Overview of Fuel Cell MEAs

at Los Alamos National Laboratory

By
John Davey, M. Wilson, J. Valerio, and G. Bender

1st Symposium on MEA Manufacturing, Dayton 8/05

Two Basic Types of MEAs

Are Made in Limited Numbers at LANL

At Los Alamos National Laboratory (LANL), membrane electrode

assemblies (MEAs) are made in small quantities for single cell
and small stack basic research investigations.

Two basic types of MEAs are used at LANL carbon supported

catalyst thin film electrodes on polymer electrolyte membranes
(PEMs) for H2/Air fuel cells and unsupported catalyst thin film
electrodes on PEMs for direct methanol fuel cells (DMFCs).

1st Symposium on MEA Manufacturing, Dayton 8/05

Hydrogen Fuel Cell MEA

4 H + + 4e + O2 2 H 2 O
Cathode Flow Channel

Air (O2)

Cathode GDL/MPL
Cathode Electrocatalyst Layer
H+

H2O

e-

Ionomer Membrane
Anode Electrocatalyst Layer

Anode GDL/MPL
Anode Flow Channel

H 2 2 H + + 2e

1st Symposium on MEA Manufacturing, Dayton 8/05

H2

Load

Hydrogen Fuel Cell MEA Fabrication

Make Carbon Supported
Catalyst, TBA Ionomer Ink

Paint and Oven Dry Decals:

Repeat Until Desired Catalyst
Loading Achieved

Clean and Cation

Exchange PEM to Na+ Form.
Dry on Heated Vacuum Table
For decal Hot Pressing

Hot Press Decals

Onto the PEM
Cation Exchange PEM
w/Electrodes to H+ Form

Insert PEM w/Electrodes and Gas

Diffusion Layers (GDLs) [the MEA]
into Fuel Cell Hardware for Testing

1st Symposium on MEA Manufacturing, Dayton 8/05

Making Carbon Supported Catalyst, TBA Ink

* Measure out desired amount of 5% Nafion 1100EW
solution (Solution Technologies) into a vial & record
the weight (e.g. 1.0 g)
* Add 20 wt% Pt carbon supported catalyst, 2.5 X dry
weight Nafion e.g. 2.5 X 1.0/20= 0.125 g, and stir
with stir bar for at least 1 hour. (E-Tek C2-20 20 wt%
Pt XC-72R)
* Add glycerol, half the amount of 5% Nafion
solution , e.g. 0.5 g, and stir for at least 15 minutes.
* Cation exchange the solubilized Nafion to TBA+ form.
Add Tetra Butyl Ammonium hydroxide (TBA-OH)
in 1 M methanol, 50 mg per gram of 5% Nafion
solution, using a micropipette or syringe (e.g. 50 mg X
1.0 = 50 mg). Stir for at least 1 hour.
* Add glycerol again, half the amount of 5% Nafion
solution , and stir for at least 24 hours.

1st Symposium on MEA Manufacturing, Dayton 8/05

Paint and Oven Dry Decals

* Clean fiberglass reinforced Teflon (Furon) decal
blanks (5, 25, 50, or 100 cm2 sizes) with isopropanol and dry them.
* Lightly spray them with a Teflon release agent
and, when they are dry, label them and record
their weights.
* With an appropriate sized camel hair brush, paint
a coat of catalyst ink on one side of each decal
and put them in a 140C drying oven for at
least 1 hour.
* Remove the decals from oven, check their
weights and repeat the painting (paint 90 to
previous direction) and drying until the desired
loading is achieved (typically 0.2 mg Pt/cm2,
14.3% of the dried ink is Pt). The final weighing
should be after a minimum of 24 hours drying.
1st Symposium on MEA Manufacturing, Dayton 8/05

Clean and Cation Exchange PEM to Na+ Form.

