Excerpt from the Proceedings of the 2011 COMSOL Conference in Stuttgart

Study of an Alkaline Electrolyzer Powered by Renewable

Energy
E. Amores Vera1,*, J. Rodríguez Ruiz 1, C. Merino Rodríguez1, P. García Escribano1
1
Centro Nacional del Hidrógeno. Prolongación Fernando el Santo, s/n - 13500 Puertollano (SPAIN)
*Corresponding author: [email protected]. Tel: +34 926 420 682

Abstract: Modeling of water electrolyzers can surplus is seen as a key strategy for energy
be considered a fundamental optimization tool storage. Centro acional del Hidrógeno
for production of hydrogen by renewable (CNH2) works actively in this direction, which
energy. This work reports the model developed is considered a strategic line in order to
in COMSOL of an alkaline water electrolysis achieve a sustainable future energy.
cell powered by a PV-module. The geometry
model was created taking as reference a Alkaline electrolysis is a highly developed
commercial electrolysis cell. The model technology in the industry and the main way to
involves transport equations for both liquid obtain sustainable hydrogen. Nowadays,
and gas phases, charge conservation and forces commercial alkaline electrolyzers are
balances for the study of coalescence designed for a constant power supply.
phenomena. Results showed changes on gas However, renewable energies are non-
profiles with the evolution of solar irradiation dispatchable because of their strong
during the day, as well as changes on void dependence on weather conditions. The
fraction and potential distribution. fluctuations in power supplies to the
electrolyzer could cause problems such as
Keywords: Water electrolysis, renewable generation of explosive mixtures, corrosion of
energy, hydrogen, void fraction, coalescence materials, lower efficiency, pressure drops,
changes of temperature, etc. The design of
alkaline electrolyzers powered by renewable
1. Introduction energy is a critical issue to avoid these
problems. For these reasons, the CFD
The production of H2 from renewable energy simulation is an important design tool.

a b

Solar irradiance profile Current density profile normalized from a

Puertollano, SPAIN - June 2009 PV module

SOLAR EERGY PV-MODULE ELECTROLYZER

Figure 1: Electrolyzer powered by a PV-module: a) irradiation profile; b) current density profile.

 This work reports the model of an alkaline the bottom inlets. Over the active surface of
electrolysis cell powered by a PV-module (Fig electrodes, water splits following the
1). Fig 1a is a typical solar irradiance profile electrochemical reactions described above,
for a sunny day in Southern Spain. Fig. 1b evolving oxygen and hydrogen, respectively
shows a current density profile implemented in for anode and cathode. The mixture of
COMSOL® from a PV-module that powered generated gases and electrolyte leaves the
the electrolyzer. To this aim, Interpolation compartment through the upper outlets (Fig 2).
Function tool was used. Maximum value of
solar radiation occurs at 14:00. 2.2. Model Geometry

Taking as reference a modified commercial

2. Model Set-Up electrolysis cell (Fig 2a), the geometry of the
model was built following fluid dynamic
2.1. Alkaline electrolysis water requirements. In this way, simplifications were
made in order to reduce the model complexity
During alkaline water electrolysis the (Fig 2c). As result, a good approximation can
following reactions take place: be made just by 2D geometry, which allows an
optimal study of the main involved variables
- On cathode, the evolution of H2 gas take (Fig 2e).
place:

4 H 2 O + 4e − → 2 H 2 ( gas ) + 4OH − 3. Formulation of the problem in

COMSOL Multiphysics®
- On anode, O2 gas is generated according
with: Depending of studied phenomena, the model
can be divided into:
4OH − → O2 ( gas ) + 2 H 2 O + 4e −
- Water electrolysis by renewable
In a typical operation, electrolyte (KOH) enters energies, with Electric Currents and
in the anodic and cathodic compartments by Two phase-flow bubbly flow modules.

1. Cathode
2. Cathodic compartment (hydrogen
generation)
3. Membrane

4. Anodic compartment (oxygen

generation)
5. Anode

Figure 2: Geometry of a commercial electrolysis cell implemented on COMSOL Multiphysics®.

