Modelling of miniature PEM fuel cells Modelling of miniature proton exchange membrane fuel cells for portable applications J.O. Schumacher1, E. Fontes3, D. Gerteisen1, F. Goldsmith1, R. Klöfkorn2, A. Hakenjos1, K. Kühn1, M. Ohlberger2, A.Schmitz1, K. Tüber1, C. Ziegler1 1. Fraunhofer Institute for Solar Energy Systems, Heidenhofstr. 2, 79110 Freiburg, schum@ise.fhg.de, Germany 2. Institute of Applied Mathematics, University of Freiburg, Herrmann-Herder-Str. 10, 79104 Freiburg, Germany 3. COMSOL AB, Tegnergatan 23, SE-111 40 Stockholm, Sweden Modelling of miniature PEM fuel cells Overview Examples of portable fuel cell systems Model based analysis of impedance spectra Modelling of self-breathing fuel cells Characterisation of an along-the-channel fuel cell Dynamic simulation of two-phase flow Conclusion and outlook Modelling of miniature PEM fuel cells Fuel cell system for a 50 Wmax laptop Modelling of miniature PEM fuel cells Fuel cell system for a professional broadcast camera • Completely integrated system with 4 fuel cell stacks • 40 W average system power • 2 Metal Hydride Storages (100 Nl H2 or 150 Whel) •Integrated DC/DC- Converter • Miniature fans for air supply Modelling of miniature PEM fuel cells Mobile power box • Portable power supply • Power: max. 100 W average 50 W • Metal Hydride Storage • Control based on micro processor • 12 V voltage supply with DC/DC- Converter Modelling of miniature PEM fuel cells Electrode agglomerate model Electrode is assumed to be made of porous spherical catalyst grains Oxygen is dissolved at the outer surface of the agglomerate Diffusion of dissolved oxygen in the grain and the film in radial direction Local current density is given by the Tafel-equation Graph: Jaouen et al., 2002 Modelling of miniature PEM fuel cells Cathode agglomerate model Mass balance Charge balance Oxygen flux in agglomerate Modelling of miniature PEM fuel cells Cathode agglomerate model Charge balance Ohm`s law Modelling of miniature PEM fuel cells Comparision of measured and simulated polarisation curves Small current density: change Influence of surface-to-volume of Tafel-slope ratio L of agglomerates cell potential / [V] cell potential / [V] L = 6 105 m-1 current density / [A/m2] L = 9 104 m-1 current density / [A/m2] Modelling of miniature PEM fuel cells Simulation of impedance spectra Perturbation of solution variables of PDEs Small perturbations: linearise and Laplace-transform PDEs Calculate impedance: Resistance [Wm2] Resistance [Wm2] Modelling of miniature PEM fuel cells Comparision of measured and simulated impedance spectra • Minimum value of the radius of the impedance arc is reached at a current density of 260mA/cm2. current density [A/m2] meas • Mass transport limitation is observed for higher current density: increase of radius of impedance arc. sim Modelling of miniature PEM fuel cells Influence of double layer capacitance on impedance spectra Double layer capacitance Small double layer capacitance: CDL = 3 107 F m-3 Two seperate semicircles appear GDL current density [A/m2] current density [A/m2] Influence of electrode Modelling of miniature PEM fuel cells Planar and self-breathing fuel cells based on printed circuit board technology Benefits of technology: • Small cell thickness • High mechanical strength • Low cost components • Well known printed circuit board production technology • Integration of electronic circuits Modelling of miniature PEM fuel cells Modelling domain and assumptions • Two dimensional model • Plug flow conditions in anodic gas channel • Convective flux of species through membrane and on cathode side neglected • No phase transition accounted for Modelling of miniature PEM fuel cells Discretisation mesh and governing equations • Multicomponent diffusion of gas species: Stefan-Maxwell equation • Electronic and protonic potential: Poisson equation • Transport of water across membrane: modified Stefan-Maxwell equation • Temperature distribution: heat equation l Modelling of miniature PEM fuel cells Hydrogen and oxygen distribution H2 molar fraction O2 molar fraction anode Arrows: total flux of hydrogen and oxygen. Vcell = 0.4 V cathode Modelling of miniature PEM fuel cells Water distribution and flux H2O molar fraction x 10-3 H2O molar fraction anode Arrows: total flux of water. Vcell = 0.4 V cathode Modelling of miniature PEM fuel cells Heat flux and temperature T [K] anode • Arrows: total flux of heat. • Cooling effect