\

Int[ J[ Hydro`en Ener`y\ Vol[ 12\ No[ 01\ pp[ 0002Ð0019\ 0887
Þ 0887 International Association for Hydrogen Energy
Pergamon Elsevier Science Ltd
All rights reserved[ Printed in Great Britain
PII] S9259Ð2088"86#99028Ð9 9259Ð2088:87 ,08[99¦9[99

OPERATIONAL CHARACTERISTICS OF HIGH!PRESSURE\ HIGH!

EFFICIENCY WATER!HYDROGEN!ELECTROLYSIS

C[ A[ SCHUG
Linde AG\ Werksgruppe Verfahrenstechnik und Anlagenbau\ Dr[ Carl!von!Linde!Strae 5Ð03\ D!71938 Hollriegelskreuth\ Germany

Abstract*After more than 4999 h of operation of the 099!kW!Pilot!Electrolyzer developed by the Gesellschaft fur
Hochleistungselektrolyseure zur Wassersto}erzeugung mbH "GHW#\ the experience accumulated so far allows for
the scale up to the Megawatt size of this high pressure electrolysis[ Several operational concepts ranging from constant
current long time tests over solar photovoltaic energy storage to subsecond compensation of power plant network
~uctuations have been successfully simulated[ The responses of the main system parameters during these simulations
are described[ For partial load operation\ the normally increased hydrogen percentage in the produced oxygen has
been stabilized by a special lye circulation control[ The material problems\ like corrosion under extreme conditions\
are solved up to now[ Some of the material aspects are discussed[ As measurement and control techniques are the
backbone of the safety system\ sensors and signal processing are brie~y mentioned[ The single cell voltage measurement
is explained[ In total\ the gained knowledge allows the design of this kind of electrolyzer for wherever its use is
technically and economically attractive[ The decreasing acceptance of air pollution improves the position of elec!
trolysis[ Beginning with an overview on high!pressure electrolyzers actually realized\ an outlook on coming projects
and future applications is given[ Þ 0887 International Association for Hydrogen Energy

0[ INTRODUCTION
Electrolysis is still a minor production path to the total
amount of hydrogen produced and used in the world[
Nevertheless the principle is well known since the early
08th century and today|s state of the art electrolyzers are
systems of high e.ciency\ high security and easy use[
Two factors are mainly responsible for the under!
representation of electrolysis in the hydrogen market]
_rst\ the low costs of hydrocarbon sources for hydrogen
and second\ the fact\ that most of the world!wide hydro!
gen production is used as feed in the chemical industry
at the same place where it is produced from hydrocarbon
sources[
The market for hydrogen from electrolyzers will
increase\ when hydrogen is used as tra.c fuel and energy
storage media[ The ecological demands\ which might be
summarized under the two key phrases {{Zero Emission
Vehicle|| and {{Regenerative Energies||\ will soon be rea!
son enough to change the economical weighting of hydro!
gen from electrolyzers vs that from hydrocarbons[
The following description of operational charac!
teristics will show that the e.ciency and ~exibility of
modern electrolyzers meet the need for a converter
between ecological electric power and a storable energy
carrier[
1[ RESULTS
1[0[ The 099!kW!pilot!electrolyzer
Figure 0 shows a simpli_ed process ~ow diagram of
the 099!kW!pilot!electrolyzer of the GHW ð0Ł[ The main
components can easily be recognized in Fig[ 1\ where a
photo showing an opened pressure vessel is presented[
One of the most evident characteristics of this elec!
trolyzer is that the stack of cells is kept in a pressure
vessel\ resulting in almost no pressure di}erence between
inside and outside the stack[ Therefore it is possible to
use synthetic material for the insulating cell frames even
at a scale of one square metre cell surface[ The frames of
the stack\ mounted between two steel plates\ must bare
only the pressure drop of the electrolyte within the stack[
As the feed water is used to _ll the pressure vessel
before it ~ows freely into the electrolyte over an ascending
pipe\ the surroundings of the stack are not only kept at
the same pressure but also at the same temperature as the
stack itself[ The temperature of the electrolysis process is
kept constant via a large heat exchanger between the
electrolyte and the water in the pressure vessel[ The water
temperature can be stabilized very smoothly by means of
an electric heater and a separate cooling circuit[
It is well known\ that the electric losses of alkaline

