Int. J. Electrochem. Sci.

, 6 (2011) 2566 - 2580

International Journal of
ELECTROCHEMICAL
SCIENCE
www.electrochemsci.org

Configuration Designs and Parametric Optimum Criteria of an

Alkaline Water Electrolyzer System for Hydrogen Production
Houcheng Zhang, Shanhe Su, Guoxing Lin, Jincan Chen*

Department of Physics, Xiamen University, Xiamen 361005, People’s Republic of China

*
E-mail: [email protected]

Received: 2 May 2011 / Accepted: 5 June 2011 / Published: 1 July 2011

An alkaline water electrolyzer system for hydrogen production and its semi-empirical equations are
directly used to analyze and optimize the performance of the system. The results obtained through
thermodynamic-electrochemical analysis show clearly that for such an alkaline water electrolyzer
system, there exist some optimal values of the electrolyte concentration under different operating
temperatures and the Joule heat resulting from the irreversibilities inside the alkaline water electrolyzer
is larger than the additional heat needed in the water splitting process. Consequently, some new
configurations for utilizing the surplus heat in the alkaline water electrolyzer are put forward to
improve the performance of the system. The general performance of these new configurations is
discussed, from which the lower bound of the operating current density is determined. In order to
further optimize the characteristics of these configurations, a multi-objective function including both
the efficiency and hydrogen production rate is originally put forward and used to determine the upper
bound of the operating current density. The optimum criteria of main parameters and the optimally
working region of the alkaline water electrolyzer system are given. In addition, the effects of some
important parameters on the performance of the system are analyzed in detail.

Keywords: Alkaline water electrolyzer, overpotentials, configuration design, multi-objective function,

parametric optimum criterion

1. INTRODUCTION

Hydrogen energy is expected to be useful as the secondary energy in the near future, for
example as a fuel for transportation, electricity generation in fuel cells, or other applications [1-8].
Unfortunately, the vast majority of hydrogen used today is produced by fossil-fuel-based processes
which may result in gas emissions such as COx, SOx and NOx. On the other hand, the fossil-fuel-based
hydrogen production processes are both subject to large price fluctuations and a limit in global supply
[9-12]. The development of renewable, efficient and economical hydrogen production technologies to
Int. J. Electrochem. Sci., Vol. 6, 2011 2567

replace fossil-fuel-based hydrogen production methods is key step towards a sustainable “hydrogen
economy” [13-16].
Water electrolysis integrated with photovoltaics, nuclear power stations or wind turbines is one
of the most promising methods for large-scale renewable hydrogen production [17-20]. The
electrolysis of aqueous alkaline solutions has historically been one of the most popular routes for
hydrogen production [21-24]. Recently, most studies related to alkaline electrolysis emphasize on the
development of new advanced electrocatalyst materials [25-29] and the increase in the operating
temperature of the electrolysis cell [9, 19, 30, 31]. Comparatively, the detailed systematical
configuration design and parametric optimum are rare in the current literature, but they are of
importance for better understanding the performance improvement and operating mechanism of an
alkaline water electrolyzer and worthwhile to be further studied.
In the present paper, we evaluate and analyze the performance of an alkaline water electrolyzer
system for hydrogen production, based on its semi-empirical equations, and structure some new
configurations of an alkaline water electrolyzer system so that the redundant heat in the alkaline water
electrolyzer may be utilized. The performance characteristics of these new configurations are discussed
and optimized. Some significant results are obtained.

2. THE POWER INPUT OF AN ALKALINE WATER ELECTROLYZER SYSTEM

The schematic diagram of an alkaline water electrolyzer system for hydrogen production is
shown in Fig. 1.

Figure 1. The schematic diagram of an alkaline water electrolyzer system.

Int. J. Electrochem. Sci., Vol. 6, 2011 2568

The system mainly consists of an alkaline water electrolyzer using circulating KOH solution as
electrolyte, a separator and two heat exchangers. The model established here is general and reasonable
as it can be connected to any power generation system and the waste heat contained in the products can
be efficiently utilized. Water, electricity and heat, if necessary, are provided to the alkaline water
electrolyzer to drive the water splitting reactions. The generated H2 and residual H2O flow out at the
cathode and the generated O2 flows out at the anode. Since a large fraction of the heat added to the
feed water is remained in the products at the outlet, it is desirable to recover the waste heat from the
products through heat exchanger 1. After leaving heat exchanger 1, O2 is cooled down to reference
condition (T0 = 298.15 K and p0 = 101.33 kPa) and can be used as by-product. The H2/H2O mixture
flows into the separator, H2 is cooled down and stored as fuel; and the hot H2O is circulated for the
next H2 production cycle. Due to the inefficiency of exchanger 1 and different thermodynamic
parameters of reactant/products, the feeding water should be further heated through exchanger 2 before
reaching the temperature of the alkaline water electrolyzer.
According to Fig. 1, the overall water electrolysis reaction is that H2O plus electricity and heat
turns to H2 and O2, i.e., H2O+heat+electricity→H2+ (1 / 2) O2. The total energy required for electrolytic
hydrogen production △ H(T) is the sum of thermal energy demand Q(T) and electrical energy demand
△ G(T), i.e.,

