See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/292577629

International Journal of hydrogen Energy

Article  in  International Journal of Hydrogen Energy · January 2016

CITATIONS READS

3 2,257

4 authors, including:

Cian O'Reilly John Cassidy

Technological University Dublin - Tallaght Campus Technological University Dublin - City Campus
2 PUBLICATIONS   6 CITATIONS    118 PUBLICATIONS   1,485 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

CREST Research Papers View project

Focas Research Institute View project

All content following this page was uploaded by John Cassidy on 31 March 2021.

The user has requested enhancement of the downloaded file.

 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 4 1 ( 2 0 1 6 ) 2 1 9 7 e2 2 0 1

Available online at www.sciencedirect.com

ScienceDirect

journal homepage: www.elsevier.com/locate/he

Operation of an inexpensive bipolar alkaline

electrolyser producing a mix of H2/O2 fuel

Cian O'Reilly a, Michael Farrell b, David Harvey c, John Cassidy a,*

a
School of Chemical and Pharmaceutical Sciences, Dublin Institute of Technology, Kevin St., Dublin D08 NF82,
Ireland
b
School of Electrical and Electronic Engineering, Dublin Institute of Technology, Kevin Street, Dublin D08 NF82,
Ireland
c
NuNrg Reformers Ltd, Fardrum, Athlone, Co., Westmeath, Ireland

article info abstract

Article history: This paper describes the operation of a bipolar alkaline electrolyser which is at least 60%
Received 13 October 2015 efficient at evolving a hydrogen/oxygen mix. The electrolyser consists of 12 stainless steel
Received in revised form (SS316L) electrodes of area 5400 cm2 in a sealed polypropylene unit. A pulsed potential
20 November 2015 waveform is applied to the electrodes in 0.12 M KOH electrolyte yielding on the order of
Accepted 23 November 2015 320 dm3/kWh of the hydrogen/oxygen mix. This compares favourably with commercial
Available online 18 December 2015 devices that are designed to yield hydrogen alone.
Copyright © 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
Keywords: reserved.
Hydrogen oxygen mix
Bipolar alkaline electrolyser

Two main types of industrial electrolyser units are being

Introduction
As fossil fuels run out at an alarming rate, exacerbated by an
increase in living demand in China and India, there is still no
great progress in identifying alternatives. While fracking and
nuclear power have competed with renewable forms of en-
ergy such as wind, tide and solar, there is scope for the so
called Hydrogen Economy [1] to expand.
The majority of hydrogen is synthesised using steam
reforming methods, and only a small quantity using elec-
trolysis; about 4% according to numerous papers [2,3]. Water
electrolysis is attracting greater interest because it offers the
possibility of obtaining large amounts of hydrogen without
the consumption of fossil fuels, emission of pollutant gases or
use of nuclear power [4].
produced today. The first uses a high KOH concentration
(25%e35%wt/wt). In this alkaline electrolyser, the hydroxide
ion is the charge carrier and the reactions are [5,6].
Anode 2OH
ðaqÞ #1=2O2ðgÞ þ H2 O þ 2e
(1)
Cathode H2 OðaqÞ þ 2e
#H2ðgÞ þ 2OH
(2)
In some cases the distance between the anode and cathode
is about 1 mm, and these are termed zero gap alkaline water
electrolysers [7].
With regard to the structure of the alkaline electrolyser
cells there are two types. Monopolar alkaline electrolysers
have alternate electrodes that are directly connected to
opposite terminals of the DC power supply. This yields a
number of cells that are in parallel with each other.

* Corresponding author. Tel.: þ353 1 4024779; fax: þ353 1 4024989.

