PEM ELECTROLYSIS HYDROGEN PRODUCTION SYSTEM

DESIGN FOR IMPROVED TESTING AND OPTIMIZATION

N.V. Dale 1,*, C. Y. Biaku1, M. D. Mann1, H. Salehfar 2 , A. J. Peters2

Abstract

This paper describes an improved experimental system for a proton exchange

membrane (PEM) electrolyzer to produce hydrogen under precise controlled
conditions. This system design allows increased control and monitoring of various
electrolyzer parameters, such as temperature and pressure, over a commercial off-
the-self system. Temperature control enables finding the optimum operating
temperature for a corresponding current density. This will facilitate peak
efficiency to be obtained regardless of operating current, which is beneficial in
variable power sources such as renewable energy. This system also allows the
study of pressure behaviour and hydrogen production of an electrolyzer stack at
different operating temperatures. Additionally, this system can be equipped for
compressed hydrogen storage by using an electrochemical compressor with an
experimental thermoelectric humidity control set up.

Key words: PEM electrolysis, hydrogen, deionized water.

1. Introduction
The problems associated with fossil fuel and the world’s growing dependency on
it has necessitated the search for an alternative. Among all, hydrogen seems to be
a perfect alternative. It is seen as a potential energy carrier for the future. High
specific enthalpy of combustion makes it a potential candidate as a fuel for
transportation. The need to mitigate the effects of green house gases can be
fulfilled with water electrolysis hydrogen production using renewable energies
such as wind, solar. Proton exchange membrane (PEM) water electrolysis using
renewable energies has been identified as a self-sustained and clean energy
system. Water electrolysis using renewable energy is currently not a cost
competitive method of hydrogen production compared to other technologies,
however considering the environmental and social benefits it is seen as ideal
method of hydrogen production. A raw material for this hydrogen production,
water, is abundantly available on earth.
The University of North Dakota (UND) has established a test facility to conduct
research into renewable hydrogen production. UND was awarded a three year
grant for this research by the Department of Energy Experimental Program to
Stimulate Competitive Research (EPSCoR). This test facility consists of a 6 kW
PEM electrolyzer system with specially designed control system and two 1.2 kW
PEM fuel cells.

1
Department of Chemical Engineering, University of North Dakota, Grand Forks, ND 58202.
2
Department of Electrical Engineering, University of North Dakota, Grand Forks, ND 58202.
* Corresponding author: Tel: +1-701-777-2553,Fax: +1-701-777-3773, [email protected]
The system is designed for PEM electrolysis hydrogen production allowing
advanced control and monitoring over parameters such as temperature and
pressure. This helps determine the optimum operating condition for PEM
electrolyzer at various pressures.

2. PEM Electrolysis System Design

The overall system is designed to allow the precise control over operating
temperature, hydrogen system pressure, water resistivity, water flow, stack
current and safety. Along with the temperature, pressure and current-voltage
sensors, the main components of the system are a 6 kW PEM electrolyzer stack,
hydrogen-water phase separator, two 6 kW Xantrex DC power supplies which are
capable to deliver up to 200 A to the electrolyzer, a temperature controlled water
loop, a two-tube desiccant drying system and a back pressure regulator to control
the operating pressure. Figure 1 shows the overall PEM electrolysis system.
A National Instruments (NI) Signal conditioning Extension for Instrumentation
(SCXI) data acquisition system is used with Lab View program to monitor,
control and record operational data. A safety interlock loop allows system
operation only after series of vital components status check.
Water quality is important aspect of PEM electrolyzer. The manufacturer defines
minimum water resistivity to be 1MΩ-cm [1]. High resistivity is associated with
water purity. Contaminants such as electrolytes and ions found in water make it
conducting for electricity. Removing these contaminants increases the resistivity
of the water. To remove these contaminants and ions the water is filtered and
deionized (DI) using mixed bed resins and carbon filters. To avoid any further
contamination of DI water, polypropylene tubing is used before it enters the
electrolyzer. The polypropylene reservoir tank also used as a oxygen-water
separator.
A temperature control unit (chiller) controls the inlet DI water temperature
thereby providing control of the operating temperature of electrolyzer. This
system is designed to allow higher temperature testing by maintaining DI water
temperature with the chiller and a heater provided in oxygen-water phase
separator. The mixed bed filters currently limit the operation to roughly 60°C: at
this point resins used for deionization breaks down. For this reason to perform
high temperature tests, first the resistivity of water is raised higher than the
required level and then the temperature of DI water is raised with a heater. This
temperature controlled DI water, with the help of chiller, is then supplied to the
stack bypassing the mixed bed resins and carbon filter. This allows tests at desired
temperature and water quality. The resistivity of the DI water is monitored in the
oxygen-water phase separator, before pumping water into the stack. The flow of
the DI water to the stack is controlled between 1.5 to 2.5 gpm. Except at high
temperatures, if resistivity is lower than required, then water is cycled through
mixed bed filters again until desired resistivity is achieved. Two combustible gas
detectors monitor the safe operation in the test facility room. One is mounted in
the canopy hood directly above the experimental table and another to the oxygen
phase separator to monitor the accidental mixing of oxygen and hydrogen. Both
detectors are set at 10% of lower flammability limit (LFL) of hydrogen in air to
alarm and at 20% of LFL of hydrogen in air to initiate shutdown process using
data acquisition system and software program.

