Application of Electrochemical Impedance

Spectroscopy for Fuel Cell Characterization

Dr. Norbert Wagner
DLR, Institut fr Technische Thermodynamik, Stuttgart
Kronach Impedance Days 2010
Kloster Banz, April, 14
th
16
th
, 2010
Presentation outline
Introduction and motivation
Examples of porous (technical) electrodes
Theory and models of porous gas diffusion electrodes
Impedance models
Application of Ghrs porous electrode model
EIS measured at PEFC
EIS measured during oxygen reduction on silver in alkaline
solution
Outlook
Experimental set up for EIS applied for stack measurements
Electrochemical kinetic and electrode structure
-100
-80
-60
-40
-20
0
20
40
60
80
100
-80 -55 -30 -5 20 45 70
Overvoltage / mV
C
u
r
r
e
n
t

d
e
n
s
i
t
y

/

m
A
c
m
-
2
i
0
= 1 mAcm
-2
i
0
= 10 mAcm
-2
b = 25 mV/decade
HER
HOR
Butler-Volmer equation

for

hydrogen

oxydation

(HOR)

and hydrogen

evolution

reaction

(HER)

2
i = 100 mAcm
-2
Increasing power output (P=IU)

at constant cell voltage (overvoltage) by:

enlargement of active electrode surface

using porous electrodes (electrode structure)

increasing i
0

(electrode material with high

catalytic activity)
I= Surfacei= Surfacei
0

exp{(RT/zF)}
Field of application of porous electrodes
Batteries

and supercaps
Process

fluids
Hydro-
gen
GDE
Packed

bed

cathode Membrane
Auxiliary

supply
Current

collector
Water purification

and treatment

(Bio)-Organic

synthesis
Fuel

Cells
O
2 2
H
O
2 2
H O,
membrane
reactionlayer
diffusionlayer
flowfield/current collector
electrons
l c i o e e e tr cal p w r
r t n p o o s
a h d
anode
c t o e
NaCl
Cl
2
H
2
O
NaOH, H
2
Cl
-
Na
+
OH
-
+ -
Electrolysis

(Water, NaCl, etc.)
Fuel cell overvoltage and current density / voltage characteristic

Cathode
q
d
+(q
r
)
P
o
t
e
n
t
i
a
l
Current density (Current/Surface)
q
0, Cathode
q
ct,C
q
d
+(q
r
)
q
ct,A

Anode
Cell Voltage (U
C
)
q
O
Hydrogen Oxidation Reaction (HOR):
q
H
2
= RT/2F i/i
*
Oxygen Reduction Reaction (ORR):
q
O
2
/air
= RT/[(1-o)2F] [ln i - ln i
*
]
Ohmic loss
q
O

= iR
Transport limitation (diffusion)
q
d
= -

RT/2F ln (1 - i/i
lim
)
Fuel cell voltage
U
C
= U
0
- q
ct,H
2
- q
ct,O
2
/air
- q
d
-

q
O
U
0

0
Cathode
Schematic representation of main types of fuel cells
AFC
80 C
PEM
80 C
PAFC
200 C
MCFC
650 C
SOFC
1000 C
O
2
H
2
Alkaline
FC
Phosphoric
Acid
FC
Molten
Carbonate
FC
Solid
Oxide
FC
Polymer
Electrolyt
Membrane
FC
H
2
OH
-
H
+
H
+
CO
3
-
O
2
-
O H O
2 2
H H O
2 2
O H O
2 2
H H O
CO CO
2 2
2
H H O
CO CO
2 2
2
CO O
2 2
O
2
Current
Load
Oxidant
Anode
Temperature
Charge carrier
in electrolyte
Cathode
Fuel gas
Measuring methods used for fuel cell and fuel cell
components characterization : in-situ und ex-situ
methods
In-situ measuring methods
Current-voltage characteristic (U(i))
Electrochemical Impedance Spectroscopy (EIS)
Local and time resolved
Cyclic Voltammetry (CV)
Current interruption (CI))
Chronopotentiometry (CP) und Chronoamperometry (CA)
Current density distribution
Ex-situ measuring methods used for fuel cell and fuel cell
components characterization
Scanning electron microscopy (SEM) and Transmission electron microscopy
(TEM)
Energy dispersive X-ray spectroscopy (EDS)
X-ray photoelectron spectroscopy (XPS)
X-Ray Diffraction (XRD)
Thermal gravimetric analysis (TGA)
Porosimetry (Hg-Porosimetry)
Measurement of the specific surface area (BET-measurement)
Determination of gas permeability
Electrochemical Impedance Spectroscopy:
Application to Fuel Cells
Current I
U/I - Characteristic
of a Fuel Cell
C
e
l
l

