Electrochemistry of

Materials
Impedance Spectroscopy
University of Twente,
Dept. of Science &
Technology, Enschede,
The Netherlands

Bernard A. Boukamp
Solid State Ionics-17
Toronto, June/July 2009.

Research Institute
for Nanotechnology

SSI-17

My where abouts

Workshop
28 June 09

E-mail: b.a.boukamp@utwente.nl
Address:
University of Twente
Dept. of Science and Technology
P.O.Box 217
7500 AE Enschede
The Netherlands
www.ims.tnw.utwente.nl

SSI-17

Workshop
28 June 09

Electrochemical techniques

Time domain (incomplete!):

Polarisation,

(V I )

Potential Step, (V I (t) )

Cyclic Voltammetry, (V f(t)- I(V ) )
Coulometric Titration, (V - I dt )

steady state
Next slide

relaxation
dynamic
relaxation

Galvanostatic Intermittent Titration (Q V (t) ) transient

Frequency domain:
Electrochemical Impedance Spectroscopy perturbation of
equilibrium state
(EIS)

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Workshop
28 June 09

Time or frequency domain?

1.E-04

C u rre n t, [A ]

1.E-05

1.E-06

1.E-07

1000

2000

Time, [sec]

3000

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Workshop
28 June 09

Time or frequency domain?

1.E-04

C u rre n t, [A ]

1.E-05

1.E-06

1.E-07

1000

2000

Time, [sec]

3000

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Workshop
28 June 09

Advantages of EIS:

System in thermodynamic equilibrium

Measurement is small perturbation (approximately linear)
Different processes have different time constants
Large frequency range, Hz to GHz (and up)
Generally analytical models available
Evaluation of model with Complex Nonlinear Least
Squares (CNLS) analysis procedures (later).
Pre-analysis (subtraction procedure) leads to plausible
model and starting values (also later)
Disadvantage:

rather expensive equipment,

low frequencies difficult to measure

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Workshop
28 June 09

Black box approach

Assume a black box with two terminals (electric connections).

One applies a voltage and measures the current response (or
visa versa). Signal can be dc or periodic with frequency f, or
angular frequency =2f ,
with: 0 <

Phase shift and amplitude

changes with !

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Workshop
28 June 09

So, what is EIS?

Probing an electrochemical system with a small

ac-perturbation, V0ejt, over a range of frequencies.
The impedance (resistance) is given by:

V0
V () V0 e jt
=
= [ cos j sin ]
Z () =
j ( t +)
I () I0 e
I0

= 2f
j = -1

The magnitude and phase shift depend on frequency.

Also: admittance (conductance), inverse of
impedance:
I0 e j (t +) I0
1
=
= [ cos + j sin ]
Y () =
jt
Z () V0 e
V0
real +j. imaginary

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Workshop
28 June 09

Complex plane
Impedance resistance
Admittance conductance:

Zre jZim
1
= 2
Y () =
Z () Zre + Zim2

Zre jZim
1
=

Zre + jZim Zre jZim

hence:
Representation of impedance value,
Z = a +jb, in the complex plane

Yre jYim
1
Z () =
= 2
Y () Yre + Yim2

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Workshop
28 June 09

Adding impedances and

admittances

A linear arrangement of
impedances can be added in
the impedance plane:

Ztotal = Z1 + Z2 + Z3 + ... = Zn
n

A ladder arrangement of admittances

(inverse impedances) can be added in
the admittance plane:

Ytotal = Y1 + Y2 + Y3 + ... = Yn
n

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Workshop
28 June 09

Simple elements

The most simple element

is the resistance:

1
ZR = R ; YR =
R

(e.g.: electronic- /ionic conductivity,

charge transfer resistance)
Other simple elements:
Capacitance: dielectric capacitance, double layer C,
adsorption C, chemical C (redox)
See next page
Inductance: instrument problems, leads,
negative differential
capacitance !

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Workshop
28 June 09

Capacitance?

Take a look at the properties of a capacitor: C =

Charge stored (Coulombs):
Change of voltage results
in current, I:

Q = C V

A0
d

dQ
dV
I=
=C
dt
dt

dV0 e jt
Alternating voltage (ac): I (t ) = C
= jC V0 e jt
dt
Impedance:

V ()
1
=
ZC ( ) =
I () jC

Admittance:

YC ( ) = Z ()1 = jC

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Combination of elements

Workshop
28 June 09

What is the impedance of an -R-Ccircuit?

1
Z () = R +
= R j / C
jC

Admittance?