0002
0003 C[ A[ SCHUG
Fig[ 0[ Simpli_ed process ~ow diagram[
electrolysis are a function of the temperature and con!
centration of the electrolyte as well as of the ohmic losses
of the metallic wiring[ Less well known are the losses due
to the electrochemical processes at and near the elec!
trodes[ On the other hand\ the in~uence of the pressure
on the e.ciency is small\ so that electrolysis is an ener!
getically cheap way to pressurize hydrogen[ Keeping in
mind the material restrictions\ an aqueous potassium lye
of 39) and 029>C at a pressure of 29 bar is a good choice
for this kind of electrolysis and is therefore used in the
pilot!electrolyzer[
The heart of the electrolyzer is the stack of EDE!Cells\
where EDE has become a common abbreviation for Elec!
trode!Diaphragm!Electrode[ As it is rather complicated
to produce a zero gap combination of thin electrodes and
a diaphragm with a large area\ the production process is
described elsewhere ð1\ 2Ł[ Within this paper\ the stack
is treated as a black box with certain electrochemical\
hydrodynamic and thermal properties[
1[1[ The operational concepts
There are three main target groups for high!pressure!
electrolyzers] users\ who want to produce a constant
amount of hydrogen per time unit over a long period^
users\ who want to couple the electrolyzer to an energy
source of varying power like a photovoltaic _eld or wind
generators^ and users\ who want to smooth changes in
energy consumption of power plant networks[
The constant production target group is interested in
a maintenance!free\ self!controlled operation with high
e.ciency[ Figure 2 shows the e.ciency of the up to now
unactivated cells as a function of percentage of the nom!
inal current consumption\ which is 1499 amps over
9[14 m1[ Electrode catalytic activation work is in progress
to reduce the cell voltage by over 199 mV at nominal
power[ Details will be published elsewhere[
Figure 3 shows the main components for automatic
operation[ A process control system\ which needs only
the required current as operator input\ keeps all system
parameters at the optimum[ Temperature\ pressure\ feed
water ~ow\ lye circulation and di}erential pressure are
stabilized and monitored[ Failures\ which are not safety
relevant\ are indicated by alarms\ so that operators can
react in time[ One example for such a failure might be a
lack of feed water\ which can be compensated by chan!
ging to another storage vessel[ As the system can be
working with no operator running it\ the alarms can
be connected by modem to telecommunication receivers
with alphanumeric displays[
All failures\ which might a}ect safety aspects\ are tre!
ated separately by a programmable processor\ which
allows no operator activities[ This security system is tot!
ally fail!safe as it works even with no power or a lack of
compressed air[ The safety processor program ~ushes
both gas separators with nitrogen\ keeping them at nom!
inal pressure\ shuts down the current for the electrolysis\
stops all units which might increase pressure beyond the
allowed values\ and prevents the boiling in the pressure
vessel[ Starting from this safe state\ the operator can
 OPERATIONAL CHARACTERISTICS OF WATER HYDROGEN!ELECTROLYSIS 0004

