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Electrochemical process modelling: water electrolysis for hydrogen production

Philippe Mandin1, Hervé Roustan2, Jérome Hamburger3, Rolf Wüthrich4 & Gérard Picard1
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LECA UMR CNRS 7575, ENSCP, 11 rue Pierre et Marie Curie, 75231 Paris cedex, France Alcan – Centre de Recherche de Voreppe -725 rue Aristide Bergès - BP 27 – 38341 Voreppe Cedex, France 3 Transoft International, Fluidyn, 7 Bd de la Libération, 93200 Saint-Denis, France 4 E.P.F.L. – L.S.R. – CH-1015 Lausanne, Suisse philippe-mandin@enscp.fr, herve.roustan@alcan.com, jerome-hamburger@fluidyn.fr, rolf.wuethrich@epfl.ch, gerard-picard@enscp.fr Abstract. During water electrolysis for hydrogen there are bubbles which are created at the two electrodes which imply a great hydrodynamic acceleration but also a quite important electrical field and electrochemical processes disturbance. This disturbance can lead to the modification of the local current density and to anode effects for example. There is few works concerning the local modelling of coupled electroactive species transport and electrochemical processes in a biphasic electrolyte. There are also few local experimental measurements in term of chemical composition, temperature or current density which will allow the numerical calculations validation. Nevertheless, effects like the anode effect, particularly expensive on the point of the process efficiency, should need a better understanding. Nowadays, the respective roles of the local temperature increases, the electroactive specie composition or the transport properties modification due to bubbles are not known. The goal of the present work is the modelling and the numerical simulation of the hydrogen production process for a vertical electrode configuration. Bubbles presence is supposed to modify the electrical properties, the thermal properties and then the electroactive specie diffusive transport and the current density. Bubbles are also motion sources for the electrolysis cell flow, and then hydrodynamic properties are strongly coupled with specie transport and electrical field [1,2]. The present work shows hydrodynamic, electrical, thermal and chemical composition properties in a laboratory scale electrolysis cell with a vertical electrode. The numerical algorithm used was the finite volume used in the computational fluid dynamic software Fluent®.

Keywords: Biphasic Electrolysis Modelling Bubbles Phenomenological Laws

the electrical resistance increase due to bubble release. the shielding effect depending on the density of the bubbles.) [1-4] and other special processes such as e. In most cases.. F2. for simple gas evolving electrodes) because bubble-dispersed phase acts like an electrical shield. . water electrolysis and many other electrochemical processes. An accurate tool for coupled two-phase flow and electrochemical properties seems to be an important task to develop for industrial applications. g. Cl2.INTRODUCTION Gas release and induced fluid flow over electrodes exist in many electrochemical processes such as aluminium. In all these different electrochemical processes. The main purpose of this study is namely to have a description of: 1) the macroscopic coupling between bubble release and current density at electrode surface. chemical engraving [2]. THE VERTICAL ELECTRODE CONFIGURATION Figure 1 is a scheme of a classical electrochemical cell. in some other processes. a coupling effect is particularily strong (as shown by Hine [3] e. according with Tobias experiments [4]).. and therefore modifies the macroscopic cell performances. at the beginning for low current density values. This assumption allows the use of Lagrangian modelling (see biphasic flow modelling part) and also allows neglecting the shadowing resistance due to growing bubbles. the gas flow rate has to be controlled. . which is namely the local gas volume fraction of the dispersion. Y Anode Bubbles group 2D Zoom Cathode X 3D Figure 1: From the macroscopic vertical electrode to the insulated bubble The purpose of the present work is to compute a numerical solution of the coupled electrical and hydrodynamical properties in such an electrochemical cell. with a single vertical gas-evolving electrode configuration. It is shown in this figure the relation between the biphasic macroscopic boundary layer and one locally representative bubble take in. fluorine production.g. this phenomenon has to be avoided. H2. The hydrodynamical properties and the gas-flow motion in electrochemical cells is of great practical interest in electrochemical engineering science since the dispersed phase modifies the electrical properties of the electrolyte (as well as mass and heat transfers). O2. According with small current density assumption (mean current density I/A lower than 4000 A m-2. but. this is the case namely for gas production (CO2.

