Fuel Cell Technologies, Applications, and State of the Art.

A Reference Guide
A Alaswad, University of the West of Scotland, Paisley, UK
A Palumbo and M Dassisti, Politecnico Di Bari, Bari, Italy
AG Olabi, University of the West of Scotland, Paisley, UK
r 2016 Elsevier Inc. All rights reserved.

1 Background 1
2 Fuel Cell Overview 1
3 Different Types of Fuel Cells 3
4 Applications of Fuel Cells 3
4.1 Stationary Power Applications 3
4.1.1 Large stationary power plants 4
4.1.2 Medium and small stationary power plants 6
4.2 Portable Power Applications 6
4.3 Transportation Power Applications 7
5 Proton Exchange Membrane Fuel Cell 9
6 PEMFC's Components and Materials 10
6.1 Membrane Electrode Assembly (MEA) 11
6.1.1 Proton exchange membrane (PEM) 12
6.1.1.(a) Sulfonated aromatic hydrocarbon polymer membranes 13
6.1.1.(b) Inorganic−organic composite membranes 13
6.1.1.(c) Polymer blend membranes 13
6.1.1.(d) Polybenzimidazole (PBI) based acid−base membranes 13
6.1.2 Catalyst layers 14
6.1.3 Electrodes 14
6.1.4 Gas diffusion layers (GDL) 15
6.2 Bipolar Plates (BP) 15
6.2.1 Non-metal: Non-porous graphite/electrographite 15
6.2.2 Metals: Precious non-coated metals, non-coated metals, coated metals 16
6.2.3 Composites: Polymer−carbon and polymer−metal 16
7 State-of-the-Art of PEMFC Materials 16
8 Conclusions 17
References 18

1 Background

One of the biggest challenges the world is facing is to find suitable, sustainable and clean replacements of the fossil fuels. Fossil fuels
are ultimately unsustainable, and depending on them as the main power source leads to serious environmental issues such as
pollution and climate change, along with economic and political issues related to the economy security, and the political problems
affecting the exporting countries. On the other hand, the use of renewable energy is already growing. Of the 300 gigawatts of new
electricity generation capacity built globally between 2008 and 2009, about 140 GW is a capacity to generate from renewable sources.
In 2005, renewables produced 16.5% of world primary energy. According to the special report on renewable energy sources and
climate change mitigation (SRREN), renewable energy could account for almost 80% of the world's energy supply within four
decades. Renewable energy resources include solar, wind, hydroelectric power, bio-energy, geothermal energy and many others. Each
of these alternative energy sources has its advantages and disadvantages, and obviously they are in different stages of development.
Fuel cells technology is one of the most promising technologies that are needed to develop in according with the increasing
renewable energy supply. In this article, an overview of the technology and its advantages and disadvantages compared with
competitive technologies was revealed. Application of different types of fuel cells is covered in the stationary, portable and
transport power sectors. Furthermore, a special focus was made on the proton exchange membrane (PEM) fuel cells; in that its
structure was studied in detail. The current limitation and promising development in PEM technology were stated.

2 Fuel Cell Overview

According to Spiegel, “Fuel cells are electrochemical devices that convert chemical energy of the reactants directly into electricity and heat with
high efficiency. Generally speaking, a fuel cell is simply an energy conversion device for power generation.”1 Fuel cells technology allows the

Reference Module in Materials Science and Materials Engineering doi:10.1016/B978-0-12-803581-8.04009-1 1

2 Fuel Cell Technologies, Applications, and State of the Art. A Reference Guide

Figure 1 Acid electrolyte fuel cell scheme.6

direct conversion of chemical energy to electrical energy, instead of the multi-step processes involved in combustion-based heat
engines.3 However, unlike other electrochemical power sources such as batteries which store their reactants within a cell, the
reactants are fed continuously to it from external stores. Also, the electrodes in a fuel cell are not consumed as in a battery,
irreversibly in a primary cell and reversibly in a secondary cell, and do not take part in the reaction. Fuel cells are identified as one
of the most promising technologies that are significantly related to the renewable energy development.1,2 They can use a variety of
different fuels to generate power (e.g., hydrogen, methanol, fossil fuels to biomass-derived materials, etc.), and they can also
provide electricity by working with large power plants to become more decentralized and increase efficiency.1 In fact, they have
one of the highest efficiencies between the competing energy conversion devices.3 Today, fuel cells have reached a level of
development from which it is possible to indicate that they have promising markets in which electricity must be produced with
high efficiency and low environmental impact.4 Moreover, numerous fuel cell-based power plants have been built and operated
successfully, on a scale from tens of megawatt to a few milliwatts.5
The basic physical structure of a fuel cell consists of an electrolyte layer in contact with two porous electrodes, both containing
catalysts to speed up the electrochemical processes: one electrode is negatively charged (anode) and the other electrode is
positively charged (cathode), as it is shown in Figure 1. Electrochemical reactions take place at the electrodes to produce an electric
current. The basic operation of the hydrogen fuel cell is the reverse situation of the process of the electrolysis; the hydrogen and
oxygen are recombining, and an electric current is produced along with the water obtained.6 The overall reaction is described in the
following equation:

H2 ðgÞ þ 1=2O2 ðgÞ-H2 OðlÞ ½1

We can distinguish two big categories of fuel cells, depending of the kind of electrolyte which is used: acid electrolyte fuel cells
and alkaline electrolyte fuel cells. The main difference between them is the charge carrier: a positive one for the first type, and a
negative one for the second type. At the anode of an acid electrolyte fuel cell, the hydrogen gas ionizes, releasing electrons and
creating H þ ions (or protons), releasing energy, while at the cathode, oxygen reacts with electrons taken from the electrode, and
H þ ions from the electrolyte, to form water. For both these reactions to proceed continuously, electrons produced at the anode
must pass through an electrical circuit to the cathode. Also, H þ ions must pass through the electrolyte. In an alkaline electrolyte
fuel cell the overall reaction is the same as what displayed in equation,1 but the half reactions at each electrode are different. In the
alkaline electrolyte fuel cell, hydroxyl ions (OH) are made at the cathode, and then at the anode they react with hydrogen,
releasing electricity and producing water. At the cathode, oxygen reacts with electrons producing new (OH) ions. Similar to the
acid fuel cells, alkaline electrolyte fuel cells, to allow to these reactions to proceed continuously, the (OH) ions must be able to
pass through the electrolyte, and there must be an electrical circuit for the electrons to go from the anode to the cathode.6 In
Table 1 different half-reactions for both alkaline and acid fuel cells are presented.
As reported earlier, fuel cells provide an efficient and clean mechanism for energy conversion, and they are also compatible
with renewable resources and modern energy carriers (such as hydrogen) for sustainable development and energy security.3
Different low and high scalable fuel cells designs are offered. Fuel cell systems perform with the highest efficiency compared to
conventional distributed energy systems, and they are able to produce near-zero greenhouse emissions if working with renewable
clean resources.1–7 Compared with combustion engines, fuel cells have no moving parts (except for pumps or compressors in
 Fuel Cell Technologies, Applications, and State of the Art. A Reference Guide 3

Table 1 Half reactions of acid and basic electrolyte fuel cells

Acid electrolyte Basic electrolyte

þ 
Anode reaction H2-2H þ 2e H2 þ 2OH-2H2O þ 2e
Cathode reaction ½O2 þ 2H þ þ 2e-H2O ½O2 þ H2O þ 2e-2OH
Overall reaction H2 þ ½O2-H2O H2 þ ½O2-H2O

Table 2 Advantages and disadvantages of fuel cells

Advantages of fuel cells Disadvantages of fuel cells

High operating efficiency and highly scalable design Expensive

Ability to reach near-zero greenhouse emissions Electrolyte poisoning
Working with different types of fuel sources Catalyst degradation
No moving parts and nearly instantaneous recharge capability Fuel reformation technology and storage system may be required

some fuel cell plant subsystems), which allows stealthy, vibration-free and noise-less operations. Compared with batteries, on the
other hand, they provide nearly instantaneous recharge capability.1 At the same time, there are also limitations for fuel cell systems
which are not allowing the fast development of these technologies. In fact, fuel cell technologies are still expensive for all the
markets in which they could operate. Moreover, depending of the type of fuel cell considered, we could need fuel reformation
technology and storage systems, and we could have technical problems, such as electrolyte poisoning or catalyst degradation1,3
Low power density per volume, less accessibility and less durability are other challenges for fuel cell technology development.7 The
main advantages and disadvantages of fuel cell technologies have been summarized in Table 2.

