Thermo-electrochemical
cells have potential to generate thermoelectric
voltage 1 order higher than that given by semiconductor materials.
To overcome the current issues in thermoelectric energy conversion,
it is of paramount importance to grow and fulfill the full potential
of thermo-electrochemical cells. Here we report a rational supramolecular
methodology that yielded the highest Seebeck coefficient of ca. 2.0
mV K–1 around ambient temperatures. This is based
on the encapsulation of triiodide ions in α-cyclodextrin, whose
equilibrium is shifted to the complexation at lower temperatures,
whereas it is inverted at elevated temperatures. This temperature-dependent
host–guest interaction provides a concentration gradient of
redox ion pairs between two electrodes, leading to the eminent performance
of the thermo-electrochemical cells. The figure of merit for this
system, zT reached a high value of 5 × 10–3. The introduction of host–guest chemistry
to thermoelectric cells thus provides a new perspective in thermoelectric
energy conversion