Fuel Cell Technologies: 253 © Springer Nature Switzerland AG 2022 R. Neugebauer (Ed.), Hydrogen Technologies
Fuel Cell Technologies: 253 © Springer Nature Switzerland AG 2022 R. Neugebauer (Ed.), Hydrogen Technologies
Fuel Cell Technologies: 253 © Springer Nature Switzerland AG 2022 R. Neugebauer (Ed.), Hydrogen Technologies
10
Ulf Groos
Fraunhofer Institute for Solar Energy Systems ISE
Carsten Cremers
Fraunhofer Institute for Chemical Technology ICT
Laura Nousch Christoph Baumgärtner
Fraunhofer Institute for Ceramic Technologies and Systems
IKTS
Abstract
Fuel cells are energy converters that transform the chemical energy of a fuel into
electrical and thermal energy. They enable cogeneration of heat and power and
thus have the potential to become a vital component of hydrogen-based energy
supply. This chapter analyzes the functionality and properties of various types
of fuel cell.
10.1 Introduction
Fuel cells are energy converters that transform the chemical energy of a fuel into
electrical and thermal energy. As such, they enable cogeneration of heat and power.
Power generation via fuel cells creates opportunities in many areas. The cells’ po-
tential efficiency is high when compared to the combustion engine and the energy
density values of their fuels are higher than those of batteries. In addition, fuel cells
help to avoid local pollutant emissions and a wide range of fuels are available. As a re-
sult, fuel cell systems have many possible areas of application. Whether in stationary
energy production, or as a mobile energy supply for an electrical drive unit, fuel cells
have the potential to play a significant role in global power supply solutions.
Fuel cell systems can achieve high efficiency rates of over 50 percent, and if
they are powered by renewable hydrogen, they are emission-free. If the hydrogen
used is non-renewable but produced at one central location, they are emission-free
at least at the local level. In the case of fuels like methane and methanol, the cells
offer a sharp reduction in emissions compared to combustion engines. The systems
are quiet and low maintenance.
Fuel cells can be used in a wide range of applications, ranging from output
capacities of 1 watt to multiple megawatts:
As in a combustion engine, the power converter in a fuel cell system can be dimen-
sioned separately from the energy storage device. This allows power output and
operation time to be developed to fit the application in question.
Each individual fuel cell consists of a bipolar plate (BPP) with an anode and
a cathode side, along with a membrane electrode assembly (MEA). Individual
fuel cell technologies differ depending on the particular electrolytes used, as these
determine the operating temperature level. The operating temperature, in turn,
determines the types of fuel that can be used. If multiple individual cells are elec-
tronically connected in series, stacked on top of each other and supplemented with
balance-of-stack (BOS) components such as end plates, current collectors, distribu-
tor plates and monitoring units, they form a fuel cell stack. As a rule, the individual
cells of a stack are supplied with fluid in parallel. The number of individual cells
defines the total voltage level, and their active surface area determines current. To-
gether, the number of cells and their surface area allow variation in power output.
Fuel cell systems are based on fuel cell stacks, together with the support of balance-
of-plant (BOP) elements like air compressors, humidifiers, hydrogen supply, purge
valves, thermal management modules and power electronics.
Membrane fuel cells use a solid-state, ion-conducting membrane as an elec-
trolyte. In a polymer electrolyte membrane fuel cell (PEMFC), the membrane
electrode assembly is made up of a very thin catalyst-coated membrane (CCM)
10.1 Introduction 255
made of polymers with a gas diffusion layer (GDL) on each side. Bipolar plates
(BPP) are the most common means of supplying reaction gases and cooling the
stacks. Other types of membrane fuel cells include anion exchange membrane
fuel cells (AEMFC) and ceramic solid oxide fuel cells (SOFC). Alkaline (AFC),
phosphoric acid (PAFC) and molten carbonate fuel cells (MCFC) come under a dif-
ferent category. These types of fuel cell use a liquid electrolyte that is adsorbed to
a ceramic matrix and the electrode structures. Current high-temperature polymer
electrolyte membrane fuel cell (HT-PEMFC) models fall under this cell type. The
chemical interaction between phosphoric acid and polybenzimidazole within the
electrolyte membrane is so strong that these can be treated as one homogeneous
membrane. In the electrodes, however, phosphoric acid is adsorbed only as a liquid.
HT fuel cells use solid and liquid electrolytes that need to reach 600 °C to
achieve sufficient ionic conductivity. Oxygen ions (O2 ) or carbonate ions (CO2 3 )
are conducted through the electrolytes. This has the added advantage that carbon
monoxide can be converted within the cell itself. This allows a wide choice of fu-
els. Various hydrocarbon-based fuels (liquid and gas) from conventional mining
and renewable sources (e.g., biogas) can be used, up to and including ammonia
(NH3 ). High-temperature fuel cells can reduce system costs and increase system
efficiency (Fig. 10.1).
