COMPARISON OF ELECTRICAL ENERGY EFFICIENCY OF ATMOSPHERIC AND

HIGH-PRESSURE ELECTROLYSERS
Amitava Roy*, Dr Simon Watson, Prof David Infield
Centre for Renewable Energy Systems Technology (CREST), Loughborough University,
Leicestershire LE11 3TU, UK
ABSTRACT
Efforts are being made to produce highly pressurised electrolysers to increase the overall energy efficiency by
eliminating mechanical compression. However, in-depth modelling of electrolysers suggests that electrolysis at
atmospheric pressure is electrically more energy efficient if parasitic energy consumption and gas losses are
incorporated in both cases. The reversible cell voltage increases with increasing pressures. The electrode activation
and Ohmic losses, leakage current and inevitable heat losses increase the electrolysis voltage beyond the
thermoneutral voltage and consequently heat removal from the stack becomes essential. The expected gas loss at
various operating pressures is incorporated to reveal the energy consumption that would occur in practice.
Comparison of total energy consumption at various operating pressure up to 700atm is performed and atmospheric
electrolysers are found more efficient at all levels. Practical considerations such as corrosion, hydrogen
embrittlement, operational complexity, dynamic response and cost are less favourable for pressurised electrolysers.

Keywords: Atmospheric electrolysers, pressurised electrolysers, thermodynamic analysis, gas loss, energy
efficiency, practical considerations

1.

INTRODUCTION

The efficiency of electrolysers can be described in different ways, such as the stack efficiency, voltage
efficiency, overall efficiency, energy efficiency and water to hydrogen conversion efficiency. The gas losses
and some of the major parasitic losses are often ignored when calculating the overall energy efficiency. The
milestone report published by the NREL, [1], suggests that electricity costs comprise 80% of the total selling price
of hydrogen from large-scale electrolysers. This emphasises the requirement for an improvement in the electrical

Corresponding author: E-mail address: A.Roy@Lboro.ac.uk, Fax: 0044-(0) 1509-610031,Tel: 0044 -(0)-1509-228147

energy efficiency of electrolysers. The present industry trend is to develop highly pressurised electrolysers to
eliminate conventional mechanical compressors for efficiency improvement. However, the reversible cell voltage
increases significantly with increasing pressure in the first place. The use of a feed water pump becomes essential at
higher operating pressures. Electrolyte circulation pumps are also needed for better removal of the heavier bubbles
formed at extremely high pressure. On the other hand, the enthalpic voltage, thermoneutral voltage and higher
heating voltage of water electrolysis slightly decrease with increasing pressure, which favoures pressurised
electrolysis assuming the electrolysis takes place under perfectly insulated conditions. However, perfectly insulated
conditions are practically difficult to achieve. In reality, the electrode activation and Ohmic losses and leakage
current increase the electrolysis voltage much beyond the thermoneutral voltage and consequently heat removal
from the stack becomes essential. Therefore, optimising the thermoneutral, enthalpic or higher heating voltage at
high-pressure for liquid water electrolysis, to improve the overall energy efficiency is not in practice an effective
approach. The electrical-energy-efficiency is more important than the heat-energy-efficiency in terms of the costs of
hydrogen production, therefore focus should be given on reducing reversible voltage, activation loss and ohmic loss,
to bring the total electrolysis voltage closer to the thermoneutral, enthalpic or higher heating voltages.

The total thermodynamic energy or enthalpic energy required per mole of hydrogen produced is supplied in terms of
electrical energy and heat energy. The change in enthalpic energy with increasing pressure is negligible. However,
the proportion of electrical energy and heat energy varies significantly with temperature and pressure. In this paper,
we have examined the effect of pressure on electrical and heat energy demand for liquid water electrolysis. The
reversible voltage, which represents a major part of the electrical energy consumption, increases with pressure and
the entropy, multiplied by temperature (K), which represents the heat energy demand, decreases with pressure thus
keeping the enthalpic voltage almost unchanged with increasing pressure at any operating temperature below 100 0C.
Due to excess heat already generated, we should not reduce the heat demand further by operating the electrolyser at
higher pressure, as that will further increase the cooling demand and reversible voltage. The enthalpic voltage and
reversible voltage reduce with increasing temperature, irrespective of pressure. We have taken 750C as a common
operating temperature from a practical point of view for both low and high-pressure electrolysis. The thermoneutral
voltage, and higher heating voltage increase with increasing temperature, again irrespective of pressure. A key

objective of this paper is to estimate the electrical energy consumption for hydrogen production (kWh/Nm 3) at
various operating pressures and at 750C. The practical unit of kWh/Nm3 hydrogen is useful to compare with other
hydrogen production methods. It is also then straightforward to find the electrical energy efficiency using the higher
heating value of hydrogen (i.e. 142MJ/kg, 39kWh/kg, 3.5kWh/Nm 3) for liquid water electrolysis.

Nomenclature
H
G
S
T
t
p

H t , p

change in enthalpy (J)

change in Gibbs free energy (J)
change in entropy (J)
temperature (K)
temperature (0C)
pressure (atm)
change in enthalpy at t0C and p atm (J)

0
change in enthalpy at 250C and standard pressure
H 25

(J)

0
t

change in enthalpy at t0C and standard pressure

Vt , p

(J)
enthalpic voltage at t0C and p atm (V)

Vt 0

enthalpic voltage at t0C and standard pressure (V)

n
F
VHHV, t
Vtn
pw

number of electrons transferred (n =2)

Faraday constant (F = 9648530 C/mol)
higher heating voltage at t0C (V)
thermoneutral voltage (V)
vapour pressures of KOH solution (atm)

p w*

vapour pressures of water vapour (atm)

0
f [ H 2O ( l )]t

Gibbs free energy of formation of liquid

water at 250C (= -56690.2 cal)

R
Universal gas constant =8.314 J K-1mol-1
anode charge transfer coefficient for anode= 0.5
cathode charge transfer coefficient for cathode =0.5
F
Faraday constant = 96485.30 C/mol
i
operating current density in A/cm2
i0,anode exchange current density for anode = 0.016A/cm2
at 800C
i0,cathode = exchange current density for cathode 0.02A/cm2
at 800C
Cp
= specific heat capacity of hydrogen,
14.304kJ/kg/K

m
T

= mass flow rate of hydrogen, kg/s

= temperature difference, Kelvin.

This paper mainly focuses on alkaline electrolysers, however, the thermodynamic analysis, discussion about some of
the gas losses and parasitic losses are also applicable to polymer electrolyte membrane (PEM) electrolysers. The
additional electrical energy needed to power such as the extra safety mechanisms and the sophisticated control
systems required in a pressurised electrolyser should also be considered in the overall electrical energy efficiency
calculation. The inevitable increased rate of hydrogen loss in the de-oxidation unit and controlled venting of gas to
balance the electrolyte levels is also a significant design factor for pressurised electrolysers. The water replenishing
system also leads to gas losses if no pump is employed to fill the water. All these gas losses are directly proportional
to the operating pressure. The higher operating pressure reduces the reaction rate and thus increases the activation
loss. The resistivity of electrodes also increases due to metal hydride formation, the rate of which increases with
higher pressure. It can be seen that the overall practical electrolyser efficiency is a result of complex trade-offs.
Detailed models developed in MATLAB-SIMULINK have been used to quantify the operation and energy
consumption of atmospheric and pressurized electrolysers at various delivery pressures. The results from these
models and the operational data from the electrolyser of the HARI project, [2], are the basis of this paper.