Figure 1: Main components of PEM electrolysis system.

The interlock loop has designed to insure the safe operation of the system. In the
event, combustible gas detector senses the preset limit of % lower flammability
limit (LFL) while system is operating, the control software sense the alarm signal
to turn off the system. In any event, the interlock loop devices interrupt the loop;
power supplies output are turned off. Also, in any fault condition, power supply to
stack can be turned off by pressing manual emergency stop. If system is running
and the emergency stop is pressed the pressurized hydrogen is vented out through
a solenoid valve. This interlock loop enables or disables the power supplies to
electrolyzer stack depending on the state of the electromechanical relays which
are wired to combustible gas detector [2].

3. Operation
The DI water loop maintains the temperature and resistivity of water using the
chiller and carbon mixed bed filters respectively. The oxygen phase separator is
equipped with level sensing float, temperature, resistivity and combustible gas
detector sensors to monitor system performance and safety. After achieving
desired resistivity and temperature of DI water, the stack is supplied with power
using two DC power supplies and DI water run through the stack. Before entering
the stack, DI water goes through 10µm filter and sensing stage where its
temperature, flow, pressure and resistivity are monitored again for stable and safe
operation. Hydrogen gas coming out of the cathode side is separated from liquid
water in high pressure hydrogen-water separator. A coalescing filter, immediately
following the separator, removes most of the remaining liquid water from
hydrogen gas. An automatic drain connected to the coalescing filter collects and
recycles the DI water back to external reservoir with the help of hydrogen system
pressure. A two tube desiccant drying system performs the remaining drying
process of the hydrogen gas. Dry hydrogen product gas then enters the sensing
stage equipped with mass flow, temperature, pressure and dew point sensors. A
back pressure regulator can be adjusted to maintain the hydrogen system pressure.
Oxygen from anode side is separated from DI water in oxygen phase separator
where oxygen is then vented out using a check valve and DI water is reused.

4. Results and Discussion

The experimental system built at UND was designed to allow control of various
system parameters and enables detailed study of PEM stack performance and
stack characterization, model verification and improved interfacing to renewable
energy sources. This system is capable of controlling parameters such as water
resistivity, DI water flow rate, DI water temperature to stack, hydrogen system
pressure, stack current, and desiccant tube drying cycle.
The off-the-shelf HOGEN40® stack is rated to produce 1.05 Nm3 of dry hydrogen
gas at 200 psig (13.8 atm) per hour. The PEM stack consist of 20 cells connected
in series having an active area of 0.093 ft2 (86.4 cm2). This results in maximum
current density of 1.6 A cm-2 at 140 A.

Figure 2: IV characteristic curves at constant cathode pressure (165 psi) at

temperature from 10 °C to 60 °C. ∗

∗
All temperatures mentioned in the figure have +/- 0.4 °C error margins. For simplicity they are
rounded to whole number.
Figure 2 is a IV characteristic of PEM stack at different temperatures. As shown
for a given current, voltage drops as temperature increases. This increases stack
efficiency as activation and ohmic losses are reduced at increased temperature.
These losses are known as irreversible potentials. At higher temperature the stack
performs better and produces more hydrogen at a given current. These IV
characteristics are used to extract coefficients which represent stack parameters as
a function of temperature for PEM stack modelling. Stack parameters such as
charge transfer coefficient, exchange current density at anode and cathode and
cell conductivity are extracted at various temperatures. This information helps to
understand the stack operation better at various temperatures [3].
The beneficial effect of temperature can also be verified by monitoring increase in
pressure in first few minutes of operation at various temperatures by setting the
cathode side back pressure regulator at varying pressures. As shown in figure 3,
pressure increases more rapidly at higher temperature indicating more hydrogen
production.

