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Multi-phase management is crucial for performance and durability of electrochemical cells such as batteries and fuel cells. In this paper we present a generic framework for describing the two-dimensional spatiotemporal evolution of gaseous, liquid and solid phases, as well as their interdependence with interfacial (electro-)chemistry and microstructure in a continuum description. The modeling domain consists of up to seven layers (current collectors, channels, electrodes, separator/membrane), each of which can consist of an arbitrary number of bulk phases (gas, liquid, solid) and connecting interfaces (two-phase or multi-phase boundaries). Bulk and interfacial chemistry is described using global or elementary kinetic reactions. Multi-phase management is coupled to chemistry and to mass and charge transport within bulk phases. The functionality and flexibility of this framework is demonstrated using four application areas in the context of post-lithium-ion batteries and fuel cells, that is, lithium-sulfur (Li-S) cells, lithium-oxygen (Li-O) cells, solid oxide fuel cells (SOFC) and polymer electrolyte membrane fuel cells (PEFC). The results are compared to models available in literature and properties of the generic framework are discussed.
The lifetime and performance of solid-oxide fuel cells (SOFC) and electrolyzer cells (SOEC) can be significantly degraded by oxidation of nickel within the electrode and support structures. This paper documents a detailed computational model describing nickel oxide (NiO) formation as a growing film layer on top of the nickel phase in Ni/YSZ composite electrodes. The model assumes that the oxidation rate is controlled by transport of ions across the film (Wagner's theory). The computational model, which is implemented in a two-dimensional continuum framework, facilitates the investigation of alternative chemical reaction and transport mechanisms. Model predictions agree well with a literature experimental measurement of oxidation-layer growth. In addition to providing insight in interpreting experimental observations, the model provides a quantitative predictive capability for improving electrode design and controlling operating conditions.
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.
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.
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.
Lithium–sulfur (Li/S) cells are promising candidates for a next generation of safe and cost-effective high energy density batteries for mobile and stationary applications. At present, most Li/S cells still suffer from relatively poor cyclability, capacity loss under moderate current densities and self-discharge. Furthermore, the underlying chemical mechanisms of the general discharge/charge behavior as well as Li/S-specific phenomena like the polysulfide shuttle are not yet fully understood. Here we present a thermodynamically consistent, fully reversible continuum model of a Li/S cell with simplified four-step electrochemistry, including a simple description of the polysulfide shuttle effect. The model is parameterized using experimental discharge curves obtained from literature and reproduces behavior at various current densities with fairly high accuracy. While being instructively simple, the presented model can still reproduce distinct macroscopic Li/S-cell features caused by the shuttle effect, e.g., seemingly infinite charging at low charge current densities, and suboptimal coulombic efficiency. The irreversible transport of active material from the cathode to the anode results in a voltage drop and capacity loss during cycling, which can also be observed experimentally.
Aqueous lithium–oxygen batteries are promising candidates for electric energy storage. In this paper we present and discuss a multiphase continuum model of an aqueous lithium–oxygen single cell including reactions and transport in a porous gas diffusion electrode (GDE). The model is parameterized using in-house half-cell experiments and available literature data on aqueous electrolytes. We validate our transport model with cyclic voltammetry and electrochemical impedance spectroscopy measurements over a wide range of temperatures (25, 40, 55 °C) and electrolyte concentrations (0.1–2 M). We observe very good agreement between simulations and measurements during oxygen reduction conditions. A sensitivity analysis of the validated model demonstrates the influence of the porous structure on GDE performance and gives directions for the future development of electrodes.
Lithium-oxygen cells with organic electrolyte suffer high overpotentials during charge, indicating asymmetric charge/discharge reaction mechanisms. We present a multi-physics dynamic modeling and simulation study of the Li/O2 cell cycling behavior. We present three different multi-step mechanisms of the 2 Li + O2 ⇄ Li2O2 cell reaction, (A) a reversible 5-step mechanism, (B) a partially irreversible 6-step mechanism, and (C) a partially irreversible 8-step mechanism that includes reactions of a redox mediator. Model predictions are compared to experimental galvanostatic cycling data of Swagelok cells without and with 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) as redox mediator. All mechanisms are able to predict the discharge behavior in good agreement to the experimental results. The experimentally observed high charge overpotentials as well as their reduction by using a redox mediator can be qualitatively reproduced with the irreversible reaction mechanisms. However, the particular shape of the experimental charge curve with continuously increasing charge overpotential cannot be reproduced with the present mechanisms.