Reversible bipolar thermopower of ionic thermoelectric polymer composite for cyclic energy generation.

The giant thermopower of ionic thermoelectric materials has attracted great attention for waste-heat recovery technologies. However, generating cyclic power by ionic thermoelectric modules remains challenging, since the ions cannot travel across the electrode interface. Here, we reported a reversible bipolar thermopower (+20.2 mV K-1 to -10.2 mV K-1) of the same composite by manipulating the interactions of ions and electrodes. Meanwhile, a promising ionic thermoelectric generator was proposed to achieve cyclic power generation under a constant heat course only by switching the external electrodes that can effectively realize the alternating dominated thermodiffusion of cations and anions. It eliminates the necessity to change the thermal contact between material and heat, nor does it require re-establish the temperature differences, which can favor improving the efficiency of the ionic thermoelectrics. Furthermore, the developed micro-thermal sensors demonstrated high sensitivity and responsivity in light detecting, presenting innovative impacts on exploring next-generation ionic thermoelectric devices.

The cross-interface energy-filtering effect at organic/inorganic interfaces balances the trade-off between thermopower and conductivity.

The energy-filtering effect has been widely employed to elucidate the enhanced thermoelectric properties of organic/inorganic hybrids. However, the traditional Mott criterion cannot identify the energy-filtering effect of organic/inorganic hybrids due to the limitations of the Hall effect measurement in determining their carrier concentration. In this work, a carrier concentration-independent strategy under the theoretical framework of the Kang-Snyder model is proposed and demonstrated using PANI/MWCNT composites. The result indicates that the energy-filtering effect is triggered on increasing the temperature to 220 K. The energy-filtering effect gives a symmetry-breaking characteristic to the density of states of the charge carriers and leads to a higher thermopower of PANI/MWCNT than that of each constituent. From a morphological perspective, a paracrystalline PANI layer with a thickness of 3 nm is spontaneously assembled on the MWCNT network and serves as a metallic percolation pathway for carriers, resulting in a 5.56-fold increase in conductivity. The cooperative 3D carrier transport mode, including the 1D metallic transport along the paracrystalline PANI and the 2D cross-interface energy-filtering transport, co-determines a 4-fold increase in the power factors of PANI/MWCNT at 300 K. This work provides a physical insight into the improvement of the thermoelectric performance of organic/inorganic hybrids via the energy-filtering effect.