Solar Energy 78 (2005) 661669

www.elsevier.com/locate/solener

PEM electrolysis for production of hydrogen from

renewable energy sources
Frano Barbir

Connecticut Global Fuel Cell Center, University of Connecticut, 44 Weaver Road, Unit 5233 Storrs, CT 06269-5233, United States
Received 2 June 2003; received in revised form 30 August 2004; accepted 1 September 2004
Available online 19 October 2004
Communicated by: Associate Editor S.A. Sherif

Abstract
PEM electrolysis is a viable alternative for generation of hydrogen from renewable energy sources. Several possible
applications are discussed, including grid independent and grid assisted hydrogen generation, use of an electrolyzer for
peak shaving, and integrated systems both grid connected and grid independent where electrolytically generated hydrogen is stored and then via fuel cell converted back to electricity when needed. Specic issues regarding the use of PEM
electrolyzer in the renewable energy systems are addressed, such as sizing of electrolyzer, intermittent operation, output
pressure, oxygen generation, water consumption and eciency.

2004 Elsevier Ltd. All rights reserved.
Keywords: PEM electrolysis; Hydrogen; Renewable energy

1. Introduction
Hydrogen may play an important role as an energy
carrier of the future (Veziroglu and Barbir, 1991,
1998). Hydrogen may be used as fuel in almost every
application where fossil fuels are being used today, but
without harmful emissions (Barbir and Veziroglu,
1992), with a sole exemption of NOx emissions when
hydrogen is combusted (which, however, can be eectively controlled). In addition, hydrogen may be converted into useful forms of energy more eciently than
fossil fuels. And despite public perception, hydrogen is

Tel.: +1 860 486 6703; fax: +1 860 486 8378.

E-mail address: fbarbir@engr.uconn.edu

as safe as other common fuels (Swain and Swain,

1992; Thomas, 1996; Barbir, 1999a). However, hydrogen
is not an energy source. It does not occur in nature in its
elemental or molecular form. Therefore, hydrogen must
be produced. The most abundant source of hydrogen is
water, but water splitting requires energy, and because
of the laws of thermodynamics, energy required to split
water is higher than energy that can be released from
produced hydrogen. Because of that, hydrogen is like
electricityan energy carrier, a convenient form of energy. From sustainability point of view, a synergy between hydrogen and electricity and renewable energy
sources is particularly interesting.
Although several methods have been and are being
developed for production of hydrogen from renewable
energy sources, the only one currently practical is water
electrolysis. Water electrolysis is a mature technology,

0038-092X/$ - see front matter
2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.solener.2004.09.003

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F. Barbir / Solar Energy 78 (2005) 661669

and it is being used for hydrogen production capacities

ranging from few cm3/min to thousands m3/h. It is relatively ecient (>70%), but because it needs high quality
energy (electricity) hydrogen produced by water-electrolysis is expensive (>$20/GJ). There is a potential to
generate relatively inexpensive hydrogen from hydropower and nuclear plants during o-peak hours. Justi
(1987) proposed large PV power plants in North Africa
to generate hydrogen which could be shipped or piped to
Europe. Ogden and Williams (1989) evaluated solar
(PV) hydrogen option and concluded that hydrogen
could be economically produced from large PV power
plants if the cost of PVs could be brought to $0.2 to
$0.4/Wp. Coluccia et al. (1994) analyzed option of producing hydrogen from hydropower in Zaire and shipping it via pipeline to Southern Europe. A
Hydro-Quebec Hydro-Hydrogen Pilot Project seriously
considered production of hydrogen from hydropower
in Canada and shipping it to Northern Europe via
tankers (Gretz et al., 1990; Drolet et al., 1996).

