Fuel Cell Technologies: 253 © Springer Nature Switzerland AG 2022 R. Neugebauer (Ed.), Hydrogen Technologies

Download as pdf or txt
Download as pdf or txt
You are on page 1of 36

Fuel cell 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.

© Springer Nature Switzerland AG 2022 253


R. Neugebauer (Ed.), Hydrogen Technologies,
https://doi.org/10.1007/978-3-031-22100-2_10
254 10 Fuel cell technologies

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:

 1 W to 1 kW: camping, construction sites, portable generators, drones, toys


 1 to 10 kW: heat and power cogeneration for household energy, forklifts, emer-
gency generators, telecommunications, auxiliary power units (APU) for land
vehicles
 10 to 100 kW: vehicle range extenders, airport ground handling, stationary
power generation and heat and power cogeneration, auxiliary power units
(APUs) for aircraft
 50 kW to multiple MW: fuel cell power trains for cars, trucks, buses, trains,
boats, ships, aircraft; stationary heat and power cogeneration

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

Table 10.1 Overview of various fuel cell technologies


Technology Advantages Disadvantages TRL
LT-PEMFC High power density Low tolerance of contaminants 9
Long service life Complex water management
Good start-stop and cycle stability system
DMFC Good start-stop and cycle stability Low efficiency 9
High energy density (methanol) Low power density
SOFC High efficiency Medium power density 8
High tolerance of contaminants Low start-stop and cycle stability
Long service life Long startup time
HT-PEMFC High tolerance of contaminants Medium start-stop and cycle 8
Moderate startup time stability
Medium power density
MCFC Wide range of capacity Low power density 8
CO2 management Low start-stop and cycle stability
High efficiency when used with Long startup time
CO2 -based fuels
H2 as a by-product
AEMFC Precious-metal-free catalysts Low power density 3
Short service life to date

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 Low-temperature polymer electrolyte membrane


fuel cells

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.

Anode: 2H2 ! 4HC C 4e


Cathode: O2 C 4HC C 4e ! 2H2 O
Total: 2H2 C O2 ! 2H2 O

10.2.2 Stack components

With the system architecture currently available, membrane electrode assemblies


operating in an automotive fuel cell achieve power densities of approximately
1.5 W/cm2 and current densities of 2 A/cm2 at 675 mV. Platinum loading typically
reaches 0.25 to 0.4 mg/cm2 for the cathode and anode combined.
The reactions that take place in fuel cells are enabled by electrochemical cata-
lysts. Catalyst nanoparticles are deposited onto carbon particles (catalyst supports)
with varying levels of porosity by means of wet chemistry techniques. Platinum
(Pt) or Pt alloys are used as catalysts. Researchers are currently investigating core-
shell architectures and complex alloys, as well as catalysts that are not based on
precious metals. To adapt catalysts’ long-term stability to particular applications,
various carbon particle shapes are being used for catalyst support, as well as dif-
ferent degrees of graphitization.
The catalyst powder is mixed with the ionomer (for proton transport) and a sol-
vent to form a paste or ink. A coating process is then used to turn this mixture into
a catalyst layer (Fig. 10.3). The composition of the catalyst layer affects operating
behavior. When a low current is applied, high ionomer content leads to improved

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

Gas Diffusion Layer (GDL) 100 – 200 μm


O2

Polymer Electrolyte Membrane (PEM) 8 – 50 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. 10.3 Manufacturing a membrane electrode assembly (MEA). (Fraunhofer ISE)

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

Slot-die coating is the primary method used on an industrial scale today, as


this makes it possible to achieve even, high-throughput roll-to-roll coating (R2R).
However, research laboratories often use sprays coatings, as this coating method is
simple and cost effective. One currently well-established method involves coating
a decal foil and then transferring the dried catalyst layer onto the polymer elec-
trolyte membrane (PEM) via hot pressing or calendering. Direct coating of the
PEM is already being carried out in some industrial plants. The combination of the
PEM and the catalyst layer on the anode and cathode side is known as a catalyst-
coated membrane (CCM).

DEKADE project: German-Canadian fuel cell cooperation: diagnosis and


development of components for automotive fuel cells

Fig. 10.5 Manufacturing a CCM via screen printing. (Fraunhofer ISE)


260 10 Fuel cell technologies

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

Project partners: Fraunhofer ISE, University of Freiburg, Greenerity


GmbH Funded by the German Federal Ministry of Ed-
ucation and Research (BMBF)
Implementation: January 1, 2017 to December 31, 2019
Contact: Ulf Groos, head of the Fuel Cell Systems department,
Fraunhofer ISE
Information: https://www.ise.fraunhofer.de/en/research-projects/
dekade.html

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.