2.

THERMODYNAMICS OF WATER ELECTROLYSIS

The electrical energy demand is directly proportional to the reversible voltage. Eq 1 describes the balance between
electrical energy and thermal energy:

H G TS

Eq 1

LeRoy et. al., [3] describe the thermodynamics of water electrolysis. The enthalpy of water splitting is expressed as
follows:

0
0
H t , p H 25
H t0 H 25
H t , p H t0

Eq 2

Where

0
0
H t0 H 25
H t0 H 25

H2

0
0.5 H t0 H 25

O2

and

0
H t0 H 25

H 2O (l )

Eq 3

H t , p H t0 H t , p H t0

H2

0.5 H t , p H t0

O2

H t , p H t0

H 2O (l )

Eq 4

The effect of pressure on enthalpic voltage (Vt, p,), for both non-ideal hydrogen and oxygen gases is calculated, [3]
for the values for 1-100atm shown in

Table

1 using:

Vt , p Vt 0 (H t , p H t0 ) / nF

Eq 5

Table 1is expanded by linear extrapolation up to 700atm. Values up to 700atm pressure are given as at least one
company is engaged in a feasibility study of a 700atm electrolyser under a DOE, USA contract, [4]. It is clear from

Table 1, that the pressure effect on enthalpic voltage is negligible. The enthalpic voltage reduces from 1.473V at
1atm to 1.462V at 700atm at 750C i.e. only a 0.747% reduction. The temperature effect of enthalpic voltage is
expressed as in Eq 6 [3].

Vt 0 1.4850 1.490 x10 4 t 9.84 x10 8 t 2

Eq 6

Eq 7 defines the higher-heating-value voltage, (VHHV, t).

0
0
0
0
VHHV
,t Vt ( H t H 25 ) H 2 O ( l ) / nF

Eq 7

The values of {(H0t-H025) H2O (l)}/nF are obtained from the Steam tables, [5] giving the following expression for
higher-heating-voltage [3].

0
4
8 2
VHHV
,t 1.4756 2.252 x10 t 1.52 x10 t

Eq 8

LeRoy et. al. presented the pressure dependence of higher heating value for 1-100atm, which is further extrapolated
up to 700atm. The values for 750C are also interpolated in Table 2. The higher heating voltage for any temperature
and pressure up to 700atm can be calculated using Eq 8 and Table 2. For example, without the effect of pressure,
VHHV, 75C = 1.49257V and the pressure effect for 1atm at 75 0C = -0.0103mV giving the VHHV, 75C, 1atm = 1.49254V.
The pressure effect is -6.06mV for 700atm from Table 2 giving the VHHV, 75C, 700atm = 1.48648V, which is only 0.4%
reduction compared to the atmospheric-higher-heating-voltage. The percentage increase in reversible voltage for the
same conditions is 12.85%, which is explained later. The higher heating voltage of hydrogen is widely used to
calculate the energy efficiency of electrolysis.
The thermo-neutral voltage (Vtn) is denoted by Eq 9 as follows, [3].

Vtn V HHV

Y
nF

Eq 9

Where,

Y 42960 40.762t 0.06682t 2 ( J / mol)

1.5 p w /( p p w )

Eq 10

Eq 11

ln pw 0.01621 0.1380m 0.1933m

ln pw* 37.04 6276 / T 3.416 ln T

1.024 ln pw*

Eq 12

Eq 13

The vapour pressures of KOH solution (pw) at various temperatures and concentrations were obtained from the
International Critical Tables [6], and fitted to Eq 11, [3]. The value of m=7.64 for 30 (wt)% KOH solution is taken.

The vapour pressure of pure water (pw*) is calculated from Eq 13, with less than 1% error over the range 25-2500C,
[3].

0
Eq 14 gives the reversible voltage, ( E rev
.
,t , p )

0
E rev
,t , p

1
1
G 0f [ H 2O (l )]t
RT ln ( p p w )1.5 p w* / p w
nF
nF

Eq 14

The E0 rev, T (K) at any temperature (Kelvin) without the effect of pressure is given by Eq 15.

0
3
5
8 2
Erev
,T ( K ) 1.5184 1.5421x10 T 9.523x10 T ln T 9.84 x10 T

Eq 15

0
The value of E rev
1.2291V . The pressure effect on reversible voltage can be calculated with the values of
, 250 C

vapour pressure of pure water (pw*) and vapour pressure of KOH (pw) at various temperatures and concentration.
The values of vapour pressure of KOH and water calculated using Eq 12 and Eq 13 are given in Table 3.

The reversible voltage is tabulated in Table 4 incorporating both pressure and temperature effects. It is clear from
the Table 4 that the reversible voltage has increased by 12.85% at 700atm pressure compared to 1atm pressure at
same 750C temperature, thus increasing the energy consumption by the same percentage. For 1000C (liquid water)
operating temperature, this value increases by 15.6%, which could be utilised for efficiency improvement by
operating at 1atm pressure rather than at 700atm.

3.

ELECTRODE KINETICS

The electrode kinetics has been modelled using MATLAB-SIMULINK, incorporating the exchange current density,
cathodic and anodic transfer rate of reaction. The Butler-Volmer equation is used to estimate the activation
overpotential. Its value also depends on the operating current density, temperature and the OH- ion concentration,
which could be effected to some extent by void fraction of gas bubbles. Figure 1 shows the activation overpotential

as a function of current density (mA/cm2). Le Chatelier propounded his principle in 1884, which states that the yield
of a chemical reaction will increase with pressure if the volume of the products is less than the volume of the
reactants. In water electrolysis, the molar volume of the gaseous products is more than the condensed molar volume
of liquid water thus the yield of the reaction is decreased with increasing pressure.

The concentration of OH- ions at the electrode surface is reduced to some extent due to gas blanketing or increased
void fraction, especially in the modern zero gap configuration of electrolyser cells, such as the Stuarts (IMET)
Electrolyser. Modelling of bubble nucleation growth rate and the departure velocity of bubbles require detailed
investigation of mass transfer mechanism. The mass transfer depends mainly on concentration of reaction products,
which can be ascertained only by experiments and such experiments are difficult to perform, which were beyond the
scope of this paper. In most cases, these experiments were performed using a tracer, by measuring the transfer of
tracer to the electrodes (Riegel et. al.[7]). Riegel used a reference electrode, to measure the voltage between these
electrodes and determine the concentration of OH- ions. This method is fairly similar to the approach followed by
Mullar et. al.,[8]. Mullar et. al. determined the concentration of reactants as a function of cathode distance. Nagai et.
al. [9], investigated the bubble movements and void fraction incorporating various parameters such as, current
density, with and without separators, system temperature, space between electrodes, height, inclination angles,
surface roughness and wettability of electrodes. The experimental evidence suggests that that the void fraction
increases with the reduction of space and for each specific current density there is an optimum space. Nagai et. al.
also developed a physical model to represent the qualitative tendency of the experimental results. Kikuchi K et. al.
[10] investigated hydrogen concentration in water from an alkaliionwater electrolyser having a platinumelectroplated titanium electrode. Kikuchi K et. al has also investigated the supersaturated concentration of hydrogen
in electrolysed water, obtained from a flow-type electrolytic cell under various electrolysis conditions, which,
indicates that the hydrogen concentration is related to both the diffusion of dissolved hydrogen from the electrode
surface to the bulk solution and hydrogen bubble growth. All these studies provide very useful knowledge about this
process; however they are based on certain assumption, which do not particularly include the modern zero gap
configuration of the stack of the electrolyser.

