Journal of Power Sources 372 (2017) 204–211

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Journal of Power Sources

journal homepage: www.elsevier.com/locate/jpowsour

Frost induced damages within porous materials - from concrete technology T

to fuel cells technique
Susanne Palecki∗, Stanislav Gorelkov, Jens Wartmann, Angelika Heinzel
The Hydrogen and Fuel Cell Center - ZBT GmbH, Carl-Benz Straße 201, 47057 Duisburg, Germany

H I G H L I G H T S

• AWithout
procedure for testing the durability of MEAs under frost exposure has been developed.
• During freezing
purging severe damages could be found in dependence on the MEA design.
• Freezing phenomena
redistribution of pore water and micro-ice-lens formation take place.
• could be adopted from other porous materials.

A R T I C L E I N F O A B S T R A C T

Keywords: Porous media like concrete or layers of membrane electrode assemblies (MEA) within fuel cells are affected by a
Freeze-thaw attack cyclic frost exposure due to different damage mechanisms which could lead to essential degradation of the
Porous media material. In general, frost damages can only occur in case of a specific material moisture content. In fuel cells,
Fuel cells residual water is generally available after shut down inside the membrane i.e. the gas diffusion layer (GDL).
Freeze-thaw test methods
During subsequent freezing, this could cause various damage phenomena such as frost heaves and delamination
effects of the membrane electrode assembly, which depends on the location of pore water and on the pore
structure itself.
Porous materials possess a pore structure that could range over several orders of magnitudes with different
properties and freezing behaviour of the pore water. Latter can be divided into macroscopic, structured and pre-
structured water, influenced by surface interactions. Therefore below 0 °C different water modifications can
coexist in a wide temperature range, so that during frost exposure a high amount of unfrozen and moveable
water inside the pore system is still available. This induces transport mechanisms and shrinkage effects. The
physical basics are similar for porous media. While the freezing behaviour of concrete has been studied over
decades of years, in order to enhance the durability, the know-how about the influence of a frost attack on fuel
cell systems is not fully understood to date.
On the basis of frost damage models for concrete structures, an approach to describe the impact of cyclic
freezing and thawing on membrane electrode assemblies has been developed within this research work. Major
aim is beyond a better understanding of the frost induced mechanisms, the standardization of a suitable test
procedure for the assessment of different MEA materials under such kind of attack. Within this contribution first
results will be introduced.

1. Background widely spread commercialization of polymer electrolyte membrane fuel

1.1. Porous media - from concrete to fuel cells
During winter periods, automotive or stationary fuel cell systems
could be exposed to extreme climatic conditions, as repeated cycles
between +90 °C down to −40 °C over short periods of time combined
with high numbers of freeze-thaw cycles (ftc) are possible. For further
cells (PEMFC) their durability must be ensured even after repeated
cooling down and also rapid start from frozen conditions.
In fuel cells the existence of residual water after shut down within
the membrane or the gas diffusion layer (GDL) and the associated ice
formation at temperatures below 0 °C represent a basic problem. In
porous materials the pore structure could range over several orders of
magnitude which include pore water that possesses different properties

∗
Corresponding author.
E-mail address: s.palecki@zbt-duisburg.de (S. Palecki).

