2IWH 2007, 27-29 October 2007, Ghardaïa – Algeria

GENHYPEM : A RESEARCH PROGRAM ON PEM WATER

ELECTROLYSIS SUPPORTED BY THE EUROPEAN COMMISSION.
Pierre Millet 1, Serguey Grigoriev 2, Vladimir Fateev 2, Claude Etievant 3, Christophe Puyenchet 3
1
Institut de Chimie Moléculaire et des Matériaux, UMR CNRS n° 8182, Université Paris sud 11,
15 rue Georges Clémenceau, 91405 Orsay cedex France
2
Hydrogen Energy and Plasma Technology Institute of Russian Research Center “Kurchatov
Institute”, 1, Kurchatov sq., 123182 Moscow Russia
3
Compagnie Européenne des Technologies de l’Hydrogène, route de Nozay, Etablissements Alcatel,
91460 Marcoussis cedex France

ABSTRACT :
GenHyPEM (Générateur d’Hydrogène par électrolyse de l’eau PEM «Proton-Exchange
Membrane ») is a STREP program (n° 019802) supported by the European Commission in the course
of the 6th framework research program. GenHyPEM gathers partners from Belgium, Germany,
Romania, Federation of Russia and France. The main goal of the project is to develop low-cost and
high pressure (50 bars) PEM water electrolyzers for the production of up to 1 Nm3 H2/hour. This R&D
project, which started by october 1st 2005, is a 2.2 M€ research effort over three years. The purpose of
this communication is to present the current status of the project. Major results and achievements
obtained so far in different fields of academic (electrocatalysis, polymer electrolyte) and applied (stack
development and performances) research are presented.

KEYWORDS: water electrolysis, polymer electrolyte, electrocatalysis, hydrogen production

1. Introduction
The idea of using an ion-conducting polymer as solid electrolyte for electrochemical applications
(once called SPE for “Solid Polymer Electrolyte” and now more frequently referred to in the literature
as PEM for “Proton Exchange Membrane”) emerged in the late fifties of the twentieth century, at the
dawn of the US space program [1,2]. The concept was mostly used to develop H2/O2 acidic fuel cells,
the solid electrolyte being considered as a significant advantage for energy management in zero-
gravity environments. Later, the discovery of perfluoro-sulfonated membrane materials (DuPont de
Nemours Nafion® products [3]) which were able to sustain the very oxidizing conditions found at
oxygen evolving electrodes opened the way for PEM water electrolysis applications.
The development of PEM water electrolysis started in the USA at General Electric Company
which eventually commercialized small scale systems for lab-scale applications. The US Department
of Energy actively supported the development of this technology [4]. Research papers then appeared
in Switzerland at Brown Bovery Corporation [5] where the Membrel® concept was developed and in
Japan [6]. In France, research activities in this field started in 1985 at the french Commissariat à
l’Energie Atomique (CEA), Centre d’Etudes Nucléaires de Grenoble (CENG). Patented processes for
the production of efficient membrane electrode assemblies (MEA’s) were developed, and pressurised
(up to 100 bars) small size (1 kW) units were constructed and tested [7-9]. In parallel, the russian
HEPTI RRC “Kurchatov Institute” in Moscow developed PEM water electrolysers of various designs
and capacities (from a few milliliters to tens of cubic meters of hydrogen per hour) [10,11,12]. Whereas
for several decades oxygen was the most value added product obtained from water splitting using
PEM technology (oxygen generation in anaerobic environments for space and underwater
applications), the world energy situation we are facing at the beginning of the XXIst century has
renewed interest on this technology which potentially can be used to produce hydrogen from
renewable energy sources.
The involvement of the European Commission in the “hydrogen society” as led to the
GenHyPEM project, which is a three years long and 2.2 M€ project, started in october 2005. This
project gathers different academic and industrial partners : the French “Institut de Chimie Moléculaire
et des Matériaux” (ICMMO) at the University of Paris-XI (UPS), the French SME “Compagnie
Européenne des Technologies de l'Hydrogène” (CETH), the German GKN Sinter Metals Service
GmbH (GKN), the Belgium Delta Plus Engineering & Consulting SPRL company (D+), the Russian
Research Centre "Kurchatov Institute" (KI) in Moscow and the Romanian Oskar Von Miller - Institut de