256 10 Fuel cell technologies
Fig. 10.1 Fuel conversion stages in various fuel cell types and their influence on fuel-
processing complexity. (see [6])
High operating temperatures allow extraction of useful heat from the exhaust
systems, meaning high-temperature fuel cell systems are perfectly positioned to
play a major role in stationary generation of electricity and heat (cogeneration or
CHP). The high part-load efficiency of SOFC systems distinguishes them from
other converters such as gas-powered engines. However, there are drawbacks for
sectors such as mobility, as SOFCs’ energy- and time-intensive warm-up phase,
along with their limited number of thermal cycles, make them less suited to appli-
cations involving high load flexibility.
10.2.1 Overview
In PEMFCs, the hydrogen molecule is split into two protons and two electrons
on the anode side. The electrons follow an external circuit to the cathode and
can perform electrical work in the process. The protons are conducted through
the membrane electrolyte to the cathode, closing the electric circuit. At the cath-
10.2 Low-temperature polymer electrolyte membrane fuel cells 257
ode, they combine with (atmospheric) oxygen and electrons to form water, which
is discharged from the fuel cell as increased humidity.
Catalyst
Dimensions from nanoscale to macro-scale Time scale from ns to hours Particle
2 – 8 nm
Nano-scale: proton transport, catalyst Proton & electron transport
Catalyst
particle, catalyst support pores Fluidics & diffusion Support
Micro-scale: ionomer distribution, Degradation
30 – 60 nm
agglomerate, catalyst layer morphology
Catalyst Layer 5 – 15 μm
Macro-scale: Flow field
Catalyst Loading 0.02 – 0.4 mgPt /cm²
Carbon Fiber Ø 10 μm
30 cm H2
Fig. 10.2 Membrane electrode assemblies (MEA) in fuel cells present a multiscale problem.
(Fraunhofer ISE)
258 10 Fuel cell technologies
Fig. 10.4 Current density at two operating points with different Pt loading levels (on the
cathode) and different ionomer content levels. The MEA was produced by a screen-printing
process, as part of the DEKADE project, which was funded by the German Federal Ministry
of Education and Research (BMBF). (Fraunhofer ISE)
performance due to low proton contact resistance at the boundary between the elec-
trode and the membrane (Fig. 10.4). Conversely, low ionomer content allows im-
proved oxygen diffusion, increasing power output when high currents are applied.
10.2 Low-temperature polymer electrolyte membrane fuel cells 259
Scientific objectives
Development of new, sustainable catalyst systems for LT-PEMFCs, based
on stable carrier structures with optimized platinum-carrier interaction
Development of new composite membranes with nanofiber reinforce-
ment, based on the direct membrane printing process developed by the
participants, with the aim of producing an optimal membrane electrode
unit with reduced membrane thickness and improved operating stability
(Fig. 10.5)
Modeling of the membrane electrode units to optimize their structure and
component composition
Innovative electrode structuring with through-plane gradients to achieve
optimal ionomer and Pt distribution
The structures of the flow field facing to the microporous catalyst layer are too
coarse for gas molecules, so in order to enable a good gas supply, gas diffusion
layers are applied to the CCM. The gas diffusion layers are composed of non-
woven carbon-fiber materials or meshes with a thickness of 100 to 300 m, which
are equipped with a fluorinated polymer layer to make them hydrophobic. Typi-
cally, a microporous layer (MPL) 20 to 50 m thick and consisting of hydrophobic
carbon particles is then applied to the side facing the electrode. These microporous
layers assist with water management within the PEMFC.
The active area of the catalyst-coated membrane (CCM) is cut out via punching.
To make it possible for machines to handle the CCM and to enable the creation of
seals between the CCM and the gas ports and bipolar plates, polymer reinforcement
frames are laminated onto the membrane. These frames can be made of materials
such as polyethylene naphthalate (PEN). Finally, the gas diffusion layer is fixed to
each side of the membrane.
10.2 Low-temperature polymer electrolyte membrane fuel cells 261
Flow fields incorporated into bipolar plates distribute the reaction gases over
the active surface of the membrane electrode assembly. The bipolar plates dis-
tribute gases, conduct electrical currents between cells, provide a gas-tight seal
separating the anode and cathode spaces and act as a seal to shield against cooling.
Bipolar plates can be made from graphite-based or metallic materials. Compound
bipolar plates result in greater stack heights when compared to metallic plates. As
such, they must contain conductive, graphite-based filler materials to ensure the
bipolar plates can conduct electricity. The main advantage is their high corrosion
resistance. Metallic plates have good mechanical strength and are easy to machine.