http://dx.doi.org/10.1016/j.jpowsour.2017.10.065
Received 5 September 2016; Received in revised form 17 October 2017; Accepted 19 October 2017
Available online 05 November 2017
0378-7753/ © 2017 Elsevier B.V. All rights reserved.
S. Palecki et al.
with regard to their transport and freezing behaviour. This means that
at low temperatures different water modifications could be assumed. As
a result, during cooling ice formation of the macroscopic water within
larger pores as well as redistribution of unfrozen water and shrinkage
phenomena take place. With increasing number of freeze-thaw-cycles
(ftc) growth of ice lenses and dehydration of specific pore ranges can be
regarded.
The observed phenomena can be adapted to various porous mate-
rials. Well-known and in depth investigated is the phenomenon of
micro-ice-lens formation within cementitious materials under freeze-
thaw exposure [1,2]. Concrete is a nanoporous material with a pore
system that consists of various pore categories such as macropores,
capillary pores and gelpores, in which pore water with different prop-
erties exists. The correlation between pore radius and freezing point
depression has been described by Stockhausen and Brun with the ra-
dius-freezing point-relationship [3,4]. While macroscopic water, also
known as bulk water, follows the common physical laws, pre-structured
water shows a strong freezing point depression. Below 50% r. H. only
structured water is still existent, which is available as adsorbates on the
inner surfaces within pores smaller than 2 nm. Between temperatures of
−60 °C and −120 °C the last monolayer freezes on the inner surfaces.
That means around temperatures of −20 °C a high amount of non-
frozen and moveable water still exists inside the matrix [1,2].
By means of fundamental basic research over decades of years a
standardized test procedure for concrete structures could be developed,
which guarantees a reproducible and realistic testing of the durability
of a mix design under laboratory conditions [2,5]. In contrast to this, for
fuel cells no adequate test methods for the estimation of the behaviour
of MEA systems under cyclic freeze-thaw attack exists so far, so that the
damage mechanisms are not fully understood to date.
1.2. Damage mechanisms within concrete structures due to freeze-thaw
exposure
In order to enhance the durability of concrete against frost attack,
its freezing behaviour has been studied over decades of years [e.g. 1, 2,
5]. As concrete deviates from macroscopic behaviour due to its na-
nostructure, water, vapour and ice can coexist in a wide temperature
range. This phenomenon forms the basis for the development of Setzer's
micro-ice-lens-model [1]. Due to the moving frost front under which
the coexistence of the three phases water, ice and vapour is possible, a
temperature gradient is present inside the sample. During cooling the
freezing of the macroscopic water takes place primarily while the gel
pore water, available inside smaller pores, remains unfrozen (Fig. 1).
Fig. 1. Thermodynamical model developed by Setzer [1].
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Journal of Power Sources 372 (2017) 204–211
This results into high pressure differences inside the matrix. With every
degree of supercooling this pressure is increased by 1,22 MPa [1]. Due
to these high pressures frost shrinkage within smaller pores occurs. As
consequence, water is forced out of smaller pores and accumulates
subsequently at the ice lenses within larger pores. The macroscopic ice
can be hence regarded as a valve, which retards the transport of water
from the surrounding pores to the unfrozen gel. The potential difference
between unfrozen water within smaller pores (gelpores) and ice, which
has been already formed within larger pores, leads furthermore to a
redistribution of water inside the matrix. In this context transport is
possible through both, the liquid phase as well as through inner water
films. The growing of ice lenses is also known from solid science, where
frost heave mechanisms of solids can be observed during winter per-
iods.
The thawing process is about an inverse system. A melting front
penetrates the material, followed by an expansion zone. While the
temperature rises, expansion of the gel can be observed, which still
contains unfrozen water. A suction process sets in, as the sample tries to
draw back water from the ice, which is still available in lager pores.
After reaching a critical saturation the matrix is damaged due the 9%
volume expansion of ice [1,2,5].
1.3. Characteristics of fuel cell materials
Within polymer electrolyte membrane fuel cells different materials
with great variations concerning pore structure and transport properties
are combined. PEMFC systems generally consist beside the membrane,
traditionally prepared of Nafion®, of gas diffusion and catalyst layers.
This combination implies pores with different sizes and freezing beha-
viour due to variations of the impact of surface interactions on the pore
water.
The mean pore radius of the membrane lies generally in the range of
2 nm. Within the pore structure non-freezable, freezable loosely
bounded water and macroscopic water (bulk water) are available
[7,15]. According to the literature this pore water shows a freezing
point depression of approximately −20 °C [6,8]. Here, the ice crystals
are primarily formed within the center of the perfluorosulfonic clusters
of the membrane. As a result the acid concentration within the sur-
rounding water increases, which leads in combination with the denser
pore structure to high amounts of moveable, non-frozen water inside
the membrane. Even until temperatures around −120 °C parts of this
loosely bounded water remain unfrozen [10,15]. In contrast, pores in-
corporated in the GDL, which usually consists of carbon paper, carbon
cloth or non-woven materials, are up to 1.000 times larger in size. In
many cases the GDL is assembled as a two phase layer, consisting of a
macro porous carbon layer and a micro porous layer (MPL), which is a
mixture of carbon black and a hydrophobic medium. The mean pore
diameter of the MPL is in the range of 20–500 nm [9]. After cell
shutdown, free water is predominately available inside the membrane
as well as within the cathodic gas diffusions layer, particularly under
the lands of the bipolar plates [11,12,15] or near the cathodic catalyst
layer [13,14]. Another location for water accumulation is the interface
between GDL and MPL due to the low permeability of the MPL.
1.4. Damage analysis within fuel cells in combination with a cyclic freeze-
thaw exposure
The department of Energy (DOE) prescribes for 80 kWe (net) fuel
cell system for automotive applications that they should deliver 50% of
rated power in 30 s from a cold start at −20 °C, with less than 62.5 J/
We parasitic energy input for start-up and shutdown [19]. Until 2020
they should also be able to start from −40 °C after being soaked at this
temperature for 8 h. DOE targets for an 80 kWe (net) fuel cell system for
automotive applications are summarized in extracts in Table 1.
In accordance with the technical targets given by the DOE in 2016,
PEM fuel cell systems should be able to function over a broad spectrum
S. Palecki et al. Journal of Power Sources 372 (2017) 204–211