Fig[ 1[ Picture of the pilot!electrolyzer with opened pressure vessel[

choose between a programmed total shut down for repair
on the one side and restart in case of external reasons
such as power break down[
The case of energy sources with varying power has two
additional aspects[ First\ the energy production depends
on external in~uences\ which might result in unpre!
dictable phases of low or high current[ Second\ there are
times when there is no current at all\ when the electrolyzer
must be kept in a stand!by state[
As the circulating lye transports each product to the
wrong separator\ only high production rates can dilute
this source of contamination to a minor percentage[ This
holds as well for the di}usion of gas through the
diaphragm[ With no current ~owing\ the stripping of the
0005 C[ A[ SCHUG
Fig[ 2[ E.ciency of catalytic unactivated cells as function of current[
Fig[ 3[ Main components for automatic operation[
lye in the cell stack stops so the di}usion and con!
tamination is no longer the central problem[ But system
parameters as pressure and temperature\ which are nor!
mally supported by the electrolysis process itself\ must
now be sustained by external means[ In addition\ all
electrodes in use up to now tend to age each time they
are left without protective voltage\ especially at the oper!
ational temperature[ Therefore\ an additional power
source is needed during stand!by to supply the protective
voltage[
Figure 4 shows the reaction of the pilot!electrolyzer to
a photovoltaic current pro_le as recorded in a German
solar hydrogen test facility[ All system parameters remain
stable as long as the current is kept within the speci_ed
current range of 499Ð1499 amps[ As the voltage current
characteristics of electrolyzer and photovoltaic _eld are
quite di}erent\ they must be coupled by a con!
verter:recti_er\ which can easily be done by modern
thyristor technology[
Stand!by phases are realized by a special program\
which ensures that losses of gas and energy are minimized
without a}ecting safety aspects\ It is recommended to
monitor gas contamination even during stand!by\ but
this results in pressure losses due to the gas analyzers[
According to the demands of the users\ the pressure drop
can be compensated by product gases or left falling[
Using electrolysis as a network peak shaving device is
surely the most complicated case as far as process control
is concerned ð3Ł[ Power plant networks use the frequency
information to check whether the balance between power
production and power consumption is realized[ In West!
ern Europe\ the line frequency is 49 Hz and deviations of
only 0 Hz lead to disconnecting major power customers[
Normal deviations lie in the range of 2099 mHz[ As
power plants cannot change their thermal output within
a few minutes\ short term frequency smoothing is done by
throttle valves\ condenser bu}ering and regional power
transfer[ All of these methods come along with e.ciency
losses and additional investment cost[
Electrolysis can help in smoothing power network
peaks due to power plant failures or consumption chan!
ges[ Using the frequency information locally at places\
where hydrogen is used\ for example service stations in a
future hydrogen fuel scenario\ electrolyzers can change
their consumption within seconds from 09Ð019) nom!
 OPERATIONAL CHARACTERISTICS OF WATER HYDROGEN!ELECTROLYSIS
Fig[ 4[ Reactions to a photovoltaic current pro_le[
inal current and back[ Assuming a cooperation with
power plant networks\ the price for this peak shaving
current could make hydrogen from electrolysis econ!
omically attractive even in the near future[ In Germany\
for example\ the amount of current concerned is in the
range of the fuel consumption of one percent of the
registered cars\ which makes the idea of substitution
reasonable[
Figure 5 shows a typical data pro_le as it was recorded
while simulating peak shaving operation[ The input is a
current pro_le\ which was calculated from frequency data
of the Hamburgische Electricitats!Werke AG[ The orig!
inal data had a minimum at 49 HzÐ66 mHz and is typical
for a failure of one power plant block[ This happens once
or twice a week\ while the minor ~uctuations are normal
changes due to permanent consumption behaviour[
The most important system answer for peak shaving is
the sum of the cell voltages\ as the product of current times
voltages is the consumed power[ As can be seen in Fig[ 5 or
in curves with higher time resolution "not shown#\ the over!
all answer for a jump between 19) and 099) including
measurement delays and the recti_er response\ is less than
2 s[ Most of the time results from controller characteristics
of the recti_er\ which was not optimized for subsecond
control in the pilot!electrolyzer[ The capacitive and thermal
in~uence on the voltage is small\ so that the electrolyzer can
follow a power pro_le\ gained from the frequency infor!
mation\ with about 1 s delay[
The remaining parameters stay constant\ as the process
0006
control system can cope even with the tremendous change
in gas production due to current changes[ The combined
system of valves and communicating pipes minimizes the
~uctuations in the di}erential pressure below less than
204 mbar between the separators[ Compared to this\ all
other system parameters react slowly and can be treated
with standard techniques[
1[2[ Solved problems
During the construction and operation of the Pilot!
Electrolyzer several problems arose\ which could all be
solved up to the present ð4Ł[ Some of them are described
here[
One interesting question is\ which metal can be used
for vessels and pipes[ The speci_cation {{resistant against
potassium lye with 39) at 024>C|| is not su.cient\ as
hydrogen\ oxygen and feed water are additional com!
plications[ Although there is some literature about ten!
sion cracks and nickel corrosion even under the presence
of hydrogen and oxygen ð5Ł\ an optimum between sti}!
ness and corrosion resistance must be found[ One way is
to use pure nickel "1[3959\ more than 88) nickel# as an
inner shield for steel vessel and monel "1[3259# for valves
and pipes and ~anges[ The corrosion rates for pure nickel
are signi_cant only in the presence of oxygen\ but can be
ignored in the case of a shielding of some millimetres
within a steel pressure vessel[
The _rst idea\ to use nickel as material for the nearly
0007 C[ A[ SCHUG
Fig[ 5[ Reactions to a peak shaving current pro_le[
pressureless heat exchanger between lye and feed water\
was a failure[ Nickel corrosion at the feed water side leads
