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The formation of secondary phases in the porous electrodes is a severe mechanism affecting the lifetime of solid oxide fuel cells (SOFC). It can occur via various chemical mechanisms and it has a significant influence on cell performance due to pore clogging and deactivation of active surfaces and triple-phase boundary (TPB). We present a modeling and simulation study of nickel oxide formation (reoxidation) and carbon formation (coking) within the SOFC anode. We use a 2D continuum model based on a multi-phase framework [Neidhardt et al., J. Electrochem. Soc., 159, 9 (2012)] that allows the introduction of arbitrary solid phases (here: Ni, YSZ, NiO, Carbon) plus gas phase. Reactions between the bulk phases are modeled via interface-adsorbed species and are described by an elementary kinetic approach. Published experimental data are used for parameterization and validation. Simulations allow the prediction of cell performance under critical operation conditions, like (i) a non-fuel operation test, where NiO formation is taking place (Figure 1a), or (ii) an open circuit voltage (OCV) stability test under hydrocarbon atmosphere, where solid carbon is formed (Figure 1b). Results are applied for enhanced interpretation of experimental data and for prediction of safe operation conditions.
Compact solid discharge products enable energy storage devices with high gravimetric and volumetric energy densities, but solid deposits on active surfaces can disturb charge transport and induce mechanical stress. In this Letter, we develop a nanoscale continuum model for the growth of Li2O2 crystals in lithium–oxygen batteries with organic electrolytes, based on a theory of electrochemical nonequilibrium thermodynamics originally applied to Li-ion batteries. As in the case of lithium insertion in phase-separating LiFePO4 nanoparticles, the theory predicts a transition from complex to uniform morphologies of Li2O2 with increasing current. Discrete particle growth at low discharge rates becomes suppressed at high rates, resulting in a film of electronically insulating Li2O2 that limits cell performance. We predict that the transition between these surface growth modes occurs at current densities close to the exchange current density of the cathode reaction, consistent with experimental observations.
In the dual membrane fuel cell (DM-Cell), protons formed at the anode and oxygen ions formed at the cathode migrate through their respective dense electrolytes to react and form water in a porous composite layer called dual membrane (DM). The DM-Cell concept was experimentally proven (as detailed in Part I of this paper). To describe the electrochemical processes occurring in this novel fuel cell, a mathematical model has been developed which focuses on the DM as the characteristic feature of the DM-Cell. In the model, the porous composite DM is treated as a continuum medium characterized by effective macro-homogeneous properties. To simulate the polarization behavior of the DM-Cell, the potential distribution in the DM is related to the flux of protons and oxygen ions in the conducting phases by introducing kinetic and transport equations into charge balances. Since water pressure may affect the overall formation rate, water mass balances across the DM and transport equations are also considered. The satisfactory comparison with available experimental results suggests that the model provides sound indications on the effects of key design parameters and operating conditions on cell behavior and performance.
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.
In this paper we present a model of the discharge of a lithium–oxygen battery with aqueous electrolyte. Lithium–oxygen batteries (Li–O2) have recently received great attention due to their large theoretical specific energy. Advantages of the aqueous design include the stability of the electrolyte, the long experience with gas diffusion electrodes (GDEs), and the solubility of the reaction product lithium hydroxide. However, competitive specific energies can only be obtained if the product is allowed to precipitate. Here we present a dynamic one-dimensional model of a Li–O2 battery including a GDE and precipitation of lithium hydroxide. The model is parameterized using experimental data from the literature. We demonstrate that GDEs remove power limitations due to slow oxygen transport in solutions and that lithium hydroxide tends to precipitate on the anode side. We discuss the system architecture to engineer where nucleation and growth predominantly occurs and to optimize for discharge capacity.
Proton Exchange Membrane Fuel Cells (PEMFC) are energy efficient and environmentally friendly alternatives to conventional energy conversion systems in many yet emerging applications. In order to enable prediction of their performance and durability, it is crucial to gain a deeper understanding of the relevant operation phenomena, e.g., electrochemistry, transport phenomena, thermodynamics as well as the mechanisms leading to the degradation of cell components. Achieving the goal of providing predictive tools to model PEMFC performance, durability and degradation is a challenging task requiring the development of detailed and realistic models reaching from the atomic/molecular scale over the meso scale of structures and materials up to components, stack and system level. In addition an appropriate way of coupling the different scales is required.
This review provides a comprehensive overview of the state of the art in modeling of PEMFC, covering all relevant scales from atomistic up to system level as well as the coupling between these scales. Furthermore, it focuses on the modeling of PEMFC degradation mechanisms and on the coupling between performance and degradation models.
Lithium–oxygen cells with nonaqueous electrolyte show high overpotentials during charge, indicating asymmetric charge/discharge reaction mechanisms. We present a kinetic modeling and simulation study of the lithium–oxygen cell cycling behavior. The model includes a multistep reaction mechanism of the cell reaction (2Li + O2 ⇄ Li2O2) forming lithium peroxide by precipitation, coupled to a 1D porous-electrode transport model. We apply the model to study the asymmetric discharge/charge characteristics and analyze the influence of a redox mediator dissolved homogeneously in the liquid electrolyte. Model predictions are compared to experimental galvanostatic cycling data of cells without and with 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) as redox mediator. The predicted discharge behavior shows good agreement with the experimental results. A spatiotemporal analysis of species concentrations reveals inhomogeneous distributions of dissolved oxygen and reaction products within the cathode during discharge. The experimentally observed charge overpotentials as well as their reduction by using a redox mediator can be qualitatively reproduced with a partially irreversible reaction mechanism. However, the proposed models fail to reproduce the particular shape of the experimental charge curve with continuously increasing charge overpotential, which implies that part of the reaction mechanism is still open for investigation in future work.