Ultrafast Self‐Healing, Superstretchable, and Ultra‐Strong Polymer Cluster‐Based Adhesive Based on Aromatic Acid Cross‐Linkers for Excellent Hydrogel Strain Sensors

Abstract Synthetic hydrogel strain sensors rarely exhibit a comprehensive combination of mechanical properties such as ultra‐stretchability, ultrafast self‐healing, and high sensitivity. Herein, seven small molecule enhanced mechanical behaviors of polymer‐cluster based hydrogels are demonstrated. The oxidized polyethyleneimine/polymeric acrylic acid (ohPEI/PAA) hydrogels with aromatic formic acids as supramolecular cross‐linkers are prepared by simultaneous formation of ohPEI polymer clusters and PAA upon the addition of ammonium persulfate. The optimized hydrogel adhesive exhibits comprehensive excellent properties, such as high extensibility (up to 12 298%), real‐time mechanical self‐healing capability (<1 s, 93% efficiency), high uniformity, underwater adhesivity, and water‐sealing ability. The proper binding strength of hydrogel and skin (47 kPa) allows the hydrogel to be utilized as highly sensitive (gauge factor:16.08), highly conductive (2.58 mS cm −1 ), and underwater strain sensors. Specially, the adhesive strength of the adhesive to wood after dehydration is extremely high, reaching up to 29.59 MPa. Additionally, when glycerol is introduced, the obtained gel maintains the physical properties even at harsh‐temperature conditions (−40 to 80 °C). It presents that multiple and hierarchical non‐covalent interactions including multiple hydrogen bonding interactions, π–π stacking, electrostatic interactions, and dipole–dipole interactions of polymer clusters, allow for the energy dissipation and contribute to the excellent performance of the hydrogel.