v
o
l
t
a
g
e

U
Potential excitation signal - E(t)
C
u
r
r
e
n
t

r
e
s
p
o
n
s
e

s
i
g
n
a
l
-

I
(
t
)

Electrochemical Impedance Spectroscopy:
Application to Fuel Cells
Schematic diagram of the U-i characteristic of PEFC
and Electrochemical Impedance Measurements
C
e
l
l

v
o
l
t
a
g
e
Current density
Ruhespannung (ohne Stromflu)
i
Anode U
R
ac
An
A
A
=
) (
i
Cathode U
R
ac
Cath
A
A
=
) (
i
Cell U
R
c d
Cell
A
A
=
) (
Ai
AU(Cell)
U-i measured
i

n
U
n
AU = iR
M
Cathodic
Overvoltage
Anodic
Overvoltage
The Metal-Electrolyte Interface
The Metal-Electrolyte Interface
Double layer

capacity

(C
dl

)
+ -
The Metal-Electrolyte Interface
Double layer

capacity

(C
dl

)
Faraday-Impedance

(Z
F

)
Impedance spectra of a simple electrochemical
system (Z
F
=R
ct
): Nyquist representation
Imaginary part / O
Real part / O
0
-8
-6
-4
-2
2
10 3 7
R
ct

=10 O
C
dl

=1 mF
R
el

=1 O
2tf
max

=e
max

=1/C
dl

R
ct
R
el
R
el

+R
ct
f
max

=15.9 Hz
R
ct
Impedance spectra of a simple electrochemical
system (Z
F
=R
ct
): Bode representation
R
el

=1O
R
ct

=10 O
C
dl

=1 mF
2tf
max

=(1/R
ct

C
dl

)(1+R
ct

/R
el

)
1/2

at e=2tf=1: Z
C

=1/C
dl
(------)

Phase Impedance /
Frequency / Hz
0
20
40
60
80
1
2
5
10
10m 100m 1 10 100 1K 10K
R
el

+R
ct
R
el
R
ct
f
max

=52.8 Hz
R
el
Schematic representation of different steps during
electrochemical reaction as a function of distance
from electrode surface





Red
bulk
Mass
transport
n e
-

Ox
ad
*
Red
ad
*
Charge
transfer
Ox* Ox* Ox
bulk
Red* Red*
Mass
transport
Chem.
reaction
Chem.
reaction
Adsorption
Ads.
Des.
Des.
Electrode Double layer Reaction layer Diffusion layer
Ox + ne
-
Red
Multi-layer Gas Diffusion Electrodes
with different porous layers
Carbon-PTFE

Layer
(Dry

sprayed)
Ag-PTFE Layer
(Rolled

Layer)
SEM micrograph of a cross section of SOFC
Anode
Electrolyte
Cathode
SEM micrograph of a porous silver membrane
R = electrolyte resistance inside the pore per unit length
C = interface capacitance per unit length
Simple pore model of interface charging
RC-transmission line of a flooded pore
RC i
C i
R
i Z e
e
e coth ) ( =
i
m
a
g
i
n
a
r
y

p
a
r
t

/

O
real part / O
0
-3
-2
-2.5
-1
-1.5
-0.5
-1 -0.5 0 0.5 1 1.5 2
C=500mF
Pore
Nyqusit representation of Impedance of RC-
transmission line, model of a flooded pore
R
C
R = 3