1
=
Y () =
R j / C
2C 2 R
C
+j
2 2 2
1+ C R
1 + 2C 2 R2
Semicircle

time constant:
constant:
time
RC
== RC

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Workshop
28 June 09

A parallel R-C combination

The parallel combination of a resistance and a

capacitance, start in the admittance representation:

1
Y () = + jC
R

Transform to impedance representation:

1
1
1/ R jC
Z () =
=

=
Y () 1/ R + jC 1/ R jC
R jR2C
1 j
=R
2 2 2
1+ R C
1 + 2 2
A semicircle in the impedance plane!

Plot next slide

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Impedance plot (RC)

Workshop
28 June 09
8.0E+04

fmax = 1/(6.3x310-9x105)=530 Hz
6.0E+04

-Zimag, [ohm]

518 Hz

R = 100 k
C = 3 nF

4.0E+04

2.0E+04

1 MHz

0.0E+00
0.0E+00

2.0E+04

1 Hz
4.0E+04

6.0E+04

Zreal, [ohm]

8.0E+04

1.0E+05

1.2E+05

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Limiting cases

Workshop
28 June 09

What happens for << and for >> ?

<< :

1 j
2

Z () = R
R
j
R
R
j
R
C
2 2
1+

>> : Z () = R

1 j
R
R
1
1
2 2j 2 2j
2 2
1+
RC
C

This is best observed in a so-called Bode plot

log(Zre), log(Zim) vs. log(f ), or
log|Z| and phase vs. log(f )

Next slides

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Bode plot (Zre, Zim)

Workshop
28 June 09
1.E+05

Zreal
Zimag

Z re a l, -Z im a g , [o h m ]

1.E+04

1.E+03

1.E+02

-1

1.E+01

-2

1.E+00

1.E-01

1.E-02
1.E+00

1.E+01

1.E+02

1.E+03

frequency, [Hz]

1.E+04

1.E+05

1.E+06

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Bode, abs(Z), phase

Workshop
28 June 09

90

1.E+05

abs(Z)
Phase ()

75

a b s (Z ), [o h m ]

45

1.E+03

30

15

1.E+02
1.E+00

1.E+01

1.E+02

1.E+03

Frequency, [Hz]

1.E+04

1.E+05

0
1.E+06

P h a s e (d e g r)

60

1.E+04

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Workshop
28 June 09

Other representations

Capacitance: C() = Y() /j

for an (RC) circuit:

1
1

C () = Y () / j = + jC / j = C j
R
R

Dielectric:

() = Y() /jC0

C0 = A0/d

ion
d
() = Y ()
= j
A0
0
Modulus:

M() = Z() j

2CR 2 + jR
M () = Z () j =
1 + 2C 2 R 2

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Simple model

Workshop
28 June 09

Example: an ionically conducting solid,

e.g. yttrium stabilized zirconia,

Zr1-xYxO2-x .
Apply two ionically blocking electrodes,
in this case thick gold.

Schematic
arrangement of sample
and electrodes.

Measure the resistance (impedance)

as function of frequency:

Z () =
jCg +

1
1
Rion + 1
2 jCint

Equivalent circuit: (C[RC])

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Workshop
28 June 09

Low & high f - response

Low frequency regime,

series combination Rion-Cint: Z () = Rion j / 12 Cint
Straight vertical line in impedance plane.
High frequency regime,
parallel combination of Rion//Cgeom:

2
Rion
Cgeom

Rion
Z () =
j
2 2
2
2
2
1 + RionCgeom
1 + 2 Rion
Cgeom
Semicircle through the origin.

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Workshop
28 June 09

Debije model:

An ionic conductor between two blocking electrodes:

1
Y () =
Z ()

Impedance representation

Admittance representation

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Workshop
28 June 09

Other representations

Zimag
Zreal

Bode representation

Different Bode
representation

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Workshop
28 June 09

Other representations

Zimag
Zreal

Bode representation

Different Bode
representation

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Workshop
28 June 09

Diffusion, Warburg element

Semi-infinite diffusion,
Flux (current) : J = D C
(Fick-1)
x

x =0

RT
Potential
: E=E +
ln C
nF
ac-perturbation: C(t ) = CD + c(t )
D

Fick-2
Boundary
condition

C
:
=D 2
t
x

: C( x, t ) x = C

Li-battery cathode

Solution through Laplace transform: next page

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Workshop
28 June 09

Diffusion, Warburg element

Semi-infinite diffusion,
Flux (current) : J = D C
(Fick-1)
x

x =0

RT
Potential
: E=E +
ln C
nF
ac-perturbation: C(t ) = CD + c(t )
D

Fick-2
Boundary
condition

C
:
=D 2
t
x

: C( x, t ) x = C

Redox
Li-battery
on inert
cathode
electrode.

