Abstract
Transport of reactants and products in liquid-fed electrochemical cells is critical in terms of reactant utilization, concentration polarizations, and coulombic efficiencies. Design of electrochemical flow cells can benefit from adequately detailed models that capture the locally variable impact of reactant depletion and product build-up on electrochemical reactions throughout the cell. This chapter illustrates the importance of transport modeling by presenting a finite-volume, two-dimensional (2-D) model of a liquid-phase electrochemical cell with simple cell geometry, but complex multistep chemistry at each electrode incorporating parasitic reactions and/or mixed potentials. The modeled cell involves two half-cell reactions, borohydride (\(\mathrm{BH_{4}^{-}}\)) oxidation and hydrogen peroxide (H2O2) reduction, in planar flow channels with electrodes separated by flowing liquid-phase electrolytes and an ion-exchange membrane . This generic cell topology is representative of many fuel cells and flow batteries. The finite-volume model solves for conservation of mass, momentum, species, and charge in both the cathode and anode flow channels for ideal, dilute, and concentrated electrolytes. The model couples the flows to complex boundary conditions at the electrochemically active electrode surfaces and the selective ion-exchange membrane. Model results show that the balance of advection, diffusion, and migration in the liquid electrolytes results in complex profiles that predict boundary layer build-up and significant advection perpendicular to the flow path. The direct borohydride-hydrogen peroxide fuel cell transport model, used to illustrate these concepts, shows how liquid-phase transport limits conversion and dictates cell voltages within the context of the competing reactions at the two electrodes. The chapter ends by demonstrating how such a model can be implemented in design studies to explore strategies for improving practical cell performance.
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Abbreviations
- CFD:
-
computational fluid dynamics
- DBFC:
-
direct borohydride fuel cell
- DMFC:
-
direct methanol fuel cell
- FE:
-
finite element
- FV:
-
finite volume
- PEMFC:
-
proton-exchange membrane fuel cell
References
I.B. Sprague, P. Dutta: Modeling of diffuse charge effects in a microfluidic based laminar flow fuel cell, Numer. Heat Transf. Part A 59(1), 1–27 (2011)
J. Ge, H. Liu: A three-dimensional mathematical model for liquid-fed direct methanol fuel cells, J. Power Sources 160(1), 413–421 (2006)
Z.H. Wang, C.Y. Wang: Mathematical modeling of liquid-feed direct methanol fuel cells, J. Electrochem. Soc. 150(4), A508–A519 (2003)
J.Q. Zou, Y. He, Z. Miao, X. Li: Non-isothermal modeling of direct methanol fuel cell, Int. J. Hydrogen Energy 35(13), 7206–7216 (2010)
V.A. Danilov, J. Lim, I.L. Moon, H. Chang: Three-dimensional, two-phase, CFD model for the design of a direct methanol fuel cell, J. Power Sources 162(2), 992–1002 (2006)
R.O. Stroman, G.S. Jackson: Modeling the performance of an ideal NaBH4-H2O2 direct borohydride fuel cell, J. Power Sources 247, 756–769 (2014)
R.O. Stroman, G.S. Jacksonc, Y. Garsanyd, K. Swider-Lyonsa: A calibrated hydrogen-peroxide direct-borohydride fuel cell model, J. Power Sources 271, 421–430 (2014)
J. Christensen, D. Cook, P. Albertus: An efficient parallelizable 3D thermoelectrochemical model of a Li-ion cell, J. Electrochem. Soc. 160(11), A2258–A2267 (2013)
G. Qiu, A.S. Joshi, C.R. Dennison, K.W. Knehr, E.C. Kumbur, Y. Sun: 3-D pore-scale resolved model for coupled species/charge/fluid transport in a vanadium redox flow battery, Electrochim. Acta 64, 46–64 (2012)
J.S. Newman, K.E. Thomas-Alyea: Electrochemical Systems, 3rd edn. (Wiley, Hoboken 2004) p. 647
I. Sprague, P. Dutta: Role of the diffuse layer in acidic and alkaline fuel cells, Electrochim. Acta 56(12), 4518–4525 (2011)
J. Liu, C.W. Monroe: Solute-volume effects in electrolyte transport, Electrochim. Acta 135, 447–460 (2014)
R.B. Bird, W.E. Stewart, E.N. Lightfoot: Transport Phenomena, 2nd edn. (Wiley, New York 2002)
G. Ottonello: Principles of Geochemistry (Columbia Univ. Press, New York 1997)
K.S. Pitzer, G. Mayorga: Thermodynamics of electrolytes II. Activity and osmotic coefficients for strong electrolytes with one or both ions univalent, J. Phys. Chem. 77(19), 2300–2308 (1973)