Dry on Heated Vacuum Table for Hot Pressing
* Cut Nafion 112 PEM to the desired size.
* Clean the membranes by boiling them in a 3%
H2O2 solution for 1 hr., rinsing with DI H2O, and
boiling in DI H2O for another hour.
* Exchange membranes to Na+ form by boiling in
a 1% NaOH solution for 1 hr., rinsing with DI
H2O, and boiling in DI H2O for another hour.
* Store the membranes in DI H2O, until needed
for hot pressing.
* Dry membranes for hot pressing by placing wet
membranes on a heated vacuum table that is at
room temp., heat to 130C for 5 10 minutes,
cool to room temp. with vacuum still on, remove,
and store in plastic bags for hot pressing.

1st Symposium on MEA Manufacturing, Dayton 8/05

Hot Press Decals Onto the PEM

* The painted side of two decals are placed facing
each other on either side of a dried Na+ form
membrane. The decal/membrane assembly is
enveloped between two Furon sheets with a thin,
high durometer silicone rubber sheet outside one
of the Furon sheets to assure even pressure
distribution. This whole assembly is situated within
a hinged stainless steel holder.
* The stainless steel holder is placed in a 210C
preheated hot press and compressed to 110 lbs/cm2
of decal area for 5 min., removed from the press,
and cooled with a weight on the stainless steel
holder.
* The decals are then peeled away from the
membrane leaving the catalyst electrodes fused
to the membrane.

1st Symposium on MEA Manufacturing, Dayton 8/05

Cation Exchange PEM w/Electrodes to H+ Form

* Boil PEM w/Electrodes in 0.5 M H2SO4 for 1 hr.
* Rinse PEM w/Electrodes with DI H2O and then
boil in DI H2O for 1 hr.
* Dry the protonated PEM w/Electrodes on a heated
vacuum table at 60C for 15 minutes, cool to room
temperature under vacuum, remove, and store in
plastic bag for fuel cell assembly.

1st Symposium on MEA Manufacturing, Dayton 8/05

Insert PEM w/Electrodes and GDLs, the MEA,

Into Fuel Cell Hardware For Testing
* GDLs are cut to fit the particular size electrodes.
(Anodes of all sizes and 5 cm2 cathodes: E-TEKs
2-sided GDL LT 2500W; all other cathodes:
E-TEKs 1-sided ELAT V2.1 Type 20)
* Gaskets are cut for the particular size MEA
and fuel cell hardware. We typically use a 0.010
thick fiberglass reinforced silicone rubber anode
gasket and a 0.010 thick Furon cathode gasket.
We also put a 0.001 thick windowed Teflon
hydrogen crossover barrier on each side of the
MEA.
* The components are assembled in the appropriate
order in the fuel cell hardware.
* The fuel cell is ready for testing.

1st Symposium on MEA Manufacturing, Dayton 8/05

Typical H2/Air Fuel Cell Performance

2

Polarization Curve For Typical 0.2 mg Pt/cm

H2/Air Fuel Cell

(Cell 80C; H2: 160 sccm, 105C, 30 psig; Air: 500 sccm, 80C, 30 psig)

1.0

Voltage (volts)

0.8

0.6

0.4

0.2

0.0
0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

Current Density (amps cm-2)

1st Symposium on MEA Manufacturing, Dayton 8/05

1.6

1.8

Features of H2/Air Fuel Cell Inks and MEAs

The ink is a smooth homogeneous mixture in which the carbon/catalyst

particles remain in suspension due to the low density of the 20 wt% Pt
carbon supported catalyst and the high viscosity of the glycerol which
also effectively wets the carbon/catalyst particles.

The low concentration of Pt on the carbon support and low evaporation

rate of the glycerol allow for oven drying of the transfer decals, without the
complication of spontaneous combustion.

The 20 wt%Pt on XC-72 carbon : Nafion ionomer ratios in the electrodes

are 2.5 : 1 by weight and 1.8 : 1 by volume.

With the electrode decal transfer technique, the exact catalyst loading can
be determined.

The TBA+ exchanged ionomer (Nafion ) in the electrodes becomes

thermoplastic during hot pressing and flows, making effective contact
with the catalyst particles and a good bond to the membrane. It also
imparts a robust pseudo crystalline structure to the ionomer in the
catalyst layer.

