RESUMEN
Solid polymer electrolytes show their potential to partially replace conventional electrolytes in electrochemical devices. The solvent evaporation rate represents one of many options for modifying the electrode-electrolyte interface by affecting the structural and electrical properties of polymer electrolytes used in batteries. This paper evaluates the effect of solvent evaporation during the preparation of solid polymer electrolytes on the overall performance of an amperometric gas sensor. A mixture of the polymer host, solvent and an ionic liquid was thermally treated under different evaporation rates to prepare four polymer electrolytes. A carbon nanotube-based working electrode deposited by spray-coating the polymer electrolyte layer allowed the preparation of the electrode-electrolyte interface with different morphologies, which were then investigated using scanning electron microscopy and Raman spectroscopy. All prepared sensors were exposed to nitrogen dioxide concentration of 0-10 ppm, and the current responses and their fluctuations were analyzed. Electrochemical impedance spectroscopy was used to describe the sensor with an equivalent electric circuit. Experimental results showed that a higher solvent evaporation rate leads to lower sensor sensitivity, affects associated parameters (such as the detection/quantification limit) and increases the limit of the maximum current flowing through the sensor, while the other properties (hysteresis, repeatability, response time, recovery time) change insignificantly.
RESUMEN
The conductive polymer-electrolyte interface plays an important role in many electrochemical devices. An unusual situation arises when a solvent-free ionic liquid (SF-IL) is used as the electrolyte because it behaves as a molten salt rather than an electrolyte solution. On the basis of Raman spectra, it was found that the presence of ion pairs of SF-IL in the vicinity of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) results in a decrease in the oxidation level of the polymer and an increase in the HOMO-LUMO gap. The process of polymer "dedoping" and the modification of the electronic structure of the polymer are illustrated by quantum chemical calculations.
RESUMEN
Thermal treatment conditions of solid polymer polymer electrolyte (SPE) were studied with respect to their impact on the surface morphology, phase composition and chemical composition of an imidazolium ionic-liquid-based SPE, namely PVDF/NMP/[EMIM][TFSI] electrolyte. These investigations were done using scanning electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry as well as X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectroscopy. A thoroughly mixed blend of polymer matrix, ionic liquid and solvent was deposited on a ceramic substrate and was kept at a certain temperature for a specific time in order to achieve varying crystallinity. The morphology of all the electrolytes consists of spherulites whose average diameter increases with solvent evaporation rate. Raman mapping shows that these spherulites have a semicrystalline structure and the area between them is an amorphous region. Analysis of FTIR spectra as well as Raman spectroscopy showed that the ß-phase becomes dominant over other phases, while DSC technique indicated decrease of crystallinity as the solvent evaporation rate increases. XPS and ToF-SIMS indicated that the chemical composition of the surface of the SPE samples with the highest solvent evaporation rate approaches the composition of the ionic liquid.
RESUMEN
An electrochemical amperometric ethylene sensor with solid polymer electrolyte (SPE) and semi-planar three electrode topology involving a working, pseudoreference, and counter electrode is presented. The polymer electrolyte is based on the ionic liquid 1-butyl 3-methylimidazolium bis(trifluoromethylsulfonyl)imide [BMIM][NTf2] immobilized in a poly(vinylidene fluoride) matrix. An innovative aerosol-jet printing technique was used to deposit the gold working electrode (WE) on the solid polymer electrolyte layer to make a unique electrochemical active SPE/WE interface. The analyte, gaseous ethylene, was detected by oxidation at 800 mV vs. the platinum pseudoreference electrode. The sensor parameters such as sensitivity, response/recovery time, repeatability, hysteresis, and limits of detection and quantification were determined and their relation to the morphology and microstructure of the SPE/WE interface examined. The use of additive printing techniques for sensor preparation demonstrates the potential of polymer electrolytes with respect to the mass production of printed electrochemical gas sensors.
RESUMEN
The experimental study deals with the investigation of the effect of diverse crystallinity of imidazolium ionic-liquid-based SPE on conductivity and current fluctuations. The experimental study was carried out on samples consisting of [EMIM][TFSI] as ionic liquid, PVDF as a polymer matrix and NMP as a solvent. After the deposition, the particular sample was kept at an appropriate temperature for a specific time in order to achieve different crystalline forms of the polymer in the solvent, since the solvent evaporation rate controls crystallization. The ac/dc conductivities of SPEs were investigated across a range of temperatures using broadband dielectric spectroscopy in terms of electrical conductivity. In SPE samples of the higher solvent evaporation rate, the real parts of conductivity spectra exhibit a sharper transition during sample cooling and an increase of overall conductivity, which is implied by a growing fraction of the amorphous phase in the polymer matrix in which the ionic liquid is immobilized. The conductivity master curves illustrate that the changing of SPEs morphology is reflected in the low frequency regions governed by the electrode polarization effect. The dc conductivity of SPEs exhibits Vogel-Fulcher-Tammann temperature dependence and increases with the intensity of thermal treatment. Spectral densities of current fluctuations showed that flicker noise, thermal noise and shot noise seems to be major noise sources in all samples. The increase of electrolyte conductivity causes a decrease in bulk resistance and partially a decrease in charge transfer resistance, while also resulting in an increase in shot noise. However, the change of electrode material results in a more significant change of spectral density of current fluctuations than the modification of the preparation condition of the solid polymer electrolyte. Thus, the contact noise is considered to contribute to overall current fluctuations across the samples.
RESUMEN
Analyte flow influences the performance of every gas sensor; thus, most of these sensors usually contain a diffusion barrier (layer, cover, inlet) that can prevent the negative impact of a sudden change of direction and/or the rate of analyte flow, as well as various unwanted impacts from the surrounding environment. However, several measurement techniques use the modulation of the flow rate to enhance sensor properties or to extract more information about the chemical processes that occur on a sensitive layer or a working electrode. The paper deals with the experimental study on how the analyte flow rate and the orientation of the electrochemical sensor towards the analyte flow direction influence sensor performance and current fluctuations. Experiments were carried out on a semi-planar, three-electrode topology that enabled a direct exposure of the working (sensing) electrode to the analyte without any artificial diffusion barrier. The sensor was tested within the flow rate range of 0.1-1 L/min and the orientation of the sensor towards the analyte flow direction was gradually set to the four angles 0°, 45°, 90° and 270° in the middle of the test chamber, while the sensor was also investigated in the standard position at the bottom of the chamber.
RESUMEN
A systematic study was carried out to investigate the effect of ionic liquid in solid polymer electrolyte (SPE) and its layer morphology on the characteristics of an electrochemical amperometric nitrogen dioxide sensor. Five different ionic liquids were immobilized into a solid polymer electrolyte and key sensor parameters (sensitivity, response/recovery times, hysteresis and limit of detection) were characterized. The study revealed that the sensor based on 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][N(Tf)2]) showed the best sensitivity, fast response/recovery times, and low sensor response hysteresis. The working electrode, deposited from water-based carbon nanotube ink, was prepared by aerosol-jet printing technology. It was observed that the thermal treatment and crystallinity of poly(vinylidene fluoride) (PVDF) in the solid polymer electrolyte influenced the sensitivity. Picture analysis of the morphology of the SPE layer based on [EMIM][N(Tf)2] ionic liquid treated under different conditions suggests that the sensor sensitivity strongly depends on the fractal dimension of PVDF spherical objects in SPE. Their deformation, e.g., due to crowding, leads to a decrease in sensor sensitivity.
