PEM Electrolysis for Production of Hydrogen From Renewable Energy Sources

Solar Energy 78 (2005) 661–669

www.elsevier.com/locate/solener

PEM electrolysis for production of hydrogen fromrenewable 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 hydro-

gen is stored and then via fuel cell converted back to electricity when needed. Specific 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 efficiency.

� 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 effec-

tively controlled). In addition, hydrogen may be con-

verted into useful forms of energy more efficiently than

fossil fuels. And despite public perception, hydrogen is

0038-092X/$ - see front matter � 2004 Elsevier Ltd. All rights reserv

doi:10.1016/j.solener.2004.09.003

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

E-mail address: [email protected]

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

electricity—an energy carrier, a convenient form of en-

ergy. From sustainability point of view, a synergy be-

tween 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,

ed.

mailto:[email protected]

662 F. Barbir / Solar Energy 78 (2005) 661–669

and it is being used for hydrogen production capacities

ranging from few cm3/min to thousands m3/h. It is rela-

tively efficient (>70%), but because it needs high quality

energy (electricity) hydrogen produced by water-elec-

trolysis is expensive (>$20/GJ). There is a potential to

generate relatively inexpensive hydrogen from hydro-

power and nuclear plants during off-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 pro-

ducing hydrogen from hydropower in Zaire and ship-

ping 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 perfluorosulfonic acid

polymer (also known as NafionTM) 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

Fig. 1. Schematic representation of PEM

(1.482V). Protons pass through the polymer electrolyte

membrane and on the cathode combine with electrons

to form hydrogen. Passage of protons through the mem-

brane is accompanied by water transport (electroos-

motic drag).

A PEM electrolyzer cell is similar to a PEM fuel

cell. It has a polymer membrane and porous electrodes,

flow fields, current collectors and separator plates, end

plates, bus plates, manifolds. The principle of opera-

tion is just reverse of fuel cell operation. However,

the materials are typically different from PEM fuel cell

materials. Carbon materials, such as catalyst support,

porous electrode structures (carbon fiber paper or car-

bon cloth) and bi-polar plates, commonly used in fuel

cells cannot be used on the oxygen side of a PEM elec-

trolyzer due to corrosion. PEM electrolyzers therefore

primarily use metallic components (porous structures,

flow fields and separator plates). The catalyst is typi-

cally 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 reason-

able stack voltage.

Besides the cell-stack, an electrolyzer must have a

power supply/voltage regulator, water supply system,

water circulation pump, water–gas separators for hydro-

gen 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 HO-

GEN� 40 by Proton Energy Systems. This electrolyzer

is intended for industrial hydrogen generation. A version

of it, so called HOGEN�RE, has been developed for use

in conjunction with renewable energy sources. Table 1

shows HOGEN�RE specifications.

electrolysis and fuel cell processes.

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

Table 1

Specifications of HOGEN�RE PEM electrolyzer by Proton Energy Systems

Hydrogen output 0.5 or 1.0Nm3/h

Max delivery pressure 200bar

Hydrogen purity >99.9% (optionally >99.999%)

Water usage 0.5 or 1.0 l/h

Water quality (min) required deionized (ASTM Type II)

Power consumption 6.6kWh/Nm3

Electrical supply required AC: 190–240 VAC, 1 phase, 50/60Hz, 7.2 or 12kVA DC: 60–200 VDC, 150A (max)

Operating environment Indoor (optionally outdoor)

Dimensions 97 · 105 · 106cm

Weight 220kg

Installation ‘‘Plug & play’’

Controls and automation Fully automatic and unattended

F. Barbir / Solar Energy 78 (2005) 661–669 663

3. Applications

Hydrogen may be produced from PV generated elec-

tricity in a variety of applications, and used as a fuel di-

rectly, or transmitted through pipelines to the users, or

used to enhance the performance of the PVs by match-

ing their output to the user needs. Each of these applica-

tions is briefly 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).

Fig. 3. Schematic diagram of grid inde

This system circumvents the problems related to the grid

connection and generation imbalance charges. The elec-

trolyzer 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 electrolyzer�s voltage–current requirements

at any power with minimum conversion losses. Another

option would be to select the PV panels so that their i–V

output matches the electrolyzer�s i–V 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

pendent PV-hydrogen generation.


option. Some studies suggest that transmission of hydro-

gen through a pipeline in some cases may be more eco-

nomical 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 pipe-

lines from the wind farms in the Dakotas to the users

in Chicago—distance of some 1600km (Keith and

Leighty, 2002).