2. PEM electrolysis
Most of the electrolyzers used today in capacities up
to several thousand m3/h are based on alkaline (KOH)
electrolyte. Another option is to use a proton exchange
membrane as electrolyte. This peruorosulfonic acid
polymer (also known as NaonTM) has been used in
chlor-alkaline electrolysis and also in fuel cells. PEM
electrolysis is a process just reverse of a PEM fuel cell
process (Fig. 1). Water is split into oxygen, protons
and electrons on one electrode (anode) by applying a
DC voltage higher than a thermoneutral voltage

(1.482 V). Protons pass through the polymer electrolyte

membrane and on the cathode combine with electrons
to form hydrogen. Passage of protons through the membrane is accompanied by water transport (electroosmotic drag).
A PEM electrolyzer cell is similar to a PEM fuel
cell. It has a polymer membrane and porous electrodes,
ow elds, current collectors and separator plates, end
plates, bus plates, manifolds. The principle of operation is just reverse of fuel cell operation. However,
the materials are typically dierent from PEM fuel cell
materials. Carbon materials, such as catalyst support,
porous electrode structures (carbon ber paper or carbon cloth) and bi-polar plates, commonly used in fuel
cells cannot be used on the oxygen side of a PEM electrolyzer due to corrosion. PEM electrolyzers therefore
primarily use metallic components (porous structures,
ow elds and separator plates). The catalyst is typically platinum or platinum alloys. Similarly to fuel
cells, individual electrolyzer cells may be stacked into
a stack, in order to get the desired output at a reasonable stack voltage.
Besides the cell-stack, an electrolyzer must have a
power supply/voltage regulator, water supply system,
water circulation pump, watergas separators for hydrogen and (optionally) oxygen, heat exchanger, controls
and instrumentation, including the safety features.
There are only a few PEM electrolyzer manufacturers
today. Fig. 2 shows industrial PEM electrolyzer HOGEN 40 by Proton Energy Systems. This electrolyzer
is intended for industrial hydrogen generation. A version
of it, so called HOGENRE, has been developed for use
in conjunction with renewable energy sources. Table 1
shows HOGENRE specications.

Fig. 1. Schematic representation of PEM electrolysis and fuel cell processes.

F. Barbir / Solar Energy 78 (2005) 661669

663

Fig. 2. HOGEN PEM Electrolyzer by Proton Energy Systems (stack on the left and complete packaged system on the right).

Table 1
Specications of HOGENRE PEM electrolyzer by Proton Energy Systems
Hydrogen output
Max delivery pressure
Hydrogen purity
Water usage
Water quality (min) required
Power consumption
Electrical supply required
Operating environment
Dimensions
Weight
Installation
Controls and automation

0.5 or 1.0 N m3/h

200 bar
>99.9% (optionally >99.999%)
0.5 or 1.0 l/h
deionized (ASTM Type II)
6.6 kW h/N m3
AC: 190240 VAC, 1 phase, 50/60 Hz, 7.2 or 12 kV A DC: 60200 VDC, 150 A (max)
Indoor (optionally outdoor)
97 105 106 cm
220 kg
Plug & play
Fully automatic and unattended

3. Applications
Hydrogen may be produced from PV generated electricity in a variety of applications, and used as a fuel directly, or transmitted through pipelines to the users, or
used to enhance the performance of the PVs by matching their output to the user needs. Each of these applications is briey discussed below.
3.1. Grid independent solar-hydrogen generation
Instead of connecting to the grid, a PV array may be
connected to an electrolyzer to produce hydrogen, which
then may be used in a variety of applications (Fig. 3).

This system circumvents the problems related to the grid

connection and generation imbalance charges. The electrolyzer will be exposed to the variable power supply,
and a DC/DC power regulator must be a part of the
power conditioning and controls box in Fig. 3, in order
to match the electrolyzers voltagecurrent requirements
at any power with minimum conversion losses. Another
option would be to select the PV panels so that their iV
output matches the electrolyzers iV polarization curve
(Spinadel et al., 2002).
If the PV installation is in remote area (and most of
well insolated sites are indeed in remote areas) grid may
not be available at all. In that case delivery of hydrogen
through a pipeline over a long distance may be an

Fig. 3. Schematic diagram of grid independent PV-hydrogen generation.