10.2.3 System components

To enable a fuel cell stack to provide electrical power, additional balance-of-plant


(BOP) components are required. These can typically be divided into three areas:

 Process air supply (cathode circuit)


 Hydrogen supply (anode circuit)
 Thermal management (cooling circuit)

Each circuit consists of specific components, as described below (Fig. 10.6).


As a rule, the most important components in the cathode circuit consist of
a compressor to draw in and compress air from the external environment, a cooler,
and a humidifier. The compressor is the component that consumes the most power
under standard operating conditions. Upstream from the compressor, there is usu-
262 10 Fuel cell technologies

Fig. 10.6 Balance-of-plant components in a fuel cell stack. (Fraunhofer ISE)

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.

10.2.4 Operational management

A fuel cell’s performance can be mapped based on its current-voltage characteristic


(Fig. 10.7). This shows how the individual cell or stack’s current responds to to
a particular operating voltage. For a better comparison, current density, meaning
current divided by active area, is often used as an indicator.
The electrochemical reaction is heavily dependent on local operating condi-
tions within the fuel cell. The concentration of reaction gases is high at the inlet
point but decreases along the gas channel on the way to the outlet. The reaction
simultaneously generates heat, meaning that usually—depending on the coolant
supply—the local operating temperature increases between the gas inlet and out-
let. Furthermore, this reaction produces water, resulting in increased gas humidity
(Fig. 10.8).
The operating voltage of the stack, and consequently also its power output and
efficiency, depends on its material properties and geometry, as well as the following
parameters:

 Stack current: As shown by the current-voltage characteristic, current increases


when cell potential is lowered.
 Anode and cathode stoichiometry: Higher stoichiometry means increased reac-
tion gas concentration, especially at the gas outlet of a cell, which raises current
density to a moderate level. On the other hand, the demand placed on the com-
pressor, anode recirculation pump and humidifier is higher.
264 10 Fuel cell technologies

Fig. 10.7 Current-voltage characteristics of various membrane electrode assemblies with


different levels of platinum content (mPt ) and ionomer/carbon carrier (I/C) ratios. It is evident
that higher platinum content increases power output, while a moderate I/C ratio delivers
optimal results. (DEKADE, Fraunhofer ISE)

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.

The challenge for operational management and system technologies in a PEMFC


lies in how to transport reactants to individual cells so that each cell is supplied
on an equal basis. An over-stoichiometric supply leads to an equivalent rise in air
compressor performance and a corresponding reduction in system efficiency. On
the other hand, gas starvation in the individual cell causes intense degradation and
accelerates the aging process. During cooling, it is necessary to avoid rises in local
temperature at (individual) cell level, as this can cause membrane damage. Tem-
peratures must be kept within intended levels. The PEM requires high humidity to
ensure high proton conductivity. At the same time, condensation can block pores
in the catalyst layer, the microporous layer or the gas diffusion layer. This can
lead to local gas starvation of reactants to the cell, with a significant rise in local
degradation. Water management therefore plays a critical role here.
As the parameters influence each other and combine in complex ways that can
differ in every stack, manufacturers specify the respective suitable operating con-
ditions for a certain current point. This means that as a rule, all parameters are
tailored to the individual stack current. It is important to note that some operat-
ing points that produce higher power output from the cell can lead to an elevated
degradation rate.
266 10 Fuel cell technologies

10.2.5 Service life and degradation

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 High-temperature polymer electrolyte membrane


fuel cells

10.3.1 Overview

High-temperature polymer electrolyte membrane fuel cells (HT-PEMFC) work on


the same principle as LT-PEMFCs, only at higher operating temperatures, typically
of 160 to 180 °C. Their tolerance of impurities, especially in fuel, is therefore sig-
nificantly higher than that of LT-PEMFCs. They can tolerate up to 3 vol% CO in
fuel gas [1]. For this reason, HT-PEMFCs are particularly suitable for applications
where fuel cells are powered by reformed hydrocarbons or alcohols. Using HT-
PEMFCs in combination with methanol steam reformers has proven particularly
10.3 High-temperature polymer electrolyte membrane fuel cells 267

1.6
0.75
1.4

average cell voltage / V 0.70 1.2

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

current density / mA cm-2

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).

