Respuestas, 24 (2) May - August 2019, pp.

6-15, ISSN 0122-820X - E ISSN: 2422-5053

Journal of Engineering Sciences

Original Article https://doi.org/10.22463/0122820X.1826

Modeling and simulation of an electrolyser for the production of HHO in Matlab-

Simulink®
Modelamiento y simulación de un electrolizador para la producción de HHO en Matlab-Simulink®
Erick Daniel Rincón-Castrillo1*, José Ricardo Bermúdez-Santaella2, Luis Emilio Vera-Duarte3, Juan José García-Pabón4
1*
Electromechanical Engineer, [email protected], ORCID: 0000-0002-2425-3833, Universidad Francisco de Paula Santander, San José de
Cúcuta, Colombia.
2
Magister in Automation and Instrumentation, [email protected], ORCID: 0000-0001-9265-0083, Universidad Francisco de Paula Santander, San
José de Cúcuta, Colombia.
3
Magister in Thermal Engineering, Mention Thermofluidics, [email protected], ORCID: 0000-0001-8756-7779, Universidad Francisco de Paula
Santander, San José de Cúcuta, Colombia.
4
PhD in Mechanical Engineering, [email protected], ORCID: 0000-0002-1894-534X, Universidade Federal de Itajubá, Itajubá, Brasil.

How to cite: E.D. Rincon-Castrillo, J.R. Bermudez-Santaella, L.E. Vera-Duarte, J.J. García-Pabón, “Modeling and simulation
of an electrolyser for the production of HHO in Matlab-Simulink®”. Respuestas, vol. 24, no. 2, pp. 6-15, 2019.
Recibido: Agosto 10, 2018; Aceptado: Noviembre 15, 2018

ABSTRACT
Keywords: The electrolyzers work through an electrochemical process, their derivatives (H2, O2, and HHO) are used as
enriching fuels due to the electrolysis of water, being cleaner than gasoline and diesel. This article presents
Alkaline
the dynamic model of an alkaline electrolyzer that uses an electrolyte (KOH o NaHCO3) dissolved in
Electrolyser,
distilled water to accelerate the production of oxyhydrogen (HHO). The model shows the phase change that
Dynamic model,
occurs inside the electrolytic cell. The EES® software was used to determine the values of enthalpy, entropy,
Simulation,
and free energy that vary during the electrochemical reaction; the equations were simulated in Matlab-
Matlab-Simulink®,
Simulink® to observe their dynamic behavior. The Simulations presented varying every 5 g the electrolyte
EES.
until reaching 20 g. The flow rate of HHO with potassium hydroxide (20 g) is higher than 0.02 L / s, and with
sodium bicarbonate (20 g) it is above 0.0006 L / s, confirming what the literature of alkaline cells state, that
the most efficient electrolyte for its energy conversion is KOH.
RESUMEN
Palabras clave: Los electrolizadores funcionan mediante un proceso electroquímico, sus derivados (H2, O2, y HHO) debido a la
electrólisis del agua son utilizados como combustibles enriquecedores, siendo más limpios que la gasolina y diesel.
Electrolizador
Este artículo presenta el modelo dinámico de un electrolizador alcalino que utiliza un electrolito (KOH o NaHCO3)
alcalino,
disuelto en agua destilada para acelerar la producción de oxihidrógeno (HHO). El modelo muestra el cambio de
Modelo dinámico,
fase que ocurre en el interior de la celda electrolítica. Se utilizó el software EES® para determinar los valores de
Simulación,
entalpía, entropía, y energía libre que varían durante la reacción electroquímica, las ecuaciones fueron simuladas en
Matlab-Simulink®,
Matlab-Simulink® para observar su comportamiento dinámico. Las simulaciones fueron realizadas variando cada 5
EES.
g el electrolito hasta llegar a 20 g. El caudal de HHO con hidróxido de potasio (20 g) es superior a 0.02 L/s, y con
bicarbonato de sodio (20 g) está por encima de 0.0006 L/s, permitiendo confirmar lo que se enuncia en la literatura
de celdas alcalinas, donde se establece que el electrolito más eficiente para su conversión energética es KOH.

