Electron Beam Induced Radiation Damage in the Catalyst Layer of a
Proton Exchange Membrane Fuel Cell
QIANPING HE,
1
JIHUA CHEN,
2
DAVID J. KEFFER,
3
AND DAVID C. JOY
2,3
1
Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, Tennessee
2
Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee
3
Department of Materials Science and Engineering, University of Tennessee, Knoxville, Tennessee
Summary: Electron microscopy is an essential tool for
the evaluation of microstructure and properties of the
catalyst layer (CL) of proton exchange membrane fuel
cells (PEMFCs). However, electron microscopy has one
unavoidable drawback, which is radiation damage.
Samples suffer temporary or permanent change of the
surface or bulk structure under radiation damage, which
can cause ambiguity in the characterization of the
sample. To better understand the mechanism of
radiation damage of CL samples and to be able to
separate the morphological features intrinsic to the
material from the consequences of electron radiation
damage, a series of experiments based on high-angle
annular dark-field–scanning transmission scanning
microscope (HAADF-STEM), energy filtering trans-
mission scanning microscope (EFTEM), and electron
energy loss spectrum (EELS) are conducted. It is
observed that for thin samples (0.3–1 times l),
increasing the incident beam energy can mitigate the
radiation damage. Platinum nanoparticles in the CL
sample facilitate the radiation damage. The radiation
damage of the catalyst sample starts from the interface
of Pt/C or defective thin edge and primarily occurs in the
form of mass loss accompanied by atomic displacement
and edge curl. These results provide important insights
on the mechanism of CL radiation damage. Possible
strategies of mitigating the radiation damage are
provided. SCANNING 36:338–346, 2014.
© 2013 Wiley Periodicals, Inc.
Key words: STEM, EELS, radiation damage, catalyst
layer, PEMFC
Introduction
Proton exchange membrane fuel cells (PEMFCs) are
considered to be one of the most promising energy
conversion devices for applications such as mobile and
stationary power supply due to their high energy
conversion efficiency, fast start up and low/zero
emission level (Cheng et al., 2004; Yu et al., 2012).
However, there are several technological challenges
impeding their broader commercialization. For exam-
ple, the functionality and structure of the catalyst layer
(CL) located in the membrane electrode assembly
(MEA) need to be optimized for an effective utilization
of the precious metal catalysts (Xie et al., 2005) and
better water management in MEAs (Eikerling, 2006).
The CL is the component where electrochemical
reaction, ionic/electronic conduction, and reactant gas
transport are taking place simultaneously during
operation (Sun et al., 2010). Characterizing the
microstructure of the CL helps to elucidate microstruc-
ture-related process occurring during operation and
degradation mechanisms contributing to PEMFC per-
formance loss.
Transmission electron microscopy (TEM) and scan-
ning electron microscopy (SEM) are essential and
powerful analytical and imaging techniques for the
evaluation of microstructural and microchemical
changes that determine fuel cell performance stability.
Many research groups take advantage of TEM and SEM
in investigating the microstructural changes in the MEA
of PEMFC (Akita et al., 2006; Ma et al., 2009; Ficicilar
et al., 2010; Mamat et al., 2010; Choi et al., 2011).
However, while providing useful nanoscale informa-
tion, the electron beam used in SEM and TEM can cause
temporary or permanent change in the surface or bulk
structure of the specimen (Egerton et al., 2004),
especially for soft materials such as Nafion (Mauritz
Contract grant sponsor: National Science Foundation; contract grant
numbers: DGE-0801470, OCI 07-11134.5.
Address for reprints: David C. Joy, Department of Materials Science
and Engineering, University of Tennessee, Knoxville, TN 37996
E-mail: djoy@utk.edu
Received 23 May 2013; Accepted with revision 28 June 2013
DOI: 10.1002/sca.21117
Published online 29 July 2013 in Wiley Online Library
(wileyonlinelibrary.com).
SCANNING VOL. 36, 338–346 (2014)
© Wiley Periodicals, Inc.