 - Motion of bubbles next to electrode For Laminar Bubbly Flow, sum of the
surface with Two phase-flow phase momentum equations for the two phases gives:
field module of COMSOL®. a momentum equation for liquid (2):

Table 1 shows the boundary settings and initial r

∂u l r r
conditions used in the model (see Appendix). φl ⋅ ρ l ⋅ + φ l ⋅ ρ l ⋅ u l ⋅ ∇ u l = −∇ p +
∂t
 r r 
∇ ⋅ φ l ⋅ (η l + η T ) ⋅  ∇ u l + ∇ u lT − ⋅ (∇ u l ) ⋅ I  
r r 2
3.1 H2 generation by Renewable Energy   3 
r r
Charge transport was studied using Electric + φl ⋅ ρ l ⋅ g + F (2)
Currents module of COMSOL®, which solves
a current conservation problem for the scalar A continuity equation (3),
electric potential V [1]. For time dependent
studies, the continuity equation takes the form ∂
(1): ∂t
(φl ⋅ ρl + φg ⋅ ρ g ) +
r r
r ∂ ∇ ⋅ (φl ⋅ ρl ⋅ ul + φ g ⋅ ρ g ⋅ u g ) = 0 (3)
∇ ⋅ J = −∇ ⋅ d ((ε oε r ∇V )
∂t
r And a transport equation (4) for the volume
− ∇ ⋅ (σ ∇ V − J e ) = dQ j (1)
fraction of gas,
In this case, electric transport charges on
∂φ g ⋅ ρ g r
electrodes is not considered, and only ionic + ∇(φ g ⋅ ρ g ⋅ u g ) = −mgl (4)
transport is studied inside the electrolysis cell. ∂t

On the other hand, movement of gases and Where (mgl) is the mass transfer rate from gas
liquid was modeled applying Laminar Bubbly to liquid.
Flow module of COMSOL®. This application
mode describes the two-phase flow using a In order to complete the system, auxiliary
Euler-Euler model. The module solves for the equations were used:
volume fraction occupied by each of two
phases, without defining each bubble in detail. - Activation overpotentials (η) were
It is a macroscopic model for two-phase fluid defined for cathode and anode by Butler-
flow. It treats the two phases as Volmer equations form (Tafel equation):
interpenetrating media, tracking the averaged
concentration of the phases. One velocity field
is associated with each phase, and the R ·T i
η = 2.3 · · log   (5)
dynamics of each of the phases are described α ·F  io 
by a momentum balance equation and a
continuity equation. Following simplifications - Bruggeman equation (6) relates the
are considered when this module is used [2]: variation of conductivity of electrolyte
(σ) with the volume fraction of gases (f),
- The gas density is negligible for each section.
compared to the liquid density.

- The motion of the gas bubbles σ = σ o ⋅ (1 − f )1.5 (6)

relative to the liquid is determined by
a balance between viscous drag and - Gases generated fluxes on active surfaces
pressure forces. of electrodes are defined by Faraday
equation, for H2 (7) and O2 (8):
- The two phases share the same
pressure field.
i ⋅M H2
m& H2 = (7)
For this simulation, high level of bubble 2⋅F
definition was not required, and this approach
allows reducing the computational cost doing a i ⋅M O2
good approximation to our system. m& O2 = (8)
4⋅F
3.2. Motion of bubbles 4. Mesh
During the rise of gas inside the electrolyzer For electrolysis cell model, a triangular mesh
the coalescence of bubbles happens frequently. was generated (Fig 3a). Mesh elements were
To determine the motion of a bubble it is coarse predefined on the electrolyte domain,
necessary to determine the forces acting on it but normal on the membrane and electrodes
and put a balance on the amount of movement boundaries.
as in Fig 2d [3, 4]:
In the case of motion of bubbles, a physics-
- Archimedes’ principle to determine controlled mesh was used (Fig 3b). The mesh
the buoyancy. In commercial is finer on the bubble domain.
electrolyzers, the residence time of
bubbles is small due to the forces of
Archimedes and the void fraction is
small.