3 Different Types of Fuel Cells

According to Bagotsky,5 fuel cells can be specified into different types based on:

• the reactant type (as a fuel, fuel cells can use hydrogen, methanol, methane, carbon monoxide and other organic substances, as
well as some inorganic reducing agents – as the oxidizing agent, they can use pure oxygen, air, hydrogen peroxide and others);
• the electrolyte type (common electrolytes as aqueous solutions of acid, alkalies and salts, or solid electrolytes which reduce the
danger of leakage of liquids from the cell and serve as separators, keeping reactants from reaching the wrong electrode space);
• the operating temperature (low-temperature fuel cells – 120–150 1C, intermediate temperature fuel cells – 150–250 1C,
interim-temperature fuel cells – 250–650 1C, high-temperature fuel cells – over 650 1C).

In this article, an overview of the main 14 different types of fuel cells has been made, and the main features are shown in Tables
3 and 4, while the overall and half-reactions are summarized in Table 5.7–11

4 Applications of Fuel Cells

According to Ref. 7, it has been noted that fuel cell applications were distinguished as: applications with high power reliability
(telecommunication, high technology manufacturing facilities, data processing, and call centers), applications with emission
minimization or elimination (urban areas, industrial facilities, airports, vehicles), applications for areas with limited access to
utility grid (portable applications and remote areas) and applications for biological waste gases management (waste treatment
plants). However, in this section, fuel cell applications are classified into three major groups of applications: stationary applica-
tions, portable applications, and transport applications.

4.1 Stationary Power Applications

The most common type of fuel cell used in stationary power applications is the PEMFC, but SOFCs, MCFCs, AFCs, and PAFCs are
also utilized.1 In fact, both low- and high-temperature fuel cells could, in principle, be utilized for stationary applications. While
low-temperature fuel cells have the advantage that are usually faster during start-up, high-temperature systems (such as SOFCs and
MCFCs) produce heat which can directly be used for other applications, and they can also operate directly on fuels without the
external reforming,12 reaching a higher efficiency than low-temperature systems.13
4 Fuel Cell Technologies, Applications, and State of the Art. A Reference Guide

Table 3 Main features of different types of fuel cells: fuel, catalyst, and electrolyte

Fuel Catalyst Electrolyte

Low-temperature proton Hydrogen (H2) Platinum supported on carbon Solid polymer membrane (Nafion)
exchange membrane fuel cells
(LT-PEMFCs)
High-temperature proton Platinum–ruthenium sup- Nafion/PBI doped in phosphoric
exchange membrane fuel cells ported on carbon acid
(HT-PEMFCs)
Phosphoric acid fuel cells Hydrogen (H2) Platinum supported on carbon Liquid phosphoric acid (H3PO4) in
(PAFCs) silicon carbide (SiC)
Direct methanol fuel cells Liquid methanol-water solution Platinum/platinum–ruthenium Solid polymer membrane (Nafion)
(DMFCs) supported on carbon
Direct ethanol fuel cells (DEFCs) Liquid ethanol–water solution Platinum/platinum–ruthenium Solid nafion/alkaline media/
supported on carbon alkaline-acid media
Alkaline fuel cells (AFCs) Hydrogen (H2) Nickel/silver supported on Potassium hydroxide (KOH) in
carbon water solution/anion exchange
membrane (AEM)
Molten carbonate fuel cells Methane Nickel chromium (NiCr)/ Liquid alkali carbonate (Li2Co3/
(MCFCs) lithiated nickel (NiO) Na2CO3/K2CO3) in Lithium
aluminate (LiAlO2)
Solid oxide fuel cells (SOFCs) Methane Nickel–YSZ composite/ Solid yttria-stabilized zirconia
Strontium-doped lanthanum (YSZ)
manganite (LSM)
Proton ceramic fuel cells (PCFCs) Methane Nickel Protonic/zirconia

Zinc-air fuel cells (ZAFCs) Zinc Non-noble metal oxides (such Liquid alkalines
as manganese oxide –
MnO2)
Direct borohydride fuel cells Sodium borohydride (NaBH4) Gold/silver/nickel/platinum Solid nafion/anion exchange
(DBFCs) supported on carbon membrane (AEM)
Direct formic acid fuel cells Liquid formic acid (HCOOH) Palladium/platinum supported Solid nafion
(DFAFCs) on carbon
Direct carbon fuel cells (DCFCs) Solid carbon (coal, coke, Graphite or carbon-based Solid yttria-stabilzed zirconia
biomass) material/strontium-doped (YSZ)/Molten carbonate/molten
lanthanum manganite (LSM) hydroxide
Enzymatic fuel cells (BFCs) Organic matters (glucose) Biocatalyst supported on Ion exchange membrane/
carbon membrane-less
Microbial fuel cells (BFCs) Any organic matter (glucose, Biocatalyst supported on Ion exchange membrane
acetate, waste-water) carbon/platinum supported
on carbon

As can be seen from Figure 2, we can identify two main power plants: large stationary power plant (power output from 300 kW
up to 20 MW) and small-medium stationary power plants (power output from a few Watts up to 10 kW for small stationary power
plants and from 10 kW up to 300 kW for medium stationary power plants).4 Moreover, stationary fuel cells, depending on their
features, may be used for many applications, either as the primary power source instead of the grid, or in places where the grid
cannot reach (remote-area power supply-RAPS), to provide supplemental power in hybrid power systems with photovoltaics,
batteries, capacitors, or wind turbines, providing primary or secondary power (distributed power or CHP generation), or as a
backup (emergency backup power supply-EPS or UPS).1–3

4.1.1 Large stationary power plants

Fuel cells strategy can help to make the shift from large centralized power generation to decentralized distributed generation. Due
to their static nature, lower emissions, exceptional load-following, and high efficiency, fuel cells could be used for residential
electric power or CHP distributed generation either on a household basis or on a larger residential blocks basis.3 Combined Heat
and Power Systems offer increase energy efficiency through the use of both electric and thermal energy. The heat produced can be
used for space heating or other various purposes.14 Proton exchange membrane fuel cells (PEMFC) and phosphoric acid fuel cells
(PAFC) are widely used for CHP applications, in particular for household basis CHP generation,3 but they work at low tem-
peratures such as less than 100 1C and 200 1C, so that both of them need an external fuel reformer in order to use fuel other than
pure hydrogen and they have a low tolerance for CO (the product of natural gas reforming), and they exhibit operation with
electrical efficiencies only in the low 30% range.15 For these reasons, high-temperature fuel cells are more suitable for the larger
 Fuel Cell Technologies, Applications, and State of the Art. A Reference Guide 5

Table 4 Main features of different types of fuel cells: electrical efficiency, operating temperature, and charge carrier

Electrical efficiency Operating temperature Charge carrier

Low-temperature proton exchange 40–60% 60–80 1C Hydrogen ion (H þ ) (proton)

membrane fuel cells (LT-PEMFCs)
High-temperature proton exchange 50–60% 110–180 1C
membrane fuel cells (HT-PEMFCs)
Phosphoric acid fuel cells (PAFCs) 36–45% (85% with 160–220 1C Hydrogen ion (H þ ) (proton)
cogeneration)
Direct methanol fuel cells (DMFCs) 35–60% Ambient–110 1C Hydrogen Ion (H þ ) (proton)
Direct ethanol fuel cells (DEFCs) 20–40% Ambient–120 1C Hydrogen ion (H þ ) (proton)
Alkaline fuel cells (AFCs) 60–70% Below zero–230 1C Hydroxyl ion (OH)-
Molten carbonate fuel cells (MCFCs) 55–65% (85% with 600 1C-700 1C Carbonate ion (CO3)2-
cogeneration)
Solid oxide fuel cells (SOFCs) 55–65% (85% with 800–1000 1C Oxygen Ion (O2)
cogeneration)
Proton ceramic fuel cells (PCFCs) 55–65% 700 –750 1C Hydrogen ion (H þ ) (proton)

Zinc-air fuel cells (ZAFCs) 30–50 % Below zero–60 1C Hydroxyl ion (OH)-
Direct borohydride fuel cells (DBFCs) 40–50% 20–85 1C Sodium ion (Na þ )
Direct formic acid fuel cells (DFAFCs) 30–50% 30–60 1C Hydrogen ion (H þ ) (proton)
Direct carbon fuel cells (DCFCs) 70–90% 600–1000 1C Oxygen ion (O2  )
Enzymatic fuel cells (BFCs) 30% 20–40 1C Hydrogen ion (H þ ) (proton)
Microbial fuel cells (BFCs) 15–65% 20–60 1C