The zero gap configurations between perforated electrodes, membranes, current collectors (generally made of dense
nickel wire mesh) and bipolar plates could increase obstructions for free bubble movement, which ultimately could
hinder easy coalescence of bubbles to some extent. Other factors, such as, the surface roughness, surface structure of
electrodes, viscosity of KOH with varying temperature and the bubbles affinity to stick to the electrodes surface
(hydrophilic nature of surface coating) could also influence the coalescence of bubbles. The nucleation growth rate
of bubbles is affected to some extent due to increase in pressure; for example, the bubble volume will be 700 times
smaller at 700atm pressure. The bubbles will be heavier and would stay longer on the electrode surface. The
buoyancy force does not dominate the displacement of bubbles between the gas-separator and perforated electrodes
(Figure 2) as there is no space for free upward bubble movement. Once the bubbles come out to the outer surface of
electrodes, opposite to the electro-active surface, where the electrolyte is circulated (i.e. the space for current
collectors), then the buoyancy dominates the vertical velocity of bubbles. The greater gas voidage at high current
densities would be more noticeable in a zero gap configuration. It is worth mentioning that this would be a
complicated method to accurately measure and observe the bubble growth and removal from the very compact
layers of electrodes, membranes, current collectors and bipolar plates. Although future work is needed on the bubble
removal mechanism in zero gap configurations and precise measurement technique to accurately model its effects
on cell voltage for modern electrolysers, the present modelling also provides fairly good prediction. The activation
overpotential can be calculated using the Butler Volmer equation, in Eq 16 and its value is shown in Eq 17.

act

RT

anode F

ln(

i
i0,anode

RT

cathode F

ln(

i
i0,cathode

Eq 16

Where, the values of each parameter are given in the nomenclature. The operating temperature is taken as 750C.

act

8.314 x348.15
0.451
8.314 x348.15
0.451
ln(
)
ln(
) 0.3873V
0.5 x96485.309 0.016 0.5x96485.309
0.02

Eq 17

The Butler Volmer equation gives fairly accurate prediction of activation overpotential for medium to high netcurrent density depending on the rate of bubble removal from the electrode surface.

4.

OHMIC OVERPOTENTIAL

Ohmic resistance in electrolytic cell increases the voltage required for electrolysis beyond the reversible cell voltage,
which is called Ohmic overpotential. The electrodes, current collectors, bipolar plates, gas electrolyte separators and
electrolyte layer between the electrodes and gas separators constitute the Ohmic resistance of the cell, which vary
with temperature and also due to variation in void fraction of gas bubbles. The resistivity of the electrode will
increase slightly due to metal hydride formation as a result of the reaction between molecular hydrogen and nickel
and other metals that are prone to form hydrides contained in the electrodes, [11]. The rate of metal hydride
formation will increase with higher pressure, thus slightly higher Ohmic overpotential. Table 5 describes the initial
Ohmic resistance of various components of the cell of the actual electrolyser, used in the HARI project. The initial
resistance is measured at 273.15K, which is gradually reduced with increasing temperature, given by the empirical
equation as shown in Eq 18.

R final Rinitial [4 x106 ln(T 273.15) 4 x106 ln T 2 ]

Eq 18

The Eq 18 is valid when the temperature (T) is in the range of 273.15K < T < 350K. The empirical equation has
been developed by curve fitting of the measured current voltage data-sets in tune with the predicted Ohmic
overpotential as generated by the Matlab-Simulink model after several iterations.

The gas production increases at high operating current density, which increases the void fraction of gases in the
electrolyte due to presence of more gas bubbles. The increased void fraction results in increased resistance of the
electrolyte layer, which finally increases the cell voltage and is called here as the bubble voltage loss. This
phenomenon of bubble voltage loss has been modelled using an empirical equation. The empirical equation has been
developed by curve fitting of the measured current voltage data-sets in tune with the predicted Ohmic overpotential
and overall current-voltage profile as generated by Matlab-Simulink model after several iterations. Nagai et. al. [9]
has developed a relationship between the void fraction and current density, which has been referred while
developing the empirical equation of bubble voltage loss. Bubble voltage loss (V bubble) is measured in Volt, which is
a function of the operating current as shown in Eq 19.

10

Vbubble 0.00001* i 4*109 * i 2 109 * i3

Eq 19

Overall.Ohmi c.O v erpotential R final * i Vbubble

Eq 20

The final Ohmic resistance is multiplied by the operating current to find the voltage increase due to final Ohmic
resistance, which is then added to the bubble voltage loss as shown in Eq 20 to calculate the overall Ohmic potential,
which is represented in Figure 3. It shows that the overall Ohmic potential is almost equal to the voltage drop
caused by Ohmic resistance up to 150mA/cm2 current density, which rapidly increases with further increase in
current density. This phenomenon can be explained by the fact that the void fraction of gases increases rapidly in the
zero gap cell structure due to the absence of forced circulation for bubble removal. The resistance of the separator
contributes for about 79% of the total initial resistance (0.00009Ohm out of 0.000114Ohm as shown in Table 5
highlighting the scope of efficiency improvement using better separators. Ion exchange polymer membranes could
be used.

The Ohmic overpotential can change instantly without any time delay with dynamic variation in current unlike the
activation overpotential. Activation loss makes the electrolyser less dynamic, whereas the Ohmic loss allows the
electrolyser to respond immediately. However, activation loss increases logarithmically with increasing current but
the Ohmic overpotential varies linearly due to final Ohmic resistance, therefore the Ohmic resistance will cause
much higher voltage drop at higher current densities than the activation drop. Nevertheless, the bubble voltage loss
increases exponentially with increasing current density thus an optimisation is essential between the activation loss,
Ohmic loss and bubble voltage loss in order to design an electrolyser with adequate dynamic response, better
efficiency and higher gas production rate.

5.

PRACTICAL ELECTROLYSIS VOLTAGE

The SIMULINK model predicts the variation of electrolysis voltage with current density for any temperature,
pressure, total number of cycles and total stand by time. The predicted and measured cell voltage incorporating

11

temperature and pressure-effects on the reversible voltage, activation overpotential and Ohmic overpotential, for a
particular operating pressure, temperature, number of cycles and stand by time are shown in Figure 4. The relevant
values have been measured on the 34kW alkaline type Vandenborre-Stuart Energy's IMET1000 electrolyser,
operating on the HARI project test site near to Loughborough University, UK [2]. Appropriate devices have been
fitted within the electrolyser to record the average values of voltage, current, pressure, temperature, gas purity and
number of cycles at a minimum interval of every 5s. The measured and predicted stack power for dynamic operation
has been shown in Figure 5.

6.

GAS PURITY

The purity of gases depends on many factors. The mixing of electrolyte carrying dissolved gases in the gaselectrolyte-separators is one of the major causes of impurity. The solubility of gases in the electrolyte increases with
higher pressure. Having a separate anolyte and catholyte loop can increase the gas purity. The molecular diffusion
through the micro-pores of the gas-separator is another major cause of impurity in the gases. This is difficult to stop,
however, encouraging faster nucleation growth of bubbles can reduce this, which is easier at ambient pressure. The
presence of nano- or micro-bubbles at very high pressure in a narrow space for a sufficiently long time has the
undesirable effect of diffusion through the gas separators even at 5mbar (0.005atm) differential pressure.