S. Whitaker: Diffusion and dispersion in porous media, Am. Inst. Chem. Eng. J. 13(3), 420–427 (1967)
H. Wu, P. Berg, X. Li: Non-isothermal transient modeling of water transport in PEM fuel cells, J. Power Sources 165, 232–243 (2007)
D.H. Schwarz, N. Djilali: 3D modeling of catalyst layers in PEM fuel cells: Effects of transport limitations, J. Electrochem. Soc. 154(11), B1167–B1178 (2007)
E.S. Oran, J.P. Boris: Numerical Simulation of Reactive Flow, 2nd edn. (Cambridge Univ. Press, Cambridge 2001)
J. Ma, N.A. Choudhury, Y. Sahai: A comprehensive review of direct borohydride fuel cells, Renew. Sustain. Energy Rev. 14(1), 183–199 (2010)
U.B. Demirci: Direct borohydride fuel cell: Main issues met by the membrane-electrodes-assembly and potential solutions, J. Power Sources 172(2), 676–687 (2007)
R. Retnamma, A.Q. Novais, C.M. Rangel: Kinetics of hydrolysis of sodium borohydride for hydrogen production in fuel cell applications: A review, Int. J. Hydrogen Energy 36(16), 9772–9790 (2011)
D.M.F. Santos, C.A.C. Sequeira: Sodium borohydride as a fuel for the future, Renew. Sustain. Energy Rev. 15(8), 3980–4001 (2011)
B.H. Liu, Z.P. Li: Current status and progress of direct borohydride fuel cell technology development, J. Power Sources 187(2), 291–297 (2009)
C.P. de Leon, F.C. Walsh, D. Pletcher, D.J. Browning, J.B. Lakeman: Direct borohydride fuel cells, J. Power Sources 155(2), 172–181 (2006)
I. Merino-Jimenez, C. Ponce de León, A.A. Shah, F.C. Walsh: Developments in direct borohydride fuel cells and remaining challenges, J. Power Sources 219, 339–357 (2012)
G.H. Miley, N. Luo, J. Mather, R. Burton, G. Hawkins, L. Gu, E. Byrd, R. Gimlin, P.J. Shrestha, G. Benavides, J. Laystrom, D. Carroll: Direct NaBH4/H2O2 fuel cells, J. Power Sources 165(2), 509–516 (2007)
R.C. Urian, C.J. Patrissi, S.P. Tucker, C.M. Deschenes, F.W. Bielwaski, D.W. Atwater: Direct borohydride/hydrogen peroxide fuel cell development, 43rd Power Sources Conference 2008 (Curran Associates, Red Hook 2011) pp. 295–298
R.C. Urian: Air independent fuel cells utilizing borohydride and hydrogen peroxide, Mater. Res. Soc. Symp. Proc. (2010), doi:10.1557/PROC-1213-T01-09
D.M.F. Santos, C.A.C. Sequeira: Chronopotentiometric investigation of borohydride oxidation at a gold electrode, J. Electrochem. Soc. 157(1), F16–F21 (2010)
C.R. Cloutier, A. Alfantazi, E. Gyenge: Physicochemical transport properties of aqueous sodium metaborate solutions for sodium borohydride hydrogen generation and storage and fuel cell applications, Adv. Mater. Res. 15–17, 267–274 (2006)
W.C. Schumb: Hydrogen Peroxide, Am. Chem. Soc. Monogr. (Reinhold, New York 1955)
J. Newman: Current distribution on a rotating disk below limiting current, J. Electrochem. Soc. 113(12), 1235–1241 (1966)
J.M. Nielsen, A.W. Adamson, J.W. Cobble: The self-diffusion coefficients of the ions in aqueous sodium chloride and sodium sulfate at 25-degrees, J. Am. Chem. Soc. 74(2), 446–451 (1952)
A. Poisson, J. Chanu: Semi-empirical equations for the partial molar volumes of some ions in water and seawater, Mar. Chem. 8, 289–298 (1980)
T. Okada, S. Møller-Holst, O. Gorseth, S. Kjelstrup: Transport and equilibrium properties of Nafion membranes with H+ and Na+ ions, J. Electroanal. Chem. 442(1/2), 137–145 (1998)
T. Okada, H. Satou, M. Okuno, M. Yuasa: Ion and water transport characteristics of perfluorosulfonated ionomer membranes with H+ and alkali metal cations, J. Phys. Chem. B 106(6), 1267–1273 (2002)
C.E. Evans, R.D. Noble, S. Nazeri-Thompson, B. Nazeri, C.A. Koval: Role of conditioning on water uptake and hydraulic permeability of Nafion membranes, J. Membr. Sci. 279(1/2), 521–528 (2006)
D.M.F. Santos, C.A.C. Sequeira: Effect of membrane separators on the performance of direct borohydride fuel cells, J. Electrochem. Soc. 159(2), B126–B132 (2012)
N. Lakshminarayanaiah: Transport Phenomena in Membranes (Academic, New York 1969)
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Stroman, R.O., Jackson, G. (2017). Transport in Liquid-Phase Electrochemical Devices. In: Breitkopf, C., Swider-Lyons, K. (eds) Springer Handbook of Electrochemical Energy. Springer Handbooks. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-46657-5_8
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