Table 5 Half reactions for different types of fuel cells

Anode reaction Cathode reaction Overall reaction

(PEMFCs) þ
H2(g)-2H (aq) þ 2e  
2O2(g) þ 2H þ (aq) þ 2e -H2O(l)
1 H2(g) þ 12O2(g)-H2O(l)
(PAFCs) H2(g)-2H þ (aq) þ 2e  
2O2(g) þ 2H þ (aq) þ 2e -H2O(l)
1 H2(g) þ 12O2(g)-H2O(l)
(DMFCs) CH3OH(l) þ H2O(l)-CO2 þ 6H þ þ 6e  3 þ 
2O2 þ 6H þ 6e -3H2O(l)
CH3OH(l) þ 32O2(g)-CO2(g) þ 2H2O(l)
(DEFCs) CH3CH2OH þ 3H2O-2CO2 þ 12H þ þ 12e  3O2 þ 12H þ þ 12e  -6H2O CH3CH2OH þ 3O2-2CO2 þ 3H2O
(AFCs) 2H2(g) þ 4(OH)  (aq)-4H2O(l) þ 4e  O2(g) þ 2H2O(l) þ 4e  -4(OH)  (aq) 2H2(g) þ O2(g)-2H2O(l)
(MCFCs) CO32 þ H2(g)-H2O(g) þ CO2(g) þ 2e  CO2(g) þ ½O2(g) þ 2e  -CO32 H2(g) þ ½O2(g) þ CO2(g)-H2O(g) þ CO2(g)
(SOFCs) H2(g) þ O2-H2O(g) þ 2e  
2O2(g) þ 2e -O2
1  H2(g) þ 12O2(g)-H2O(g)
(PCFCs) Zirconia Electr. Zirconia Electr. /
CH4 þ 4O2-CO2 þ 2H2O þ 8e  2O2 þ 8e  -4O2
Protonic Electr. Protonic Electr. 2O2 þ 8 /
CH4 þ 2H2O-CO2 þ 8e  þ 8H þ þ 8H þ H þ þ 8e  -4H2O
 
Zn(g) þ 4(OH)  (aq)-Zn(OH)42 þ 2e  2H2O þ 2O2 þ Zn þ 2(OH) -Zn(OH)42
  1 1
2O2 þ H2O þ 2e -2(OH)
1
(ZAFCs)
(DBFCs) NaBH4 þ 8OH  -NaBO2 þ 6H2O þ 8e  2O2 þ 8e þ 4H2O-8OH 

NaBH4 þ 2O2O2-NaBO2 þ 2H2O
(DFAFCs) HCOOH-CO2 þ 2H þ þ 2e  
2O2 þ 2H þ þ 2e -H2O
1 HCOOH þ 12O2-CO2 þ H2O
(DCFCs) C þ 2CO32-3CO2 þ 4e  
O2 þ 2CO2 þ 4e -2CO32 C þ O2-CO2

Figure 2 Stationary applications for fuel cells.

6 Fuel Cell Technologies, Applications, and State of the Art. A Reference Guide

residential block basis CHP generation,3 and in particular, for these applications, SOFC are the best candidates. At a higher
temperature, SOFC system has greater advantages for the combined supply of heating and electricity over these technologies.15
Fuel cell systems used for CHP generation could be designed to be either grid-independent or grid-assisted. The first case is more
complicated with higher cost, as the system will have to meet dynamic load fluctuations, but it is possible to solve the problem
over sizing the fuel cell system and integrating it with battery-banks or ultracapacitors. On the other hand, gird-assisted systems
export electricity to the grid during low load demands and import electricity from the grid during peak load demands. For both
cases, a thermal storage mechanism is required for an effective CHP system.3

4.1.2 Medium and small stationary power plants

The range of applications of medium-small power plants is very large. They are designed primarily for a combined supply of
electric power and heat to individual structures of different sizes: individual cottages, administrative and office buildings and
hospitals.5 Fuel cell-based power plants of small power are built to supply electric power to individual residential or administrative
quarters or to remote individual power costumers.5 The main applications in this field concern plants for electricity production
and cogeneration for buildings, and for industrial and commercial applications. In parallel to the above listed advantages, other
significant features of these plants are the production of premium quality power, the possibility of using an independent source
that can operate for ‘onsite’ production or as a continuous power backup or as an uninterrupted power supply (EPS).4 Most fuel
cells used for low-power plants were PEMFCs. The Japanese company Ebara Ballard developed a 1-kW power plant for combined
heat and power production. The unit was designed to operate for 10 years, in accord with requirements set by the Japanese
government. A similar unit is also designed for an operating time of 10 years was developed by the Japanese company Fuji electric.
These units cost $12 000–$16 000.5
Due to their high energy and power densities, high modularity, longer operation times, compact size, and ability to operate
under unkind ambient conditions, fuel cells are becoming an encouraging alternative for batteries in the electro power system
(EPS) market, especially in the telecommunications market, with PEMFCs and DMFCs as the dominantly-chosen fuel cell types.3
Due to the fact that the EPS market requires high reliability but not necessarily high operational lifetimes, fuel cells found EPS to
be one of its most successful markets, such as data centers, banks, and government agencies. Other users who can use units of this
type are the surgery wards in hospitals, the computer units in traffic control and financial institutions, and the systems of
emergency lighting in public spaces.3–5
Another important application of small power units is in remote-area power supply (RAPS). In grid-isolated locations, such as
islands, deserts, forests, remote technical installations, and remote research facilities, providing power could be a problem. All of
these locations and other more fall under the remote-area power supply (RAPS) category.3 An interesting project concerns plans to
use fuel cells in the Antarctic base on Bechervaise Island. This project, supported by a grant of $600 000 from the Australian
government, involves the production of hydrogen by electrolysis with wind energy and its use in low-power fuel cell units
producing electric power and heat.5

4.2 Portable Power Applications

The increasing demand for quality, density and time performance of power supply is the principal driving force in the
portable power production market, which includes an increasing number of new products (cassette and mini disk players, laptop
computers, cellular phones). In this market there is always a competition between the different technologies, because products
must be smaller, cheaper, and lighter, with an increasing number of functions.4 Moreover, the fields of telecommunications,
computers, Internet and social networks have become essential for humans, and this implies the need for a fully reliable electricity
supply.13 For all these reasons fuel cells are particularly appropriate as portable power systems due to the fact that they have good
potential in terms of energy density, durability, simple design and low cost. A fuel cell can operate as long the fuel is supplied to
the device and this can be easily done from a very small and light tank.4
Portable applications of fuel cells are mainly focused on two main markets, as we can see in Figure 3. The first is the market of
portable power generators designed for light outdoor personal uses (e.g., camping and climbing), light commercial applications
such as portable signage and surveillance, and power required for emergency relief efforts.3 In fact, fuel cells can provide electrical
power in places where the grid connection is not available. For example, in a vacation place outdoors (camping area), the use of a
fuel cell for electrical power instead of a diesel generator, avoiding harmful emissions, help to preserve the environment and causes
no problems noise to other people in the environment.13 The second market is the market of consumer electronic devices (e.g.,
laptops, cell phones, radios, camcorders, i-pods, and basically any electronic device that traditionally runs on a battery).1 The
modularity and high energy density of fuel cells make them strong potential candidates for future portable personal electronics.3
Fuel Cells may be also used to provide power as a primary or support system for telecommunications switching nodes, trans-
mission towers, reception or other electronic devices that can benefit from the DC power supplied by a fuel cell.13 Other rapidly-
growing markets in the portable sector include portable battery chargers in addition to miniature demonstration and educational
remote control (RC) vehicles, toys, kits, and gadgets by manufacturers, such as Horizon hydrocar educational kit.3
 Fuel Cell Technologies, Applications, and State of the Art. A Reference Guide 7

Figure 3 Portable applications for fuel cells.

In particular, there is a growing demand of power systems for portable electronic equipment in the military market,13,16 which
means a growing application of portable DMFCs and PEMFCs due to their silent operation, high power and energy density, and
low weight compared to current battery-based portable equipment.3 Moreover, the military market accepts higher prices for the
trade-off of better performance and weight.1 PEM fuel cell power plants offer high efficiency operation. However, the problem with
the large PEM fuel cells (42 kW) is that they need hydrogen fuel to operate, while hydrogen should be generated from existing
logistic fuels.17
While there are several types of fuel cell using liquid fuel, a direct methanol fuel cell system (DMFC) is considered to be the
most promising candidate for portable and mobile applications. In addition to the DMFC systems, the direct borohydride fuel cell
(DBFC) system has attracted attention since the last 15 years for application in portable power supplies due to its high specific
energy and compact structure. While the DBFC system could be more competitive than the DMFC system in terms of cell size and
volume, its total cost for generation in real operation, considering the problem of the fuel crossover, is higher than that of the
DMFC.13,18

