Fuel Cells: Opportunities and Challenges: Stefano Campanari, Giulio Guandalini

C H A P T E R
18
Fuel cells: opportunities and challenges
Stefano Campanari*, Giulio Guandalini
Department of Energy, Politecnico di Milano, Milan, Italy
* Corresponding author. e-mail address: [email protected]
1. Introduction 2. Fundamentals
In recent years, the technology of fuel cells In the following sections, the fundamental
(FCs), whose origins date back to over a cen- operating principles of FCs are briefly presented,
tury ago, has undergone considerable devel- evidencing the differences with respect to tradi-
opment. Numerous prototypes and significant tional thermodynamic cycles and to other elec-
large-scale demonstrations have been devel- trochemical devices. The various types of FC
oped and tested, also in the industrial envi- are then presented, classified by electrolyte ma-
ronment, based on strong research efforts in terials, operating temperatures, and main appli-
new materials, geometries, cell types, and ap- cation fields.
plications. Target applications of FCs include
the transport sector (with FC vehicles for in-
creasingly large fleets of cars, buses, trucks,
2.1 Operating principles
as well as applications for marine propulsion) With respect to traditional machines, the fun-
and the electrical energy generation, parti- damental processes exploited by FCs to convert
cularly of the distributed type (with FC plants in electricity the energy content of chemical com-
spanning from microcogeneration of power pounds are completely different. Specifically, the
and heat to multi-MW electricity generation). conversion process accomplished in FCs is based
Moreover, new applications and opportunities on electrochemical reactions that are similar, but
are envisaged, ranging from industrial utiliza- not identical, to those taking place in ordinary
tion of by-product fuels to the use for CO2 cap- storage batteries. The FC converts chemical en-
ture processes, to the power-to-power energy ergy directly into electrical energy, through elec-
storage concepts. This chapter presents an over- trochemical reactions that can be ideally isobaric
view of FC fundamentals and types, discussing and isothermal. The conversion does not involve
the main research and development challenges, combustion and does not rely on the conversion
followed by some examples of new and existing of chemical energy into heat, nor on the subse-
applications. quent heat-to-mechanical work transformation,
Catalysis, Green Chemistry and Sustainable Energy

https://doi.org/10.1016/B978-0-444-64337-7.00018-5 335 Copyright © 2020 Elsevier B.V. All rights reserved.
336 18. Fuel cells: opportunities and challenges
FIGURE 18.1 Energy conversion steps in a conventional machine (thermodynamic conversion) and in a fuel cell (electro-
chemical conversion).
which is instead typical of conventional ma- losses, mechanical losses, etc.), but in FCs, such
chines (Fig. 18.1). Oppositely, the FC electro- losses are reduced thanks to the simplicity of
chemical process relies on a direct extraction of the involved processes. All told, the result is
electricity from the oxidation of a fuel. that the electrical efficiency demonstrated in
The main advantage of this process is the high small to medium size FC plants, approaches,
efficiency that it can reach: the transformation and in some cases even exceeds, that of the
implies energy losses that are generally lower largest, most efficient traditional thermal (or
for the direct electrochemical conversion with combustion-based) power stations.
respect to the conventional thermodynamic In addition to holding a potential efficiency
pathway, based on more complex transforma- advantage, a second positive and intrinsic fea-
tions. Indeed, while the Second Law of Ther- ture of FC plants is to avoid the necessity to carry
modynamics limits the maximum efficiency in a out a combustion process: this allows one to
heat-to-work transformation, even for ideal ther- avoid the consequent production of pollutants
modynamic cycles (e.g., the Carnot cycle), FCs that are typical of combustion (such as nitrogen
do not feature such transformation and are sub- oxides, unburnt hydrocarbons, carbon monox-
jected only to the general a priori limit imposed ide, particulate matter, sulfur oxides, or others,
by the laws of thermodynamics on the overall depending on the fuel type and the combustion
conversion of chemical to electrical energy, process).
which in case of ideal processes is represented For a detailed description of specific FC types,
by the maximum or reversible work1 associated see the next section. Here, let it suffice to recall
with the fuel utilized. When moving from ideal that in a typical FC, the anode side of the device
to real processes, additional losses appear, as (the negative electrode, where oxidation of the
typical of any energy conversion system (e.g., fuel takes place, with the production of elec-
losses through heat exchange across finite tem- trons) is fed with the fuel, while the oxidiz-
perature gradients, irreversible thermo-fluid- ing gas (e.g., air) is supplied to the cathode (the
dynamic transformations including pressure positive electrode, where the electrons reduce
1
The maximum or reversible work, later defined Wrev, is a quantity corresponding also to the fuel exergy, once it is
neglected the fraction of ideal work which is theoretically recoverable through the difference in chemical composition
of the exhaust gases and ambient air.
IV. Selected examples and case history

2. Fundamentals 337
oxygen). Electrons flow in an external circuit energy; that is, the full consumption of the chem-
connected between the anode and the cathode, ical reactants makes them “go dead.” In the case
providing an electric current and power to an of rechargeable storage batteries, the reactants
external load. The chemical reaction takes place can be regenerated periodically by recharging,
inside the cell, giving rise to the electron flow, an operation that is accomplished at the ex-
via the exchange of ions through the electrolyte, pense of an external electricity source; and thus,
thus closing the circuit between the two elec- although the process can be repeated, it is dis-
trodes. Fuel is provided continuously at the continuous. Instead, the FC is a stable system
anode, generally in gaseous phase, and is typi- of energy conversion that can, at least in theory,
cally rich in hydrogen; while air (or pure oxygen, produce electrical energy for as long as the elec-
where available) can be fed at the cathode. An trodes are replenished with fuel and an oxidizing
example of reaction (see the next section for agent. The operating lifetime of the FC is limited
other types) is presented in Fig. 18.2. only by the progressive degradation (or mal-
Electrochemical reactions like those repre- function) of its constituent components. At any
sented in Figs. 18.1 and 18.2 are also featured rate, this degradation is typical of all electro-
by batteries. However, a FC differs from a typ- chemical systems, including batteries, which are
ical battery in a number of ways. First of all, well known to reduce their voltage output dur-
the latter is a system intended to accumulate en- ing their lifetime.
ergy, and the total amount of chemical reactants FCs are fabricated through the deposition of
in the electrode/electrolyte assembly defines the thin film layers containing the basic components
maximum storable energy. For this reason, all of the cell (anode, electrolyte, and cathode). Indi-
batteries eventually stop producing electrical vidual cells may then be stacked one on the other
FIGURE 18.2 Example of schematic operation of a fuel cell, evidencing the flow path of reactants, products, and ions
exchanged through the electrolyte.

FIGURE 18.3 Expanded view of a planar

fuel cell, where the core component layers
(anode-electrolyte-cathode) are piled in a stack.
to form a “pile” (see Fig. 18.3) separated by inter- like natural gas) which is converted locally
connecting layers, the latter traversed by chan- into a gas with high hydrogen content. In this
nels guiding the gases flowing on the two sides second case, the system includes a fuel
of the cell (fuel and oxidizer or comburent). processing and treatment system, which, on
The interconnecting layers are also labeled bipo- the one hand, converts the fuel into a H2-rich
lar plates, since they connect a positive and a gas (generally through reactions termed
negative pole (being in contact with the two elec- “reforming”) and, on the other, removes
trodes of two subsequent cells). The reactants are impurities or potentially damaging elements
distributed to the “pile” of cellsdcalled an FC to within acceptable concentrations for use in
stackethrough external gas manifolds, adopting the cell. The treatment system depends on the
a parallel flow or crossflow arrangement for the type of FC; the constituent materials of the
fuel and oxidizer along the cell (Fig. 18.3 shows a electrodes can bind with some substances, for
crossflow configuration). The stack is then closed example, sulfur compounds, leading to
by endplates, ensuring a compression of the pile contamination and performance
(necessary to keep a stable and complete contact degradations, at times even irreversible ones.
between the cells) through tension rods [1]. • FC power density (output per unit surface
In the light also of the foregoing considera- area) is generally limited to 0.1e1.5 W/cm2
tions, some of the most important features of a (referred to cell active area), with higher
FC are summed up in the following: values for the polymeric membrane FC used
in mobility applications. High-power plants
• The main fuel used in FCs is gaseous
(on the order of MWs) therefore require
hydrogen. Hydrogen can be produced
significant cell and stack active areas,
elsewhere (e.g., from renewables with
bringing about large sizes and footprint.
electrolysis), or the system may be fed with a
• The electrical energy produced is direct
different fuel (e.g., a hydrocarbon-based fuel
current (DC). Thus, in general, the connection

