Ionic thermoelectric (i-TE) material with mobile ions as charge carriers has the potential to generate large thermal voltages at low operating temperatures. This study highlights the role of ions in i-TE hydrogels employing a poly­(vinyl alcohol) (PVA) polymer matrix and a number of ion providers, e.g., KOH, KNO3, KCl, KBr, NaI, KI, and CsI. The relationship between the intrinsic physical parameters of the ion and the thermoelectric performance is established, indicating the ability to influence the hydrogen bond by the ion is a crucial factor. Among these i-TE hydrogels, the PVA/CsI hydrogel exhibits the largest ionic Seebeck coefficient, reaching 52.9 mV K–1, which is the largest of all i-TE materials reported to date. In addition, our work demonstrates the influence of ions on polymer configuration and provides an avenue for ion selection in the Soret effect in ionic thermoelectrics.

The Seebeck coefficient of Fe2+/3+ thermogalvanic cells is inversely proportional to the donor number of organic solvent additives, which cause rearrangement of the Fe2+/3+ solvent shell.

Ionic thermoelectric (i-TE) materials have attracted much attention due to their ability to generate ionic Seebeck coefficient of tens of millivolts per Kelvin. In this work, we demonstrate that the ionic thermopower can be enhanced by the introduction of multiple ions. The multi-ionic hydrogel possesses a record thermal-to-electrical energy conversion factor (TtoE factor) of 89.6 mV K À 1 and an ionic conductivity of 6.8 mS cm À 1 , which are both better than single salt control hydrogel. Subsequently we build a model to explain thermal diffusion of the ions in multi-ionic hydrogels. Finally, the possibility of large-scale integrated applications of multi-ionic hydrogels is demonstrated. By connecting 7 i-TEs hydrogels, we obtained an open-circuit voltage of 1.86 V at ΔT = 3 K. Our work provides a new pathway for the design of i-TEs and low-grade heat harvesting.

Ionic thermoelectric materials attract widespread attention due to their large Seebeck coefficient compared with electronic thermoelectric counterparts whose main charge carriers are electrons or holes. The present work shows that the ion-polymer matrix interaction can alter the Seebeck coefficient to a great extent. To further shed light on the role of ions, seven water-soluble inorganic chlorides are utilized in this work, to highlight the influence of the cationic softness parameter on the Seebeck coefficient in a PEDOT:PSS ionic conductor. We notice that cations with a positive or a small negative softness parameter value exhibit a negative Seebeck coefficient, resulting from limited thermal diffusion of the cations that are strongly bound to PSS- anions. Conversely, cations with a sufficiently negative softness parameter exhibit fast thermal diffusion due to weak binding to PSS- and, thus, lead to a positive Seebeck coefficient. Based on the established relationship, robust thermoelectric materials with a tunable Seebeck coefficient ranging from –9.63 mV/K to +3.07 mV/K are demonstrated. Our work highlights the important role of ionic properties and provides a pathway for the rational selection of ions in ionic thermoelectrics.

Despite rapid advances in stretchable electrodes, successful examples of polymeric dry electrodes are limited. Especially in wearable health monitoring, it is urgent to develop biocompatible electrodes that possess intrinsic skin-compliance while maintaining a high conductivity. Herein, a strategy is demonstrated to synergistically regulate the interpenetration behavior and molecular crystallinity in the blend via embedding a novel double network, i.e. physically cross-linked poly­(vinyl alcohol) (PVA) and covalently cross-linked polyethylene glycol diacrylate (PEGDA), into the PEDOT:PSS matrix. The favorable interaction energy between PVA and PEGDA enables well-distributed microstructure with finer phase separation in the film, affording a low Young’s modulus of 16 MPa with a high conductivity of 442 S/cm. Consequently, the optimal polymeric electrode can acquire high-quality electromyogram (EMG) and electrocardiogram (ECG) signals. Our results provide a feasible approach for producing skin-compliant polymeric electrodes toward next-generation health monitors.