4.3 Transportation Power Applications

The transportation industry is one of the main important fields in the development of clean energy technologies. This is due to the
fact that the transportation industry is responsible for 17% of the global greenhouse gas emissions every year,3 so that important
changes are expected from this sector in order to reach the aims of the Kyoto protocol.4 The industry's outlook is to invest in
technologies that would offer both significant reductions in harmful emissions and better energy conversion efficiencies. Fuel cells
offer the transportation industry near-zero harmful emissions without having to compromise the efficiency of the vehicle’s
propulsion system. In fact, fuel cells have demonstrated efficiencies that are almost twice of the conventional internal combustion
engines efficiency. Considering the advantages of smooth operation, fuel flexibility, modularity, and low maintenance require-
ments, due to the absence of moving parts, fuel cells become an ideal future alternative for current combustion engines. However,
the fuel cell industry is still facing a number of challenges to commercialization in the transport sector. Fuel cell cost is one major
challenge, the durability of the unit and its performance is another important one. The hydrogen storage and hydrogen fuel
infrastructure all need to be taken in consideration.
In particular, the PEMFC technology can be ideally suited for transportation applications due to its high power density, high
energy conversion efficiency, compactness, lightweight, and low operating temperature. However, among all applications, for fuel
cells the transportation application involves the most stringent requirements regarding volumetric and gravimetric power density,
reliability, and costs. However, the high cost of this technology represents the biggest challenge for its commercialization. Another
arising fuel cell technology for transportation applications is DMFC, even if it is less advanced as compared to the PEMFC
technology and affected by problems of reduced power density caused by methanol permeation through the membrane and
poisoning of the catalysts. Another possible developing technology in the field of transportation applications is SOFC. In contrast
PEMFCs, SOFCs allow trouble-free use of hydrocarbon fuels, even if it is complicated. Moreover, they do not demonstrate any
significant poisoning problem. These positive features have been recognized recently, leading several companies to develop SOFCs
as Auxiliary Power Units (APU) for gasoline vehicles.12
According to Ref. 3, fuel cell transportation applications were specified as shown in Figure 4, into the following markets:
auxiliary power units (APUs), light traction vehicles (LTVs), light-duty fuel cell electric vehicles (L-FCEVs), heavy-duty fuel cell
electric vehicles (H-FCEVs), aerial propulsion, and marine propulsion. Currently, PEMFCs, DMFCs, and SOFCs are the fuel cell
types being developed for APU applications with pure hydrogen, natural gas, LPG, gasoline, methanol, and diesel as potential
fuels. Other more energy-intensive vehicles, such as commercial airplanes, military vehicles and cargo ships, require APUs with
high energy ratings, for which high-temperature fuel cells (SOFCs and MCFCs) become better candidates.3,17
Light traction vehicles (LTVs) include scooters, personal wheel-chairs, motorbikes, airport tugs, golf carts, electric-assisted
bicycles, etc. in addition to material handling vehicles and equipment (e.g., carts, wheel carts, forklifts, tow trucks, pallet trucks,
8 Fuel Cell Technologies, Applications, and State of the Art. A Reference Guide

Figure 4 Transportation applications for fuel cells.

etc). One of the most important future application in this field will be fuel cell-based motorcycle, because, even if they have a
small size, motorcycles are a major source of pollution in cities.13 Forklifts have been the most successful demonstration of fuel
cells in the transportation sector, and one of the most successful demonstrations for fuel cells overall. Until now, for example,
around 1300 fuel cell-powered forklifts are operative in the US market today.3 Due to their advantages, PEMFCs are the most
popular fuel cells in light fuel cell electric vehicles (L-FCEVs) research and development.3 The principle of how FCEVs work is
simple; they use low-temperature fuel cells (mainly PEM) to generate electricity from hydrogen, and then the electricity is used to
drive the vehicle or stored in batteries or ultracapacitors.19 Since fuel cells generate electricity from chemical reactions, they do not
combust fuel and therefore do not produce harmful emissions and produce much less heat than internal combustion engines. In
fact, the only by-product of a hydrogen fuel cell is water. Despite all PEMFC advantages, the fuel favoured by many car manu-
facturers is methanol, because from it we can produce hydrogen on-board by steam reforming. But, with this process, we have
slower response times, and extensive gas clean-up procedures need to be carried out to supply the fuel cell with the fuel.
Because of this issues and the size of the reformer and gas-cleaning unit a DMFC would be more desirable for mobile systems.12
There are a lot of car manufacturers which are increasingly progressing for the commercialization of L-FCEVs (e.g., General Motors,
Toyota, Mazda, Daimler AG, Volvo, Volkswagen, Honda, Hyundai, Nissan).3 In 2007, the vehicle manufacturer Honda presented
the model FCX Clarity at Los Angeles automobile saloon. This model is available for the consumer since the summer of 2008. This
was the first fuel cell vehicle platform-exclusive in the world manufactured in series.13 At the 2010 Fuel Cell Expo in Tokyo,
Japanese automakers announced a program designed to deploy two million FCEVs in Japan by 2025, at which point the industry
estimates FCEVs would be fully competitive.19
Heavy-duty fuel cell electric vehicles (H-FCEVs) include buses, heavy-duty trucks, locomotives, vans, utility trucks, service fleets,
and other large load vehicles which use fuel cells for the electric propulsion system.3 A number of fuel cell buses have been noted
in operation worldwide during the last few years.13 In 2012, more than 30 fuel cell buses in Western Europe, and other 25 in the
United States were deployed. Fuel cell electric buses (FCEBs) are becoming one of the best public demonstration tools and R&D
data sources in the H-FCEVs industry. PEMFCs and PAFCs are the most commonly-used types of fuel cells stacks used in the
industry, taking the advantages of regenerative braking energy recovery and high dynamic response performance. However, the
immaturity of fuel cell technologies and the lack of mass production and manufacturing are making FCEBs economically-
uncompetitive with conventional buses and other competing arising technologies.3
Fuel cells application in marine transportation is increasing during the last years. Potential use of fuel cells as auxiliary power
units on surface ships, is becoming an actual chance and probably in the future fuel cell systems will share with diesel engines the
marine propulsion task. Promising future marine propulsion markets for fuel cells include ferries, boats, yachts, and cargo ships,
but mostly submarines and underwater vehicles.20 Fuel cells offer their regular advantages for ships and ferries, such as low
emissions, high efficiency, and static operation, but they have also issues related to reliability, lifetime, shock resistance, and
tolerance to the salt content of sea air which have to be resolved.3 Therefore, according to Ref. 20, marine applications of fuel cells
are not so developed as in other transport sectors such as automotive or aerial propulsion. Fuel cell technology, so far, does not
assure a clear improvement in the respect of certain requirements of space taken (volume) and weight which are required for a
ship. Moreover, the marine environment is very hostile especially with regard to dynamic loads and the high corrosion. The
application of fuel cell technology in this field needs to be adapted to these circumstances in order to operate normally with a
 Fuel Cell Technologies, Applications, and State of the Art. A Reference Guide 9

required life cycle. There is a lack of infrastructure to facilitate the commercialization of this technology and, in general, the price of
the energy generated by fuel cells is still higher than the ones obtained by internal combustion engines conventional systems.
Currently, PEMFCs, SOFCs, and MCFCs are the most potential technologies for the marine fuel cell market. However,
researches demonstrated that, based on a life cycle assessment, using MCFCs with on-board reformation holds no good when
compared with conventional diesel engines regarding energy and environment. This is mainly due to the immaturity of MCFC
technology, the low durability of MCFC stacks, and the use of energy-intensive materials and manufacturing processes due to the
lack of commercial production.3 On the other hand, in 2003, the first yacht with a hybrid PEMFCs/batteries system for both
propulsion and APU was demonstrated in Germany and, also in Germany, the world's first commercial passenger-ship was put
into service in 2008. Submarines that use oxygen/hydrogen fuel cells for propulsion and auxiliary load requirements have also
been successfully deployed. PEMFC are the main technology considered to provide a new generation of conventional submarines
with an Air Independent Propulsion system (AIP) through Germany, Greece, Italy, Portugal, and Spain.20
The space industry was one of the first fields to adopt fuel cells in. NASA used AFCs and PEMFCs technologies for its manned
space programs during the 1960s. Fuel cells are attractive for space applications due to their many advantaged compared to other
power generation technologies. However, the fact that water is a by-product of the electrochemical reactions within a fuel cell
makes it even more attractive for space applications where air, water, and food supplies are of most importance. On the other
hand, the market of manned military and commercial air vehicles is still impractical for fuel cells due to the market’s high energy
density, power density, durability, and reliability requirements, especially for the development of small unmanned aerial vehicles
(UAVs). The stealth nature of UAVs is facilitated by fuel cells’ static operation, and low heat dissipation that represents together
two advantages over UAVs with internal combustion engines. UAVs are mainly used for surveying, surveillance, and reconnais-
sance purposes due to their stealth nature and lack of risk to human life.3
In conclusion, if we want to compare the different scenarios for the application of fuel cell technologies, as it is shown in
Table 6, we can clearly find that PEMFCs are the ones with the largest range of possible markets. In fact, due to their numerous
advantages, they could be employed in a wide range of different fields. However, there are some issues to be solved before PEMFC
can be properly commercialized, including the current high cost of the unit, the need to improve its durability and performance,
and the need to a stable and economical supply of high-purity hydrogen. However, we have to consider viewpoints such as the
health and environmental benefits as well as the infrastructural aspects of traditional power supply and demand.21