2. Fundamentals 339
to a power distribution grid requires a power 2.2 Classification
conditioner, that is, an inverter system for
converting DC to alternating current (AC). The most widely used classification of FC
This involves power losses, as the efficiency takes into account the type of electrolyte used:
of such conversion is never perfect (at most the properties of the electrolyte, in fact, deter-
95%e97%). mine the most important characteristics of the
• Efficiency tends to be higher at partial loads, cell, such as the species involved in the electro-
due to internal loss reduction at low currents: chemical reactions, the operating temperatures,
in practical applications, it turns out that the the effects of potential contaminations due to im-
efficiency remains nearly constant from 30% purities, or the compatibility with specific gases.
to 100% of the nominal load, with a slight In principle, electrolytes can be defined as ion
peak at intermediate loads. This behavior is conductors, in contradistinction to both electron
quite different from the one of conventional conductors, such as metals (for example, Fe,
machines (e.g., gas turbines, reciprocating Cu) and semiconductors, as well as mixed con-
engines), which typically suffer a significant ductors. Electrolytes for FCs come in various
performance drop at partial load. forms: (A) liquids at nearly ambient tempera-
• They can adjust rapidly to load variations. ture; (B) electrolyte solutions (substances ioni-
• They produce heat useable for cogeneration cally dissociated in a solvent); (C) polymeric
or, in the case of higher-temperature models, membranes, usually operated with high humid-
in thermodynamic cycles for the further ification and presence of liquid water; (D) molten
production of electrical energy. salts, either pure or in mixtures (Li, Ca, Na, K
• Their operation involves no combustion, so chlorides, and carbonates); and (E) solid oxides
within the cells the production of combustion- (e.g., zirconium oxides, ZrO2) and proton-
related pollutants like nitrogen oxides is nil. conducting ceramics, in which the features of
The sulfur compounds production is also the lattice structure influence both the trans-
virtually zero because of the adoption of fuel ported ion (O¼ -, H þ ) and the temperature range
sulfur removal systems upstream of the FC. in which conduction is active, according to the
• Their operation involves no moving parts and motion capability of the involved ions (e.g., be-
is therefore noise- and vibration-free. cause of doping and vacancies or induced local
• FC construction is modular. Consequently, defects in the lattice). Most ionic electrolytes
the successive addition of single small power- have a nil or negligible electronic conductivity,
output units allows reaching increasingly while some materials belong to the so-called
large plant size (single cell power-output mixed ionic-electronic conduction (MIEC) family
varies from a few hundred W to a kW or so). and feature a significant ionic and electronic
The efficiency of FC plants is therefore largely conductivity (such as cerium oxides, particularly
independent of size, except for the scaling promising for low-temperature solid oxide FCs).
effects on all auxiliary components The conductivity of all the aforementioned
(compressors and pumps of the feed and ionic conductors increases with temperature,
coolant circuits, electrical components). thanks to the greater ion mobility; this behavior
• FC systems can be highly efficient in is opposite to the decrease of conductivity
converting the fuel chemical energy into versus temperature typically found in electron
electricity (with typical efficiencies in the conductors such as metals, which are constitu-
range 40%e60% or more), largely ents of the electrodes. At any rate, the electro-
independently of cell size and, as stated lyte holds a predominant role in determining
above, of load as well. the overall resistive losses of the cell. Moreover,

the electrolyte delimits the operating tempera- 2.3 Theoretical background

ture range of the FC, and this, in turn, deter-
mines the types of chemical reactions that can The following section provides a brief de-
take place, as well as their kinetics and equi- scription of FC operating principles from a theo-
libria. One consequence of this, for example, is retical viewpoint. The thermodynamic equations
that in low-temperature cells, some reactions used can, for the most part, be extended to all
can only develop efficiently and quickly with types of FCs, with some adaptations depending
the aid of expensive catalysts (e.g., Pt-based on the specific reactions they exploit.
metals), while at higher temperatures, less no- First, the FC principles can be discussed
ble materials (for example, nickel) may suffice by assuming cell operations to be reversible
as catalysts, or a catalyst may not be required (ideal conditions). The maximum or reversible
at all because the reactions occur spontaneously. work obtainable in an ideal FC, in the hypothe-
Moreover, at low temperatures the presence in sis of working at constant temperature and
the fuel gas or in the air of some chemical com- pressure,2 is given by the change in Gibbs free en-
pounds, such as CO and CO2, can damage the ergy for the electrochemical reaction featured by
cells due to binding and degradation of the cata- the cell [2]:
lyst, ruining its activity, or due to binding with Wrev ¼ DG ¼ nFErev ½J = molfuel (18.1)
the electrolyte, impeding its function. Therefore,
CO can in general only be introduced without where n is the number of electrons taking part in
complications into high-temperature cells, where the reaction (n ¼ 2 for hydrogen oxidation), F is
it can be efficiently consumed, whereas it repre- Faraday’s constant (96,485 C/mol of electrons),
sents a contaminant for the low-temperature and Erev is the reversible potential of the cell
FCs. Likewise, the presence of CO2 may be prob- (here assumed to be positive in sign).
lematic in some cases, necessary in others, or The relation between DG of any reaction and
completely indifferent. the respective enthalpy and entropy change is
As the dominant reaction in FCs is H2 oxida- DGr ¼ DHr-TDSr, where, as mentioned, DGr is
tion, that is a combination of hydrogen and oxy- the maximum extractable work; the term TDSr
gen atoms, the electrolyte will have to transport is generally positive and, for a FC working under
ionic species either containing hydrogen or reversible conditions, represents the minimum
oxygen atoms. Thus, depending upon their heat produced and released to the environment
type, FCs work either by transporting oxygen- or to other processes.
containing ions from the air side (cathode) to For any given reaction of the form aA þ bB/
the fuel side (anode) or oppositely transporting cC þ dD (where aed are the stoichiometric coef-
hydrogen-containing ions from the fuel side to ficients and AeD the chemical species), the
the air side. change in Gibbs free energy (negative in sign)
Table 18.1 shows the main types of FCs can also be expressed by the equation:
together with their basic features (electrolyte,
½Cc ½Dd
transported ion, and operating temperature DG ¼ DG0 þ RT ln ½J = molfuel (18.2)
range). ½Aa ½Bb
2
Actual temperature variations in real cells, due to heat release from the reactions and due to internal losses, are
generally not negligible; however they are rather small in relative terms compared to the absolute temperature level.
Pressure losses are typically low.

2. Fundamentals 341
TABLE 18.1 Classification of the main types of fuel cells.
Transported Operating
Acronym Electrolyte ion temperature Main application domains
AFC Alkaline KOH solution (liquid) OH 70e120 C Aerospace, stationary power
PEM Polymer membrane H þ
80e120 C Transport, stationary power,
(solid, humidified) and cogeneration
PAFC Phosphoric acid H3PO4 (liquid) Hþ 200 C Stationary power and cogeneration
MCFC Molten Li, K, or Na carbonates (liquid) CO¼
3 600e700 C Stationary power and cogeneration
SOFC Metal oxide (solid) O ¼
500e1000 C Stationary power and cogeneration
where the square brackets indicate the activities the cell can be written as P]VI, and it is also pro-
of the chemical species involved. In the most portional to the voltage. Thus, the voltage of a
frequent cases the reactants are a mixture of FC is the parameter of merit most commonly
gases, schematized as ideal gases, and the activ- used to quantify performance.
ity coincides with the molar concentration, or In the case of hydrogen, the oxidation reaction
equivalently, with the gases normalized paris H2þ 1/2 O2 / H2O, and the standard refer-
tial pressures (i.e., the ratio ppart/pref with ence potential is E0 ¼ 1.229 V at 25 C (with the
pref ¼ 1 bar, maintaining the argument of the log- production of liquid water) or E0 ¼ 1.18 V when
arithm dimensionless). water is produced in the gaseous state. The dif-
Substituting in the relation between DG and ference between the two potentials is due to
E yields the Nernst equation: the contribution of the heat of evaporation.
ni As the temperature changes, the value of E0
RT P ppart: reactants varies as does Erev (since variations in the loga-
0
Erev ¼ E þ ln ½V (18.3)
nF P ppart: products ni rithmic term have less influence on the total
potential). Such variations depend on the type
expressing the cell reversible voltage, where E0
of reactions at play. For the reactions typical of
(from DG0) is a temperature-dependent reference
FCs, the result is plotted in Fig. 18.4, where it
potential (typically referred to standard condi-
tions, 25 C and 1 bar), and ni indicates the stoi-
chiometric reaction coefficients.
The electrical efficiency of an FC under ideal
conditions can be then expressed by comparing
the electric output with the energy input in terms
of the fuel’s lower heating value (LHV):
Wel;rev Wel;rev =nF Erev
hel ¼ ¼ ¼ ½ (18.4)
LHV LHV=nF ELHV
and is therefore proportional to the cell voltage.
The term ELHV is simply the electrical equivalent
of the fuel’s heating value. FCs produce elec-
trical energy as DC. For a given reactant flow FIGURE 18.4 Reversible potential of different oxidation
and fixed cell current, the power produced by reactions as a function of temperature.

