Analysis of a model for the operation of a vanadium redox battery

Although the vanadium redox battery (VRB) has recently attracted considerable interest as an energy storage technology, it has a relatively poor energy-to-volume ratio and a system complexity compared with other technologies; however, modelling can assist in optimizing cell and stack design. This paper analyzes a 2D time-dependent single-phase isothermal model for the operation of a single cell in a VRB. Unlike in all previous work, asymptotic methods are used to determine the characteristic current density scale in terms of operating conditions and cell component properties. Also, the analysis reveals that the fluid mechanics decouples from the electrochemistry, at leading order; an asymptotically reduced model is then proposed which preserves the original geometrical resolution. This approach is recommended for accurate and computationally efficient VRB stack models, as has been achieved for polymer electrolyte fuel cells; this will be a prerequisite for the use of modelling in stack design and thence large-scale commercialization of the VRB. Finite-element methods are used to compute results for the 1D steady state high-stoichiometry limit; although an idealized case, it is recommended for the in-situ experimental acquisition of VRB electrokinetic data that can then be used for the model when applied under more general operating conditions.

[1]  Michael Vynnycky,et al.  Validated Reduction and Accelerated Numerical Computation of a Model for the Proton Exchange Membrane Fuel Cell , 2009 .

[2]  Frank C. Walsh,et al.  Dynamic modelling of hydrogen evolution effects in the all-vanadium redox flow battery , 2010 .

[3]  Takashi Hikihara,et al.  A Coupled Dynamical Model of Redox Flow Battery Based on Chemical Reaction, Fluid Flow, and Electrical Circuit , 2008, IEICE Trans. Fundam. Electron. Commun. Comput. Sci..

[4]  Michael Vynnycky,et al.  Asymptotically Reduced Model for a Proton Exchange Membrane Fuel Cell Stack: Automated Model Generation and Verification , 2010 .

[5]  Frank C. Walsh,et al.  Non-isothermal modelling of the all-vanadium redox flow battery , 2009 .

[6]  C. Siegel.  Review of computational heat and mass transfer modeling in polymer-electrolyte-membrane (PEM) fuel cells , 2008 .

[7]  Huamin Zhang,et al.  Investigation on Concentrated V(IV)/V(V) Redox Reaction by Rotating Disc Voltammetry , 2007 .

[8]  Michael Vynnycky,et al.  Analysis of a Two-Phase Non-Isothermal Model for a PEFC , 2005 .

[9]  Bengt Sundén,et al.  Transport phenomena in fuel cells , 2005, Hydrogen, Batteries and Fuel Cells.

[10]  Ned Djilali,et al.  Computational modelling of polymer electrolyte membrane (PEM) fuel cells: Challenges and opportunities , 2007 .

[11]  W. Moore,et al.  Basic Physical Chemistry , 1983 .

[12]  Liquan Chen,et al.  Research progress of vanadium redox flow battery for energy storage in China , 2008 .

[13]  J. Deconinck,et al.  Study of ion transport models for electroanalytical simulation. Part 2: experimental comparison. , 2009, The journal of physical chemistry. A.

[14]  Maria Skyllas-Kazacos,et al.  A study of the V(II)/V(III) redox couple for redox flow cell applications , 1985 .

[15]  Frank C. Walsh,et al.  Modelling the effects of oxygen evolution in the all-vanadium redox flow battery , 2010 .

[16]  Yasushi Katayama,et al.  Investigations on V(IV)/V(V) and V(II)/V(III) redox reactions by various electrochemical methods , 2005 .

[17]  Anthony G. Fane,et al.  New All‐Vanadium Redox Flow Cell , 1986 .

[18]  Maria Skyllas-Kazacos,et al.  Investigation of the V(V)/V(IV) system for use in the positive half-cell of a redox battery , 1985 .

[19]  M. Verbrugge,et al.  Mathematical model of a gas diffusion electrode bonded to a polymer electrolyte , 1991 .

[20]  D. Lide.  Handbook of Chemistry and Physics , 1992 .

[21]  Jiujun Zhang,et al.  A review of water flooding issues in the proton exchange membrane fuel cell , 2008 .

[22]  Michael Vynnycky,et al.  Supporting electrolyte asymptotics and the electrochemical pickling of steel , 2009, Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences.

[23]  M. Gattrell,et al.  Study of the Mechanism of the Vanadium 4+/5+ Redox Reaction in Acidic Solutions , 2004 .

[24]  Maria Skyllas-Kazacos,et al.  Electrochemical behaviour of vanadium(V)/vanadium(IV) redox couple at graphite electrodes , 1992 .

[25]  Abel Hernandez-Guerrero,et al.  Current density and polarization curves for radial flow field patterns applied to PEMFCs (Proton Exchange Membrane Fuel Cells) , 2010 .

[26]  M. Pourbaix.  Atlas of Electrochemical Equilibria in Aqueous Solutions , 1974 .

[27]  Tomoo Yamamura,et al.  Electron-Transfer Kinetics of Np3 + ∕ Np4 + , NpO2 + ∕ NpO2 2 + , V2 + ∕ V3 + , and VO2 + ∕ VO2 + at Carbon Electrodes , 2005 .

[28]  G. Weyns,et al.  Ion transport models for electroanalytical simulation. 1. Theoretical comparison. , 2009, The journal of physical chemistry. B.

[29]  Yasushi Katayama,et al.  Investigation on V(IV)/V(V) species in a vanadium redox flow battery , 2004 .

[30]  J. Qian,et al.  The electrochemical reduction of VO2+ in acidic solution at high overpotentials , 2005 .

[31]  Frank C. Walsh,et al.  A dynamic performance model for redox-flow batteries involving soluble species , 2008 .

[32]  Michael Vynnycky,et al.  Asymptotic Reduction for Numerical Modeling of Polymer Electrolyte Fuel Cells , 2009, SIAM J. Appl. Math..

[33]  Michael Vynnycky,et al.  On the application of concentrated solution theory to the forced convective flow of excess supporting electrolyte , 2010 .

[34]  David Sinton,et al.  High-performance microfluidic vanadium redox fuel cell , 2007 .

[35]  Dongjiang You,et al.  A simple model for the vanadium redox battery , 2009 .