Islamic University of Technology (IUT)

The Organization of Islamic Cooperation (OIC)

MPE FINAL YEAR

PRE-THESIS REPORT
WASTE HEAT RECOVERY FROM A PROTON EXCHANGE MEMBRANE FUEL CELL USING ORGANIC

WASTE HEAT RECOVERY FROM A

PROTON EXCHANGE MEMBRANE
FUEL CELL USING ORGANIC
RANKINE CYCLE
RANKINE CYCLE

A Thesis by

RUQAIYA ISLAM MISHI

NAZMUS SHAMEER ISLAM
MD. AR RAFI BIN ARIF

Department of Mechanical and Production

Engineering

Islamic University of Technology

Month (Year)
2024
 Table of Contents
ABSTRACT .............................................................................................................................. 5

CHAPTER 1: INTRODUCTION ........................................................................................... 6

1.1 Fuel Cell Technology ....................................................................................................... 6

1.2 Heat Recovery from Fuel Cells........................................................................................ 8

CHAPTER 2: OBJECTIVE OF THE STUDY ................................................................... 10

CHAPTER 3: LITERATURE REVIEW ............................................................................ 11

CHAPTER 4: Methodology .................................................................................................. 14

4.1 Fundamentals of a PEMFC ............................................................................................ 14

4.1.1 PEM Electrolyzer Equation .................................................................................... 14

4.1.2 Electrochemical Reactions ...................................................................................... 15

4.1.3 Activation losses ..................................................................................................... 16

4.1.4 Ohmic losses ........................................................................................................... 17

4.1.5 Concentration losses ............................................................................................... 17

4.2 PEM Fuel Cell Thermal Model...................................................................................... 18

4.3 Organic Rankine Cycle .................................................................................................. 19

4.4 Performance Criteria ...................................................................................................... 22

CHAPTER 5: MODELLING & VALIDATION ................................................................ 24

5.1 Modelling & validation of PEM Fuel Cell .................................................................... 24

5.2 Parameters and Result .................................................................................................... 30

5.3 Modelling & Validation of Basic Organic Rankine Cycle ............................................ 31

REFERENCES....................................................................................................................... 32
 Table of Figures

Figure 1: The Proposed System ............................................................................................... 10

Figure 2: Working of the hydrogen fuel cell ........................................................................... 14
Figure 3: Components of an Organic Rankine Cycle .............................................................. 21
Figure 4: Nernst Simulation Model ......................................................................................... 24
Figure 5: Saturation Pressure of Water Vapor ......................................................................... 24
Figure 6: Partial Pressure of Hydrogen and Oxygen ............................................................... 25
Figure 7: Molar Fraction at inlet .............................................................................................. 25
Figure 8: Molar Fraction at Outlet ........................................................................................... 25
Figure 9: Output Voltage of PEM Fuel Cell ............................................................................ 26
Figure 10: Activation loss in fuel cell ...................................................................................... 26
Figure 11: Fuel Cell Membrane Interface ................................................................................ 27
Figure 12: Concentration of Oxygen ....................................................................................... 27
Figure 13: Concentration of Hydrogen .................................................................................... 27
Figure 14: Ohmic Loss in Fuel Cell ......................................................................................... 27
Figure 15: Total Internal Resistance ........................................................................................ 28
Figure 16: Membrane Resistivity............................................................................................. 28
Figure 17: Concentration Loss in Fuel Cell ............................................................................. 28
Figure 18: Comparison between basic ORC model parameters using CoolProp .................... 31

Tables

Table 1: Input Parameters of PEMFC ...................................................................................... 30

Table 2: Validation of the developed model compared with the result from validated article 30
Table 3: Equations for the basic ORC Model .......................................................................... 31
 ABSTRACT
One of the fastest growing technology fuel cell technologies is that of the Proton Exchange
Membrane Fuel Cell. They can be a good alternative to traditional plants for applications where
distributed generation (DG) is needed. The reason being its high-power density and extensive
capability in recovering the heat that is generated during the electrochemical reaction at
cathode. Here, in this article a hybrid power system is suggested that would integrate a PEM
fuel cell and an Organic Rankine Cycle (ORC) for the purpose of heat recovery. The goal and
the purpose are to effectively use the generated waste heat by the PEMFC during the
electrochemical reaction which takes place at cathode. Constructing an experimental model for
a PEM Fuel Cell would be quite expensive. Therefore, it is imperative to employ mathematical
modeling and simulations to thoroughly analyze and enhance its performance. Mathematical
modelling of the fuel cell was done using MATLAB/Simulink to achieve a stable state. Both
the model and the thermodynamic rules were used to analyze the performance of the system.
Furthermore, a heat recovery system employing an Organic Rankine Cycle was utilized.
 CHAPTER 1: INTRODUCTION
The utilization of different fuel types has increased by a factor of 10 as technology has
advanced. Consequently, modern society heavily depends on fossil fuels like oil, coal, and gas
to fulfill its daily energy needs, leading to their gradual exhaustion. Although new supplies
have been discovered, the utilization of fossil fuels poses a significant problem. During the
combustion process, carbon dioxide (CO2) is released, leading to the greenhouse effect. The
2018 recorded a 1.5% increase in CO2 emissions. The greenhouse effect leads to an increase
in the Earth's temperature, which in turn produces global warming. This is a significant issue
that is accountable for the melting of the polar ice caps. Rising sea levels cause hazards such
as tsunamis and coastal flooding. As environmental contamination worsens, there is an
increasing need for clean and abundant energy. The world's growing population has increased
demand for power and energy. To reduce environmental damage, the globe is increasingly
turning to alternate energy sources. The most environmentally friendly and pure energy source
is renewable energy. Renewable energy technologies, such as solar, tidal power, and wind have
made substantial progress in the last decade. The sole drawback of renewable energy lies in its
dependence on external factors such as wind velocity and solar radiation. These extraneous
elements are dependent on nature and are beyond human control. Fuel cells provide an added
means of generating renewable energy and offer the best solution to meet the perpetual demand
for energy [1]. The sole drawback of renewable energy lies in its dependence on external factors
such as wind velocity and solar radiation. Researchers aim to reduce production costs and make
them cheaper for commercial use.