C = 0.5 F
RC i
C i
R
i Z e
e
e coth ) ( =
R
0
R
0

= R/3 = L/3r
2

= specific

electrolyte

resistance
r = pore

radius
L = pore

lenght
L
r
100 mHz
Nyqusit representation of porous electrode
impedance with faradaic impedance element
i
m
a
g
i
n
a
r
y

p
a
r
t

/

O
real part / O
0
-3
-2
-2.5
-1
-1.5
-0.5
-0.5 0 0.5 1 1.5 2 2.5
C=500mF
C+Rpor(3 Ohm)
C//R(1.5 Ohm)
r
c r
ct
r = 3 O
c = 500 mF
r
ct

= 1.5 O
Simple pore model with faradaic

processes in pores

RC-transmission line of a flooded pore
Theory of Agglomerated Electrodes
metal side
electrolyte side
ionic
current
Gas (backing) side
electrolyte side
ionic
current
M. Eikerling, A.A. Kornyshev, E. Lust, J. Electrochem. Soc., 152 (2005) E24

m
Z
Z
e

met al electrolyte pores
porous l ayer
Z
s1
Z
sn
Z
si
Z
pn
Z
pi
Z
p1
Z
q1
Z
qi
Z
qn
H. Ghr in Electrochemical Applications/97, www.zahner.de
Cylindrical homogeneous porous electrode model (H. Ghr) I
Cylindrical homogeneous porous electrode model (H. Ghr) II
Ions (H
+
, OH
-
,..)
I I


P
o
r
e

E
l
e
c
t
r
o
d
e
,

p
o
r
o
u
s

l
a
y
e
r

Electrolyte
Z
q

Z
p
Z
S

Z
o

Z
n

Current (e
-
)
q s p Z Z Z + ) ( Z* =
Z Z
Z Z
p s
p s

+ ( )
Z
#

=
C = cosh S = sinh
Z Z
Z
p s +
|
\

|
.
|
*
Z Z
Z
p s +
|
\

|
.
|
*
P = q
0

= v =
s p
p
Z Z
Z
+
Z
Zo
* Z Z
Z
p s +
*
q
n

=
Z
Zn
*
s = = 1-p
Z
Z Z
s
p s +

+ + +
+ + +
C C p s S p q
s
q
S q q C q q
n o
n o n o
( ) ( )
( ) ( )
1 2
1
2
2
Z = Z
#
+Z*
Authors Reference Model and system
J. -P Candy, P Fouilloux, M. Keddam, H.
Takenouti
Electrochim. Acta, 26(1981) 1029 Ni in alkaline solution
R. De Levie Electrochim. Acta, 8(1963) 751 Transmission line model,
J.S. Newman and C.W. Tobias J. Electrochem. Soc., 109(1962) 1183 Steady-state
J. Giner, C. Hunter J. Electrochem. Soc., 116(1969) 1124 Flooded-agglomerate model, Pt-GDE, OCR in
alkaline solution
K. Mund, F.v. Sturm Electrochim. Acta, 20(1975) 463 HOR on Ni in alkaline

solution
S. Sunde, Electrochim. Acta, 42(1997) 2637 Composites, SOFC
P. Bjrnbom Electrochim. Acta, 32(1987) 115 Steady state model
R. Holze, W. Vielstich J. Electrochem. Soc., 131(1984) 2298 OCR in alkaline

solution
T.E. Springer, I.D. Raistrick J. Electrochem. Soc., 136(1989) 1594 Flooded-agglomerate and thin film model,
differential element of a pore wall
H. Ghr Poster ISE Erlangen, 1983 Homogeneous porous model, Pb

in sulfphuric

acid
G. Paasch, K. Micka, P. Gersdorf Electrochim. Acta, 38(1993) 2653 Macrohomogeneous