Solution through Laplace transform: next page

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Workshop
28 June 09

Warburg element, cont.

Laplace transform: c( x, t ) C( x, p)

2C( x, p)
Transform of Fick-2: p C( x, p) = D
x2
General solution:

C( x, p) = A cosh x p / D + B sinh x p / D

RT
Transform of V (t): E( p) =
C( x, p)
D
nFC
C( x, p)
Transform of I (t): I ( p) = nFD
x x=0
(Fick-1)

Boundary
Boundary
condition:
condition:

C( x, p ) x = 0

SSI-17

Workshop
28 June 09

Warburg impedance

Define impedance in Laplace space!

E( p)
RT
Z ( p) =
=
I ( p) (nF )2 CD D p
Take the Laplace variable, p, complex:
p = s + j .
Steady state: s 0,
which yields the impedance:

RT
with:
1/ 2
1/ 2
RT
=
(

)
Z () =
Z
j
0
Z
=
0
(nF )2 CD jD
(nF )2 CD 2D

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Workshop
28 June 09

Transmission line

Real life Warburg,

semi-infinite coax cable
with r /m and c F/m:

ZW () =

r
jc

Combination:
Electrolyte resistance, Relyte
Equivalent
Double layer capacitance, Cdl
circuit
Charge transfer resistance, Rct
Warburg (diffusion) impedance, Wdiff

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Workshop
28 June 09

Equivalent Circuit Concept

se
m

ic
ir

cl
e

45

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Workshop
28 June 09

Instruments

Measurement methods
Bulk, conductivity:
two electrodes
pseudo-four electrodes
true four electrodes
Electrode properties:
three electrodes

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Workshop
28 June 09

Respect for old scientists!

Image from the
past:
Hand balanced
bridges:

R1
Zsample = Zcomp.
R2
Very accurate,
but limited
range
& time
consuming!

SSI-17

Ionic & MIEC conductivity

Workshop
28 June 09

I+, V+ Two-electrode measurement,

influence of cables! For 100 kHz & 10 H:
I-, V5
5
Z cable = + jL = j 2 10 10 6.3

I+
V+
VII+
V+
VI-

Pseudo 4-point, inductance eliminated, but

still additional capacitance of coax cables.

Twist cables in cell for low inductance!

True 4-point measurement.
Voltage probes for mixed conductors!
Ionic and/or electronic probes.
Spurious capacitances still possible.

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Workshop
28 June 09

Potentiostat, electrodes
Vpwr.amp = A k Vk
A= amplification
Vwork Vref =
Vpol. + V3 + V4
Current-voltage
converter
provides virtual
ground for
Work-electrode.

General schematic

Source of
inductive effects

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Workshop
28 June 09

Cell morphology and

reference electrodes

Thin cell geometry is very unreliable for 3electrode impedance measurement.

Even with equal size electrodes, a small mismatch
can cause the reference electrode to feel the
counter electrode dispersion.
(Nice treatment of problem with FEMLAB by Stuart
Adler in J.El.chem.Soc.)

SSI-17

Workshop
28 June 09

Solutions for reference el.

Solutions for optimal placing of the reference electrode.

Left: two compartment cell. Right: single compartment cell.

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Workshop
28 June 09

Data validation

Kramers-Kronig relations (old!)

Real and imaginary parts are linked
through the K-K transforms:
Kramers-Kronig
conditions:
causality
linearity
stability
(finiteness)

Response only
Response
due
to input
State
of
scales
linearly
signalmay
system
with input
notsignal
change
during
measurement

SSI-17

Putting K-K in practice

Workshop
28 June 09

Relations,

2 Z re ( x) Z re ()
Real imaginary: Z im () =
dx
2
2

0
x

not a singularity!

2 xZ im ( x) Z im ()
Imaginary real: Z re () = R +
dx
2
2
0
x
Problem:
Finite frequency range: extrapolation
of dispersion ) assumption of a model.

[1] M. Urquidi-Macdonald, S.Real & D.D. Macdonald,

Electrochim.Acta, 35 (1990) 1559.
[2] B.A. Boukamp, Solid State Ionics, 62 (1993) 131.

SSI-17

Workshop
28 June 09

Linear KK transform

Linear set of parallel RC circuits:

k = RkCk

Create a set of values: 1 = max-1 ; M = min-1

with ~7 -values per decade (logarithmically spaced).