5 Proton Exchange Membrane Fuel Cell

The proton exchange membrane (PEM) fuel cell consists of a cathode, an anode and an electrolyte membrane. Hydrogen is
oxidized at the anode and the oxygen is reduced at the cathode. Protons are transported from the anode to the cathode through the
electrolyte membrane and the electrons are carried over an external circuit load. On the cathode, oxygen reacts with protons and
electrons producing heat and forming water as a by-product.1 The complete process of a PEMFC is shown in Figure 5. Depending
on the operating temperature, we can distinguish two different types of PEMFCs. The first type, Low-Temperature Proton Exchange
Membrane Fuel Cell, operates in a range of 60–80 1C.3 The second type operates in a range of 110–180 1C,3 therefore, it is called
High-Temperature Proton Exchange Membrane Fuel Cell. The standard electrolyte material used in Low-Temperature PEM fuel
cells is a fully fluorinated Teflon-based material produced by DuPont for space applications in the 1960s, which is generally called
Nafion.1 For High-Temperature PEM fuel cells, it is possible to use Nafion or Polybenzimidazole (PBI) doped in phosphoric acid.
Platinum is classically used in the catalyst for Low-Temperature PEMFCs,6 while Platinum–Ruthenium is used for High-

Table 6 Possible applications for fuel cells

Applications PEMFC DMFC SOFC MCFC PAFC AFC MFC

Stationary CHP X X X
RAPS X X X X
EPS X X X X
Portable Power generators X X
Consumer electronics X X X
Battery chargers X X
Army X X
Transportation APUs X X X X
LTVs X X
L-FCEVs X
H-FCEVs X X
Aerial propulsion X X X
Marine propulsion X X X
10 Fuel Cell Technologies, Applications, and State of the Art. A Reference Guide

Figure 5 Electrochemical process in a PEMFC.7

Table 7 Main features of LT-PEMFC and HT-PEMFC3

LT-PEMFC HT-PEMFC

Electrolyte Solid polymer membrane (Nafion) Nafion/PBI doped in phosphoric acid

Catalyst Platinum supported on carbon Platinum–ruthenium supported on carbon
Operating temperature 60–80 1C 110–180 1C
Electrical efficiency 40–60% 50–60%
Fuel Hydrogen (H2) Hydrogen (H2)
Charge carrier Hydrogen ion (H þ ) (proton) Hydrogen ion (H þ ) (proton)

Table 8 Advantages and disadvantages of PEMFCs

Advantages Disadvantages

High energy density Needed to pure hydrogen

Compact design Needed to pure oxygen
Max values of specific power per unit volume and weight Water flooding
Fast start-up time Expensive
Low operating temperature Platinum catalyst poisoning (CO)
Easy and safe handling –
Min maintenance (no moving parts) –
Continuous electrical energy supply –

Temperature PEMFCs catalyst.3 The electrical efficiency for Low-Temperature PEM fuel cells is about 40–60%, while for High-
Temperature PEM fuel cells it is about 50–60%.3 The main aspects of LT-PEMFCs and HT-PEMFCs are shown in Table 7.
Due to the compact design, the maximum values of specific power per unit of volume or weight are higher for these power
sources than for all other batteries of conventional type.5 These cells run at low temperatures, and this is an advantage because it
leads to a rapid start-up process, but also a disadvantage because of the problem of slow reactions rates, which is addressed by
using sophisticated catalysts and electrodes.3,6 PEMFCs have been used in largest range of applications. In particular, they are
considered the most promising candidates for transport applications, due to their high power density, fast start-up time, high
efficiency, low operating temperature, and easy and safe handling. However, the PEMFC technology still has many challenges
including high cost, low durability and hydrogen storage problems which limit the wide-world commercialization of it (Table 8).

6 PEMFC's Components and Materials

As it has been reported earlier, Proton Exchange Membrane Fuel Cells have emerged as promising emission-free technologies and
they have been chosen as one of the potential solution to accomplish the power requirements of the 21st century.22–23 The PEMFC
was the first type of fuel cell to find an application; it has been used as a power source for NASA's Gemini space flights in the
 Fuel Cell Technologies, Applications, and State of the Art. A Reference Guide 11

Figure 6 MEA and other components of a PEMFC stack.28

1960s.24 Then, through the activities of General Electric, they experienced an impressive renaissance in the 1980s.25 In recent
times, PEMFCs have begun to move from the demonstration phase to commercialization due to the notable research efforts in the
past years.26 The main components of a single PEMFC as shown in Figure 6, according to Refs. 24, 26, and 27 are:

• Membrane Electrode Assembly (MEA) which is sub-components (proton conducting electrolyte, cathode/anode porous
electrodes, anodic/cathodic catalyst layers and gas diffusion layer). It is the heart of the fuel cell. Every single component will be
discussed in the following paragraphs.
• Anode/cathode current collectors with the reactant flow fields (also called bipolar plates in some applications). They act as
electron conductors and they are in contact with the anode/cathode gas diffusers.
• Auxiliaries to facilitate thermal and water management, and for gas transportation (e.g., Anode/Cathode gas channel that
supply the fuel cell with reactants).

Moreover, individual fuel cells can be connected to achieve higher voltage and power in a multi-cell stack. The power output of
a given fuel cell stack will depend on its size. Increasing the number of cells in a stack increases the voltage, while increasing the
surface area of the cells increases the current.24

6.1 Membrane Electrode Assembly (MEA)

Membrane electrode assembly (MEA) is considered the ‘heart’ of the PEM fuel cell, because it is typically sandwiched by two flow
field plates that are often mirrored to make a bipolar plate when cells are stacked in series for greater voltages.27,29 According to
Ref. 24, the MEA structure and composition are of vital importance in order to minimize all forms of over-potential, maximize the
power density, minimize the noble metal loading and thus reduce the cost per kW of the PEMFC. The Membrane and Electrode
Assembly (Figure 6) is composed of the following sub-components:24,26

• The proton conducting electrolyte. A polymer membrane that allows the transport of water and protons and separates the reactants
H2 and O2;
• Cathode/Anode porous electrodes. They transport reactants/products to and from the catalyst layers and conduct electrons from the
catalyst layer to the collector plates. In the meantime, liquid water coming from MEA fills the gas diffuser pores. The graphite
matrix of the gas diffusers provides a path for the electrons to be transported between the collector plates and the catalyst layers
of the MEA. Then, two different processes can be noticed in the cathode and in the anode: in the cathode, the air mixture will be
partially transported through the cathode gas diffuser towards the cathode catalyst layer. In the anode, Hydrogen gas from the
anode gas channels is transported through the anode gas diffuser towards the anode catalyst layer.
• Anodic/Cathodic catalyst layers. They are deposited on the electrode or the proton conducting membrane, where the electro-
chemical reactions take place. In particular, at the Anode catalyst layers, hydrogen gas coming from anode gas diffuser will
oxidize and protons will dissolve in the liquid water that passes the proton exchange membrane (PEM), while at the Cathode
12 Fuel Cell Technologies, Applications, and State of the Art. A Reference Guide

catalyst layers oxygen coming from the cathode gas channels will dissolve in the liquid water and will react with the protons
coming from the anode through the PEM and with the electrons coming from the anode through an external circuit.
• Gas diffusion layer. It ensures that reactants effectively diffuse to the catalyst layer and transports electrons to and from the
catalyst layer.