1/8
 2IWH 2007, 27-29 October 2007, Ghardaïa – Algeria

Conceptie, Cercetare si Proiectare research centre. The main objective of the GenHyPEM project is to
develop an efficient PEM water electrolyzer which can produce up to 1000 Nliter H2 / hour at high (1
A.cm-2) current density and high (50 bars) operating pressure.

2. The GenHyPEM project

2.1. Consortium
The GenHyPEM project, which is coordinated by the University of Paris-XI gathers 6 partners
from 5 different countries. The main characteristics of this project are summarized in figure 1.

Figure 1 : consortium description and general topic of the GenHyPEM project

Additional support is provided by Region Ile de France concerning management activities and
dissemination of knowledge.

2.2. Objectives
It is expected that PEM water electrolysis will play a significant role in the hydrogen society as
a key process for producing hydrogen from renewable energy sources but before this, significant cost
reductions are still required. For this purpose, the GenHyPEM project is addressing four major topics :

¾ electrocatalysis (PXI and KI leaders)

Because of the high acidity of membrane materials used in state-of-the-art PEM water
electrolyzers, expensive noble-metals or their oxides (platinum for hydrogen evolution and iridium for
oxygen evolution) are required as electrocatalysts. Reducing costs requires either the development of
new preparation procedures with lower noble-metals loadings or the use of alternative, non-noble
metal catalytic compounds, provided for example by molecular chemistry and bio-mimetic approaches.
These three options are separately addressed within the course of the project.

¾ solid electrolyte (OVM leader)

Solid polymer electrolytes in state-of-the-art technology rely on perfluorinated membrane
materials such as Nafion® products. These materials gather most of the qualities which are needed to
perform PEM water electrolysis. However, they suffer from several drawbacks : (i) a still elevated price
which postpone large scale dissemination of the technology; (ii) at high operating pressure, large

2/8
 2IWH 2007, 27-29 October 2007, Ghardaïa – Algeria

cross-permeation phenomena which lead to high level contamination of oxygen by hydrogen and
potentially to high risk levels; (iii) the operating temperature is limited to 100°C since above that value,
membranes loose their mechanical strength. The objective of the GenHyPEM project is to develop
and test alternative low-cost membrane materials as well as surface treatments of existing
perflurosulfonic materials for high pressure and high temperature operation.

¾ current collectors (GKN leader)

Current distributors in state-of-the-art (< 10 m3.h-1 H2) electrolysers consist of porous titanium
sheets of uniform porosity. Fabrication costs are in direct relation with the number of units
manufactured. However, optimization of the pore structure is of crucial importance in connexion with
current lines distribution at the current collector / electrocatalytic layer interface, as well as at
membrane surface. Uneven current distribution can lead to local hot points which in turn can damage
the membrane and shorten its lifetime.

¾ stack optimization and testing (CETH and D+ leaders)

Another key factor for cost-reduction considerations is to increase current density, operating
pressure and temperature. In the GenHyPEM project, the possibility of operating the stack at high (1
A.cm-2) current density as nominal rate is considered. High-pressure-operation (50 bars) is tested in
relation with safety considerations. Prototype-scale experiments are performed using 1000 Nliter.hr-1
H2 electrolyzers.

