Article

An artificial interphase enables reversible magnesium chemistry in carbonate electrolytes

  • Nature Chemistryvolume 10pages532539 (2018)
  • doi:10.1038/s41557-018-0019-6
  • Download Citation
Received:
Accepted:
Published:

Abstract

Magnesium-based batteries possess potential advantages over their lithium counterparts. However, reversible Mg chemistry requires a thermodynamically stable electrolyte at low potential, which is usually achieved with corrosive components and at the expense of stability against oxidation. In lithium-ion batteries the conflict between the cathodic and anodic stabilities of the electrolytes is resolved by forming an anode interphase that shields the electrolyte from being reduced. This strategy cannot be applied to Mg batteries because divalent Mg2+ cannot penetrate such interphases. Here, we engineer an artificial Mg2+-conductive interphase on the Mg anode surface, which successfully decouples the anodic and cathodic requirements for electrolytes and demonstrate highly reversible Mg chemistry in oxidation-resistant electrolytes. The artificial interphase enables the reversible cycling of a Mg/V2O5 full-cell in the water-containing, carbonate-based electrolyte. This approach provides a new avenue not only for Mg but also for other multivalent-cation batteries facing the same problems, taking a step towards their use in energy-storage applications.

  • Subscribe to Nature Chemistry for full access:

    $59

    Subscribe

Additional access options:

Already a subscriber?  Log in  now or  Register  for online access.

Additional information

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

References

  1. 1.

    Mohtadi, R. & Mizuno, F. Magnesium batteries: current state of the art, issues and future perspectives. Beilstein. J. Nanotechnol. 5, 1291–1311 (2014).

  2. 2.

    Muldoon, J., Bucur, C. B. & Gregory, T. Quest for nonaqueous multivalent secondary batteries: magnesium and beyond. Chem. Rev. 114, 11683–11720 (2014).

  3. 3.

    Aurbach, D., Weissman, I., Gofer, Y. & Levi, E. Nonaqueous magnesium electrochemistry and its application in secondary batteries. Chem. Rec. 3, 61–73 (2003).

  4. 4.

    Aurbach, D. et al. Prototype systems for rechargeable magnesium batteries. Nature 407, 724–727 (2000).

  5. 5.

    Song, J., Sahadeo, E., Noked, M. & Lee, S. B. Mapping the challenges of magnesium battery. J. Phys. Chem. Lett. 7, 1736–1749 (2016).

  6. 6.

    Matsui, M. Study on electrochemically deposited Mg metal. J. Power Sources 196, 7048–7055 (2011).

  7. 7.

    Ling, C., Banerjee, D. & Matsui, M. Study of the electrochemical deposition of Mg in the atomic level: why it prefers the non-dendritic morphology. Electrochim. Acta 76, 270–274 (2012).

  8. 8.

    Aubrey, M. L., Ameloot, R., Wiers, B. M. & Long, J. R. Metal–organic frameworks as solid magnesium electrolytes. Energ. Environ. Sci. 7, 667–671 (2014).

  9. 9.

    Higashi, S., Miwa, K., Aoki, M. & Takechi, K. A novel inorganic solid state ion conductor for rechargeable Mg batteries. Chem. Commun. 50, 1320–1322 (2014).

  10. 10.

    Pandey, G. P., Agrawal, R. C. & Hashmi, S. A. Magnesium ion-conducting gel polymer electrolytes dispersed with fumed silica for rechargeable magnesium battery application. J. Solid State Electr. 15, 2253–2264 (2011).

  11. 11.

    Lu, Z., Schechter, A., Moshkovich, M. & Aurbach, D. On the electrochemical behavior of magnesium electrodes in polar aprotic electrolyte solutions. J. Electroanal. Chem. 466, 203–217 (1999).

  12. 12.

    Yoo, H. D. et al. Mg rechargeable batteries: an on-going challenge. Energ. Environ. Sci. 6, 2265–2279 (2013).

  13. 13.

    Muldoon, J. et al. Electrolyte roadblocks to a magnesium rechargeable battery. Energ. Environ. Sci. 5, 5941–5950 (2012).

  14. 14.

    Liebenow, C., Yang, Z. & Lobitz, P. The electrodeposition of magnesium using solutions of organomagnesium halides, amidomagnesium halides and magnesium organoborates. Electrochem. Commun. 2, 641–645 (2000).

  15. 15.

    Mohtadi, R., Matsui, M., Arthur, T. S. & Hwang, S.-J. Magnesium borohydride: from hydrogen storage to magnesium battery. Angew. Chem. Int. Ed. 51, 9780–9783 (2012).

  16. 16.

    Gregory, T. D., Hoffman, R. J. & Winterton, R. C. Nonaqueous electrochemistry of magnesium applications to energy storage. J. Electrochem. Soc. 137, 775–780 (1990).

