Cross-Linking of Sugar-Derived Polyethers and Boronic Acids for Renewable, Self-Healing, and Single-Ion Conducting Organogel Polymer Electrolytes

Abstract

This report describes the synthesis and characterization of organogels by reaction of a diol-containing polyether, derived from the sugar d-xylose, with 1,4-phenylenediboronic acid (PDBA). The cross-linked materials were analyzed by infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA), scanning electron microscopy (FE-SEM), and rheology. The rheological material properties could be tuned: gel or viscoelastic behavior depended on the concentration of polymer, and mechanical stiffness increased with the amount of PDBA cross-linker. Organogels demonstrated self-healing capabilities and recovered their storage and loss moduli instantaneously after application and subsequent strain release. Lithiated organogels were synthesized through incorporation of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) into the cross-linked matrix. These lithium–borate polymer gels showed a high ionic conductivity value of up to 3.71 × 10–3 S cm–1 at 25 °C, high lithium transference numbers (t + = 0.88–0.92), and electrochemical stability (4.51 V). The gels were compatible with lithium-metal electrodes, showing stable polarization profiles in plating/stripping tests. This system provides a promising platform for the production of self-healing gel polymer electrolytes (GPEs) derived from renewable feedstocks for battery applications.

Xylose- and Nucleoside-Based Polymers via Thiol–ene Polymerization toward Sugar-Derived Solid Polymer Electrolytes

“…For example, in 2022, Chen and co-workers exploited the high functionality of the natural polysaccharide chitosan to form cross-linked organogel polymer electrolyte networks with high room temperature ionic conductivity (1.1 × 10 −3 S cm −1 ) and lithium-ion transport number (0.82). 2 In a different approach, we also recently reported an organogel polyether electrolyte derived from D-xylose (a renewable sugar), which was crosslinked with boronic acid groups to achieve even higher room temperature ionic conductivity (3.7 × 10 −3 S cm −1 ) and lithium transference numbers (t + = 0.88−0.92), as well as a wide electrochemical stability window of +4.51 V. 3 However, solid polymer electrolytes (SPEs) are also promising contenders that offer the potential of improved safety and electrochemical, mechanical, and thermal stability (and thus compatibility with Li metal anodes) relative to liquids and polymer gels. As such, we reported the synthesis and characterization of bioderived cross-linked SPEs from D-xylose and 10-undecenoic acid (derived from castor oil).…”

Intrinsically Stretchable Conductive Self-Healable Organogels for Strain, Pressure, Temperature, and Humidity Sensing

“…However, these gels may get damaged easily in practical applications, which limits their potential scopes. Thus, self-healing conductive gels that can act like wound-healing behaviors of human skins to restore their structures and all functionalities after damage would thereby make themselves durable and reliable. – Since the presence of water contents inside hydrogels makes their applications limited at subzero and high temperatures, organogels appeared as alternative solutions to resolve this freezing issue. , Increased developments of autonomous self-repairing and outstanding conductivities have been achieved through recent organogel-based studies, – but further investigations will be required to achieve all desirable functions. Moreover, it is important for the sensing materials to have flexible properties, which make them suitable for strain- and pressure-sensing applications.…”

Hierarchical Mesoporous Metal–Organic Frameworks with Boric Acid Sites on the Inner Surface of Small Mesopores for the Extraction of Nucleotides in Human Plasma Samples

“…Conversely, the complex dissociates to yield cis-diols at a pH lower than the pK a of the boronic acid. 24,25 Based on the property, BA adsorbent materials have been widely used as selective adsorbents for cis-diol compounds. From the structure of the materials, the present materials prepared by either one-pot or postmodification have adsorption sites distributed on the inner and external surfaces of the pores.…”

“…In principle, as the ambient pH is equal to or greater than the p K a of the boronic acid, the boronic acid can adduct with cis -diols to form five- or six-membered cyclic esters. Conversely, the complex dissociates to yield cis -diols at a pH lower than the p K a of the boronic acid. , Based on the property, BA adsorbent materials have been widely used as selective adsorbents for cis -diol compounds. From the structure of the materials, the present materials prepared by either one-pot or post-modification have adsorption sites distributed on the inner and external surfaces of the pores. , To reduce protein adsorption, our group and Bo’s group utilized at least a three-step chemical modification to construct a three-dimensional block polymer coating on the matrix surface, where the inner layer of the polymer is a boronate adsorption layer and the outer layer is a hydrophilic polymer layer.…”