However, they do present some disadvantages, for example, metal surfaces tend to
form oxides and their corrosion resistance is not as good. Consequently, an addi-
tional surface coating must be applied to ensure a low level of electrical contact
resistance between the plate and its neighboring GDL in the long term, and to pre-
vent possible contamination through corrosion. Graphite coatings, precious-metal
films, metal nitride/carbide films and conductive polymer films are often applied
to the surfaces of metallic bipolar plates.
Manufacturing a stackable bipolar plate unit involves incorporating the flow
field, cutting out and coating the bipolar plates, and finally welding together two
plates and applying a seal. Manufacturing bipolar plate production requires enor-
mous precision from the forming, cutting and joining technology. At present, the
forming technology can produce bipolar plates from sheets 0.07 to 0.1 mm thin
with channels up to 0.8 mm deep.
ally an air filter that removes dust particles and any corrosive gases from the
incoming air.
The anode circuit is made up of a recirculation pump or a similar device,
a mechanism for water separation, and a blow-off or purge valve. Recirculation
ensures a high level of hydrogen utilization, as well as sufficient gas flow to elim-
inate condensing moisture from the fuel cell. Since (atmospheric) nitrogen and
other inert gases can diffuse from the cathode to the anode, these must be regularly
removed via a purge valve. This typically happens at timed intervals dependent on
the cell’s cumulative power generation. A condensation unit ensures that excess
water produced is removed from the anode gas flow. The gas flow ejected through
the purge valve will still contain some hydrogen. However, in vehicles, this flow is
fed into the cathode exhaust in most cases, for reasons of space. A measurement
technique developed by Fraunhofer ICT and certified by the testing agency TÜV
Süd AG allows transient monitoring of the H2 concentration in the exhaust gas, in
order to ensure the threshold values for safe operation are not exceeded.
The cooling circuit consists of a coolant pump, heat exchangers and a device
for regulating the coolant flow and stack temperature. Generally, the coolants used
are frost-resistant and cannot conduct electricity.
Every fuel cell system has a starter and buffer battery. This ensures that dur-
ing the startup process, the crucial peripheral components of the system can start
10.2 Low-temperature polymer electrolyte membrane fuel cells 263
running even before the fuel cell itself builds up sufficient power. In vehicles,
the buffer battery covers extreme load peaks, which prevents fuel cell degrada-
tion caused by large gradients in potential or insufficient gas supply. Furthermore,
the battery can recover energy from regenerative braking and so increase overall
operational efficiency, while reducing mechanical wear and tear during braking.
The power electronics adapt the electrical parameters to electrically couple the
fuel cell with the battery and electric engine in the powertrain.
Compressed gas tanks are used to store hydrogen in vehicles. Global stan-
dards for tank pressurization levels have been established: 700 bar for cars; 300
to 350 bar for buses and trains. For trucks, various solutions are under discussion,
ranging from compressed gas tanks with pressures of 300, 350 or 700 bar to liquid
or cryo-compressed hydrogen tanks. As a rule, multiple cylindrical tanks are used,
connected together via valve switches and tubing.
Fig. 10.8 Typical current density profile of an LT-PEMFC. This graphic depicts the char-
acterization of an along-the-channel test cell produced by Fraunhofer ISE as part of the
DEKADE project. The steep current ramp at the cathode inlet is due to the low proton
conductivity of a dry membrane and then the humidification of the membrane due to the
strong electro-chemical fuel cell reaction with high oxygen concentration. The oxygen con-
centration and current density decrease simultaneously along the length of the air flowfield
channels. (DEKADE, Fraunhofer ISE)
10.2 Low-temperature polymer electrolyte membrane fuel cells 265
Gas pressure at anode and cathode inlets: As a rule, pressure increases cell
power output, but it also leads to higher compressor losses in the system.
Gas humidity at anode and cathode inlets: Gas humidity is an important vari-
able in the cell because cell membrane resistance decreases where humidity is
higher. At high humidity levels, water can block up the cell, causing output to
fall further.
Stack temperature, usually controlled via cooling liquid inlet temperature and
cooling liquid flow: As a rule, temperature increases cell power output, due to
a rise in electrode activity. However, excessively high temperatures cause the
membrane to dry out, leading to degradation.
Anode gas composition and speed: Hydrogen gas is usually circulated around
the anode so that the fuel is consumed to the greatest possible extent. Over
time, this leads to an accumulation of inert gases in the anode circuit. Gas flow
affects desorption of water droplets, gas mixing and the homogeneous supply
of hydrogen to the anode.
Dynamic effects that may continue over a long period, e.g., membrane humidity,
saturation of the pores with water, catalyst contamination and platinum oxida-
tion.