  17. 17.

    Connor, J. H., Reid, W. E. & Wood, G. B. Electrodeposition of metals from organic solutions. V. Electrodeposition of magnesium and magnesium alloys. J. Electrochem. Soc. 104, 38–41 (1957).

  18. 18.

    Aurbach, D., Moshkovich, M., Schechter, A. & Turgeman, R. Magnesium deposition and dissolution processes in ethereal grignard salt solutions using simultaneous EQCM-EIS and in situ FTIR spectroscopy. Electrochem. Solid. St. 3, 31–34 (2000).

  19. 19.

    Aurbach, D. et al. Progress in rechargeable magnesium battery technology. Adv. Mater. 19, 4260–4267 (2007).

  20. 20.

    Chusid, O. et al. Solid-state rechargeable magnesium batteries. Adv. Mater. 15, 627–630 (2003).

  21. 21.

    Ha, S.-Y. et al. Magnesium(II) bis(trifluoromethane sulfonyl) imide-based electrolytes with wide electrochemical windows for rechargeable magnesium batteries. ACS Appl. Mater. Interf. 6, 4063–4073 (2014).

  22. 22.

    Gautam, G. S., Canepa, P., Richards, W. D., Malik, R. & Ceder, G. Role of structural H2O in intercalation electrodes: the case of Mg in nanocrystalline xerogel-V2O5. Nano Lett. 16, 2426–2431 (2016).

  23. 23.

    Yu, L. & Zhang, X. G. Electrochemical insertion of magnesium ions into V2O5 from aprotic electrolytes with varied water content. J. Colloid Interface Sci. 278, 160–165 (2004).

  24. 24.

    Rahaman, M. S. A., Ismail, A. F. & Mustafa, A. A review of heat treatment on polyacrylonitrile fiber. Polym. Degrad. Stab. 92, 1421–1432 (2007).

  25. 25.

    Piper, D. M. et al. Conformal coatings of cyclized-PAN for mechanically resilient si nano-composite anodes. Adv. Energy Mater. 3, 697–702 (2013).

  26. 26.

    Son, S. B. et al. A stabilized PAN-FeS2 cathode with an EC/DEC liquid electrolyte. Adv. Energy Mater. 4, 1300961 (2014).

  27. 27.

    Pamula, E. & Rouxhet, P. G. Bulk and surface chemical functionalities of type IIIPAN-based carbon fibres. Carbon 41, 1905–1915 (2003).

  28. 28.

    Wang, Z. X., Huang, B. Y., Xue, R. J., Huang, X. J. & Chen, L. Q. Spectroscopic investigation of interactions among components and ion transport mechanism in polyacrylonitrile based electrolytes. Solid State Ion. 121, 141–156 (1999).

  29. 29.

    Bredas, J. L., Beljonne, D., Coropceanu, V. & Cornil, J. Charge-transfer and energy-transfer processes in π-conjugated oligomers and polymers: a molecular picture. Chem. Rev. 104, 4971–5003 (2004).

  30. 30.

    Borodin, O., Zhuang, G. R. V., Ross, P. N. & Xu, K. Molecular dynamics simulations and experimental study of lithium ion transport in dilithium ethylene dicarbonate. J. Phys. Chem. C. 117, 7433–7444 (2013).

  31. 31.

    Xu, K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chem. Rev. 104, 4303–4417 (2004).

  32. 32.

    Selim, R. & Bro, P. Some observations on rechargeable lithium electrodes in a propylene carbonate electrolyte. J. Electrochem. Soc. 121, 1457–1459 (1974).

  33. 33.

    Shiga, T., Kato, Y., Inoue, M., Takahashi, N. & Hase, Y. Anode material associated with polymeric networking of triflate ions formed on Mg. J. Phys. Chem. C 119, 3488–3494 (2015).

  34. 34.

    Xu, K. Electrolytes and interphases in Li-ion batteries and beyond. Chem. Rev. 114, 11503–11618 (2014).

  35. 35.

    Dlubek, G., Brummer, O., Meyendorf, N., Dekhtyar, I. Y. & Fedchenko, R. G. Positron-annihilation studies on correction of structural crystal defects in plastically deformed PDFE alloys. Phys. Status Solidi A 42, K15–K18 (1977).

  36. 36.

    Amin, R., Balaya, P. & Maier, J. Anisotropy of electronic and ionic transport in LiFePO4 single crystals. Electrochem. Solid St. 10, A13–A16 (2007).

  37. 37.

    Gershinsky, G., Yoo, H. D., Gofer, Y. & Aurbach, D. Electrochemical and spectroscopic analysis of Mg2+ intercalation into thin film electrodes of layered oxides: V2O5 and MoO3. Langmuir 29, 10964–10972 (2013).