porous electrode model
W. Scheider J. Phys. Chem., 79(1975) 127 Model with pore branching
S. Srinivasan, H. D. Hurwitz, J. O'M Bockris J. Chem. Phys., 46(1967) 3108 Thin

film model
M. Kramer, M. Tomkiewicz J. Electrochem. Soc. 131(1984) Stochastic approach with interpenetrating
network
A. Winsel, E. Bashtavelova J. Power Sources, 73(1998) 242 Agglomerate-of-spheres model
M. Tomkiewicz, B. Aurian-Blajeni J. Electrochem. Soc. 135(1988) 2743 True effective medium approach
H. Keiser, K.D. Beccu, M.A. Gutjahr Electrochim. Acta, 21(1976) 539 Various geometries of single pore, Ni-GDE
Brief Overview of Porous electrode models and
Applications
Electrochemical Impedance Spectroscopy:
Experimental Set-up
Electrochemical

workstation
PEFC
Flow

contoller
Pressure

regulator
Humidifier
Bode diagram of measured EIS at
different cell voltages (current densities) I
Phase
o
Impedance / O
Frequency / Hz
0
20
40
60
80
10m
30m
100m
300m
1
3
10m 100m 1 10 100 1K 10K 100K
O

E=1024 mV; I=0 mA

E=841 mV; I=1025 mA
A

E=597 mV; I=9023 mA
+

E=317 mV; I=17510 mA
Bode diagram of measured EIS at
different cell voltages (current densities) II
Phase
o
Impedance / mO
Frequency / Hz
0
20
40
60
80
10
20
15
30
50
10m 100m 1 10 100 1K 10K 100K
Diffusion
R
M
Charge transfer

of ORR
O

V=597 mV; i=400 mAcm
-2

V=497 mV; i=530 mAcm
-2
A

V=397 mV; i=660 mAcm
-2
+

V=317 mV; i=760 mAcm
-2
Charge
transfer

of
HOR
N. Wagner, K.A. Friedrich, Dynamic Operational Conditions. In: J. Garche, C. Dyer, P. Moseley, Z. Ogumi, D. Rand and B. Scrosati, editors.

Encyclopedia of Electrochemical

Power Sources, Vol. 2. Amsterdam: Elsevier, 2009, pp. 912-930
Common Equivalent Circuit for Fuel Cells
C
dl,a
R
M
R
ct,a
C
dl,c
R
ct,c
Z
diff
Z
diff
Diffusion

of H
2
EIS at Polymer Fuel Cells (PEFC):
Common equivalent circuit and boundary case
C
dl,a
R
M
R
ct,a
Porous electrode with pore
electrolyte resistance (R
por
)
and
surface layer resistance (R
S
)
C
dl,c
R
ct,c
C
N
R
N
C
dl,a
R
M
R
ct,a
C
dl,c
R
ct,c
Equivalent

circuit

of the PEFC: anode and cathode

simulated

without

pores, without

diffusion

(valid

for

example

at lower

current

densities)
Bode diagramm of the EIS, measured at the PEFC at
80C, symmetrical gas supply of the cell
Phase
o
Impedance / O
Frequency / Hz
0
20
40
60
80
10m
100m
1
10
10m 100m 1 10 100 1K 10K 100K
O
2
/O
2
H
2
/H
2
EIS at Polymer Fuel Cells (PEFC):
Contributions to the cell impedance at different current densities
0
0.04
0.08
0.12
0.16
0.2
0 100 200 300 400 500 600 700
Current density /mAcm
-2
C
e
l
l

i
m
p
e
d
a
n
c
e

/
O
h
m
0
0.2
0.4
0.6
0.8
0 200 400 600
Current densi ty /mAcm
-2
C
e
l
l

i
m
p
e
d
a
n
c
e

/
O
h
m
Evaluation of the U-i characteristics from EIS
100
300
500
700
900
1100
0 200 400 600 800
Current densi ty /mAcm
-2
C
e
l
l

v
o
l
t
a
g
e

/
m
V
measured

curve: U
n

= f(i
n

)
calculated

curve: U
n

= i
n

R
n

(without

integration)
A
calculated

curve

using

method

II: U
n

= a
n

i
2
n

+b
n

i
n

+c
n
x calculated

curve

using

method

I: U
n

= a
n

i
n

+b
n
R
U
I
n n
=
c
c
Integration method

I:
U U
U
I
U
I
I I
n n n n n n
= + -
1
1
2 1 1
( ) ( )
c
c
c
c
Integration method

