PROTON EXCHANGE MEMBRANE FUEL CELLS:

UNDERSTANDING PROTON CONDUCTANCE ON A

NANOSCALE
AFM Phase

AFM Current

50 nm

Nicholas Economou and Steven K. Buratto

Department of Chemistry and Biochemistry; CNSI
University of California, Santa Barbara

PROTON EXCHANGE MEMBRANE FUEL CELLS

Rela+ve to current, i.e. fossil fuel based,
energy conversion technologies:
Advantages

PEMFC

High eciency (40 to 50%)

High power density
Rapid response to varying loads
Low opera+ng temperature (<100 C)
Disadvantages
Expensive
Catalyst and membrane

Chemical Energy

FC

Electrical Energy

Low duty cycle

chemical and mechanical stability

Thermal Energy

Mechanical Energy

Applications of PEM Fuel Cells

Proton exchange membrane fuel cells

Membrane

F
O

Proton exchange
membrane

CF3

Nafion

O
S
n

Proton exchange membrane fuel cells

Membrane Electrode
Assembly
(MEA)

Electrode

Membrane

Electrode

Carbon cloth
electrode

Proton exchange membrane fuel cells

Electrode

Membrane

Electrode

500 um

Carbon cloth gas diusion layer

Proton exchange membrane fuel cells

~50 nm
Electrode

Membrane

Electrode

= Pt catalyst (~5 nm)

100 nm

Carbon supported pla<num catalyst layer

Fuel cell performance depends on

proton conduc<on and catalysis
O2 (g) + 4H+(aq) + 4e-

Pt

H2O(l)

e-

Cathode

Membrane
H+

e-

H+

H+
e-

e-

2H2 (g)

e-

Pt

e-

4H+(aq) + 4e-

= Pt catalyst (~5 nm)

100 nm

H+

Anode

Image the surface domains responsible for proton transport

Atomic Force Microscopy (AFM)
Tapping mode phase imaging

Phase shifts related to tip-sample power dissipation

amplitude

time

Chemical
information

Nafion 212 at Ambient Conditions (30 75% RH)

1050 g equivalent weight
AFM Phase Image
50 um thick
= hydrophilic
= hydrophobic

102
98 deg

19.4% hydrophilic

94

Ave domain = 94nm2

10.9 nm diameter
50 nm

ODea, J.R., Buratto, S.K. J. Phys. Chem. B2011,115, 10141020

Controlled Relative Humidity Environment

2-98% Relative Humidity
Humidified or dry N2

Closed fluid cell allows for varying

RH imaging

?
20 nm

Phase image of Nafion

45% RH

Nafion Under Dehydrated Conditions

Phase

Height

50 nm

Vacuum dried at 90C for 3 days, imaged at 3% RH

Only 5% hydrophilic domains!
ODea, J.R., Economou, N.J., Buratto, S.K. Macromolecules2013, 46 (6), 2267 - 2274

Morphology of hydrated Nafion (98% RH)

Schmidt-Rohr and
Chem, Nat. Mat., 2008.

Hydrated Nafion membrane

500 nm
Height

-1.5 nm

1.5 nm

500 nm
Phase

45

75

ODea, J.R., Economou, N.J., Buratto, S.K. Macromolecules2013, 46 (6), 2267 - 2274

Conductive Probe AFM (contact mode)

How does morphology influence proton conduction?

Cathode:
O2(g) + 4H+ + 4e- 2H2O(l)

Anode:
2H2(g) 4H+(aq) + 4e-

We can control temperature, relative humidity, gas flow

rates, bias voltage

current

NANOFC
CAFM OF HYDROGEN FUEL CELL

H2 IN

H2 OUT

Current imaging of half fuel cell under hydrated

conditions (98% RH)

Height

Current

ODea, J.R., Economou, N.J., Buratto, S.K. Macromolecules2013, 46 (6), 2267 - 2274

Creating a Model for Fibrils from AFM Data

Ambient conditions (height)

Hydrated conditions (height)

(phase)
Increasing H2O

80 nm

hydrophobic

hydrophilic

Fibril features have hydrophobic skin and water center

80 nm correlation length (79 + 48)

Comparing AFM to X-ray Scattering Data

Increasing H2O
0.00785-1

80 nm

Increasing H2O
Ultra small angle scattering data agrees well with AFM images
at high relative humidity
Rubatat et al. Macromolecules, 2004, 37, 7772 - 7783

Short Side Chain (SSC) PFSA Membranes

Hyflon Ion E87-05 (SSC)
875 E.W.