If this circuit fits the data, the data must

be K-K transformable!
[3] B.A.Boukamp, J.Electrochem.Soc, 142 (1995) 1885

SSI-17

Actual test

Workshop
28 June 09

Fit function simultaneously to

real and imaginary part:

1 ji k
Z KK (i ) = R + Rk
2
2
1
+

k =1
i
k
M

Set of linear equations in Rk,

only one matrix inversion!
Display relative residuals:

real =

Zre,i Z KK, re (i )
Zi

, imag =

Shortcut to KKtest.lnk

It works like a
K-K compliant
flexible curve

Zim,i Z KK,im (i )
Zi

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Workshop
28 June 09

No information in Rk values

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Workshop
28 June 09

Smooth between data points

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Workshop
28 June 09

Example K-K check

Impedance of a sample, not in

equilibrium with the ambient.

2KK = 0.910-4
2CNLS = 1.4 10-4

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Workshop
28 June 09

Finite length diffusion

Particle flux at x=0:

~ dC( x, t )
J (t ) = D
dt x=0

Ficks 2nd law:

dC( x, t ) ~ d2C( x, t )
=D
dx2
dt

But now a boundary

condition at x = L.
Activity of A is measured at the interface at x=0. with
respect to a reference, e.g. Amet

SSI-17

Workshop
28 June 09

Finite length diffusion

Replace concentration
by its perturbation:

c( x, t ) = C( x, t ) C 0

Impermeable
dC( x, t )
boundary at x =L:

dx

= 0 FSW
x=l

Ideal source/sink
with C = CL (=C0): C( x, t ) = Cl = C 0
x=l

General expression
for permeable
dC( x, t )
boundary:

dx

x =l

FLW

= k C( x, t ) x=l Cl

General!

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Workshop
28 June 09

FLD, continued

Voltage with respect to reference C0 (a0):

RT ax=0
RT d ln a
E(t ) =
ln 0 =
c( x, t ) x=0
0

nF a
nFC d ln C
Current through interface at x = 0:

~ dc( x, t )
I (t ) = nF S J (t ) = nF S D
dx x=0
Assumption: a << a0:
Relation a C from
titration curve:

a
a0 + a
a a
=
ln 0 = ln
ln
1 + 0 0
0
a
a
a a

da a0 dln a a
a
= 0

=
dC C dln C C c( x, t ) x=0

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Workshop
28 June 09

Up to the Frequency Domain!

Laplace transformation of E(t) and I(t)

gives the complex impedance (with p=j):

E()
=
FSW Z () =
I ()

Z0

E()
Z () =
=
I ()

Z0

FLW

Laplace space
solution of Fick-2:

j
~
~ cothl D
jD

with:
R T Vm d ln a
=
Z0 = 2 2

n F S d ln c
Vm d E
=

nFS d

j
~
~ tanhl D
jD

p
p
C( p) = A cosh x ~ + B sinh x ~
D
D

SSI-17

Dispersions

Workshop
28 June 09

High frequencies:
Vs nF d E
Cint =
VM d

Z() = Z0 (j )-1/2
= Warburg diffusion
Low frequency limit:
FSW = capacitive
FLW = dc-resistance
Impedance representation of
FSW and FLW.

SSI-17

Workshop
28 June 09

General finite length

diffusion

Generic finite
length diffusion:

Z () =

Z0

jD coth l

jD k coth l

j
D

j
D

+k

+ jD

If k =0 then
blocking interface
FSW
If k = then ideal
passing interface
FLW
Plot for different
values of k.

SSI-17

Workshop
28 June 09

A Simple Example

H.J.M. Bouwmeester

AgxNbS2 is a layered structure,

consisting of two-dimensional NbS2
layers. Insertion and extraction of Ag+
ions goes in an ideal manner (see graph).
Isostatically pressed and sintered
sample. Some preferential orientation
(in the proper direction!) will occur.
Simple cell
design for EIS
measurements.

SSI-17

Workshop
28 June 09

Circuit Description Code

The Circuit Description Code presents an

unique way to define an equivalent circuit
in terms suitable for computer processing.
Elements: R, C, L, W
Finite length diffusion:
T = FSW = Tanhyp (Adm.)

Cothyp (Imp.)

O = FLW = Cothyp (Adm.)

Tanhyp (Imp.)

Constant Phase Element:

Q = CPE = Y0(j )n (Adm.)

Z0(j )-n (Imp.)