10.3.2 Stack components

As previously mentioned, the HT-PEMFC resembles the LT-PEMFC in its basic


structure. In most commercial stacks, however, graphite-based bipolar plates are
used, as these can better withstand highly corrosive conditions at temperatures of
up to 180 °C and potential light wetting with phosphoric acid. A major difference
between the HT-PEM fuel cells and the LT-PEMFCs is the type of membrane elec-
trode assembly used. In the current state-of-the-art technology, polybenzimidazole
(PBI) membrane are used, with the addition of phosphoric acid as an electrolyte.
268 10 Fuel cell technologies

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.

HT-Linked project: High-performance, aging-resistant HT-PEMFC mem-


brane electrode assemblies based on new connection methods for cata-
lysts, carriers and proton conductors

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.

Project partners: Freie Universität Berlin (free university of Berlin),


Fraunhofer ICT, Technische Universität Berlin (technical
university of Berlin), University of Freiburg, University
of Stuttgart, Freudenberg Sealing Technologies, Fischer
Eco Solutions, Riva Batteries Funded by the German
Federal Ministry of Education and Research (BMBF)
Implementation: October 1, 2015 to March 31, 2019
Contact: Prof. Christina Roth, FU Berlin (currently University of
Bayreuth), coordinator Dr. Carsten Cremers, Fraunhofer
ICT, deputy coordinator

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]

10.3.3 System components

An important characteristic of HT-PEMFCs is their high proton conductivity,


which can occur even without water thanks to the Grotthuss mechanism. It is not
generally necessary to include a humidifier in the system structure. These days,
most HT-PEMFCs are used in systems with an upstream fuel reformer. Systems
featuring inline reforming always differ in structure from those powered by pure
hydrogen. This difference will always apply to fuel cells in cases where reformate
is fed directly into the stack as fuel gas, in place of pure hydrogen production
within the system via a separation process. Due to the high proportion of inert
gases present, closed-loop fuel cycles are generally not possible here. As the an-
ode exhaust gas always contains residue from unconsumed hydrogen and other
flammable gases, it must be burned off before it exits the system, for safety reasons.
In systems featuring allothermal reformer processes, this burn-off should ideally
take place in the reformer’s heating system. In terms of fuel inlets, HT-PEMFC
systems have the advantage over LT-PEMFC systems in that there is no need for
intense purification to remove carbon monoxide from the reformate. To reduce
270 10 Fuel cell technologies

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.

IAPUNIT project: Development of an innovative auxiliary power unit for


military purposes based on high-temperature PEM fuel cell and reforming
technology for military logistic fuels (Phase I)

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

Project partners: Fraunhofer ICT (Germany), AVL List GmbH (Austria),


Catator A.B. (Sweden), Jožef Stefan Institute (Slovenia),
National Institute of Chemistry (Slovenia), Eindhoven
University of Technology (Netherlands), Graz University
of Technology (Austria)
10.4 Direct methanol fuel cells 271

Clients: European Defence Agency, based on an agreement be-


tween the Federal Republic of Germany, the Republic of
Austria, the Kingdom of the Netherlands, the Republic
of Slovenia and the Kingdom of Sweden
Implementation: January 29, 2019 to January 28, 2021
Contact: Dr. Carsten Cremers, Fraunhofer ICT

10.4 Direct methanol fuel cells

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.

10.4.2 Stack components

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

Table 10.2 DMFC: cell reactions in acidic and alkaline cells


Acid Anode CH3 OH C H2 O ! CO2 C 6 HC C 6 e
Cathode 1:5 O2 C 6 HC C 6 e ! 3 H2 O
Total CH3 OH C 1:5 O2 ! CO2 C 2 H2 O
Alkaline Anode CH3 OH C 6 OH ! CO2 C 5 H2 O C 6 e
Cathode 1:5 O2 C 3 H2 O C 6 e ! 6 OH
Total CH3 OH C 1:5 O2 ! CO2 C 2 H2 O
272 10 Fuel cell technologies

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.

10.4.3 System components

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 Alkaline fuel cells

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.