Various processes contribute to PEM fuel cell degradation. These occur at different
speeds, depending on operational management. The following operational modes
and events reduce service life:
Highly dynamic operation. For this reason, a small battery storage device is
often used to intercept extremely dynamic fluctuations in power demand.
Repeated start-stop cycles, especially during air/air situations (air on anode and
cathode), which occur after long downtime periods, for example
High voltages, high temperatures and dry operation
Undersupply of hydrogen or air
The complex process of quantifying these influences is currently the focus of vari-
ous research projects.
In reality, fuel cells operated under stationary conditions in a laboratory expe-
rience a degradation rate of below 10 µV/h. As such, operating hours in the many
tens of thousands are a realistic prospect. For stationary systems, there are reports
of service lives of 40,000 hours, with a decline in performance of below 10 percent.
However, even fuel cells that power buses have already demonstrated operating pe-
riods in excess of 20,000 hours.
Contaminants from incoming air and hydrogen can clog up the catalyst and
such cause degradation. Sulfur-based gases, in particular, cause irreversible dam-
age. Carbon dioxide and carbon monoxide can reduce performance, but this is
reversible.
10.3.1 Overview
1.6
0.75
1.4
stack power / kW
1.0
0.65
0.8
0.60 0.6
0.4
Ref 1 (55vol.% H2; 0.5 vol.% CO; 5 ppm H2S)
0.55
λ A = 1.4, T = 165 °C
0.2
λ A = 1.7, T = 165 °C
λ A = 1.4, T = 175 °C
0.50 0.0
50 100 150 200 250 300 350 400 450 500
Fig. 10.9 Testing how the operating conditions of anode stoichiometry and operating tem-
perature affect the operational performance of a commercial HT-PEMFC stack of type
Serenergy S165L-35 with NATO F-34 reformate as a substitute; this test was carried out
as part of the EDA project IAPUNIT. Increasing anode stoichiometry and/or operating tem-
perature makes it possible to achieve a nominal power of 1.5 kW using this fuel gas
effective, as the gas flow produced by the reformer can be fed in directly with-
out further purification. There are many such combined systems in development
or already available on the market. These range from 55 W portable energy sup-
ply devices to range extenders for battery-powered cars and commercial vehicles
(Fig. 10.9).
Ionic interaction between the weakly alkaline PBI and the phosphoric acid acti-
vates proton conductivity, which is higher than that of a conventional PAFC. In
addition, the membrane can be made much thinner than the ceramic matrix used in
the PAFC. During cell activation, phosphoric acid is deposited on the catalyst layer,
among others. In HT-PEMFCs, the catalyst is typically applied to the gas diffusion
layers (GDL), where it is mainly bound with PTFE. Using PBI as a binder leads
to excessive phosphoric acid deposition and so to mass transportation losses when
the current is high.
Scientific objectives
The aim here is to improve performance and stability of membrane electrode
assemblies for HT-PEMFCs by modifying the connections between catalyst
and carrier, catalyst system and electrolyte, and electrode and membrane.
In this project, Fraunhofer ICT investigated carrier modifications aimed at
improving the electrolyte connection, as well as methods for testing and
evaluating HT-PEMFC membrane electrode assemblies.
The catalysts used correspond to those currently used in the LT-PEMFC. Stud-
ies conducted in the HT-Linked project have shown that carbon support corro-
sion does not exponentially increase alongside temperature, as had been assumed
(Fig. 10.10).
10.3 High-temperature polymer electrolyte membrane fuel cells 269
Fig. 10.10 Investigation of corrosion in a 40 percent Pt/C catalyst using differential elec-
trochemical mass spectrometry (DEMS) under LT-PEMFC conditions (left) and under
HAT-PEMFC conditions (right) [2]
CO content in the fuel gas to tolerable levels, a simple water-gas shift reaction
will suffice. In the case of a methanol steam reformer working at up to 300 °C, no
further measures are required.
Scientific objectives
Developing a fuel cell APU for armored wheeled vehicles like the GTK
Boxer. Phase I of the project saw the development and validation of the
central components: fuel desulfurizer, fuel processor and fuel cell. In the
process, Fraunhofer ICT developed operating strategies for commercial HT-
PEMFC stacks in this type of systems and evaluated possible forms of
packaging. The planned second phase is set to focus constructing and testing
an integrated system with power output of 8 kW.
Fig. 10.11 Flowchart showing a simplified version of the basic IAPUNIT system
structure
10.4.1 Overview
Another variant on this type of system is the direct methanol fuel cell (DMFC),
which offers advantages such as the high energy density of methanol and the ease
of using and refueling the system. Methanol in the form of an aqueous solution is
supplied directly to the cell, where it undergoes electrochemical oxidization. The
following cell reactions arise in acid and alkaline cells (Table 10.2). At normal op-
erating temperatures of up to 80 °C, the cell’s power density lags far behind that of
hydrogen systems, meaning that the DMFC is only advantageous for applications
with lesser power requirements of up to 1 kW.