can be seen that the reversible oxidation po- Let us now consider real operating condi-
tentials for H2 and CO decreases substantially tions, which are characterized by irreversibility.
with temperature, while that of CH4 remains The aforementioned ideal (reversible) theory
nearly constant. This means that in terms of ideal would be applicable only at “idle” conditions: a
performance, high-temperature cells are at a dis- FC featuring sufficiently high reaction rates on
advantage in comparison to low-temperature appropriate catalytic surfaces, preventing the
ones. Referring to the types in Table 18.1, the interference of any competing electrochemical
theoretical advantage is nearly 0.15e0.2 V for a process will, in an open, idle circuit, yield the
polymer electrolyte membrane (PEM) or a phos- reversible voltage Erev deduced before [2]. How-
phoric acid fuel cell (PAFC) with respect to a ever, under conditions of nonzero output cur-
molten carbonate fuel cell (MCFC) or a solid ox- rent, losses of various types occur, where the
ide fuel cell (SOFC). However, as will be seen in most important are ohmic, diffusion, and kinetic.
the following paragraphs, due to a series of los- Under such conditions the real (measurable)
ses, true cell voltages will be less than the revers- values of the cell voltage will be always lower
ible potential, and so in practice, such differences than the reversible one; at the same time, the cor-
will be substantially reduced or altered. responding part of the Gibbs free energy that is
The Nernst equation allows one to evaluate not converted to electricity is irreversibly con-
the effect of varying the reactant composition verted into additional heat.
on the theoretical cell voltage: using a richer The main losses, stemming from polarizations
oxidant or fuel (e.g., pure oxygen instead of air, of different types, include these:
or prehydrogen instead of diluted hydrogen)
• Ohmic polarization: Ohmic losses are caused
allows achieving higher cell voltages. The same
by the resistance to both electron flow in the
positive effect occurs when operating the FC
materials of the electrodes and ion flow
under pressure, thanks to the increase of partial
through the electrolyte, the latter being
pressures of the reactants: if we consider hy-
typically the dominant effect, yielding a
drogen oxidation, the Nernst equation becomes
voltage decay (DVohm) that is proportional to
the following:
the current flow.
• Concentration polarization: Local
RT ðpH2 Þ ðpO2 Þ1=2
Erev ¼ E0 þ ln ½V (18.5) consumption of the reactants by the
2F ðpH2O Þ electrochemical reactions occurring in the cell
active sites establishes concentration
with an overall positive effect of pressure thanks
gradients with respect to the bulk flow
to the logarithmic term.
conditions, reducing the local concentrations
The composition of the reactants in an FC
of reactants and decreasing the cell potential
changes along the reactant flow path from inlet
(DVconc).
to outlet, as they are subject to the electrochemi-
• Activation polarization: Electrochemical
cal reactions. This involves a drop in the cell po-
reactions begin to take place when the
tential: the cell voltage is levelized at the lowest
reactants overcome an activation barrier
potential, allowed by the local Nernst potential
(DVact), analogous to that occurring for
for the gas composition at different points within
chemical reactions.
the anodic and cathodic compartments. In fact,
electrodes are generally good electron conduc- The overall effect of such polarizations, there-
tors and represent iso-potential surfaces, so the fore, is to reduce the cell voltage (or the efficiency
cell potential is uniform and cannot exceed the of the FC) by a degree that increases with increas-
minimum local Nernst potential. ing current, as shown in Fig. 18.5. Oppositely,

2. Fundamentals 343
FIGURE 18.5 Fuel cell polarization curve
(or voltage-current, VeI curve).
the voltage increases at partial load and so does reforming, the cell utilization factor becomes
the efficiency: the situation is inverse to the this:
typical behavior of traditional fuel-to-electricity nH2;consumed
conversion machines, yielding an advantage for Uf ¼ ½ (18.7)
nH2;in þ nCOin þ 4 nCH4;in
systems operating frequently at variable loads,
that is, at currents below full capacity. where each molecule of methane entering the
FCs are not generally designed to utilize all cell, according to the steam methane reforming
of the reactants input to the electrodes in a single process,4 yields three molecules of hydrogen,
passage for the electrochemical reactions. The plus one of CO, which is in turn converted to
actual fraction utilized out of the total reactants H2 via the wateregas shift reaction. Operating
input is usually below 1, because of the pre- at a fuel utilization rate below unity (Uf < 1)
viously described risk of incurring high po- does not allow for attaining the theoretical
larization losses and scarcity of reactants at maximum work even in ideal reversible condi-
the cell active sites.3 Thus, a utilization factor, tions since only part of the fuel is converted
Uf, must be defined for the fuel: for low- into oxidized reaction products, nor is it feasible
temperature cells, hydrogen, H2, is the only to force fuel conversions of over 90%e95%,
fuel, so we have this: without incurring in too high losses due to the
nH2;in nH2;out nH2;consumed low concentration of the reactants.
Uf ¼ ¼ ½ (18.6) Thus, by accounting for the fuel utilization
nH2;in nH2;in
factor, overall, the true efficiency of a FC is as
One of the advantages of high-temperature follows:
cells (MCFCs and SOFCs) is the ability to also
use CH4 and CO as fuels, via internal reform- Vcell Uf
hreal;DC ¼ ½ (18.8)
ing and shift reactions. Accounting for internal ELHV
3
An exception is the case of FCs which are fed with high purity reactants, e.g., pure hydrogen at the anode of a PEM
fuel cell, where ‘dead-end’ configurations with nearly 100% utilization are also possible.
4
steam reforming can occur effectively in presence of abundant steam (e.g., steam-to-carbon ratio above 2.5e3),
appropriate catalysts (e.g., Nickel) and sufficiently high temperatures (e.g., above 600e700 C).

which refers to the electrical energy produced 3. Fuel cell types

with a DC output at the FC electrode terminals.
In a way wholly analogous to the fuel utiliza- As already introduced, FCs are generally
tion factor, it is also possible to define an air uti- classified based on their electrolyte type (see
lization factor (or an utilization factor for the Table 18.1). The electrolyte influences the cell
oxidant stream, whatever oxidizer is used): operating conditions and the corresponding
nO2;in nO2;out nO2;consumed typical reactions, which are listed in Table 18.2;
Ua ¼ ¼ ½ (18.9) it is considered a possibility to oxidize hydrogen
nO2;in nO2;in
(the most common fuel for FCs), but also carbon
which is proportional to the quantity of oxygen monoxide or methane, e.g., from syngas fuels or
extracted from the air to oxidize the fuel; in gen- natural gas, which may be utilized as fuels by
eral, this is kept at values well below 1 (for high-temperature FCs (MCFC, SOFC).
example, 0.2e0.5) to prevent significant losses In the following section, we briefly summa-
from arising as well as to ensure a large cooling rize the main types of FCs and their technologic
capacity from the air flow. It must be remem- features.
bered that all chemical energy in the utilized
fuel that is not converted into electricity is
released within the FC in the form of heat, which 3.1 Polymer electrolyte membrane
would yield an increase of the cell temperature, fuel cells
unless a cooling media is present; for this pur- In this type of FC the electrolyte is made up
pose, in most FCs, air acts not only as an oxidizer of a humidified polymer membrane, which acts
but also as a coolant. as conductor of Hþ ions or protons. Such a cell
Lastly, as already mentioned, a FC module pro- design has been variously designated as either
duces DC output, which, for most applications, solid polymer FC, PEM, or proton exchange
has to be transformed into AC (similarly to what membrane fuel cell (PEMFC) or also polymer
happens for photovoltaic cells) through inverter electrolyte fuel cell/proton exchange fuel cell
devices in a power conditioner. In conclusion, (PEFC).
the overall efficiency of a FC for the production When PEM-type cells are fed with hydrogen,
of AC electrical energy is given by the equation: their net electrical efficiency can exceed 50% and
Vcell Uf approach 60%. Future distributed generation ap-
hreal;AC ¼ hDC=AC ½ (18.10) plications may someday be able to exploit such
ELHV
high efficiencies, if hydrogen comes to be distrib-
uted in capillary networks on a wide scale, as is
TABLE 18.2 Fuel cell reactions. For the case of DMFC, (g) and (L) indicate gas or liquid state, respectively.
Fuel cell Transported ion Anode reaction Cathode reaction