Table 1 catalyst layer and changes within the pore structure can take place after
Extract of the technical targets of 80-kWe (net) integrated transportation fuel cell power repeated freeze-thaw exposure [10,13,15,17]. First approaches to de-
systems operating on direct hydrogena [19].
scribe the damage process by means of a degradation model for PEMFC
Characteristics Units 2015 2020 Ultimate under freeze-thaw exposure have been undertaken by different authors
Targets Targets [10,15,17].
To avoid any frost induced damages within the membrane or the gas
Cold start-up time to 50% of rated power
diffusion layer, the removal of residual water out of the cell for instance
@–20 °C ambient temperature seconds 20 30 30
@+20 °C ambient seconds < 10 5 5 by means of purging is recommended as well as the application of
temperature deicing agents after shut down. Different sources in the literature report
Start-up/shutdown cycles – 5.000 5.000 from diverse experiences and disadvantages of such measures [16,18].
durabilityb In most cases, a lower degree of damage could be noticed but the re-
Assisted start from low °C – −40 −40
lationship between moisture content and extent of damage has been not
temperaturesc
Unassisted start from low °C −30 −30 −30 stated so far. However, it is well-known that often purging of the cells
temperaturesc results into accelerated aging of the membrane and delayed startup of
PEMFCs.
a
Targets exclude hydrogen storage, power electronics, and electric drive. In most cases the previous test arrangements do not allow a precise
b
Measured according to protocol given in [19], with less than 5% decrease in voltage
temperature control inside the cell. In case of in-situ-test arrangements
at 1.2 A/cm2.
c
8-h soak at stated temperature must not impact subsequent achievement of targets. e.g. temperature control trough the cooling channels, a non-uniform
heat transfer and temperature distribution are given as also stated by
of external environmental conditions, in fact from −40° to +40 °C. other authors [6,18]. Here, completely different damage phenomena
In general, it has to be distinguished between ice formation due to could be observed due to variations within formation of micro-ice-
cyclic temperature attack and ice formation during cold start. Latter is a lenses and redistribution of water. For testing the suitability of MEA
matter of freezing of supercooled water, whereas ice is suddenly formed materials in advance, a reliable test method for this type of exposure
at temperatures far beyond the actual freezing point. The induced has to be developed with respect to real conditions.
failure mode can be separated from those which can be observed after
cyclic temperature attack. 2. Experimental
Although the number of investigations into the behaviour of fuel
cells under cyclic freeze-thaw exposure has been increased during the 2.1. Test program and boundary conditions
last years, the damage mechanisms are not fully understood to date.
Published results differ significantly from each other due to great var- In practice, fuel cells are exposed to a multiaxial temperature attack,
iations within test arrangement, test conditions and tested materials. influenced by the thickness of the insulation material and the type of
This implies minimal temperature, holding period of the minimum application. For automotive applications numerous cells are assembled,
temperature, freezing and heating rate, proceeding between the sepa- penetrated during winter periods by a migrating frost i.e. thawing front
rate cycles (e.g. air purging, interim operation), type of testing (in situ/ and an appropriated temperature gradient. For an accelerated lab test
ex situ), as well as stack design, operation time and last but not least only an extract of such a large-sized stack can be considered. By im-
MEA manufacturing processes. Especially the bonding has an important plementation of a laterally sealed short stack, a one dimensional heat
impact on the durability, as otherwise delamination phenomena could transport can be generated. This represents practical conditions as the
be advanced [11]. tested short stack can be regarded as one detail of a large-sized stack.
All in all the literature refers so far to physical damages of the Under this consideration the test arrangement as given within Fig. 2 has
membrane and the gas diffusion layer as well as significant performance been used. Here, the orientation of the temperature gradient - in-plane
and electrochemical losses. A physical damage due to frost attack can or cross-plane - has to be taken into account as water movements and
be expressed by both, a complete failure of the membrane, emerged ice formation are influenced by the direction of the migrating frost
from cracks and holes, as well as by degradation of the catalyst and/or front. As consequence a one dimensional damage front is formed inside
gas diffusion layers. Beyond this, also delamination phenomena of the the stack, according to the exposed gradient.
Under consideration of the targets given by the DOE fuel cells for