7.

DIFFERENTIAL PRESSURE

This has a direct relationship to gas impurity; but it also causes structural damage to the gas-separators. The
differential pressure-control across the gas-separators is one of the most important operations of any pressurised
electrolyser. The balancing of electrolyte level and associated solenoid valve synchronisation to release the gas from
the system is a complex process. In a bipolar zero gap cell geometry, the pressure between the membrane and either
anode or cathode can vary instantly with fluctuating current input. A high operating pressure for the electrolyser
tends to result in a high differential pressure due to inefficient bubble removal and slightly higher response time
required by the control system for valve opening and closing to release gases. This differential pressure then causes
the gas to diffuse to one gas compartment or the other. The mixing of hydrogen in oxygen has been measured up to

12

2.5% at 120atm pressure by a research organisation in Jlich, Germany [12]; therefore, a significantly higher gasimpurity can be expected at 700atm pressure if the same gas separator is employed.

8.

GAS LOSSES AND ENERGY CONSUMPTION

Gas loss occurs during de-oxidation and drying in common to both atmospheric and pressurised systems but at
different proportions. The gas loss in pressurised electrolysers occurs in the water filling system. The water filling
mechanism depends on the electrolyser manufacturer. The KOH is scrubbed from the gas while replenishing the
reactant water. The water filling mechanism in the Hydrogenics (Stuart Energy -Vandenborre) electrolyser installed
in the HARI project [2], is controlled by several solenoid valves (26 nos.) operating synchronously which has about
2.5% hydrogen loss when operating at 25atm pressure. This loss will increase at higher pressure proportionately if
the same method is employed. To avoid that, a feed-water pump is used to fill water at higher pressure (30atm) but
at some cost in terms of energy consumption and investment, [[13] to [20]]. Although, low flow liquid pumps are
available, however, it is sometimes difficult to get a pump operating at a very high output pressure from ambient
pressure for a very small discharge rate. On the other hand, no hydrogen loss occurs in the atmospheric electrolyser
while filling water under gravity force. A KOH pump is often used with a pressurised electrolyser to increase the
bubble removal rate at higher pressure but with an increased energy cost. The impurity of oxygen in the hydrogen
gas is removed by the de-oxidation unit but this consumes hydrogen and produces water vapour in the hydrogen gas.
The drier is used to absorb the moisture from the gas stream. The moisture content of the gas is then adsorbed in the
molecular sieve. When the drier is fully saturated then the stand-by-drier starts working and the moist drier is
depressurised by venting the wet gas to the atmosphere. This depressurisation causes immediate loss of hydrogen.
Electrical coil heating starts at this point to regenerate the drier bed and this continues for a prescribed duration.
Once the drier bed is heated enough, about 10% of the rated hydrogen production is flushed through it to remove the
traces of air and water for approximately 12 hours at about 6atm pressure. The hydrogen loss and electricity
consumption in this stage of regenerating the drier bed depends on the capacity of the drier. The impurity in the
gases depends mainly on the current density and gas-separator's quality. The hydrogen impurity present in the
oxygen gas cannot be reclaimed and is considered as a direct loss of hydrogen as the oxygen is generally vented to
the atmosphere. Pressurised electrolysers need nitrogen purging if the pressure is reduced to near ambient pressure

13

causing further hydrogen loss, which is not included when calculating the total gas loss given in Table 6. The
inevitable losses through the couplings and through-leakage of valves are high at elevated operating pressure though
this is also not considered in Table 6. The HARI project has experienced several nitrogen purging cycles and
significant gas losses (about 1500Nm3 from November 2003 to December 2005) mainly due to internal-leakage of
valves.

The moisture content in hydrogen varies inversely with the operating pressure. Therefore, the atmospheric
electrolyser has the drawback of higher moisture content in the gas. However, this helps slightly in reduced cooling
demand due to higher latent heat of evaporation of water. Ultimately, atmospheric electrolysers require a
compression stage and as a result the moisture content from the gas is reduced when compressed due to
condensation. Compressors are available in the market with moisture removal features operating with atmospheric
electrolysers. To take an example, the drier gas loss in atmospheric electrolysis combined with compression up to
700 atm is equal to the drier gas loss of 700atm electrolysis.

Electrolysers having pressures more than 30atm generally employ feed-water pumps. Table 7 shows the feed-water
pump energy for an electrolyser having 8Nm3/h hydrogen production rate, for which the water supply rate would be
2.2 x 10-6 m3/sec with a pump efficiency of 75%. Using Eq 21, the power of the feed water pump can be calculated:

Pump.PowerWatt Water. pressureatm * flow.ratem3 / s Eq 21

Onda et al., [20] have suggested that 700atm-pressure electrolysers with feed-water pumps would require 5% less
power in total, than atmospheric electrolysers with four-stage compressors, assuming 50% efficiencies for both
compressor and pump. They have also noticed that the total power would be almost equal, if 75% efficiencies of
compressor and pump were assumed. Metal diaphragm compressors can achieve 75% or more compression
efficiency as demonstrated by Andra's Hofer Compressors for large flow rates, [21]. Metal hydride compressors
have a number of features which make them attractive for use with atmospheric electrolysers, e.g. low power
consumption, scalability, cost, etc. The HERA Hydrogen-(Ergenics), [22], metal hydride compressor can absorb

14

hydrogen at ambient pressure and increase the pressure up to 200atm or higher in a multi-stage process. It consumes
recyclable heat energy at 25kJ/mol hydrogen, which is available as a by-product of electrolysers, fuel cells or
internal combustion engines. The electrical energy consumption will be significantly less than that required for
mechanical compression, when powered by waste heat, which reduces the cost of hydrogen production, [22].
However, Onda et. al. did not include activation overpotential and Ohmic losses in their calculation of electrolysis
voltage. They also did not incorporate other parasitic losses such as balance of plant, drier regenerating energy
consumption, gas losses, gas venting, pressure drop, cooling demands, etc. The parasitic energy consumption is
much higher in smaller pressurised electrolysers due to many solenoid valves, added safety and monitoring devices,
control electronics circuits, KOH pump, pressure and level control mechanisms, etc. Also, the difference in parasitic
energy consumption in pressurised and atmospheric electrolysers is much higher for smaller electrolysers compared
to larger ones. Very large (MW size) pressurised electrolysers will have reduced parasitic loss compared with their
smaller counterparts but need added safety devices due to the increased hazards associated with KOH liquid and
hydrogen under high-pressure (700atm).

The reduced rate of evaporation of water in the pressurised electrolyser increases cooling demand. As an estimate,
about 41kJ heat/Nm3 hydrogen is absorbed from the system for evaporation of water in the atmospheric electrolyser,
whereas 0.05kJ/Nm3 is absorbed in 700atm electrolysers. The actual energy consumption (kWh/Nm 3) in pressurised
electrolysers incorporating the loss of hydrogen is described in Table 8. The actual overall energy consumption in
the Hydrogenics (Stuart Energy- Vandenborre-IMET1000), 25atm electrolyser is about 5.56kWh/Nm3 in its first
cycle if the inevitable hydrogen loss is incorporated in the calculation. We also have experienced about 11% cell
voltage rise due to corrosion in the electrolyser, within 250 on-off cycles in the first 6 months of its installation,
which leads to total energy consumption of 6.023kWh/Nm3. However the cell voltage rise due to corrosion slowed
down gradually and it is fairly stabilised after about 1500 on-off cycles. The corrosion rate increases for several
reasons and higher operating pressure is one of the major causes. However, assuming equal corrosion in the 700atm
pressure electrolyser after 250 on-off cycles, the overall energy consumption would be 6.3 kWh/Nm3, incorporating
the gas losses.

