i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 7 4 3 6 e7 4 4 1

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Modelling electrolyte conductivity in a water electrolyzer cell

Michael Caspersen a,*, Julius Bier Kirkegaard b
a
b

Technical University of Denmark, Anker Engelunds Vej 1, 2800 Kgs. Lyngby, Denmark
Niels Bohr Institute, Blegdamsvej 17, 2100 Kbenhavn , Denmark

article info

abstract

Article history:

An analytical model describing the hydrogen gas evolution under natural convection in an

Received 9 January 2012

electrolyzer cell is developed. Main purpose of the model is to investigate the electrolyte

Received in revised form

conductivity through the cell under various conditions. Cell conductivity is calculated from

3 February 2012

a parallel resistor approximation depending on the gas phase distribution. The results are

Accepted 4 February 2012

supported by applying a two-phase numerical model which shows good agreement with

Available online 3 March 2012

the analytical approach. The model can prove useful to optimize design factors of an
electrolyzer cell for future use in that it provides clear tendencies for electrolyte conduc-

Keywords:

tivity from combinations of pressure, current density and electrolyte width among others.

Electrolyzer cell

Copyright 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights

Electrolyte conductivity

reserved.

Analytical approximation
Stochastic simulation

1.

Introduction

During the last decade focus on global CO2 reduction has

increased massively, and the search for new non-emission
sustainable technologies has gained interest when working
towards the fossil fuel free society. At the same time the world
energy consumption is expected to increase in the future, which
sets requirements to efficient and clean energy production.
Hydrogen is considered a useful energy carrier. Water
electrolysis as a production method seems promising as it is
a cheap and simple process. But even though it is already
commercialized to some extend [1], there is still a lot of
progress to be made due to various issues such as stability and
durability as well as production and material costs.
When electrolysis is utilized, highly pure hydrogen gas can
be collected at the electrode, but this gas development leads to
quite a predicament when it comes to process technique as
the produced hydrogen gas acts as physical resistors in the
electrolyte thereby reducing efficiency of the cell due to the
insulating properties of the gas phase.

In the case of no forced electrolyte flow the overall flow

pattern will be controlled by gas buoyancy. The gas development thereby turns the conditions of the process into a twophase flow problem involving altered conditions for the electrolyte flow, conductivity and also current density distribution
at electrodes as the most pronounced issues. Gas bubbles
released into the electrolyte will act as electrical resistors thus
redistributing and reducing current fields and consequently
the overall efficiency of the cell.
Knowledge of the hydrogen gas significance has led to an
increased interest in trying to identify and characterize gas
phase effects on e.g. fluid flow patterns, current density variations across the electrode as well as parameters influencing
gas evolvement. Advantages from simulating process conditions by numerical models are a gaining focus and various
models have been developed in the recent years.
Experimental work has been carried out several times, yet
so far only a limited number of mathematical models have
been developed to describe the process conditions in an
electrolyzer cell. Also, due to complexity of the matter no

* Corresponding author.
E-mail address: mcaspersen@gmail.com (M. Caspersen).
0360-3199/$ e see front matter Copyright 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2012.02.023

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 7 4 3 6 e7 4 4 1

single study is able to take into account all important factors

and each model is restricted to some certain aspects.
Vogt conducted experiments [2] related to observation of
gas evolvement at the electrode in an electrolysis cell
depending on current density. He observed that at low current
densities gas evolution would primarily happen by molecular
diffusion, while at higher values bubbles nucleate at the
surface and grow under supply of dissolved gas from the
electrolyte.
From practical experiments Hine and Murakami [3]
measured a drop in current density along a vertical electrode caused by gas bubble development at the electrode e the
reason for this being a decrease in electrolyte conductivity
near the electrode as bubbles created physical barriers for
active reaction sites. The measurements were conducted for
both natural as well as forced convection of electrolyte.
It was further concluded by Vogt [4] that modelling of the
cell should take a non-uniform gas bubble distribution into
account to make up for differences in electrical conductivity of
the electrolyte.
Nagai et al. [5] conducted experiments on electrode interspacing in an electrolyzer cell and found different optimum
values for various current densities and a physical model was
proposed.
Reigel et al. [6] identified two possible flow regimes
controlled by current density; increased current density leads
to establishment of electrolyte back flow as a consequence of
hydrogen bubble evolution near the electrode.
Boissanneau and Byrne [7] determined the flow field of gas
particles in an electrochemical cell with vertical electrodes for
chlorine production under natural convection. It was shown
that in spite of the flow being laminar local turbulent flow was
still found adjacent to gas particles.
With a mathematical model Byrne et al. [8,9] simulated the
electrolyte flow velocity amongst others as an effect of current
density, but no emphasis has been put into the presence and
influence of bubbles thus keeping the model to a single flow
model.
Mat et al. [10] created a mathematical model for a twophase flow in an electrolyzer cell to imitate actual observations on gas evolving in a forced electrolyte flow, which was
successfully done.
This model was adopted by Abbasi and Rahimzadeh [11]
who further simulated the gas void velocity and fraction
close to the electrode as well as the impact of varying current
density. Among other observations it was found that the gas
release rate increased with higher flow velocity due to faster
movement of evolved gas on the electrode thereby increasing
area of reactive sites.
Dahlkild [12] developed a mathematical flow model characterizing the gas volume fraction near a single, vertical
electrode in a two-phase electrolyte. A buoyancy boundary
layer was included in the model, through which the current
density was found to be practically constant. Over the entire
vertical electrode a clear non-uniform distribution was found
in agreement with earlier models as contributed to the varying
electrolyte conductivity in the two-phase area. It was
concluded that modelling of the potential drop through the
boundary layer has much greater significance than models for
bubble transport mechanisms.