SSI-17

The CPE

Workshop
28 June 09

Constant Phase Element:

YCPE = Y0 n {cos(n /2) + j sin(n /2)}
n=1

Capacitance: C = Y0

n=

Warburg:

n=0

Resistance: R = 1/Y0

n = -1

Inductance: L = 1/Y0

= Y0

All other values, fractal?

Non-ideal capacitance, n < 1 (between 0.8 and 1?)

SSI-17

Non-ideal behaviour

Workshop
28 June 09

General observations:
Semicircle (RC ) depressed
vertical spur (C ) inclined
Warburg
less than 45
Deviation from ideal dispersion:
Constant Phase Element (CPE),
(symbol: Q )

YCPE

n
n
= Y0 ( j) = Y0 cos + j sin
2
2

,
nn == 1,1, ,
0, -1,
-1, ??
0,

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Workshop
28 June 09

The Fractal Concept

How to explain this non-ideal behaviour?

1980s: Fractal behaviour (Le Mehaut)
= fractal dimensionality
i.e.: What is the length of the coast line of England?
) Depends on the size of the measuring stick!

) Self similarity (

SSI-17

Fractals

Workshop
28 June 09

Fractal line

Self similarity!
similarity!
Self
Sierpinski carpet

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Workshop
28 June 09

Fractal electrode
Cantor bar
arrangement

Impedance of the network:

1a
a
Z()= R +
a Z ()
22
Z = R+
2
j
CC+Z+() + 2
jaC
a
1
Z
(
)

R+
aR
22
aC++ 2
jC
aaR
R + ...

aR

a2R

a3R

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Workshop
28 June 09

Arriving at the CPE

a Z ()

Frequency scaling relation: Z = R +
jC Z () + 2
a
In the low frequency
limit this reduces to:
Which is satisfied by
the formula:

a
Z = Z ()
a 2

Z () = A( j)n

with n = 1 ln2/lna
Fractal dimension of Cantor bar, d = ln2/lna
Hence: n = 1 d
S.H. Liu and T. Kaplan, Solid State Ionics 18 & 19 (1986) 65-71.

SSI-17

Workshop
28 June 09

Where we are at:

Unfortunately, experiments with rough electrodes

showed no relation between microstructure and fractal
dimension from EIS measurements.
For bulk response at high frequency (dielectric response):
Theory by Klaus Funke (University of Mnster):
Concept of mismatch and relaxation
(See literature).
General assumption:
assumption:
General
one dimensional
dimensional transport
transport with
with no
no lateral
lateral interaction!
interaction!
one

SSI-17

Workshop
28 June 09

Different presentation

Sometimes useful to
rephrase the CPE:

PZT, dielectric
response:

d Y0
r =
0 A

Y () = Y0 ( j) = (Y0 j) , withY0 = Y01/ n

n

SSI-17

Workshop
28 June 09

Circuit Descriptions Code

Breaking it down from
the outside.
Find the parallel and
series boxes.
Fill in with increasing
nesting level.

1:
0 = series
2:
1 = parallel
3:
2 = series, etc. 4:
5:

(C[
])
(C[(
)(
)])
(C[(Q[
])(C[
])])
(C[(Q[R(
)])(C[RQ])])
(C[(Q[R(RQ)])(C[RQ])])

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Workshop
28 June 09

Reading the CDC

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Workshop
28 June 09

Equivalencies

Equivalent circuits with

identical frequency
dispersion (spectra):

Ra = RdRe/(Rd + Re)
Rb = Re2/(Rd + Re)
Cc = Cf [Rd/(Rd + Re)]2

Two circuits with identical dispersion

S. Fletcher, J.El.chem.Soc., 141 (1994) 1823

But many
many more
more combinations
combinations exist,
exist,
But
not only
only exactly
exactly identical
identical responses,
responses,
not
but also
also identical
identical within
within the
the experimental
experimental error!
error!
but
Physical meaning! Change experimental conditions: (P, T, , )

SSI-17

CNLS data analysis

Workshop
28 June 09

Model function, Z(,ak), or equivalent circuit.

Adjust circuit parameters, ak, to match data,
Minimise error function:
n

S = wi Zre,i Zre (i ) + Zim,i Zim (i )

i =1

with: wi = Zi
for k = 1 ..M

Z (i , ak )

(weight factor)

d
S =0
dak

Non-linear, complex model function!

Effect of minimisation

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Workshop
28 June 09

Non-linear systems

Function Y (a1..aM) is not linear in its parameters, e.g.:

Z () = Z0 k + ( j)

= Z (, Z0 , k , , )

Linearisation: Taylor development around guess values, ajo:

Y ( x, a1..aM )
Y ( x, a1..aM ) = Y ( x, a ..a ) +
a j
j
D
1

a j + ....