15

The power of the compressor can be calculated for various pressures depending upon the number of stages of
compression from atmospheric pressure. Eq 22 gives the power of the compressor. For example, up to 50atm
pressure, a two-stage compressor can be suitable. Three stage compressors can be used for pressures between 75atm
and 500atm and four-stage compressors can be used for pressures between 600atm and more than 1000atm. Table 9
describes the compressor energy assuming the gas flow rate as 8Nm3/h and the efficiency of the metal diaphragm
gas compressor as 75%.

Wcompressor ,kW C p * T * m

Eq 22

The total energy consumption in an atmospheric electrolyser system including compressor energy is shown in Table
10, assuming the rated current density of 440mA/cm2 at 750C, number of on-off cycles as one and 8Nm3/h hydrogen
production rate. Figure 6 shows the overall energy consumption for pressurised electrolysers at various pressures
and an atmospheric electrolyser with a compressor at the corresponding pressures incorporating gas losses. The
700atm-pressurised electrolyser consumes 16.6% more energy compared to atmospheric electrolysers with external
compression to 700atm pressure. We have taken a conservative estimate in Table 6 of gas purity, which is reflected
in Figure 6. However, if we assume 2.5% hydrogen in oxygen at 700atm pressure which has been measured at a
significantly lower pressure of 120atm, [12] then the total gas loss will be 5.82% at 700atm, which will increase the
energy consumption to 5.89kWh/Nm3, that is 19.9% higher energy consumption than the atmospheric system. It is
worth mentioning that if the practical hydrogen leaks (e. g. internal-leakage of valves etc) at higher operating
pressures were incorporated in Figure 6, then the difference in energy consumption between the two systems would
be even higher. Table 11 compares the total energy consumptions of atmospheric and pressurised systems and the
percentage increase of energy consumption is also shown. The electrical energy efficiency can now be calculated
based on the higher heating value of hydrogen as 3.5kWh/Nm3. The efficiency of a 700atm-pressurised electrolyser
will be 60.9% and 59.4% respectively for 5.74kWh/Nm3 and 5.89kWh/Nm3 hydrogen production energy. Similarly,
the efficiency of the atmospheric electrolyser with a compressor will be 71.1% for a total hydrogen production
energy of 4.92kWh/Nm3, including compression up to 700atm pressure. The Hydrogenics (Stuart EnergyVandenborres alkaline electrolyser -IMET1000) operating in the HARI project, [2], has an energy efficiency of

16

62.9%, for its energy consumption of 5.56kWh/Nm3 at 25atm pressure, including gas losses. With reference to PEM
electrolysers (HOGEN 380) of Proton Energy Systems, the electrical energy efficiency will be 55.5%, for their
energy consumption of 6.3kWh/Nm3 at 13atm pressure, [1], without incorporating gas losses. It is interesting to note
that the energy efficiency of pressurised electrolysers is better in the range of 50-100atm compared to either 25atm
or 200-700atm due to optimisation between gas loss, parasitic energy and pump energy (Table 11). However
atmospheric electrolysers are more energy efficient at all pressures.

9.

PRACTICAL CONSIDERATIONS

The practical aspects of operating electrolysers at higher pressure should be analysed. The membranes or gas
separators and electrodes are the sensitive components of the electrolyser stack. The membranes are subject to
rupture at higher differential pressure. The corrosion and degradation of metallic parts of the stack including the
electrodes, bipolar plates, and current collectors are increased at higher pressure. All these contribute towards
reduced stack life. The solar hydrogen project at Neunburg Vorm Wald, Germany, experienced significant
operational problems and degradation in their high-pressure electrolyser compared to their low-pressure electrolyser
operating under the same conditions. The alkaline type low-pressure electrolyser operated for more than 13 years
and remained the main hydrogen production unit, [23].

The general trend for high-pressure electrolysers often necessitates the encapsulation of the stack and other
components in one pressure vessel made by a thick layer of stainless steel [24], [25]. The pressure vessel is then
filled with water at the same pressure as the stack using a pump. This helps reduce the differential pressure between
the inside and outside of the stack and reduces the chances of leakage from the stack and increases the durability of
seals, O-rings, gaskets, etc. However, this increases the heat capacity of the whole system significantly thus making
it less responsive dynamically. The temperature plays a major role in the efficiency of the electrolysis. It will take
much longer to reach the optimum operating temperature from a cold start. The increase in heat capacity reduces the
thermodynamic response, which makes this type of pressurised electrolyser system less useful when powered by a
fluctuating energy source. As the future sustainable production of large quantities of hydrogen will rely on
fluctuating renewable sources of energy, this is a significant drawback for a pressurized electrolyser. During

17

intermittent power supply from renewable energy sources, it is difficult to maintain the optimum temperature of the
electrolyser stack, which leads to higher cell voltage. The higher heat capacity of the electrolyser further aggravates
this problem. The parasitic loads are generally much higher in pressurised electrolyser due to extra instrumentation
and control systems. These electrolysers when powered by the stand alone renewable energy sources, incur
significant stand-by energy loss over a long period, as they generally spend most of the time in the stand by mode.
In the HARI project, the electrolyser has spend about 90% time in stand by mode in last 2years and consumed
standing power (from 125W to 200W), thus increases the overall energy consumption (kWh/Nm3) significantly. The
high stand by loss in this case is mainly due to over-sizing the electrolyser. It has been found that the average energy
consumption (kWh/Nm3) of electrolyser increases by 14.3% if batteries are used to supply the stand-by loads of the
electrolyser. The energy consumption increases by about 48% in case of fuel cells powering the standing loss. On
the other hand atmospheric electrolysers can be simply switched off, thus no stand by loss. This analysis shows that
the accurate sizing of electrolysers is very crucial for efficient stand-alone energy systems.

The potential risk of splashing or leakage of hot jets of KOH from high-pressure electrolysers must be considered in
a risk assessment and the risk further increases due to higher rate of hydrogen embrittlement. Pressurised
electrolysers have significantly greater numbers of joints and couplings than atmospheric ones, which also increases
the risk of leakage. On the other hand, any potential failure or leakage of KOH from atmospheric electrolysers will
take place slowly and liquid will tend to fall vertically downwards thus greatly reducing the risk of caustic burns.
Recent anecdotal reports of KOH leakage at various electrolyser installations should be considered in the risk
assessment of pressurised electrolysers.

The maintenance problems of pressurised electrolysers are high with the current state of technology, requiring
highly skilled technicians. The cell stack of the 25atm pressurised electrolyser used in the HARI project started
leaking after about 15months of operation, and the stack subsequently has failed after 22 months with 10% run time
due to high impurity of gases and severe KOH leaks from the stack. A new stack has recently been installed using
new separators/membranes and some other modification. The research and operational experience from this project
is being applied to design a low cost novel electrolyser suitable for renewable energy powered operation. On the

18

other hand the maintenance requirements of atmospheric electrolysers are less, although the maintenance of the
compressor can become an issue depending on its type. However, the periodic maintenance of seals and diaphragms
of the compressor is a relatively easy job. In addition, it should be stressed that stand-alone compressors are widely
used in industry in contrast to pressurised electrolysers. A piston compressor has also been in automatic operation
in the HARI project to boost pressure from 25 atm to 137atm without any major problem so far.