AFC OH
H2 þ 2ðOHÞ /2H2 O þ 2e
1=2 O2 þ H2 O þ 2e /2ðOHÞ
PEM, PAFC Hþ H2 / 2Hþ þ 2e 1=2 O2 þ 2H þ þ 2e /H2 O
DMFC Hþ CH3OH(l) þ H2O(l) / CO2(g) þ 6Hþ(g)þ6e 6Hþ(g)þ6e- þ 3/2O2(g)
/ 3H2O(l)
MCFC CO¼
3 H2 þ CO¼ ¼
3 / H2 O þ CO2 þ 2e CO þ CO3 / 2CO2 þ 2e

1=2 O2 þ CO2 þ 2e /CO¼
3
SOFC O¼ H2 þ O¼ / H2 O þ 2e CO þ O¼ / CO2 þ 2e CH4 1=2 O2 þ 2e /O¼

þ 4O¼ / 2H2 O þ CO2 þ 8e

3. Fuel cell types 345
natural gas today. Direct use of hydrogen R&D activities are pursuing the development
is nowadays related to mobility applications (e.g., of electrolyte membranes allowing a higher tem-
FC vehicles with onboard hydrogen storage [3,4]) perature operation (e.g., up to 120 C, where the
or specific industrial uses (e.g., coupling with the catalysts tolerance to impurities is improved), as
availability of excess hydrogen from industrial well as the extension of cell lifetime and reduction
processes [5]), as well as considered within the of catalysts cost (reducing the required quantity
power-to-hydrogen-to-power concept [6,7]. or developing alternative catalytic materials, as
In the context of PEM use in stationary appli- well as recycling efficiently the most precious
cations, primarily for combined heat and power Pt-based catalytic materials at cell end of life).
(CHP) at medium-to-small scales, different man- A further variant of the PEM is the HT-PEM
ufacturers offer modules with power outputs (operating at 120 Ce200 C), using polybenzimi-
varying from just a few kW to hundreds of dazole (PBI)-doped polymeric membranes with
kW, which can be run on natural gas and include phosphoric acid (PBI/H3PO4) as electrolyte,
reforming and gas conditioning (with sulfur yielding an efficient proton conductivity. The con-
clean-up) systems. Such systems attain electrical duction mechanism is similar to the case of PAFC
efficiencies varying from 30% to 40% when (see in the following). The HT-PEM is able to over-
including a natural gas reformer, depending on come some of the issues affecting PEM: in partic-
size, with total efficiencies (electricity þ heat) ular, systems are able to operate without
near 80% for the first commercial plants [8]. humidification and work with lower Pt catalyst
For CHP applications, PEM units are generally loading, tolerating more impure fuel streams (at
linked to a supplementary, standby boiler to operating temperatures above 150 C, the affinity
satisfy peaks in thermal load. of Pt for CO is reduced and CO tolerance rises
PEM FCs are able to operate at very high up to 1%e3%), while the higher temperature
current density (e.g., up to above 1e2 A/m2), waste heat can be more easily utilized for other
enabling the construction of very compact and processes (e.g., CHP). The main drawback with
lightweight stacks; in addition, the low oper- respect to conventional PEM FC is the operation
ating temperatures of PEM FCs allow fast with much lower current densities and, conse-
startup times and transients. Both such features quently, lower power density (making them less
make PEMs particularly suitable for transport attractive for mobile uses), in addition to more se-
applications, where they nowadays find increas- vere issues with durability and degradation.
ingly wide use (ranging from the application in
cars and light vehicles to the use in heavy trans-
port vehicles, materials handling vehicles, trains,
3.2 Direct methanol fuel cells
and ships). On the other hand, the fuel used in This type of FC, DMFC, is derived from the
PEM FCs must be rich in hydrogen and nearly PEM technology, from which it takes several
free from contaminants like carbon monoxide components including the electrolyte based on
(otherwise poisoning the most used platinum- polymeric membranes. The main advantage of
based catalysts) or impurities like metallic ions, DMFC is the direct feeding of a liquid fuel, which
while the oxidizer can be air. If the fuel is gen- is methanol, allowing a great simplification of
erated through hydrocarbons reforming, most the fuel processing ahead of the FC. The typical
difficulties arise from the necessity to keep the cell reaction requires feeding at the anode a
CO concentration well below 10 ppm (while a 50% molar mixture of methanol and water (so
reformed syngas may have 1% CO or more), us- that methanol is 64% by mass). The main draw-
ing additional chemical reactors in a dedicated backs of DMFCs are the slow reaction kinetics
fuel processing section. (requiring high catalysts loading) and the

tendency of the electrolyte to allow a significant TABLE 18.3 Fuel cell energy balance for medium size
cross-over of methanol (bringing about loss of PAFC modules (400 kWe) fueled by
fuel and reduction of cell lifetime), so the electri- natural gas, with reference to the fuel
inlet chemical energy (LHV basis).
cal efficiency is rather low (e.g., 20%e25%). Main
applications that are currently envisaged are for Energy balance (% of fuel inlet)
portable units used for recharging electronic de-
Electrical energy (net) 43
vices (typically in the 1e50 W scale) or UPS sys-
tems with limited power (1e5 kW). Recovered heat 47
DC/AC losses 2.5
3.3 Phosphoric acid fuel cells Auxiliary consumptions 3.5
This type of FC, PAFC, has been under devel- Waste heat and heat losses 7
opment since the 1960s and has reached a certain
degree of technologic maturity. The electrolyte the market penetration of this type of FC has
employed is a highly concentrated solution of been slow, due to competition with conventional
phosphoric acid (H3PO4), which acts as ion CHP technologies (e.g., internal combustion en-
conductor for the Hþ formed from spontaneous gines); on the other hand, R&D suggests that
dissociation of the acid, while maintaining suffi- further costs reductions are forthcoming with
cient thermal stability at operating temperatures PEM, while greater efficiencies can be achieved
of 150e220 C. with the higher temperature technologies of
A significant number of PAFC plants (nearly MCFC and SOFC.
400 units) have been installed worldwide, each
with a capacity on the order of 100e400 kW.
Moreover, several demonstration plants are
functioning at MW levels. PAFCs manufacturers
3.4 Molten carbonate fuel cells
are currently marketing only units running on MCFCs usually adopt a high-temperature
natural gas with a steam-reforming-based fuel mixture of alkaline carbonate (Li, Na, K) as the
processor, with power outputs of 400 kW or electrolyte, which is contained in a ceramic ma-
above, to obtain the best compromise between trix of lithium aluminate (LiAlO2). The cell oper-
economy, in terms of specific plant cost, and effi- ates at 600e700 C, at which temperatures the
ciency. The achievable electrical efficiency rea- carbonate forms a very conductive molten salt,
ches up to 45% (depending on size and the with the carbonate ions, CO2e 3 , acting as ion
possible pressurization, adopted in few cases) conductor. One advantage of MCFCs is that at
with utilization factors of 85% for the fuel and such high temperatures, expensive noble metals,
50%e70% for air. Availability (w95%) and use- such as the platinum used in other FCs, are not
ful lifetime (up to over 40,000 h) have reached needed as electro-catalysts, as the reaction ki-
satisfactory levels. As shown in Table 18.3, a netics is favored by the high temperatures.
typical 400-kW PAFC module (Doosan Purecell Thus, the anode is made of a 10% Ni or Cr
model 400 [9]) can produce electrical energy alloy or NieAl alloys, where nickel sufficiently
with a 43% efficiency and, additionally, steam promotes the electrochemical reactions,
at 120e140 C for cogeneration, thereby yielding while the cathode is made from a Ni and Li ox-
an overall efficiency of up to 85%e90%. ide. The electrode layers are about 1 mm thick.
Emissions of this CHP unit are remarkably low On the other hand, the high-temperature molten
(e.g., below 9 g/MWh for NOx and 5 g/MWh salt electrolyte is corrosive for the cell metallic
for CO). Despite the significant results obtained, parts (electrodes, with issues of Ni dissolution,