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F. Barbir / Solar Energy 78 (2005) 661669

option. Some studies suggest that transmission of hydrogen through a pipeline in some cases may be more economical than transmission of electricity over a long
distance (Justi, 1987; Coluccia et al., 1994; Oney et al.,
1994; Keith and Leighty, 2002). Recently, there was a
proposal, accompanied by a techno-economic study, to
ship megawatts of wind power through hydrogen pipelines from the wind farms in the Dakotas to the users
in Chicagodistance of some 1600 km (Keith and
Leighty, 2002).

grid operator. In that case the excess power from the

PVs (above that can be absorbed by the grid in that particular moment) is used to generate hydrogen (Fig. 5).
However, the problems with intermittent electrolyzer
operation and its low capacity factor remain. A variation of this scheme is to operate the electrolyzer at constant power and dump the excess power from the PV
power plant into the grid (o course providing there is
enough absorbing capacity in the grid).
3.4. Integrated PV-hydrogen utility energy system

3.2. Grid-assisted PV-hydrogen generation

If grid is available, one way to eliminate problems
with intermittent electrolyzer operation is to combine
the PVs with an input from the grid (Fig. 4). The power
conditioning/controls unit facilitates that the electrolyzer receives constant power DC input, by combining
the output from the PVs with the required input from
the grid. This way the electrolyzer may operate all the
time at its design point. The capacity factor may reach
high 90s (the only down-time would be for maintenance), which would signicantly improve economics,
i.e., reduce the cost of hydrogen.
3.3. PVs for grid-electricity and hydrogen generation
An electrolyzer may be used to peak shave the output from the PV power plant if that is required from the

One way to deliver a constant or any required load

prole to the grid is to equip the PV array or PV power
plant with an energy storage device, such as a regenerative fuel cell (a combination of electrolyzer and a fuel cell
with hydrogen storage), as shown in Fig. 6. The electrolyzer and fuel cell functions may be included in a single
stack (unitized version) or in two separate stacks (discrete version). In order to ll the hydrogen tank, a compressor may be required or the electrolyzer may be
designed to provide high pressure. Proton Energy Systems reported operating pressures with PEM electrolyzers up to 200 bar (Anderson et al., 2002; Barbir et al.,
2002). The power conditioning and controls unit has
an extremely complex function in this conguration. It
must direct power from the PVs to either the grid or
the electrolyzer, switch to fuel cell power when there is
not enough power from the wind turbine, and provide

Fig. 4. Schematic diagram of grid-assisted PV-hydrogen generation.

Fig. 5. Schematic diagram of PV installation for grid-electricity and hydrogen generation.

F. Barbir / Solar Energy 78 (2005) 661669

665

Fig. 6. Schematic diagram of integrated PV-hydrogen utility energy system.

voltage regulation, both from the PVs to the electrolyzer

and from the fuel cell to the grid. The renewable fuel cell
system is typically less costly than a battery bank for
high power/long duration storage, approximately above
5 kW h (Barbir et al., 2002). Due to presently high costs
of electrolyzers and fuel cells and a low capacity factor
in this conguration, the cost of delivered electricity
would be several times higher than the cost of PV generated electricity (Barbir, 1999b), even when the generation imbalance charges are taken into account.
Therefore, this conguration may be used only where
the quality of delivered electricity justies the cost.
3.5. Grid independent integrated PV-hydrogen energy
system
A similar system may be used for autonomous, grid
independent power supply (Fig. 7). In this case, energy
storage is an imperative, and the regenerative hydrogen
fuel cell may be competitive with other energy storage
options (batteries, ywheel, compressed air, pumped hydro, ultracapacitors, etc.). The only dierence between
this and the previously described system is in the power
conditioning and control unit, which in this case does
not have to synchronize with the grid, but it has to provide desired AC or DC voltage outputs. One option is to
use PV-generated hydrogen as a fuel for cooking and
heating in the house and/or for a fuel cell or hydrogen
combustion engine powered vehicle (this may be an