Introduction energy imbalance due to the fact that the reaction can
be exothermic (it gives off energy) or endothermic
Voltaic cells and electrolytic cells are fuel cells that (it needs to be supplied with energy), from this
operate by means of an electrochemical process in perspective the spontaneity of these devices is
which reagents and products are subjected to an studied [1].
*Corresponding author.
E-mail address: Erick Daniel Rincón Castrillo ([email protected])
Peer review is the responsibility of the Universidad Francisco de Paula Santander.
6 This is an article under the license CC BY-ND (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Erick Daniel Rincón-Castrillo, José Ricardo Bermúdez-Santaella, Luis Emilio Vera-Duarte, Juan José García-Pabón

Fuel cells are a cleaner choice compared to gasoline

and diesel used in internal combustion engines [2].
The efficiency of the cells is another parameter that
must be taken into account, being approximately
twice as high as the thermal engines because the latter
are affected by the following limitations established
by Carnot’s Theorem [3].

There are several types of fuel cells, currently the

classification that is made for these devices is taking
into account the type of electrolyte they use, this way
we have the AFC (Alkaline Fuel Cells), PEMFC
(Proton Exchange Membrane Fuel Cells), DMFC
(Direct Methanol Fuel Cells), PAFC (Phosphoric
Acid Fuel Cells), MCFC (Fused Carbonate Fuel
Cells) and SOFC (Solid Oxide Fuel Cells) [2]. The
versatility of the cells has allowed them to have
a field of application in the industry specifically
Figure 1 Alkaline fuel cell.
in transportation, stationary power systems and Source: [2]
portable systems, the last three sectors is where its
impact has been most noticeable [1], [4]. The electrolysis of water in an alkaline medium in
an electrolyser is generated by means of a redox
The effect caused by fuel cells in industry is largely reaction (oxidation - reduction) that occurs in the
due to their efficiency in conversion and energy input, electrodes [5], this process is shown in Figure 1.
to understand the above is necessary to understand
the principle of operation of these devices being Materials and methods
necessary to identify the mathematical equations
that model their dynamic behavior. Alkaline electrolytic cell

In this article the modeling of an electrolyzer or The phase change (liquid to gaseous state) of the
alkaline electrolytic cell (AFC) with a single output water that occurs in the alkaline electrolyser to be
will be carried out, for the study of the production modelled, occurs when energy is supplied to the
of oxyhydrogen gas (HHO) as a clean energy, electrochemical reaction in the form of electrical
in this way it can be used as an enriching fuel or work (non-spontaneous process) [5], [6].
enhancer in the processes where combustion takes
place. In this research, concepts of thermodynamics, In order to know in detail what happens in the
chemistry, thermochemistry, and electrochemistry electrodes of the cell, the generation of gaseous
are taken into account for the approach of the oxygen in the anode is presented by means of (1),
equations, thus enunciating a thermodynamic and the generation of gaseous hydrogen is shown in
model, electric model, chemical model, and thermal the cathode with (2).
model. The EES software is used to determine the
value of the variables of the thermodynamic model Anode:
(enthalpy, entropy and free energy), the equations of
1
the other models are simulated in Matlab-Simulink® 2OH − (aq ) → O2 ( g ) + H 2O(l ) + 2e − (1)
because some do not present linearity, and others are 2
empirical electrochemical relations. Where:

Respuestas, 24 (2) May - August 2019, pp. 6-15, ISSN 0122-820X - E ISSN: 2422-5053 7
 Modeling and simulation of an electrolyser for the production of HHO in Matlab-Simulink®

In the electrolytic cell there is a conversion of

OH − (aq ) : Hydroxyl ion (water-based solution) electrical energy to chemistry, in this process there
O2 ( g ) : Oxygen (gaseous) are some thermodynamic variables that suffer energy
H 2O(l ) : Water (Liquids) imbalance, it is for this reason that the mathematical
e − : Electrons model is divided into four stages: thermodynamic
model, electrical model, chemical model, and
Cathode: thermal model.

2 H 2 O(l ) + 2e − → H 2 ( g ) + 2OH − (aq ) (2) Thermodynamic model

Where: To get the most energy available for useful work,

a status function, called free energy (G) [7], [8], is
H 2 ( g ) : Hydrogen (gaseous) defined by (4).