- Friction force according to the drag

coefficient

- Horizontal force of the bubble-

electrode and bubble-bubble
interactions

- Pump force.

These phenomena can be modeled in

COMSOL® by laminar two-phase flow, phase
field. This application mode describes the (a) (b)
two-phase flow dynamics using a Cahn- 10 mm 2 mm
Hilliard equation. The equation describes the
process of phase separation, by which the two Figure 3: Mesh generation for the used geometry:
components of a binary fluid spontaneously a) mesh for hydrogen generation model; b) mesh for
bubbles motion model.
separate and form domains pure in each
component.

COMSOL Multiphysics® solves the Cahn- 5. Results

Hilliard equation by two equations (9), (10):
5.1. Polarization Curve
∂φ r γλ In Fig 4, a typical polarization curve is shown
+ u ⋅ ∇φ = ∇ ⋅ 2 ∇ψ (9)
∂t ε [6, 7]. According with other authors [8],
oxygen and hydrogen overpotentials are the
 ε 2  ∂f ext main source of reaction resistances, and at high
( )
ψ = −∇ ⋅ ε 2∇φ + φ 2 − 1 ·φ +  
 (10) current densities, it is very significant the
 λ  ∂φ effect of Ohmic losses.
Where (u) is the fluid velocity, (γ) is the
mobility, (λ) is the mixing energy density, and
(ε) is the interface thickness parameter. The
(ψ) variable is referred to as the phase field
help variable [5].

The transport of mass (3) and momentum (11)

is governed by the incompressible Navier-
Stokes equations including surface tension (st):
r r
∂u
ρ
∂t
r r
[ r
( r
+ ρ (u ⋅ ∇ )u = ∇ ⋅ − pI + µ ∇u + ∇u T + )]
r r r r Figure 4: Polarization curve, including over-
Fg + Fst + Fext + F (11) potentials and ohmic losses contributions.
5.2. I-V Distributions The predicted void fraction of hydrogen at 4
different points along the electrode surface is
On Fig 5 it is possible to follow the dynamic reported on Fig 7. H is the height of the
evolution of potential distribution over the electrode and point x=0 corresponds with the
electrolysis cell during operation. Applied surface of electrode. As can be seen, next to
potential increases with increasing of current the electrode surface volume fraction reaches
density. Attending current vector arrows, it can the highest value, and decreases towards the
be seen higher values of current next to membrane. Void fraction also increases from
electrodes extremes, which is in agreement bottom to top of electrode due to accumulated
with observed for electrochemical models by generation of gas, and effect of forced
other authors [9]. convection [12], as observed in Fig 6.

Figure 7: Void fraction distribution at four

locations.
Figure 5: Potential distribution of electrolysis cell
when it is powered by a PV-module.

Influence of current density on generated gas is

5.3. Gas generation profile reported on Fig 8. As expected, hydrogen void
fraction increases at higher current density
Evolution of hydrogen profile can be evaluated values. From this plot it can be also deduced
from picture on Fig 6. Hydrogen void fraction that higher the current density, higher the gas
(occupied space by hydrogen bubbles) draws a penetration at lateral direction, because of
typical profile next to electrode surface [10, increasing of lateral velocity of gas [13].
11]: void fraction progressively increases on
vertical direction of electrode.