1.1 Fuel Cell Technology

Fuel cells operate based on electrochemical principles, with polymer electrolyte membrane fuel
cells (PEMFC) being a widely recognized technology within the field of fuel cell systems.
Researchers are closely checking this technology because of its safety, cleanliness, and
efficiency as an energy source. According to research, PEMFCs have a longer lifetime and are
less expensive than other fuel cell technologies [2]. The polymer electrolyte membrane fuel
cell (PEMFC) is the most widely used type of fuel cell. It has the ability to produce zero
emissions when pure hydrogen is utilized. Additional benefits encompass a notable power-to-
size ratio, reduced operational heat, and an impressive conversion efficiency ranging from 50%
to 60%. Fuel cells are expensive to install experimentally because of their complex
architecture. Software-generated fuel cell simulation models have become essential to research
and development to overcome this problem. The primary objective of these models is to
replicate fuel cell behavior in a practical manner, enabling researchers to analyze the factors
that influence fuel cell performance. In addition to making fuel cells simpler, simulations also
help lower the cost of experimental implementations. Furthermore, time savings are another
benefit of using simulations as opposed to the time-consuming and intricate procedure of
building a real fuel cell system and seeing its reactions by changing its settings.

The efficiency of fuel cells is something that scientists are constantly working to improve. In
their study, Wang et al. [3] presented a comprehensive analysis of the progress in PEMFC
technology and highlighted its frequent utilization in the context of buses and lightweight cars.
Francesconi et al. [4] investigated the performance of fuel cells by manipulating factors such
as pressure and temperature during the process of hydrogen reforming to generate ethanol as a
fuel. According to the study's findings, fuel cell performance is greatly impacted by pressure.

Researching proton exchange membrane fuel cells (PEMFCs) in hot climates was Li et al.'s
primary focus [5] Some have proposed using an acid-base polymer in place of the membrane
to allow PEMFCs to function at temperatures between 100 and 200 °C, which are higher.
Thermodynamic, steady-state, and dynamic models of a proton exchange membrane fuel cell's
(PEMFC) operations were built by Azri et al.[6] using a similar electric circuit. A Horizon H-
500 fuel cell stack was subjected to a MATLAB study. Power output and stack voltage were
among the several PEMFC characteristics studied. A study was carried out by Benchouia et al.
[7] to examine the pros and cons of PEMFCs, or proton exchange membrane fuel cells. We
compared the modeling results with those from an experimental fuel cell stack to ensure the
accuracy of the results.

It was discovered by Santarelli et al. [8] how to figure out specific PEMFC operating
parameters. The initial analysis focused on critical variables such as cell resistance, exchange
current density, internal current density, and limiting current density. The polarization curve
was subsequently simulated, and parameter analysis inside the model demonstrated the
concurrent estimation of three curve parameters: cell resistance, internal current density and
cathode exchange current density. The model facilitated the analysis of parameter performance
across different operational conditions by modifying the cell temperature within the range of
50 to 80 °C. It also determined the correlation between the polarization curve and the operating
temperature.
1.2 Heat Recovery from Fuel Cells

Fuel cells exhibit less than perfect efficiency, resulting in the dissipation of any unconverted
energy as heat. Utilizing this surplus heat provides the opportunity to energize a secondary
autonomous system. Opting for fuel cell heat recovery is a method to optimize their utilization
and enhance overall efficiency.

Lin et al. [9] explored three ways to use heat recovered from fuel cells:

1. Hydrogen Refueling: The fuel reformation process is powered by the recovered heat,
which converts methanol or hydrocarbons into pure hydrogen fuel for either the fuel cell
itself or other devices.

2. High-Temperature Power Boost: High-temperature fuel cells, such as Solid Oxide

Fuel Cells utilize the captured heat to drive a gas turbine, thereby enhancing the overall
production of energy.

3. Neighborhood Energy Hub: Fuel cells act as combined heat and power units for
residential areas, using electricity from electrochemical reactions and excess heat for space
heating.

The incorporation of a vapor absorption cycle that utilizes the heat recovery concept from a
high-temperature PEMFC was examined by Guo et al [10] . The absorption cycle served as a
heat pump and a refrigeration cycle simultaneously, and the power densities for all scenarios
were assessed.

1.3 Organic Rankine Cycle (ORC)

The most popular way to generate electricity is by using the organic Rankine cycle (ORC), a
thermodynamic cycle that efficiently transforms energy from a source of low-temperature heat
into electricity. The ORC's operational temperature range of 80 to 100 °C makes it a sensible
choice to integrate it into the PEMFC, or proton exchange membrane fuel cell. The ORC avoids
heat and pressure losses in the fluid by injecting it straight from the fuel cell, which is how it
works [11]. ORC systems are extensively utilized across various industries because to their
safety, extensive flexibility, and exceptional thermal efficiency in recovering waste heat at low
temperatures. These businesses encompass geothermal power [12] generation, solar power[13],
and internal combustion engine waste heat recovery [14] . The working fluid of the Organic
Rankine Cycle (ORC), which serves as the coolant for the fuel cell, is directly provided by the
fuel cell. For the sake of simplicity, we shall ignore the heat and pressure losses of the fluid
[11].

