Impedance Spectroscopy (IS) is a general term for the technique referring to small-signal measurements of the linear electrical response of a domain of interest. This method is based on the analysis of the system’s electrical response to yield helpful information about its domain-dependent physicochemical properties (generally, the analysis is carried out in the frequency domain). Nowadays, there are many areas of application where IS can be used to evaluate or enhance the development of emerging products and processes. As a contribution to this field of research, this paper presents relevant theoretical–practical aspects of the interpretation and analysis of the electrical behavior of materials based on IS and IS modelling. The work starts by historically introducing IS and then goes through different domains of application of the technique, such as Materials Science and correlated areas. Afterwards, an introduction to IS usage for constructing equivalent electrical circuits is presented, aiming at modelling the materials’ electrical behavior, followed by examples from the literature that use the two possible circuit development approaches, the series and the parallel association of circuit elements. Lastly, the authors present a case study of their most recent efforts of a circuit model development of relative humidity (RH) sensors based on heterogeneous mixed metal oxide (MMO) nanostructures, used to understand and identify existing contributions to the overall electrical response of the sensors to moisture; in their case, the electrical response of the MMO sensors was modelled with a high level of superposition between the experimental and fitted data, using a parallel combination of circuit elements, which is an unconventional one.

Proton conductors are ceramic materials with a crystalline or amorphous structure, which allow the passage of an electrical current through them exclusively by the movement of protons: H⁺. Recent developments in proton-conducting ceramics present considerable promise for obtaining economic and sustainable energy conversion and storage devices, electrolysis cells, gas purification, and sensing applications. So, proton-conducting ceramics that combine sensitivity, stability, and the ability to operate at low temperatures are particularly attractive. In this article, the authors start by presenting a brief historical resume of proton conductors and by exploring their properties, such as structure and microstructure, and their correlation with conductivity. A perspective regarding applications of these materials on low-temperature energy-related devices, electrochemical and moisture sensors, is presented. Finally, the authors’ efforts on the usage of a proton-conducting ceramic, polyantimonic acid (PAA), to develop humidity sensors, are looked into.

Humidity sensors are in high demand for many applications, such as environmental monitoring and air and food quality control. Despite many inorganic and organic materials exhibit moisture sensing properties, the electrical response of many existing sensors is not stable along the time. Polyantimonic acid (PAA) is characterized by elevated proton conductivity and by high thermal stability: consequently, it is seen as promising proton conductor for usage in humidity sensing devices. In this work, for the first time, PAA-based bulk solid membranes were produced and tested as potential materials for relative humidity (RH) detection and their moisture sensitivity was evaluated. Two different amounts of binder were used for moulding the solid sensors: the ones with 10% of binder were designated as 90PAA, while the ones with 20% were named 80PAA. The structures of the solid samples were investigated by X-ray diffraction (XRD) technique, adsorption–desorption curves via Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) techniques. The electrical behaviour was examined at ambient temperature by electrical impedance spectroscopy in the entire relative humidity (RH) interval (0–100%) and in the frequency range of 40 Hz up to 60 MHz. Electrical response of the materials was correlated with the structural features of the membranes. Both 90PAA and 80PAA sensors showed total resistance 3 × 10⁵ and 3.5 × 10⁵ Ω at 10% RH, respectively. A linear decrease of the resistance on RH was observed in the range 30–90% RH for both sensors. The electrical response of the evaluated PAA-based sensors displays good repeatability and reproducibility: the ones with lower binder content showed higher moisture sensitivity as well as very good time stability over 1 year.

A vibrational and conformational analysis of the linear alkylpolyamine 1,3-diaminopropane (1,3-dap) is reported, using vibrational spectroscopy (Raman, Fourier Transform Infrared (FTIR) and inelastic neutron scattering (INS)) coupled to theoretical approaches at the Density Functional Theory (DFT) level. The quantum mechanical calculations were carried out using the mPW1PW functional and the 6-31G* basis set, for the isolated molecule, the condensed phase, and solutions in both water and carbon tetrachloride. The most stable geometries were calculated to be GGG′G and TG′GG′ for the gaseous phase and the CCl₄ solution, and TTTT, TGTT and TTTG for the condensed phase and the aqueous solution. Since the relative populations obtained for the different 1,3-dap conformers were very similar, the corresponding experimental spectra reflect the presence of a mixture of species. The vibrational data obtained for 1,3-dap in its pure form – unprotonated, totally protonated (N-ionised) and N-deuterated – as well as for its aqueous and CCl₄ solutions, were assigned in the light of the theoretical results presently obtained and experimental data previously gathered for similar compounds.

Humidity sensors are of huge importance in diverse domains. Several types of materials present a moisture-sensing capacity; however, frequently, their electrical response does not display time stability. Due to its high thermal stability, high ionic conductivity, and different conduction mechanism contributing to its overall conductivity, polyantimonic acid (PAA) is seen as a promising material for humidity-sensing devices. In the present work, crystalline PAA was obtained via a simple and safe hydrolysis technique using SbCl₃ as a precursor. Bulky sensor samples were produced using different amounts of polyvinyl alcohol (10–20 wt.% PVA) as a binder. The obtained PAA solid sensors were tested at room temperature (RT) in order to evaluate their moisture detection/measuring ability in the relative humidity range 0–100%; the evaluation was carried out with electrical impedance spectroscopy. The sample’s structure and morphology were studied using diverse experimental techniques (porosimetry, scanning electron microscopy, X-ray diffraction analysis, and thermogravimetry analysis, etc.). The sensors’ electrical response was in line with the found structural and morphological features. The slope of the resistance variation with an RH percentage concentration between 1 kΩ and 1.5 kΩ was noted for all sensors (showing no changes with time) in the interval between 30 and 100% RH. A good repeatability and reproducibility of the evaluated sensors’ electrical response was observed: the ones that displayed a higher sensitivity were the ones with a high PVA binder content, higher than previously published results for PAA, as well as a very good time stability along the time and low hysteresis.

The development of innovative proton-conducting materials for low-temperature fuel cells (FCs) is, today, a central topic among the scientific community. Polyantimonic acid (PAA) is characterized by high conductivity and sufficient thermal stability; however, PAA-based solid membrane fabrication with high proton conductivity remains challenging. Additionally, PAA cannot be compacted into solid shaped electrolytes without a binder. In a previous work, using a fluoroplastic binder, the authors fabricated and investigated proton conductivity of bulk PAA-based membranes in the temperature range 25–250 °C. In the present research, the authors opted to use another binder, poly(vinyl alcohol), PVA (which already allowed to obtain PAA sensors with higher sensitivity to moisture, low hysteresis, and similar aging than the produced previously with the fluoroplastic binder), for fabricating new solid membranes. The sample’s structure and morphology were studied using diverse experimental techniques (Thermogravimetric analysis, X-ray diffraction analysis, etc.). Electrical Impedance spectroscopy, EIS, was used to assess the electrical response and respective time stability of the membranes; it also allowed the development of an equivalent model circuit to better interpret the samples’ electrical behavior and respective contributions. The samples with 20 wt% PVA content showed improved protonic conductivity and chemical stability up to 100 °C, when compared to previous prepared and reported ones using the fluoroplastic binder.