• Energy Research

Numerous technologies, such as batteries and fuel cells, depend on electrochemical kinetics. In some cases, the responsible electrochemistry and charged-species transport is complex. However, to date, there are essentially no general-purpose modeling capabilities that facilitate the incorporation of thermodynamic, kinetic, and transport complexities into the simulation of electrochemical processes. A vast majority of the modeling literature uses only a few (often only one) global charge-transfer reactions, with the rates expressed using Butler–Volmer approximations. The objective of the present paper is to identify common aspects of electrochemistry, seeking a foundational basis for designing and implementing software with general applicability across a wide range of materials sets and applications. The development of new technologies should be accelerated and improved by enabling the incorporation of electrochemical complexity (e.g., multi-step, elementary charge-transfer reactions and as well as supporting ionic and electronic transport) into the analysis and interpretation of scientific results. The spirit of the approach is analogous to the role that Chemkin has played in homogeneous chemistry modeling, especially combustion. The Cantera software, which already has some electrochemistry capabilities, forms the foundation for future capabilities expansion.

Numerous technologies, such as batteries and fuel cells, depend on electrochemical kinetics. In some cases, the responsible electrochemistry and charged-species transport is complex. However, to date, there are essentially no general-purpose modeling capabilities that facilitate the incorporation of thermodynamic, kinetic, and transport complexities into the simulation of electrochemical processes. A vast majority of the modeling literature uses only a few (often only one) global charge-transfer reactions, with the rates expressed using Butler–Volmer approximations. The objective of the present paper is to identify common aspects of electrochemistry, seeking a foundational basis for designing and implementing software with general applicability across a wide range of materials sets and applications. The development of new technologies should be accelerated and improved by enabling the incorporation of electrochemical complexity (e.g., multi-step, elementary charge-transfer reactions and as well as supporting ionic and electronic transport) into the analysis and interpretation of scientific results. The spirit of the approach is analogous to the role that Chemkin has played in homogeneous chemistry modeling, especially combustion. The Cantera software, which already has some electrochemistry capabilities, forms the foundation for future capabilities expansion.

AbstractThis paper presents a multi‐scale model of a solid oxide fuel cell (SOFC) stack consisting of five anode‐supported cells. A two‐dimensional isothermal elementary kinetic model is used to calculate the performance of single cells. Several of these models are thermally coupled to form the stack model. Simulations can be carried out at steady‐state as well as dynamic operation. The model is validated over a wide range of operating conditions including variation of temperature, gas composition (both on anode and cathode side), and pressure. Validation is carried out using polarization curves and impedance spectra. The model is then used to explain the pressure‐induced performance increase measured at constant fuel utilization of 40%. Results show that activation and concentration overpotentials are reduced with increasing pressure.

AbstractThis paper presents a multi‐scale model of a solid oxide fuel cell (SOFC) stack consisting of five anode‐supported cells. A two‐dimensional isothermal elementary kinetic model is used to calculate the performance of single cells. Several of these models are thermally coupled to form the stack model. Simulations can be carried out at steady‐state as well as dynamic operation. The model is validated over a wide range of operating conditions including variation of temperature, gas composition (both on anode and cathode side), and pressure. Validation is carried out using polarization curves and impedance spectra. The model is then used to explain the pressure‐induced performance increase measured at constant fuel utilization of 40%. Results show that activation and concentration overpotentials are reduced with increasing pressure.

Abstract In this article the high-temperature behavior of a cylindrical lithium iron phosphate/graphite lithium-ion cell is investigated numerically and experimentally by means of differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), and external short circuit test (ESC). For the simulations a multi-physics multi-scale (1D+1D+1D) model is used. Assuming a two-step electro-/thermochemical SEI formation mechanism, the model is able to qualitatively reproduce experimental data at temperatures up to approx. 200 °C. Model assumptions and parameters could be evaluated via comparison to experimental results, where the three types of experiments (DSC, ARC, ESC) show complementary sensitivities towards model parameters. The results underline that elevated-temperature experiments can be used to identify parameters of the multi-physics model, which then can be used to understand and interpret high-temperature behavior. The resulting model is able to describe nominal charge/discharge operation behavior, long-term calendaric aging behavior, and short-term high-temperature behavior during extreme events, demonstrating the descriptive and predictive capabilities of physicochemical models.

Abstract In this article the high-temperature behavior of a cylindrical lithium iron phosphate/graphite lithium-ion cell is investigated numerically and experimentally by means of differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), and external short circuit test (ESC). For the simulations a multi-physics multi-scale (1D+1D+1D) model is used. Assuming a two-step electro-/thermochemical SEI formation mechanism, the model is able to qualitatively reproduce experimental data at temperatures up to approx. 200 °C. Model assumptions and parameters could be evaluated via comparison to experimental results, where the three types of experiments (DSC, ARC, ESC) show complementary sensitivities towards model parameters. The results underline that elevated-temperature experiments can be used to identify parameters of the multi-physics model, which then can be used to understand and interpret high-temperature behavior. The resulting model is able to describe nominal charge/discharge operation behavior, long-term calendaric aging behavior, and short-term high-temperature behavior during extreme events, demonstrating the descriptive and predictive capabilities of physicochemical models.

Abstract The operation of a pair of anode-to-anode-facing solid oxide fuel cells (SOFCs) via in situ catalytic partial oxidation (CPO) of n-butane was investigated. In this simple “no-chamber” setup, butane is partially oxidized by heterogeneous reactions inside the porous anodes, providing processed fuel and the heat required for SOFC operation. The cell couple yielded a power density of up to 270 mW cm−2, and the maximum total power obtained was 1.2 W with cell sizes of 13 mm × 23 mm. The maximum electrical efficiency was 1.3%. High CO concentrations of up to 1000 ppm were detected in the exhaust gas, indicating that the cell couple could not efficiently consume the complete provided fuel. A flame, lit at the exhaust, minimized the carbon monoxide level while having insignificant influence on the cell performance. Thermal insulation of the cell couple improved the output remarkably, showing the strong influence of temperature on cell performance. The two cells had a distance of only 2 mm, suggesting a potential for high volumetric power densities in multi-cell configurations for a self-sustained combined heat and power system.

Abstract The operation of a pair of anode-to-anode-facing solid oxide fuel cells (SOFCs) via in situ catalytic partial oxidation (CPO) of n-butane was investigated. In this simple “no-chamber” setup, butane is partially oxidized by heterogeneous reactions inside the porous anodes, providing processed fuel and the heat required for SOFC operation. The cell couple yielded a power density of up to 270 mW cm−2, and the maximum total power obtained was 1.2 W with cell sizes of 13 mm × 23 mm. The maximum electrical efficiency was 1.3%. High CO concentrations of up to 1000 ppm were detected in the exhaust gas, indicating that the cell couple could not efficiently consume the complete provided fuel. A flame, lit at the exhaust, minimized the carbon monoxide level while having insignificant influence on the cell performance. Thermal insulation of the cell couple improved the output remarkably, showing the strong influence of temperature on cell performance. The two cells had a distance of only 2 mm, suggesting a potential for high volumetric power densities in multi-cell configurations for a self-sustained combined heat and power system.