(Invited) Zwitter Ion-Promoted Hybrid Sepiolite Membranes for Energy Applications
Authors: Makkar Priyanka , Mukhopadhyay Kausik 
Published: August 2024

Functionalized natural clays exhibit significant potential as electrode materials, solid-state electrolytes and separators in energy storage and conversion devices. Features that evoke interest in clay minerals are their (1) porous structures and adsorption properties, (2) tunable surface areas, (3) remarkable thermal and mechanical stabilities, (4) abundant natural reserves, and (5) cost. By tweaking such features along with functionalization with desired molecules, they can be used as an ideal candidate for solid-state electrolyte and battery separators. Naturally occurring clays possess layered silicate structures with interchangeable, intercalated ions and tunable chemical properties. Among them, sepiolite, which is a hydrated magnesium silicate, is one of the most appealing clays having a high-aspect ratio. The blocks and channels in sepiolite with discontinuity in the external silica sheet expose a significant number of surface-silanol groups directly accessible to functionalize with organic and inorganic species. Moreover, its exceptionally high surface area and high cation exchange capacity (CEC) compared to other clays enables easy functionalization, thereby imparting exceptional mechanical durability and material properties that can be used for myriads of applications.
In this work a sustainable, cost-effective, environmentally benign, carbon-neutral, and bio-friendly sepiolite clay composites have been developed using betaine and ionic liquid without the use of polymers, metals, or carbon-based precursors.
Betaine-modified sepiolite clay composites have been synthesized to fabricate flexible and mechanically robust membranes. These membranes are characterized using powder X-ray diffraction, ATR-FTIR, XPS, surface area analyses, rheology, and imaging techniques (e.g., SEM). Morphological analyses reveal sepiolite possesses needle-shaped morphology in a highly aggregated state. The addition of betaine disaggregates such bundles, forming a 3D network with unique “clay anemone” structures. The XRD patterns are consistent with the literature reflecting no change in the d-spacing and corresponding 2θ value (d100 2θ = 7.4 ͦ) before and after betaine treatment. This provides strong evidence of modification limited to the external surface. ATR-FTIR spectra of the sepiolite-betaine composite membranes show the presence of 935, 1330,1391, and 1616 cm-1 frequencies that correspond to C-N-C, N-C-H, C-N and C=Ostretching respectively. This suggests the successful functionalization of sepiolite clay by betaine through an intercalation mechanism. Further, the electrochemical properties of betaine-modified sepiolite membranes are investigated by electrochemical impedance spectroscopy (EIS) measurements to study the ion dynamics of the hybrid membranes. The room temperature ionic conductivities of these membranes are measured using lithium perchlorate (LiClO4) in ethylene carbonate (EC) and dimethyl carbonate (DMC) mixed solvent (1:1). The concentration of LiClO4 is varied to monitor the change in ionic conductivity and ease of ion transfer through the membranes. The highest ionic conductivity is observed in 0.1M LiClO4 concentration which is superior to the ionic conductivity of sepiolite or hybrid materials with carbon-based precursors, metal ions, quantum dots, or polymers. Viscoelastic properties of the sepiolite slurries with varying concentrations of betaine are also studied to investigate the interaction mechanism between the sepiolite-betaine system and correlate the impact of these interactions on the structure and ionic conductivity of the hybrid sepiolite membranes. Contrary, the IL-sepiolite membranes exhibit superior ionic conductivity compared to betaine-sepiolite membranes, which gives a distinct advantage in the physicochemical and electrochemical properties. The composites are synthesized with varying concentrations of ionic liquid-to-clay ratios and pressed into pellets for conductivity measurements. The highest ionic conductivity of 1 x 10-2 S/cm is achieved by modifying the clay with 10 wt. % IL specimens. This helps to improve the ionic conductivity of the IL-clays. The XRD spectra of sepiolite-IL composites show almost no change in the 2 theta values and peak intensities compared to the pristine sepiolite, confirming the crystalline structure of the sepiolite clay is intact after functionalization with IL. The ATR-FTIR confirms the IL-sepiolite modification with the appearance of a new band at 1345 cm-1 that is attributed to -CH stretching frequencyfrom the alkyl chains of IL present in the clay structures.
We have developed a new approach using earth-abundant silicate-based materials to synthesize hybrid zwitterion-modified sepiolite clay membranes. Such materials are not only flexible and mechanically durable, but they also exhibit enhanced ionic conductivity and show exceptional thermal and chemical durability at temperatures above 300 °C and with most aggressive organic solvents, making them a superior candidate for an ergonomic and eco-friendly membrane-based separator for energy devices and gas absorption. Current work is in progress to understand the fundamentals underlying the unique structure-property relationship of hybrid sepiolite, zwitterion-silicate interactions, and conductivity variance with sepiolite architectures, thereby exploiting newer and better properties for application in catalysis, flexible electronics, and biomedical fields.

Figure 1