Elsevier

Polymer

Volume 224, 14 May 2021, 123707
Polymer

Polymers for aluminium secondary batteries: Solubility, ionogel formation and chloroaluminate speciation

https://doi.org/10.1016/j.polymer.2021.123707Get rights and content
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Highlights

  • Polymers are tested to prepare chloroaluminate gel electrolytes by dissolution.

  • Only PEO, PCL and PDMS are found to be soluble and able to form gels.

  • Spectroscopy and DFT show how polymers modify chloroaluminate species equilibrium.

  • Polymer concentration has to be very low to produce gels retaining electroactivity.

  • Then, use of UHMW polymers is essential to obtain electroactive gel electrolytes.

Abstract

This work deals with the search of polymers apt for the preparation of solid-like chloroaluminate-based electrolytes. To accomplish this, the solubility and gelling ability of a large set of polymers in the deep eutectic solvent AlCl3:urea (uralumina) are studied, followed by the characterization of the electrochemical activity of the gels. The polymers are directly dissolved in urea:AlCl3 without auxiliary solvents following a fast and scalable gel preparation methodology previously reported for ultra-high molecular weight (UHMW) polyethylene oxide (PEO). The list of polymers studied includes diverse chemical structures, different thermal properties and different aggregation states at the mixing temperature of 70 °C, defined by the thermal stability of AlCl3:urea. To avoid a molecular weight influence on the ionogel rheological properties, polymers with molecular weight close to 100,000 g mol−1 have been chosen. The polymers considered include poly(ε-caprolactone) (PCL), poly(dimethyl siloxane) (PDMS), poly(vinyl pyrrolidone) (PVP), polyformal, thermoplastic polyurethanes, polymethacrylates, polyacetates and the elastomer SEBS. It was found that together with polyethylene oxide, only poly(ε-caprolactone) and poly(dimethyl siloxane) are soluble and produce gel electrolytes with AlCl3:urea. The solubility rules of polymers in chloroaluminates are discussed. The stripping/plating of Al and the ionic conductivity of PEO, PDMS and PCL ionogels are studied by cyclic voltammetry and impedance spectroscopy. PDMS proves to be as efficient as PEO to produce ionogels at low polymer concentration, that are also self-standing and electroactive, whereas a higher concentration of PCL is required to produce self-standing gels. The molecular structure of the ionogels and the modification of the chloroaluminate speciation is studied by vibrational spectroscopies, and supported by DFT calculations.

Keywords

Polymer gel electrolyte
Chloroaluminate ionogel
Aluminium secondary battery

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