E-mail address: john.cassidy@dit.ie (J. Cassidy).
http://dx.doi.org/10.1016/j.ijhydene.2015.11.121
0360-3199/Copyright © 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
2198 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 4 1 ( 2 0 1 6 ) 2 1 9 7 e2 2 0 1
The second type are bipolar alkaline electrolysers which
consist of a stack of electrodes, only two of which are connected
to the power supply [5]. The two electrodes on either end of the
stack are connected, while the intermediate isolated electrodes
act as both anode on one side and cathode on the other.
In another type of electrolyser, which is not as popular,
there is a membrane which allows Hþ pass from the anode
compartment to the cathode compartment. These are proton
exchange membrane electrolysers (PEM), which are typically
less that 40% efficient [8,9].
The reactions are:
Anode H2 O#1=2O2 þ 2Hþ þ2e

Cathode 2Hþ þ 2e
#H2ðgÞ
For electrolysers, experimental variables such as the na-
ture of anode and cathode, electrode porosity, temperature,
type of electrolyte and nature of the membrane all have been
varied to optimise the efficiency of gas generation.
The majority of electrolysers have systems in place which
allow the oxygen and hydrogen to be separated. In fact the
quality of hydrogen from electrolysers in general is of much
higher quality that obtained from steam reforming. This
hydrogen can be used for heating, fuel cells [10] or transport
[11].
There have been a limited number of publications on the
generation of the hydrogen/oxygen mixture using alkaline
electrolysers [12]. In particular the purpose of generating the
mixed gases was primarily for use as a fuel additive for com-
bustion engines [13e16].
Efficiency of the process
Generally authors have merely been interested in the
hydrogen generated alone and they would have found a
maximum volume of 340 dm3 of H2/kWhr (or 2.94 kWhr for
1 Nm3 of H2). According to Marini [6], advanced alkaline
electrolysers can yield about 227 dm3 H2/kWh. The aim of this
present work is to describe a bipolar alkaline electrolyser and
its characteristics for mixed H2/O2 production, which can be
used as a fuel.
Experimental arrangement
A solution of 0.12 M KOH was prepared using deionised water.
The cell takes the form of 12 electrodes, each 15 cm  15 cm.
These are assembled in a polypropylene cell, which is linked
to a reservoir containing approximately 3 L of electrolyte. The
electrodes are stainless steel, SS316L. The dimensions of the
cell are approximately 20 cm  10 cm  17 cm high and the
gross weight is 0.8 kg, making it portable. Initially a voltage of
28 V is applied by the DC power supply into the controller. The
voltage is modified by the controller [17], which was con-
structed in house, to give an pulse width modulated waveform
as shown in Fig. 1. As the temperature of the cell rises the
conductivity increases and the duty cycle of the waveform,
ton/T, is reduced in order to maintain an approximate constant
average current I avg.
In Fig. 1 there is an indication of the applied potential from
the controller, Imax is the peak current and therefore the
average current Iavg ¼ Imax*(ton/T), where ton is the time
when the current is on and T is the total period. Vmax is the
peak voltage and so the average cell power is given by equa-
tion (5).
Pavg ¼ Vmax*Imax*ðton=TÞ or Pavg ¼ Vmax*Iavg (5)
The cell peak voltage and average current are measured
using an oscilloscope and the above equation is used to
determine the cell average power. This is then used in the
calculation of the cell efficiency i.e volume of gas produced per
(3)
kWh. The power supply was a Rapid SPS-9602 Switching Mode
power Supply, PSU, (input 240 V AC, 50 Hz, output 1e30 V DC,
(4) 30 A). Typical current densities for this device are about
2 mA/cm2. The current was measured using a Fluke 375 clamp
meter. The voltage was measured using a Waveteck voltmeter
and a Tectronix THS 720 p digital oscilloscope.
Safety information
0.12 M KOH is corrosive, but while in the cell poses no danger.
The concentration is less than has been used elsewhere [5,6].
The hydrogen evolved is light and diffuses upward rapidly and
should not pose a flammability threat if handled properly.
Hydrogen is very light (density is 6.9% that of air) and is more
diffusive than air (by 4 times) and gasoline (by 12 times). A leak
dissipates rapidly as it rises from the source, reducing the risk
of explosion. In the event of a fire, the flame does not radiate
heat, unless used as a constant flame or ignited in a closed
space [11].
Results and discussion
The cell is sealed with a 2 mm neoprene gasket and is linked to
a reservoir. Initially the cell is flooded with electrolyte. How-
ever once the electrolysis starts a void comprising the
hydrogen/oxygen mix develops at the top of the cell forming a
headspace. The key to the design of the cell is that the elec-
trodes fit into grooves in the polypropylene casing snugly,
preventing any current leaking from one compartment to
another.
Tables 1 and 2 show how the cell operates over 2 h at
approximately 9 A and 12 A respectively. As the temperature
increases and the water evaporates, the KOH concentration
increases, making the current control system essential. The
volume of the oxygen/hydrogen mix was found by displace-
ment. Looking at Tables 1 and 2, it is clear that the flow rate of
the generated gases can be varied by changing the current. As
the current increases from approximately 9 A to approxi-
mately 12 A, the time taken to generate 2 dm3 of gas drops
from 90 s to 80 s.
In Table 1 the average gas production is 319 L/kWh (63%
efficient), with a high of 331 dm3 (65% efficient), and Table 2
the average gas production is 311 L/kWh (61% efficient). The
maximum theoretical efficiency is calculated as
510 dm3/kWh. These were calculated using peak voltage and
average current. Broadly the typical efficiency is at least 60%.
 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 4 1 ( 2 0 1 6 ) 2 1 9 7 e2 2 0 1 2199