Since the working fluid dictates the system's total performance, it is the most crucial component
to consider while developing an ORC system[15]. Using conventional, one-component
working fluids in ORC systems might not always provide the best results. More and more
researchers are looking into zeotropic mixed working fluids as a potential solution to these
limitations. Rankine cycles use water as their working fluid, which is heated and pressured to
a point where it vaporizes into steam in the boiler. The functioning fluid of an Organic Rankine
Cycle (ORC) is a zeotropic mixture, in contrast. This combination is suitable for use at lower
temperatures because its vaporization point is much lower than water's. The zeotropic mix's
non-isothermal phase transition makes it very compatible with the heat source and condensing
fluid.

The Rankine cycle and the organic Rankine cycle both works using the same basic idea. The
primary objective is to generate superheated vapor's kinetic energy from the working fluid's
thermal energy as effectively as possible. As the system expands, the turbine is powered by
this vapor, which is both hot and under pressure. Thermodynamic efficiency of zeotropic
mixtures and typical organic working fluids in an ORC system was studied by Dong et al.[16]
utilizing pinch analysis. In conclusion, given certain operating constraints, zeotropic organic
working fluids perform better than pure working fluids in ORC systems.
 CHAPTER 2: OBJECTIVE OF THE STUDY

The main goal of this research is to recover waste heat from a proton exchange membrane
fuel cell (PEMFC) by means of an Organic Rankine Cycle (ORC). The specified aims of the
study include:

• To develop an accurate PEM Fuel Cell model using MATLAB/Simulink.

• To validate the model developed by comparing with the result from validated articles.
• To calculate the generated waste heat during the electrochemical reaction at cathode.
• To validate the basic Organic Rankine Cycle Model using CoolProp in Python.
• To test different Zeotropic Fluid as the Refrigerant for the Organic Rankine Cycle
(ORC).

Figure 1: The Proposed System

The proposed setup includes a number of interconnected parts, including a pump, a pressure
regulator, a condenser, a turbine, a PEM fuel cell, a humidifier and air compressors. An
insulating layer is integrated into the PEM fuel cell stack to reduce heat dissipation to the
environment.
 CHAPTER 3: LITERATURE REVIEW
Typically, the electrical efficiency of PEMFCs ranges from 40% to 60% during continuous
operation, with approximately half of the chemical energy being lost as heat. Waste heat
recovery is an essential method for enhancing the thermal efficiency of fuel cells, which has
garnered growing attention. The typical temperature range for a Proton Exchange Membrane
Fuel Cell (PEMFC) is usually between 60-80°C [17]. To prevent the negative effects of
overheating, which can affect the longevity of the system [18], as well as the occurrence of
low-temperature water flooding [19] during the operation of a proton exchange membrane fuel
cell (PEMFC), it is necessary to regulate the stack operating temperature by using a sensible
thermal management approach [20]. The primary technological challenge in PEMFC thermal
management systems is to effectively regulate the operating temperature within a consistent
and best range, while simultaneously harnessing the waste heat produced by the chemical
reactions to enhance the overall efficiency.

Different methods for Waste heat recovery technologies of Fuel Cells have been implemented
among which the combination of fuel cells with thermal generators (TEGs), combined heat and
power (CHP) and Organic Rankine Cycle (ORC) are notable. Several articles in the literature
have addressed the issue of waste heat recovery in PEM fuel cell systems. The combined heat
and power (CHP) application is an often-used method for waste heat recovery.

Hwang et al.[21], [22] created a heat recovery device and integrated it into a PEM fuel cell
cogeneration system to generate electricity and hot water at the same time. The maximum
efficiency in combined heat and power was approximately 81%. Briguglio et al. [23] conducted
an experiment on a 5 KW PEM fuel cell system in a cogeneration setup to capture waste heat.
They achieved this by connecting a heat exchanger directly to the cathode outlet. The findings
showed that the overall efficiency of the system experienced a significant boost of up to 85%
when the heat exchanger operated at its designated power level. Yu et al. [24] and Aki et al.
[25] also conducted a comparable investigation on residential power generating fuel cell
systems. Shabani et al. [26] examined the operation of a combined heat and power (CHP)
system that utilizes the heat produced in a proton exchange membrane (PEM) fuel cell in a
solar-hydrogen system. The goal was to enhance the overall energy efficiency of power
delivery in distant places. The thermal energy extracted from the PEM fuel cell can also be
used for fuel reforming. Cao et al. [27] introduced an innovative fuel reforming system that
utilizes the waste heat produced by a PEM fuel cell system. The findings indicated that the
efficiency of the power plant might be enhanced by over 20%. Furthermore, Chen et al. [28]
documented the development of a novel hybrid power system that integrates a proton exchange
membrane (PEM) fuel cell with a semiconductor thermoelectric generator. The excess heat
generated by the PEM fuel cell was utilized as a high-temperature heat source for the
thermoelectric generator to produce power. Zhang et al. [29] introduced an innovative hybrid
power system that combines a PEM fuel cell with a refrigeration cycle to effectively utilize the
waste heat generated by the fuel cell for refrigeration purposes. Forde et al. [30] used a metal
hydride storage unit with a PEM fuel cell stack to enhance the release of hydrogen from the
metal hydride storage. This was achieved by using the waste heat generated by the fuel cell
stack.