H (T )  Q(T )  G(T ) , (1)

where Q(T)=T△ S(T), △ S(T) is the entropy change in the water splitting reactions, △ G(T) is the
change in the Gibbs free energy, and T is the operating temperature of the alkaline water electrolyzer.
Generally, the standard thermodynamic parameters such as △ H(T), △ S(T) and △ G(T) have different
values at different temperatures even under a constant pressure condition. These thermodynamic
parameters can be calculated from the data in Table 1 [32-35].

Table 1. Thermodynamic parameters for the reactant/products at 101.325 kPa, where (g) and (l)
represent gas phase and liquid phase, respectively.

Compound G(T0) H(T0) S(T0) Heat Capacity(Cp)

(J mol-1) (J mol-1) (J mol-1) (J mol-1 K-1)
H2 (g) -38,960 0 130.68 27.28+0.00326T+50000/T2
O2 (g) -61,120 0 205.00 29.96+0.00418T-167000/T2
H2O (l) -306,690 -285830 69.95 75.44

For an electrochemical process operating at constant pressure and temperature, the minimum
input work required is equal to the change in Gibbs energy G(T ) . According to Faraday’s law, the
voltage required for a reversible electrochemical process can be expressed as [23, 24, 36, 37]

G (T )
U rev  , (2)
ne F
Int. J. Electrochem. Sci., Vol. 6, 2011 2569

where ne is the number of electrons transferred per hydrogen molecule and F is Faraday’s
constant.

Table 2. Parameters used in the modeling.

Parameter Value
Faraday constant, F (C mol-1) 96,485
Number of electrons, ne 2
Universal gas constant, R (J mol-1 K-1) 8.314
Low heating value of H2, LHV (KJ mol-1) 241.83
Partial pressure of product H2, PH 2 (atm) 1
Partial pressure of product O2, PO2 (atm) 1
Partial pressure of product H2O, PH 2O (atm) 1
Constant, c1 (A. m-2) 174,512
Constant, c2 (K) 5485
Transfer coefficient,  0.1668
Area of single-cell polar plate, Ap (m2) 0.064
Limiting current density, j L (A m-2) 2000
Thickness of the electrolyte, tele (m) 0.01
Effectiveness of the heat exchangers,  0.7
Inlet flow rate of water, N H 2O ,in (mol s-1) 6.6×10-4
Temperature of the AFC, T (K) 353
Temperature of the external heat source, Ts (K) 400
Temperature of the environment, T0 (K) 298.15

When a water electrolyzer comes into operation, the required voltage U is always larger than
the reversible voltage U rev because of the irreversibilities resulting from the water splitting reactions
and may be expressed as

U  U rev  U act  U con  U ohm , (3)

RT  j
where U act  ln   is the activation overpotential losses related to the electrochemical
ne F  j0 
 c 
kinetics [32, 36, 38], j0  c1 exp  2  is the exchange current density, c1 and c2 are constants which
 T 
RT  j 
are independent of T ,  is the transfer coefficient; U con  ln  L  is the concentration
ne F  jL  j 
t
overpotential losses caused by mass transfer [32, 38], j L is the limiting current density; U ohm  j ele is
k
Int. J. Electrochem. Sci., Vol. 6, 2011 2570

the ohmic overpotential losses caused by the resistance of electrolyte as the resistance of electrodes can
be neglected compared with that of electrolyte [32, 39], t ele is the thickness of the KOH electrolyte,
and k is the specific conductivity of the KOH solution. Based on the experiment data, Gilliam et al.
[40] developed an equation which can be used to describe the relationship between the specific
conductivity  of aqueous KOH solution and electrolyte concentration M, i.e.,

 2.041M  0.0028M 2  0.005332MT  207.2M / T  0.001043M 3  0.0000003M 2T 2

 , (4)
100

which was very valid for temperatures from 0 0C to 100 0C and for KOH concentrations from 0
to 12 M [40].

