Skip to main content

Thank you for visiting 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.

Extending insertion electrochemistry to soluble layered halides with superconcentrated electrolytes


Insertion compounds provide the fundamental basis of today’s commercialized Li-ion batteries. Throughout history, intense research has focused on the design of stellar electrodes mainly relying on layered oxides or sulfides, and leaving aside the corresponding halides because of solubility issues. This is no longer true. In this work, we show the feasibility of reversibly intercalating Li+ electrochemically into VX3 compounds (X = Cl, Br, I) via the use of superconcentrated electrolytes (5 M LiFSI in dimethyl carbonate), hence opening access to a family of LixVX3 phases. Moreover, through an electrolyte engineering approach, we unambiguously prove that the positive attribute of superconcentrated electrolytes against the solubility of inorganic compounds is rooted in a thermodynamic rather than a kinetic effect. The mechanism and corresponding impact of our findings enrich the fundamental understanding of superconcentrated electrolytes and constitute a crucial step in the design of novel insertion compounds with tunable properties for a wide range of applications including Li-ion batteries and beyond.

Your institute does not have access to this article

Access options

Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Fig. 1: Electrolyte engineering to unlock reversible Li+ intercalation in VX3 phases.
Fig. 2: Evolution of the material crystal structure upon cycling.
Fig. 3: Determination of the charge compensation mechanism.
Fig. 4: Superconcentrated electrolytes thermodynamically prevent vanadium-halide dissolution.

Data availability

The Crystallographic Information Files (CIF) files for the VBr3, VI3, Li0.5VBr3, Li0.5VI3, LiVCl3, LiVBr3 and LiVI3 are given as Supplementary Information files. Other experimental data are included within the paper and its Supplementary Information files. Source data are available from the corresponding authors upon reasonable request.


  1. Kong, T., Guo, S., Ni, D. & Cava, R. J. Crystal structure and magnetic properties of the layered van der Waals compound VBr3. Phys. Rev. Mater. 3, 084419 (2019).

    CAS  Article  Google Scholar 

  2. Kong, T. et al. VI3—a new layered ferromagnetic semiconductor. Adv. Mater. 31, 1808074 (2019).

    Article  Google Scholar 

  3. Song, T. et al. Switching 2D magnetic states via pressure tuning of layer stacking. Nat. Mater. 18, 1298–1302 (2019).

    CAS  Article  Google Scholar 

  4. Berthelot, R., Carlier, D. & Delmas, C. Electrochemical investigation of the P2–NaxCoO2 phase diagram. Nat. Mater. 10, 74–80 (2011).

    CAS  Article  Google Scholar 

  5. Steffen, R. Intercalation reactions of ruthenium-(III)-chloride via electron/ion transfer. Solid State Ion. 22, 31–41 (1986).

    CAS  Article  Google Scholar 

  6. Skyllas-Kazacos, M., Cao, L., Kazacos, M., Kausar, N. & Mousa, A. Vanadium electrolyte studies for the vanadium redox battery—a review. ChemSusChem 9, 1521–1543 (2016).

    CAS  Article  Google Scholar 

  7. Dey, A. N. & Sullivan, B. P. The electrochemical decomposition of propylene carbonate on graphite. J. Electrochem. Soc. 117, 222–224 (1970).

    CAS  Article  Google Scholar 

  8. Fong, R. Studies of lithium intercalation into carbons using nonaqueous electrochemical cells. J. Electrochem. Soc. 137, 2009–2013 (1990).

    CAS  Article  Google Scholar 

  9. Jeong, S.-K., Inaba, M., Iriyama, Y., Abe, T. & Ogumi, Z. Electrochemical intercalation of lithium ion within graphite from propylene carbonate solutions. Electrochem. Solid State Lett. 6, A13–A15 (2002).

    Article  Google Scholar 

  10. Yamada, Y., Takazawa, Y., Miyazaki, K. & Abe, T. Electrochemical lithium intercalation into graphite in dimethyl sulfoxide-based electrolytes: effect of solvation structure of lithium ion. J. Phys. Chem. C 114, 11680–11685 (2010).