The Organic Rankine Cycle (ORC) system has superior performance in the area of recovering
low temperature waste heat, such as in ocean thermal energy conversion (OTEC), and The
ORC system has been effectively integrated with Solid Oxide Fuel Cells (SOFC) [31], [32],
[33] or Molten Carbonate Fuel Cells (MCFC) [34] to capture and utilize the waste heat
generated by the fuel cells. The combination of a Proton Exchange Membrane (PEM) fuel cell
and an Organic Rankine Cycle (ORC) is a viable method for improving energy conversion.
Pan Zhao et al. [35] considered hybrid power system consisting of PEM Fuel Cell System and
an ORC which can utilize the waste heat production in the PEM fuel cell system. They studied
a hybrid power system consisting of a Proton Exchange Membrane (PEM) fuel cell stack and
an Organic Rankine Cycle (ORC). The purpose of this system is to enhance electrical efficiency
by harnessing the waste heat produced by the PEM fuel cell stack. A mathematical model has
been created to replicate the hybrid power system's behavior during stable operating conditions.
Subsequently, a parametric analysis is carried out to investigate the impact of some crucial
parameters on the system's performance.

Marandi et al. [36] combined a PEMFC system with a parallel two-stage ORC and hydrogen
evaporation cooling system to investigate the energy, exergy and exergy economy of the
system. Shespoli et al. [37] conducted an analysis on the impacts of the mass flow rate and
pressure on the net power and thermal efficiency of a system by integrating a regenerative
organic Rankine cycle (RORC) and a PEMFC system. The findings indicated that the system's
efficiency could achieve 44.3% when R123 was utilized as the working fluid. Lee et al. [38]
integrated a high-temperature polymer electrolyte membrane fuel cell (HT-PEMFC) with an
Organic Rankine Cycle (ORC) system to evaluate the efficiency of the hybrid system. The
power output of the combined system was found to be 17-21% greater than that of the HT-
PEMFC system operating without ORC. Perna et al. [39] proposed an integrated system
comprising of an HT-PEMFC power unit and an ORC system. The hybrid system was utilized
to provide both heat and power to a residential utility. Two working fluids, namely R142b and
R245fa, were examined. In the aforementioned tests, the Organic Rankine Cycle (ORC) system
was linked to the Proton Exchange Membrane Fuel Cell (PEMFC) cooling system using heat
exchangers. These two systems operated separately, resulting in elevated expenses and system
intricacy. Zhao et al. [40] introduced a simplified system that combines a Proton Exchange
Membrane Fuel Cell (PEMFC) with an Organic Rankine Cycle (ORC). They conducted a
performance analysis of several organic working fluids used in this system. The investigation
revealed that R123 had superior performance compared to other fluids. As a result, the overall
electrical efficiency of the PEMFC-ORC system was enhanced by roughly 5%. Liu et al. [11]
introduced an innovative PEMFC-ORC system that utilizes working fluids to directly cool the
PMEFC stack. The fuel cell saw the most exergy loss in the system, with the heater and
compressor at the cathode also exerting a substantial impact on both the system power and
exergy loss.
 CHAPTER 4: Methodology
In order to simulate a working model of a PEMFC, it is necessary to understand the basic
working behind the fuel cell.

4.1 Fundamentals of a PEMFC

A fuel cell consists of three main components:

➢ An electrode for fuel (anode)

➢ An electrode for oxygen (cathode)
➢ Electrolyte between cathode and anode

The electrode is made from a porous material that is combined with platinum. The porous
electrode allows the gases to pass through it.

4.1.1 PEM Electrolyzer Equation

The hydrogen gas is brought into the fuel cell through the fuel inlet port. By the time it reaches
the anode, the hydrogen has reacted with the platinum catalyst. Separation of the molecular
hydrogen into its component protons (H+) and electrons (e-) is achieved. Current flows because
electrons evacuate from the outside circuit. In order to reach the cathode, the protons must
transit through the acidic electrolyte.

Anode: 𝐻2 (𝑔) → 2𝐻 + + 2𝑒 −

On the cathode, injection of oxygen takes place through the air inlet port. The electrons from
the outer circuit bind with the protons and molecular 𝑂2 in order to produce water.

1
Cathode: 2 𝑂2 (𝑔) + 2𝐻 + + 2𝑒 − → 𝐻2 𝑂

Figure 2: Working of the hydrogen fuel cell

Fig-2: Working of the hydrogen fuel Cell

The overall reaction of the system can be written as:

 1
Overall Reaction: 𝐻2 (𝑔) + 2 𝑂2 (𝑔) → 𝐻2 𝑂

4.1.2 Electrochemical Reactions

The reversible open circuit voltage of the reaction in a hydrogen-oxygen fuel cell can be
mathematically represented using the well-known Nernst equation.

−𝛻𝐺° 𝑅𝑇𝑓𝑐 𝑃𝐻2 √𝑃𝑂2

𝐸𝑛𝑒𝑟𝑛𝑠𝑡 = + 𝑙𝑛⁡( 𝑠𝑎𝑡 )
𝑛𝑒 𝑛𝑒 𝐹 𝑃𝐻2𝑂

The variables in the equation are as follows: ∇𝐺° represents the change in Gibbs free energy,
𝑛𝑒 represents the number of electrons involved in the electrochemical reaction, 𝐹 represents
the Faraday constant, 𝑅 represents the universal gas constant, 𝑇𝑓𝑐 represents the operating
temperature of the PEM fuel cell in Kelvin, Pj represents the effective partial pressure of
reactant j, and 𝑃𝐻𝑠𝑎𝑡
2𝑂
represents the saturation pressure of water vapor.