II:
U a I b I c
n n n n n n
= + +
2
with:
a
R R
I I
n
n n
n n
=

+
+
1
1
2 ( )
b R a I
n n n n
=
+ + 1 1
2
c U a I b I
n n n n n n
=

1 1
2
1
EIS at Polymer Fuel Cells (PEFC):
Contributions to the overal U-i characteristic determined by EIS
200
300
400
500
600
700
800
900
1000
1100
0 100 200 300 400 500 600 700 800
Current density / mAcm
-2
C
e
l
l

v
o
l
t
a
g
e
/

m
V













E
0
A E
K
A E
A
A E
M
A E
Diff.
}
}
}
}
C
dl,a
R
M
R
A
C
dl,c
R
K
C
N
R
N
Evaluation of EIS with the porous electrode model
I
I
I
I
0
0.02
0.04
0.06
0.08
0.1
0 200 400 600 800
Current density /mAcm
-2
R
p
,
a
;

R
c
t
,
a
;

R
p
o
r
,
a

/
O
h
m

|
|
.
|

\
|

=
2
1
2
1
,
,
, ,
,
tanh
) (
a ct
a por
a ct a por
a p
R
R
R R
R
Porous electrode resistance (R
p, a
), charge transfer
resistance (R
ct, a
) and electrolyte resistance (R
por, a
)
in the pore of the anode at different current densities
Evaluation of EIS with the porous electrode model
i-V characteristic and current dependency of pore electrolyte resistance
of the anode and cathode

R
el,por,Anode

R
el,por,Kathode
0
5
10
15
20
25
30
35
40
0 2 4 6 8 10 12 14 16 18
Current / A
P
o
r
e

e
l
e
c
t
r
o
l
y
t
e

r
e
s
i
s
t
a
n
c
e

/

m
O
h
m
0
200
400
600
800
1000
1200
C
e
l
l

v
o
l
t
a
g
e

/

m
V
Impedance Measurements during Oxygen Reduction
Reaction (ORR) in 10 N NaOH, on Silver Electrodes
at Different Current Densities
10m 100m 1 3 10 100 1K 10K 100K
500m
1
2
1.5
5
|Z| / O
0
15
30
45
60
75
90
|phase| /
o
frequency / Hz
45 mA
40 mA
35 mA
30 mA
25 mA
20 mA
15 mA
10 mA
5 mA
100 mA
95 mA
90 mA
85 mA
80 mA
75 mA
70 mA
65 mA
60 mA
55 mA
50 mA
1 2 3 4 5
0
-4
-2
Z' / O
Z
'
'

/

O
-50
5 mA
10 mA
15 mA
20 mA
100 mA
i / mA
Evaluation of EIS measured during ORR
Equivalent circuit and R
ct
= f(i)
200
400
600
800
-500 -400 -300 -200 -100
current/mA
R / mO
N
1
2
3
4
5
6
1 170.8 mO
2 5.521 mOs
-1/2
19.38 s
-1
3 61.37 mF
o
942.8 m
4 1
309.9 mO
3.18 mO
5 508.6 mO
6 73.35 nH
Outlook
Further improvement of porous electrode models
Combination and extension of existent and new models
Application of EiS to segmented cells
Experimental validation of models using
PEFC and DMFC electrodes with different porous structure
Gas Diffusion Electrodes (GDE) for Oxygen Consumption Reaction
(OCR) in alkaline solution using different gas compositions
Experimental EIS set-up for stack measurements