1st Symposium on MEA Manufacturing, Dayton 8/05

Direct Methanol Fuel Cell

CH 3OH (aq)

O 2 (Air), H2O
eH 2O
CH 3OH

CH 3OH + H 2O

6 H + + 3/2 O 2 + 6 e-

H+
CO 2 + 6 H + + 6 e-

H 2O

Electroosmotic
drag

Anode

Cathode

Anode: Pt-Ru black, ~80 m2/g Cathode: Pt black, ~28 m2/g

Membranes: Nafion 117, 115, 1135

CH3OH(l) + 3/2 O2 2 H2O(l) + CO2

V = 1.21 V (at 25C)

G = - 702.5 kJ mol-1 = 6.1 kWh kg-1

1st Symposium on MEA Manufacturing, Dayton 8/05

DMFC MEA Fabrication

Make Unsupported Pt-black
Cathode Ink

Clean and Cation

Exchange PEM to H+ Form

Paint Cathode Ink Directly on PEM

Held on a Heated Vacuum Table,
then Cure and Cool
Make Unsupported Pt/Ru-black
Anode Ink

Flip-Over the PEM w/Cathode and

Paint On the Anode Ink. Then Cure,
Cool, and Remove the PEM w/Electrodes

Insert the PEM w/Electrodes and the

Gas Diffusion Layers(GDLs) [the MEA]
into the Fuel Cell Hardware for Testing

1st Symposium on MEA Manufacturing, Dayton 8/05

Make Unsupported Pt-black Cathode Ink

* Measure into a vial/jar the amount of Pt-black
catalyst (Johnson Matthey HiSpec 1000) needed for
the desired loading (typically 6 mg Pt/cm2) and the
size and the number of cathodes to be painted. A
waste factor also is included.
* Add DI H2O, 10 X catalyst wt., and sonicate this
mixture in a ice bath for 10 min.
* Add 5% Nafion 1100EW solution, such that dry
Nafion will be 10 wt% of the dry electrode, and
again sonicate in an ice bath for 10 min.
* Weigh out the appropriate amount of ink into a
vial/jar for the desired loading (waste factor
included) of each cathode to be painted, cap the
vial/jar, and store it in an ice bath for painting.

1st Symposium on MEA Manufacturing, Dayton 8/05

Clean and Cation Exchange PEM to H+ Form

* Cut the Nafion 117 PEM to the desired size.
* Clean the membranes by boiling them in a 3%
H2O2 solution for 1 hr., rinsing with DI H2O, and
boiling in DI H2O for another hour.
* Exchange the membranes to H+ form by boiling in
a 0.5 M H2SO4 solution for 1 hr., rinsing with DI
H2O, and boiling in DI H2O for another hour.
* Store the membranes in DI H2O, until needed
for direct painting on the membranes.

1st Symposium on MEA Manufacturing, Dayton 8/05

Paint Cathode Ink Directly on PEM Held on a

Heated Vacuum Table, then Cure and Cool
* Place wet, pre-cut Nafion 117 membrane(s) on a room
temperature vacuum table with a porous Teflon sheet
beneath it. Place a white silicone mask over the
membrane(s) covering all but the electrode areas to be
painted. Tape the edges of area to be painted.
* Turn on the vacuum and heat the vacuum table to 70C
for painting. Turn on the infared lamp directed on
vacuum table.
* With the appropriate size camel hair brush, paint all the
cathode ink in the vial/jar onto membrane. Apply
numerous thin coats (about 20), successively at 90 to
each other. Each coat should be dry before the
subsequent coat is applied.
* Set the vacuum table to 80C for 20-40 min. of curing
turn off the heat and allow the table to cool to room
temperature with the aide of a fan.
1st Symposium on MEA Manufacturing, Dayton 8/05

Make Unsupported Pt/Ru-black Anode Ink

* Measure into a vial/jar Pt/Ru-black catalyst (Johnson
Matthey HiSpec 6000) needed for the desired
loading (typically 10 mg Pt-Ru/cm2) and the size
and the number of anodes to be painted. A waste
factor is included.
* Add DI H2O, 10 X catalyst wt., and sonicate this
mixture in a ice bath for 10 min.
* Add 5% Nafion 1100EW solution, such that dry
Nafion will be 15 wt% of the dry electrode, and
again sonicate in an ice bath for 10 min.
* Weigh out the appropriate quantity of ink into a
vial/jar for the desired loading (waste factor
included) of each anode to be painted. Cap the
vial/jar and store it in an ice bath for painting.

