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Pressure dynamics in metal-oxygen (metal-air) batteries: a case study on sodium superoxide cells
(2014)
Electrochemical reactions in metal–oxygen batteries come along with the consumption or release of gaseous oxygen. We present a novel methodology for investigating electrode reactions and transport phenomena in metal–oxygen batteries by measuring the pressure dynamics in an enclosed gas reservoir above the oxygen electrode. The methodology is exemplified by a room-temperature sodium–oxygen battery forming sodium superoxide (NaO2) in an electrolyte of diethylene glycol dimethyl ether (diglyme) and sodium trifluoromethanesulfonate (NaOSO2CF3, NaOTf). The experiments are supported by microkinetic simulations with a one-dimensional multiphysics continuum model. During galvanostatic cycling over 30 cycles, a constant oxygen consumption/release rate is observed upon discharge/charge. The number of transferred electrons per oxygen molecule is calculated to 1.01 ± 0.02 and 1.03 ± 0.02 for discharge and charge, respectively, confirming the nature of the oxygen reaction product as superoxide O2–. The same ratio is observed in cyclic voltammetry experiments with low scan rate (<1 mV/s). However, at higher scan rates, the ratio increases as a result of oxygen transport limitations in the electrolyte. We introduce electrochemical pressure impedance spectroscopy (EPIS) for simultaneously analyzing current, voltage, and pressure of electrochemical cells. Pressure recording significantly increases the sensitivity of impedance toward oxygen transport properties of the porous electrode systems. In addition, we report experimental data on the diffusion coefficient and solubility of oxygen in electrolyte solutions as important parameters for the microkinetic models.
Mit längerfristigen Nutzerbefragungen in zwei unmittelbar benachbarten Bürogebäuden in Freiburg wurden das Temperaturempfinden der Nutzer und deren Zufriedenheit mit dem thermischen Raumkomfort zweimal täglich erfasst. Ein Bürogebäude wird im Sommer mit einem maschinellen Nachtlüftungskonzept konditioniert und das zweite verfügt über eine Betonkerntemperierung und eine Zu- und Abluftanlage. Auf Basis der vorhandenen Daten aus der Erhebung wurde mit Hilfe von Regressionsanalysen ein Modell zur Vorhersage der Komforttemperatur berechnet und mit den Modellen in DIN EN 15251 verglichen.