Short side chain PFSAs are candidates for high

T/Low RH operation
Better crystallinity, mechanical properties
How does the morphology of these materials
compare to Nafion under extreme conditions?

Nafion 212
Phase (50% RH)
19.4% hydrophilic
102
98
94
50 nm

Ave domain = 94nm2

10.9 4 nm diameter

deg

20% hydrophilic
Hyflon Ion E87-05
25.6% hydrophilic
106
103
100
deg

50 nm

25% hydrophilic

Ave domain = 119nm2

12.3 5 nm

Nafion 212

Phase (3% RH)

Phase (50% RH)

Phase (95% RH)

50 nm

5% hydrophilic

20% hydrophilic

40% hydrophilic

Hyflon Ion E87-05

50 nm

12% hydrophilic

25% hydrophilic

32% hydrophilic

3M Multi-Acid Side Chain Ionomers

More

acid groups = more proton conductivity

More side chains = less crystalline
Made from same sulfonyl amine precursor as PFSA,
does side chain modification change morphology?

3M PFSA

3M PFIA

Schaberg et al. ECS transactions 2010

3% RH

10.9% hydrophilic

50% RH

95% RH

22.8% hydrophilic

36.7% hydrophilic

100nm

3.8 % hydrophilic

21.2% hydrophilic

34.0% hydrophilic

Conductive Imaging as a Function of T and RH

100C, 27% RH

25C, 80% RH

3M PFIA

140C, 6% RH

0 pA

0 pA

300 pA

0 pA

1.3 nA

3M PFSA

5 pA

2 m
0 pA

2 pA

0 pA

80 pA

0 pA

300 pA

Current Distributions by Temperature

825 E.W. PFSA

625 E.W. PFIA

25C (80%RH)
80C (40% RH)
100C (27%RH)
120C (15% RH)
140C (6%RH)
160C (3% RH)

PFIA shows higher average currents across all RH/temps

PFIA can maintain some conductivity up to 150C, while
PFSA is non-conductive at 130C

Economou et al. In Preparation

CONCLUSIONS
AFM

is a sensitive technique for mapping the pore

structure at the surface of polymer electrolyte
membranes
At low RH Nafion loses its pore structure and after
extensive dehydration, rearranges
Under high RH and flooded conditions fibril features
form on the Nafion surface, which have a reverse
micelle structure
SSC Membranes maintain higher hydrophilic surface
area at low RH and undergo less structural
rearrangement at conditions relevant to fuel cell
operation
The 3M polymers show better water retention at low
RH, the PFIA is especially well suited for low RH/
high T operation

Acknowledgements
Nick Economou
Dr. Jimmy ODea
Army Research Office
NSF Chemistry
NSF Graduate Research
Fellowship - Nick
Asylum Research
3M

Comparison of Morphological Data on Nafion

AFM phase

TEM

SAXS Model

20 nm

20 nm

94 nm2
domains

80 nm2
domains

52 nm2
domains

Hydrophilic domain size compares well to

TEM but larger than SAXS model
Elliott, J. A. et al. Soft Matter, 2011

Imaging Nafion with AC-mode C-AFM

200 nm
0 nm

20 nm

Height

90

120

Phase

0pA

Current

Allows simultaneous collection of current and phase

Also allows us to resolve individual channels in current
image
Reduces current by at least 1 order of magnitude

3pA

Surface vs. Bulk Phase Images

Surface

Cross-Section

Nafion

Individual domains are comparable in size

Increased clustering
Increased hydrophilic surface area 20% -> 32%

200 nm

Cross-Sectional Imaging
Surface

Cross-section

1 m

1 m

Cryofractured N212 membrane in water

Worm-like morphology exists in the interior of the membrane

Conductive AFM shows fibril formation

3M PFIA 625 E.W.

3M PFSA 825 E.W.

5 m

0 pA

60 pA

0 pA

100 pA

With these polymers, pre-treatment (100C) does not induce

fiber formation, but hot-pressing (130C) does