6.1.1 Proton exchange membrane (PEM)

Proton exchange membranes (PEMs) are the key components in fuel cell systems. Three different roles can be identified for the
polymeric membrane in the PEM fuel cells as follows: to charge carrier with protons, to separate of the reactant gases, and to
perform as an electronic insulator that prevents electrons from passing through the membrane.30 The ideal membrane might
possess both acidic as well as basic sites with such a small distance in between that effective proton transfer is possible without an
extra proton-carrying phase.31 In particular, according to Refs. 22 and 30, to achieve high efficiency in fuel cell applications, the
polymer electrolyte as membrane must possess the following desirable properties: high proton conductivity to support high
currents with minimal resistive losses, zero or near-zero electronic conductivity, high mechanical strength and stability, chemical
and electrochemical stability under operating conditions, good oxidative and hydrolytic stability, moisture control in stack, cost
effectiveness, low permeability to fuel, and low electro-osmotic drag coefficient. In particular, the electrolyte membrane must resist
oxidation, reduction, and hydrolysis. It must retain rigidity and other mechanical properties across a wide range of humidity and
in about 801 temperatures. Since membranes are in close proximity to the electrodes, they have also to be able to resist attack from
electrode materials and catalysts, while working productively with them.29 For most PEMFCs, the proton exchange membranes are
currently based on perfluorosulphonic acid (PFSA) polymers (e.g., Nafion)32 which operate effectively only under fully hydrated
conditions.30 Nafion and related polymers are comprised of perfluorinated back-bones, which provide chemical stability, and of
sulfonated side-groups which aggregate and facilitate hydration. It is these hydrated, acidic regions which allow relatively facile
transport of protons, but also restrict PEMFCs to low temperatures of operation.33
By 1964, DuPont recognized that Nafion had properties that were very desirable as a membrane separator in chloralkali cells
used for production of chlorine and caustic soda, but in the 1960s the chloralkali industry was not ready for this development.
Meanwhile, in the United States, GE was developing PEM fuel cells for the US space program, with the aim to provide electricity
and water for an animal orbiting in space in a satellite.34 The first prototype PEM developed by GE for the Gemini space program
was based on the sulfonated polystyrene divinylbenzene copolymer, but the membranes were chemically unstable to the oxidative
environment of the fuel cell, and the very short lifespan and high cost of the membrane limited its application. Then, GE
determined that membranes from the Nafion polymer had the required oxidative stability and proton conducting property that
would enable GE to meet their commitment to the NASA space program.22,34 In fact, one of the biggest changes in the PEMFC
technology, was when the polystyrene sulfonic acid membrane, used as an auxiliary power source in every one of NASA's Gemini
flights in the 1960s, was replaced by Du Pont’s perfluorosulfonic acid membrane (Nafion) in the 1970s.24 This fluorinated sulfonic
acid Nafion membrane developed by DuPont Co. was selected as a standard membrane for polymeric electrolyte fuel cells. It soon
became a standard for PEMFC and remains so till today.30 For more than 35 years, DuPont has supplied Nafion perfluorinated
membranes for fuel cells in the US space and military programs.34
During the period 1977–1984, DuPont invested in building a monomer, polymer, and membrane fabrication plant in
Fayetteville NC to meet the needs of the Chloralkali market and, during the early 1990s, the interest in PEM fuel cell technology as
an alternative power source to internal combustion engine began to gain support.34 Today, Nafion membranes play an integral
role in the success of recent PEM fuel cell demonstration programs in portable, stationary, and transportation applications. It is
still in demand for space and other high specification applications but, despite its use in few concept prototypes, it cannot be
seriously contemplated for everyday road vehicles or domestic applications.30,34 However, Nafion functions only in a highly
hydrated state and therefore it is limited to operation at temperatures up to around 80 1C under-ambient pressure in order to
maintain a high water content in the membrane, while PEMFC operating at high temperatures has in recent years been recognized
and considered by some researchers as a potential promising solution to meet these technical challenges.32
Several challenges for the PEMFC power technology are associated with low operating temperature.32 Low-temperature
polymer electrolyte membrane fuel cell (LT-PEMFC) suffers from several disadvantages including heat and water management, CO
catalyst poisoning and fuel crossover. On one hand, Nafion copolymer has many advantages, because it possesses excellent
electrochemical properties below 80 1C, under highly humidified conditions. In fact, it is a good proton conductor with adequate
mechanical and chemical properties, which, under favorable conditions, lasts well, resisting acids, bases, and oxidants. As a film-
forming thermoplastic, it is easy to process and commercially available in several varieties. But, on the other hand, it has also some
disadvantages, because it is sensitive to contaminants and permeable to methanol, it suffers from poor ionic conductivity under
low humidity conditions, leading to inferior ionic conductivity at high temperatures, which means a decrease of performances for
operations above 80 1C. Moreover, over-hydration and excessive dehydration upset its morphology, and because its originators
were primarily interested in power density and durability under orbital conditions, it is expensive.22,23,29 In fact, the operating of
perfluorosulfonic acid membranes is limited by the dependence of proton conductivity on the presence of water, which is needed
for acid dissociation and for proton mobility. This determines the window of operation of perfluorosulfonic acid membranes to
those conditions which guarantee certain water content of the membrane.31 All these limitations have prompted the development
 Fuel Cell Technologies, Applications, and State of the Art. A Reference Guide 13

of new membranes and techniques and they lead to the development of high-temperature polymer electrolyte membrane fuel cell
(HT-PEMFC), which operates in a temperature range from 100 1C to 200 1C, relative to the well-developed PEMFC technology
typically operating at 80 1C.22,32
Accordingly, several groups are pursuing ‘water-free’ proton conducting membranes that do not require hydration. They also
enable the PEMFC to be operated under ‘warm’ conditions thus further improving its efficiency. Moreover, the benefits of ‘warm’
temperature operation, which include increased activity of the catalysts, decreased susceptibility of the anode catalyst to poisoning
by impurities in the fuel stream, greater integration with high-temperature H2 generators, and greater ease of thermal management,
are all forgone in conventional PEM fuel cells. Capital cost could also be further reduced because at warmer conditions less Pt
could be used.30,35 However, high-temperature operation often leads to dehydration, which deteriorates the membrane perfor-
mance. HT-PEMFCs also suffer from other disadvantages like reduced proton conductivity and low mechanical stability. These
issues motivate the development of new membranes and new techniques that allow operation at low and high temperature
without sacrificing proton conductivity or mechanical strength.22,23 For these reasons, according to Ref. 23, different approaches
have been adopted to retain the water at high temperatures including: incorporation of inorganic additives to hydrophobic
polymer membranes, use non aqueous, using low volatile solvents to replace water as the proton acceptor within the polymer
membrane and utilization of a solid state protonic conductor.

6.1.1.(a) Sulfonated aromatic hydrocarbon polymer membranes

Sulfonated hydrocarbon polymers show improvement in mechanical properties and proton conductivity at elevated temperatures,
with good performance as a result. The introduction of metallic oxides into the polymer matrix increased the water retention
properties of membrane.23 Hydrocarbon membranes provide some definite advantages over perflourinated membranes, because
they are cheaper, commercially available and their structure permits the introduction of polar sites. In order to enhance stability at
elevated temperatures, aromatic hydrocarbons can be incorporated directly into the backbone of a hydrocarbon polymer or
polymers modified with bulky groups in the backbone to render them suitable for conduction of protons.30 Sulfonated aromatic
hydrocarbon polymer membranes include Sulfonated poly (p-phenylene), Sulfonated poly(ether ketone), Sulfonated polysulfone,
Sulfonated poly (arylene ether sulfone), Sulfonated poly(aryl ether ether nitrile), Sulfonated poly(sulfide ketone), Sulfonated
polyimide.23

6.1.1.(b) Inorganic–organic composite membranes

Addition of inorganic fillers, especially silicate-based nanomaterials, to the polymer membrane is used to partially overcome the
typical Nafion limitations. This is because of the lower cost, easy availability, high hydrophilicity, and higher thermal stability of
the inorganic silicates. Addition of silicates to the polymer membrane has also improved the mechanical, thermal and barrier
properties, along with water uptake of the composite membranes, resulting in superior performance at higher temperature
compared to that of the virgin membrane.22 Composite membranes include Fluorinated polymer/SiO2 composite, Polyalk-
oxysilane/phosphotungstic acid composite, Nafion/PTFE/Zirconium phosphate (Zr(HPO4)2) composite, Nafion/TiO2 composite,
PVA/SiO2/Silicotungstic acid (SiW) composite, Cs2.5H0.5PMO12O40/polybenzimidazole (PBI)/H3PO4 composite, Nafion/SiO2
composite, Sulfonated poly(ether sulfone) (SPES)/boron phosphate (BPO4) composite, Polyoxadiazole/silica composite, and
Linear PEI/SiO2 composite.23

6.1.1.(c) Polymer blend membranes

These membranes have low water uptake, reduced crossover, high proton conductivity, good thermal stability, and high
mechanical flexibility and strength.30 Polymer blend membranes include Nafion/poly(1-vinyl-1,2,4-triazole) blend, Sulfonated
PBIBI/poly(vinylidene fluoride) blend, Poly(benzimidazole)/polyether blend, PPO/poly(styrene-b-vinylbenzylphosphonic acid)
blend, and Sulfonated poly(ether ether ketone)/polysulfone blend.23

6.1.1.(d) Polybenzimidazole (PBI) based acid–base membranes

Acid–base complexes have been considered as a viable alternative for membranes that can maintain high conductivity at elevated
temperatures without suffering from dehydration effects. In general, the acid–base complexes considered for fuel cell membranes
involve incorporation of an acid component into an alkaline polymer base to promote proton conduction.30 From a technological
application point of view, PBI based fuel cells seem most suited for stationary power applications, for example, based on natural
gas reforming and combined heat and power (CHP) generation. For automobile applications more challenges exist by considering
start-up time and thermal/load cycling, however, an auxiliary power unit (APU)-like system is of special interest. No gas humi-
dification is mandatory, which enables the elimination of the complicated humidification system, compared with Nafion cells.
Other operating features of the PBI cell include easy control of air flow rate and cell temperature (in a wider range). The latter,
together with the increased temperature gradient, would potentially simplify the cooling system.30,32 Various synthesis methods
and characteristics of the membrane based on polybenzimidazole (PBI) doped with phosphoric acid (PA) were covered by
Wainright et al. in 1995.28 The first patent was filed by Savinell and Litt, after which numerous patents on PBI membranes and fuel
cells have been issued to Savinell’s group, Hoechst Celanese and Aventis, Honda, Motorola, Danish Power Systems, Plug Power,
14 Fuel Cell Technologies, Applications, and State of the Art. A Reference Guide

among others.32 Nowadays, the phosphoric acid-doped polybenzimidazole (PBI/H3PO4) membrane seems so far the most
successful system for high-temperature PEMFC preferably under-ambient pressure.30
During the past few years, many advances have been made but there are still technical and economic obstacles in the
commercialization of PEMFCs, and many efforts have been made to develop membranes for PEMFC's with improved performance
and durability, while other studies have been done on reducing the cost of fuel cell membranes. Today's research is based on
materials that can accelerate commercialization of fuel cell but, despite the limitations of perfluorinated sulfonated polymers,
Nafion and its close relatives continue to be the electrolyte of choice in demonstration PEMFCs because of their combination of
very high conductivity and adequate mechanical properties.30,33