DMFC stacks differ from PEMFC stacks at the fine-detail level. On the anode
side, DMFC membrane electrode assemblies use catalysts made of a platinum-
ruthenium alloy. These accelerate methanol oxidation via a bifunctional mech-
anism, i.e., they provide an extra catalytic center for splitting water. Studies by
Fraunhofer ICT have shown that this bifunctional mechanism can work in alkaline
environments too [3]. Furthermore, the catalyst loading is also significantly greater
on each side because the methanol oxidization rate is slow. This hinders oxygen
reduction, partly due to methanol crossover, but mainly due to a pronounced ten-
dency to flooding caused by very large water flows. For this reason, unsupported
catalysts are often used. In addition, membranes up to 180 m thick are used to
limit the damaging effects of methanol crossover.
The bipolar plates are also fundamentally different. Since aqueous methanol
solution, which is a good heat carrier, is already being pumped through the stack,
there is no need for a supplemental coolant. As such, milled graphite-compound
bipolar plates can be manufactured in one piece from solid materials, meaning the
costly process of joining half-plates can be omitted.
The DMFC stacks differ fundamentally from the LT-PEMFC at a system level. An
aqueous methanol solution serves as the fuel. To limit methanol crossover to the
cathode, methanol concentration in the stack does not usually exceed 3 wt%. As
these very dilute methanol solutions have such low energy density, pure methanol
or a methanol-water mixture of about 60 wt% methanol is added from outside. This
is achieved by bringing the heavily-diluted methanol solution within the stack into
a closed-loop cycle, while methanol that has been consumed is added from outside.
This allows the stack to operate with extremely high anode stoichiometries. In
modern systems, to further limit methanol crossover, methanol concentration in
this inner closed-loop cycle is dynamically aligned with the load. When loads are
lower, concentration is reduced by suspending the addition of methanol until the
desired level is reached.
DMFCs’ low current density, which normally lies in the region of 200 to
300 mA/cm2 , means they require significantly less air supply than a high-perfor-
mance PEMFC system. For this reason, a membrane pump is often used for air
supply, particularly in portable systems. Over-stoichiometric quantities of water
accumulate on the cathode side, which results in the consumption of water from
the anode circuit. To achieve the required high energy densities, it is therefore
necessary to separate water from the cathode exhaust air and feed it back into
the closed anode loop. In today’s systems, this can be achieved at ambient tem-
peratures of up to 45 °C for the most part. At higher ambient temperatures, it is
not possible to achieve sufficient water recovery levels. In this case, a mixture of
methanol and water must be used as fuel. This is also referred to as “desert fuel.”
10.5 Alkaline fuel cells 273
10.5.1 Overview
Reactions within a fuel cell are influenced not only by temperature, but also by
pH value and the materials selected for the electrocatalysts and other structural
elements. This last factor can be attributed to the fact that when pH values are
low, protons can oxidize non-precious metals. For this reason, only “adequately
precious” materials can be used in acid cells.
n
M C nHC ! Mn C H2
2
The alkaline fuel cell category includes classic alkaline fuel cells (AFC) and anion
exchange membrane fuel cells (AEMFC), which are still in development. Certain
groups in the USA also use the term hydroxide exchange membrane fuel cells
(HEMFC), in order to illustrate that such cells are the exact opposite to a proton-
exchange membrane fuel cell.
Alkaline fuel cells use an alkaline solution as an electrolyte—usually a KOH so-
lution, although NaOH is also used. In most AFCs, this solution is fixed in a porous
ceramic matrix. In the past, alkaline fuel cells where the electrolyte was pumped
around the stack were produced, similar to the alkaline electrolyzers of today.
One major challenge with alkaline fuel cells is absorption of CO2 from the
ambient air, which results in the formation of carbonate or hydrogen-carbonate
ions.
In classic AFCs, potassium or sodium carbonate forms during this process and
precipitates as a solid, which damages the electrodes. AFCs have therefore mainly
only been used in applications where pure oxygen is available as an oxidation
agent. Due to the lower overpotential of the oxygen reduction reaction, which is
weaker than in PEMFCs, hydrogen- and oxygen-powered AFCs can achieve higher
efficiency levels.
In contrast to AFCs, AEMFCs use a solid-state ionic conductor based on an
alkaline anion exchange membrane. As alkaline groups, these membranes contain
mostly quaternary amines NRC
3 OH . As with PEMs, AEMs build up water dur-
ing operation, resulting in the formation of aqueous alkaline regions that ions are
conducted through. On the other hand, contact with CO2 can lead to the formation
274 10 Fuel cell technologies
of carbonate- (CO2
3 ) and hydrogen-carbonate (HCO3 ) ions, but these do not form
solid salts with the polymer-bound quaternary amines and so do not bring about
precipitation reactions. However, carbonation does lead to reduced conductivity
[4, 5], which limits cell performance.