D
M

D
a1D ..aM

Derivative of error sum with respect to aj :

S
Y ( xi , a1..M ) Y ( xi , a1..M )
D
= 0 = 2wi yi Y ( xi , a1..M ) +
ak
a j
ak
a j
i
k

SSI-17

NLLS-fit

Workshop
28 June 09

A set of M simultaneous equations, in matrix form:

a =

solution:

a = -1 =

Y ( xi , a1..M ) Y ( xi , a1..M )
= wi

a j
ak
i

With:

j,k

and:

Y ( xi , a1..M )
k = wi [ yi Y ( xi , a1..M )]
ak
i

Derivatives are taken in point ao1..M.

Iteration process yields new, improved values: aj = aoj + aj.

SSI-17

Workshop
28 June 09

The derivatives!

Having the derivatives is essential!

best method, calculate the derivatives on basis

of the function: accuracy and speed.

Second best: numerical evaluation* (for proper

derivatives we have to calculate F(xi,a1..M)
2M +1 times!!

F ( xi , a1.., a j + a j ,..aM ) F ( xi , a1.., a j a j ,..aM )

F ( xi , a1..M ) =
a j
2a j
* This is actually an approximation

SSI-17

Workshop
28 June 09

Marquardt-Levenberg

Analytical search: fast and accurate near true minimum

slow far from minimum
(and often erroneous)
Gradient search or steepest descent (diagonal terms only):
fast far from minimum
slow near minimum

Hence, combination!
Multiply diagonal terms with (1+).

<< 1, analytical search

>> 1, gradient search

Successfuliteration:
iteration:
Successful
Sold
new<<S
SSnew
old

decrease

(=/10).
/10).
decrease (=
Otherwiseincrease
increase
Otherwise
(=10)
10)
(=

Bottom line: good starting parameter estimates are essential!

SSI-17

Workshop
28 June 09

Error estimates

For proper statistical analysis the weight factors, wi,

should be established from experiment.
Other (dangerous) method:
Step 1: set weight factors, wi = g i-2
Step 2: assume variances can be replaced by parent
distribution, hence 2 1

(with = N M 1)

Step 3:

2
2
[
]

1
y
Y
(
x
,
a
)
1
1
S

2
i
i 1..M
=
= S
=
1
=
2
2
i
i
i wi i g

Hence proportionality factor, g = S/.

SSI-17

Workshop
28 June 09

Error analysis NLLS-fit

Based on this assumption we can derive

the variances of the parameters: a2k = g k , k

[ ]

= g k ,k

Error matrix, , also contains the covariance of the

parameters:
= g
aj

ak

j ,k

j,k 0, no correlation between aj and ak.

j,k 1, strong correlation between aj and ak.

Only acceptable for many data points AND

random distribution of the residuals

SSI-17

Workshop
28 June 09

Weight factors and error

estimates

Errors in parameters:
estimates from CNLS-fit procedure
assumption: error distribution equal to parent distribution
only valid for random errors,
no systematic errors allowed!
Residuals graph:
Large error estimates:
strongly correlated
parameters (+ noise).
Option: modification of
weight factors.

re =

Zre,i Zre (i )
Z (i )

, im =

Zim,i Zim (i )
Z (i )

SSI-17

Workshop
28 June 09

Two different CNLS-fits

Example of correct
error estimates:

R(RC)(RC)

CDC: R(RQ)(RQ)
2 2.410-5
R1 999
R2 4000
Q3 1.0310-9
-n3 0.898
R4 8020
Q5 1.0310-7
-n5 0.697

0.8%
1.7%
7%
0.6%
0.9%
3.6%
0.7%

And of incorrect
error estimates:
CDC: R(RC)(RC)
Values seem O.K.
but look at the
residuals!

2 3.810-3
R1 1290
4%
R2 4650
2.7%
C3 2.3810-103.8%
R4 6580
2.6%
C5 6.0710-9 7.3%

SSI-17

Workshop
28 June 09

Residuals plot!

Systematic deviation,
Trace, bad fit

Good fit (not bad for

a straight simulation!)

SSI-17

Workshop
28 June 09

Subtraction procedure

Partial CNLS-fit of recognizable structure

Semicircle
Straight line (CPE, Cap., Ind.)
Subtract dispersion as series- or parallel component
Repeat steps until garbage is left
Be aware of errors due to consecutive subtractions
Sometimes restart and do a partial fit of a larger
group of parameters

SSI-17

Workshop
28 June 09

Fingerprinting

Classification of capacitance
source

approximate value

geometric
grain boundaries
double layer / space charge
surface charge /adsorbed species
(closed) pores
chemical capacitances
stoichiometry changes

2-20 pF
(cm-1)
1-10 nF
(cm-1)
0.1-10 F/cm2
0.2 mF/cm2
1-100 F/cm3
large (~1000 F/cm3)

Modified after: Peter Holtappels, TMR symposium Alternative anodes...,

Jlich, March 2000.