Fig. 2. Comparison of practical (left) and la-

boratory conditions (right) of fuel cell stacks for
simulation of freeze-thaw exposure. Test ar-
rangement and boundary conditions within the
chosen climate chamber.

206
S. Palecki et al.
automotive applications should withstand temperatures until −40 °C
[19]. In this context, a temperature cycle between −40 °C and a
standard ambient temperature of +20 °C has been used for accelerated
durability testing of PEMFC stacks. Continuous measurements of the
stack temperature have been carried out by means of thermocouples,
implemented at different locations inside the stack. Beside the doc-
umentation of the local stack temperature as well as the direction of the
temperature gradient, also phase transitions of the pore water could be
detected on the basis of this data. After some reference measurements
between liquid and air cooled test arrangements, a standard climate
chamber has been chosen for easier handling, respected that the
chamber guarantees an even temperature distribution and precise ad-
herence of minimum temperature. Besides this, investigations of the
influence of various variation parameters like minimum temperature,
soaking time and freezing/thawing rate on the damage behaviour of
PEMFC stacks have been conducted. These measurements have been
performed on liquid cooled 5 cells stacks with an active area of 50 cm2,
representing a typical stack size for lab testing. The basic stack design
has been defined as standard for continuing investigations so that only
the MEA setup will be varied in the future for the assessment of its
suitability. However, for the analysis of the impact of the freezing
conditions on the damage mechanisms, one type of a commercial MEA
has been used (see Table 2). The damage analysis and stack perfor-
mance have been carried out by different test methods (Table 3).
2.2. Temperature measurements during freeze-thaw cycling
The received results from the variation of the boundary conditions
and the recorded temperature data led to a fixing of a freezing/thawing
rate of 10 K/h and a soaking time of 4 h at Tmin, Tmax. Each cycle lasts
20,15 h with minimum temperature of −40 °C ( ± 1 K) in the center of
the stack and an air temperature of −42,5 °C ( ± 1 K) respectively. This
cycle guarantees appropriate time span with respect to water move-
ments inside the cells as well as complete freezing and thawing of the
stack center. Fig. 3 shows the run of the air temperature inside the
climate chamber as well as the temperature within cell 3. The ther-
mocouples have been inserted through small insulated holes inside the
cooling channels of the bipolar plates and brought close to the surface
of the GDL. The stack has been exposed to freeze-thaw cycling without
purging of the cells and with in-plane isolation. Intervals of 5 cycles
have been applied in between operation of the stack.
From this figure the phase transition of the pore water of the MEA
could be clearly identified. During the first freeze-thaw cycle of a stress
interval two distinctive ice formation peaks could be noticed. The first
phase transition of the macroscopic water takes place with a moderate
freezing point depression of −5 °C. The second peak occurs around a
temperature of −9 °C. These two peaks represent the formation of
micro-ice-lenses and the evidence of pre-structured water or pore water
with stronger freezing point depression, as it is the case within smaller
pores inside the denser structures of the MEA layers. During the second
Table 2
Applied stack and MEA design for fixing of boundary conditions.
Component Parameter
Stack Number of cells 5 ftc the stack has been operated as described above without purging of
Torque 2 Nm/screw
Active area 50 cm2
BPP End plate material aluminum
BPP material carbon-based compound
Flow field multi-channel parallel
meander
Channel width/depth 1 mm/1 mm
Membrane/MEA Membrane material/ Nafion®/20,3 μm
thickness
MEA Design 5 layers with subgasket; GDE
Pt loading 0.2 mg/cm2
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Journal of Power Sources 372 (2017) 204–211
ftc this additional peak is already no longer evident. This corresponds to
findings made during tests on concrete. An explanation for this beha-
