Rational molecular design of polymeric materials toward efficient triboelectric energy harvesting

In the periodic table, halogenic elements have a larger electron affinity (EA = −270~−349 kJ/mol) than any other group, allowing them to accommodate extra electrons for triboelectric energy harvesting. However, because halogenic elements are not homopolymerizable, carbon (EA = −122 kJ/mol)-based polymers (i.e. PTFE, PVDF) are often employed for structural use and mechanical integrity at the expense of reduced electron affinity, intrinsically sacrificing triboelectric energy harvesting. Herein, we report the first example of triboelectric energy harvesting with sulfur backbone-based inorganic polymers synthesized via inverse-vulcanization process of elemental sulfur, a by-product of petroleum refining process. Fluorinated polymeric sulfur demonstrated 6-fold and 3-fold increase in triboelectric energy outputs in voltage and currents respectively in comparison with commercial PTFE film. Such high energy harvesting was achieved by high electron affinity of sulfur (−200 kJ/mol) and by its hypervalency via expanded-octet which provided coordination of two additional bonds with halogens compared to carbon. The triboelectric open-circuit voltage output reached 1366 V and demonstrated direct powering of 630 LEDs under the minimal force of ~30 N. This yellow chemistry-based molecular engineering paves a way for a new class of triboelectric materials toward low-cost, eco-friendly, and scalable triboelectric energy harvesting applications.