SSI-17

Workshop
28 June 09

Gas phase capacitance

Capacitance of gas volume (e.g. O2):

PV=nRT
PV=nRT

dE
i dt
or: C =
dt
dE
O2 produced: i dt = 4F dn
RT P + dP RT dP (RT )2 dn
Nernst: dE =
ln

=
4F
4F P
4F V
P
Capacitance: i = C

Combination: C = 4F V P
ox

RT

Example:
air, 700C, Vol. = 10 mm3
Cox = 0.456 F !

SSI-17

Workshop
28 June 09

Conclusions on fitting

Many parameter, complex systems modelling:

Use Marquardt-Levenberg when quality starting

values are available

Simplex (or Genetic Algorithm) for optimisation of

rough guess starting values, as input for M-L NLSF

Check residuals when calculating Error Estimates

Look for systematic error contributions, remove if

feasible.

Provide error estimates in publications!

Its human to err, its dumb not to include
an error estimate with a number result

SSI-17

Workshop
28 June 09

Fitting to the Extreme

PbZr0.53
Ti0.47
O33//gold
//gold electrodes
electrodes
PbZr
0.53Ti
0.47O

N22 (1.2
(1.2 Pa
Pa O
O22),), 580C,
580C, 0.1
0.1 Hz
Hz 65
65 kHz
kHz
N

2CNLS =
6.210-8
2K-K =
5.810-8

SSI-17

Workshop
28 June 09

Subtraction of (Qdiel Rel)

SSI-17

Workshop
28 June 09

Subtraction of (Qdiel Rel)

SSI-17

Workshop
28 June 09

The hidden R(RQ)

With electrode
electrode
With
response subtracted
subtracted
response
(C[RW])
-- (C[RW])

SSI-17

Workshop
28 June 09

After subtraction of Cdl

SSI-17

Workshop
28 June 09

The proof of the pudding

One of the possible equivalent

circuits

Electrode response (Randles

circuit) in analogy with liquid
electrolyte with redox couple.

CDC: (QR[R(RQ)(C[RW])])
ps2 =

6.210-8

err. [%]

Q1

3.210-9 S.sn

7.9

-n1

0.886

0.6

R2

2800

0.01

R3

2290

1.7

R4

3420

1.8

Q5

2.88 10-7 S.sn 6.0

-n5

0.668

1.0

C6

1.74 10-8 F

0.5

R7

68100

1.7

W8

4.19 10-7 S.s1/2 1.6

SSI-17

Workshop
28 June 09

Consistency of model
Arrhenius graph of
Cdl and Wdiff
(ionic electrode
response) .
N2 (Po2 ~1.2 Pa).
Above TC Warburg
is activated with
EAct =653 kJ.mol-1.
Parameters have been
scaled by the
geometric factor!

SSI-17

Workshop
28 June 09

Impedance & mixed

conductivity (solid state)
Generally accepted
Equivalent Circuit for
mixed conducting oxides.
Electrode dispersion
causes problem in analysis.

Simplified (but wrong) model,

assuming electrodes impermeable
for oxygen. (Au/MIEC/Au)

SSI-17

Workshop
28 June 09

Jamnik & Maier Model

System

Discretisation of
transport in solid and
across interfaces
Transport coordinate
Reaction coordinate
Chemical capacitance

Jamnik & Maier, Phys. Chem. Chem. Phys. 3 (2001) 1668-78.

SSI-17

Workshop
28 June 09

Jamniks intercalation model

Arguments of tanh
(FSW) and coth (FLW)
functions are equal:

RLi+

Ri Re
Z =
+
Ri + Re 1 + jRLi+ C
1 (Ri Re )2 tanh j
+
4 Ri + Re
j
J. Jamnik,

Solid State
Ionics, 157
(2003) p.19-28

coth j
1
+ (Ri + Re )
4
j
Time constant:

= 14 L2 / D = 14 (Ri + Re ).Cchem.