to green dots of oxide\ which leave holes with diameters
of around one millimetre and depths of some micrometre[
All components\ which had contact to the feed water and
are made of pure nickel\ had to be replaced[
To reduce costs\ the experience of pressure electrolysis
was used for the decision to take a metal with approxi!
mately 14) Ni as basic material and to accept monel as
material for subcomponents such as valves and sensors[
PTFE "Poly!Tetra!Fluor!Ethylene# is the favourite
material for coatings and seals in potassium lye[ In fact
no problems arose from PTFE degradation wherever it
was used in lye[ But there is one aspect\ which must be
kept in mind\ when using PTFE in pressure electrolysis[
It is well known\ that PTFE cannot hold back water
vapour\ but at 29 bar and 024>C\ even water from the
potassium lye creeps through the coatings[ As soon as
the pressure is released\ during shut down for example\
the locked!in water blows up the coating[ When the coat!
ing is used for electrical insulation\ as for example in
capacitive level sensors\ the creeping water leads to elec!
trical short circuits[ So\ in using PTFE as coating\ pres!
sure release drillings and electrical resistance calculations
must be kept in mind[
Another speci_c problem is that\ as mentioned above\
pressure electrolyzers must be operated with changing
currents[ Low gas production leads to a higher percentage
of contaminating gases\ because the two main sources for
gases going to the wrong separator are nearly inde!
pendent of the current[ One source for the contamination
is the di}usion of gas through the diaphragms and seals
within the cell block[ The other source is gas dissolved in
the lye[ Each half of the lye stream is saturated with the
corresponding gas during electrolysis and the separators
cannot remove the dissolved gas\ but only the bubbles[
The two lye streams are mixed within the pump and a
quarter of the gas soluble in the total lye ~ow is stripped
on the wrong side\ once it passes through the cell block
again[
Using the right seals and diaphragms\ the di}usion
within the block can be minimized to an unimportant
amount\ but the lye transport mechanism remains[ Keep!
ing in mind the two duties of the lye cycle\ namely heat
and gas transport\ the in~uence can nevertheless be
reduced[ A lye circulation control reduces the lye ~ow to
a minimum\ which is necessary to prevent a dry out of
the diaphragm\ as long as the temperature rise within the
block is small[ As soon as the electrical losses require
more heat transport out of the block\ the lye ~ow is raised
until the temperature rise within the block is kept at the
allowed maximum[ An empirical relationship between lye
~ow\ current and voltage is used for fast reactions and
_ne tuning is done by a temperature controller with ~ow
as a manipulated variable[
As can be seen in Fig[ 6\ the method is able to keep the
more critical contamination percentage of hydrogen in
oxygen within a range of 9[3Ð9[5) as long as the current
 OPERATIONAL CHARACTERISTICS OF WATER HYDROGEN!ELECTROLYSIS
Fig[ 6[ Results of lye circulation control[
remains between 19) and 099) nominal current[ An
extension to 019) is not problematic\ but in the range
down to 09) of the nominal current\ some work must
still be done[
Especially in the case of lye ~ow reduction\ there
should be a kind of safety control for the things going on
within the block[ Within the separators\ no in~ammable
gas mixture can exist as the gas analysis stops the process
at already 49) of the in~ammability limit[ Within the
block\ such a control is not possible by means of gas
analysis but by an indirect method[ A local rise in con!
tamination within the cells as well as a metallic short
cut\ which could be responsible for a ignition\ are both
detectable by a change of voltage drop along the con!
cerned cells[ Therefore each single cell voltage is mea!
sured and compared with the actual mean cell voltage[
Deviations of one or more cells from the mean value lead
to an automatic switch!o} of the current and therefore
to an instantaneous ~oating of the block[ Even though
an ignition restricted to the block would be a minor
accident as far as safety is concerned\ damage at the cell
can be avoided by using this single cell voltage super!
vision[
After this rather detailed discussion of problems\ the
following will present themes of more general interest[
1[3[ Overview and outlook
As mentioned above\ hydrogen production from elec!
trolysis is still a future market[ Yet electrolyzers are com!
mercially available for the laboratory scale of production
of high purity hydrogen[ Without wanting to give full
0008
details\ some other high!pressure electrolyzers should be
mentioned in addition to that of the GHW[
What is meant by laboratory scale can be explained
by the technical data of a commercial advertisement]
maximum power 1999 W\ maximum pressure 29 bar\
e.ciency between 59) and 89)\ maximum temperature
69>C maximum current density 3 kA:m1 ð6Ł[
A rather complete overview of water electrolysis is
given by Sandstede ð7Ł\ although some of the data are
no longer valid[ The GHW!electrolyzer\ for example\ is
presented with data of 0 bar and 4 kA:m1[
One of the most advanced electrolyzer programs is that
of the Gec Alsthom Group together with Electricite de
France ð8Ł[ They concentrate on the o}!peak power
aspect and have realized prototype electrolyzers in the
MW range[
Although international e}ort in electrolyzer devel!
opment has reached a peak\ there is research still going
on[ Finding a solution for high e.ciency catalytic acti!
vated electrodes which do not need a protective potential
in the current!free state\ would be a major breakthrough[
In Germany\ the next projects to be realized are the
coupling of a high!pressure\ high!e.ciency electrolyzer
to a solar test _eld in Neunburg vorm Wald and the
demonstration of the total energy chain from peak shav!
ing electrical power over electrolysis to public buses run!
ning on hydrogen ð09Ł[
2[ CONCLUSION
As has been described above\ high!pressure\ high!
e.ciency electrolysis is a reasonable way into a future
0019 C[ A[ SCHUG
hydrogen energy scenario[ The systems are safe\ easy to
maintain and ~exible enough to be used for all kinds of
electrical power[ Demonstration projects realized tog!
ether with power plant networks will bridge the way into
a near future where hydrogen as tra.c fuel is rec!
ommended for ecological reasons[
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