Self-Recovery, Fatigue-Resistant, and Multifunctional Sensor Assembled by a Nanocellulose/Carbon Nanotube Nanocomplex-Mediated Hydrogel.

Flexible sensors have attracted great research interest due to their applications in artificial intelligence, wearable electronics, and personal health management. However, due to the inherent brittleness of common hydrogels, preparing a hydrogel-based sensor integrated with excellent flexibility, self-recovery, and antifatigue properties still remains a challenge to date. In this study, a type of physically and chemically dual-cross-linked conductive hydrogels based on 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofiber (TOCN)-carrying carbon nanotubes (CNTs) and polyacrylamide (PAAM) matrix via a facial one-pot free-radical polymerization is developed for multifunctional wearable sensing application. Inside the hierarchical gel network, TOCNs not only serve as the nanoreinforcement with a toughening effect but also efficiently assist the homogeneous distribution of CNTs in the hydrogel matrix. The optimized TOCN-CNT/PAAM hydrogel integrates high compressive (∼2.55 MPa at 60% strain) and tensile (∼0.15 MPa) strength, excellent intrinsic self-recovery property (recovery efficiency >92%), and antifatigue capacity under both cyclic stretching and pressing. The multifunctional sensors assembled by the hydrogel exhibit both high strain sensitivity (gauge factor ≈11.8 at 100-200% strain) and good pressure sensing ability over a large pressure range (0-140 kPa), which can effectively detect the subtle and large-scale human motions through repeatable and stable electrical signals even after 100 loading-unloading cycles. The comprehensive performance of the TOCN-CNT/PAAM hydrogel-based sensor is superior to those of most gel-based sensors previously reported, indicating its potential applications in multifunctional sensing devices for healthcare systems and human motion monitoring.

Nanocellulose-Mediated Electroconductive Self-Healing Hydrogels with High Strength, Plasticity, Viscoelasticity, Stretchability, and Biocompatibility toward Multifunctional Applications.

Conducting polymer hydrogels (CPHs) have emerged as a fascinating class of smart soft matters important for various advanced applications. However, achieving the synergistic characteristics of conductivity, self-healing ability, biocompatibility, viscoelasticity, and high mechanical performance still remains a critical challenge. Here, we develop for the first time a type of multifunctional hybrid CPHs based on a viscoelastic polyvinyl alcohol (PVA)-borax (PB) gel matrix and nanostructured CNFs-PPy (cellulose nanofibers-polypyrrole) complexes that synergizes the biotemplate role of CNFs and the conductive nature of PPy. The CNF-PPy complexes are synthesized through in situ oxidative polymerization of pyrrole on the surface of CNF templates, which are further well-dispersed into the PB matrix to synthesize homogeneous CNF-PPy/PB hybrid hydrogels. The CNF-PPy complexes not only tangle with PVA chains though hydrogen bonds, but also form reversibly cross-linked complexes with borate ions. The multi-complexation between each component leads to the formation of a hierarchical three-dimensional network. The CNF-PPy/PB-3 hydrogel prepared by 2.0 wt % of PVA, 0.4 wt % of borax, and CNF-PPy complexes with a mass ratio of 3.75/1 exhibits the highest viscoelasticity and mechanical strength. Because of a combined reinforcing and conductive network inside the hydrogel, its maximum storage modulus (∼0.1 MPa) and nominal compression stress (∼22 MPa) are 60 and 2240 times higher than those of pure CNF/PB hydrogel, respectively. The CNF-PPy/PB-3 electrode with a conductivity of 3.65 ± 0.08 S m-1 has a maximum specific capacitance of 236.9 F g-1, and its specific capacitance degradation is less than 14% after 1500 cycles. The CNF-PPy/PB hybrid hydrogels also demonstrate attractive characteristics, including high water content (∼94%), low density (∼1.2 g cm-3), excellent biocompatibility, plasticity, pH sensitivity, and rapid self-healing ability without additional external stimuli. Taken together, the combination of such unique properties endows the newly developed CPHs with potential applications in flexible bioelectronics and provides a practical platform to design multifunctional smart soft materials.