Int. J.

of Thermal & Environmental Engineering

Volume 9, No. 2 (2015) 53-60

Effect of Operating Parameters on Performance of

Alkaline Water Electrolysis
Md S. Opu*
Oorja Fuel Cells, Fremont, California, USA, 94539

Abstract
In this fundamental research investigation, the simple fundamental experimental design with two platinum wire as
anode/cathode electrode and KOH solution as electrolyte were used throughout the experiments. The effect of
electrolyte volume and concentration, electrode location and submerged length into the electrolyte, distance between two
electrode and operating temperature on efficiency of water electrolysis was investigated. The results showed that the
performance of alkaline water electrolysis is significantly affected by distance between electrode, electrolyte
concentration and operating temperature. Higher rate of hydrogen production can be possible at smaller gap between
electrodes with higher concentration of electrolyte operating at higher temperature.

Keywords:

electrolyte temperature of 70-900C, cell voltage of 1.85 - 2.05

V and consume 4-5 KWh of energy for every m3 of hydrogen
1. Introduction generated [11]. There have been various attempts to improve
efficiency and reduce energy consumption of water electrolysis
Hydrogen is an important energy source for sustainable process, such as development of new cell geometry,
development[1-5]. Fuel cells use hydrogen to generate power electrocatalytic materials for electrodes, etc [11]. In contrast, a
and produce only water [6]. Moreover, hydrogen is believed as more popular way of improving electrolysis efficiency is
safe for commonly used fuels [7]. The large scale hydrogen increasing the process temperature, which lowers the voltage
consumptions requires large scale production. Presently, the required to electrolyze the water. At elevated temperature (800
hydrogen production is dominated by reforming of natural gas - 900oC), the electric power consumption is expected to be
and gasification, which is neither renewable nor clean [6-8]. about 3 KWh/m3hydrogen. However, this technology with
Hydrogen can be produced from water via different existing elevated temperature is still in its developmental stage [11].
technology like photocatalysis, thermochemical cycles, and In this project, we studied the effects of operating parameters
water electrolysis [6, 8-10]. These methods offer renewable on improving the efficiency of water electrolysis. As alkaline
and clean production of hydrogen fuel and, therefore, have water electrolysis is one of the simplest methods for hydrogen
attracted increasing research interests in recent years. Among production, this research focused on the study of water
these technologies, water electrolysis is the most promising electrolysis using potassium hydroxide, KOH, as the
technology for large-scale hydrogen production [1, 10]. electrolyte. The reactions can be written as:
However, a significant challenge exists for water electrolysis,
Total reaction:
which is to improve its efficiency, which in turn reduces
energy consumption at high hydrogen production rate. → + (1)
The driving force of chemical reactions in water electrolysis is
electrical energy. By passing a current through electrodes in a
Anode:
solution of water and electrolytes, water molecules (H2O)
decompose to hydrogen (H2) and oxygen (O2) gas through an 2 → O+ +2 (2)
electrochemical reaction. Typical electrolysis plants with
normal or slightly elevated pressure usually operate at
*
Corresponding author. Tel.: +1 510 378 4703
E-mail addresses: [email protected]
© 2015 International Association for Sharing Knowledge and Sustainability
DOI: 10.5383/ijtee.09.02.001

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 Tange / Int. J. of Thermal & Environmental Engineering, 9 (2015) 53-60

Cathode: iii. Two electrodes - Electrode is an electrical conductor,

which provides the physical interface between the
2 +2 → +2 (3) electrical circuit providing the energy and the
electrolyte. For example, graphite rods, platinum
The theoretical minimum cell voltage to start water plates act as conductors /electrodes. We used
electrolysis, called reversible potential calculated by Gibbs free Platinum wire for both anode and cathode electrode.
energy ∆G o, is -1.23V@25°C.
The following Figure 1 shows the electrolyte, battery (power
The objective of this research is to demonstrate the effects of supply) and electrodes (cathode and anode) required for
operating parameters to increase reaction efficiency by electrolysis.
lowering the voltage required for water electrolysis reactions to
occur and thus reducing the total energy consumption of the
process.

2. Water Electrolysis Experimental Setup

Design of water electrolysis experimental Apparatus:

i. An electrolyte - It is a substance containing free ions

which are the carriers of electric current in the
electrolyte. If the ions are not mobile, as in solid salt,
then electrolysis can not occur. For example, an
aqueous solution of common salt can act as an
electrolyte because it contains free Na + and Cl- ions,
which are the carriers of electric current in solution
but solid sodium chloride, can not act as an because
it does not have free Na+ and Cl- ions. We use KOH
as our electrolyte throughout our experiments as it
has the highest conductivity.

ii. A direct current (DC) supply - It provides the

electrical energy necessary to create or discharge the
ions in the electrolyte. Electrons in the external
circuit carry electrical current. Electrolysis is the
passage of a direct electric current through an ionic
substance that is either molten or dissolved in a
suitable solvent, resulting in chemical reactions at
electrodes and separation of materials. BK Precision
Model 9130 was used as DC power supply for this
experiment. The specifications for this power supply
are shown in Table 1.

