Organic modification of silica-based ionogels improves the electrolyte/electrode contact and influences their functional properties

Abstract

The energy transition necessitates sustainable energy storage to address the mismatch between the production and consumption of renewable electricity. Sodium-ion batteries (SIBs) are a promising candidate for stationary energy storage as an alternative for lithium-ion batteries (LIBs). In spite of their lower energy density, SIBs have advantages over LIBs.1 Sodium is considerably more abundant than lithium (2.83% versus 0.01%) and, evenly distributed across the Earth, implying that SIBs may be less expensive and more sustainable than LIBs.1,2 Conventional LIBs contain flammable organic liquid electrolytes (e.g. alkyl carbonates) with limited thermal stability. Thermal runaway can therefore lead to cell ignition, causing a significant safety hazard. Non-flammable electrolytes can be based on ionic liquids, which are molten salts with flame retarding properties and negligible vapor pressures. However, the possibility of leakage and related environmental hazards remains a concern.3 This risk can be mitigated by the use of solid electrolytes. Apart from circumventing safety issues, solid electrolytes may allow a significant increase in energy density. After all, they take up less dead volume than liquid electrolytes and can allow the use of alkali metals as negative electrodes. An attractive type of solid electrolyte is the class of silica-based ionogels, owing to their high ionic conductivity, thermal stability, and broad electrochemical window.4 They comprise an ionic liquid electrolyte (ILE, a salt dissolved in ionic liquid) confined in the pores of a solid silica matrix. The silica matrix is electrochemically inactive but influences the functional properties of the resulting solid material. Ionogels based on solely silica (SiO2) as matrix tend to crack easily when subjected to pressure as the rigid Si-O-Si bonds result in high Young’s modulus materials. Furthermore, materials with high Young’s moduli cannot adapt easily to electrode surfaces, resulting in higher charge-transfer resistances (Rct) between the solid electrolyte and electrode. One way to reduce the stiffness of silica-based ionogels is to modify the silica matrix with e.g. organic groups. Ormosils® are a class of materials completely consisting of organically modified silica and show mechanical properties from glassy to rubbery depending on the amount of organic modification.5 Here, the concepts of ionogels and Ormosils® are combined to produce sodium-ion conducting organically modified ionogels. Two different phenyl-bearing silanes (phenyltrimethoxysilane, PhTMS, or diphenyldimethoxysilane, DPhDMS) are for the first time used as organic modifiers in silica-based ionogels. A non-aqueous sol-gel route with formic acid (FA) is used to synthesize the monoliths. Incorporating phenyl groups allow to reduce the Young’s modulus from 29 MPa down to 6 MPa. The charge-transfer resistances (Rct) of Na|ionogel|Na2Ti3O7 half cells, determined with electrochemical impedance spectroscopy (EIS), followed the trend of the ionogels’ Young’s modulus. Through NMR spectroscopy, pi-stacking was observed between the matrix phenyl moieties and IL imidazolium cations. Furthermore, the organic modification diminished the formation of hydrogen bonds between IL anions and matrix silanol groups. This shows that the organic modification of the matrix can have a pronounced effect on the coordination of the ILE components, which ultimately determine the solid electrolyte’s functional properties. In summary, incorporating phenyl groups in the silica matrix of ionogels improves the mechanical properties and charge transfer resistances, but impairs ionic conductivity.

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