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The Ruddlesden‒Popper phases pertain to numerous promising materials with the mixed ionic-electronic conductivity used in devices such as oxygen-conducting membranes, solid oxide fuel cells (SOFC), and electrolyzers, which operate in the intermediate temperature region. Their high total conductivity and oxygen mobility make these materials candidates for the mentioned applications. The structure, the oxygen mobility, and the electrochemical characteristics of the promising materials La1.7Ca0.3Ni1 – xCuxO4 + δ (x = 0–0.4) are studied. According to the high-precision XRD data, all synthesized materials are single-phased and have the tetragonal structure. The unit cell parameter c and the cell volume increase upon doping with copper. The content of overstoichiometric interstitial oxygen decreases with doping and the compositions with the high copper content become oxygen deficient. The samples are characterized by the nonuniform oxygen mobility. By and large, the trend for the decrease in the oxygen mobility with the increase in the Cu content is observed in the series of La1.7Ca0.3Ni1 – xCuxO4 + δ samples. By impedance spectroscopy studies, it is shown that the electrodes with the La1.7Ca0.3Ni1 – xCuxO4 + δ functional layers with the copper content x 0.2 have a higher electrochemical activity. The factors responsible for the efficiency of electrodes are analyzed. The results obtained in this study demonstrate that La1.7Ca0.3Ni0.6Cu0.4O4 + δ materials are the candidates for the air electrodes in electrochemical devices.
The Ruddlesden‒Popper phases pertain to numerous promising materials with the mixed ionic-electronic conductivity used in devices such as oxygen-conducting membranes, solid oxide fuel cells (SOFC), and electrolyzers, which operate in the intermediate temperature region. Their high total conductivity and oxygen mobility make these materials candidates for the mentioned applications. The structure, the oxygen mobility, and the electrochemical characteristics of the promising materials La1.7Ca0.3Ni1 – xCuxO4 + δ (x = 0–0.4) are studied. According to the high-precision XRD data, all synthesized materials are single-phased and have the tetragonal structure. The unit cell parameter c and the cell volume increase upon doping with copper. The content of overstoichiometric interstitial oxygen decreases with doping and the compositions with the high copper content become oxygen deficient. The samples are characterized by the nonuniform oxygen mobility. By and large, the trend for the decrease in the oxygen mobility with the increase in the Cu content is observed in the series of La1.7Ca0.3Ni1 – xCuxO4 + δ samples. By impedance spectroscopy studies, it is shown that the electrodes with the La1.7Ca0.3Ni1 – xCuxO4 + δ functional layers with the copper content x 0.2 have a higher electrochemical activity. The factors responsible for the efficiency of electrodes are analyzed. The results obtained in this study demonstrate that La1.7Ca0.3Ni0.6Cu0.4O4 + δ materials are the candidates for the air electrodes in electrochemical devices.
The influence of the method of organising the cathode microstructure based on Pr2CuO4 (PCO) on the electrochemical characteristics of a model electrolyte-supported solid oxide fuel cell (SOFC) has been investigated. It is shown that an increase in the thickness of the PCO cathode layer and the introduction of a pore-forming agent contribute to an increase in the power density of the SOFC test cell compared to a sample with an initial unmodified cathode structure, whose power density at 850°C was 34 mW/cm2. It was found that the optimum thickness of the cathode layer to achieve maximum electrochemical performance was in the range of 40-50 μm, while the power density achieved was 116 mW/cm2 at 850°C. At the same time, the transition from a single-phase PCO cathode to a composite of PCO-Ce0.9Gd0.1O1.95 (60/40 wt. %) provides an increase in power density up to 130 mW/cm2 at 850°C, while the dynamics of its decrease with reducing temperature is slower compared to the single-phase cathode. The analysis of the changes in the values of the total electrode polarisation resistance of the model SOFC, determined by impedance spectroscopy, as a function of the method of cathode formation, showed that during the transition from the initial sample to the samples with increased thickness of the cathode layer and the composite cathode, a twofold (in the first case) and threefold (in the second case) decrease in the level of polarisation losses is observed, which correlates with an increase in the power density. The proposed methods of modifying the initial cathode microstructure based on PCO show a positive dynamic of increasing the electrochemical activity of the cathode/electrolyte interface and the power density characteristics of the fuel cell as a whole.
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