Designing a New Ionomer from Scratch - Pushing Polypoms to the Limit
James L. Horan,
a
Mei-Chen Kuo,
a
Sonny Sachdeva,
a
Hui Ren,
c
Andrew S. Perdue,
a
Steven F. Dec,
b
Michael A. Yandrasits,
d
Steven J. Hamrock,
d
Matthew H. Frey,
c
and
Andrew M. Herring.
a
a
Department of Chemical Engineering, Colorado School of Mines, Golden, Colorado
80401, USA
b
Department of Chemistry and Geochemistry, Colorado School of Mines, Golden,
Colorado 80401, USA
c
3M Corporate Research Materials Laboratory, 3M Center Bldg., St. Paul, MN 55144,
USA
d
3M Fuel Cell Components Program, 3M Center, St Paul, MN 55144, USA
We have fabricated proton conducting films using monomers
based on vinyl substituted silicotungstic acid heteropoly acids
(HPAs) and acrylate co-monomers. In this work we probe the
limits of this system based on increasing the weight loading of the
HPA to 85 wt%. Although impressive proton conductivities can
be achieved with these films under hotter and drier operating
conditions than in conventional proton exchange membranes, the
materials have mechanical limitations. We show that very
different film morphologies can be prepared based on whether or
not the film is polymerized thermally or by UV light. In general
the UV cured films have superior proton conductivity, but have a
linear morphology resulting in a brittle film. The thermally cured
films have a clustered morphology with good mechanical attributes
but have poor proton conductivity.
Introduction
Proton exchange membrane (PEM) fuel cells are still the most desirable component of
future zero emission, high efficiency automobiles. However, their unit cost, ease of
operation, and reliability must be reduced which includes eliminating the humidifier from
the fuel cell system. Currently the commercial proton exchange membrane (PEM) is
fabricated from a perfluorosulfonic acid (PFSA) polymer such as Nafion
®
. Unfortunately
PFSA ionomers must be fully hydrated to achieve their maximum proton conductivities
and practical levels of proton conductivity can only be achieved in vehicles operating at
an inlet RH of 80% which still necessitates the use of a humidify and undesirable
complex water management and recovery. To achieve the goal of a PEM that can operate
at temperatures from freezing to 120ºC using dry inlet gases it will be necessary to
develop new PEMs that are based new chemistries.
The heteropoly acids (HPAs) are a class of inorganic oxides that have some of the
highest solid state proton conductivities known at room temperature, although the actual
proton conductivity achieved depends strongly on the hydration state of the HPA (1, 2).
In previous work we have shown that the HPAs have very high proton conductivities at
room temperature and can be operated at ambient conditions in a fuel cell using dry gases
(3). Importantly we demonstrated that some of the protons in HPA have very impressive
ECS Transactions, 25 (1) 1101-1107 (2009)
10.1149/1.3210663 ©The Electrochemical Society
1101
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