By using Eqs. (2)-(4) and the parameters listed in Table 2 [38, 41], the electrochemical
characteristics of an alkaline water electrolyzer are clearly shown in Fig. 2.

Figure 2. Three dimensional figures of the required voltage versus electrolyte concentration and
current density for different operating temperatures.
Int. J. Electrochem. Sci., Vol. 6, 2011 2571

It shows that the voltage required increases as the operating current density is increased, while
it decreases as the operating temperature is increased. The influence of the electrolyte concentration on
the required voltage is negligible when the operating current density is small and increases with the
increase of the operating current density. When the alkaline water electrolyzer system is operated at
high current densities, the voltage required first decrease and then increase as the electrolyte
concentration is increased, and consequently, there exists a minimum input voltage, as shown in Fig. 2.
By using numerical calculation, the concrete values of the optimum concentration M min for some given
operating temperatures are listed in Table 3. It is seen from Table 3 that M min increases with the
increase of the operating temperature.

Table 3. The optimal electrolyte concentrations for different operating temperatures.

T(K) 343 353 363

M min (mol L-1) 7.383 7.543 7.671

By using Eqs.(2)-(4), the electric power required by the alkaline water electrolyzer can be
expressed as

I RT  j  RT  jL  ne Ftele
P  IU  [G (T )  ln    ln   j ], (5)
ne F   j0    jL  j  k

where I  jAe is the electric current through the alkaline water electrolyzer and Ae is the
effective surface area of the alkaline water electrolyzer.

3. THE DIFFERENT CONFIGURATIONS AND EFFICIENCIES OF AN ALKALINE

WATER ELECTROLYZER SYSTEM

For an alkaline water electrolyzer, the Joule heat produced per unit time may be expressed as

QJ  I (U act  U ohm  U con ) . (6)

Practically, the Joule heat produced in the electrolyzer is unnecessarily released to the
environment and may be directly used to supply to the water splitting reactions. Thus, the thermal
energy required for the electrolyzer per unite time may be reduced from Q to

QAE  (Q  QJ ) . (7)

According to Fig. 1 and Refs. [33, 39, 41], the heat supplied by the external heat source for
heating compensatory water can be calculated by the following equation:
Int. J. Electrochem. Sci., Vol. 6, 2011 2572

N H 2O,in T
N T T T

QH 2O 
 T0 p,H2O  H2 ,out T0 p,H2
C dT  C dT  N O2 ,out 
T0
C p ,O2 dT  N H 2O ,out  C p , H 2O dT 
T0 
 I  T I C p ,O2
  N H 2O ,in 1/   1 
T

  
2 F  T0
C p , H 2O dT 
2F T0
(C p , H 2 
2
)dT , (8)

where N i are the inlet or outlet flow rates of species i (H2O, H2 or O2),  is the effectiveness of
the heat exchanger, C p ,i are the molar heat capacities of species i at one atmospheric pressure [33-35],
and T0 is the environment temperature.

Figure 3. The curves of QAE and QTE varying with the current density for different temperatures,
where QTE  QAE (1  T0 / T )  QH2O (1  T0 / Ts ) and jQ is the current density when QTE  0 .

It may be easily proved from Eq. (8) and the data in Tables 1 and 3 that QH 2O  0 . According to
the above analysis, we can further obtain the curves of Qk (k=AE and TE) varying with j, as shown in
Fig. 3, where QTE  QAE (1  T0 / T )  QH2O (1  T0 / Ts ) , jQ is the current density when QTE  0 , and Ts is
the temperature of the external heat source used to heat up H2O. It is clearly seen from Fig. 3 that the
electrolyzer works at the temperatures between 343 K and 363 K, QAE  0 , QTE  0 in the region of
j  jQ , and QTE  0 in the region of j  jQ .
According to Fig. 1 and the above analysis, the efficiency of the system can be expressed as
[33]
Int. J. Electrochem. Sci., Vol. 6, 2011 2573

N H 2 ,out LHV
 , (9)
T0
P  QH 2O (1  )
Ts

where LHV is the lower heating value of H2.

It is worthwhile to point out that besides Fig. 1, one can design some new configurations for an
alkaline water electrolyzer system, as shown in Fig. 4.

Figure 4. The part schematic diagrams of an alkaline water electrolyzer system for hydrogen
production with (A) QTE  0 and (B) QTE  0 . The other parts of the system are the same as
those in Fig. 1.