attractive option in a remote location where fuel delivery

is not regular).
Similar systems have already been demonstrated in
USA, Germany, Italy, Finland, Switzerland, Spain and
South Korea (Dienhart and Siegel, 1992; Rosa et al.,
1994; Galli et al., 1994; Collier, 1994; Szyszka, 1996;
Oud and Steeb, 1996; Lehman et al., 1997; Vanhanen
et al., 1998; Hollmuller et al., 1998). The power output
of existing demonstration projects varies from 1 kW to
350 kW.
This system may also incorporate a wind turbine for
added security and versatility of power supply. Combined wind and solar (PV) systems are in operation at
the Desert Research Institute (Reno, Nevada), and at
the Hydrogen Research Institute (HRI), at the Universite du Quebec, Trois Rivieres (Agbossou et al., 2001).
These independently conceived systems use both photovoltaics and wind turbines to generate hydrogen fuel.
They are relatively small systems using wind/solar
hydrogen generation with a compressed hydrogen storage system, 5 kW electrolyzers, and incorporating a fuel
cell which regenerates the electricity. Both use a combination of battery and hydrogen energy storage, in which
a small battery bank acts as an energy buer, and the
bulk of the energy storage is in the form of hydrogen.
A system consisting of an electrolyzer, fuel cell, and
hydrogen and oxygen tanks has been proposed for a high
altitude unmanned aircraft (Mitlitsky et al., 1993). Such
an airplane would be powered by electric propellers using

Fig. 7. Schematic diagram of grid independent integrated PV-hydrogen energy system.

F. Barbir / Solar Energy 78 (2005) 661669

PVs placed on the top of the wings. Excess power during

the day would be used to electrolyze water into hydrogen
and oxygen, which could be stored in the structural elements for the wing, and then used during the night in a
fuel cell to generate electricity for aircraft propulsion.
This process could continue day after day without need
to bring the aircraft down. Such an aircraft would be
far less expensive than satellites. In this case, the eciency and the mass of the electrolyzer, fuel cell and
hydrogen and oxygen storage are critical for accomplishing the mission. This energy storage system has potential
to be much lighter than the batteries, with specic energy
in excess of 400 W h/kg, and when hydrogen and oxygen
are stored in structural elements with little additional
weight energy density may exceed 700 W h/kg.
A similar system is used in a water rocket concept
(Mitlitsky et al., 1999). It makes sense from safety and
weight points of view to carry water into the orbit,
and then use PVs to generate electricity to electrolyze
water into hydrogen and oxygen. These gases would
be stored for use as propellants for repositioning the satellite and for electricity generation via fuel cell during
periods when the PVs are not insolated.

4. Issues
Operation of a PEM electrolyzer in conjunction with
renewable energy sources, and particularly with a PV
panel or array, has several specic issues that will be discussed below.
4.1. Relative sizing of an electrolyzer and PV array
An electrolyzer may be sized to receive all the power
generated from a PV array, but it would operate with
the same capacity factor as the PV array, which is determined by the sun availability. Capacity factor is a coefcient of utilization of installed capital, and therefore it
is an important factor in determining the economics of
any power generating or energy conversion device. A
more economical option may be to size the electrolyzer
at a power lower than the PV maximum power output.
In that case some of the power from the PV would be
unutilized, or stored in the batteries, but the electrolyzer
would operate with a higher capacity factor. For any
combination of PV availability and load proles, there
is an optimum electrolyzer capacity (Barbir, 1999b).
Economics of PV-hydrogen systems greatly depends on
the conguration of the system and its application, in
addition to the available solar insolation.
4.2. Intermittent operation
Direct coupling of an electrolyzer with a PV array
implies intermittent operation with highly variable