viour could be the lack of water transports during the thawing phase,
when relaxation of the system takes place because of increasing tem-
perature. Here, the return transport of water seems to be disabled or
retarded by the pore structure, so that the distribution of the water
inside the various layers is different compared to the previous situation.
As expected, a hysteresis between freezing and thawing takes place. The
thawing of the pore water inside the MEA can be observed around 0 °C.
With increasing number of operations and intervals of ftc, the
amount of freezable water tends to be higher compared to the starting
situation, which could be seen from more decisive phase transitions
(Fig. 4). This leads to the conclusion that changes inside the pore
structure i.e. between the layers have been already occurred. Within
Fig. 4 an identical standard stack has been tested with variation of the
amount of ftc per frost interval. In this case the stack has been operated
after each ftc. After 8 ftc first leakage of the membrane could be already
observed as also visualized by infrared camera screening after dis-
sembling of the separate MEAs. With this test method pin holes or
cracks within the active area of the MEA could be detected due to
passage of hydrogen and the associated exothermal reaction. Those
defects are represented through hot spots or hot zones.
The formation of ice particles has been tried to detect by means of a
confocal microscope. During the 30th freeze-thaw cycle the MEA of cell
1 has been removed from the stack at an air temperature of −42.5 °C.
In Fig. 5 it can be seen that several ice lenses have been formed inside
the porous structure of the GDL under the channels. After melting of
these lenses, empty spaces are left which could have a direct impact on
the pore structure of the GDL. It is questionable if these areas will un-
dergo a relaxation after end of ftc cycling.
2.3. Operation and performance measurements
The testing of the MEA inside the defined standard stack included
also intervallic operations of the stacks. This implied at first the in-
itialization of each stack until steady-state performance of the stack is
achieved. The boundary conditions can be taken from Table 4. At the
same time, a reference stack has been operated in addition in order to
distinguish between aging of the stacks due to repeated operation and
because of frost exposure.
After the initialization process, the first operation interval could
start with running at 0.4 A/cm2 for 1 h. The polarization curves have
been recorded and single-cell electrochemical impedance spectroscopy
measurements have been carried out at each operating point. This was
followed by further operation at 0.4 A/cm2 for 10 min and a shutdown
procedure, including N2 purging of the cooling channels. The in-
troduced results have been received without purging of the cells
themselves e.g. by means of dry gases.
In case of three identical polarization curves, frost exposure has
been started. For this step, the stack was removed from the test stand
and laterally sealed with polystyrene (EPS). The time span between
stack operation and installation inside the climate chamber has been
limited to 15 min in order to prevent influences due to environmental
conditions. Fig. 6 shows the polarization curves of an in-plane frost
exposed test stack with single ftc intervals. This means that after each
the cells. From these curves it could be seen that even after the first
interval decisive performance losses could be already identified for this
type of MEA. The used MEA design corresponds to the previous in-
troduced setup (Table 2) and has been chosen with respect to fixing of
boundary test conditions rather to performance criteria.
The single evaluation of the polarization curves showed an influ-
ence of the frost exposure on the cell position. The used degradation
factor as exemplarily given within Fig. 6b point out severe performance
losses of cell one while for cell three only slight changes could be no-
ticed. This depends certainly on the direction of the temperature
S. Palecki et al. Journal of Power Sources 372 (2017) 204–211

Table 3
Overview of applied test methods.