3. Results
3.1. Electrocatalysis
As discussed above, electrocatalysis in state-of-the-art PEM water electrolyzers requires
noble metals (Pt on the cathodic side for hydrogen evolution and Ir-based compounds on the anodic
side for oxygen evolution). Several plating procedures have been reported in the literature [5-11]. The
electrocatalyst active layer can be either plated onto the current collector which is then pressed onto
the membrane or directly deposited at the membrane surface using either chemical or electrochemical
routes.
3.1.1. Electro-catalysts deposited onto the polymer membrane
Using electroless techniques, uniform catalysts coatings can be platted onto the polymer
membrane (figure 2). There are several advantages to prepare membrane-electrode assemblies
(MEAs) that way : (i) the catalytic layer is more adherent (the possibility of continuous operation over
20,000 hours has been demonstrated); (ii) the MEAs are less prone to dimensional changes when the
membrane is dried; (iii) such MEAs can be easily removed from the stacks during maintenance
operation. Typical polarization curves measured at lab-scale (25 cm2) are plotted in figure 3. The black
curve was obtained using platinum for both the hydrogen evolution reaction (HER) and the oxygen
evolution reaction (OER). The green curve was obtained using platinum for the HER and iridium for
the OER. The significant reduction in cell voltage (580 mV at 0.8 A.cm-2) comes from the iridium black
which is known to be much more efficient than platinum for the OER.

Figure 2 : platinum black deposited onto a Figure 3 : Cell voltage vs. current density
Nafion® 117 membrane. relationships measured during water
electrolysis.

3/8
 2IWH 2007, 27-29 October 2007, Ghardaïa – Algeria

It can be seen from figure 3 that the cell efficiency (red curve) remains high, even at high
current density (ca. 80% at 0.8 A.cm-2). In electrolysis stacks, parasite ohmic drops may reduce the
overall efficiency. But losses may be used to produce heat and maintain operating temperature close
to nominal values.

3.1.2. Electro-catalysts deposited onto carriers

Following research trends developed in fuel cells R&D activities, a very promising route for
lowering noble metal loadings in PEM water electrolysis is to develop composite electroactive
structures in which nano-sized particles are deposited at the surface of electronic conducting carriers
of very large surface area. Beside the development of more efficient electrocatalysts, increasing the
roughness factor of an electrode is indeed the most efficient way to reduce reaction overvoltages. For
the HER, carbon-based materials appear to be the most interesting carriers. Carbon blacks of large
active areas such as Vulcan® (product family from Cabot Co.) with typical surface areas in the range of
200-300 m2.g-1, can be used for this purpose. Using electroless techniques, ie. the chemical reduction
of precursor salts, nano-sized particles of platinum (a mean particle diameter of ca. 10-20 nm can be
obtained) can be deposited at the surface of the carbon powder (figure 4), leading to very efficient
electrodes for the HER (figure 6). Alternatively, other carbon carriers such as carbon nano-tubes
(CNT) can also be used (figure 5), leading to similar responses in acidic media (figure 7). The
roughness factor of these catalytic materials can be tuned by adjusting the amount of metals. A
compromise has to be found between noble metal loadings (cost considerations) and roughness
factors.

Figure 4 : Transmission Figure 5 : Transmission electron micrograph of Pt40

electron micrograph of wt.% / CNT catalyst (KI).
Pt40wt.% / Vulcan XC72
catalyst (KI).

0,010

0,010

0,005

0,005
I, A

0
I, A

-0,005
-0,005

-0,010
-0,010
-0,5 0 0,5 1,0 1,5 -0,5 0 0,5 1,0 1,5

E, V E, V

Figure 6 : CV of a Pt10/Vulcan electrode. Figure 7 : Cyclic voltammogram (20

mV.s-1) for electrode made with Pt40/CNT
(40mass% Pt on CNT) catalyst.