It is seen from Fig. 4(A) that when QAE  0 and QTE  0 , the surplus heat QAE generated in the
electrolyzer may be used to heat the water through an additional heat exchanger, i.e., heat exchanger 3
shown in Fig. 4(A). The heat QAE (1  T0 / T )Ts / (Ts  T0 ) , which has the same temperature level as the
Int. J. Electrochem. Sci., Vol. 6, 2011 2574

external heat source connected to heat exchanger 2, is transferred to the water, so that the heat supplied
by the external heat source may be reduced from QH 2O to QH2O  QAE (1  T0 / T )Ts / (Ts  T0 ) . In such a
case, the efficiency of the system can be expressed as

N H 2 ,out LHV
 . (10)
T0 T0
P  QAE (1  )  QH 2O (1  )
T Ts

It is seen from Fig. 4(B) that when QAE  0 and QTE  0 , one part of the surplus heat QAE may
be used to replace the heat QH 2O supplied by the external heat source and to heat the water so that the
temperature of the water attains that of the electrolyzer, and the other part of the surplus heat QAE is
released to the environment.
The heat transferred from the electrolyzer to heat exchanger 2 is equal to
QH2O  QAE (1  T0 / T )Ts / (Ts  T0 ) , which has the same temperature level as the external heat source,
and the heat released to the environment is [ QAE  QH2O ]  QAE 1  (1  T0 / T )Ts / (Ts  T0 ) . In such a
case, neither Eq. (9) nor Eq. (10) may be directly used to calculate the efficiency of the system, while
the efficiency of the system should be determined by

N H 2 ,out LHV
η= . (11)
P

Equations (9)-(11) clearly show that the performance of an alkaline water electrolyzer depends
on a set of thermodynamic and electrochemical parameters such as the operating temperature, current
density, electrolyte thickness, electrolyte concentration, and so on. The related parameters are
summarized in Table 2, and these parameters are kept constant in the following calculation unless
mentioned specifically.

4. OPTIMIZATION ON THE PERFORMANCE OF AN ALKALINE WATER

ELECTROLYZER

Using Eqs. (9)-(11), one can obtain the curves of the efficiency versus the current density, as
shown in Fig. 5, where curves I and II correspond to the systems shown in Figs. 1 and 4, respectively.
It is seen from Fig. 5 that the efficiency first increases and then decreases as the current density is
increased. When the current density approached to the limiting current density, the efficiency
decreases quickly. Moreover, the efficiency of the system (Curve II) shown in Fig.4 is larger than that
(Curve I) shown in Fig. 1. It is natural because the redundant heat QAE generated in the alkaline water
electrolyzer is utilized in the systems shown in Fig. 4. Below, we will only discuss the performance of
the systemic configurations shown in Fig. 4.
Int. J. Electrochem. Sci., Vol. 6, 2011 2575

It is also seen from Fig. 5 that for an alkaline water electrolyzer system, there is a maximum
efficiency ηmax and a corresponding current density jm . When    max , there always exist two
corresponding current densities for a given efficiency, where one is smaller than jm and the other is
larger than jm . Under the same efficiency, one always hopes to obtain a higher H2 production rate
N H 2 ,out .

Figure 5. The curves of the efficiency and new multi-objective function varying with the current
density for different configurations, where curve I corresponds to the system shown in Fig. 1,
curves II and III correspond to the systems shown in Fig. 4, and jm and jZ are the current
densities at the maximum efficiency  max and maximum new multi-objective function Z max ,
respectively.

According to Faraday’s law, the rate of electrochemical reaction  is determined by

  I / (ne F ) [18, 33, 42], and consequently, the production rate of H2 can be expressed as

jAe
N H 2 ,out = . (12)
ne F

Equation (12) indicates clearly that the hydrogen production rate is proportional to the current
density. Thus, taking into account both the efficiency and the hydrogen production rate, one can
determine that the optimal current density should be located in the region of
Int. J. Electrochem. Sci., Vol. 6, 2011 2576

j  jm . (13)

When the system is operated in this region, the hydrogen production rate N H 2 ,out will increase as
the efficiency  is decreased, and vice versa. Thus, in the optimal region of j  jm , the reasonable
choice of both the efficiency  and the hydrogen production rate N H 2 ,out must be still considered
simultaneously. Equations (10)-(12) just provide some theoretical bases for solving this problem.
Using Eqs. (10)-(12), we may introduce a multi-objective function as [43-45]