power output. The problem is that at very low loads

the rate at which hydrogen and oxygen are produced
(which is proportional to current density) may be lower
than the rate at which these gases permeate through electrolyte, and mix with each other. This may create hazardous conditions inside the electrolyzer. Hydrogen
ammability limits in oxygen are between 4.6% and
93.9%, but the alarms and automatic shutdown of the
electrolyzer are set at much safer concentrations. Hydrogen permeation rate at 80 C through Naon 117, typically used in PEM electrolyzers, should be less than
1.25 10
4 cm3/s/cm2 at atmospheric pressure, corresponding to a current density of 0.002 A/cm2 (Kocha
et al., 2002), which is rather negligible compared to
1 A/cm2, a typical current density in PEM electrolyzers
at full power. However, hydrogen permeation rate increases linearly with pressure, which means that at
200 bar hydrogen loss would be 0.4 A/cm2. Fig. 8
shows hydrogen permeation through Naon 117 in an
electrolyzer conguration as a function of pressure and
temperature. Oxygen permeation rate through hydrated
Naon membrane is considerably lower (Sakai et al.,
1986).
Another problem related to operation with a highly
variable power source is thermal management. The electrolyzer takes time to reach its normal operating temperature, but due to intermittent operation it may operate
most of the time at a temperature below nominal, which
results in a lower eciency.
4.3. Output pressure
A PEM electrolyzer may be designed to generate
hydrogen at elevated pressure. This includes adequate
membrane support, appropriate gasketing and accounting for material creep. Proton Energy Systems sell PEM
electrolyzers that generate hydrogen at 14 bar (200 psig),
but it has reported operation at 200 bar (3000 psi) in the
laboratories. Pressurization during electrolysis results in
slightly higher cell voltages (as predicted by the Nernst
1.4
H2 Permeation ( g H2 /cm 2s)

666

1.2
1

75 C

0.8

55 C

0.6

25 C

0.4
0.2
0

1000

2000

3000

4000

Pressure (PSI)

Fig. 8. Hydrogen permeation through Naon 117 in an

electrolyzer conguration as a function of pressure and
temperature.

F. Barbir / Solar Energy 78 (2005) 661669

equation), which corresponds to an isothermal compression work. It is therefore the most ecient way of compression. The only loss is hydrogen permeation through
the polymer membrane. High hydrogen pressure is often
required if hydrogen is to be stored in high pressure
tanks for later use, or used as a fuel in an automobile,
or shipped through pipelines.
4.4. Oxygen generation
The water electrolysis results in both hydrogen and
oxygen being produced on the opposite sides of the
membrane. The electrolyzer produces stoichiometric
amounts of oxygen, i.e., for every two moles of hydrogen a mol of oxygen is produced as well. Oxygen is typically vented (unless oxygen generation is the primary
purpose of water electrolysis such as in submarines),
but if needed oxygen may be captured and stored for
later use (for example in fuel cell). Storage and handling
of oxygen, particularly at elevated pressures, requires
special care.

by the current density, which in turn directly corresponds to the rate of hydrogen production per unit of
electrode active area. A higher voltage would result in
more hydrogen production, but at a lower eciency.
Typically, cell voltage is selected at about 2 V, but a lower nominal voltage (as low as 1.6 V) may be selected, if
the eciency is more important than the size (and capital cost) of the electrolyzer.
Another source of ineciency is hydrogen permeation (loss) through the polymer membrane. This is typically insignicant at low operating pressures, but it may
signicantly aect the overall eciency at very high
pressures (>100 bar).
In addition there are power losses in voltage regulation and some power is needed for the auxiliary equipment (pumps, fans, solenoid valves, instrumentation
and controls). Typical industrial electrolyzers have electricity consumption between 4.5 and 6.0 kW h/N m3, corresponding to the eciency of 6580%. Fig. 9 shows
typical PEM electrolyzer eciency curves at various
pressures.
The electrolyzer eciency is therefore:

4.5. Water consumption

gEL

Theoretically from 1 l of water 1.24 N m of hydrogen

can be produced. Actual water consumption is about
25% higher, since both gases leave the electrolyzer wet,
and some water is lost from the system due to oxygen exhaust and periodic hydrogen purge. This is particularly
important for the systems that are supposed to work
in a closed loop with a fuel cell. If the fuel cell uses air
instead of pure oxygen, some water is lost there due to
air exhaust from the fuel cell.
4.6. Eciency
The eciency of an electrolyzer is inversely proportional to the cell potential, which in turn is determined