The ohmic medium hypothesis implies: j = σ. immediately detached from the electrode surface.s-1) produced at the electrode because of the interfacial electrochemical reaction is: q = M.m-2. The bubble motion obeys: ∂(M. species or electricity.[∂2Vz/ ∂z2 + ∂2Vz / ∂x2] + ρ. density and motion diffusion coefficient µ are supposed the liquid electrolyte one.F).∂φ/∂z) / ∂z + ∂(σ. the electrical field vector (V.∂Vx / ∂x = . jn is the local current density normal to electrode component. it should be well-known. The horizontal force is a very difficult to access property. heat.(1-ε)1.σ. Because this acceleration value is very important for the biphasic boundary layer development along the electrode. bubbles are supposed constant diameter spheres dp (=10-4 or 10-3 m).∂P / ∂z + µ. Its magnitude expression is Fhorizontal = M.Vz)/ ∂z + ∂(ρ. though the thickness of the bubble layer is an important factor for the macroscopic cell resistance.Vz.jn/(n.m-1) respectively.Vz.G + K (E2) Horizontal motion conservation: (E3) ρ.grad φ.bforce. It is the result of the bubble-electrode and bubble-bubbles interactions. is the Faraday constant.E = .s-2). The local gas mass flow rate q (kg.Vx. n is the electron number exchanged in the electrochemical reaction and F = 96500 C.mol-1. where ε is the void fraction and σ0 is the liquid electrolyte conductivity.2) macroscopic simulations use as inputs phenomenological laws like bubble accelerations or equivalent diffusion coefficients for motion. where M is the gas molar weight.5. .VB) / ∂t = ΣFext = FArchimede + Ffriction + Fhorizontal (E4) The hydrodynamic modeling is completed with the electrical potential φ (V) field modeling under the Ohm law diffusion transport assumption: ∂(σ.Vx.∂Vz / ∂z + ρ.Vx)/ ∂x = 0 (E1) Vertical motion conservation: ρ. It has been decided in the present work to correlate these properties with local macroscopic properties in the biphasic boundary layer such as void fraction or continuous phase velocity gradient.m-1). where bforce is the equivalent horizontal acceleration (m.J = M. It is not the case. MACROSCOPIC SCALE MODELLING The mathematical model is the Lagrangian-Eulerian Naviers-Stokes one for the biphasic flow (liquid electrolyte + gas bubbles) and the electrical charge conservation under the ohmic medium assumption: Mass conservation: ∂(ρ.∂Vx / ∂z + ρ. But the electrical conductivity is supposed to obey the Bruggeman law: σ = σ0. with j the current density vector (A m-2) and E. In this work.∂φ/∂x)/∂x = 0 (E5) The equations have to be completed with phenomenological equations for density ρ (kg m-3) and motion and electricity diffusive transport µ (Pl) and σ (S. In the following results.[∂2Vx/ ∂z2 + ∂2Vx / ∂x2] These continuous medium properties are coupled with the motion conservation of bubbles through the motion source coupling term K.∂Vz / ∂x = .∂P / ∂x + µ.