3. Fuel cell types 347
and interconnections) and prone to a progressive yttrium. The cell operates in a temperature range
loss by evaporation, so, especially if operated un- of 600 to 1000 C, more frequently in the so-called
der pressure, issues of lifetime extension still intermediate temperature range (700e800 C),
exist and represent one of the most crucial chal- where sufficient conduction of oxygen ions
lenges for this technology. (O2) takes place within the electrolyte crystal-
The high operating temperatures endow line lattice, allowing one to run the cell according
MCFCs with high efficiencies and greater fuel to the oxygen transport mechanism shown in
flexibility than with PEM or PAFCs. The most Table 18.2. The SOFCs are indeed generally oxy-
diffused designs can be run on natural gas, gen ion conducting (OeSOFC) in practically all
via internal reformers located within the cell applications; although research is also pursuing
itself [10]. hydrogen ion conducting types (HeSOFC or
Contrary to other types of FCs like PEM or proton conductive SOFC, using different elec-
SOFC, complexity in stack development and sys- trolytes like perovskite-type BaCeO3-based
tem integration makes it unlikely that commer- ceramics). In the most common design, the elec-
cial MCFC units with power outputs below trodes are made of cobalt- or nickel-zirconium
several hundred kWe or at MWe scale will be oxides (anode) and manganese-lanthanum com-
developed. From the perspective of the overall pounds (cathode). However, a number of new
energy balance, as shown in Table 18.4, about materials are proposed with the scope of
30% of the fuel heating input can be recovered allowing operation at lower temperature (e.g.,
for cogeneration from exhaust gases at exit tem- 500e600 C), reducing costs and increasing life-
peratures near 300 C. Higher performance is time. The electrodes and electrolyte are de-
expected from plants with outputs above 1e2 posited in successive, alternating layers using
MWe, which is the size more frequently pro- specific production techniques (e.g., screen print-
posed by the manufactures [11]. ing, plasma sprays) and sintered to form the cell
structure; single cells are then joined through in-
terconnections to form complete stacks.
3.5 Solid oxide fuel cells Despite the considerable difficulties that aries
from the high temperatures at play in terms
In SOFCs the electrolyte belongs to the family of material costs and durability, thermomechan-
of solid metal oxides and is generally a ceramic ical compatibility, and the exacting demands
material such as zirconium oxide doped with of the manufacturing technologies, SOFCs offer
several advantages that have sustained their
TABLE 18.4 Fuel cell energy balance for MW-class development:
MCFC modules (1400 kWe) fueled by
natural gas, with reference to the fuel • The solid electrolyte eliminates the obstacles
inlet chemical energy (LHV basis). associated with management of the three
Energy balance (% of fuel inlet) stagesdgas, liquid, soliddcharacteristic of
the other cell types and related to liquid
Electrical energy (net) 48 electrolyte equilibrium, electrode flooding,
Recovered heat 32 and gas seepage.
DC/AC losses 3
• The solid electrolyte enables the design and
construction of cells with diverse geometries:
Auxiliary consumptions 4 nowadays, tubular and planar shaped cells
Waste heat and heat losses 13 are being proposed through various

configurations and based on various hybrid-cycle units, where they are integrated
manufacturing processes. with gas turbine cycles or Rankine type bottom-
• Thanks to the high operating temperatures, ing cycles for multi-MW power plants [13].
the reaction kinetics are fast. Fuels like SOFCs are currently still in a rather early stage
carbon monoxide can be utilized directly. In of development: new generations of prototypes
cells operating above 700e800 C, also natural are undergoing testing, new materials are pro-
gas can be used directly: heat dissipation of posed for lowering the operating temperatures,
the electrochemical reactions sustains the and technologic updates are therefore frequent.
thermal duty of the endothermic reforming Based on available cost projection studies and
reactions, with a highly efficient thermal the features of existing prototypes, in the me-
integration of the reforming process within dium term, plant costs are expected to decrease
the stack and the cell anodes. R&D is also to below 1000 V/kW.
pursuing the development of new anode An overall comparison of FC types, from the
materials allowing the direct feeding of point of view of their performances and applica-
methane at even lower temperatures (e.g., tion stage, is presented in Table 18.5.
500e600 C).
• As opposed to MCFCs, there is no need to
feed or replenish CO2 to the anode, and 4. Applications
operating under pressure does not pose
material degradation issues. FC applications range from stationary elec-
• The high operating temperatures allow for an tricity generation to drivetrain solutions in the
efficient and consistent thermal recovery, as transport sector, exploiting the high efficiency
well as integration with gas-steam and the intrinsic modularity of this technology.
thermodynamic cycles in the so-called hybrid In this section, the development of FC for the
cycles, maximizing the energy conversion transport sector is not discussed, despite it being
efficiency. a fast-growing sector driving the research on ma-
terials and stack technologies. Instead, we focus
Regarding its current state of development, on stationary applications based on commercial
the largest SOFC demonstration plants have or almost commercial technologies, which repre-
power outputs in the range of a few MW, based sent development and business opportunities for
on 25e100 kWe modular stack units. The electri- the greening of the chemical and energy sectors.
cal efficiency of these cells currently varies from The different FC technologies presented ear-
50% to 60% depending on the manufacturer and lier can fit the proposed applications better or
the design for CHP applications or electricity- worse, according to the available fuel (pure hy-
only power generation, operating at atmospheric drogen, natural gas, etc.), to the possibility of co-
pressure. Particularly remarkable results have generation (exploiting also the high-temperature
also been achieved at a very small scale, with heat dissipated from the FC) and to the require-
2-kW micro-CHP units reaching 60% net electric ments of intermittent or part load operation
efficiency from natural gas [12]. In CHP applica- (such as for balancing the fluctuations of renew-
tions, the overall efficiency including heat recov- able energy sources).
ery is near 80%e85%. Depending on design, the
temperature of the offgases may range from 400
to 500 C. 4.1 Industrial hydrogen recovery
In addition, it is anticipated that SOFCs could
The chemical industry accounts for nearly
reach electrical efficiencies well above 70% in
10% of world energy demand and 7% of GHG

4. Applications 349
TABLE 18.5 Comparison of performances and applications for the most promising fuel cell technologies.
Low-temperature fuel cells High-temperature fuel cells
Fuel cell type PEM PEM D reformer DMFC MCFC SOFC Hybrid cycles
Main fuel Hydrogen Natural gas Methanol Natural gas Natural gas Natural gas
a
Power range 10 kWe 1e20 kW 1 We5 kW 400 kWemulti 1 kWemulti 300 kWemulti
2 MW MW MW MW
Net electric 45%e55% 33%e38% 20%e25% 47%e50% 45%e60% 65%e75%
efficiencyb
Main Transport, Residential, Portable, Stationary Stationary Stationary
application industry UPS UPS power power power
Current costs 2000e4000 6000e1,0,000 6000e1,0,000 3000e4000 4000e6000 n.a.
V/kW V,/kW V,/kW V/kW V/kW
a
Power range with wider or most common R&D activities.
b
Net electric efficiency (ref. LHV) of the most efficient configurations and/or for the larger sizes.
emissions [14], including processes in which hy- industries or burnt to produce steam) in Europe,
drogen is a by-product. A number of studies have while the remaining is vented, but the share re-
sought to quantify the amount of industrial re- duces markedly in other countries such as China.
sidual hydrogen available worldwide. The EU In this framework, the possibility of using excess
project “Roads2HyCom” [15] produced among hydrogen to cogenerate electricity and heat,
other results a map showing hydrogen produc- locally consumed by the chemical plant, finds
tion sites in Europe, breaking down the hydrogen an ideal candidate in the highly efficient and
sources into three categories: the “merchant” clean technology of PEM FC. The deployment
category supplying hydrogen to other industrial of such technology could contribute through en-
customers, while the “captive” category retains ergy savings and global emissions reduction to
hydrogen on site for its own use. Only “by- the plant economics and environmental goals.
product” hydrogen has no further use within the Chlorine and caustic soda production pro-
process or on site and can be made available for cesses use an electric current passed through
other applications, such as FC-based cogeneration. brine (a solution of saltdsodium chloride,
In particular, electrochemical processes, such NaCldin water). The brine dissociates and
as the industrial production of caustic soda and recombines through electrolysis reactions into
chlorine, produce hydrogen as a waste prod- gaseous chlorine, dissolved caustic soda, and
uct that can be transported for external use or hydrogen. The overall reaction occurring in the
help to sustain the internal energy consumption. chlor-alkali process is the following:
This by-product is usually sufficiently clean
and well suited for FC applications, and the 2NaCl þ 2H2 O/Cl2 þ 2H2 þ 2NaOH (18.11)
scale of these industrial sites is usually very
large, resulting in high volumes of hydrogen. The chlorine, caustic soda, and hydrogen are
Hydrogen recovery out of the electrochemical always manufactured in a fixed ratio, generating
process depends on the installation: it reaches a large quantity of caustic (1.1 tonNaOH/tonCl)
about 90% (usually as feedstock for nearby and hydrogen (28.5 kg/tonCl or 315 Nm3/tonCl).
Electrolysis is nowadays mainly accomplished