7437

Finally, Wedin and Dahlkild [13] also made a numerical

model simulating the effect of bubble size and gas production rate on the electrolyte flow in natural convection with
a two-phase model. The model was found to be consistent
with experimental observations made by Boissanneau and
Byrne [7].
From the above description it should be apparent that so
far emphasis has been on parameters controlling gas development, while characterization of the actual electrolyte is less
covered. To our knowledge no existing mathematical model
describes the electrical conductivity properties of the electrolyte, as previous work mainly focuses on flow patterns/
velocity and phenomena related to the electrode.
The purpose of this study, on the other hand, is to model
the electrical conductivity of the electrolyte in an electrolysis
cell depending on cell geometry and physical resistances in
the electrolyte, i.e. primarily gas bubbles. We do not attempt
to develop a model that takes all effects into account. This is
a very complex matter. On the contrary, we search for a model
that gives analytical results that may easily be manipulated to
deduce tendencies in the conductivity of the electrolyte as
a function of the physical parameters relating to the cell.
The results shown here further serves as input to the
ongoing discussion on zero vs. non-zero gap configuration,
emphasizing the altered physical conditions that goes with
gas phase evolution.
Description of the electrolyzer cell has been approached
via the application of both an analytical and a numerical
model. The analytical approach gives a firm relation to the
governing equations determining the physical appearance,
while two-phase numerical model of a single electrode under
natural convection is presented with the aim of confirming
the analytical results, and for further implementation of
various physical factors.

2.

The considered half cell

In Fig. 1 the observed electrolysis cell is illustrated. Oxygen gas

is developed from the anode and hydrogen gas from the
cathode with the two electrodes separated by a membrane.
The gas development at each electrode is running according to the following reactions:
Cathode : 4H2 O 4e /2H2 4OH
Anode : 2H2 O/O2 4H 4e and H OH /H2 O
Total : 2H2 O/2H2 O2
Only the cathode side of the system is considered here, but
may just as well be applied on the anode side.

3.

Modelling the cell

The cell is divided into vertical intervals. Across each interval

the resistance is constant. As bubbles enter each interval this
resistance changes. We take the bubbles as insultors. Let M
lwDz=V denote the maximum number of bubbles in an

7438

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 7 4 3 6 e7 4 4 1

Electrolyte
width, w

dNi
kB TU
v

Ni1  Ni
dt
eapVRi Dz

(3)

We seek the steady state solution and accordingly set

dNi =dt 0 for each interval. Combining Eqs. (1)e(3) and by
letting Dz / 0 we arrive at
dnz C
nz  C 0
dz
a

(4)

where n(z) is a measure of bubbles per height, a lw=V and

C kB TUls0 =eapVwv.
We solve this with the boundary condition n(0) 0 and
notice that the conductivity up through the cell is given by
sz s0 1  nz=a. This gives us


C
sz s0 exp  z
a

(5)

which shows that the conductivity falls exponentially up

through the cell with characteristic length

H2

O2

a veapw2

C kB TUs0

(6)

We can now find the mean conductivity of the cell

hsi

1
h

Zh
szdz s0




L
h
1  exp 
h
L

(7)

Membrane

Anode

where h is the height of the cell.

In general we wish to compare cells that give the same
output. For the purpose of this we wish to describe the voltage
as a function of the desired mean volume current density J.
Ohms law gives us

Cathode

Fig. 1 e Illustration of the electrolyzer cell.

interval of electrolyte width w, cathode length l and height Dz.