These relations between an intensive local property like velocity V.15 -1 Profile on line 1 Diam. Values of bforce between 0 to 5000 (m. In the present macroscopic scale study.1 0 0 0. Line 1 ANODE dP = 10-4 accumulation CATHODE 0.2 0. The boundary layer thickness is about one millimetre and leads to hydrodynamic stress s = ∂Vz/∂x from zero to 500 s-1. of heat q.s 0.175 0. of species k.0025 abscisse curviligne / m 0.075 0. bforce = 1500.7 Void fraction (-) 0.6 0. it is now presented bubble scale studies which allow the identification of equivalent diffusion properties law and horizontal force.4 0.5 0. species k mass fraction Yk and electrical potential φ . Jk or of electrical charge j.2 0.void fraction profile along electrode The more the bubbles are confined in the vicinity of the wall (with a higher concentration).3 0.4 3000 Tobias bforce = 0. bforce = 5000.0075 0.005 0.3 y (m) Figure 2: Left.1 0.4 4000 j (A m ) -2 0. bforce = 3000.01 Figure 3: Hydrodynamic field induced by bubbles (left). the bubble forces have to be well modelled.2 0. the void fraction contours in the electrode vicinity (centre) and the biphasic boundary layer profiles for the two diameters.125 0. And hence.05 0.0. In the second part. Figure 3 shows at the left the electrically induced electrolyte flow due to the evolving bubbles. the more the resistivity is important. BUBBLE SCALE MODELLING Phenomenological laws The previously presented conservation laws completed with specific thermochemical data are not sufficient to express all the introduced unknown like the transport fluxes of motion τ. the horizontal force Fx has been supposed constant to identify its order of range.2 0.3 y (m) 0. In the presented form the model is not yet predictive because numerous phenomenological are arbitrarily fixed. Right. 2000 0 0. de bulles : Bubble diameter vitesse axiale / m.1 0.s-²) were tested and are confronted with experimental measurements obtained by Tobias with a segmented electrode (Figure 3). Current density profiles along electrode for three different tested values of bforce. temperature T.1 0.025 0 10 -3 m -4 10 m dp↑ 0 0.

These three coefficients are introduced with an isolated diffusive transport law: ∂Φ/∂t = div (DΦ grad Φ). Rayleigh or Bruggeman.5).ε)(1.9 0. s = ∂Vz/∂x the local hydrodynamic stress. Jφ is the associated flux. This kind of very simple modeling is often not satisfactory for numerous materials and further investigations have been done by authors like Maxwell. species k Dk and electrical σ.ε)(1.2 0. This equivalent formulation was investigated numerically according to a systematic experimental design and comparison between numerical results and theoretical formulations are shown in figure 4. which are difficult to determine for biphasic flows. They often appear like an opposed gradient law when the non-convective transport is supposed purely diffusive.1 0 0. the void fraction. but for more porous media (ε = 0.5 0.ε)3/2 (Bruggeman law).DΦ s/ DΦ f))/ (1+ DΦ s/ DΦ f + (1.45 Maxw ell-Wagner Rayleigh Bruggeman conductivités calculées Maxw ell général 0. fuel cells electrode materials are mathematically formalized using four scalars which are ε.05 (1. σ/σ0 1 0.65 0. The last author relates the equivalent electrical conductivity σ with the electrolyte conductivity σ0 and the void fraction α: σ = σ0 (1. Two classical models for biphasic media are the serial and parallel. the associated equivalent diffusive coefficient because of the biphasic state.75 0. the discrepancy can be about 20%. the bubble diameter. In this case. the Bruggeman law is no longer usable and we have made numerical calculations to investigate the Rayleigh theoretical expression: DΦ / DΦ f = (1+ DΦ s/ DΦ f – (1. and Vb the local bubble vertical velocity.95 1.DΦ s/ DΦ f)) . This is the case for the three diffusivity properties: thermal λ.3 0. for each of these phenomena. The calculation of the equivalent heat transfer diffusion coefficient DΦ =λ for biphasic medium has to be different because in this case none of the two phases are heat insulators (both solid and gaseous phases transfer heat). porous or multiphase media such as the present flow.8 0. The electro-induced flow is biphasic and the determination of its properties should take into account the properties of both gaseous and liquid phases. Classically.55 0. Numerical investigations were done to determine. dp.6 0.4 0. where Φ is an unknown function (T or Yk or φ) with DΦ (m2 s-1) its associated diffusive coefficient.85 0.ε) Figure 4: Biphasic equivalent electrical conductivity investigation Numerical results show that the accordance between theoretical and numerical calculations of the equivalent diffusivity are rather good when the void fraction is small.7 0.(V) are called the Onsager relations. considering the void fraction and the temperature of both.