FIGURE 18.6 Example of 100-

and 300-cm2 PEM stacks with
metallic bipolar plates for automo-
tive and mobile applications (left)
and 3.3-kW air-cooled PEM stack
for outdoor uninterruptable power
systems (UPS) systems (right). Image
courtesy of ZBT GmbH (ph: N. van der
Schoot).
within membrane cells (a technology that has A larger 2-MWel PEM FC unit was later
substituted the former mercury-diaphragm cells installed within the European Project
thanks to a superior environmental compati- DEMCOPEM-2MW [16], coordinated by
bility, so use of mercury has been discouraged Nouryon (NL), at the site of Ynnovate Sanzheng
or phased-out by legislation in several coun- Fine Chemicals Co. Ltd. in Yingkou (China). The
tries), although alternative technologies also project demonstrated the PEM FC technology
exist (including the ODC-oxygen depolarized scale-up, integrated at a representative scale
cathode or ODC process, which features a lower
electrical consumption at the price of higher
complexity, requiring oxygen feeding, and not
generating by-product hydrogen). An example
of the integration of the FC system in the chlor-
alkali plant is shown in Figs. 18.6e18.8.
While a significant number of chlor-alkali
plants employ self-generation of electricity
through conventional NG-fueled CHP plants,
only a few projects have addressed the use
of by-product hydrogen from the chlor-alkali
industry for electricity generation or CHP.
Some demonstrations have been carried out
in chlor-alkali plants, such as in Delfzijl (the
Netherlands), where a 70-kWe PEM power plant
has been tested since 2007 in the AzkoNobel
plant, and in Lillo (Belgium), where a 1-MWe
PEM power plant was built at a Solvay site by FIGURE 18.7 Example of SOFC stack with anode sup-
MTSA and Nedstack (NL) and operated between ported structure and multiple cells per layer Courtesy of Solid-
2011 and 2015. Power SpA.

4. Applications 351
FIGURE 18.8 Integration of a fuel cell system in a chlor-alkali plant for hydrogen recovery and cogeneration.
(being also currently the world’s largest PEM paper; its production relies on an energy-
installation) in an actual chlorine production fa- intensive electrolysis process that is different
cility. The project aimed at high system efficiency from the chlor-alkali but shares the production
(at least 50% electrical and up to 85% total, of by-product hydrogen). Another example of
including available heat) and lifetime, employ- industrial process making hydrogen available
ing specific cell membrane-electrode assembly as by-product is the ethylene cracking, such as
(MEA) production processes at Johnson Matthey in Dow’s plant (Yara Sluiskil, The Netherlands)
(UK), with PEM stacks manufactured by Ned- [17] that exports pure hydrogen for other indus-
stack Fuel Cell Technology (NL). The plant, trial processes. The integration of PEM FC in an
designed and built by MTSA (NL), was launched oil refinery has been assessed in Japan [18].
in 2016 and collected more than 11,000 operating Hydrogen as a by-product is an interesting
hours, recovering over 870 tons of hydrogen and and cheap source of hydrogen to initiate the
generating electricity and heat, with a final GHG deployment of hydrogen applications; however,
emission avoidance of over 15 kton CO2 [5]. the purity and reliability of the hydrogen feed is
Based on the hydrogen availability in over 180 generally one of the bottlenecks of this applica-
chlorine plants, it is estimated that the potential tion, possibly requiring complex and expensive
of such application would be above 1000 MWel purification sections or reducing the overall
installed in China, which is currently the world’s plant availability.
largest chlorine producer (totalizing 25 Mton/
year in 2016, about 42% of global production [5]).
PEM FCs have also been evaluated for the
integration with other industrial processes. In a
4.2 Cogeneration
project developed by VTT in Finland, a 50-kW During the last years, several demonstration
PEM was installed and tested for over 4400 h projects and research efforts have been pursuing
in connection with a sodium chlorate production the application of FCs in stationary cogeneration
factory (sodium chlorate is a white crystalline (CHP), mainly using natural gas as a fuel, for
powder predominantly used for bleaching the purpose of distributed cogeneration at

residential or commercial scale. High volumes of (or first law) efficiency between 80% and 90%.
micro-CHP units (up to nearly 300,000 units with The possible integration of fuel processing and
0.75e1 kWel scale) have been deployed in Japan an FC-based CHP system is presented in
through large-scale publicly funded projects, Figs. 18.9 and 18.10.
strongly contributing to the development of At today’s capital and maintenance costs, FC
this technology [19]; similar applications have micro-CHPs are significantly more expensive
been promoted in the European Union and than traditional heating technologies. However,
United States through smaller financed projects as serial production begins, economies of scale
(e.g., Ene.field, PACE [20]), in parallel with regu- are expected to cause the costs to drop further
lation and support schemes evolution. with respect to the values shown in Table 18.5.
The use of FCs for cogeneration has several Moreover, FCs have already demonstrated
advantages, such as high net electric efficiency, good reliability: during the Ene.field project,
modularity, very low pollutant and noise emis- more than 1000 small stationary FC systems for
sions, and fast ramp-up; these characteristics residential and commercial applications in 10
make them suitable for distributed cogeneration, countries were tested, with an availability of
in particular in an urban context. As for other the systems in a 6-month period above 99%
high efficiency CHP technologies, these systems and only 1%e2% of the failures due to the FC
contribute to the reduction of GHG emissions, stack itself.
reducing the primary energy input with respect High-temperature FC technologies (MCFC
to the separated generation of electricity and heat. and SOFC) are also suitable for cogeneration
In case of CHP systems based on low- purposes. Various fuels, such as hydrogen, meth-
temperature FCs, the units require a preliminary ane and other hydrocarbons, can be used with
fuel conversion process, usually including a a simplified pretreatment with respect to the
steam methane reformer and one or more watere PEMFC solution. In fact, stream-reforming can
gas shift reactors, to obtain a syngas that is rich be conducted in the cell itself, simplifying the
in hydrogen and a sufficiently low CO content. balance of plant. In addition, the heat dissipation
For instance, CO must stay below 10 ppm in of the electrochemical reactions sustains the ther-
PEM FC and below nearly 1% in PAFC units. mal duty of the endothermic reforming reac-
Conventional PEM FC micro-CHP systems tions, making much more efficient the overall
have typically an electric efficiency between conversion of hydrocarbons to electricity; the
33% and 38% (while the efficiency reaches up net electric efficiency reaches up to 60% LHV in
to 43% in 400 kW-class PAFC units) and a total SOFCs, with the additional benefit of high-
FIGURE 18.9 The 1-MWel fuel cell system at Solvay in Lillo, Belgium (left) and 2-MWel fuel cell system at Ynnovate Co.
Ltd. in Yingkou, Liaoning province, China (right) for hydrogen recovery in chlor-alkali plants.

4. Applications 353
FIGURE 18.10 Schematic of possible CHP system integration based on different fuel processing levels and different fuel
cell technologies.
temperature heat recovery from the exhaust

gases. Despite MCFC and SOFC-based cogene-
ration being still under development to improve
system lifetime, operability (high-temperature
stacks suffer heat cycles and start-stop transients,
requiring several hours for a cold startup), and
costs, some units are already commercially avail-
able. While MCFC manufacturers focus on large-
scale and multi-MW units, SOFC cogeneration
units are proposed from the single kW scale.
Aisin Seiki, in cooperation with Osaka Gas, Kyo-
cera, and Chofu, proposed a 3-kWel SOFC cogen-
eration system in 2014, available in Japan, using
proprietary ceramic technologies to deliver 52%
generation efficiency and an overall efficiency
of 90% with exhaust heat recovery [21]. SOLID-
power also proposes a SOFC-based cogeneration
system (Fig. 18.11), with net electrical efficiency
of up to 60% and overall efficiency of 85% [12].
As mentioned earlier, the current research
is focused on reliability improvement and capi-
tal cost reduction, targeting also system simpli-
fication, acting on fuel processor and balance
of plant components. On the other hand, differ-
ent solutions are also at research stage, including
high-temperature PEM FC (HT-PEM), innovative
FIGURE 18.11 Schematic of a 1.5-kWel SOFC CHP sys-
systems for fuel pretreatment (such as mem- tem (courtesy of SolidPower SpA) with FC module in the up-
brane reforming reactors), or systems based on per part, and water treatment, gas cleaning, and power
different fuels (such as methanol). management system in the bottom section.