4/8
 2IWH 2007, 27-29 October 2007, Ghardaïa – Algeria

For the oxygen evolution reaction (OER), carbon-based carriers are not sufficiently stable.
They must be replaced by other carriers such as oxides, more stable under oxygen evolution. A
problem appears when thermal decomposition processes of precursor salts are used. It is then difficult
to avoid particles aggregation and to obtain high surface areas. In state-of-the-art MEAs, iridium black
is used as anodic catalyst, with typical loadings of a few mg.cm-2. Figure 8 shows typical polarization
curves measured on a single cell (25 cm2) using Pt nanoparticles deposited on Vulcan and CNTs for
the HER and iridium black for the OER.
1.9

1.8

Pt40/Vulcan
Pt40/CNT
1.7
U,V

1.6

1.5

1.4

1.3
0 0.2 0.4 0.6 0.8 1 1.2 1.4
i, А/sq.cm

Figure 8 : Polarization curves measured during PEM water electrolysis at T = 90°C

using carbon-supported platinum for the HER and iridium black (2.4 mg.cm-2) for the
OER; S = 25 cm2; Nafion® 115.

Current densities above 1 A.cm-2 can be obtained, with a cell voltage of less than 1.8 Volt,
corresponding to a cell efficiency close to 80%. Most of the cell irreversibilities remain located on
anodic sides, where the OER overvoltage if the larger term of the cell voltage. At present, iridium-
based anodic catalysts are the most efficient known. Ruthenium is slightly more efficient but unstable
at potentials above 1.45 Volt.

3.2. Stack performances

Filter-press stacks can be used to increase the productivity of the electrolysis unit. Figure 9
shows a GenHy®1000 electrolysis stack consisting of twelve 250 cm2 producing cells. The unit can
produce up to 1 Nm3 H2 / hour in the pressure domain ranging from the atmospheric pressure up to 30
bars.

Figure 9 : GenHy®1000 electrolysis stack

5/8
 2IWH 2007, 27-29 October 2007, Ghardaïa – Algeria

Figure 10 shows a polarisation curve recorded in the early stages of operation at 50°C. At 0.4
A.cm-2, a mean cell voltage of 2.1 Volt per cell is obtained, indicating that parasite ohmic losses are
reducing the overall efficiency down to 70 %. During operation, the mean cell voltage rapidly falls
below 2.0 V/cell. Stable performances have been recorded over 1,000 hours of continuous operation.

Figure 10 : Cell voltage vs. current density relationships measured during water
electrolysis on a 12 cells stack (250 cm2, 50°C).

3.3. Development of electrolysis units

PEM water electrolyzers can be used for miscellaneous applications, where either hydrogen or
oxygen of electrolytic grade are required. Production rates range from a few tens of Nliter H2 / hour up
to 2500 Nliter H2 / hour. Figure 11 shows a GenHy®100 PEM water electrolyzer which can be used for
laboratory applications (production of hydrogen and oxygen of electrolytic grade).

Figure 11 : GenHy®100 PEM water electrolyzer for laboratory applications (CETH).

Larger systems have also been developed. Figure 12 shows an automated GenHy®2500 unit
which can be operated at 500 mA.cm-2 and which can deliver gases up to 6 bars. The unit can be
remotely managed using a PC. Figure 13 shows a larger system which is used for operation at 30
bars. High pressure water electrolysis is interesting for direct storage of hydrogen in pressurized

6/8
 2IWH 2007, 27-29 October 2007, Ghardaïa – Algeria

bottles. Some reports have been published indicating operating pressures of a few hundreds bars but
such system cannot be used for domestic applications such as those considered in this research
programme.

Figure 12 : GenHy®2500 PEM water Figure 13 : 5 Nm3 H2/hour 30 bars PEM water
electrolyzer for laboratory electrolyzer (Kurchatov Institute).
applications (CETH).