The two previous semirreactions allow to arrive at

∆G = ∆H − T ∆S (4)
the general reaction (3) that governs the process,
it is necessary to mention that the change of phase
Where:
that is carried out is thanks to the electrolysis
(decomposition of the water molecule by the passage
∆H : Change of enthalpy
of the current in it) [7].
∆S : Change of entropy
1 ∆G : Free energy exchange
H 2O(l ) + Weléctrico → H 2 ( g ) + O2 ( g ) (3)
2 T : Temperature
Alkaline electrolytic cell modeling
In a non-spontaneous electrochemical process the
Figure 2 shows the electrolyzer modeled in change of free energy ( ∆G ) is equivalent to the
SolidWorks®, consisting of a stack of cells composed electrical work (Welectric) that is necessary to
of 9 plates (1 positive, 2 negative, and 6 neutral) of supply for the reaction to occur [9], in (5) the above
316 stainless steel, 2 sheets of acrylic, and 10 PVC can be appreciated, non-spontaneity is represented
rings. by leaving the work expressed in a positive way.

a) b)

Figure 2. Electrolyzer modeled in SolidWorks®, a) diagonal view, b) cross-section view.

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Erick Daniel Rincón-Castrillo, José Ricardo Bermúdez-Santaella, Luis Emilio Vera-Duarte, Juan José García-Pabón

∆G=Welectric (5) precise way they are left expressed in such a way
that they depend on the temperature through (9), so
The electrical work is equivalent to the irreversible it is stated [12], [13].
voltage (Uirrev) of the electrolyser, for this reason Table I. Adjusted values OF r, s, and t.
the above equation is expressed with a voltage that
is irreversible by the present losses [10] by means
of (6).

∆G
U irrev = (6)
zF
Source: [11]
Where:
z : Number of electrons ( 2e − ) The power consumed by the cell is directly
F : Faraday Constant (96500 C) proportional to the number of cells (N) that make up
the stack, this relationship is established with (10).
When a reversible reaction is assumed, i.e. without Weléctrico = NIU (10)
losses, the process energy (H) is worked with as
shown in (7) with a reversible voltage (U_rev). The calculation is made by means of the product be-
∆H tween the number of cells connected in series ( nc )
U rev = (7)
zF with the number of cells connected in parallel ( nr )
The effect of irreversibilities (losses) can be seen when by means of (11).
calculating the irreversible and reversible voltages
N = (nc )(nr ) (11)
that result in U irrev = 1.22 v and U rev = 1.48 v , these
stress values were calculated from enthalpy and By setting the temperature (T) of the electrolyte this
entropy values under standard reaction conditions, part consists of 2 equations (power consumed with
i.e. at 25 °C and 1 bar. (10), and voltage between electrolyser terminals
expressed in (9)) with 2 unknowns (U, I) and its
The electric model is designed to determine the
resolution determines the operating point of the
current (I) and voltage of the electrolyzer, the
electrolyser.
relationship between these two variables is modeled
by means of (8) found in [11], [12].
Chemical model
r  t  Faraday’s law states that the rate of production of
U = U rev + I + s log  I + 1  (8)
A  A  oxyhydrogen in a cell is proportional to the transfer
of electrons in the electrodes, i.e., to the intensity
Where: supplied by the electrical work, (12) shows this
relationship [11].
r , s, t : Coefficients • NI
A : Electrode area v HHO = nF (12)
zF
r1 + r2T   t + t / T + t3 / T 2  The expression used for the calculation of Faraday’s
U =+
U rev I + s log  1 2 I + 1  (9)
A   A  Efficiency is that proposed by [11], where the effect
of stray currents is modelled. It is determined by
The coefficients r, s and t model the overvoltages means of (13), is caused by stray currents and these
(irreversibilities), to express their value in a more increase by current densities.

Respuestas, 24 (2) May - August 2019, pp. 6-15, ISSN 0122-820X - E ISSN: 2422-5053 9
 Modeling and simulation of an electrolyser for the production of HHO in Matlab-Simulink®

( I / A) 2
nF = f 2 (13)
( I / A) 2 + f1

The dependence of the coefficients f1 and f 2 with

the temperature is obtained by means of the experi-
mental tests carried out by [11], by means of mea-
surements in different points of operation, obtaining
polynomial expressions depending on the tempera-
ture with (14), and (15).

f1 (T ) = a f 1 ⋅ T + b f 1 (14)

Figure 3. Dependence of f1 on reaction temperature.

f 2 (T ) = c f 2 ⋅ T 2 + d f 2 ⋅ T + e f 2 (15)
Of (17) we have:
In the calculation of Faraday’s Efficiency the values
mA2
of f1 , and f 2 , in Table II you can see these data for a f 1 = 2.5
cm 4 °C
certain temperatures, enunciated by [11].

mA2
Table II. Coefficient values f1 and f2.
b f 1 = 50
cm 4

Figure 4 shows a curve (grade 2 polynomial),

because a quadratic dependence on the temperature
of the electrochemical reaction in the least squares
setting has been assumed.