CO2 C 2 OH ! CO2


3 C H2 O
CO2 C OH ! HCO
3

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

Table 10.3 Electrode reactions in AEMFCs and PEMFCs


Anode-side hydrogen oxidation PEMFC H2 ! 2 HC C 2 e
AEMFC H2 C 2 OH ! 2 H2 O C 2 e
Cathode-side oxygen reduction PEMFC 0:5 O2 C 2 HC C 2 e ! H2 O
AEMFC 0:5 O2 C H2 O C 2 e ! 2 OH

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 Solid oxide fuel cells

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

Fig. 10.12 Idealized visu-


alization of gas supply and
material conversion in an
SOFC. (see [7])

10.6.2 Stack components

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

Electrolyte Anode Cathode Porous Metal Substrate

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)

Glass Sealing Cover Plate

Interconnect
Cathode Plate
Contact
Cell (MEA)

Nickel mesh

Ground Plate

Fig. 10.15 Exploded view of an SOFC stack with electrolyte-supported cells

10.6.3 System components

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)

can be used (Fig. 10.17, center). Electrical preheaters and—especially in portable


devices—ignition burners are used to heat up SOFC systems. Porous substances
(in this case, silicon carbide foam prepared via pressure-less sintering, Fig. 10.17,
right) also play an important role in ensuring secure operation with good combus-
tion properties.
Heat exchangers are used for internal heat transfer. One target of thermal man-
agement in SOFC systems is to use exhaust gas heat within the system (regener-
ation) in such a way that the system is thermally self-sustaining, i.e., no further
heating is required to operate it. This makes it possible to achieve high levels of
electrical efficiency. A high degree of heat extraction is important in stationary
heat and power cogeneration facilities, for example. Usually, the exhaust gas heat
is used to preheat the cathode air as required. Therefore, the thermal management
in SOFC systems via heat exchangers must ensure efficient heat transfer while also
10.6 Solid oxide fuel cells 279

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).

M3 foundation project: developing a portable fuel cell device

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

Fig. 10.20 The portable


100 Wel eneramic® SOFC
system

The component optimization and integration achieved in this project brought


about a significant reduction in volume (approx. 69 percent) and weight (ap-
prox. 68 percent). The project participants successfully brought the required
control system and the eneramic® system (TRL 8) to production readiness.

Project partners: Fraunhofer IKTS


Implementation: January 1, 2006 to December 31, 2015
Contact: Daniela Herold, group manager, Fraunhofer IKTS

10.6.4 Operational management

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.

10.6.5 Service life and degradation

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

Fig. 10.22 Illustration of


the temperature profile in
a SOFC stack using a 3D
thermofluidic stack model,
with indicators showing the
cathode air flow. (Fraun-
hofer IKTS)

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 Molten carbonate fuel cells

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

Fig. 10.23 Diagram of an Consumer Load


individual MCFC’s mode of
e-
operation
H2 O2
CO CO2
- -
e e
CO32-
CO32-
H2
H2O O2
CO2

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

10.7.2 Stack components

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.

Fig. 10.24 Diagram of an


individual MCFC repeating
unit. When these individual
cells are stacked one on
top of another, they form
a complete stack
10.7 Molten carbonate fuel cells 285

To combat matrix degradation, stable phase-pure powders must be developed to


serve as passive matrix components. This helps to reduce coarsening. This requires
various synthesis steps. By using radiographic and nuclear magnetic resonance
spectroscopy to characterize the intermediate products, it is possible to adapt pro-
cess steps to obtain a stable powder.

Fraunhofer Attract project—INNOVELLE: Innovative ceramic layer systems


for molten carbonate fuel cells with extended long-term stability and life-
time

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:

 Fundamental analysis of MCFC degradation processes


 Reduction of matrix material coarsening
 Development of advanced processes for evaluating the electrochemical
impedance spectra of active MCFC components
 Research into new high-temperature anti-corrosion coatings for applica-
tions involving molten salts
 Research into non-stick coatings for applications involving molten salts

Project partners: Fraunhofer IKTS


Implementation: March 1, 2013 to February 28, 2019
Contact: Mykola Vinnichenko, Fraunhofer IKTS

The active components can be studied during operation in half-cell configuration


(Fig. 10.25a). To investigate electrochemical processes and the influence of vari-
ous process parameters on them, as well as the effect of degradation mechanisms
on the performance of active components, the cells are characterized using electro-
chemical impedance spectroscopy (Fig. 10.25b). Based on the impedance spectra,
classic equivalent circuit diagram modeling can be used to determine the charac-
teristic parameters at different operating conditions to show their influence on the
limiting processes (Fig. 10.25c). New methods for evaluating spectra based on the
286 10 Fuel cell technologies

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)