Fig. 1 e Plot of current, voltage and power against time. ton is the length of time when the pulse is on and T is the total
period. The frequency is 1.5 kHz.

This efficiency can be compared to the closest system in
the literature to this current work. Symes et al. [12] generate a
mix of oxygen and hydrogen using SS316 or Ni, 0.1MKOH and a
current density of 10 mA/cm2. They obtain 7 cm3 of gas per
second at 4 V and 40 A. This calculates to about 156 dm3/kWh,
which is about 31% efficient.
Why is ours more efficient? Although the current density in
the paper by Symes is 10 mA/cm2, the total current is greater
at 40 A. Any resistance in the system would cause a large
voltage drop since the electrolyte concentration is so small.
Such large currents put a huge demand on the rate of reaction
at the electrodes and the activation overpotential will be great.

Table 1 e Cell efficiency for the cell operating at approximately 9 A.

Time (min) Peak voltage (V) Average current (A) from PSU Temp ( C) 2 dm3 displacement Cell efficiency
Time (sec) dm3/kWh
1 27.8 9.98 32.7 88 294.9
15 27 9.52 40 90 311.2
30 26.6 9.38 45.1 89 324.2
45 26.6 9.48 49.9 89 320.8
60 26.6 9.27 52.4 91 320.9
75 26.2 9.47 52.7 88 329.8
90 26.2 9.43 55.2 88 331.2
105 26.2 9.39 57.9 91 321.6
120 26.2 9.48 59.4 91 318.5
2200 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 4 1 ( 2 0 1 6 ) 2 1 9 7 e2 2 0 1

Table 2 e Cell efficiency for the cell operating at approximately 12 A.

Time (min) Peak voltage (V) Average current (A) from PSU Temp ( C) 2 dm3 displacement Cell efficiency
Time (sec) dm3/kWh
1 26.8 11.51 24 77 303.1
15 26 11.48 30.9 81 297.8
30 25.2 11.9 36.8 79 303.9
45 24.4 12.1 44.3 79 308.7
60 24.4 11.96 49.5 80 308.4
75 24 11.8 52.9 79 321.8
90 24.4 11.88 55.6 80 310.5
105 23.8 11.91 60.7 80 317.5
120 23.8 11.98 61.7 81 311.8
135 23.6 11.89 62.6 81 316.8
150 23.4 11.75 64.3 80 327.3