The saturation pressure of water vapor can be represented by the following empirical formula:

𝑙𝑜𝑔10 (𝑃𝐻𝑠𝑎𝑡
2𝑂
) = −2.1794 + 0.02953𝑡 − 9.1837 × 10−5 𝑡 2 + 1.4454 × 10−7 𝑡 3

Where t is the operating temperature in Celsius and can be calculated as: 𝑡 = ⁡ 𝑇𝑓𝑐 − 273.15

The effective partial pressure of Hydrogen 𝑃𝐻2 at anode and oxygen 𝑃𝑂2 at cathode are assumed
to be the same across the entire cell, and are calculated by:

1
𝑃𝐻2 = (0.5𝑃𝐻𝑠𝑎𝑡
2𝑂
) −1
1.653𝑖
exp ( 1.334 ) . 𝑥𝐻𝑠𝑎𝑡
2𝑂
[ 𝑇𝑓𝑐 ]

0.291𝑖
𝑃𝑂2 = 𝑃 [1 − 𝑥𝐻𝑠𝑎𝑡
2𝑂
− 𝑥𝑁𝑐ℎ𝑎𝑛𝑛𝑒𝑙
2
𝑒𝑥𝑝 ( 0.832 )]
𝑇𝑓𝑐

Here, 𝑃 is the operating pressure of PEM fuel cell and 𝑖 denotes the current density. 𝑥𝑁𝑐ℎ𝑎𝑛𝑛𝑒𝑙
2

represents the molar fraction of nitrogen. The term 𝑥𝐻𝑠𝑎𝑡

2𝑂
is the molar fraction of water in the
gas stream at saturation for a given temperature and is given by:

𝑃𝐻𝑠𝑎𝑡
2𝑂
𝑥𝐻𝑠𝑎𝑡
2𝑂
=
𝑃
The molar fraction of nitrogen in the air stream is given by a log mean average between the
molar fraction of nitrogen in a humidified stream of air at the inlet and the molar fraction at the
outlet is calculated by:

(𝑥𝑁2,𝑖𝑛 − 𝑥𝑁2,𝑜𝑢𝑡 )
𝑥𝑁𝑐ℎ𝑎𝑛𝑛𝑒𝑙 =
2 𝑥𝑁
ln⁡ (𝑥 2,𝑖𝑛 )
𝑁2,𝑜𝑢𝑡

Where,

𝑥𝑁2,𝑖𝑛 = 0.79(1 − 𝑥𝐻𝑠𝑎𝑡

2𝑂
)

1 − 𝑥𝐻𝑠𝑎𝑡
2𝑂
𝑥𝑁2,𝑜𝑢𝑡 =
𝜆𝑎𝑖𝑟 − 1 0.21
1+( )(
𝜆𝑎𝑖𝑟 0.79)

Where 𝑥𝑁2,𝑖𝑛 , 𝑥𝑁2,𝑜𝑢𝑡 are the molar fraction of nitrogen at the inlet and outlet, respectively, 𝜆𝑎𝑖𝑟
is the stoichiometric rate of air.

Typically, the measured voltage of a fuel cell is lower than the calculated reversible voltage
determined by the Nernst equation. This discrepancy is caused by irreversible losses, including
activation overvoltage, ohmic overvoltage, and concentration overvoltage.

Therefore, the actual voltage output of a PEM fuel cell can be written as:

𝑉𝑓𝑐 = 𝐸𝑁𝑒𝑟𝑛𝑠𝑡 − 𝑉𝑎𝑐𝑡 − 𝑉𝑜ℎ𝑚 − 𝑉𝑐𝑜𝑛𝑐

Where 𝑉𝑎𝑐𝑡 , 𝑉𝑜ℎ𝑚 , 𝑉𝑐𝑜𝑛𝑐 are the activation overvoltage, ohmic overvoltage and concentration
overvoltage, respectively.

4.1.3 Activation losses

Activation overvoltage results from the kinetics of charge transfer reaction across the electrode-
electrolyte interface. It can be expressed by the semi-empirical model as:

𝑉𝑎𝑐𝑡 = −[−0.948 + 𝜉𝑇𝑓𝑐 + 0.000076𝑇𝑓𝑐 (ln(𝐼)) − 0.000193𝑇𝑓𝑐 (ln(𝐶𝑂2,𝑐𝑜𝑛𝑐 ))]

Where 𝐼 denotes the current flowed through the fuel cell, 𝐶𝑂2,𝑐𝑜𝑛𝑐 is the oxygen concentration
at cathode/membrane interface, 𝜉 can be shown as:
 𝜉 = 0.00286 + 0.0002 ln(𝐴𝑐𝑒𝑙𝑙 ) + 0.000043ln⁡(𝐶𝐻2,𝑐𝑜𝑛𝑐 )

Where the term 𝐶𝐻2,𝑐𝑜𝑛𝑐 is the hydrogen concentration at anode/membrane interface, 𝐴𝑐𝑒𝑙𝑙 is
the fuel cell active surface area.