Z  N H 2 ,out , (14)

which is the product of the efficiency  and the hydrogen production rate N H 2 ,out . Curve III in
Fig. 5 shows the characteristics of the new multi-objective function varying with the current density,
where Z *  Z / Ae , Z max
*
is the maximum value of Z * , and jZ is the current density corresponding to
*
Z max . It is seen from Fig. 5 that the new multi-objective function first increases and then decreases as
the current density is increased. In the region of j  jZ , the efficiency decrease quickly as the current
density is increased. It results in a net decrease of the new multi-objective function. Thus, one can
further determine that, in general, jZ is the upper bound of the optimized current density and the
system should be operated in the region of

jm  j  j Z . (15)

5. EFFECTS OF SOME PARAMETERS ON THE PERFORMANCE OF THE SYSTEM

Obviously, the performance of an alkaline water electrolyzer depends on a set of

thermodynamic and electrochemical parameters. Below, we will discuss the effects of some important
parameters on the performance of the system.
Figure 6(A) shows the influence of the operating temperature on the performance of the
system. In the region of jm  j  jZ , the efficiency of the system increases as the operating temperature
is increased. The maximum efficiency and the current density at the maximum efficiency also increase
with the increase of the operating temperature. It may be explained as follows. At higher operating
temperatures, the electrodes of the electrolyzer are more reactive, leading to a higher exchange current
density and thus a lower activation overpotential. Moreover, as the operating temperature is increased,
the mass transfer within the electrolyzer is improved so that there is a net decrease of the resistance. As
a result, the input voltage decreases with the increase of temperature and it results in a reduced
electrical energy input.
Figure 6(B) shows the influence of the electrolyte thickness on the performance of the system.
In the region of jm  j  jZ , the efficiency of the system decreases as the electrolyte membrane
thickness is increased. The larger the current density is, the larger the influence of the electrolyte
membrane thickness on the efficiency of the system. This phenomenon can be explained as follows:
Int. J. Electrochem. Sci., Vol. 6, 2011 2577

the thicker the electrolyte membrane is, the larger the ohm overpotential losses and the electrical
energy input. It necessarily results in a lower efficiency for a thicker electrolyte membrane.

B
Int. J. Electrochem. Sci., Vol. 6, 2011 2578

Figure 6. The efficiency versus current density curves for different (A) operating temperatures, (B)
electrolyte membrane thickness, (C) effectiveness of the heat exchangers, and (D) inlet flow
rates of H2O, where jm is the current density at the maximum efficiency  max .

Figure 6(C) shows the influence of the effectiveness of the heat exchangers on the performance
of the system. The efficiency of the system increases as the effectiveness of the heat exchangers is
Int. J. Electrochem. Sci., Vol. 6, 2011 2579

increased. However, the influence mainly happens in the vicinity of j = jm . When j is large, QAE is
much larger than QH 2O so that the influence of the effectiveness of the heat exchangers is negligible.
Figure 6(D) shows the influence of the inlet flow rate of H2O on the performance of the system.
The efficiency of the system decreases as the inlet flow rate of H2O is increased. The influence mainly
happens in the vicinity of j = jm , while the influence of the inlet flow rate of H2O is negligible in the
other regions.

6. CONCLUSIONS

Based on semi-empirical equations and thermodynamic-electrochemical analyses of an alkaline

water electrolyzer system, the performance of the system is evaluated and optimized. It is found that
when the electrolyte concentration is increased, the input voltage of the electrolyzer first decreases and
then increases for other given parameters. The result will be helpful to find one optimal value of the
electrolyte concentration so that the input voltage of the electrolyzer obtains its minimum value. It is
confirmed that the Joule heat resulting from the irreversibilities inside the electrolyzer is larger than the
additional heat needed in the water splitting process. Moreover, some new configurations of an
alkaline water electrolyzer system are put forward. It is found that the performance of the new
configurations is better than that of the system that the redundant heat is directly released into the
environment. According to the performance characteristics of the new configurations, the lower bound
of the operating current density is determined. By considering both the efficiency and the hydrogen
production rate of the system, a multi-objective function is introduced to further optimize the
performance of the system, and consequently, the upper bound of the operating current density is also
determined. Finally, the influence of some parameters on the performance of the alkaline water
electrolyzer system operated in the optimal region is discussed in detail. The results obtained here may
provide some guidance for the optimum design and operation of practical alkaline water electrolyzer
systems for hydrogen production.

ACKNOWLEDGEMENTS
This work has been supported by the National Natural Science Foundation (No. 51076134) and the
Fundamental Research Fund for the Central Universities, People’s Republic of China.

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