Source: [11]

With the data from Table II, the coefficients of the

polynomials (17) and (18) are calculated by mak-
ing an adjustment of minimum squares to relate f1 ,
and f 2 with temperature, because the function is not
known.
Figure 3 shows a straight line (grade 1 polynomial),
because a linear dependence on the temperature of
the electrochemical reaction has been assumed in the
least squares setting. Figure 4. Dependence of f2 on reaction temperature.

Of (18) we have:

c f 2 =−1.25e − 5°C −2

d f 2 0.001°C −1
=
e f 2 = 0.97

10 Respuestas, 24 (2) May - August 2019, pp. 6-15, ISSN 0122-820X - E ISSN: 2422-5053
Erick Daniel Rincón-Castrillo, José Ricardo Bermúdez-Santaella, Luis Emilio Vera-Duarte, Juan José García-Pabón

Thermal model (irreversible) applied to the cell through (20).

The overvoltages r, s and t present in the electric mo- U rev

nU = (20)
del are a function of the temperature, it is for this U irrev
reason that the thermal model is raised, in order to
obtain the value of this one, for which a balance of The voltage efficiency may be greater than the unit
energy is made in the electrolyser with (16). because the irreversible voltage is less than the
reversible voltage.
∆E=Eentrada - Esalida (16)
Electrolyte heat
∆E = Q P
− ∆V
In the literature of alkaline cells (AFC) when
Where: modeling is considered, the energy provided by the
electrolyte in the reaction is not studied. Contrary to
∆E : Energy shift
the previous thing in this investigation the energetic
Q : Heat at the entrance contribution of the conductor of second species for
this process is analyzed.
Because the mathematical model focuses on the
phase change of the solution (electrolyte dissolved The heat of the electrolyte models the calorific or
in water) that occurs by means of an electrochemical energy potential provided by KOH or NaHCO
reaction at atmospheric pressure, the work ( P∆V ) is during the electrolysis of water, for its calculation
neglected in (17). the speed constant (k) and the concentration (CA)
must be taken into account by means of (21) [14].
dE
= Q (17) •
dt Q electrolito = kC A2 (21)
In order to calculate the behaviour of temperature
over time, it is necessary to calculate all the heat The speed constant varies with temperature as
involved in the energy balance and obtain the described by (22) [15] [16].
resulting heat, as expressed in (18) [11]. −
E
k = ko e RT
(22)
dT • • •
Ct = Q generado + Q electrolito − Q perdido (18)
dt Where:
Where:
E : Activation energy
Ct : Thermal capacitance
J
R : Ideal gas constant ( 8.3144 )
Heat generated mol °C
For the calculation of the frequency factor (Ko) the
The heat generated is the one contributed to the moles of the reagents, and of the products must be
solution in the reaction due to the irreversibilities in considered, as well as it expresses it.
the electrolysis process, by means of (19) this energy
transfer is modelled.
[ H 20 ][O20 ]
• ko = (23)
Q generado Weléctrico (1 − nU ) (19)
= [ H 2O ]
It is necessary to know the activation energy (E) to
The voltage efficiency relates the thermoneutral determine the constant speed of the reaction, thus
voltage (reversible) and the actual voltage establishing an energy variation at standard conditions

Respuestas, 24 (2) May - August 2019, pp. 6-15, ISSN 0122-820X - E ISSN: 2422-5053 11
 Modeling and simulation of an electrolyser for the production of HHO in Matlab-Simulink®

(T= 25 °C, and P°=1 bar), at how the electrochemical Where:

reaction is carried out experimentally (24).
∆E o =∆H o − (∆n) RT (24) L : Thickness of acrylic sheet
K : Thermal conductivity of acrylic
To determine the concentration (CA) it is necessary A : Surface of acrylic sheet
to identify the solubility of potassium hydroxide
(119 g in 100 g of water), and sodium bicarbonate With the above values of L, K and A, the
(10.3 g in 100 g of water), taking into account that thermal resistance of the acrylic film is
900 g of distilled water are used during the process. calculated (Rt = 6.66 k/W), this value takes great
relevance in the simulation.
Heat lost
Implementation of the model in Matlab-Simulink®
The heat lost models the amount of energy expelled
into the environment, by means of (25) the above is The thermodynamic variables (H, S, and G) used in
shown. This is the expression that finally allows the the model have been obtained as a function of the
calculation of the temperature [17]. standard conditions (T=25 °C, and P°=1 bar) of an
electrochemical reaction, the commercial tool EES®
• Tr − Ta was used.
Q perdido = (25)
Rt
For the implementation of the mathematical model
Where: in Simulink, the previously defined equations are
Tr : Reaction temperature added and the respective connection is made. Figure
5 shows the subsystems of the process, where you can
Ta : Ambient temperature see the proposed models that simulate the behavior
of the electrolytic cell, in which the input variables
The thermal resistance is calculated on the acrylic are the voltage (13.8 V) supplied by the DC source
sheets that are part of the electrolyzer as expressed in the process, and the electrolyte mass (in kg) in the
in (26). solution, in order to analyze the reaction temperature
L and HHO volumetric flow.
Rt = (26)
KA