667

1:482 i
iloss gDC

V cell
i
1n

where Vcell is the individual (average) cell potential (V), i

is the operating current density (A/cm2), iloss is the internal current and hydrogen loss (A/cm2), gDC is the eciency of DC/DC voltage regulator, n is the ratio
between parasitic power and net power consumed by
the electrolyzer.
Coupling of a source such as PV array with an electrolyzer may result in somewhat lower eciency, due to
the losses related to power/voltage matching. DC/DC
voltage regulators may be designed to operate with the
eciency as high as 9395%, but this high eciency
may be achieved only in a very narrow power range.
In a highly variable mode of operation such as with

electrolyzer efficiency (HHV)

1
0.9
0.8
0.7
0.6
0.5
0.4
200 psi

0.3

2000 psi

0.2

3000 psi

0.1
0
0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

H2 generation rate (g/h/cm)

Fig. 9. Electrolyzer stack eciency for dierent delivery pressures.

0.08

668

F. Barbir / Solar Energy 78 (2005) 661669

2.8

Cell Voltage (Volts)

2.6

Time = 2,000 to 14,000 hr

Decay rate = 3 V/cell hr

2.4

2.2
Time = 400 to 2,000 hr
Decay rate = 20 V/cell hr

2.0

1.8

1.6
0

2,000

4,000

6,000

8,000

10,000

12,000

14,000

Operating Hours

Fig. 10. Voltage increase with time during continuous electrolysis. (single cell, 929 cm2, 1.1 A/cm2, 10 bar, 5155 C).

the input from a PV array, this eciency may be considerably lower. If there is a good match between the polarization curves of PVs and electrolyzers, experience from
a handful of PV/electrolysis pilot plants shows that they
can be matched directly (with no power tracking electronics) with relatively high eciency, >93% coupling
eciency (Steeb et al., 1990).
4.7. Performance degradation with time
When sizing an electrolyzer for operation in conjunction with the PVs, one must take into account voltage increase with time. If the eciency or the hydrogen
generation rate are important, then end of life electrolyzer performance must be taken into account rather
than beginning of life performance. Voltage increase is
steeper in the rst couple of thousands of hours of operation, 2050 lV/h, but then it levels o (<3 lV/h), as
shown in Fig. 10 (Anderson et al., 2002). The reasons
for voltage increase are equilibration of water content
in the membrane, and oxidation of catalyst and other
metallic components. With good design and careful
selection of materials, this performance degradation
may be minimized.

5. Conclusions
PEM electrolysis is a viable alternative for generation
of hydrogen in conjunction with renewable energy
sources. It particularly matches and complements the
photovoltaics. It may be coupled either directly, if the
polarization iV curves are well matched, or a DC/DC

regulator may be used with or without maximum power

point tracking. PEM electrolyzers are simpler than conventional alkaline electrolyzers, and can be operated in
variable power input mode. PEM electrolyzers can generate hydrogen (and optionally oxygen) at pressures up
to 200 bar, with very little additional power consumption, which may be attractive for the application where
hydrogen needs to be stored or used at elevated pressure.
PEM electrolyzers produce hydrogen with very high
purity (up to 99.999), which may be used in a fuel cell.
Economics of PV-hydrogen is determined not only
by the cost of the PV array and the electrolyzer, but also
by the capacity factor (of both PVs and electrolyzer),
and the electrolyzer eciency. Depending on conguration of the system and application, the capacity factors
of the PVs and the electrolyzer do not necessarily have
to be the same. Economics must also take into account
the cost of the competitive technology or commodity
(electricity and fuel). Because of high cost of the PVs
and the electrolyzer, generation of hydrogen currently
may be justied only in demonstration projects, or in remote areas or for special applications.
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