4. Conclusions and perspectives

Whereas large scale production of electrolytic hydrogen is achieved is the industry using the
mature alkaline process, PEM water electrolysis technology provides a safer and more efficient way
for producing electrolytic hydrogen and oxygen from renewable energy sources. Stack efficiencies as
high as 80% can be obtained at high (1 A.cm-2) current densities. Hydrogen can be safely produced at
pressures ranging from 1 to 6 atmospheres, offering the possibility of direct storage in hydride tanks.
In the perspective of the hydrogen society, these electrolyte-free systems offer an interesting
alternative solution for the satisfaction of domestic needs. In particular, such electrolyzers can be used
to develop auxiliary power units (APU) as as well as hydrogen refueling stations.
Although cost considerations still postpone the large scale development of PEM electrolyzers,
the use of catalyst carriers and the development of a new generation of efficient catalytic structures
allow a significant reduction of catalyst costs. Also, as reported elsewhere, different alternative and
low-cost electrocatalysts are currently investigated, both for hydrogen and oxygen evolution [13,14].
The vocation of the GenHyPEM project is to develop low-cost electrolytic hydrogen generators based
on the PEM technology. Optimized electrolytic generators with up to 2500 Nliters H2 per hour output
capabilities are currently developed and tested by industrial partners and commercialized for
miscellaneous industrial applications. The possibility of operating such systems at higher operating
pressure for direct storage in pressurized vessels is also considered [15].

Acknowledgement : on behalf of the GenHyPEM consortium, financial support from the European
Commission within the 6th Framework Programme (GenHyPEM, STREP no 019802) and from Région
Ile de France are gratefully acknowledged.

7/8
 2IWH 2007, 27-29 October 2007, Ghardaïa – Algeria

References
[1] W.T. Grubb Jr., J. Electrochem. Soc., 106, 275 (1959)
[2] W.T. Grubb Jr., General Electric Company, US Patent n° 2,913,511 (november 17th, 1959)
[3] W.R. Wolfe, DuPont de Nemours, US Patent n° 1,184,321 (may 15th, 1968)
[4] “Solid Polymer Electrolyte Water Electrolysis Technology Development for Large-Scale Hydrogen
Production”, US Department of Energy, DOE/ET/26 202-1 (1981)
[5] S. Stucki, R. Muller, Proceeds. 3rd World hydrogen Energy Conference (WHEC), Tokyo, Japan, 4,
p. 1799, 1980
[6] T. Ohta, I. Abe, Proceeds. 5th World hydrogen Energy Conference (WHEC), Toronto, Canada, 1, p.
47, 1984
[7] R. Durand, P. Millet et M. Pinéri, French Patent n° EN 87 17 637 (june 17th, 1987)
[8] P. Millet, R. Durand, M. Pinéri, J. Appl. Electrochem., 19, 162, 1989
[9] P. Millet, R. Durand, M. Pinéri, Int. J. Hydrogen Energy, 15, 245, 1990
[10] Porous electrode for electrochemical water decomposition with solid polymer electrolyte,
Copyright Certificate of USSR (Russian Federation) n° 1377302, 1987
[11] Technique of membrane-electrode assembly obtaining, Copyright Certificate of USSR (Russian
Federation) n° 1429594, 1988
[12] S.A. Grigoriev, V.I. Porembsky, V.N. Fateev, Int. J. Hydrogen Energy, 31, 171, 2006
[13] O. Pantani, E. Anxolabehere, A. Aukauloo, P. Millet, “Electroactivity of Cobalt complexes for the
reduction of protons into di-hydrogen. Application to PEM water electrolysis”, Proceeds. 16th World
Hydrogen Energy Conference (WHEC), Lyon, France, n° 317, pp. 1-8, 2006
[14] T. Medhoui, E. Anxolabehere, A. Aukauloo, P. Millet, “Biomimetic approaches for the
development of non-noble metal electrocatalysts. Application to PEM water electrolysis”, Proceeds.
16th World Hydrogen Energy Conference (WHEC), Lyon, France, n° 390, pp. 1-9, 2006
[15] V. Fateev, S. Grigoriec, P. Millet, S. Korobtsev, V. Porembsky, M. Pepic, “High pressure PEM
electrolyzer hydrogen safety problems”, 2nd International Conference on Hydrogen Safety, San
Sebastian, Spain, 11-13 september 2007

8/8