Biomass Hydrogel Electrolytes toward Green and Durable Supercapacitors: Enhancing Flame Retardancy, Low-Temperature Self-Healing, Self-Adhesion, and Long-Term Cycling Stability.

Hydrogels have shown promise as quasi-solid-state electrolytes for flexible supercapacitors but face challenges such as poor self-repair, unstable electrode adhesion, limited temperature range, and flammability. Herein, an all-round green hydrogel electrolyte (silk nanofibers (SNFs)/peach gum polysaccharide (PGP)/borax/glycerol (SPBG)-ZnSO4) addresses these issues through dynamic cross-linking of peach gum polysaccharide and silk nanofibers with borax, integrating varieties of key property including high water retention, broad temperature tolerance (-20 to 90 °C), excellent self-adhesion (60.7 kPa for carbon cloth electrodes), satisfactory flame retardancy (limited oxygen index of 51%), low-temperature self-healing (-20 °C), and good ionic conductivity (7.68 mS cm-1). The resulting supercapacitor exhibits excellent cycling stability with 98.2% capacitance retention after 40,000 long cycles at 25 °C. The specific capacitance retention remains above 90% even after 15,000 cycles at high/low temperatures (50 °C/-20 °C). Furthermore, the flexible supercapacitor demonstrates stable performance under mechanical stimuli (180° bending and perforation), highlighting the potential of biomass hydrogels in flexible energy storage devices.

Low-temperature, ultra-fast, and recyclable self-healing nanocomposites reinforced with non-solvent silylated modified cellulose nanocrystals.

Developing polymeric materials with remarkable mechanical properties and fast self-healing performance even at low temperatures is challenging. Herein, the polymeric nanocomposites containing silane-treated cellulose nanocrystals (SCNC) with ultrafast self-healing and exceptional mechanical characteristics were developed even at low temperatures. First, CNC is modified with a cyclic silane coupling agent using an eco-friendly chemical vapor deposition method. The nanocomposite was then fabricated by blending SCNC with matrix prepolymer, prepared from monomers that possess lower critical solution temperature, followed by the inclusion of dibutyltin dilaurate and hexamethylene diisocyanate. The self-healing capability of the novel SCNC/polymer nanocomposites was enhanced remarkably by increasing the content of SCNC (0-3 wt%) and reaching (≥99 %) at temperatures (5 & 25 °C) within <20 min. Moreover, SCNC-3 showed a toughness of (2498 MJ/m3) and SCNC-5 displayed a robust tensile strength of (22.94 ± 0.4 MPa) whereas SCNC-0 exhibited a lower tensile strength (7.4 ± 03 MPa) and toughness of (958 MJ/m3). Additionally, the nanocomposites retain their original mechanical properties after healing at temperatures (5 & 25 °C) owing to the formation of hydrogen bonds via incorporation of the SCNC. These novel SCNC-based self-healable nanocomposites with tunable mechanical properties offer novel insight into preparing damage and temperature-responsive flexible and wearable devices.

Proton Hydrogel-Based Supercapacitors with Rapid Low-Temperature Self-Healing Properties.

Hydrogel-based supercapacitors are an up-and-coming candidate for safe and portable energy storage. However, it is challenging for hydrogel electrolytes to achieve high conductivity and rapid self-healing at subzero temperatures because the movements of polymer chains and the reconstruction capability of broken dynamic bonds are limited. Herein, a highly conductive proton polyacrylamide-phytic acid (PAAm-PA) hydrogel electrolyte with rapid and autonomous self-healing ability and excellent adhesion over a wide temperature range is developed. PA, as a proton donor center, endows the hydrogels with high conductivity (102.0 mS cm-1) based on the Grotthuss mechanism. PA can also prevent the crystallization of water and form multiple reversible hydrogen bonds in the polymer network, which solves the dysfunction of self-healing hydrogels in a cryogenic environment. Accordingly, the hydrogel electrolytes demonstrate fast low-temperature self-healing ability with a self-healing efficiency of 79.4% within 3 h at -20 °C. In addition, the hydrogel electrolytes present outstanding adhesiveness on electrodes due to the generation of hydrogen bonds between PA and activated carbon electrodes. As a result, the integrated hydrogel-based supercapacitors with tight bonding electrode/electrolyte interface deliver a 139.5 mF cm-2 specific capacitance at 25 °C. Moreover, the supercapacitors display superb self-healing ability, achieving 92.1% of capacitance recovery after three cutting-healing cycles at -20 °C. Furthermore, the supercapacitors demonstrate only 6.4% capacitance degradation after 5000 charging-discharging cycles at -20 °C. This work provides a roadmap for designing all-in-one flexible energy storage devices with excellent self-healing ability over a wide temperature range.

Fire-resistant and low-temperature self-healing bio-based hydrogel electrolytes based on peach gum polysaccharide/sisal nanofibers for flexible supercapacitors.

The introduction of flame retardancy and low-temperature self-healing capacities in hydrogel electrolytes are crucial for promoting the cycle stability and durability of the flexible supercapacitors in extreme environments. Herein, biomass-based dual-network hydrogel electrolyte (named PSBGL), was synthesized with borax crosslinked peach gum polysaccharide/sisal nanofibers composite, and its application in flexible supercapacitors was also investigated in detail. The dynamic cross-linking of the dual-network endows the PSBGL with excellent self-healing performance, enabling ultrafast self-healing within seconds at both room temperature and extreme low temperatures. The PSBGL bio-based hydrogel electrolyte can maintain the integrity of the carbon layer structure with limiting oxygen index of 56 % after 60 s of combustion under a flame gun. Additionally, the PSBGL exhibits high ionic conductivity (30.12 mS cm-1), good tensile strength (1.78 MPa), and robust adhesion to electrodes (1.15 MPa). The assembled supercapacitors demonstrate a high specific capacitance of 187.8 F g-1 at 0.5 A g-1, with 95.9 % capacitance retention rate after 10,000 cycles at room temperature. Importantly, even under extreme temperatures of 60 °C and -35 °C, the supercapacitors can also maintain high capacitance retention rates of 90.1 % and 86.5 % after 10,000 cycles. This work fills the gap between biomaterial design and high-performance flexible supercapacitors.