Parameter Test method

Pore size distribution Mercury intrusion porosimetry (MIP)

Freezable water content, freezing point
Material structure, structural damages, distribution of ice lenses
Defects/pin holes, hot spots
Reduction of PTFE coating (GDL)
Composition of catalyst layer, distribution of catalyst particles
Chemical analysis of product water
Stack performance, electrochemical resistance
Differential scanning calorimetry (DSC)
Scanning electron microscopy (SEM), confocal microscopy
Permeation of hydrogen, infrared camera screening (IR)
Measurement of contact angle
Energy dispersive X-ray spectroscopy (EDX)
Inductively coupled plasma mass spectrometry (ICP-MS)
Polarization curve, electrochemical impedance spectroscopy (EIS), high frequency resistance (HFR)

gradient. In the case of cross-plane alignment the performance losses

are higher but the differences between the cells are lower. This em-
phasizes that the testing of single cell stacks as well as stacks with
multi-axial heat transfer do not lead to related results.

2.4. Initial state and damage analysis of the MEA materials

Besides the fixing of the climatic boundary conditions and perfor-

mance testing, also different methods for detection of the damage
phenomena as well as for initial state analysis have been applied and
checked with respect to their suitability (Table 3). Fig. 7 gives an ex-
ample of the development of the pore structure before start of operation
as well as after several amounts of ftcs. After 30 ftcs a slight shifting of
the pore size distribution in the range of mesocapillary pores could be
found. Carbon fiber fractures or rearrangement of PTFE inside the pores
but also expansion of the GDL material could be responsible for this Fig. 4. Freezing peaks within another in-plane exposed standard stack during 1st, 3rd,
7th and 8th freeze-thaw cycle. The curves represent the temperature under the land
observation. In addition a higher pore volume could be found after 30
within lower part of cell 3 at the surface of the GDL, 2 cm from the surface of the stack.
ftc, indicating changes within the GDL but also MPL layer or rather at The stack has been operated after each cycle.
the boundary to the catalyst layer. Changes of the pore size distribution
imply also a shifting of the freezing point of the pore water and could
result into variations of the amount of residual as well as freezable membrane is affected by pin holes and imprints, the catalyst layer has
water. This could explain the increase of the phase transition peak been separated from the MPL in the region of the land. Parts of this
during temperature measurements inside the climate chamber. layer could be found on the membrane. Latter shows in the range of the
The examination of the structural conditions of the separate layers channels to some extent bulges, probably because of shrinkage and
of the introduced MEA design could verify that during freeze-thaw swelling effects. This can be also seen by curling or buckling of the
cycling, ice formation takes place even at the surface of the membrane, complete membrane after disassembly of the MEA layers.
presumably at the border to the catalyst layer. In case of in-plane Defects within the remaining parts of the catalyst layer, still ar-
alignment, most frost induced effects could be seen on the cathode. The ranged in the channel region on the surface of the MPL, result from
SEM pictures in Fig. 8 show different types of damages. While the local ice formations. The CL/MPL layer shows partly severe damages at

Fig. 3. Temperature distribution within an in-plane exposed stan-

dard stack during freeze-thaw cycling. The given curve represents
the temperature inside cell 3 of the stack. The thermocouple was
positioned at the border of the cathodic flow field of the BPP in
2 cm depth at the surface of the GDL.

208
S. Palecki et al. Journal of Power Sources 372 (2017) 204–211

Fig. 5. Ice formation of macroscopic water inside the GDL under

the channel, some few minutes after stack removal at −42,5 °C out
of the climate chamber. Pictures are taken by means of confocal
microscope. Left: Colour range 0–250 μm, right: wrong coloured
extract, colour range 0–400 μm. (For interpretation of the refer-
ences to colour in this figure legend, the reader is referred to the
web version of this article.)

Table 4
Operation parameters.

Parameter Unit Normal operation U/I characteristic

Electrical load A 20 2- Imax

Gas flow rate anode l/min 1,39 3,33
Gas flow rate cathode l/min 3,5 8,33
Stoichiometry λ (A/C) – 2/2 2/2
Stack temperature °C 60 60
Rel. moisture gassing % ∼ 100 ∼ 100

the border to the land, especially in the lower part of the stack, where
water accumulations are rather increased. The carbon fibers of the
subjacent GDL broke through the MPL and could also be responsible for
pin holes inside the membrane. Here, the edge of the land seems to be
more critical. During ice formation and growing of ice lenses the related
Fig. 7. MIP measurement of stressed MEA assemblies after 0ftc (initial state), 17 ftc and
volume expansion produces high stresses predominantly in the channel 30 ftc with slight shifting of mesocapillary pore content and increase of total pore volume.
regions on the structure of the CL/MPL. In dependence on the amount
of freezable water and the formed ice lenses inside the CL/MPL or at the
border between MPL and GDL, a critical amount of moisture content