References
1. Schmidt T.J., Baurmeister J. (2006): Durability and reliability in high-temperature
reformed hydrogen PEFCs. ECS Transactions 3: 861–869. https://doi.org/10.1149/1.
2356204
2. Cremers C., Jurzinsky T., Meier J., Schade A., Branghofer M., Pinkwart K., Tübke J.
(2018): DEMS and online mass spectrometry studies of the carbon support corrosion
under various polymer electrolyte membrane fuel cell operating conditions. Journal of
the Electrochemical Society 165. https://doi.org/10.1149/2.0331806jes
3. Kübler M., Jurzinsky T., Ziegenbalg D., Cremers C. (2018): Methanol oxidation reac-
tion on core-shell structured Ruthenium-Palladium nanoparticles: Relationship between
structure and electrochemical behavior. Journal of Power Sources 375. https://doi.org/
10.1016/j.jpowsour.2017.07.114
4. Inaba M., Matsui Y., Saito M., Tasaka A., Fukuta K., Watanabe S., Yanagi (2011): Ef-
fects of carbon dioxide on the performance of anion-exchange membrane fuel cells,
Electrochemistry 79: 322–325
5. Siroma Z., Watanabe S., Yasuda K., Fukuta K., Yanagi H. (2011): Mathematical model-
ing of the concentration profile of carbonate ions in an anion exchange membrane fuel
cell, Journal of the Electrochemical Society 158: B682–B689. https://doi.org/10.1149/1.
3576120
6. Steele B.C.H. (1999): Running on natural gas. Nature 400, 6745: 619. https://doi.org/10.
1038/23144
7. Bove R., Ubertini S. (eds.) (2008): Fuel cells and hydrogen energy. Vol. 1: Modeling
Solid Oxide Fuel Cells: Methods, Procedures and Techniques. Reprinted. Springer, New
York, NY
288 10 Fuel cell technologies

8. Trofimenko N., Kusnezoff M., Michaelis A. (2011): Recent Development of Electrolyte


Supported Cells with High Power Density. ECS Transactions 35 (1): 315–325. https://
doi.org/10.1149/1.3570006
9. Kusnezoff M., Trofimenko N., Müller M., Michaelis A. (2016): Influence of Electrode
Design and Contacting Layers on Performance of Electrolyte Supported SOFC/SOEC
Single Cells. Materials 9 (11): 906. https://doi.org/10.3390/ma9110906
10. Nousch L., Pfeifer T., Hartmann M. (2018): Development of a Modeling Platform for
Dynamic SOFC-System Simulation in a Wide Operational Range. In: Proceedings of
the 13th European SOFC & SOE Forum (A1320), Lucerne. ISBN 978-3-905592-23-8
11. Kusnezoff M., Beckert W., Trofimenko N. et al. (2015): Electrochemical MEA Charac-
terization: Area Specific Resistance Corrected to Fuel Utilization as Universal Charac-
teristic for Cell Performance. ECS Transactions 68 (1): 2555–2563, https://doi.org/10.
1149/06801.2555ecst
12. Pfeifer T., Nousch L., Lieftink D., Modena S. (2013): System Design and Process Lay-
out for a SOFC Micro-CHP Unit with Reduced Operating Temperatures. International
Journal of Hydrogen Energy 38 (1): 431–439. https://doi.org/10.1016/j.ijhydene.2012.
09.118
13. Reuber S., Megel S., Jürgens C. et al. (2015): Application-Oriented Design and Field
Trials of the eneramic Power Generator. ECS Transactions 68 (1): 131–141. https://doi.
org/10.1149/06801.0131ecst
14. Megel S., Dosch C., Rothe S. et al. (2013): CFY Stacks for Use in Stationary SOFC and
SOEC Applications. ECS Transactions 57 (1): 89–98. https://doi.org/10.1149/05701.
0089ecst
15. Brandner M., Bienert C., Megel S. et al. (2013): Long Term Performance of Stacks with
Chromium-Based Interconnects (CFY). ECS Transactions 57 (1): 2235–2244. https://
doi.org/10.1149/05701.2235ecst
16. Bienert C., Brandner M., Skrabs S. et al. (2015): CFY-Stack Technology: The Next De-
sign. ECS Transactions 68 (1): 2159–2168. https://doi.org/10.1149/06801.2159ecst
17. Megel S., Kusnezoff M., Beckert W. et al. (2016): CFY-Stacks: Progress in Develop-
ment. In: Proceedings of the 12th European SOFC & SOE Forum (A0908), Lucerne.
ISBN: 978-3-905592-21-4
18. Nousch L., Hartmann M., Michaelis A. (2021): Improvements of Micro-CHP SOFC
System Operation by Efficient Dynamic Simulation Methods. Processes 9 (7): 1113.
https://doi.org/10.3390/pr9071113

You might also like