7 1 0 0 DΦ s/ DΦ f 1000 Figure 5: Biphasic bubble scale motion transport: from the equivalent viscosity to the horizontal force To access the local biphasic equivalent viscosity and the local horizontal force applied on the bubble.5 0 0 . s is maximum at the electrode and minimum at the bubble boundary layer frontier (see figure 3 right). a bubble scale model has been developed. Systematic calculation are in progress. Periodic boundary conditions are used for the north and south square faces: the insulated bubble follows an almost identical bubble and is followed by an almost identical bubble. respectively. Dirichlet conditions are used for the left and right square faces: the bubble is supposed to be in a Couette flow defined with s = ∂Vz/∂x. equivalent biphasic viscosity and horizontal force are deduced from: µ = ∫∫left τ dS/s = ∫∫right τ dS/s and Fx = ∫∫bubble τ. Figure 6 shows the vertical velocity component contours for a 1 millimeter bubble diameter in a 10 s-1 (left) and 500 s-1 (right) Couette flow stress s. The Rayleigh formulation underestimate the equivalent conductivity for a biphasic medium and the mistake made can reach 15%.5 ε= 0.1 1 10 Rayleigh DΦ / DΦ f ε = 0. it is possible to define an insulated statistically representative bubble calculation domain. Now the input data and laws required for the performance calculations are presented but the model description has to be completed with source terms.5 3 2 .5 1 0 . So. 3 .Subscripts s and f refer to solid and fluid. This domain is a side c square one according with ε = Bubble volume/Square volume. .x dS. For a given diameter dp and a local porosity ε. The Naviers-Stokes numerical calculation gives the wall shear stress distribution at the bubble and also at the left and right faces. These numerical results are presented in figure 5. or large void fraction or small vertical gradients. This assumption is realistic for small bubble dimensions.5 2 1 .

The present work has presented macroscopic and bubble scale results and has shown both are coupled.9530E-03 3.3339E-01 3.0956E-01 -3.4295E-03 -8.1912E-02 -1. PICARD G.0005 -0.0005 0.4765E-03 1. dp =10-3 m.A.. J.2383E-03 0.. J of Micro.00025 0 -0.4765E-01 1.2382E-01 6. Society. They not yet have been rigorously modelled though it is now possible to compute the coupling between electrochemistry and biphasic flows. CONCLUSION The biphasic electrolysis processes are of a great interest for industrial applications. LAL A.0956E-01 2. vol 127. In the future..0. 1-8.8574E-01 -2.2383E-03 -2...6678E-03 7.001 Figure 6: vertical velocity component contours for s=10 s-1 (left) and 500 s-1 (right). FUJISAKI K.00075 0. Microeng.00075 0. 15.. HAMBURGER J.0005 0 X 0.00075 4. (2005) [3] HINE F.0005 0 X 0.1913E-03 4..00025 -0. PICARD G.0000E+00 -1...4295E-03 6.. Electrochem.3339E-01 Y -0.00025 -0. Electrochemical Society. vol 134. pp. The influence of attached bubbles on Potential Drop and Current Distribution at Gas-Evolving Electrodes.00025 0 -0.292 (1980) [4] TOBIAS C.1912E-02 0.001 Y -0. MURAKAMI M. MANDIN Ph....7147E-01 -4.9530E-03 -6.1913E-03 -7.0005 0.0005 -0. REFERENCES [1] MANDIN Ph.6678E-03 0. Physical principles and Miniaturization of Spark Assisted Chemical Engraving. HOF L.8574E-01 1. No 2 (1959) . BLEULER H..7148E-03 2.4765E-01 -3. Volume 51.W.2382E-01 -1.0005 0. Electrochimica Acta. Calculation of the current density distribution at vertical gas-evolving electrodes.0000E+00 -6.7148E-03 -4.4765E-03 -3.00075 8. Pages 1140-1156 (2005) [2] WÜTHRICH R.7147E-01 3. Issue 6. Bubble scales results have to be correlated to lead to a predictive model.0005 0. J. BESSOU S. heat transport calculation will have to be performed because of its importance.