich layered cathodes for enhanced cycle stability of lithium-ion batteries. Nat. Energy 3, 600–605 (2018).

    Article  Google Scholar 

  3. 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).

    Article  Google Scholar 

  4. Manthiram, A. A reflection on lithium-ion battery cathode chemistry. Nat. Commun. 11, 1550 (2020).

    Article  Google Scholar 

  5. Su, L., Charalambous, H., Cui, Z. & Manthiram, A. High-efficiency, anode-free lithium metal batteries with a close-packed homogeneous lithium morphology. Energ. Environ. Sci. 15, 843–854 (2022).

    Article  Google Scholar 

  6. 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 

  7. You, Y. et al. Insights into the improved high-voltage performance of Li-incorporated layered oxide cathodes for sodium-ion batteries. Chem https://doi.org/10.1016/j.chempr.2018.05.018 (2018).

  8. You, Y. et al. Subzero-temperature cathode for a sodium-ion battery. Adv. Mater. 28, 7243–7248 (2016).

    Article  Google Scholar 

  9. Zhang, S., Yao, Y. & Yu, Y. Frontiers for room-temperature sodium–sulfur batteries. ACS Energy Lett. 6, 529–536 (2021).

    Article  Google Scholar 

  10. Seh, Z. W., Sun, J., Sun, Y. & Cui, Y. A highly reversible room-temperature sodium-metal anode. ACS Cent. Sci. 1, 449–455 (2015).

    Article  Google Scholar 

  11. Xin, S., Yin, Y., Guo, Y. & Wan, L. A high-energy room-temperature sodium–sulfur battery. Adv. Mater. 26, 1261–1265 (2014).

    Article  Google Scholar 

  12. Sun, B. et al. Design strategies to enable the efficient use of sodium-metal anodes in high-energy batteries. Adv. Mater. 32, 1903891 (2019).

    Article  Google Scholar 

  13. Yang, Z. et al. Fire‐retardant, stable‐cycling and high‐safety sodium ion battery. Angew. Chem. Int. Ed. 60, 27086–27094 (2021).

    Article  Google Scholar 

  14. Gao, H., Xue, L., Xin, S., Park, K. & Goodenough, J. B. A plastic-crystal electrolyte interphase for all-solid-state sodium batteries. Angew. Chem. Int. Ed. 56, 5541–5545 (2017).

    Article  Google Scholar 

  15. Wang, H., Wang, C., Matios, E. & Li, W. Facile stabilization of the sodium-metal anode with additives: unexpected key role of sodium polysulfide and adverse effect of sodium nitrate. Angew. Chem. Int. Ed. 57, 7734–7737 (2018).

    Article  Google Scholar 

  16. Lamb, J. & Manthiram, A. Stable sodium-based batteries with advanced electrolytes and layered-oxide cathodes. ACS Appl. Mater. Interfaces 14, 28865–28872 (2022).

    Article  Google Scholar 

  17. Fang, W. et al. Stable sodium-metal anode enhanced by advanced electrolytes with SbF3 additive. Rare Met. https://doi.org/10.1007/s12598-020-01576-1 (2020).

  18. Jiang, Y. et al. Artificial heterogeneous interphase layer with boosted ion affinity and diffusion for Na/K‐metal batteries. Adv. Mater. 34, 2109439 (2022).

    Article  Google Scholar 

  19. Zhu, M. et al. Dendrite-free sodium-metal anodes enabled by a sodium benzenedithiolate-rich protection layer. Angew. Chem. Int. Ed. 59, 6596–6600 (2020).

    Article  Google Scholar 

  20. Wang, A. et al. Processable and moldable sodium-metal anodes. Angew. Chem. Int. Ed. 56, 11921–11926 (2017).

    Article  Google Scholar 

  21. Cao, R. et al. Enabling room-temperature sodium-metal batteries. Nano Energy 30, 825–830 (2016).

    Article  Google Scholar 

  22. Zheng, J. et al. Extremely stable sodium-metal batteries enabled by localized high-concentration electrolytes. ACS Energy Lett. 3, 315–321 (2018).

    Article  Google Scholar 

  23. Wang, Y. et al. Enhanced sodium-metal/electrolyte interface by a localized high-concentration electrolyte for sodium-metal batteries: first-principles calculations and experimental studies. ACS Appl. Energ. Mater. 4, 7376–7384 (2021).

  24. Jin, Y. et al. Highly reversible sodium-ion batteries enabled by stable electrolyte-electrode interphases. ACS Energy Lett. 5, 3212–3220 (2020).

    Article  Google Scholar 

  25. Niu, C. et al. High-energy lithium metal pouch cells with limited anode swelling and long stable cycles. Nat. Energy https://doi.org/10.1038/s41560-019-0390-6 (2019).