    CAS  Article  Google Scholar 

  11. Yamada, Y. et al. General observation of lithium intercalation into graphite in ethylene-carbonate-free superconcentrated electrolytes. ACS Appl. Mater. Interfaces 6, 10892–10899 (2014).

    CAS  Article  Google Scholar 

  12. Yamada, Y. et al. Unusual stability of acetonitrile-based superconcentrated electrolytes for fast-charging lithium-ion batteries. J. Am. Chem. Soc. 136, 5039–5046 (2014).

    CAS  Article  Google Scholar 

  13. Suo, L. et al. ‘Water-in-salt’ electrolyte enables high-voltage aqueous lithium-ion chemistries. Science 350, 938–943 (2015).

    CAS  Article  Google Scholar 

  14. Wang, J. et al. Superconcentrated electrolytes for a high-voltage lithium-ion battery. Nat. Commun. 7, 12032 (2016).

    CAS  Article  Google Scholar 

  15. Yamada, Y. et al. Hydrate-melt electrolytes for high-energy-density aqueous batteries. Nat. Energy 1, 16129 (2016).

    CAS  Article  Google Scholar 

  16. Wang, J. et al. Fire-extinguishing organic electrolytes for safe batteries. Nat. Energy 3, 22–29 (2018).

    CAS  Article  Google Scholar 

  17. Yamada, Y., Wang, J., Ko, S., Watanabe, E. & Yamada, A. Advances and issues in developing salt-concentrated battery electrolytes. Nat. Energy (2019).

  18. Yue, J. et al. Interface concentrated‐confinement suppressing cathode dissolution in water‐in‐salt electrolyte. Adv. Energy Mater. (2020).

  19. Sun, D., Okubo, M. & Yamada, A. Optimal water concentration for aqueous Li+ intercalation in vanadyl phosphate. Chem. Sci. 12, 4450–4454 (2021).

    CAS  Article  Google Scholar 

  20. Dokko, K. et al. Solvate ionic liquid electrolyte for Li–S batteries. J. Electrochem. Soc. 160, A1304–A1310 (2013).

    CAS  Article  Google Scholar 

  21. Yamada, A. Enriching battery chemistry. Joule 2, 371–372 (2018).

    Article  Google Scholar 

  22. Mendiboure, A., Delmas, C. & Hagenmuller, P. Electrochemical intercalation and deintercalation of NaxMnO2 bronzes. J. Solid State Chem. 57, 323–331 (1985).

    CAS  Article  Google Scholar 

  23. Dubouis, N. et al. Chasing aqueous biphasic systems from simple salts by exploring the LiTFSI/LiCl/H2O phase diagram. ACS Cent. Sci. 5, 640–643 (2019).

    CAS  Article  Google Scholar 

  24. Dubouis, N., France-Lanord, A., Brige, A., Salanne, M., & Grimaud, A. Anion specific effects drive the formation of Li-salt based aqueous biphasic systems. J. Phys. Chem. B 125, 5365–5372 (2021).

    CAS  Article  Google Scholar 

  25. Soubeyroux, J. L., Cros, C., Gang, W., Kanno, R. & Pouchard, M. Neutron diffraction investigation of the cationic distribution in the structure of the spinel-type solid solutions Li2−2xM1+xCl4 (M = Mg, V): correlation with the ionic conductivity and NMR data. Solid State Ion. 15, 293–300 (1985).

    CAS  Article  Google Scholar 

  26. Xin, N., Sun, Y., He, M., Radke, C. J. & Prausnitz, J. M. Solubilities of six lithium salts in five non-aqueous solvents and in a few of their binary mixtures. Fluid Phase Equilib. 461, 1–7 (2018).

    CAS  Article  Google Scholar 

  27. McEldrew, M., Goodwin, Z. A. H., Bi, S., Bazant, M. Z. & Kornyshev, A. A. Theory of ion aggregation and gelation in super-concentrated electrolytes. J. Chem. Phys. 152, 234506 (2020).

    CAS  Article  Google Scholar 

  28. Marchandier, T. et al. Crystallographic and magnetic structures of the VI3 and LiVI3 van der Waals compounds. Phys. Rev. B 104, 014105

  29. Takada, K., Yamada, Y. & Yamada, A. Optimized nonflammable concentrated electrolytes by introducing a low-dielectric diluent. ACS Appl. Mater. Interfaces 11, 35770–35776 (2019).