4.3 Application to CO2 capture ions extracted from the air at the cathode side
and transported across the electrolyte (either as
The ambitious objective of reducing the an- O¼ or combined with CO2 in CO¼ 3 ions). The elec-
thropogenic CO2 emissions requires contributions trochemical oxidation then allows keeping sepa-
from several technologies, including carbon rated the CO2 in the exhaust gases from the
capture and sequestration (CCS). Among many depleted air, making the effluents suitable for a
investigated solutions, recent research activities complete and efficient CO2 purification process
have been concentrated on FCs, which share (see Fig. 18.12 showing the concept applied
the unique capability of bridging high efficiency with an SOFC).
with the possibility of capturing the produced In addition to such a possibility, MCFCs fea-
CO2. The FC technology can be potentially ture the capability to work as an “active con-
exploited both in large centralized plants (tens centrator,” where the cathode of an MCFC can
to hundreds of MWel) and small decentralized be fed in principle with any CO2 -rich exhaust
power generation units (few kWel to MW scale) gas coming from a conventional plant (e.g., a
because of its modular nature. Most R&D pro- fossil fuelebased power plant, or an industrial
posals consider the integration of FCs in power process); from such effluent, O2 and CO2 are
cycles, with CCS, based on natural gas or coal as extracted in the form of carbonate ions, trans-
primary fuel, and adopting high-temperature ferred through the electrolyte, and reacted at
FCs, namely SOFC and MCFC [22e24]. the MCFC anode, resulting in an anode exhaust
The majority of the studies focused on the that is primarily rich in CO2 and water and al-
integration of power production and CO2 cap- lows easily completing the CO2 purification
ture within coal or NG-based power plants and separation process (Fig. 18.13).
consider hybrid cycles, where high-temperature A large number of possible plant config-
FCs are integrated with a simple or modified urations is proposed in the open literature
Brayton cycle, in some cases adding a bottoming for large-scale MCFC and SOFC-based power
cycle (e.g., based on steam or ORC) [12,22]. plants. Moreover, high-temperature FCs are also
A common advantage of high-temperature envisaged for CCS applied to other industrial
FCs (MCFC and SOFC) for the purpose of CCS processes, such as the production of cement,
applications is the possibility to carry out the steel, or within refineries [25e27].
oxidation of the fuel in the anode with oxygen
FIGURE 18.12 Conceptual application of SOFC to CCS systems, exploiting the extraction of oxygen from air (transferred
through O¼ ions across the electrolyte) and the resulting high concentration of CO2 at the anode outlet.

4. Applications 355
FIGURE 18.13 Conceptual application of MCFC to CCS systems. where the MCFC acts as an "active concentrator," trans-
porting CO2 (in the form of CO¼
3 ions) across the electrolyte.
4.4 Power-to-power energy storage and mismatching the demand. This solution pro-
grid balancing vides flexibility for stabilization purposes and
can be a cost-efficient option if abundant renew-
Replacing fossil fuels requires a massive in- able power is available as projected for a future
crease in renewable energy sources (RES) power energy system [6]. Renewable energy from
generation as well as an increasing electrifica- wind turbines and PV panels is also a viable en-
tion of all end use sectors. Due to the decrease ergy supply alternative for off-grid communities
in costs, wind and solar are the most promising and remote technical installations, which indeed
renewable power sources: according to EU plans require storage, possibly for seasonal periods.
for the long-term, they will constitute between The main nonfossil fuelebased competitors
30% and 60% of total electricity production on for providing balancing services to the electric
average. These two trends pose serious chal- infrastructure in high-RES scenarios are batteries
lenges to the stability of the energy system due and pumped-hydro storage. The first can pro-
to the intermittent and variable energy flows: vide a highly efficient electricity storage, but
on the supply side, wind and solar power exhibit only for limited periods of time and with high
strong short- and long-term variations, while on investment costs due to the low energy density.
the demand side, hourly, daily, weekly, monthly, The latter is more suitable for storing large
and seasonal variations are also significant, espe- amounts of energy over long periods of time,
cially in the building sector. In general, multiple but its capacity is limited. Moreover, compared
options to balance supplyedemand differences to the high technical potential (e.g., 30e80 TWh
exist, where the most promising are involving in the European Union) [28], restrictions due
the sector coupling, i.e., technologies able to in- to environmental impact, regulation, and social
fluence at the same time the electricity, transport, acceptance strongly limit the readily available
and heating sectors. Hydrogen provides both a capacity and the possibility to install additional
mechanism for sector coupling as well as the op- plants. Oppositely, hydrogen can be stored
tion to store energy at large scale over long pe- for long periods of time and at large scale at
riods of time or to transport it from regions of competitive costs [7], compared to conventional
supply to centers of demand. large-scale energy storage, such as pumped
The power-to-gas (P2G) technology produces hydro. A key advantage of the hydrogen-based
“green” hydrogen from water electrolysis, ex- storage systems is indeed given by the potential
ploiting renewable electricity excess or application to seasonal and multiweek

timeframes, coupled with very large energy capacity, in particular regarding the high-
quantities, provided that a sufficiently large stor- temperature technology.
age tank or reservoir (including the use of under- In the short-term, the commercial applications
ground caverns) is available. of FCs are mainly in the field of portable or
The final use of hydrogen can follow different backup generators, of UPS, e.g., for data centers,
pathways, contributing to decarbonize several which should be independent on the electric
sectors: (i) direct use in FC vehicles or conversion grid), or in installations conditioned by strict re-
to liquid fuels (power-to-liquids, P2L), (ii) use as quirements of low environmental impact, as
feedstock for the chemical industry, or (iii) direct in urban sites or natural parks and reserves. In
reconversion to electricity through an FC (power- fact, for these specific applications, the advan-
to-power, P2P), possibly in a cogeneration unit. tages of low emissions level and high energy
All of these solutions will contribute to the density (and no self-discharge, in the cases of
decarbonization of the energy system, exploiting P2P with respect to conventional batteries) over-
the potential of sector coupling. come the still high specific investment costs,
The direct reconversion to electricity has ad- possibly with incentives or initial funding from
vantages in terms of flexibility of the storage public institutions.
time horizon, high single-step energy conversion In the transport sector, all the main car manu-
efficiency, efficient part-load operation, and easy facturers developed in the last years prototypes
scalability due to its modular nature. On the of fuel cell electric vehicles (FCEV) based on
other hand, P2P suffers from high investment the PEM FC technology. The stricter regulation
costs and low round-trip efficiencies (RTE): on pollutants and GHG emissions, as well as
values of RTE around 30%e40% are common, the increasing cost of fossil fuels, all push for a
considering the use of conventional electrolysis deployment of this technology in the short to
(60%LHV efficiency) and compressed hydrogen medium term. Despite the strong effort put in
storage at 80 bar, including compression con- the vehicle development, the bottleneck is still
sumption [29]. For comparison, pumped-hydro the slow and tricky evolution of the clean pro-
storage installations are characterized by an effi- duction of hydrogen (e.g., from RES through
ciency of 70%e75% and lifetime above 40 years. electrolysis of water) and the subsequent de-
ployment of a sufficiently large infrastructure
for transport and distribution of hydrogen into
5. Conclusions and future trends new or refurbished refilling stations.
The FCs have also the possibility to be an
During the last decade, FC technology has important player in the electric system, mainly
gone through remarkable improvements, both impacting in the distributed generation field.
in terms of performance and reliability. Nowa- This technology can support the integration of
days, the main goal of research is the reduction the energy sectors, with the diffusion of small-
of costs and the increase in plant lifetime. While scale highly efficient cogeneration units, possibly
in the automotive sector the use of a PEM FC located next to the final user thanks to their low
can have a target lifetime limited up to 5000 h, environmental impact, up to a limit, of being
the stationary applications require more than microunits sized for single residential users. As
40,000e50,000 h of operation. The first target is previously discussed, a great potential has been
already reached by commercial units with satis- demonstrated also in the by-product hydrogen
factory performance, while the durability goals recovery from industrial and chemical plants,
for FCs in stationary applications have been in the CCS, and in P2P applications, where again
tested only in a few pilot plants with a relevant the hydrogen and FC technology may act as