  26. Shi, P. et al. A highly concentrated phosphate-based electrolyte for high-safety rechargeable lithium batteries. Chem. Commun. 54, 4453–4456 (2018).

    Article  Google Scholar 

  27. Zeng, Z. et al. A safer sodium-ion battery based on non-flammable organic phosphate electrolyte. Adv. Sci. 3, 1600066 (2016).

    Article  Google Scholar 

  28. Jiang, X. et al. A non-flammable Na+-based dual-carbon battery with low cost, high voltage, and long cycle life. Adv. Energy Mater. 8, 1802176 (2018).

  29. He, J., Bhargav, A., Shin, W. & Manthiram, A. Stable dendrite-free sodium–sulfur batteries enabled by a localized high-concentration electrolyte. J. Am. Chem. Soc. 143, 20241–20248 (2021).

    Article  Google Scholar 

  30. Mu, L. et al. Deciphering the cathode–electrolyte interfacial chemistry in sodium layered cathode materials. Adv. Energy Mater. 8, 1801975 (2018).

    Article  Google Scholar 

  31. Su, L. et al. Multiscale operando X-ray investigations provide insights into electro-chemo-mechanical behavior of lithium intercalation cathodes. Appl. Energy 299, 117315 (2021).

    Article  Google Scholar 

  32. Su, L. et al. Tailoring electrode–electrolyte interfaces in lithium-ion batteries using molecularly engineered functional polymers. ACS Appl. Mater. Interfaces 13, 9919–9931 (2021).

    Article  Google Scholar 

  33. Lamb, J., Stokes, L. & Manthiram, A. Delineating the capacity fading mechanisms of Na(Ni0.3Fe0.4Mn0.3)O2 at higher operating voltages in sodium-ion cells. Chem. Mat. 32, 7389–7396 (2020).

    Article  Google Scholar 

  34. Lamb, J. & Manthiram, A. Surface-modified Na(Ni0.3Fe0.4Mn0.3)O2 cathodes with enhanced cycle life and air stability for sodium-ion batteries. ACS Appl. Energ. Mater. 4, 11735–11742 (2021).

    Article  Google Scholar 

  35. Lamb, J., Jarvis, K. & Manthiram, A. Molten‐salt synthesis of O3‐type layered oxide single crystal cathodes with controlled morphology towards long‐life sodium‐ion batteries. Small 18, e2106927 (2022).

    Article  Google Scholar 

  36. Hafner, J. & Kresse, G. Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251–14269 (1994).

    Article  Google Scholar 

  37. Hafner, J. & Kresse, G. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).

    Article  Google Scholar 

  38. Burke, K., Ernzerhof, M. & Perdew, J. P. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Article  Google Scholar 

  39. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

    Article  Google Scholar 

  40. Martínez, L., Andrade, R., Birgin, E. G. & Martínez, J. M. PACKMOL: a package for building initial configurations for molecular dynamics simulations. J. Comput. Chem. 30, 2157–2164 (2009).

    Article  Google Scholar 

  41. Pack, J. D. & Monkhorst, H. J. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).

    Article  MathSciNet  Google Scholar 

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Acknowledgements

This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering under award number DE-SC0005397.

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Authors and Affiliations

  1. Materials Science and Engineering Program and Texas Materials Institute, The University of Texas at Austin, Austin, TX, USA

    Jiarui He, Amruth Bhargav, Laisuo Su, Julia Lamb, Woochul Shin & Arumugam Manthiram

  2. Advanced Photon Source, Argonne National Laboratory, Lemont, IL, USA

    John Okasinski

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Contributions

J.H., A.B. and A.M. conceived the idea. J.H. performed electrolyte formulations, collected electrochemical data and wrote the paper. A.B. performed the FTIR, NMR and pouch cell experiments. J.O. and L.S. performed the Synchrotron-based operando ED–XRD and corresponding analysis. J.L. provided the NFM cathode. W.S. performed theoretical calculations. A.M. supervised the project and edited the paper. All authors discussed the results and reviewed the paper.

Corresponding author

Correspondence to Arumugam Manthiram.

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Competing interests

J.H., A.B. and A.M. declare that this work has been filed as International Patent Application number PCT/US2023/029298. All other authors declare no competing interests.

Peer review

Peer review information

Nature Energy thanks Michel Armand and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–30, Tables 1–5 and discussion.

Supplementary Video 1

The carbonate electrolyte easily catches fire.

Supplementary Video 2

The conventional LHCE easily catches fire.

Supplementary Video 3

TMP acts as an effective fire extinguisher, scavenging the active hydrogen radicals and preventing the combustion chain reaction, so the NaFSI–NaNO3–TMP electrolyte shows impressive non-flammability.

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He, J., Bhargav, A., Su, L. et al. Tuning the solvation structure with salts for stable sodium-metal batteries. Nat Energy 9, 446–456 (2024). https://doi.org/10.1038/s41560-024-01469-y

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