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 electro-

lyzer 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 mainte-

nance), which would significantly 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 out-

put from the PV power plant if that is required from the

Fig. 4. Schematic diagram of grid-as

Fig. 5. Schematic diagram of PV installation fo

grid operator. In that case the excess power from the

PVs (above that can be absorbed by the grid in that par-

ticular moment) is used to generate hydrogen (Fig. 5).

However, the problems with intermittent electrolyzer

operation and its low capacity factor remain. A varia-

tion of this scheme is to operate the electrolyzer at con-

stant power and ‘‘dump’’ the excess power from the PV

power plant into the grid (off course providing there is

enough absorbing capacity in the grid).

3.4. Integrated PV-hydrogen utility energy system

One way to deliver a constant or any required load

profile to the grid is to equip the PV array or PV power

plant with an energy storage device, such as a regenera-

tive fuel cell (a combination of electrolyzer and a fuel cell

with hydrogen storage), as shown in Fig. 6. The electro-

lyzer and fuel cell functions may be included in a single

stack (unitized version) or in two separate stacks (dis-

crete version). In order to fill the hydrogen tank, a com-

pressor may be required or the electrolyzer may be

designed to provide high pressure. Proton Energy Sys-

tems reported operating pressures with PEM electrolyz-

ers up to 200bar (Anderson et al., 2002; Barbir et al.,

2002). The power conditioning and controls unit has

an extremely complex function in this configuration. 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

sisted PV-hydrogen generation.

r grid-electricity and hydrogen generation.

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

5kWh (Barbir et al., 2002). Due to presently high costs

of electrolyzers and fuel cells and a low capacity factor

in this configuration, the cost of delivered electricity

would be several times higher than the cost of PV gener-

ated electricity (Barbir, 1999b), even when the genera-

tion imbalance charges are taken into account.

Therefore, this configuration may be used only where

the quality of delivered electricity justifies 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, flywheel, compressed air, pumped hy-

dro, ultracapacitors, etc.). The only difference 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 pro-

vide 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

Fig. 7. Schematic diagram of grid independen

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 1kW to

350kW.

This system may also incorporate a wind turbine for

added security and versatility of power supply. Com-

bined wind and solar (PV) systems are in operation at

the Desert Research Institute (Reno, Nevada), and at

the Hydrogen Research Institute (HRI), at the Univer-

site du Quebec, Trois Rivieres (Agbossou et al., 2001).

These independently conceived systems use both photo-

voltaics and wind turbines to generate hydrogen fuel.

They are relatively small systems using wind/solar

hydrogen generation with a compressed hydrogen stor-

age system, 5kW electrolyzers, and incorporating a fuel

cell which regenerates the electricity. Both use a combi-

nation of battery and hydrogen energy storage, in which

a small battery bank acts as an energy buffer, 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

t integrated PV-hydrogen energy system.


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 ele-

ments 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 effi-

ciency and the mass of the electrolyzer, fuel cell and

hydrogen and oxygen storage are critical for accomplish-

ing the mission. This energy storage system has potential

to be much lighter than the batteries, with specific energy

in excess of 400Wh/kg, and when hydrogen and oxygen

are stored in structural elements with little additional

weight energy density may exceed 700Wh/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 sat-

ellite and for electricity generation via fuel cell during

periods when the PVs are not insolated.

0

0.2

0.4

0.6

0.8

1

1.2

1.4

0 1000 2000 3000 4000Pressure (PSI)

H 2 P

erm

eatio

n (µ

g H 2

/cm

2 s)

75 C55 C25 C

Fig. 8. Hydrogen permeation through Nafion 117 in an

electrolyzer configuration as a function of pressure and

temperature.

4. Issues

Operation of a PEM electrolyzer in conjunction with

renewable energy sources, and particularly with a PV

panel or array, has several specific issues that will be dis-

cussed 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 deter-

mined by the sun availability. Capacity factor is a coef-

ficient 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 profiles, there

is an optimum electrolyzer capacity (Barbir, 1999b).

Economics of PV-hydrogen systems greatly depends on

the configuration 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 elec-

trolyte, and mix with each other. This may create haz-

ardous conditions inside the electrolyzer. Hydrogen

flammability 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. Hydro-

gen permeation rate at 80 �C through Nafion 117, typi-

cally used in PEM electrolyzers, should be less than

1.25 · 10�4 cm3/s/cm2 at atmospheric pressure, corre-

sponding to a current density of 0.002A/cm2 (Kocha

et al., 2002), which is rather negligible compared to

1A/cm2, a typical current density in PEM electrolyzers

at full power. However, hydrogen permeation rate in-

creases linearly with pressure, which means that at

200bar hydrogen loss would be �0.4A/cm2. Fig. 8

shows hydrogen permeation through Nafion 117 in an

electrolyzer configuration as a function of pressure and

temperature. Oxygen permeation rate through hydrated

Nafion membrane is considerably lower (Sakai et al.,

1986).