Studies have shown that for an alkaline electrolyser, with
Ni electrodes in KOH, that bubble formation varies with cur-
rent density and electrolyte concentration [18]. At 22 C in
0.5 M KOH, the bubble diameter increased from 0.6 mm to
about 1 mm, for both O2 and H2, whe the current density
increased from 0.3 to 0.6 mAcm
2. It was found that at very
high current density (200 mAcm
2, that a curtain of fine
bubbles formed at the Ni surface leading to a resistive barrier.
It was found that by increasing the KOH electrolyte concen-
tration from 0.5 M to 4.0 M caused a decrease in the critical
diameter of the bubbles due to an increase in viscosity. In the
current work at low electrolyte concentration ( 0.12 M) and
relatively low current densities, the bubble evolution is
efficient.
Commercial devices generally produce hydrogen alone. If
we take the ratio of generated hydrogen to oxygen to be 2:1, we
can predict the efficiencies of commercial systems [4]. Com-
mercial systems have a range from 4.3 to 7.5 kWh/Nm3 for H2
generation. If we include the oxygen, these values correspond
to 350e200 dm3/kWh respectively. The most efficient is a bi-
polar electrolyser manufactured by ELT at 350 dm3/kWh [4].
Our device compares favourably to this commercial system.
One other system in the literature [13] indicates that 5 dm3 of
mixed gas is produced at 12 V and 10 A. However this yields an
unrealistic 2500 dm3/kWh.
Conclusions
This is one of the few studies in the literature that evaluates
mixed evolved gases. There are some conclusions that can be
drawn from this work.
 The current density used in this cell (2 mA/cm2) is lower
that some other electrolysers eg 1A/cm2 in Refs. [19,20].
This ensures reliable operation and long service of the
electrodes.
 This work uses a much cheaper electrode that some of the
such as Pt or RuO2 in Ref. [21]. The SS316S is a good
competitor with Raney Nickel, used in commercial
electrolysers.
 The electrolyte concentration in this work is less than
others in the literature. ex 4 M NaOH [20] and 25e35% wt/wt
[5,6]. This makes the device safer for commercial use.
 The efficiency of our system (up to 65%) compares
favourably with the best commercial electrolyser (69%).
 Most electrolysers focus on either oxygen or hydrogen
generation, while this practical cell does both. Our cells can
be connected in parallel, producing whatever quantity of
gas is required.
 The device is inexpensive and portable.
This device can be used as a source of fuel, either for
combustion (since it has the ideal stoichiometry of H2:O2) or in
a combustion engine, where it can be supplied to the engine
via the air intake valve. The device is currently being evalu-
ated for use in HGVs and buses. Because the cell operates at a
relatively high temperature (approx. 60  C), water vapour is
also introduced into the engine, reducing the combustion
temperature and thus NOx emissions. Work has shown that
when such a gas is introduced into the air intake of a diesel
engine, the emissions are improved through lower levels of
CO and unburnt hydrocarbons [14]. In addition the fuel con-
sumption decreases [15].
Appendix
In the case of reactions (1) and (2), there are 1.5 mol of gas
produced with the passage of a total of 2 electrons. Faraday's
Constant states that there are 96,485 coulombs of charge per
mole of electrons. Since C ¼ Amps * secs, then.
Amps hours per mole of gas is 2 * 96,485/(1.5 * 3600).
Taking the minimum voltage to generate H2 and O2 to be
1.23 V and taking 1 W ¼ 1 V * 1 A then (2 * 96,485 * 1.23)/