Figure 3: Pressure rise characteristic for first minute when cathode pressure set at
165 psi using back pressure regulator
More studies are being conducted to investigate the pressure rise at the beginning
of operation. The expected pressure rise is logarithmic with time, but the
beginning pressure rise showed an ‘S’ shaped nature, shown in figure 4, which
needs detailed study to explain this behavior. The prime suspect for this ‘S’
shaped curve is physical phenomena in stack such as expansion/contraction of
electrode membrane assembly under influence of sudden pressure increase or
other components between the stack and back pressure regulator like the high
pressure water-hydrogen separator, coalescing filter and two tube desiccant dryer.
Figure 4: Pressure rise behavior for first few seconds when cathode pressure set at
165 psi using back pressure regulator.

12

10
pressure psi

0 1 2 3 4 5 6
sec time

Figure 5: Pressure rise behavior for first 7 seconds at 30°C, cathode pressure set at
165 psi.
Figure 5 shows the ‘S’ shaped rise in pressure at 30°C for the first seen seconds
of the operation. This rise is observed at all temperatures of operation. This rise is
observed only upto 12 psi above atm at the beginning of operation. After a few
seconds the pressure rises almost linearly.
5. Additional work
Hydrogen from electrolysis using renewable energy sources has substantial
environmental benefits. Some applications of hydrogen such as fuel cells,
compressed storage in metal cylinders and power plant electric generator cooling
requires hydrogen with almost no water vapor which corresponds to low dew
point. The renewable hydrogen production experimental system at UND is being
equipped to a novel thermoelectric humidity control set up. This technique
utilizes the Peltier effect to reduce and control the dew point of hydrogen gas by
water condensation and desublimation. This thermoelectric cooler based system
can allow controlling the dew point to match the variable flow rate of hydrogen in
renewable electrolysis system [4].
Additionally, UND’s system will be equipped with PEM electrochemical
compressor to compress product hydrogen from PEM electrolyzer. A critical
element limiting hydrogen’s use as an energy carrier is its low volumetric energy
density. It can be overcome by storing gaseous hydrogen in compressed form.
PEM cells can be used to compress the product hydrogen with high efficiency and
no product contamination, an advantage over the conventional hydrogen
compressor [5].The research will be aimed at compression of hydrogen using
PEM cells and subsequent storage in composite tanks. The studies will be done to
address the limiting factors of electrochemical compression like cell internal
resistance, construction of cell hardware and hydrogen back diffusion through the
membrane. Also, the optimized humidification level for stable performance of a
compression PEM cell will be investigated.

6. Acknowledgment
The authors would like to thank Department of Energy’s Experimental Program
to Stimulate Competitive Research (EPSCoR) (Grant No: FE02-04ER 46115) and
the National Science Foundation Research Infrastructure Improvement (Grant
No:EPS-0447679 )for funding this research. Also, Proton Energy Systems and the
National Renewable Energy Laboratory for their continued technical support in
the development of UND’s electrolyzer, hydrogen and fuel cell test facility.

7. References
1. HOGEN® Hydrogen Generation Systems: Technical Specifications, Proton
Energy Systems, Inc., PD-0600-0002 Rev.11.05.
2. Kevin Harrison: Design, Integration and Control of Proton Exchange
Membrane Electrolyzer for Wind Based Renewable Energy
Application,( dissertation) , University of North Dakota, August 2006
3 C.Y.Biaku, N.V.Dale, A.J.Peters,M.D.Mann,H.Salehfar,T.Han: A Semi-
Empirical Study of the Temperature Dependence of the Anode Charge
Transfer Coefficient of a 6 kW PEM Electrolyzer, Int.J.of Hydrogen Energy,
In review.
4. K.W.Harrison, A.J.Peters, C.Y.Biaku, N.V.Dale, M.D.Mann, H.Salehfar:
Hydrogen Dew Point Control Utilizing Thermoelectric Devices, Int. J .of
Hydrogen Energy, In review.
5. R.Srobel, M.Oszcipok, M.Fasil, B.Rohland, L.Jorissen, J.Garche: The
compression of hydrogen in an electrochemical cell based on a PE fuel cell
design, J. of Power Sources, 105(2002)