(Invited) Overview of Ionic Liquid Electrolytes Doped with δ-Metal Halides for Advanced Post-Lithium-Ion Batteries
Authors: Di Noto Vito , Vittadello Michele , Greenbaum Steve G , Vezzu Keti , Pagot Gioele 
Published: February 2024

Humankind is currently facing a global transition towards a green electrification of both energy production and transportation. There is an urgent need to find new approaches for the storage of energy derived from renewable sources, such as solar irradiation, wind and waves. In addition, electric cars require energy storage or conversion systems capable of providing engine power. To these ends, secondary batteries are an attractive and viable solution, especially in the form of the relatively mature Li-ion technology. Unfortunately, Li power sources suffer from high cost, low Li earth-crust abundance, and toxicity of their electrochemical components (e.g., the Co-based cathodes). Such disadvantages demand the exploration of new energy storage devices based on alternative chemistries (e.g., Na, Mg, Ca).
Since their discovery [1-5], electrolytes based on disordered or delta metal halide salts (e.g., δ-MgCl2, δ-LiCl, δ-MgI2) have received widespread attention due to their intriguing physical-chemical properties. Subsequently, electrolytes comprised of ionic liquid solvents dispersing various δ-metal halide salts were investigated [6-9]. These latter ion-conducting systems are characterized by: (i) very high room-temperature ionic conductivity; (ii) wide thermal, chemical and electrochemical stability; and (iii) high coulombic efficiency and very low overpotentials in the metal deposition and stripping processes.
In this contribution, a comparison of different families of ionic liquids will be proposed. In particular, the effects of the use of δ-metal halide salts (e.g., δ-MgCl2, δ-LiCl, and δ-NaCl) on the thermal stability, vibrational features, and electrochemical properties of the resulting electrolytes will be considered. The conductivity mechanisms will be analyzed side-by-side, revealing how ionic conductivity is modulated by the metal ions (e.g., Mg2+, Li+, Na+), on the basis of broadband electrical spectroscopy results.

Acknowledgments

The authors acknowledge support in the form of the following grants: project “Interplay between structure, properties, relaxations and conductivity mechanism in new electrolytes for secondary Magnesium batteries” (Grant Agreement W911NF-21-1-0347-(78622-CH-INT)) of the U.S. Army Research Office; project “ACHILLES” (prot. BIRD219831) of the University of Padua; project “VIDICAT” (Grant Agreement 829145) of the FET-Open call of Horizon 2020; project “Polymer electrolytes for Sodium Batteries” (Grant Agreement 72957-00 01) sponsored by Natrion Inc. and the CUNY Sensor CAT.

References

[1] V. Di Noto, S. Lavina, D. Longo and M. Vidali, Electrochim. Acta 43 (1998) 1225-1237.
[2] V. Di Noto and M. Vittadello, Solid State Ion. 147 (2002) 309-316.
[3] V. Di Noto, M. Vittadello, G. Pace, S. Biscazzo and S. Lavina, Macromol.
Chem. Phys. 203 (2002) 1201-1210.
[4] V. Di Noto, D. Longo, V. Münchow, J. Phys, Chem.
B 103 (1999), 2636-2646.
[5] M. Vittadello, D. I. Waxman, P.J. Sideris, Z. Gan, K Vezzù, E. Negro, A. Safari, S. G. Greenbaum, V. Di Noto, Electrochim. Acta 57 (2011), 112-122.
[6] F. Bertasi, C. Hettige, F. Sepehr, X. Bogle, G. Pagot, K. Vezzù, E. Negro, S.J. Paddison, S.G. Greenbaum, M. Vittadello and V. Di Noto, ChemSusChem 8 (2015) 3069-3076.
[7] F. Bertasi, F. Sepehr, G. Pagot, S.J. Paddison and V. Di Noto, Adv.
Funct. Mater. 26 (2016) 4860-4865.
[8] G. Pagot, K. Vezzù, S. G. Greenbaum and V. Di Noto, J. Power Sourc. 492 (2021) 229681.
[9] G. Pagot, J.A. Kieser, F. Brombin, K. Vezzù, J. Janek and V. Di Noto, J. Power Sourc. 565 (2023) 232910.