In this paper we present the results of potentiostatic single
cell cold start-up measurements under isothermal conditions
at−10 ◦C. The current density is increasing very fast after initial
start-up and later it decays towards zero. This behaviour
is ascribed to freezing of product water in the cathode. To
find out the main influencing operational parameters on the
cold start behaviour, statistic methods are used. Finally, a
statistic-based prediction model of the current decay during
isothermal cold start was developed.
To get a deeper insight into the dynamic processes in
the cathode during cold start-up dynamic electrochemical
impedance spectroscopic analyses were done, which show
that the membrane/contact resistance as well as the charge
transfer resistance is changing with the amount of produced
water.
Impedance spectroscopy at 80 ◦C was also used by Cho et
al. to find out changes of single fuel cell characteristics by ex
situ thermal cycling. The author concludes that the contact
resistance in the fuel cell is increasing after thermal cycles
because of worse contact between the membrane and the
electrode, whereas the membrane ionic conductivity itself
is not affected [6]. The impact of ex situ thermal cycling on
the degradation of Nafion® membranes was examined by
McDonald et al. It is reported that the ionic conductivity and
the mechanical properties are hardly changing. However,
opening up of the molecular structure of the polymer in
connection with enlargement of hydrophilic areas was found
[7]. Cappadonia et al. investigated Nafion® membranes by
thermal cycling and it was found that two different water
environments exist below 0 ◦C. Water phase transition
depends on the water content in the membrane. Higher water
contents lead to larger pore diameters in the membrane
and therefore to a lower freezing temperature of water.
In water-rich samples phase transitions were observed at
260K [8].
Nevertheless, performance degradation can be observed,
as described in [6,9]. A degradation rate of about 2.8% at
80 ◦C and 0.6V per-freeze-thaw cycle down to −10 ◦C is
observed as well as a reduction of about 6% per thermal cycle
of the electrochemical active surface area of the cathode.
It was found that the pore size distribution in the electrode
changes to larger pores by thermal cycles.
Our measurements with cylic voltammetry (CV) also
show degradation of the cathode electrode surface by isothermal
sub zero operation, and furthermore changes in hydrophobicity
of both, the microporous layer (MPL) and the
gas diffusion layer (GDL) on the cathode side. We finally
also found performance degradation at 450mV and 30 ◦C of
more than 5% per each cold start experiment.