AEMFC performance has long lagged far behind that of PEMFCs. More re-
cently however, reports have emerged of these cells achieving power densities
comparable to PEMFCs, due to the use of catalysts made of a platinum-ruthenium
alloy for anode-side hydrogen oxidation, or alternatively the use of ionomers in
the electrodes. In the context of this development, it must be noted that elec-
trode reactions in AEMFCs are fundamentally different from reactions in PEMFCs
(Table 10.3).
The main difference is that water is consumed at the cathode and then reformed
at the anode. The positive influence of PtRu on the anode reaction can be explained
by the bifunctional mechanism that occurs during water formation, as in DMFCs.
There is also a considerable risk of the cathode drying out. This has been identified
as a primary cause of premature aging.
10.6.1 Overview
In solid oxide fuel cells (SOFC), the solid electrolyte is made out of zirconium
oxide, which enables sufficient oxygen ion conduction at operating temperatures of
over 600 °C. The presence of hydrogen or carbon monoxide on the anode side, and
oxygen on the cathode side, enables a cell reaction whereby electrons are released
and flow to the cathode side (Fig. 10.12).
In an external, high-temperature process, upstream from the fuel cell stack,
fuel is converted to a reformate with the highest possible hydrogen and carbon
monoxide content (reforming). Internal reforming of short-chain hydrocarbons like
methane within the stack is possible, but this is rarely carried out due to detrimen-
tal effects on energy density and costs. Hydrogen, on the other hand, only requires
preheating before it can be fed directly into the stack.
10.6 Solid oxide fuel cells 275
In addition to tubular cell structures, planar cells are also common; these are cat-
egorized based on their supporting layer (Fig. 10.13). In this kind of cell, the
electrolyte consists of zirconium dioxide doped with yttrium or scandium. Each
side is coated with porous, current-conducting electrodes (electrolyte-supported
cell, ESC). This allows reactants to diffuse to the electrolyte, as well as enabling
supply and discharging of electrons. The combination of an electrolyte with anode
and cathode material is called a membrane electrode assembly (MEA) (Fig. 10.14).
Researchers are currently endeavoring to develop cell materials, membrane
electrode assemblies and entire fuel cell stack systems, with the aim of creating
stacks that are stable over long periods of time and multiple thermal cycles and
that deliver a high performance in terms of energy output. Fig. 10.15 shows an
SOFC stack with electrolyte-supported cells (ESC). Aside from the main compo-
nents, other elements like glass-ceramic seals and protective and contact layers are
also an important part of stack development [8, 9].
ESC A SC C SC M SC
Fig. 10.13 Diagrams of planar SOFC cell types: ESC: Electrolyte-supported cell; ASC:
Anode-supported cell; CSC: Cathode-supported cell; MSC: Metal-supported cell
276 10 Fuel cell technologies
Fig. 10.14 FESEM image of a membrane electrode assembly in a solid oxide fuel cell
(SOFC). (Fraunhofer IKTS)
Interconnect
Cathode Plate
Contact
Cell (MEA)
Nickel mesh
Ground Plate
Integrating SOFC stacks requires specially developed system components and sys-
tem designs. These must consider the heating, fuel preparation, afterburning and
thermal management processes (Fig. 10.16). A system concept is developed to suit
the specification (e.g., fuel, heat extraction) and requirements (e.g., high electrical
efficiency) of the particular area of application.
The fuel preparation concept must be studied separately and has major impli-
cations for both system efficiency and the complexity of system integration [10].
Depending on the fuel, different reforming processes are conducted outside the
10.6 Solid oxide fuel cells 277
Fig. 10.16 SOFC system components for a portable system (100 We ) based on propane/
butane
Fig. 10.17 Examples of SOFC system components. Left: Reformer with cordierite honey-
comb for partial oxidation of a propane-butane mixture. Center: ceramic foam afterburner.
Right: Ceramic foam ignition burner. (Fraunhofer IKTS)
SOFC stack, using air (partial oxidation), steam (steam reforming) or carbon diox-
ide (dry reforming).
Catalyst-supported partial oxidation is a simple option for reforming short-
chain hydrocarbons like methane or propane/butane and can be implemented in
systems with relative ease. Reformer and catalyst design and targeted thermal inte-
gration of these components are crucial to achieving the desired temperature profile
for the required operating points. Fig. 10.17 (left) shows an example of a reactor
used for partial oxidation of propane/butane.