1st Symposium on MEA Manufacturing, Dayton 8/05

Flip-Over the PEM w/Cathode and Paint On the Anode Ink.

Then Cure, Cool, and Remove the PEM w/Electrodes
* Flip-over the PEM w/cathode, mask with the silicone
sheet, turn on the vacuum, and heat the vacuum
table to 70C for painting.
* Paint all of the anode ink, in the vial/jar onto the
masked membrane, using an appropriate size camel
hair brush, . Apply numerous thin coats (>30),
successively at 90 to each other. Each coat should
be dry before the subsequent coat is applied.
* Set the vacuum table to 80C for 20-40 minutes of
curing; turn off the heat and allow the vacuum table
to cool to room temperature with the aide of a fan;
turn off the vacuum, remove the PEM w/electrodes,
and store in a plastic bag until needed.

1st Symposium on MEA Manufacturing, Dayton 8/05

Insert PEM w/Electrodes and GDLs, the MEA, into

Fuel Cell Hardware for Testing
* Cut GDLs to fit the particular size MEA.
(Anodes: E-TEKs ELAT 1-sided V2.02 || Cathodes:
E-TEKs 2-sided GDL LT 2500W)
* Cut gaskets for the particular size MEA and fuel cell
hardware. This is typically a 0.010 thick fiberglass
reinforced silicone rubber anode gasket and a
0.010 thick Furon cathode gasket. Also, put a
0.001 thick Teflon MeOH crossover barrier, with
an electrode window, on each side of the MEA.
* Assemble the components, in the appropriate order,
in the fuel cell hardware.
* The fuel cell is ready for testing.

1st Symposium on MEA Manufacturing, Dayton 8/05

Typical DMFC Fuel Cell Performance

Cell 80C, 100 cm2 ; MeOH:14 ml min-1 ; Air: 900 sccm, 0 psig
1.0

Voltage (volts)

0.8

0.6

0.4

0.2

0.0
0.0

0.1

0.2

0.3

Current Density (amps cm-2)

1st Symposium on MEA Manufacturing, Dayton 8/05

0.4

Features of DMFC Fuel Cell Inks and MEAs

To achieve optimum performance in DMFCs, high catalyst loadings are

required: 5 mg Pt/cm2 on the cathode and 10 mg Pt-Ru/cm2 on the anode.

Supported catalyst are not used because, at the high catalyst loadings
necessary for good performance, the electrodes are so thick that mass
transport limitations dominate.

The primary solvent in the inks is H2O because spontaneous combustion

can occur in the presence of concentrated, finely dispersed catalyst and
organic solvents, particularly during the electrode drying process.

These high density unsupported catalyst, H2O-based inks do not form the
smooth homogenous consistency of the H2/Air fuel cell ink. The DMFC ink
must be painted directly after being made because the dense catalyst
particles are progressively settling out.

TBA+ exchange of the ink ionomer is problematic. The TBA-OH in 1 M

MeOH solution causes agglomeration of the ink catalyst in these H2Obased inks. We are working on a solution for this.

1st Symposium on MEA Manufacturing, Dayton 8/05

Features of DMFC Fuel Cell Inks and MEAs (contin.)

Pt/Ru catalyst is used on the anode because the Ru catalyzes the

disassociation of H2O, at a lower overpotential, providing OH- for the
oxidation of the CO intermediate to CO2. With Pt alone, this is the rate
limiting step and the fuel cell operates at lower cell voltages.

Methanol crossover from the anode to the cathode wastes methanol and
competes with protons at the cathode resulting in a mixed potential effect
that can lower the cell potential by as much as 100 mV.