10.

FUTURE SCOPE OF ATMOSPHERIC AND PRESSURISED ELECTROLYSERS

The analysis, which has been described above would suggest that atmospheric electrolysers are more energy
efficient than pressurised electrolysers. They have fewer gas losses, higher stack life and require less maintenance.
Presently, the combined cost of an atmospheric electrolyser with an external compressor is about 30% cheaper than
a pressurised electrolyser at the equivalent operating pressure, [26]. Atmospheric electrolysers have a proven record
of operation for many years around the world, [27], [28]. Norsk Hydro says their conventional atmospheric
electrolysers are more energy efficient than their pressurised systems for higher production rates, [28]. Large
electrolysers would be needed in future in forecourts for fuelling vehicles or in various manufacturing industries,
where the hydrogen selling price would be less using atmospheric electrolysers. Large-scale atmospheric
electrolysers could be more suitable for the production of hydrogen fuel to be used for electricity grid balancing and
peak-shaving with their improved efficiency and dynamic response. Most hydrogen consumption devices such as
fuel cells, internal combustion engines and catalytic burners operate within the range of 0.5-5atm, which can be
delivered using external compressors relatively easily. Where space is readily available, e.g. a salt cavern or
underground tankers, then large quantities of hydrogen can be stored at low pressure. If both hydrogen production
and consumption are happening in a synchronous way for example in food processing industries, then the
requirements of hydrogen storage will be less important, which is an ideal situation for atmospheric electrolysers. If
the hydrogen needs to be stored for long-term and in large quantities, then the use of high-pressure external
compressors will be an efficient and economical approach.

The Department of Energy, USA has established a goal under the Matsanuga Hydrogen Implementation Act for
efficiency of hydrogen storage of a volumetric density of 70 kg/m3 and 7 wt % gravimetric densities for

19

transportation applications. The Act states: The high-pressure gaseous storage is a relatively simple technology on
the surface, offering dormancy, easy filling and requiring only appropriate valving and metering to supply product
but it has the disadvantages of low volumetric densities and the perception of being excessively hazardous. For this
reason, it is often seen as a transitional stage of hydrogen storage development, [29]. The prospective development
of efficient metal hydride hydrogen storage could become more attractive than the compressed gas storage for
transportation applications due to higher energy density and increased safety. With the development of metal
hydride compressors, atmospheric electrolysers could become economically feasible even for smaller production
volumes and be suitable for the niche market of fuelling vehicles with higher efficiency and lower cost of hydrogen.

Although there are few hydrogen compressors available for inlet ambient pressure and low flow rates, [30], the
problem of small production volumes (<25Nm3/h) with atmospheric electrolysers relates to the easy availability of
suitable compressors. Low volume atmospheric electrolysers need a large buffer tank between the electrolyser and
compressor in order to match the flow rate of the compressor and that tends to favour pressurised electrolyser
development. However, there is a similar problem even with pressurised (>100atm) electrolysers for small
production volumes because the pressurised electrolyser needs a feed-water pump to avoid significant amounts of
gas losses. For a hydrogen production rate of 8Nm3/h, the required flow rate of water will be 0.0022l/s, which is
difficult for a small pump to deliver at high pressure. Therefore a bigger pump will be necessary and will operate
periodically but that will increase the capital cost and size.

In the absence of commercial metal hydride compressors coupled with atmospheric electrolysers, grid-connected
steady-state medium-pressure (up to 25-100atm) electrolysers can be suitable for smaller production volumes (525Nm3 /h) assuming small discharge and high-pressure feed water pump should be available. They also need to be
more reliable and durable compared with current technology. In the case of high-pressure (>300atm) electrolysers,
the issues of low energy efficiency, complication, restricted dynamic response in conjunction with renewable energy
sources and higher cost need to be addressed for successful commercial reality in the home fuelling market.

20

Electrolysers which operate at pressures of around 700atm involve unnecessary complication, entail increased risk
and have a high cost. In many cases, their role could be better filled using atmospheric electrolysers.

11.

CONCLUSION

This paper has analysed the thermodynamics and gas losses associated with practical water electrolysis. It has been
shown that the reversible voltage increases by more than 12.85% in 700atm-pressurised electrolysers compared to
an atmospheric system. The optimising of thermo-neutral voltage with higher operating pressure for efficiency
improvement is not appropriate as, in practical electrolysers, excess heat is generated due to activation and Ohmic
losses. The reversible voltage should be kept low to increase electrical efficiency, which is possible with an
atmospheric system. The energy consumption in using feed-water pumps and gas compressors is incorporated in the
total energy consumption at various pressures. The energy consumption in 700atm electrolysers is about 16% higher
than the combined energy consumption of atmospheric electrolysers and compressors. Comparison of total energy
consumption at various operating pressures up to 700atm is performed and atmospheric electrolysers are found more
efficient at all levels. The durability, on-off cycle, differential pressure, pressure drop, gas purity and dynamic
response and cost issues do not favour the pressurised electrolysers.

The efficiency of a 700atm-pressurised electrolyser and an atmospheric electrolyser including compression up to

700atm pressure will be 60.9% and 71.1% respectively. The Hydrogenics alkaline electrolyser (IMET1000)
operating in the HARI project, [2], has an average energy efficiency of 62.9%, for its energy consumption of
5.56kWh/Nm3 at 25atm pressure, including gas losses.

Atmospheric electrolysers will be appropriate for large-scale hydrogen production, such as, for vehicle fuelling in
forecourts, balancing of electrical grids and peak shaving. They are also suitable for long-term, mass storage of
hydrogen using external compressors. In addition, their better dynamic response makes them more suitable than
pressurised electrolysers for hydrogen generation powered by fluctuating renewable energy sources. However for
long-term but small quantity storage, pressurised electrolysers might be preferable where energy efficiency is less
important, provided the reliability of operation and durability is improved from the current status. Moreover, with

21

higher reliability and commercialisation of small-scale metal hydride hydrogen compressors, atmospheric
electrolysers could become more attractive than pressurised electrolysers even for small production capacity such as
home fuelling of cars.

ACKNOWLEDGEMENTS
The authors would like to acknowledge Prof Tony Marmont for his financial support in the HARI project. The
authors thank the team members of the HARI project, Rupert Gammon, Murray Thomson, Matt Little and, for their
mutual support. The Government of India fellowship to conduct research in the UK is gratefully acknowledged. The
first author also acknowledges the National Institute of Technical Teachers' Training and Research (NITTTR),
Bhopal, India for sponsoring his study leave.

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Ivy J., Summery of electrolytic hydrogen production: Milestone completion report, NREL/MP-560-35948,
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[2]

HARI project: Hydrogen Economy Comes to the UK, Website last accessed on 02-01-2006.
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Nagaia N., Takeuchia M., Kimurab T., Okaa T., Existence of optimum space between electrodes on hydrogen
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[10]

Kikuchi K., Takeda H., Rabolt B., Okaya T., Ogumi Z., Saihara Y., Noguchi H., Hydrogen concentration in
water from an AlkaliIonWater electrolyzer having a platinum-electroplated titanium electrode, Journal of
Applied Electrochemistry 31: 13011306, 2001.

[11]

Azhazha V, Grib A, Khadzhay G, Merisov B, Pugachov A., Influence of hydrogen on electrical resistivity of
Ti66Ni20Cu10Si4 amorphous alloy, Int. J. Hydrogen Energy 2003; 26:415-418.

