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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.
Dissertation D. Dongol
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.
Electrochemical impedance spectroscopy (EIS) is a widely-used diagnostic technique to characterize electrochemical processes. It is based on the dynamic analysis of two electrical observables, that is, current and voltage. Electrochemical cells with gaseous reactants or products (e.g., fuel cells, metal/air cells, electrolyzers) offer an additional observable, that is, the gas pressure. The dynamic coupling of current and/or voltage with gas pressure gives rise to a number of additional impedance definitions, for which we use the term electrochemical pressure impedance. It also gives rise to different experimental probing approaches. In this article we present a model-based study of electrochemical pressure impedance spectroscopy (EPIS). Possible quantifications and realizations of EPIS are discussed. The study of generic cell geometries consisting of gas reservoir, diffusion layer(s) and electrochemically active layer(s) reveals distinct spiral-shaped features in the Nyquist plot. Using the example of a sodium/oxygen (Na/O2) cell, the dynamic spatiotemporal behavior of the state variables is quantified and interpreted. Results are compared to first experimental EPIS measurements by Hartmann et al. [J. Phys. Chem. C118, 1461, 2014]. A sensitivity analysis highlights the properties of EPIS with respect to geometric, transport, and kinetic parameters. We demonstrate that EPIS is sensitive to transport parameters that are not well-accessible with standard EIS.
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.
A wide range catalyst screening with noble metal and oxide catalysts for a metal–air battery with an aqueous alkaline electrolyte was carried out. Suitable catalysts reduce overpotentials during the charge and discharge process, and therefore improve the round-trip efficiency of the battery. In this case, the electrodes will be used as optimized cathodes for a future lithium–air battery with an aqueous alkaline electrolyte. Oxide catalysts were synthesized via atmospheric plasma spraying. The screening showed that IrO2, RuO2, La0.6Ca0.4Co3, Mn3O4, and Co3O4 are promising bi-functional catalysts. Considering the high price for the noble metal catalysts further investigations of the oxide catalysts were carried out to analyze their electrochemical behavior at varied temperatures, molarities, and in case of La1−x Ca x CoO3 a varying calcium content. Additionally all catalysts were tested in a longterm test to proof cyclability at varied molarities. Further investigations showed that Co3O4 seems to be the most promising bi-functional catalyst of the tested oxide catalysts. Furthermore, it was shown that a calcium content of x = 0.4 in LCCO has the best performance.