Afterburner design must also be considered, including suitable flow manage-
ment, good combustion properties, and appropriate heat management. In the af-
terburning process, equipment such as porous burners consisting of ceramic foam
278 10 Fuel cell technologies
Fig. 10.18 Left: SOFC system cathode air heat exchanger with a multilayer structure. Right:
Gas flow through a 3D simulation model of a cathode air heat exchanger with corresponding
gas temperatures. (Fraunhofer IKTS)
Fig. 10.19 Left: A compact assembly of the hot system components of an SOFC, including
the ignition burner, reformer, stack, afterburner and heat exchanger. Right: Cross section of
a hotbox. (Fraunhofer IKTS)
being well integrated, to keep heat losses to a minimum and to achieve high levels
of thermal efficiency. Fig. 10.18 shows an example of an air preheater with a mul-
tilayer structure. A 3D simulation model is used to study the gas flow through the
device and its effect on gas temperatures.
In the most advanced technology available in SOFC system development at
present, all hot components are integrated in such a way as to minimize external
heat losses where possible, e.g., by using a shared insulation box (hotbox). To
achieve this, it is important for the hotbox to have a compact structure and for
the components to be closely integrated. Multiple layers of microporous insulation
are arranged around the components to maintain operating temperatures of over
700 °C (Fig. 10.19).
Research objective
The aim of the M3 project was to develop a portable fuel cell device based
on camping gas (propane/butane) with an electrical output of 100 Wel , as
well as high efficiency and high energy density (Fig. 10.20). This involved
the following steps:
280 10 Fuel cell technologies
Stack development
Component development (reformer, ignition burner, heat exchanger, af-
terburner)
System development
Optimization of component and integration design, with the aim of in-
creasing system-wide volumetric and gravimetric energy density
SOFC stacks can operate efficiently over a wide partial-load range. Fig. 10.21 il-
lustrates the efficiency of a 1000 Wel SOFC system powered by natural gas. In
contrast to the full-load operating point of 1000 Wel , the (net) electrical efficiency
of 38.8 percent at 600 Wel declines by only 2.4 percent. Stack modeling is used here
to estimate stack output, facilitate dimensioning and run system analyses [11, 12].
This allows modeling of stack performance at various temperatures as well as dif-
10.6 Solid oxide fuel cells 281
Fig. 10.21 Electrical efficiency (gross and net) and internal consumption by BOP compo-
nents in a 1000 Wel SOFC system based on natural gas, with partial oxidation. (Fraunhofer
IKTS)
ferent gas compositions and quantities, e.g., in cases of partial load. The goal is
to ensure efficient, secure, low-degradation operation of the SOFC stack and its
system components at different load points.
Characterizing stack performance under different conditions is necessary for
stationary and transient process analyses. This characterization can be used in var-
ious software tools [10, 11]. For example, a 3D thermofluidic model can be used
to analyze the stack’s thermal properties within the hotbox. This sheds light on in-
ternal mass flow distribution and the temperature profile to be expected within the
stack (Fig. 10.22; [13]).
These insights allow optimization of the specific design of the stack and its
thermal integration. Essentially, it is necessary to aim for a temperature profile as
homogeneous as possible, to facilitate homogeneous material conversion and uni-
form conditions across the entire stack. If certain zones are permanently hot, this
can bring about thermomechanical stress and cracks, causing more severe degra-
dation.
SOFC stacks have already demonstrated the levels of long-term stability and dura-
bility across cycles necessary for the use of these SOFC systems in electricity and
282 10 Fuel cell technologies
heat supply. To prove their capacity to withstand long-term use, SOFC stacks are
being tested during continuous operation and across thermal start-stop cycles. In
continuous operation over 20,000 hours, degradation rates as low as 0.4 to 0.7 per-
cent per 1000 hours have been achieved [13]. In start-stop cycle tests of more than
100 full thermal cycles, scientists have demonstrated degradation rates of 0.5 to
0.7 percent per 10 cycles [14–17].
The aim of future development activities is to bring down these rates and in-
crease the number of possible thermal cycles. Other strategies and application
scenarios under discussion involve bypassing thermal cycles, either by conducting
targeted dimensioning of the SOFC system in combination with storage devices
like batteries or thermal storages or by including hot-standby operation [18].
10.7.1 Overview
Molten carbonate fuel cells (MCFC) use molten alkali carbonates suspended in
a microporous membrane as an electrolyte. Operating temperatures for MCFCs
range from 580 to 650 °C. In the most common cell types, short-chain hydrocar-
10.7 Molten carbonate fuel cells 283
Anode
Cathode
Electrolyte
bons like methane can be reformed (indirectly or directly) within the stack, while
high-value hydrocarbons must normally undergo external pre-reforming.
Stationary MCFC systems are used in the higher output ranges of 0.3 to 4 MW.