Fig. 6. In-plane frost exposed test stack with the presented MEA
design and without prior purging of the cells. a) Polarization curves
at start of frost exposure (0ftc) and after single ftc intervals in-be-
tween periods of operation (1-5ftc). b) Introduction of degradation
factor at 30 A in dependence on the amount of ftcs. Operation with
a stack- and gas temperature of 332 K (stack
temperature:ΔT < +3 K; gas temperature: ΔT < +/−1 K),
φ = 100%, operating points: 50, 45, .., 5, 2, 0 A).

209
S. Palecki et al.
Fig. 8. SEM analysis of the introduced MEA design (GDE (CL/MPL)) after 30 ftcs and interval stack operation without purging of the cell. 5 cycles per interval have been applied.
could be received inside the pore structure, leading to micro cracking of
the CL and further fracture of the denser MPL. On the opposite side of
the GDL this could be seen in terms of frost heaves. The described da-
mage types correlate with observations made by other authors and
correspond to own experiences made on concrete.
3. Conclusions and outlook
During a cyclic freeze-thaw exposure a frost and thawing front mi-
grate into the material, followed by the formation of a temperature
gradient. This involves high pressures inside the system because of the
coexistence of water, ice and vapour. With regard to fuels cells and the
wide range of different pore sizes, it can be also assumed that during
freezing a redistribution of water and local ice lens formation take place
as it is the case within concrete structures. Furthermore, shrinkage
processes within smaller pores are the consequence. During thawing a
melting front penetrates the material which is combined with an ex-
pansion zone, resulting into a suction process during which water is
drawn back along the melting front.
For cementitious materials the damage mechanisms and transport
phenomena are meanwhile well-known and verified by experimental
studies. In contrast to this, the knowledge about frost damage beha-
viour of membrane electrode assemblies within fuel cells is not suffi-
ciently. Furthermore, the to date published observations regarding
damage types and phenomena differ significantly from each other due
to great variations within the test arrangement and further proceeding.
This also implies that to some extent the chosen test setups do not
guarantee a practical and reproducible simulation of this type of ex-
posure. In order to assess the suitability of a MEA or stack design during
winter times a precise test procedure has to be developed.
Under these aspects, investigations have been carried out in order to
answer open questions concerning the influence of boundary conditions
on the damage behavior of PEMFC stacks.
By means of one MEA design the boundary conditions have been
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Journal of Power Sources 372 (2017) 204–211
fixed so far with respect to given targets. Different test methods have
been used for detailed analysis of the origin and stressed MEA perfor-
mance and material properties. Without purging of the cells severe
damages could be found within the various layers, depending on the
used MEA design. Failure modes could be found in terms of delami-
nation of CL, formation of pin holes and cracks inside the membrane as
well as significant performance losses. This paper only gave an extract
of these results. For detailed description of the damage mechanisms it is
necessary to incorporate various types of MEA designs into the test
program as this is another important variation parameter. The so far
received results indicate that the tested MEA design represents an as-
sembly with low freeze thaw durability. Running investigations with
different composition of MEA materials show much lower degree of
damages.
Nevertheless, the presented results verify that the theoretical
background and the appearing freezing phenomena can be adopted
from other porous materials. Further investigations will be carried out
with variation of the MEA components and material combinations in
order to give a comprehensive overview of the relevant damage me-
chanisms. For future comparison of cyclic freeze-thaw data of PEMFCs a
well-defined testing procedure with consideration of practical condi-
tions is essential.
Acknowledgement
The results have been received within the framework of the research
project “Development of a standardized test procedure for the assess-
ment of the damage behavior of membrane-electrode-assemblies of
polymer electrolyte fuel cells under cyclic freeze-thaw exposure” (No.
18224N), which has been funded by the German Federation of
Industrial Research Associations (AiF).
S. Palecki et al. Journal of Power Sources 372 (2017) 204–211

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