According to Henry’s law, the oxygen and hydrogen concentration can be expressed as:

498
𝐶𝑂2,𝑐𝑜𝑛𝑐 = 1.97 × 10−7 𝑃𝑂2 𝑒𝑥𝑝 ( )
𝑇𝑓𝑐

−77
𝐶𝐻2,𝑐𝑜𝑛𝑐 = 9.174 × 10−7 𝑃𝐻2 𝑒𝑥𝑝 ( )
𝑇𝑓𝑐

4.1.4 Ohmic losses

Ohmic overvoltage occurs due to the dissipation of electrical energy as a result of resistance in
the fuel cell. The aforementioned sort of resistance is present in various components of a fuel
cell, including the ionic resistance inside the membrane, the combined ionic and electronic
resistance within the electrodes, and the electronic resistance within the bipolar plates and
terminal connections. According to Ohmic’s law, the ohmic overvoltage can be defined as:

𝑉𝑜ℎ𝑚 = 𝐼𝑅𝑖𝑛𝑡

Where 𝑅𝑖𝑛𝑡 denotes the total internal resistance, it is a complicated function of temperature and
current. A general expression for resistance used in earlier publication is written as:

𝑟𝑚𝑒𝑚 𝐿
𝑅𝑖𝑛𝑡 =
𝐴𝑐𝑒𝑙𝑙

Where 𝑟𝑚𝑒𝑚 represents the membrane resistivity. An empirical expression for Nafion
membrane resistivity is:

𝑇𝑓𝑐 2
181.6 [1 + 0.03𝑖 + 0.062 (303) 𝑖 2.5 ]
𝑟𝑚𝑒𝑚 =
303
[𝜁 − 0.634 − 3𝑖]exp⁡ [4.18 (𝑇𝑓𝑐 − )]
𝑇𝑓𝑐

Where 𝜁 is the water content of the membrane.

4.1.5 Concentration losses

The concentration overvoltage occurs due to the difference in concentration between the
reactants or products at the electrode surface and the surrounding solution. It could be presented
as:
 𝑅𝑇𝑓𝑐 𝑖𝐿
𝑉𝑐𝑜𝑛𝑐 = 𝑙𝑛 ( )
𝑛𝑒 𝐹 𝑖𝐿 − 𝑖

Where 𝑖𝐿 is the limiting current density.

The power output by the PEM fuel cell stack is calculated as:

𝑊𝑓𝑐 = 𝑁𝑐𝑒𝑙𝑙 𝑉𝑓𝑐 𝐼

Where 𝑁𝑐𝑒𝑙𝑙 is the number of cells in stack.

Assuming that air is ideal gas, isentropic compression in the air compressor can be stated as:

𝑇𝑜𝑢𝑡,𝑠
= 𝜋 ((𝜅−1)/𝜅)
𝑇𝑎𝑚𝑏

Where 𝜋 is the pressure ratio, 𝜅 denotes the isentropic exponent, 𝑇𝑜𝑢𝑡,𝑠 , 𝑇𝑎𝑚𝑏 are the outlet
temperature of isentropic process and ambient temperature, respectively.

The isentropic efficiency is:

𝑇𝑜𝑢𝑡,𝑠 − 𝑇𝑎𝑚𝑏
𝜂𝑐𝑜𝑚𝑝 = ⁡
𝑇𝑜𝑢𝑡,𝑐𝑜𝑚𝑝 − 𝑇𝑎𝑚𝑏

Where 𝑇𝑜𝑢𝑡,𝑐𝑜𝑚𝑝 is air temperature at the air compressor outlet. The actual compression power
is:

𝑚̇𝑎𝑖𝑟 ((𝜅 − 1)/𝜅)𝑅𝑇𝑎𝑚𝑏 (𝜋 ((𝜅−1)/𝜅) − 1)

𝑊𝑐𝑜𝑚𝑝 =
𝜂𝑐𝑜𝑚𝑝

Where 𝑚̇𝑎𝑖𝑟 is the mass flow rate of air.

4.2 PEM Fuel Cell Thermal Model

The electrochemical reaction serves as the energy source in a functioning fuel cell.
Nevertheless, a significant portion of energy is lost as thermal energy, amounting to over 50%
under normal circumstances. To prevent the fuel cell from overheating, it is necessary to
eliminate the excess thermal energy. The net thermal energy can be determined using the
thermodynamic energy balance within the cell as:

𝑄̇𝑛𝑒𝑡⁡ = 𝑄̇𝑐ℎ − 𝑊𝑓𝑐 −

̇ 𝑄𝑠,1

Where 𝑄̇𝑛𝑒𝑡⁡ is the net heat energy, 𝑄̇𝑐ℎ is the chemical energy, 𝑄̇𝑠,1 is the sensible and latent
heat.
The theoretical power delivered to the fuel cell stack is directly dictated by the quantity of
hydrogen consumed. The consumption rate of hydrogen, oxygen, and the generation rate of
water in a fuel cell can be determined by utilizing the stack current and cell numbers as:

1
𝜂̇ 𝐻2,𝑐𝑜𝑛𝑠 = 𝑁𝑐𝑒𝑙𝑙
2𝐹

1
𝜂̇ 𝑂2,𝑐𝑜𝑛𝑠 = 𝑁𝑐𝑒𝑙𝑙
4𝐹

1
𝜂̇ 𝐻2 𝑂,𝑔𝑒𝑛𝑒 = 𝑁𝑐𝑒𝑙𝑙
2𝐹

Nevertheless, it is imperative that the rate at which the reactant flows into the fuel cell's input
matches or exceeds the rate at which the reactant is used. This is crucial in order to prevent any
deterioration or malfunction of the membrane within the fuel cell. The stoichiometric rate is
used solving this problem, the reactant molar flow is determined by:

1
𝜂̇ 𝐻2 = 𝜆𝐻2 𝑛̇ 𝐻2 ,𝑐𝑜𝑛𝑠 = 𝜆𝐻2 𝑁𝑐𝑒𝑙𝑙
2𝐹

1
𝜂̇ 𝑂2 = 𝜆𝑂2 𝑛̇ 𝑂2,𝑐𝑜𝑛𝑠 = 𝜆𝑂2 𝑁𝑐𝑒𝑙𝑙
4𝐹

The theoretical power released due to electrochemical reaction is given by:

𝑄̇𝑐ℎ = 𝑛̇ 𝐻2,𝑐𝑜𝑛𝑠 . 𝐻𝐻𝑉

Where HHV denotes the higher heating value of hydrogen.

