Reconciling the Stability‐Degradability Paradox in Triboelectronics via Bond‐Level Heterogeneous Dynamic Networks

The pursuit of high‐performance yet fully degradable electronics remains a formidable challenge, as these two attributes are often mutually exclusive in conventional material designs. Here, we propose and demonstrate a generalizable bond‐level heterogeneity strategy to fundamentally reconcile this conflict, using Fe 2+ /Fe 3+ mixed‐valence dynamic networks as a paradigm. We engineer a chitosan‐based hydrogel wherein robust Fe 3+ crosslinks constitute a static skeleton for mechanical and electronic stability, while labile Fe 2+ bonds serve as dynamic hinges enabling autonomous self‐healing (5 min) and programmable degradation. This synergistic “rigid‐flexible” duality triggers a cooperative polarization effect, yielding an exceptional triboelectric output of 115 V and 45.5 mW/m 2 . Notably, this performance is achieved within a material that concurrently exhibits wide‐temperature operability (−20°C to 80°C), rapid self‐healing (5 min), inherent antibacterial efficacy (>99.8%), and most importantly, a fully validated closed‐loop lifecycle—a combination of attributes previously unreported in sustainable triboelectric materials. Crucially, we validate this lifecycle: the hydrogel undergoes controllable degradation over four months, and the resulting residues are directly upcycled into new devices that retain >95% of the original performance. This work transcends a single‐material advance by establishing a bond‐level design paradigm that intrinsically unites high performance with circularity, providing a blueprint for sustainable electronics with built‐in end‐of‐life valorization.