6.1.2 Catalyst layers

The catalyst layer is either applied to the membrane or to the gas diffusion layer. In either case, the objective is to place the catalyst
particles, platinum or platinum alloys, within close proximity of the membrane. In both the anode and cathode, the catalyst layer
is the location of the half-cell reaction in a PEM fuel cell.27 As a consequence of low-temperature operation, precious metals are
required for electrocatalysts.33 For hydrogen/air fuel cells, Pt nanoparticles supported on carbon are utilized for both the anode
and cathode. Proprietary Pt-based alloys may instead be used in the anode of fuel cells using ‘impure’ hydrogen (hydrogen
obtained by steam reforming of hydrocarbon fuels). Platinum and/or platinum alloys are still the best electrocatalysts and are used
in the state-of-the-art fuel cells.27,32,33 According to Ref. 36, there are three different developing technologies for materials in
electrocatalysts: continuous platinum group metal nanostructures (conventional Pt-based PEMFC cathodes utilize Pt-based
nanoparticles dispersed on a high surface area support), reversible platinum group metal and non-precious catalysts. In parallel
with electrolyte development for low-temperature fuel cells, laboratories worldwide are pursuing advanced electrocatalysts with
the objectives of enhancing reaction kinetics, decreasing Pt loadings, and mitigating the CO poisoning of the anode. The most
effective catalyst remains alloyed Pt–Ru. In particular, methanol is adsorbed onto Pt clusters and then fragmented into dehy-
drogenation products, essentially CO. Electro-oxidation of CO is subsequently catalyzed by oxygen-like species absorbed onto
neighboring Ru sites. In order for this bi-functional catalysis mechanism to be effective, Pt and Ru must be arranged in a specific
configuration on the catalyst surface.35

6.1.3 Electrodes
Electrodes are playing a critical role in the function of fuel cells. Inside the electrodes, transport of gaseous or liquid species, ions,
and electrons must all be facilitated, and at the points where all three meet, the electrocatalysts must reduce the O2 and oxidize the
fuel, at the cathode and anode, respectively.35 The large amount of platinum in original PEM fuel cells is one of the reasons why
fuel cells were excluded from commercialization.37,27 Part of the optimization of an electrode design is the attempt to correctly
distribute the amount of volume in the catalyst layer between the transport media for each of the three phases to reduce transport
losses.27 Thus, the electrodes must be porous, electronically and ionically conducting, electrochemically active, and have high
surface areas. Desirable characteristics of fuel cell electrodes include also chemical and thermomechanical compatibility with the
electrolyte, chemical stability under reducing (anode) or oxidizing (cathode) atmospheres, resistance to poisoning by impurities in
the fuel or oxidant stream, and architectural stability over long periods of operation.35
However, researchers are looking to develop new types of electrodes. In particular, according to Ref. 37, the limited supply and
high cost of the Pt used in PEMFC electrocatalysts necessitate a reduction in the Pt level. We can do that in two different ways:
develop Pt electrodes with low Pt content (through an enhancement of the Pt utilization by increasing the active Pt sites, thinning
the active layer thickness and introducing smaller, carbon supported, nanometer-sized, Pt particles), or with a total or partial
substitution of Pt with other metals, one example in this regard is using Palladium because of the fact that Pt and Pd have very
similar properties (same group of the periodic table, same FCC crystal structure, similar atomic size). Moreover, the cost of
palladium is about three times lower than that of platinum, so it could be a good substitute for Pt as electrode catalyst in fuel cells,
and Pd is at least fifty times abundant on the earth than Pt. Pd-based catalysts can substitute conventional Pt catalysts in PEMFCs
with only a slightly loss in cell performance, particularly at high current densities. In general, electrode designs are differentiated by
the structure and fabrication of the catalyst layer. It is possible to identify two employed electrode main design methods, according
to Ref. 27 including PTFE-bound methods, and thin-film methods.
Before the development of the thin-film catalyst layer, PTFE-bound catalyst layers were the conventional ones. In these catalyst
layers, the catalyst particles were bound by a hydrophobic PTFE structure commonly cast to the diffusion layer. In order to provide
ionic transport to the catalyst site, the PTFE-bound catalyst layers are typically impregnated with Nafion by brushing or spraying.
Nevertheless, researchers have continued to work on developing new strategies for Nafion impregnation. Some of the original low-
platinum loading PEM fuel cells featuring PTFE-bound catalyst layers were fabricated by Ticianelli et al.38 at the Los Alamos
National Laboratory. Thin-film methods are the most common electrode design currently employed, and it is characterized by the
thin Nafion film that binds carbon supported catalyst particles. The thin Nafion layer provides the necessary proton transport in
the catalyst layer. This is a significant improvement over its predecessor, the PTFE-bound catalyst layer, which requires the less
effective impregnation of Nafion.27
 Fuel Cell Technologies, Applications, and State of the Art. A Reference Guide 15

6.1.4 Gas diffusion layers (GDL)

Gas diffusion layers ensure that reactants effectively diffuse to the catalyst layer and transports electrons to and from the catalyst
layer. It also assists in water management by allowing an appropriate amount of water to reach the membrane for hydration.27For
the gas diffusion layer (GDL) component, there are three key approaches being investigated by materials developers; namely,
carbon-fiber paper, cloth materials and non-woven materials.25 However, most commercial PEM fuel cells still employ conven-
tional carbon cloth or paper. In particular, they are constructed from porous carbon paper, or carbon cloth, and they are typically
wet-proofed with a PTFE (Teflon) coating to ensure that the pores of the gas diffusion layer do not become congested with liquid
water.27

6.2 Bipolar Plates (BP)

Bipolar plates (BPs) play a key role in the PEMFC function.39,40 They uniformly distribute fuel gas and air, conduct electrical
current from cell to cell, remove heat from the active area and prevent leakage of gases and coolant.40 Therefore, we can say that
they facilitate water and thermal management through the cell, and provide conduits for reactant gases.41 BPs also significantly
contribute to the volume, weight, and cost of PEM fuel cell stacks. Hence, there are vigorous efforts worldwide to find
suitable materials for BPs.40 According to Ref. 41, the key characteristics of bipolar plates material that are suitable for trans-
portation applications are; high corrosion resistance, interfacial contact resistance, do not dissolve and produce metal ions, possess
steady low Ohmic resistance throughout the operation, high surface tension with water contact angle, light weight, high
mechanical strength, high volume cost-effective manufacturability. According to Refs. 39–41, the materials investigated so far can
be mostly classified as shown in Figure 7 in three groups; non-metal (non-porous graphite/electrographite), metals (precious non-
coated metals, non-coated metals, coated metals) and composites (polymer–carbon and polymer–metal).

6.2.1 Non-metal: Non-porous graphite/electrographite

Currently, graphite composites (both natural as well as synthetic) are considered as a potential material for PEM bipolar plates
because of their low surface contact resistance, their high corrosion resistance and their excellent chemical stability to survive the
fuel cell environment. They also have very low resistivity, resulting in highest electrochemical power output. On the other hand,
graphite has low mechanical strength (brittleness). They are also permeable to gases with poor cost effectiveness for high volume
manufacturing processes relative to metals such as aluminum, stainless steel, nickel, titanium, etc. Since durability and cost
represent the two main challenges hindering the fuel technology from penetrating the energy market and competing with other
energy systems, considerable attention was recently given to metallic bipolar plates for their particular suitability to transportation
applications.41,42