(1.5 * 3600 * 1000) kWh per mole of gas ¼ 0.0439 kWh/mole of gas
or taking the volume of 1 mole of gas at standard temperature
and pressure to be 22.4 L one obtains 0.0439 kWh/(22.4 dm3 gas)
or 22.4/0.0439 dm3/kWh ¼ 510 dm3/kWh ¼ 0.51 m3/kWh. since
1 W * 1s ¼ 1 J and 1000 W * 3600s ¼ 3600 kJ ¼ 1 kWh.
references
[1] Bockris JO. The origin of ideas on a hydrogen economy and
its solution to the decay of the environment. Int J Hydrogen
Energy 2002;27:731e40.
 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 4 1 ( 2 0 1 6 ) 2 1 9 7 e2 2 0 1
[2] Balat M. Potential importance of hydrogen as a future
solution to environmental and transportation problems. Int J
Hydrogen Energy 2008;33:4013e29.
[3] Kothari R, Buddhi D, Sawhney RL. Comparison of
environmental and economic aspects of various hydrogen
production methods. Renew Sustain Energy Rev
2008;12:553e663.
[4] Ursa A, Gandia LM, Sanchis P. Hydrogen production from
water electrolysis: current status and future trends. Proc IEEE
2012;100:410e26.
[5] Zeng K, Zhang D. Recent progress in alkaline water
electrolysis for hydrogen production and applications. Prog
Energy Combust Sci 2010;36:307e26.
[6] Marini S, Salvi P, Nelli P, Pesenti R, Villa M, Berrettoni M, et al.
Advanced alkaline water electrolysis. Electrochim Acta
2012;82:384e91.
[7] Pletcher D, Li X, Wang S. A comparison of cathodes for zero
gap water electrolysers for hydrogen production. Int J
Hydrogen Energy 2012;37:7429e35.
[8] Carmo M, Fritz DL, Mergel J, Stolten D. A comprehensive
review on PEM water electrolysis'. Int. J Hydrogen Energy
2013;38:4901e34.
[9] Xu W, Scott K. The effects of ionomer content on PEM water
electrolyser membrane electrode assembly performance. Int
J Hydrogen Energy 2010;35:12029e37.
[10] Sorensen B. Hydrogen and fuel cells. London,(: Academic
press; 2005.
[11] Sharma S, Ghoshal SK. Hydrogen the future transportation
fuel- from production to applications. Renew Sustain Energy
Rev 2015;43:1151e8.
View publication stats
2201
[12] Symes D, Al-Duri B, Bujalski W, Dhir A. Cost effective design
of the alkaline electrolyser for enhanced electrochemical
performance and reduced electrode degradation. Int J Low
Carbon Technol Adv Access 2013:1e8.
[13] Yilmaz CAC, Uludamar E, Aydin K. Effect of hydroxyl (HHO)
gas addition on performance and exhaust emissions in
compression ignition engines. Int J Hydrogen Energy
2010;35:11366e72.
[14] Selvi Rajaram P, Kandasamy A, Arokiasamy Remigious P.
Effectiveness of oxygen enriched hydrogen-HHO gas addition
on direct injection diesel engine performance, emission and
combustion characteristics. Therm Sci 2014;18:259e68.
[15] Musmar SA, Al-Rousan AA. Effect of HHO gas on combustion
emissions in gasoline engines. Fuel 2011;90:3066e70.
[16] Chaiwongsa P, Pornsuwancharoen N, Yupapin PP. Effective
hydrogen generator testing for on-site small engine. Phys
Procedia 2009;2:93e100.
[17] D., Harvey, Patent applied 2015/0359.
[18] Zhang D, Zeng K. Evaluating the behaviour of electrolytic gas
bubbles and their effect on cell voltage in alkaline water
electrolysis. Ind Eng Chem Res 2012;51:13825e32.
[19] Wu X. Scott K,CuxCo3-x O4 ( 0x 1) nanoparticles for oxygen
evolution in high performance alkaline exchange membrane
water electrolysers. J Mater Chem 2011;21:12344e51.
[20] Li X, Walsh FC, Pletcher D. Nickel based electrocatalysts for
oxygen evolution in high current density alkaline water
electrolysers. Phys Chem Chem Phys 2011;13:1162e7.
[21] Pletcher D, Li X, Wang S. A comparison of cathodes for zero
gap alkaline water electrolysers for hydrogen production. Int
J Hydrogen Energy 2012;37:7429e35.