References 357
a link among different sectors of the energy W Work
system. h Efficiency
n Stoichiometric coefficient
In conclusion, FCs are a technology that is un-
dergoing a growing and continuous develop-
ment, with very high potential in increasing Subscript
efficiency and reducing environmental impact
in several energy and industrial sectors. a Oxidant (air)
AC Alternating current
act Activation
conc Concentration
List of abbreviations and acronyms DC Direct current
el Electric
AFC Alkaline electrolyte fuel cell f Fuel
CCS Carbon capture and sequestration LHV Lower heating value
CHP Combined heat and power ohm Ohmic
DMFC Direct methanol fuel cell rev Reversible
FC Fuel cell
FCEV Fuel cell electric vehicles
GHG Greenhouse gases References
HT-PEM High-temperature PEM fuel cell
LTFC Low-temperature fuel cell [1] U.S. DOE (Department of Energy), in: Fuel Cell Hand-
MCFC Molten carbonate fuel cell book, seventh ed., EG&G Services. Inc., 2004.
MEA Membrane-electrode assembly [2] J. Larminie, A.L. Dicks, in: Fuel Cell Systems
MIEC Mixed ionic-electronic conduction Explained, second ed., Wiley, 2003. ISBN: 978-0-470-
NG Natural gas 84857-9.
O&M Operation and maintenance [3] California Air Resources Board “2018 Annual Evalua-
ORC Organic Rankine cycle tion of Fuel Cell Electric Vehicle Deployment &
P2G Power-to-gas Hydrogen Fuel Station Network Development”, arb.-
PAFC Phosphoric acid fuel cell ca.gov, July 2018.
PBI Polybenzimidazole [4] B. Emonts, M. Reuß, P. Stenzel, L. Welder, F. Knicker,
PEM Polymer electrolyte membrane T. Grube, K. G€ orner, M. Robinius, D. Stolten, Flexible
PEMFC Proton exchange membrane fuel cell sector coupling with hydrogen: a climate-friendly fuel
R&D Research and development supply for road transport, International Journal of
RES Renewable energy source Hydrogen Energy 44 (26) (2019) 12918e12930,
RTE Round-trip efficiency https://doi.org/10.1016/j.ijhydene.2019.03.183.
SOFC Solid oxide fuel cell [5] S. Campanari, G. Guandalini, J. Coolegem, J. ten Have,
P. Hayes, A.H. Pichel, Modeling, development and
testing of a 2 MW PEM fuel cell plant fueled with
List of symbols hydrogen from a chlor-alkali industry, ASME Journal
of Electrochemical Energy Conversion and Storage
E Electric potential (JEECS) (2019), https://doi.org/10.1115/1.4042923.
E0 Reference electric potential [6] G. Guandalini, S. Campanari, M.C. Romano, Power-to-
F Faraday’s constant gas plants and gas turbines for improved wind energy
G Free Gibbs energy dispatchability: energy and economic assessment,
H Enthalpy Applied Energy 147 (2015) 117e130, https://doi.org/
LHV referred to the Lower Heating Value 10.1016/j.apenergy.2015.02.055.
n Molar flow rate [7] P. Colbertaldo, S.B. Agustin, S. Campanari, J. Brouwer,
p Pressure Impact of hydrogen energy storage on California electric
R Universal gas constant power system: towards 100% renewable electricity, Interna-
S Entropy tional Journal of Hydrogen Energy 44 (2019) 9558e9576,
T Temperature https://doi.org/10.1016/j.ijhydene.2018.11.062.
U Utilization factor [8] E4Tech ‘The Fuel Cell Industry Review: 2018’, 2019.
V Cell voltage http://www.fuelcellindustryreview.com/.

[9] http://www.doosanfuelcell.com, 2019. plants and natural gas-fired combined cycles, ASME
[10] M. Farooque, et al., Direct Fuel Cell Development and Journal of Electrochemical Energy Conversion and
Demonstration Activities at Energy Research Corpora- Storage 15 (2018), https://doi.org/10.1115/1.4038601.
tion Fuel Cell Seminar, Palm Springs, 1998. [23] V. Spallina, P. Nocerino, M.C. Romano, M. Van Sint
[11] https://www.fuelcellenergy.com/, 2019. Annaland, S. Campanari, F. Gallucci, Integration of
[12] https://www.solidpower.com, 2019. solid oxide fuel cell (SOFC) and chemical looping com-
[13] S. Campanari, L. Mastropasqua, M. Gazzani, P. Chiesa, bustion (CLC) for ultra-high efficiency power genera-
M.C. Romano, Predicting the ultimate potential of tion and CO2 production, International Journal of
natural gas SOFC power cycles with CO2 capture e Part Greenhouse Gas Control 71 (2018) 9e19, https://
A: methodology and reference cases”, and “Part B e doi.org/10.1016/j.ijggc.2018.02.005.
Applications, Journal of Power Sources 325 (2016) [24] S. Campanari, P. Chiesa, G. Manzolini, S. Bedogni, Eco-
598e614, https://doi.org/10.1016/j.jpowsour.2016.05.104 nomic analysis of CO2 capture from natural gas com-
and 10.1016/j.jpowsour.2016.05.134, 194-208. bined cycles using molten carbonate fuel cells,
[14] IEA (International Energy Agency), Technology Applied Energy 130 (October 2014) 562e573, https://
RoadmapdEnergy and GHG Reductions in the Chem- doi.org/10.1016/j.apenergy.2014.04.011.
ical Industry Via Catalytic Processes, OECD/IEA, [25] M. Spinelli, M.C. Romano, S. Consonni, S. Campanari,
Paris, France, 2013. M. Marchi, G. Cinti, Application of molten carbonate
[15] Anon, Final Report e ROADS2HYCOM (Research fuel cells in cement plants for CO2 capture and clean
Coordination, Assessment, Deployment and Support power generation, GHGT12-2014, Austin, USA Oct.
to HyCOM), 2011. https://cordis.europa.eu/ 2014 and, Energy Procedia 63 (2015) 6517e6526,
publication/rcn/11063_en.html. https://doi.org/10.1016/j.egypro.2014.11.687.
[16] http://www.demcopem-2mw.eu/, 2019. [26] L.Mastropasqua, L. Pierangelo, M. Spinelli, M. C.
[17] https://www.gasuniewaterstoFCervices.nl/, 2019. Romano, S. Campanari, S. Consonni “Molten Carbon-
[18] T. Haneda, A. Akisawa, Technical, economic, and envi- ate electrochemical membranes for low-carbon retrofits
ronmental assessment of PEFC power generation sys- in the steel industry”, 14th Int. Conf. on Greenhouse
tem using surplus hydrogen produced from an oil Gas Control Technologies, GHGT-14, Oct. 2018, Mel-
refinery, ASME Journal of Electrochemical Energy bourne, Australia.
Conversion and Storage 14 (4) (2017). [27] L. Mastropasqua, M. Spinelli, M. C. Romano, S. Cam-
[19] R. Rose, ENE-FARM Installed 120,000 Residential Fuel panari, S. Consonni “Decarbonising the oil refinery in-
Cell Units, 2015. www.h2-international.com. dustry: CO2 capture with a Molten Carbonate
[20] R. Nielsen, C.B. Prag, Learning Points From Demon- electrochemical membrane integrated into a natural
stration of 1000 Fuel Cell Based Micro-CHP Units, gas reforming process” 14th Int. Conf. on Greenhouse
2018. http://enefield.eu. Gas Control Technologies, GHGT-14, Oct. 2018, Mel-
[21] S.J. McPhail, J. Kiviaho, B. Conti, The Yellow Pages of bourne, Australia.
SOFC Technologies e International Status of SOFC [28] Fuel Cells and Hydrogen 2 Joint Undertaking,
Deployment 2017, Helsinki, 2017. ISBN 978-951-38- “Hydrogen Roadmap Europe e A Sustainable
8603. Pathway for the European Energy Transition,”, 2019
[22] M. Spinelli, S. Campanari, M.C. Romano, S. Consonni, (Available on: fch.europa.eu).
T.G. Kreutz, H. Ghezel-Ayagh, S. Jolly, M. Di Nitto, [29] M. Lehner, R. Tichler, et al., Power-to-Gas: Technology
Molten carbonate fuel cells as means for post- and Business Models, Springer, London, 2014.
combustion CO2 capture: retrofitting coal-fired steam

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Catalysis, Green Chemistry and Sustainable Energy

IV. Selected examples and case history

IV. Selected examples and case history

FIGURE 18.3 Expanded view of a planar

IV. Selected examples and case history

IV. Selected examples and case history

the electrolyte delimits the operating tempera- 2.3 Theoretical background

IV. Selected examples and case history

IV. Selected examples and case history

IV. Selected examples and case history

IV. Selected examples and case history

which refers to the electrical energy produced 3. Fuel cell types

Fuel cell Transported ion Anode reaction Cathode reaction

SOFC O¼ H2 þ O¼ / H2 O þ 2e CO þ O¼ / CO2 þ 2e CH4 1=2 O2 þ 2e /O¼

IV. Selected examples and case history

IV. Selected examples and case history

DC/AC losses 2.5

3.3 Phosphoric acid fuel cells Auxiliary consumptions 3.5

IV. Selected examples and case history

IV. Selected examples and case history

IV. Selected examples and case history

Low-temperature fuel cells High-temperature fuel cells

IV. Selected examples and case history

FIGURE 18.6 Example of 100-

IV. Selected examples and case history

IV. Selected examples and case history

IV. Selected examples and case history

temperature heat recovery from the exhaust

IV. Selected examples and case history

IV. Selected examples and case history

IV. Selected examples and case history

IV. Selected examples and case history

IV. Selected examples and case history

IV. Selected examples and case history

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