Figure 7 Classification of materials for Bipolar Plates.39

16 Fuel Cell Technologies, Applications, and State of the Art. A Reference Guide

6.2.2 Metals: Precious non-coated metals, non-coated metals, coated metals

Metals are considered potential candidates for BP material since they have got good mechanical stability, good electrical and
thermal conductivity, very wide alloy choices, better durability to shocks and vibration, no permeability, and much superior
manufacturability and cost effectiveness when compared to carbon-based materials, they can be easily stamped to desired shape to
accommodate the flow channels and they have existing pathways for high-volume, high speed mass production. However, they are
not able to resist corrosion in the harsh acidic and humid environment inside the PEM fuel cell without forming oxidants, passive
layers, and metal ions that cause considerable power degradation. The dissolved metal ions may lead to poisoning of PEM
membrane and hence lowering of ionic conductivity.41 Moreover, a corrosion layer on the surface of a BP increases the electrical
resistance and decreases the output of the cell. In the light of these issues, two types of metallic plates have been studied, non-
coated and coated metals with a protective layer. Considerable attempts are being made using noble metals, stainless steel and
various coated materials with nitride- and carbide-based alloys to improve the corrosion resistance of the metals used without
sacrificing surface contact resistance and maintaining cost effectiveness.41,43
Stainless steels (SSs) are the only materials in the non-coated metals category that have received considerable attention due to
their relatively high strength, high chemical stability, low gas permeability, wide range of alloy choice, and applicability to mass
production and low cost.41 SSs have been tested and used as BPs by different researchers, which showed that corrosion rate is low
and PEM cell output is stable for thousands of hours. On one hand, such thin passive film prevents the SS from further corrosion.
On the other hand, it also increases the interfacial contact resistance due to the high electrical resistance of chromium oxide.
Coated metals can be used to avoid corrosion; metallic bipolar plates are coated with protective coating layers. Coating should be
conductive and adhere to the base metal without exposing it. Further the coefficient of thermal expansion of the base metal and the
coating should be as close as possible to eliminate the formation of micro-pores and micro-cracks in coatings due to unequal expansion.
Two types of coatings are being developed, carbon-based and metal-based. Carbon-based coatings include graphite, conductive
polymer, diamond-like carbon, and organic self-assembled monopolymers. Noble metals, metal nitrides, and metal carbides are some
of the metal-based coatings. Nobel metals such as gold and platinum perform very similar to Poco graphite bipolar plates and in some
cases showed more superior performance. However, the high cost of these metals has prohibited their utilization for commercial use.44

6.2.3 Composites: Polymer–carbon and polymer–metal

Polymer composites offer alternative routes to BP materials. Composites are lightweight and can be molded into any shape and
size, which makes them attractive for PEM fuel cells stacks. Composite plates can be categorized in metal-based or carbon-based
composites. A metal-based composite bipolar plate combines porous graphite, polycarbonate plastic and stainless steel in an effort
to leverage the benefits of the different materials. Since the production of porous graphite plates is not as time consuming or
expensive as producing non-porous graphite plates, it can be used while impermeability can be provided by the stainless steel and
polycarbonate components. Stainless steel also provides rigidity to the structure while the graphite resists corrosion. The poly-
carbonate provides chemical resistance and can be molded to any shape to provide for gaskets and manifolding. The layered plate
appears to be a very good alternative from stability and cost standpoints. Composite bipolar plates still have the challenges in
operating at a moderate temperature range due to the material's nature, and in cold-starting of the fuel cell stack.45,39

7 State-of-the-Art of PEMFC Materials

The renewable energy sources are one of the promising concepts to meet the increasing world power demands in the lights of the fossil
fuel depletion. In particular, the fuel cell will play an important role in using this new technology efficiently, while reducing pollution
emissions released to the atmosphere.46 Patents granted in different alternative energy sectors between the years 2002 and 2012 were led
in each single year by the fuel cell industry. 44% of the patents in the fuel cell sector between 2002 and 2012 went to developers from
the United States, followed by Japan, Korea, and Germany; with General Motors, Honda, Toyota, Samsung, and UTC Power securing
more than 60% of these patents. The number of patents granted is a reflection of the level of industrial research taking place in the
different renewable sectors.3 As it has been shown in the previous sections, advantages of fuel cells include high conversion efficiency of
fuel to electrical energy, quiet operation, zero or very low emission, waste heat recoverability, fuel flexibility, durability, and reliability.
Moreover, different combinations of fuels and oxidants are possible for FCs. Hydrogen is an ideal non polluting fuel for FCs, since it has
the highest energy density than other fuels, and its resultant bi- product is just water.47 Consequently, fuel cells seem to promise a good
storage of excessive energy and provide electricity back up. In particular, talking about hydrogen fuel cells, PEMFCs are showing the
most promise at the moment due to its higher efficiency and safer operating temperature of about 80 1C.
The present state-of-the-art PEM fuel cell is based on perfluorosulfonic acid membranes, manufactured and sold in various
thicknesses and equivalent weights by DuPont, Asahi Kasei, Asahi Glass, 3 M and Gore. For operation in the 20–80 1C range, no
alternative membranes are present which offer stack manufacturers a better performance than the perfluorosulfonic acid mem-
branes. For operation in the 80–120 1C range, modifications of the perfluorosulfonic acid membranes are proposed.48 Membranes
with a low equivalent weight, with improved mechanical properties, are in development at Asahi Glass and Asahi Kasei. For
operation in the 120–180 1C range, the only membrane available is H3PO4–PBI. In this temperature range, the proton
 Fuel Cell Technologies, Applications, and State of the Art. A Reference Guide 17

conductivity of the membrane is still relatively low. New research is in progress to develop hydrocarbon membranes to replace the
current perfluorinated membranes.47 Different materials such as carbon nanotubes (CNTs) have been synthesized and studied to
improve fuel cell performance. The utilization of CNTs properties on Pt catalyst and Nafion membrane was found very promising.
Thermomechanical properties and methanol permeability of Nafion membranes were greatly improved by incorporation of CNTs.
CNTs-containing Nafion composite membranes were fabricated using a melt-mixing-compression-molding process. The Nafion
composite membrane containing 1 wt% of CNTs shows dramatic improvement in thermomechanical stability compared to the
pure Nafion. The proton conductivity decreases with the incorporation of CNTs.46
In terms of the electro-catalysts, although platinum is still the main constituent for both the anode and the cathode catalysts,
alloying can lead to higher performance.46,41 At the anode, Pt–Ru is the optimum choice for operation on reformate. At the
cathode, Pt–Co can lead to lower noble metal loading and improved stability.41 For cost reduction and ease of high-volume
manufacturing of the GDL they must be available as a rolling goods material. To contribute in the achievement of this objective,
Ballard Materials Products have developed and commercialized a continuous carbon-fiber based gas diffusion material for use by
all PEMFC manufacturers.25 Bipolar plates made of graphite composites can be mass-manufactured by either injection molding or
compression molding, leading to substantial cost reduction of the bipolar plates. For applications where size and weight are more
important than endurance, metal plates and expanded foil are an attractive option. If strength is an additional criterion, only metal
plates are a viable possibility. A number of the currently used graphite composite-based bipolar plate materials are expected to be
suitable for operation above 120 1C. In any case, H3PO4–PBI is most likely incompatible with metal-based bipolar plates.41
However, even if this technology is close to being competitive, it is not ready for large scale industrial deployment: FC still must be
optimized, particularly by increasing their limited lifespan.48

8 Conclusions

In this article all the aspects relative to the fuel cell technologies and their applications has been made. From the result, it is
possible to notice that PEMFC have the largest range of applications possible among all the different types that have been studied.
In particular, they are the most promising technology in the field of Light-Duty vehicles, because of their different advantages, such
as the lightweight, the low temperature and the high power density. Today, the most used materials for PEMFC components are
Nafion membranes for the electrolyte for Low-Temperature PEMFC and H3PO4–PBI membranes for High-Temperature PEMFC,
while for the electrocatalysts Platinum and Platinum alloys are still the most preferred, even if they are still too expensive for the
market. For the Bipolar Plates, graphite is the most common material, even if there are other materials developed that can be used
in particular conditions, while for the GDL the choice is for porous carbon cloth, or carbon paper, wet-proofed with a PTFE
(Teflon) coating. A list of the most common materials is provided in Table 9.

Table 9 Main PEMFC components and their materials

Component Functions Most used materials Other materials developed

Proton exchange Charge carrier for protons Nafion Sulfonated aromatic hydrocarbon polymer
membrane (PEM) membranes
Separate the reactant gases PBI Inorganic–organic composite membranes
Electronic insulator Polymer blend membranes
Polybenzimidazole (PBI) based acid–base
membranes

Electrodes and catalyst Location of the half-cell Platinum Pt electrodes with lower Pt content
layers reactions Platinum alloys Total/partial substitution of Pt with other
metals

Gas diffusion layers Ensures that reactants Porous carbon Continuous carbon-fiber based gas
effectively diffuse to the diffusion materials
catalyst layer
Electrical conductorfor electrons Paper or carbon cloth
to/from the catalyst layer
Teflon coating

Bipolar plates Conduct current between cells Graphite Non-metals: non-porous graphite/
electrographite
Facilitate water and thermal Metals: precious non-coated metals, non-
management through the cell coated metals, coated metals
Provide conduits for reactants Composites: polymer–carbon and
polymer–metal
18 Fuel Cell Technologies, Applications, and State of the Art. A Reference Guide

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