Guiyab, Jim Pauline C.

Hugo, Krizelle Ann B.

BS Chemistry 4-1

2011-02597-MN-0
2011-00051-MN-0
Prof.
Dalton
R.
Fortin

Anti-corrosion of Metal-based
Bipolar Plates on Proton
Exchange Membrane Fuel Cells

Outline
I.

Introduction
a. PEM Fuel Cell
i. Definition and background
ii.
Parts of the PEM fuel cells
b. Bipolar Plates
II.
Mechanism
III. Environmental and Operational Factors Affecting Metal Bipolar Plates
IV.
Anti-corrosion of metal bipolar plates on fuel cells
a. Plate material
b. Plate coating

I.

Introduction

Proton Exchange Membrane Fuel Cells

Fuel cells are power conversion devices that transform the chemical
energy stored in form of a fuel and an oxidant directly into electrical energy
through clean and efficient electrochemical oxidation processes. One of the
most developed type of fuel cell used is the Proton Exchange Membrane or
the Solid Polymer Fuel Cells.
A PEM fuel cell is an electrochemical cell that is fed hydrogen, which is
oxidized at the anode, and oxygen that is reduced at the cathode. These
PEMFCs were developed by General Electric in the United States in 1960s for
use in the Gemini space flights by NASA.
Advances in this technology were stagnant until the late 1980s when
the fundamental design underwent significant reconfiguration. Possibly, the
most significant barrier that PEM fuel cells had to overcome was the costly
amount of platinum required as a catalyst.

Parts of PEMFC
At the heart of the PEM fuel cell is the membrane electrode assembly
(MEA). The MEA is pictured in Figure 2. The MEA consists of a proton
exchange membrane, catalyst layers, and gas diffusion layers (GDL).
Typically, these components are fabricated individually and then pressed to
together at high temperatures and pressures. MEA is typically sandwiched by
two flow field plates that are often mirrored to make a bipolar plate when
cells are stacked in series for greater voltages. The bipolar plate constitutes
the structural backbone of the fuel cell assembly normally absorbing the
greater cost of a fuel cell.
The electrolyte in the PEM is a solid polymer in which protons are
mobile. Most common theme used is the use of sulphonated fluoropolymers,
usually fluoroethylene (Figure 3).

Figure 1. Schematic diagram of a single typical PEMFC

Figure 2. An example of a membrane electrode assembly (MEA).

Bipolar Plates
In a fuel cell, the voltage
produced is quite small, about

Figure 3. Example structure of a sulphonated fluoroethylene.

0.7 V. To produce a useful voltage many cells have to be stacked in series.

One way to do this is to connect the edge of each anode to the cathode of
the next cell. But the problem with this method is that the electrons have to
flow across the face of the electrode to the edge. If each cell is operating at
0.7 V, even a small voltage drop is important so unless the current flow is
very low, or the electrode is a good conductor, or very small, this method is
not used.
A

bipolar

plate (Figure

4)

is

used

for

much

better

cell

interconnection. This makes connections all over the surface of one cathode
and

the

anode

of

the

next

cell

(hence

bipolar); at the same time, the bipolar plate serves as a means of feeding
oxygen to the cathode and fuel gas to the anode.
Bipolar plates serves there purposes: separation of the fuel and
oxidant gases, rigidity for the MEA, and electron flow through the fuel cell
stack. From a cost perspective, inexpensive metals such as stainless steel
and aluminum could easily be processed into bipolar plates. Because bipolar
plates take up almost 80% of the mass of the fuel cell, thin nature of the
metal substrate allows for smaller stack designs with reduced weight.

Figure 4. Single cell, with end plates for taking current from all over the face of the electrodes.
Figure 5. Two bipolar plates of very simple design

II.

Mechanism

III.

Environmental and Operational Factors Affecting Metal

Bipolar Plates

Electrolyte

Corrosive

Operational Parameters Affecting

Typical Corrosion

Environment

Metal Corrosion

Reactions

sulfuric acid
aqueous
containing

polymer,

PE
M

protonconducting
electrolyte

fluoride ions
pH range 0-3.5
0.1-1M H2SO4
1-5 ppm F other anions:
2-

2-

CO3 , HCO3 ,
SO4 , HSO4 ,
SO32-

IV.

high power density operations

(1.0-1.5 W/cm2)

solutions
solid

operating at <100C

strong oxidizing and humid

uniform
electrochemical
dissolution
metal oxide
film

atmosphere at the cathode-side

(high vapour and O2
concentrations)

formation
pitting/pinhole
attack

large cathode overpotential (at

galvanic

ca. 0.6V (SCE))

reducing anode atmosphere
(high H2 concentration)
negligible anode overpotential
(at ca. -0.1V (SCE))

coupling
membrane and
electrocatalyst
poisoning
by ion leaching

Anti-corrosion of metal bipolar plates on fuel cells

In PEMFC, both chemical and electrochemical corrosion may
erode the metallic plates. Also, the metallic bipolar plates losing
electrons may result in dissolution of metallic ions which may poison
the MEA. On the cathode, metallic oxide grows due to recovery
reaction by gaining the electrons. It may increase the surfaces
electrical resistance.
Here are some of the developments on the anti-corrosion of
metal bipolar plates on fuel cells.

A. Plate Material
Material

Corrosion Rate (m/year)

Aluminum

~250

Copper

>500

Gold

<15

Graphite

<15

Nickel

>1000

Silver

<15

Tin

>10000

Titanium

<100

Tungsten

<100

Zinc (Zincate)

>2000

Gold-nickel

~500

Phosphorus Copper

~500

Phosphorus Nickel

<30

Stainless Steel

<100

Tin-Zinc

---

Zinc-Nickel

---

B. Plate Coating
Few are adaptable to bipolar plate coatings since the mechanism
for corrosion protection is the rapid formation of a stable surface
oxide (passivation) which prevents further corrosion. Unfortunately,
such oxides are usually not conductive which departs from the high
conductivity requirement of PEMFC bipolar plates.
Surface Modifications

any means useful to alter the properties of a near-surface

region without adding new layers.

Single-Layer Coatings

A wide range of distinct coating processes has been used

to form protective/conductive single layers, mostly based
on cladding, plating, thermal deposition and polymerization
of composite coatings. Nitride, carbide, oxide, metal alloys

and polymer-based composites are the most frequently

employed coating layers.
Multi-Layer Coatings

normally based on the use of overlay coatings (overcoat)

on the top of a porous, but well adherent inner coating
layers

References
Frangini, S., & Zaza, F. (2011). Anti-Corrosion Methods for Fuel Cell Metal
Bipolar Plates: A Review of Recent Patent Literature. Recent Patents on
Corrosion Science, 93-107.
Larminie, J., & Dicks, A. (2003). Fuel Cell Systems Explained. West Sussex,
England: John Wiley & Sons.
Lee, S.-J., Huang, C.-H., & Chen, Y.-P. (2003). Investigation of PVD coating on
corosion resistance of metallic bipolar plates in PEM fuel cell. Journal of
Materials Processing Technology, 688-693.
Lee, S.-J., Huang, C.-H., Lai, J.-J., & Chen, Y.-P. (2004). Corrosion-resistant
component for PEM fuel cells. Journal of Power Resources, 162-168.
Lister, S., & McLean, G. (2004). Review: PEM Fuel Cell Electrodes. Journal of
Power Resources, 61-76.
Woodman, A. S., Anderson, E. B., Jayne, K. D., & Kimble, M. C. (1999).
Development of Corrosion-Resistant Coatings for Fuel Cell Bipolar
Plates. Massachussetts: American Electroplaters and Surface Finishers
Society.