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alkalische Wasserelektrolyse bei hohem Druck Projekt-Nr.: 261 107 99 Dr.-Ing. Bernd Emonts
Forschungszentrum Jlich GmbH Institut fr Werkstoffe und Verfahren der Energietechnik (IWV 3).

[13]

Lehman PA., Chamberlin CE., Pauletto G., Rocheleau MA., Operating experience with a photovoltaichydrogen energy system. Int. J. Hydrogen Energy 1997; 22, No.5, pp.465-470.

[14]

Galli S., Stefanoni M., Development of a solar hydrogen cycle in Italy, Int. J. Hydrogen Energy 1997; 22,
No.5, pp. 453-458.

[15]

Kreuter W., Hofmann H., Electrolysis: The important energy transformer in a world of sustainable energy,
Int. J. Hydrogen Energy 1998; 23, No.8, pp. 661-666.

[16]

Yamaguchi M., Shinohara T., Taniguchi H., Development of 2500cm2 Solid polymer Electrolyte water
electrolyser in WE-NET, New Energy Laboratory, Fuji Electric Corporate Research and Development Ltd.,
Nagasaka, Yokosuka city, 240-0194, Japan.

[17]

Schug CA., Operational characteristics of high pressure, high efficiency water-hydrogen electrolysis, Int. J.
Hydrogen Energy 1998; 23, No.12, pp. 1113-1120.

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Dutton A. G., Ruddell A. J., Falchetta M, Prischich D., Dienhart H., Hug W., Bleijs J. A. M., Hydrogen
generation from stand-alone wind powered electrolysis systems, Final report, 1April 1994 to 31 December
1996, Contract No. JOU2-CT93-0413.

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Menzl F., Wenske M., Lehmann J., Fachhochschule Strulsund, ELWATEC Gmbh, Oberwerder D-04668,
Grimma, Germany, Wissenschaftliche Schriftenreihe, Nummer 2: Regenerative Energien.

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Onda K., Kyakuno T., Hattori K., Ito K., Prediction of production power for high-pressure hydrogen by highpressure electrolysis; Journal of power sources 132 (2004) 64-70.

[21]

Andra's Hofer Compressors, Website last accessed on 02-02-2005.

http://www.andreas-hofer.de/english/htm/pdf-infos/diaphragmcompressor10-02.pdf

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HERA Hydrogen -Ergenics- Metal hydride micro compressors: www.ergenics.com,

23

Advanced thermal hydrogen compressors, DaCosta D. H., Golben M. Website last accessed on 02-02-2005.
http://www.eere.energy.gov/hydrogenandfuelcells/pdfs/v10_dacosta.pdf
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[23]

Szyszka A., Toward a (solar) hydrogen energy scheme, Thirteen successful years of SWB's Solar Hydrogen
Demonstration Project at Neunburg vorm Wald, Germany, Field of Solar Hydrogen Solar Hydrogen Plant
No. 23, Manuscript dated July 30, 1999. http://www.neuhaus.com/swb/web_index_e.htm Website last
accessed on 02-02-2005.

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GHW Presents Advanced Pressurized Alkaline Electrolyzer at HYFORUM,

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last accessed on 02-02-2005.

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Mitsubishi Corporation Succeeds in Generating 35MPa High-Pressure Hydrogen Without a Compressor

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02-02-2005.

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lectrolysers_Eng.pdf Website last accessed on 02-02-2005.

[29]

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1994.

[30]

Low inlet pressure and low flow hydrogen compressor, http://www.rixindustries.com/products_hydr.html

24

Table 1 Pressure dependence of the enthalpic voltage (mV), Vt, p

t (0C)
25
75
100

1 atm
-0.0152
-0.0103
-0.0078

25 atm
-0.578
-0.429
-0.354

50 atm
-1.143
-0.844
-0.694

75 atm
-1.686
-1.241
-1.018

Pressure
100 atm 200 atm 300 atm 400 atm 500 atm
-2.208 -4.43
-6.64
-8.85
-11.07
-1.616 -3.24
-4.86
-6.48
-8.1
-1.320 -2.65
-3.97
-5.29
-6.62

25

600 atm
-13.28
-9.73
-7.95

700 atm
-15.5
-11.35
-9.27

Table 2 Pressure dependence of higher heating voltage (mV), (V HHV, t, p - V0HHV, t) (mV)
t (0C)
25
75
100

1 atm
-0.0152
-0.0103
-0.0078

Pressure
25 atm 50 atm 75 atm 100 atm 200 atm 300 atm 400 atm 500 atm 600 atm 700 atm
-0.370 -0.720 -1.048 -1.354 -2.71
-4.06
-5.41
-6.76
-8.15
-9.47
-0.247 -0.473 -0.681 -0.867 -1.73
-2.6
-3.463 -4.328 -5.19
-6.06
-0.185 -0.350 -0.497 -0.624 -1.25
-1.87
-2.49
-3.11
-3.74
-4.36

26

Table 3 Vapour pressure (atm)

Vapour
pressure
pw*(water)
pw (KOH)

298.15K 323.15K 348.15K 373.15K

(250C)
(500C) (750C) (1000C)
0.03103 0.1201 0.3755 0.99157
0.01725 0.0689 0.2216
0.599

27

Table 4 Reversible voltage at various temperature and pressure

Tempera
ture
1 atm
250C
1.229
750C
1.19
1000C 1.153

25 atm 50 atm 75 atm 100 atm

1.299 1.312
1.32
1.325
1.268 1.283 1.292 1.299
1.252 1.269 1.279 1.286

Pressure
200 atm
1.339
1.315
1.303

28

300 atm 400 atm

1.347 1.352
1.324
1.33
1.313
1.32

500 atm 600 atm

1.356
1.36
1.335 1.339
1.325 1.329

700 atm
1.354
1.343
1.333

Table 5 Ohmic resistance of individual components of a cell at 0 0C

Components
KOH layer
Nickel electrode
Nickel current collector
(wire mesh)
Nickel bipolar plate
Gas separator (VITO)
Total initial resistance

Electrode
area, m2
0.1
0.1
0.1

Resistivity, m2/m
0.012
6.8x10-8
5x10-8

Thickness,
m
0.0001
0.001
0.003

Number
of unit
2
2
2

Resistance,

0.1
0.1

6.8x10-8
0.000009 - m2

0.002
-

1
1

0.00000000136
0.00009
0.000114

29

0.000024
0.00000000136
0.000000003

Table 6 Hydrogen gas loss (%) at various operating pressure

Gas loss

Pressure
1 atm 25 atm 50 atm 75 atm 100 atm 200 atm 300 atm 400 atm 500 atm 600 atm 700 atm
Water*
0
2.5
Drier**
4.93
2.8
2.08
1.73
1.2
1.02
0.93
0.88
0.84
0.82
Due to O2 in 0.4x2 0.407x2 0.414x2 0.42x2 0.43x2 0.46x2 0.48x2 0.51x2 0.54x2 0.57x2 0.6x2
H2

H2 in O2
1
1
1.01
1.02
1.03
1.06
1.08
1.12
1.14
1.16
1.2
Total
1.8 9.244
4.64
3.94
3.62
3.18
3.06
3.07
3.1
3.14
3.22
*
Assuming a pump is employed from 50atm to 700atm to fill the water into the electrolyser stack to prevent gas losses. The
absence of feed water pump at 25atm results into gas loss.
** Assuming the drier bed has adsorbing capacity of 225Nm3 moist hydrogen at 25atm at 250C temperature according to
Vandenborre-Stuart electrolyser. The same drier would adsorb 6300Nm3 moist gas at 700atm.