The sensible and latent heat can be estimated by:

𝑄̇𝑠,1 = 𝐶𝐻2 (𝜂̇ 𝐻2,𝑜𝑢𝑡 𝑇𝑓𝑐 − 𝜂̇ 𝐻2,𝑖𝑛 𝑇𝑎𝑚𝑏 ) + 𝐶𝑂2 (𝜂̇ 𝑂2,𝑜𝑢𝑡 𝑇𝑓𝑐 − 𝜂̇ 𝑂2,𝑖𝑛 𝑇𝑜𝑢𝑡,𝑐𝑜𝑚𝑝 )

+ 𝐶𝑁2 (𝜂̇ 𝑁2,𝑜𝑢𝑡 𝑇𝑓𝑐 − 𝜂̇ 𝑁2,𝑖𝑛 𝑇𝑜𝑢𝑡,𝑐𝑜𝑚𝑝 ) + 𝜂̇ 𝐻2 𝑂,𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒 (𝑇𝑓𝑐 − 𝑇𝑎𝑚𝑏 )𝐶𝐻2𝑂

+ 𝜂̇ 𝐻2 𝑂,𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒 𝐻𝑣

Where 𝐶𝐻2 , 𝐶𝑂2 , 𝐶𝑁2 , 𝐶𝐻2 𝑂 are the specific heat capacity of hydrogen, oxygen, nitrogen and
water respectively, 𝐻𝑣 represents the vaporization heat of water.

4.3 Organic Rankine Cycle

To generate power from low-temperature heat sources, the organic Rankine cycle (ORC) is the
thermodynamic cycle of choice. Since the operating temperature range of the PEMFC is 80 to
100°C, an ORC is a reasonable choice. The fluid used to cool the fuel cell is really the working
fluid of the operating reaction chamber (ORC). To keep things simple, we will not take into
account the fluid's pressure and heat losses. Within the tags, the enclosed text can be observed.
This cycle is very much like a Rankine cycle in operation. The variation becomes apparent due
to variations in the working fluid. Water is the working fluid of choice for Rankine cycles due
to the fact that it may evaporate and become steam under specific boiler settings including
temperature and pressure. In contrast to the Rankine cycle, an ORC uses a zeotropic mixture
as its working fluid. In comparison to water, the zeotropic combination has a substantially
lower boiling point. Operations that don't need a lot of heat will benefit from this.

The organic Rankine cycle functions on a comparable concept to the Rankine cycle. The
primary objective of the cycle is to transform the thermal energy of the working fluid into the
kinetic energy of superheated vapor. The vapor possesses immense energy and pressure due to
its exceedingly high temperature. The turbine can be powered by utilizing the kinetic energy
of the vapor's expansion.

The ORC, as illustrated in Figure 1, is composed of the same constituent elements as the
Rankine cycle. The initiation of the cycle occurs at the pump, where a saturated liquid
representing the working fluid is introduced. By means of an isentropic compression process,
the pressure of the pump is brought into alignment with the operating pressure. Evaporator, or
evaporator. The fluid undergoes a slight increase in temperature as its specific volume
decreases. After undergoing the pressurization procedure, the fluid is directed towards the
evaporator.

Boilers are an integral part of Rankine cycles, which produce superheated steam by evaporating
water that has been heated. One component of an ORC is an evaporator. As a heat exchanger,
the evaporator makes it easier for heat to go from the heat source to the working fluid. The heat
transfer that takes place between an external heat source and the discharged heated fluid of a
PEMFC is the main focus of this investigation. In this way, the heated fluid can be transferred
to the ORC's working fluid through the evaporator. After the fluid has vaporized, it enters a
superheated state with very high temperatures and pressures.
 Figure 3: Components of an Organic Rankine Cycle

Isentropic expansion occurs in the vapor subsequent to its introduction into the turbine, owing
to its elevated temperature. The rotation of the turbine blades is caused by this expansion. The
connection of a generator to the turbine induces power generation. The expansion of the fluid
results in a reduction of its thermal conditions with respect to temperature and pressure.

The fluid is introduced into the condenser at this point. During this phase, the fluid may
manifest as a saturated mélange consisting of both liquid and vapor, which possesses a notable
quality value. In the capacity of a heat exchanger, the condenser transfers heat to a sink. The
sink maintains a lower temperature in comparison to the condenser. By transferring heat from
the condenser to the drain, the working fluid is cooled. The process is repeated when the
condenser releases the fluid in a state of complete saturation as a liquid.

The Organic Rankine Cycle can be summarized as follows:

❑ Isentropic Compression (Pump)

❑ Constant Pressure Heat Addition (Evaporator)
❑ Isentropic Expansion (Turbine)
❑ Constant Pressure Heat Rejection (Condenser)
To simplify the theoretical simulation of ORC system, some assumptions are employed as
follows:

I. The system reaches a steady state.

II. There is no heat transfer with the environment.
III. The pressure drops through the PEM fuel cell stack, condenser, reheater, pipe and
connection tubes are negligible
IV. The stream at the condenser outlet is the saturated liquid.
V. The turbine and pump have a given isentropic efficiency, respectively.
VI. The heat losses from the pump and turbine to surroundings are neglected.
VII. The mechanical conversion efficiencies of turbine and pump are assumed to be 100%.

The net heat energy must be removed by the coolant from the PEM fuel cell stack so that it
does not overheat. An organic working fluid is proposed to absorb net thermal energy under
constant pressure circumstances in order to produce vapor.