V is the volume of a bubble.
Our model is built on the approximation that the resistance
in the ith interval depends linearly on the fraction of bubbles
Ni in the interval:
Ri R0

M
1
R0
M  Ni
1  Ni =M

(1)

where R0 is the resistance of the interval had there been no

bubbles. This approximation is inspired by the resistance of
parallel conductors. R0 can be related to the conductivity s0 of
the electrolyte
R0

w
s0 lDz

(2)

The bubbles rise by their constant terminal speed v, and

thus per unit time an amount of (v/Dz)Ni leaves the ith
interval, and an amount (v/Dz)Ni1 enters the interval.
Furthermore Ii/ea molecules are produced by the electrolysis,
where Ii U/Ri is the current in the interval, e is the fundamental charge and a is the number of atoms to make up the
molecule (in this case 2). We can relate this to a number of
bubbles by diving by the number of molecules that make up
a bubble, given by the ideal gas law: m1 pV/kBT. Hence we
have a differential equation for the number of bubbles in an
interval:

wJ
hsi

(8)

where hsi given by Eq. (7) also depends on U. Solving, we

obtain
UJ


K
wJ
ln 1 
s0
K

(9)

where K veapw2 =kB Th. This is the voltage across the electrolyte required to have a mean volume current density J in
the cell. We see the current can only be obtained if wJ < K. We
stress that this is not the voltage across the entire cell, since
additional polarization phenomena are neglected.
We have ignored the stochastic aspect of the process. We
should require Ni N0 and that the bubbles form at random
location in the interval. Furthermore by letting Dz tend to zero we
ignore the vertical components of the current paths. We ignore
this somewhat already by assuming (1) holds, but the motion is
completely restricted for infinitesimal interval heights.
In order to examine these assumptions and support the
results we set up a numerical model. The model iterates
through time and creates only whole bubbles placed at
random unoccupied locations in the cell. The mathematical
modelling of the simulation is roughly the same, with the
exceptions given. We do not use the analytical results in the
simulation so in order to obtain the steady state solution for a
given current density we implement a discreet PID-controller

7439

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 7 4 3 6 e7 4 4 1

that controls the voltage. The results match the analytical

approach with minor deviations.

1,4

4.

Operational conditions

We assume that the electrode and membrane surfaces are

non-permeable meaning that no drag effect on electrode and
membrane wall is present, and so it does not influence the
bubble rise speed.
Furthermore we ignore effects such as polarization
phenomena, i.e. the electrical and reaction related resistances
[14]. Our model is an investigation of the electrolyte, and other
effects related to the electrodes and membrane must be
considered separately.
The model considers a hydrogen cell under natural convection state, where the predefined velocity profile of bubbles is set
according to physical observations in an actual cell. We neglect
the horizontal spatial distribution of the bubbles. This is a direct
consequence of Eq. (1).
To get numerical results the specific conductivity of the
electrolyte must be specified. In our graphs we use the
conductivity of an 30 wt% aqueous potassium hydroxide solution, which is a normal concentration in alkaline electrolysis [1].
The specific conductivity of the solution is determined in
accordance with the findings made by Gilliam et al. [15] who
developed empirical correlations between specific conductivity
and KOH concentration over a range of temperatures.

5.

Discussion of results

In Fig. 2 the electrolyte conductivity dependence on pressure

is shown. The results illustrate how tremendous an effect can
be obtained by increasing pressure in the electrolyzer cell. At
current densities of 100e200 mA/cm2 the effect is relatively
small, but there is still a noticeable increase in conductivity
from raising the pressure just a few bar. This effect is due to
the ideal gas equation predicting a decreased gas volume
present in the electrolyte and hence a larger conducting

Conductivity [S/cm]

1,2

1,0

0,8
100 mA/cm2

0,6

200 mA/cm2
500 mA/cm2

0,4
0

Bubble Rise Speed [cm/s]

Fig. 3 e Conductivity as function of bubble rise speed for

various current densities (1 bar).

volume. In the inset of Fig. 2 we have fixed the pressure at

1 bar and the conductivities dependence on the current
density is shown. The dependency is almost linear until close
to J K/w where the cell is completely filled by bubbles.
As the current is increased the pressure influence becomes
more distinct and higher values are necessary for reaching the
same conductivity. Hence, drop in conductivity due to gas
evolution can be compensated for by increasing pressure,
feasible in modern electrolyzer cells [1].
We note also that the pressure and the bubble rise speed
appear identically in the governing equations, which means
that the same effect can be obtained by forcing a higher bubble
rise speed, see Fig. 3. In the limit of either the rise speed v or
pressure p tending towards infinity, Eq. (7) reduces to hsi s0 .
Furthermore, there may be a synergy effect between these
parameters in that smaller bubbles at higher pressure would
move at higher velocities due to smaller frictional force
between the two phases. This can be predicted by Stokes Law.
Related to the increase of gas evolution at higher current
densities is the illustration in Fig. 4, showing the vertical
component of conductivity along an electrode with h 10 cm.
During gas evolution the electrodes become inhomogeneously
polarized as a result of the uneven gas phase distribution
along the electrode, see Fig. 1. This follows from natural
bubble buoyancy, which has also been shown in former