Figure 6: Hydrogen volume fraction evolution for Figure 8: Void fraction of gas for different values
electrolysis cell during a day operation. of current density.
Figure 9: Detail of coalescence phenomena between hydrogen bubbles

5.4. Coalescence phenomena [4] Mandin Ph., Hamburger J., Bessou S.,
Picard G. Modelling and calculation of the
Fig 9 shows a model of coalescence between current density distribution evolution at
two bubbles of hydrogen using COMSOL vertical gas-evolving electrodes,
Multiphysics®. Electrochimica Acta 51 (2005) 1140-1156

During electrolysis of water, the bubbles rise [5] COMSOL. Multiphysics 3.5 - Chemical
by buoyancy and join in the upper regions of Engineering Module Model Library.
the cell. The study of coalescence lets us know Burlington, MA: COMSOL, Inc.; 2008
the dynamic of the gas: generation,
distribution, evolution, etc. [6] Djafour A., Matoug M., Bouras H,
Bouchekima B, Aida M.S., Azoui B.,
Photovoltaic-assisted alkaline water
6. Conclusions electrolysis: Basic principles, Int. J. Hydrogen
Energy, 36, 4117-4124, 2011.
• COMSOL® was used to model the
behavior of an electrolysis cell for [7] Ðukic A., Firak M., Hydrogen production
hydrogen production. using alkaline electrolyzer and photovoltaic
(PV) module, Int. J. Hydrogen Energy, 36,
• The distribution of oxygen and hydrogen 7799-7806, 2011.
gas when the cell is powered by a PV
module was obtained. [8] Zeng K., Zhang D., Recent progress in
alkaline water electrolysis for hydrogen
• Using the model developed in production andapplications, Prog. Energ.
COMSOL®, we determined the current Combust., 36, 307-326 (2010)
and potential distribution along the
electrolysis cell. [9] Katukota S.P., Nie J., Chen Y., Boehm R.
F. Numerical investigation for hydrogen
• COMSOL® can model phenomena of production using exchange water electroysis
localized coalescence. cell, COMSOL Users Conference 2006 Las
Vegas

7. References [10] Sasaki T., Nagai N., Murai Y.,

Yamamoto F., Particle Image Velocimetry
[1] COMSOL Multiphysics - User’s Guide. measurement of bubbly flow induced by
Electric Currents AC/DC Module. Burlington, alkaline water electrolysis, Proceedings of
MA: COMSOL, Inc.; 2007 PSFVIP-4 , Chamonix, France, 2003.

[2] COMSOL Multiphysics - User’s Guide. [11] Aldas K., Pehlivanoglu N., Mat M.D.,
Bubbly Flow Model, Chemical Engineering Numerical and experimental investigation of
Module. Burlington, MA: COMSOL, Inc; 2007 two-phase flow in an electrochemical cell, Int.
J. Hydrogen Energy , 33, 3668–3675 (2008)
[3] Mandin Ph., Ait A., Roustan H.,
Hamburger J., Picard G. Two-phase [12] Mat M.D., Aldas K., Olusegun J. I., A
electrolysis process: From the bubble to the two phase flow model for hydrogen evolution
electrochemical cell properties, Chem Eng in a electrochemical cell, Int. J. Hydrogen
Process 47 (2008) 1926-1932. Energy, 29 (2004) 1015-1023
[13] Aldas K. Application of a two phase flow
model for hydrogen evolution in a
electrochemical cell, Appl. Mathematics and
Computation, 154 (2004) 507-519

9. Acknowledgements

The authors acknowledge financial support

from Ministerio de Ciencia e Innovación
(MICINN, Spain), Junta de Comunidades
Castilla-La Mancha (JCCM) and Fondos
Europeos de Desarrollo Regional (FEDER).

Project PSE 120000-2009-3.

10. Appendix

Table 1: Constants, Sub-domain and Boundary

Settings

Symbol Value Description

Pressure
p 1 bar
operation
Temperature
T 348 K
operation
Exchange current
io,c 0.02 A/m2
density (cathode)
Exchange current
io,a 0.016 A/m2
density (anode)
Electrolyte (30%
σ0 130 S/m
KOH) conductivity
Membrane (PTFE)
σ 67 S/m
conductivity
Inlet
v0 0.1 m/s
velocity
8.31 J K-1 Ideal gas
R
mol-1 constant
Faraday
F 96485 C
constant
Charge transfer
α 0.5
coefficient