The heat transmitted from the net heat energy to the working fluid in the PEM fuel cell stack
is:

𝑄̇𝑓𝑐 = 𝑄̇𝑛𝑒𝑡 = 𝑚̇(ℎ1 − ℎ4 )

The power output of turbine is given by:

𝑊𝑡𝑢𝑟𝑏 = 𝑚̇(ℎ1 − ℎ2 )

In the condenser, the heat rejection is given by:

𝑄𝑐 = 𝑚̇(ℎ2 − ℎ3 )

The work consumption by the pump is:

𝑊𝑝𝑢𝑚𝑝 = 𝑚̇(ℎ4 − ℎ3 )

Where 𝑚̇ is the mass flow rate of working fluid, he is the enthalpy.

4.4 Performance Criteria

The effectiveness of the suggested hybrid power system can be assessed by examining the
thermal efficiency of the ORC system, the electrical efficiency of the PEM fuel cell, and the
overall electrical efficiency.
The thermal efficiency of the ORC is the ratio of the net power production to the heat addition,
as specified by the first law of thermodynamics. It can be mathematically written as:

𝑊𝑡𝑢𝑟𝑏 − 𝑊𝑝𝑢𝑚𝑝
𝜂𝑡ℎ𝑚 =
𝑄̇𝑖𝑛

The PEM fuel cell electrical efficiency is calculated as follows:

𝑊𝑓𝑐 − 𝑊𝑐𝑜𝑚𝑝
𝜂𝑓𝑐 =
𝑛̇ 𝐻2,𝑐𝑜𝑛𝑠 . 𝐻𝐻𝑉

The overall electrical efficiency is calculated by:

𝑊𝑓𝑐 + 𝑊𝑡𝑢𝑟𝑏 − 𝑊𝑐𝑜𝑚𝑝 − 𝑊𝑝𝑢𝑚𝑝

𝜂𝑒𝑙𝑒𝑐 =
𝑛̇ 𝐻2,𝑐𝑜𝑛𝑠 . 𝐻𝐻𝑉
 CHAPTER 5: MODELLING & VALIDATION
5.1 Modelling & validation of PEM Fuel Cell
The electrochemical equations of PEM cell that is described are used to create a mathematical
model in MATLAB/Simulink environment.

The figure-4 shows the ideal voltage ie, Nernst equation-

Figure 4: Nernst Simulation Model

The figure-5 shows the saturation pressure of water vapor-

Figure 5: Saturation Pressure of Water Vapor

The figure-6 shows the partial pressure of hydrogen at anode and oxygen at cathode-
 Figure 6: Partial Pressure of Hydrogen and Oxygen

The figures-7,8 shows the molar fraction of nitrogen in air stream at inlet and outlet -

Figure 7: Molar Fraction at inlet

Figure 8: Molar Fraction at Outlet

The figure-9 shows the actual output voltage of a PEM fuel cell-
 Figure 9: Output Voltage of PEM Fuel Cell

The figure-10 shows the activation loss-

Figure 10: Activation loss in fuel cell

 Figure 11: Fuel Cell Membrane Interface

The figure-12,13 shows the hydrogen and oxygen concentration-

Figure 12: Concentration of Oxygen

Figure 13: Concentration of Hydrogen

The figure-14 shows the ohmic loss in fuel cell-

Figure 14: Ohmic Loss in Fuel Cell

The figure-15,16 shows the total internal resistance and membrane resistivity -
 Figure 15: Total Internal Resistance

Figure 16: Membrane Resistivity

The figure-17 shows the concentration loss in fuel cell-

Figure 17: Concentration Loss in Fuel Cell

The figure-18 shows the power output by PEM fuel cell stack-
Fig-18: Power output in PEM fuel cell stack
5.2 Parameters and Result

Symbol Parameter Value

ne Number of electrons 2
F Faraday constant 96,485 C mol-1
R Universal gas constant 8.314 J mol-1K-1
Tamb Ambient temperature 293.15 K
Pamb Ambient pressure 101.325 kPa
Ncell No. of cells in stack 13,000
Acell Active surface area 232 cm2
iL Limiting current density 1.5 A cm2
L Membrane thickness 0.00254 cm
P Operating pressure of PEM 303.96 kPa
fuel cell
Tk Operating temperature of 358.15 K
PEM
fuel cell stack
i Stack operating current 0.6 A cm2
density
λair Stoichiometric rate of air 2
Table 1: Input Parameters of PEMFC [40]

Parameter Validated Model Developed model

Fuel Cell operating voltage 0.653 V 0.623 V
PEMFC stack net electrical 1006.7 kW 1127 kW
power output
Table 2: Validation of the developed model compared with the result from validated article [40]
5.3 Modelling & Validation of Basic Organic Rankine Cycle
For understanding the functionalities and working principles of an organic Rankine cycle, a
simple organic Rankine cycle was modelled using python. The refrigerant considered for this
simple model was R11.

Parameters Equations

heat transmitted from the net heat energy 𝑄̇𝑓𝑐 = 𝑄̇𝑛𝑒𝑡 = 𝑚̇(h1 − h4 )
to the working fluid in the PEM fuel cell

Power Output of the Turbine 𝑊𝑡𝑢𝑟𝑏 = 𝑚̇(h1 − h2 )

Condenser Heat Rejection 𝑄𝑐 = 𝑚̇(h2 − h3 )

Pump Work 𝑊𝑝𝑢𝑚𝑝 = 𝑚̇(h4 − h3 )

Table 3: Equations for the basic ORC Model [40]

Figure 18: Comparison between basic ORC model parameters using CoolProp

A basic French CoolProp Model was taken into consideration for the learning purposes and a
successful execution of the code was made possible using the parameters necessary.
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