Figure 5. Subsystems of the proposed models.

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Erick Daniel Rincón-Castrillo, José Ricardo Bermúdez-Santaella, Luis Emilio Vera-Duarte, Juan José García-Pabón

To solve (11) because it is a nonlinear expression,

the Newton-Raphson method was used that lineari-
zes the function by an assumed tangent line obtained
by applying a two-point rule.

Results and analysis

The modeling and simulation of the alkaline

electrolyser takes into account the energy contributed
•
by the electrolyte ( Q electrolito ) in the reaction, contrary
to the approaches of the mathematical models of Figure 7. Temperature variation of the electrolyser with NaHCO3 .
[11], [12], [17] consulted in the literature concerning
this type of cells, in these investigations the When comparing Figure 6 and Figure 7 it is impor-
calorific potential contributed by the second species tant to highlight the difference between the tempe-
conductor in the process is not considered. Next, the ratures, with 20 g of sodium bicarbonate is obtained
effect of the calorific potential of the electrolyte on in the simulation more than 25.8 °C, with the same
the temperature, and flow (volumetric flow) of HHO amount of potassium hydroxide is above 45 °C the
when sodium bicarbonate ( NaHCO3 ), and potassium temperature of the reaction generated in the cell, this
hydroxide ( KOH ) are used is analyzed. occurs because the solubility of KOH (119 g in 100
Figure 6 shows the behaviour of the electrolyser g of water) is higher compared to NaHCO3 (10.3 g
temperature using, it was dosed every 5 g until in 100 g of water), in turn the flow of the current
reaching 20 g to perceive the increase in temperature increases, and the temperature rises; with this the
at different concentrations of the electrolyte, the directly proportional relationship between the varia-
simulated maximum value is above 45°C. On the bles is evident, before the increase of some of them
other hand, the establishment time for the different the others are also increasing. The time of establish-
quantities supplied coincides in 25 s. ment of the temperature with KOH is less (25 s), that
is to say, the reaction is faster due to the chemical
properties of the electrolyte.

Figure 8 and Figure 9 show the variation of the HHO

flow rate in the electrolyser with KOH, and NaH-
CO3, according to the simulation a HHO flow rate
above 0.02 L/s with potassium hydroxide (20 g) is
recorded, in the case of sodium bicarbonate (20 g) a
lower flow rate is produced (above 0.0006 L/s).

Figure 6. Temperature variation of the

electrolyser with KOH.

Figure 7 shows the variation of the electrolyser

temperature using NaHCO3 , as well as with potassium
hydroxide, the amount of sodium bicarbonate was
simulated every 5 g to 20 g, a maximum temperature
reached for this last concentration above 25.8 °C was
recorded, and the settling time for all curves is 35 s.
Figure 8. HHO flow rate of the electrolyser with KOH.

Respuestas, 24 (2) May - August 2019, pp. 6-15, ISSN 0122-820X - E ISSN: 2422-5053 13
 Modeling and simulation of an electrolyser for the production of HHO in Matlab-Simulink®

5 g to 20 g) both the temperature and flow increased,

this behavior is presented because the current flow
is gradually higher, thus happens experimentally in
this type electrochemical processes.

In the simulation of the electric and chemical

model, it was necessary to calculate some correcting
coefficients of adjustment with the nominal
operating conditions, and constructive parameters
of the electrolyzer, the results were Alpha = 1.038,
Figure 9. HHO flow rate of the electrolyser with NaHCO3 . and Beta = 1.082, these values allow to establish
the proximity or the existing closeness between the
The electric current circulating through the simulated mathematical model, and the behavior of
electrolyser affects the temperature as previously an electrolytic cell experimentally.
mentioned and the HHO flow of the cell, as the
simulation increases the concentration of the References
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