    CAS  Article  Google Scholar 

  30. 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).

    CAS  Article  Google Scholar 

  31. Famprikis, T., Canepa, P., Dawson, J. A., Islam, M. S. & Masquelier, C. Fundamentals of inorganic solid-state electrolytes for batteries. Nat. Mater. 18, 1278–1291 (2019).

    CAS  Article  Google Scholar 

  32. Liu, Z. et al. Anomalous high ionic conductivity of nanoporous β‑Li3PS4. (2013).

  33. Herklotz, M. et al. A novel high-throughput setup for in situ powder diffraction on coin cell batteries. J. Appl. Crystallogr. 49, 340–345 (2016).

    CAS  Article  Google Scholar 

  34. Avdeev, M. & Hester, J. R. ECHIDNA: a decade of high-resolution neutron powder diffraction at OPAL. J. Appl. Crystallogr. 51, 1597–1604 (2018).

    CAS  Article  Google Scholar 

  35. Briois, V. et al. ROCK: the new Quick-EXAFS beamline at SOLEIL. J. Phys. Conf. Ser. 712, 012149 (2016).

    Article  Google Scholar 

  36. Leriche, J. B. et al. An electrochemical cell for operando study of lithium batteries using synchrotron radiation. J. Electrochem. Soc. 157, A606–A610 (2010).

    CAS  Article  Google Scholar 

Download references


We gratefully acknowledge I. Aguilar and V. Meunier for their help with ICP measurements, P. Lemaire for the scanning electron microscopy and energy dispersive X-ray spectroscopy measurements, and T. Koç and R. Dugas for their help with all-solid-state battery measurements. N.D. acknowledges the Ecole Normale Supérieure for his Ph.D. scholarship. T.M. acknowledges the Ecole Normale Supérieure Paris-Saclay for his Ph.D. scholarship. A.G. acknowledges support from the Region Ile-de-France in the framework of DIM ResPore for the ICP-MS instrument purchase. A.G. acknowledges financial support from the Agence Nationale de la Rercherche (ANR) MIDWAY (project no. ANR-17-CE05-0008). N.D., T.M., G.R., F.M., A.I., B.P., M.D., J.-M.T. and A.G. thank the French National Research Agency for its support through the Labex STORE-EX project (ANR-10LABX-76-01). Use of the 11-BM mail service of the Advanced Photon Source at Argonne National Laboratory was supported by the US Department of Energy under contract no. DE-AC02-06CH11357 and is gratefully acknowledged. X-ray absorption spectroscopy experiments were performed on the ROCK beamline (financed by ANR-10-EQPX-45) at the SOLEIL synchrotron, France, under proposal no. 20200810. ALBA experiments were performed through academic proposal 2020024152.

Author information

Authors and Affiliations



N.D., T.M., J.-M.T. and A.G. designed the research. T.M., N.D. and J.-M.T. carried out the synthesis. T.M., F.F. and M.A. performed the structural characterizations, further analysed with the help of G.R.; N.D. conducted the electrochemical and solubility measurements. F.M. assembled and tested the solid-state batteries. B.P. and M.D. conducted and analysed the NMR experiments. A.I. performed the X-ray absorption spectroscopy operando experiments and analysed the data. All the authors discussed the scientific results and contributed to the writing of the manuscript.

Corresponding authors

Correspondence to Jean-Marie Tarascon or Alexis Grimaud.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature Materials thanks Yi-Chun Lu, Atsuo Yamada 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

Supplementary Figs. 1–16 and references.

Supplementary Data 1

CIF file for VBr3.

Supplementary Data 2

CIF file for VI3.

Supplementary Data 3

CIF file for Li0.5VBr3.

Supplementary Data 4

CIF file for Li0.5VI3.

Supplementary Data 5

CIF file for LiVCl3.

Supplementary Data 6

CIF file for LiVBr3.

Supplementary Data 7

CIF file for LiVI3.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Dubouis, N., Marchandier, T., Rousse, G. et al. Extending insertion electrochemistry to soluble layered halides with superconcentrated electrolytes. Nat. Mater. 20, 1545–1550 (2021).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:

Further reading


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