An understanding of the doping and ion distributions in light-emitting electrochemical cells (LECs) is required to approach a realistic conduction model which can precisely explain the electrochemical reactions, p-n junction formation, and ion dynamics in the active layer and to provide relevant information about LECs for systematic improvement of function and manufacture. Here, Fourier-transform infrared (FTIR) microscopy is used to monitor anion density profile and polymer structure in situ and for time-resolved mapping of electrochemical doping in an LEC under bias. The results are in very good agreement with the electrochemical doping model with respect to ion redistribution and formation of a dynamic p-n junction in the active layer. We also physically slow ions by decreasing the working temperature and study frozen-junction formation and immobilization of ions in a fixed-junction LEC device by FTIR imaging. The obtained results show irreversibility of the ion redistribution and polymer doping in a fixed-junction device. In addition, we demonstrate that infrared microscopy is a useful tool for in situ characterization of electroactive organic materials.

The thermoelectric (TE) phenomena are intensively explored by the scientific community due to the rather inefficient way energy resources are used with a large fraction of energy wasted in the form of heat. Among various materials, mixed ion-electron conductors (MIEC) are recently being explored as potential thermoelectrics, primarily due to their low thermal conductivity. The combination of electronic and ionic charge carriers in those inorganic or organic materials leads to complex evolution of the thermovoltage (V_oc) with time, temperature, and/or humidity. One of the most promising organic thermoelectric materials, poly(3,4-ethyelenedioxythiophene)-polystyrene sulfonate (PEDOT-PSS), is an MIEC. A previous study reveals that at high humidity, PEDOT-PSS undergoes an ionic Seebeck effect due to mobile protons. Yet, this phenomenon is not well understood. In this work, the time dependence of the V_oc is studied and its behavior from the contribution of both charge carriers (holes and protons) is explained. The presence of a complex reorganization of the charge carriers promoting an internal electrochemical reaction within the polymer film is identified. Interestingly, it is demonstrated that the time dependence behavior of V_oc is a way to distinguish between three classes of polymeric materials: electronic conductor, ionic conductor, and mixed ionic–electronic conductor

PEDOT-Tos is one of the conducting polymers that displays the most promising thermoelectric properties. Until now, it has been utterly difficult to control all the synthesis parameters and the morphology governing the thermoelectric properties. To improve our understanding of this material, we study the variation in the thermoelectric properties by a simple acido-basic treatment. The emphasis of this study is to elucidate the chemical changes induced by acid (HCl) or base (NaOH) treatment in PEDOT-Tos thin films using various spectroscopic and structural techniques. We could identify changes in the nanoscale morphology due to anion exchange between tosylate and Cl- or OH-. But, we identified that changing the pH leads to a tuning of the oxidation level of the polymer, which can explain the changes in thermoelectric properties. Hence, a simple acid-base treatment allows finding the optimum for the power factor in PEDOT-Tos thin films.

We report spectroelectrochemical studies to investigate the charge storage mechanism of composite polypyrrole/lignin electrodes. Renewable bioorganic electrode materials were produced by electropolymerization of pyrrole in the presence of a water-soluble lignin derivative acting as a dopant. The resulting composite exhibited enhanced charge storage abilities due to a lignin-based faradaic process, which was expressed after repeated electrochemical redox of the material. The in situ FTIR spectroelectrochemistry results show the formation of quinone groups, and reversible oxidation-reduction of these groups during charge-discharge experiments in the electrode materials. The most significant IR bands include carbonyl absorption near 1705 cm(-1), which is attributed to the creation of quinone moieties during oxidation, and absorption at 1045 cm(-1) which is due to hydroquinone moieties.

The conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) has shown promise as air electrode in renewable energy technologies like metal-air batteries and fuel cells. PEDOT is based on atomic elements of high abundance and is synthesized at low temperature from solution. The mechanism of oxygen reduction reaction (ORR) over chemically polymerized PEDOT: Cl still remains controversial with eventual role of transition metal impurities. However, regardless of the mechanistic route, we here demonstrate yet another key active role of PEDOT in the ORR mechanism. Our study demonstrates the decoupling of conductivity (intrinsic property) from electrocatalysis (as an extrinsic phenomenon) yielding the evidence of doping of the polymer by oxygen during ORR. Hence, the PEDOT electrode is electrochemically reduced (undoped) in the voltage range of ORR regime, but O-2 keeps it conducting; ensuring PEDOT to act as an electrode for the ORR. The interaction of oxygen with the polymer electrode is investigated with a battery of spectroscopic techniques.