Table 1: Specifications of BK precision DC power supply,

model 9130 Figure 1: Apparatus required for electrolysis

Our experimental electrolyzer was constructed for baseline

Output Voltage 0-30 V experiment with 200 ml, 0.4 M potassium hydroxide (KOH)
electrolyte. Each electrode was made up of a 5 cm long, 0.5
Output Current 0-3 A mm diameter straight platinum wire, with a 2 cm length
submerged in KOH solution. The two electrodes were kept 1
Load (Utilizing Remote Sensing) ≤0.01%+ 3mV cm apart. The electrodes were connected to a DC power supply
(BK Precision Model 9130). The effective surface area of
Ripple & Noise ≤0.5mVrms & 5mVp-p electrode in electrolyte was calculated to be about 0.316 cm2.
A mercury thermometer was used to monitor the temperature
Voltmeter Resolution 10 mV
of the electrolyte during testing. A hotplate stirrer is used in
Voltmeter Accuracy ≤0.05%+ 5mV purpose of pushing the flow of reactant to the catalyst surface
sites for faster reaction kinetics during experiments.
Current Meter Accuracy ≤0.15+ 5mA
Current Meter Resolution 1 mA

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 Tange / Int. J. of Thermal & Environmental Engineering, 9 (2015) 53-60

Figure 2: Design of experimental setup for baseline experiment and parametric study

3. Material and Method

This section aims to provide a concise review of the method

used to evaluate the performance of water electrolysis.

3.1 Faraday’s Law of Electrolysis

Faraday's 1st Law of Electrolysis states that the mass of a
substance altered at an electrode during electrolysis is directly
proportional to the quantity of electricity transferred at that
electrode. In other words, hydrogen produced in water
electrolysis is directly proportional to the current applied to the
cell, so-called Current Efficiency.
Accordingly, hydrogen generation rate can be computed from
the experimentally measured current density, I, by using the
following conversion:

(A/cm2)
Hydrogen Generation (sccm/cm2) = (3.1)
.

in which sccm denotes cubic centimeter per minute at STP Figure 3: Hydrogen generation rate as a function of input
(standard temperature and pressure). power density for a practical water electrolyzer. The curve
is plotted with arbitrary number showing the actual trend,
Figure 3 displays a relationship between hydrogen generation not with any specific experimental data values.
(sccm/cm2) and input power density (W/cm2) for a practical
electrolysis process. The input power density is the product of 3.2 Performance Curve
current density (I) and cell voltage (V): The performance of electrolysis cells are typically compared
Power density by plotting their polarization curves, which is obtained by
plotting the cell voltage against the current density. The
= Current Density x Cell Voltage (4) primary sources of increased voltage over reversible potential,
which corresponds to a zero reaction rate, may include ohmic
loss of electrolyte, overvoltage associated with oxygen and
hydrogen reactions, and ohmic loss caused by electric
resistance of electrodes and circuitry. Both overvoltage and
ohmic loss increase with the increasing current density. Fig. 4
shows an example of the distribution of cell voltage [5].

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4. Results and Discussion

To optimize the parameters first experimental design approach

was to study the parameters effect on water electrolysis
performance. The experimental design for is shown in Table 2.
The performance measurement can be defined by the eq. (5)

cell = rev + HOR +| ORR | + +

(5)
Where,

rev = Reversible cell potential

HOR = Hydrogen overpotential

| ORR |= Oxygen overpotential
= Ohmic overpotential due to OH- transport resistance
= Ohmic overpotential due to electron transport resistance
The impact of various parameters on these different
overpotentials is also denoted in column 3 of Table 2.
Figure 4: Polarization curves and distribution of cell voltage

In this research, the polarization curves would be made and

presented at various operating parameters.

Table 2: Experimental design of parametric and reproducibility study

We used only one material for electrode and it was platinum chosen for our experimental electrolyte. We used data at 60, 80
and it is considered to have the fastest kinetics for hydrogen and 100 sec and average the data for any specific current
evolution reaction rate [14]. For the simplicity of the density. Accordingly, based on these discussion, from
experimental design only atmospheric condition was carried experiment number 1-5, shown in Table 2, we didn’t perform
out throughout the all experiments. The thermometer was any experiments and we already chose the optimal condition
always put close to the biker wall. As KOH has the highest and materials based on our limitation and fundamental simple
conductivity among the entire alkaline electrolyte exists, it was experimental design. To compare the different parameters

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 Tange / Int. J. of Thermal & Environmental Engineering, 9 (2015) 53-60

effect on performance we established a baseline experimental

design, which represented by column 6 in Table 2. The
experimental condition for the baseline experiments is
atmospheric pressure and room temperature. It consists with
simple straight design two platinum as anode and cathode apart
from each other precisely 1 cm and submerged approximately
2 cm in the center of the biker containing 0.4 M 200 ml KOH
solution.
Based on experimental design the first experiment was done to
find out the effect of stir-bar rotation, which is experiment
number 6 in Table 2. We used magnetic stir plate and made the
stir-bar rotation setting of 3, 6 and without any stir-bar rotation
to measure the effect of stir-bar rotation on performance and
the result is shown in Figure 5. It predicts that stirring is good
to improve the performance of kinetic region but also increase
mass transport resistance.