The gas impurity values beyond 100atm pressure are conservative estimates in the absence of actual data. It could
significantly increase with higher pressure [9].
The drier gas loss corresponding to the compressor's output pressure must be added to this value.

30

Table 7 Power of the feed-water pump

Pressure
1 atm 25 atm 50 atm 75 atm 100 atm 200 atm 300 atm 400 atm 500 atm 600 atm 700 atm
Feed water
0.01467 0.022 0.02935 0.05869 0.088 0.1174 0.147 0.176 0.2054
Pump (kW)
Energy
(kWh/Nm3)

0.0018 0.0028 0.0037 0.00734 0.011

31

0.015

0.018

0.022

0.026

Table 8 Energy consumption (kWh/Nm3) in pressurised electrolysers

Pressure
1 atm 25 atm 50 atm 75 atm 100 atm 200 atm 300 atm 400 atm 500 atm 600 atm 700 atm
9.244
4.64
3.94
3.62
3.18
3.06
3.07
3.1
3.14
3.22
4.15 4.345 4.384 4.407 4.422
4.459
4.482 4.498
4.51
4.52
4.53

Gas loss (%)

Stack energy
kWh/Nm3*
Parasitic energy 0.3
0.6
0.63
0.64
0.66
0.72
0.77
0.84
0.89
0.95
1
kWh/Nm3*
Pump energy
0.0018 0.0028 0.0037 0.00734 0.011 0.015 0.018 0.022 0.026
kWh/Nm3
Total energy*
5.045 5.015 5.05
5.09
5.17
5.26
5.35
5.418 5.492 5.556
without gas loss
kWh/Nm3
Total energy*
5.56
5.259 5.257 5.28
5.34
5.42
5.52
5.6
5.67
5.74
with gas loss
kWh/Nm3
*
Assuming the rated current density of 440mA/cm2 at 750C and number of on-off cycle as one and 8Nm3/h hydrogen
production rate. The parasitic power loss will be less for larger systems.

32

Table 9 Power of the hydrogen compressor

Pressure
Compressor stages
2-stage
3-stage
4-stage
Pressure (atm)
25 atm 50 atm 75 atm 100 atm 200 atm 300 atm 400 atm 500 atm 600 atm 700 atm
Gas Compressor 1.339 1.719
1.75
1.894
2.26
2.485
2.65
2.782 2.658 2.738
power (kW)
Energy
0.1674 0.2149 0.2187 0.2368 0.2824 0.3106 0.3313 0.3477 0.3322 0.3423
(kWh/Nm3)*
*
The Energy (kWh/Nm3) is required to compress hydrogen at the corresponding pressures from 1atm.

33

Table 10 Energy consumption (kWh/Nm3) in an atmospheric electrolyser with a compressor.

Pressure
1atm 25atm 50atm 75atm 100atm 200atm 300atm 400atm 500atm 600atm 700atm
6.73
4.6
3.88
3.53
3
2.82
2.73
2.68
2.64
2.62
4.15
-

Gas loss (%)

Stack energy
(kWh/Nm3)
Parasitic energy
0.3
(kWh/Nm3)
Compressor energy
0.1674 0.2149 0.2187 0.2368
(kWh/Nm3)
Total energy without 4.45 4.6174 4.6649 4.6687 4.6868
gas loss
(kWh/Nm3)
Total energy with
- 4.9506 4.889 4.857 4.858
gas loss
(kWh/Nm3)

34

0.2824

0.3106

0.3313

0.3477 0.3322 0.3423

4.7324

4.7606

4.7813

4.7977 4.7822 4.7923

4.878

4.897

4.915

4.929

4.912

4.92

Table 11 Comparison of total energy consumptions of atmospheric and pressurised systems

Pressure (atm)

25

50

75

100

200

Total energy atmospheric 4.9506 4.889 4.857 4.858 4.878

system (kWh/Nm3)
Total energy pressurised
5.56 5.259 5.257 5.28 5.34
system (kWh/Nm3)

300

400

500

600

700

4.897

4.915

4.929

4.912

4.92

5.42

5.52

5.6

5.67

5.74

Percentage increase (%) 12.31% 7.57% 8.24% 8.69% 9.47% 10.68% 12.31% 13.61% 15.43% 16.66%

35

Activation Overpotential temperature=750C, i0, anode=

2

Current density (A/cm 2)

Figure 1

Activation overpotential

36

0.45

0.4

0.35

0.3

0.25

0.2

0.15

0.1

0.05

0.45
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
0

Activation overpotential
(V)

0.016A/cm , i0, cathode=0.02A/cm , charge transfer

coefficient for anode and cathode=0.5

Figure 2 Schematic diagram of cell structure

37

Ohmic overpotential including bubble voltage

Temperature=348.15K

Ohmic overpotential (V)

0.14
0.12

overpotential based on Ohmic

resistance only

0.10

overpotential including bubble voltage

loss and Ohmic resistance

0.08
0.06
0.04
0.02
0.00
0

50

100

150

200

250

300

350

400

450

Current density (mA/cm )

Figure 3 Overall Ohmic overpotential including bubble voltage loss

38

Electrolysis cell voltage

2
1.9
1.8
1.7
1.6
1.5
1.4
1.3
1.2
1.1
1

Predicted voltage, V

Current Density (mA/cm2)

Figure 4

Practical electrolysis voltage

39

475

450

425

400

375

350

325

300

275

250

225

200

175

150

125

100

75

50

25

Measured voltage, V

Cell voltage (V)

Temperature=348.15K, Pressure=18atm, On-of f cycle=712, Stand by time=4933.17

x 10

Measured and predicted stack power

Predicted Power (resolution 0.01s)
Measured Power (resolution 5s)

Measured and predicted stack power (W)

4.5
4
3.5
3
2.5
2
1.5
1
0.5

200

400

600

800

1000 1200 1400 1600 1800 2000 2200

Time (s)

Figure 5 Measured and predicted stack power

40

atmospheric electrolyser
pressurised electrolyser

5
4
3
2

700 atm

600 atm

500 atm

400 atm

300 atm

200 atm

75 atm

100 atm

50 atm

25 atm

Energy consumption
(kWh/Nm 3)

Pressure

Figure 6

Comparison of energy consumption

41

List of Figures .................................................................................................................... Page No.

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6

Activation overpotential ........................................................................................... 36

Schematic diagram of cell structure .......................................................................... 37
Overall Ohmic overpotential including bubble voltage loss ..................................... 38
Practical electrolysis voltage ..................................................................................... 39
Measured and predicted stack power ........................................................................ 40
Comparison of energy consumption ......................................................................... 41

NOTICE: this is the authors version of a work that was accepted for publication in International Journal of Hydrogen
Energy. Changes resulting from the publishing process, such as peer review, editing, corrections, structural
formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been
made to this work since it was submitted for publication. A definitive version was subsequently published in Roy A,
Watson S J and Infield D G (2006). Comparison of electrical energy efficiency of atmospheric and high-pressure
electrolysers. International Journal of Hydrogen Energy 31 pp 1964-1979. DOI:
http://dx.doi.org/10.1016/j.ijhydene.2006.01.018 .

42