of ribs. Vcell = 0.4 V cathode Modelling of miniature PEM fuel cells Electronic and protonic potential, current direction Electronic potential fe [V] Arrows indicate the technical current direction. Protonic potential fp [V] Modelling of miniature PEM fuel cells Comparison of Experiment and Simulation Experiment Simulation • Opening ratio = cathode opening width / current collector rib width. • Limiting current is determined by oxygen supply through cathode opening. Modelling of miniature PEM fuel cells Current distribution in cathode gas diffusion layer cathode electrode cut line (e) GDL (e) membrane Normalised x-coordinate (e) Normalised y-coordinate Modelling of miniature PEM fuel cells PEM fuel cell model based on FLUENT CFD-software Submodels: • The electrochemical submodel predicts the local current-tovoltage relation in the MEA. • The electrical submodel accounts for electron flow and ohmic heat generation. • The MEA submodel describes transport of water and ions through a Nafion membrane. Modelling of miniature PEM fuel cells ‚Along - the - Channel‘ • Flow-field geometry: Parallel channels • Determination of spatially resolved current density • Measured values: temperature, gas flow-rates, relative humidity current per segment [A] Segmented fuel cell 0,16 row 1 row 2 row 3 0,14 0,12 0,10 0,08 0,06 0,04 0,02 0 1 2 3 4 5 6 7 8 9 position 10 11 12 13 14 15 16 Modelling of miniature PEM fuel cells • Comparison of measurement (dots) and simulation (lines) • Variation of air flow rate on the cathode side • All model parameters are kept constant except air flow and average current Current Density [A/cm²] Current distribution along the channel 0.24 0.22 0.20 0.18 0.16 0.14 0.12 0.10 0.08 0.06 600sccm 300sccm 50sccm 1 2 3 4 5 6 7 8 9 101112131415 Segment Position gas flow direction: 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 600sccm 300sccm 50sccm Temperature of air in the channel 1 2 3 4 5 6 7 8 9 101112131415 Segment Position 600sccm 300sccm 50sccm 1 2 3 4 5 6 7 8 9 101112131415 Segment Position Membrane protonic resistivity 335 330 325 320 315 310 305 300 295 290 Protonic Resistivity [Wm] Relative humidity of air at MEA Relative Humidity Relative humidity of air in the channel Relative Humidity Analysis Temperature [K] Modelling of miniature PEM fuel cells 600sccm 300sccm 50sccm 1 2 3 4 5 6 7 8 9 101112131415 Segment Position 600sccm 300sccm 50sccm 1 0.1 1 2 3 4 5 6 7 8 9 101112131415 Segment Position Modelling of miniature PEM fuel cells Profiles of flow velocity and temperature including inlet region velocity profile temperature profile Modelling of miniature PEM fuel cells Dynamic simulation of two phase flow Modelling concept by Mario Ohlberger (Institute for Applied Mathematics, Freiburg). Solution of the PDEs for: Two phase flow in porous media Species transport in the gas phase Energy balance in the porous media Potential flow of electrons and protons Adaptive grid generation in space / time Colours: pressure distribution for counter-flow case. Problem: Determination of material parameters Modelling of miniature PEM fuel cells Two-phase flow in porous gas diffusion layer and electrodes phase-transition Mass balance Darcy-law Water and gas saturation Capillary pressure Modelling of miniature PEM fuel cells Model geometry and discretization mesh Modelling of miniature PEM fuel cells Simulation examples H2 Mass fraction of gas components and saturation of liquid water Colors: Red: 1, Blue: 0 O2 Wasserdampf flüssiges Wasser Modelling of miniature PEM fuel cells Conclusion Agglomerate model • The agglomerate model reproduces both, measured polarisation curves and impedance spectra. • Change of active agglomerate surface-to-volume ratio depending on the operation point? Planar fuel cells • Our two-dimensional one-phase model includes all relevant processes of planar fuel cells: gas transport, heat transport, electrochemical reaction. • The model serves as a design tool for selfbreathing planar fuel cells. Modelling of miniature PEM fuel cells Conclusion Current distribution • We validated the CDF model with locally distributed current measurements. • The CFD model agrees to measurement results if the cell is operated in the one-phase regime. Two-phase flow • We are working on a dynamic two-phase flow model taking into account liquid water transport in porous media. • The model is extended to 3D. Parallel computing and adaptive grid generation is utilised.