  38. 38.

    Zhou, B., Shi, H., Cao, R. F., Zhang, X. D. & Jiang, Z. Y. Theoretical study on the initial stage of a magnesium battery based on a V2O5 cathode. Phys. Chem. Chem. Phys. 16, 18578–18585 (2014).

  39. 39.

    Leger, C., Bach, S., Soudan, P. & Pereira-Ramos, J.-P. Structural and electrochemical properties of ωLi x V2O5 ( 0.4 x 3) as rechargeable cathodic material for lithium batteries. J. Electrochem. Soc. 152, A236–A241 (2005).

  40. 40.

    Yue, Y. & Liang, H. Micro- and nano-structured vanadium pentoxide (V2O5) for electrodes of lithium-ion batteries. Adv. Energy Mater. 7, 1602545 (2017).

  41. 41.

    Novák, P. & Desilvestro, J. Electrochemical insertion of magnesium in metal oxides and sulfides from aprotic electrolytes. J. Electrochem. Soc. 140, 140–144 (1993).

  42. 42.

    Nam, K. W. et al. The high performance of crystal water containing manganese birnessite cathodes for magnesium batteries. Nano Lett. 15, 4071–4079 (2015).

  43. 43.

    Sa, N. Y. et al. Is alpha-V2O5 a cathode material for Mg insertion batteries? J. Power Sources 323, 44–50 (2016).

  44. 44.

    Lim, S.-C. et al. Unraveling the magnesium-ion intercalation mechanism in vanadium pentoxide in a wet organic electrolyte by structural determination. Inorg. Chem. 56, 7668–7678 (2017).

  45. 45.

    Novák, P., Scheifele, W., Joho, F. & Haas, O. Electrochemical insertion of magnesium into hydrated vanadium bronzes. J. Electrochem. Soc. 142, 2544–2550 (1995).

  46. 46.

    Novak, P., Imhof, R. & Haas, O. Magnesium insertion electrodes for rechargeable nonaqueous batteries: a competitive alternative to lithium? Electrochim. Acta 45, 351–367 (1999).

  47. 47.

    Glushenkov, A. M. et al. Growth of V2O5 nanorods from ball-milled powders and their performance in cathodes and anodes of lithium-ion batteries. J. Solid State Electr. 14, 1841–1846 (2010).

Download references

Acknowledgements

This work was supported by the Laboratory Directed Research and Development (LDRD) programme at the National Renewable Energy Laboratory (NREL). The authors greatly appreciate the constructive suggestions from H. Guthrey and D. H. Kim at NREL. The Alliance for Sustainable Energy, LLC (Alliance), is the manager and operator of NREL. Employees of the Alliance, under contract no. DE-AC36-08GO28308 with the US Department of Energy, authored this work.

Author information

Affiliations

  1. National Renewable Energy Laboratory, Golden, CO, USA

    • Seoung-Bum Son
    • , Steve P. Harvey
    • , Adam Stokes
    • , Andrew Norman
    •  & Chunmei Ban
  2. Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD, USA

    • Tao Gao
    •  & Chunsheng Wang
  3. Department of Physics, Colorado School of Mines, Golden, CO, USA

    • K. Xerxes Steirer
  4. Department of Materials Science, Colorado School of Mines, Golden, CO, USA

    • Adam Stokes
  5. Electrochemistry Branch, Sensor and Electron Devices Directorate, US Army Research Laboratory, Adelphi, MD, USA

    • Arthur Cresce
    •  & Kang Xu

Authors

  1. Search for Seoung-Bum Son in:

  2. Search for Tao Gao in:

  3. Search for Steve P. Harvey in:

  4. Search for K. Xerxes Steirer in:

  5. Search for Adam Stokes in:

  6. Search for Andrew Norman in:

  7. Search for Chunsheng Wang in:

  8. Search for Arthur Cresce in:

  9. Search for Kang Xu in:

  10. Search for Chunmei Ban in:

Contributions

S.-B.S. and C.B. developed the protocol for fabricating the Mg2+-conducting interphase on Mg electrodes and performed electrochemical testing. C.B. supervised the work. K.X. synthesized APC electrolyte. T.G and C.W. contributed to the conductivity measurements. S.H. measured and analysed TOF-SIMS spectra of the Mg electrode. K.S. and A.C. measured and analysed XPS spectra of the Mg electrode. A.N. and A.S. performed FIB and STEM-EDS analysis. S.-B.S., C.B., K.X. and C.W. prepared the manuscript.

Competing interests

The authors declare no competing interests.

Corresponding author

Correspondence to Chunmei Ban.

Supplementary information

  1. Supplementary Information

    Supplementary data and characterization, Supplementary Figs. 1–15