Crystalline‐to‐Amorphous Transformation in Cellulose: Engineering Bifunctional Dynamers toward High‐Strength, Rapidly Self‐Healing Ionogels for Flexible Devices

Abstract Flexible ionogels that concurrently deliver high mechanical strength and rapid, efficient self‐healing are essential for next‐generation wearable electronics and soft robotics. Yet, in cellulose‐based systems, this dual functionality is hindered by a fundamental trade‐off: crystalline order imparts strength but suppresses dynamic repair, while amorphous domains enable healing but compromise mechanical integrity. To overcome this dichotomy, a crystalline‐to‐amorphous transformation strategy is introduced that reconfigures cellulose into a bifunctional dynamer‐simultaneously structural and dynamic. Specifically, quasi‐amorphous dialdehyde hydroxypropyl cellulose (DAHPC) is engineered as an active, multifunctional component within a lipoic acylhydrazide‐based ionogel network, replacing conventional passive fillers. The quasi‐amorphous DAHPC chains exhibit high segmental mobility and abundant hydrogen‐bonding sites, fostering hierarchical physical entanglements and microphase‐separated domains that dramatically enhance toughness and tensile strength. Crucially, the aldehyde groups on DAHPC engage in reversible acylhydrazone exchange with acylhydrazide moieties, establishing a dynamic covalent network that enables rapid, thermally triggered self‐healing. The resulting ionogel achieves an exceptional fracture strength of >4.2 MPa, skin‐like stretchability (>80% strain), and autonomous self‐repair with >96% efficiency at 60 °C within 6 h. This work presents a sustainable, molecularly informed design paradigm that harmonizes strength, elasticity, and self‐recovery in bio‐derived ionogels‐paving the way for high‐performance, eco‐conscious materials in flexible and wearable electronics.