Another problem related to operation with a highly

variable power source is thermal management. The elec-

trolyzer takes time to reach its normal operating temper-

ature, but due to intermittent operation it may operate

most of the time at a temperature below nominal, which

results in a lower efficiency.

4.3. Output pressure

A PEM electrolyzer may be designed to generate

hydrogen at elevated pressure. This includes adequate

membrane support, appropriate gasketing and account-

ing for material creep. Proton Energy Systems sell PEM

electrolyzers that generate hydrogen at 14bar (200psig),

but it has reported operation at 200bar (3000psi) in the

laboratories. Pressurization during electrolysis results in

slightly higher cell voltages (as predicted by the Nernst


equation), which corresponds to an isothermal compres-

sion work. It is therefore the most efficient way of com-

pression. 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 hydro-

gen a mol of oxygen is produced as well. Oxygen is typ-

ically 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.

4.5. Water consumption

Theoretically from 1l of water 1.24Nm3 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 ex-

haust 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. Efficiency

The efficiency of an electrolyzer is inversely propor-

tional to the cell potential, which in turn is determined

0

0.1

0.2

0.3

0.4

0.50.6

0.7

0.8

0.9

1

0 0.01 0.02 0.03 0.H2 generation

elec

troly

zer e

ffici

ency

(HHV

)

Fig. 9. Electrolyzer stack efficiency f

by the current density, which in turn directly corre-

sponds 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 efficiency.

Typically, cell voltage is selected at about 2V, but a low-

er nominal voltage (as low as 1.6V) may be selected, if

the efficiency is more important than the size (and capi-

tal cost) of the electrolyzer.

Another ‘‘source’’ of inefficiency is hydrogen perme-

ation (loss) through the polymer membrane. This is typ-

ically insignificant at low operating pressures, but it may

significantly affect the overall efficiency at very high

pressures (>100bar).

In addition there are power losses in voltage regula-

tion and some power is needed for the auxiliary equip-

ment (pumps, fans, solenoid valves, instrumentation

and controls). Typical industrial electrolyzers have elec-

tricity consumption between 4.5 and 6.0kWh/Nm3, cor-

responding to the efficiency of 65–80%. Fig. 9 shows

typical PEM electrolyzer efficiency curves at various

pressures.

The electrolyzer efficiency is therefore:

gEL ¼ 1:482

V cell

i� ilossi

gDC

1þ nð1Þ

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

is the operating current density (A/cm2), iloss is the inter-

nal current and hydrogen loss (A/cm2), gDC is the effi-

ciency 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 elec-

trolyzer may result in somewhat lower efficiency, due to

the losses related to power/voltage matching. DC/DC

voltage regulators may be designed to operate with the

efficiency as high as 93–95%, but this high efficiency

may be achieved only in a very narrow power range.

In a highly variable mode of operation such as with

04 0.05 0.06 0.07 0.08 rate (g/h/cm²)

200 psi2000 psi3000 psi

or different delivery pressures.

Time = 400 to 2,000 hrDecay rate = 20 µV/cell hr

Time = 2,000 to 14,000 hrDecay rate = 3 µV/cell hr

1.6

1.8

2.0

2.2

2.4

2.6

2.8

0 2,000 4,000 6,000 8,000 10,000 12,000 14,000

Operating Hours

Cel

l Vol

tage

(Vol

ts)

Fig. 10. Voltage increase with time during continuous electrolysis. (single cell, 929cm2, 1.1A/cm2, 10bar, 51–55�C).


the input from a PV array, this efficiency may be consid-

erably lower. If there is a good match between the polar-

ization 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 elec-

tronics) with relatively high efficiency, >93% coupling

efficiency (Steeb et al., 1990).

4.7. Performance degradation with time

When sizing an electrolyzer for operation in conjunc-

tion with the PVs, one must take into account voltage in-

crease with time. If the efficiency or the hydrogen

generation rate are important, then end of life electro-

lyzer performance must be taken into account rather

than beginning of life performance. Voltage increase is

steeper in the first couple of thousands of hours of oper-

ation, 20–50lV/h, but then it levels off (<3lV/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 i–V curves are well matched, or a DC/DC

regulator may be used with or without maximum power

point tracking. PEM electrolyzers are simpler than con-

ventional alkaline electrolyzers, and can be operated in

variable power input mode. PEM electrolyzers can gen-

erate hydrogen (and optionally oxygen) at pressures up

to 200bar, with very little additional power consump-

tion, 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 efficiency. Depending on configura-

tion 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 justified only in demonstration projects, or in re-

mote areas or for special applications.

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