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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.

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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.


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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.

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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.

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

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