Conductivity [S/cm]

1,4
1,2
1
0,8
0,6

100 mA/cm2
200 mA/cm2

Fig. 2 e Conductivity as function of pressure for various

current densities. The inset shows for fixed pressure (1 bar)
the conductivity as a function of the mean volume current
density J.

0,4
0

3
4
5
6
7
8
Height above bottom [cm]

10

Fig. 4 e Electrolyte conductivity along electrode height (1 bar).

7440

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 7 4 3 6 e7 4 4 1

1,4

Conductivity [S/cm]

1,2

1,0

0,8
100 mA/cm2

0,6

200 mA/cm2
500 mA/cm2

0,4
0

0,1

0,2

0,3

0,4

0,5

Here the most favourable separation distance between electrode and membrane is investigated. Considering only the
ohmic resistance from the electrolyte, the smallest possible
separation distance may at first seem favourable. As our
results suggest though, consideration of resistance due to
bubbles has to be taken into account and the optimal separation distance at higher current densities is shifted outwards.
This has also been put forward by other authors [14,16]. This is
a likely tendency when considering the physical blocking
effect from bubbles at small distances versus the rising effect
from electrolyte resistance at higher values. Thus, in respect
to zero-gap configuration it is underlined that the setup must
preferably include a true zero-gap, at which both of these
factors can ideally be eliminated.

Electrolyte width, w [cm]

Fig. 5 e Effect of electrolyte width on conductivity at

various current densities (1 bar).

6.

studies [12,17]. Fig. 4 shows an exponential decrease in

conductivity along the electrode height, which correlates well
to various resistances in the electrolyte when bubbles block
the electrical current fields. A significant increase in magnitude of the slope is seen with increasing current density,
which would be expected as the gas phase density becomes
more uneven between top and bottom.
At small separation distances for cathode and membrane,
i.e. electrolyte width, the conductivity decrease drastically, as
seen in Fig. 5. This is an obvious consequence of a narrow gap
that is quickly filled with gas phase. At lower current densities
the tendency is less pronounced, which is simply attributed to
lesser gas production. Similar effects are found in Refs. [3,5]. It
is interesting though, that the dramatic increase in conductivity lies within a narrow range of electrolyte widths. This
seems likely to origin from a gas crowding effect. At higher
current densities the crowding effect is more pronounced due
to more gas formation, thus requiring larger electrolyte
widths. As part of the ongoing discussion this dilemma speaks
in favour of zero-gap electrode setup.
Influence on cell conductance from increasing current
density in relation to cell geometry layout is shown in Fig. 6.
120

100

Conductance [S]

100 mA/cm2
200 mA/cm2

80

500 mA/cm2
60

Conclusions

In this work an analytical, approximate model has been

developed in order to investigate the effects of hydrogen gas
evolution on the electrolyte conductivity in an electrolyzer cell
under a natural convection state. A stochastic numerical
model has been developed to support the results.
Our model predicts that electrolyte conductivity along the
cathode height decreases exponentially with greater decline
for higher current densities. This is a direct consequence of
the increased gas phase density at higher vertical positions of
the electrode.
When investigating the relationship between electrolyte
width and pressure the model predicts these factors in practice has minor effect on conductivity at lower current densities. On the other hand, it is evident how the electrolyte width
becomes less dominating at increased pressure. Accordingly,
pressure increase has a larger effect at lower interspacing
values. This situation correlates well with reality, where
bubble size reduction as function of pressure in all probability
affects conductivity due to more effective mass transfer paths.
At higher current densities we find that the pressure in the
cell and rise speed of the electrolyte have tremendous effects
on the conductivity of the electrolyte.
Furthermore, the value of the cell width that maximizes
the conductance of the electrolyte is seen shifted towards
higher values for increasing current densities.
The numerical model supporting the analytical approach
further offers possibilities for future optimization of more
advanced cell simulation. Further development of this model
will presumably be on bubble size effect and flow field simulation
to include effects from forced convection conditions. Contributions from polarization phenomena will also be considered.

40

references
20

0
0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

Electrolyte width [cm]

Fig. 6 e Effect of electrolyte width on conductance at

various current densities (1 bar).

1,0

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