Figure 6: Impact of electrolyte volume in cell performance

Figure 5: Effect of stirbar rotation on water electrolysis cell

performance

Figure 7: Effect of electrode location submerged in the

One might think that the amount of electrolyte solution has electrolyte solution
impact on ohmic performance of the cell. So we design the
experiment with three different amount of 150, 200, 250 ml of
electrolyte volume, denoted by experiment number 7 in the
The performance of any electrochemical cell depends on
Table 2 and compare the result with baseline. The Figure 6
available reaction surface sites as in our case platinum surface
represents the effect of electrolyte volume and confirms that it
area. The platinum surface area in our experimental design
has minimal impact on performance as expected due to same
depends on the submerged length of the two straight-designed
length of electrode surface submerged into the electrolyte. The
platinum into the electrolyte solution. The general way to
cell does not experience any ohmic loss for different amount of
express the performance is plot of voltage requirements versus
electrolyte solution as long as the distance between the
current, in terms of current density, which normalized the
electrode and electrolyte concentration are fixed.
current with surface area. So the overall performance would
Depending on the placement of the electrodes in different
not be changed due to normalized surface area. The
horizontal location inside the biker with the electrolyte solution
experiment number 9 in Table 2 has the purpose to compare
may affect the performance. Considering this in mind, we
these phenomena. 3 levels of experiment of submerged length
designed the experiment as described by experiment number 8
of 1.5, 2, 2.5 cm were conducted and the result is shown in
in the Table 2 to place the electrode in center, close to biker
Figure 8. It confirms that electrode submerged length has no
wall and half distance between center and close to biker wall
impact if the unit in x-axis is normalized to current density
and investigated the impact of electrode location. Figure 7
instead of current.
describes the effect of electrode location submerged in the
electrolyte solution. It proves that electrode location has
minimal impact on performance.

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Figure 8: Effect of electrode submerged length into the Figure 9: Impact of distance between the electrodes on cell
electrolyte on cell performance performance
The resistance of electrolyte depends on various factors. One
of them would be distance between anode and cathode
electrode. The longer the distance between the electrode, the
tougher the situation should be for OH- ions to move from one
electrode to another and releases its electron. When the space
between the pair of electrodes decreases the performance of the
cell increases due to the resulting decreases in electrical
resistance between the electrodes that in turn leads to an
increase in the electrical current [15]. To obtain the result how
this distance may impact on cell performance, we construct the
experiment number 10 in Table 2. Figure 9 shows that cell
performance has almost linear relation with distance between
electrodes.
The ohmic performance of water electrolysis should be
strongly depends on concentration of the electrolyte solution.
The higher concentration means that higher number of
available reactant at the electrode surface area for reaction at
same power input which leads to increase in hydrogen
production efficiency. Figure 10 corresponding to Figure 10: Effect of electrolyte concentration on water
experimental number 11 in Table 2 shows that electrolyte electrolysis cell
concentration has strong effect on cell performance. This
behavior is attributed to the increase in the electrical We do not need to conduct experiments for experiment number
conductivity of the solution due to the increase in the 12 in Table 2. For our limitation for further different design of
concentration of the potassium hydroxide. Increasing the the electrodes, we only did only one straight design electrode
electrical conductivity leads to an increase in the electrical experiment.
current passing through the solution and consequently to a A more popular way of improving electrolysis efficiency is
decrease of requirement of less voltage at same current density increasing the process temperature, which lowers the voltage
operation. required to electrolyze the water. Heating the electrolyte
provides the extra energy gain by the electrolyte and leads to
lower the necessary Gibb’s free energy, which makes the
reaction to happen. Temperature effect was studied at room
temp. (~26°C) and 610C and the comparison result is plotted in
Figure 11. At observed from the data, cell performance
increases with temperature due to reduced reversible potential,
kinetic loss and ohmic loss.

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Individual Value Plot of Voltage

90% CI for the Mean
4.0

3.5

3.0
Voltage

2.5

2.0

1.5

1.0
Temp Room 61 Room 61 Room 61 Room 61
CD_set 3 32 158 316

Figure 11: Effect of temperature on water electrolysis. (CD and CI inside the plots refer to current density and confidence
interval respectively)

5. Conclusions [4] Wei G, Wang Y, Huang C, Gao Q, Wang Z, Xu L.

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