Cathode Pt-black electrode : Nafion weight ratio is 9 : 1 and volume ratio

is 0.84 : 1.00. The anode electrode Pt/Ru-black : Nafion weight ratio is
5.67 : 1.00 and volume ratio is 0.67 : 1.00

1st Symposium on MEA Manufacturing, Dayton 8/05

Brush Painting Application Method

Advantages* It is simple
* Complex apparatus is not needed
* Quantity of waste is small
* Efficient for making small numbers of MEAs
Disadvantages* Uniformity of catalyst over the electrode is
not always good with same painter and
between painters may be worse
* Prohibitive requirement of man hours at
scaled-up production levels
* Waste might become significant at scaledup production

1st Symposium on MEA Manufacturing, Dayton 8/05

Decal Transfer Application Method

Advantages* It is easy to achieve more precise catalyst
loadings
* Numerous decals could be painted (sprayed or
roller applied) side by side increasing
production and reducing over-painting waste
* Lends itself to hot pressing, which produces a
robust electrode that is strongly bonded to the
PEM
Disadvantages* It is a slow, many step process painting
decals, drying decals, hot pressing decals,
protonating PEM w/electrodes, and drying PEM
w/electrodes
* It may be difficult to automate for scaled up
production

1st Symposium on MEA Manufacturing, Dayton 8/05

Doctor Blading Application Method

Advantages* Good catalyst uniformity using a
reproducible process
* Reduced number of coats required
Disadvantages* Automation may require expensive
apparatus
* Nature of the ink must be such that it can
be applied and dried in small number of
thicker coats without any sacrifice of
performance
* May not be the best method for
automated production

XRF Image of Pt Distribution on

Anode of Segmented MEA

(ten equivalent 7.7 cm2 segments)

1st Symposium on MEA Manufacturing, Dayton 8/05

Doctor Blading Application Method (2)

Equivalent VIR Curves for the Different Segments
of the Segmented Fuel Cell
1.0

Cell Voltage / V

0.9

0.8

Seg01,
Seg02,

Seg06
Seg07

Seg03,

Seg08

Seg04,

Seg09

Seg05,

Seg10

0.7

0.6
Anode: 810 sccm H2 , TA=105C, p=30psig

0.5

Cathode: 4000 sccm Air, TC=80C, p=30psig

Cell temp. = 80C, 0.2 mg Pt/cm2 at each electrode

0.4
0.0

0.2

0.4

0.6

0.8

Current density / A cm-2

1st Symposium on MEA Manufacturing, Dayton 8/05

1.0

1.2

Ultrasonic Spraying Application Method

Advantages* Good catalyst distribution uniformity
* Good reproducibility
* Good application for numerous thin coats of
ink
* Lends itself to automation (computer
controlled positioning of spray nozzle)
Disadvantages* Complex and expensive
* Not good for ink mixtures where the
components may easily separate out (e.g.
not good for our DMFC inks)
* Catalyst waste may be significant if spraying
masked PEMs rather than adjacent transfer
decals

1st Symposium on MEA Manufacturing, Dayton 8/05

Publications
[1] M. Wilson and S. Gottesfeld, High performance catalyzed membranes of ultra-low Pt
loadings for polymer electrolyte fuel cells, J. Electrochem. Soc., 139, L28 (1992).
[2] M. Wilson, J. Valerio and S. Gottesfeld, Low platinum loading electrodes for polymer
electrolyte fuel cells fabricated using thermoplastic ionomers, Electrochimica Acta,
40, 355 (1995).
[3] P. Zelenay et al. US Patent 6,696,382 B1, 2/24/2004
[4] G. Bender, Characterizing Spatial Conditions Within a PEFC Using the Segmented Cell
Approach, Technical University of Munich, 2005

1st Symposium on MEA Manufacturing, Dayton 8/05

Acknowledgements

Thanks to the DOE EERE Hydrogen Program, managed by Nancy Garland,

for funding of fuel cell research at LANL over the years

Thanks to the LANL fuel cell team for all their contributions in developing
the MEA fabrication process over the years

1st Symposium on MEA Manufacturing, Dayton 8/05