They can reach electrical efficiency levels of up to approximately 47 percent. These
systems have reached a high level of technological advancement (TRL 8) and have
many possible areas of application. They can be used simply as optimized power
generators, or for process steam extraction during heat and power cogeneration.
Developments around MCFC applications in the field of carbon capturing are of in-
terest to the steel and cement industries, as well as coal- and gas-fired power plants.
This prospect of actively separating CO2 from gas flows arises from MCFCs’
method of operation (Fig. 10.23). Carbonate ions (CO2 3 ) are passed through the
liquid electrolyte. These ions form at the cathode when oxygen reacts with CO2 ,
which must be added to the cathode gas. On the anode side, carbonate ions trans-
ported through the electrolyte react with hydrogen to form CO2 , which can be
concentrated, and water. In contrast to other methods of CO2 separation, this pro-
cess generates electrical energy instead of consuming it, because it takes place
during standard MCFC operation. This leads to an even greater reduction in CO2
emissions.
While the MCFC system has its advantages, it also presents certain technical
problems that have yet to be resolved; these restrict its potential for wider com-
mercial use. Some of the most pressing problems include the cell components’
degradation and aging mechanisms, which are caused by the liquid electrolyte’s
high reactivity. This limits the service life of today’s cell stacks to five years. Many
ongoing development projects aim to increase service life to seven to ten years.
284 10 Fuel cell technologies
The planar structure of MCFC cells allows multiple cells (consisting of cathode,
electrolyte and anode) to be stacked together with current collectors and contact
plates. Fig. 10.24 shows a typical repeating unit in a fuel cell stack. Like SOFCs,
MCFCs feature an electrical series circuit and a fluidic parallel circuit. Compared to
SOFCs, MCFC technology takes up significantly more floor area: approx. 0.7 m2 .
The cathode consists of nickel oxide, which is doped with lithium from the elec-
trolyte when it is first put into operation. The cathode material must have a porosity
of 60 to 70 percent to allow the triple phase boundary (TPB) between electrode,
electrolyte and gas phase to form. This is important, as this is the site of the elec-
trochemical reaction between CO2 and O2 .
The anode is made of nickel, with some aluminum and chromium content to
ensure mechanical stability under the operation conditions. The anode porosity of
45 to 70 percent is a crucial factor and must be adjusted precisely to modulate
electrolyte distribution inside the cell.
The electrolyte is a mixture of different alkali carbonates, mainly lithium,
sodium and potassium, which are in molten state at the cell’s normal operat-
ing temperature. This molten electrolyte is immobilized between the electrodes
in a solid, porous ceramic structure (matrix). The matrix consists of a lithium
aluminate nanopowder.
Severe material degradation in modern MCFCs principally affects the active
(anode and cathode) and passive cell components (matrix). There are various
chemical mechanisms in the active components that lead to loss of stack output
and ultimately make these systems uneconomical.
In the electrolyte, the degradation of matrix materials plays a particularly im-
portant role. As operating periods lengthen, the matrix powder is coarsened and
capillary forces are weakened. The matrix can no longer securely hold the molten
electrolyte, resulting in electrolyte loss. This in turn leads to a loss of output power
up to the complete breakdown of the cell and its entire system.
Research objective
The aim of the INNOVELLE project was to lay the foundations for extend-
ing MCFC service life, and as such, the project addressed various MCFC
components. This included manufacturing and optimizing matrix materials
and characterizing active materials, as described below:
a b
d
c
Fig. 10.25 (a) Structural diagram of a half-cell; (b) impedance spectrum for a cathode half-
cell under standard operating conditions; (c) processes in the identified frequency ranges;
(d) evaluation of relaxation times with improved separation of reaction steps
distribution of relaxation times (Fig. 10.25d) are being used to achieve a better
separation of reaction steps in the spectrum. This method enables improved iden-
tification of limiting processes, which in turn allows targeted optimization of the
active components.
This development can be scaled up from half-cells to full cells. In the context
of manufacturing new materials (e.g., matrix powder) in particular, the transition
from the laboratory-scale (10 to 20 g) to the pilot-plant scale (approx. 25 kg) is
an important factor for verifying the cell’s extended service life. Upscaling in this
way requires the creation of suitable cell- and stack structures, so that conditions in
these cells and stacks are similar to those of large commercial setups (Fig. 10.26).
Using this methodology, it is possible to conduct laboratory-scale studies regard-
ing the possibility of service life extensions for other new MCFC materials, e.g.,
different types of anode, cathode and matrix materials. This makes it possible to
draw conclusions about the suitability of materials without the costly and resource-
intensive process of constructing an entire stack.
References 287
Fig. 10.26 A ten-cell MCFC test stack for investigating new MCFC materials: photograph
(left) and simulation (right) illustrating the temperature profile. (Fraunhofer IKTS)
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288 10 Fuel cell technologies