SSI-17

Workshop
28 June 09

Simplification for Re 0

For Re0 the first term disappears. We focus now on

the 3rd and 4th term (second term deals with processes
at te interface). Setting Re=0 yields:

Ri e j e j e j + e j
1 tanh j 1 coth j
Z () = Ri
+ Ri
=
+ j j

j
j
4
4
e e
j
j
4 j e + e
( e j e j )2 + ( e j + e j )2
j 2
j 2

Ri
R
2
e
2
e
+
i

=
=
j 2
j 2
4 j e j 2 e j 2
e e
4 j

Ri
coth 2 j
=
2 j
L coth L j / D
Inserting expressions for and Ri: Z () =
Cchem jD

SSI-17

Workshop
28 June 09

Gerischer in electrodes
Possible mechanisms
leading to a Gerischer
type response.

OOadad

The ALS model #)

Fick-2:
electrolyte
electrolyte
#)

OHadad
OOadad,,HHadad,,OH

Slow adsorption
& diffusion *)

dc( x,t )  d2 c( x,t )

=D
k c( x,t )
2
dt
dx

HH22OOadad

electrolyte
electrolyte

S.B. Adler, J.A. Lane and B.C.H. Steele, J.Elchem.Soc. 143 (1996) 3554-64.

*) R.U. Atangulov and I.V. Murygin, Solid State Ionics 67 (1993) 9-15.

SSI-17

Workshop
28 June 09

Alternative explanation

Leaky transmission line.

Series resistance, r1, in
/m. Parallel
capacitance, c, in F/m.
Parallel resistance, r2, in
m.
For semi-infinite circuit:

Zs
r1
Z0
Z () =
=
=
1 / r2 + jc
Yp
k + j
With k = (r2c)-1 and Z0 = (r1/c)1/2

Transmission line with

side branches can lead
to fractal response!
I.D. Raistrick in:

Impedance Spectroscopy, ed.

J. Ross Macdonald, (Wiley 1987)

SSI-17

Workshop
28 June 09

YSZ-Tb example

Example: mixed conducting YSZ-Tb

Stabilized zirconia: Zr1-x-yYxTbyO2-0.5x-
Zr = 4 +

[V
Y = 3 +, hence oxygen vacancies:
O ] = 2[Y ]

Tb = 3 + / 4 +, hopping conduction (+ vacancies for Tb3+)

Electronic conductivity depends on pO2.

SSI-17

Workshop
28 June 09

Au/YSZ-Tb27.3/Au
dispersions

0.9bar,
bar,Au-electrodes
Au-electrodes
ppOO22==0.9
0.01Hz
Hz--65
65kHz
kHz
0.01

SSI-17

Workshop
28 June 09

A possible model?

Assumption: electrodes
impermeable for oxygen.
At electrodes:
(+) oxidation and
(-) reduction of Tb-sites,

e.g. at the cathode (-):

+e

TbZr, OO TbZr, VO
-O
dc ie
dc
~
~
st
Ficks 1 :
J x = L = D
=
, J x =+ L = + D
dx 2 F
dx
(c = excess
concentration)
The kk cc term
term is
is related
related
The
2
nd

c
d
c
d
~
to aa reaction
reaction of
of the
the
Ficks 2 :
to
= D 2 kc
excess concentration.
concentration.
dt
dx
excess

SSI-17

Workshop
28 June 09

Model development
In YSZ the following reactions can occur:
VO + MZr

and: [VO MZr] + MZr

[VO MZr]

[MZr VO MZr] ,

is either Y3+ or Tb3+.

where MZr
Hence, we
we have
have aa Faradaic
Faradaic diffusion
diffusion
Hence,
process coupled
coupled with
with aa chemical
chemical reaction!
reaction!
process
Relation voltage-concentration, with W =

d ln a
:
d ln c

RT
RT a 0 + a
RT
Vx = L =
ln
=
a =
Wc
0
0
0
2F
a
2 Fa
2 Fc

SSI-17

Workshop
28 June 09

There is life in Laplace

space!

Laplace transformations:
Ficks second law:

2
~ d c( s)
sc( s) = D
kc( s)
2
dx

~
~
General solution: c( s) = A cosh x ( k + s) / D + B sinh x ( k + s) / D
Boundary conditions
(symmetry):
A = 0,
Impedance:

~
c(s) x = L = B sinh L ( k + s) / D

~
V RTW tanh L ( k + s) / D
Z (s) =
= 2 0
~
i 4 F c
( k + s) D
Which is not yet the Gerischer !!

SSI-17

Workshop
28 June 09

Resolving the complications

Step 1: replace s by: + j. For steady state, 0.

~
Step 2: tanh(x) 1 for large x, hence for L2k/D > 100,
~
or: D < 0.01 L2k.
Resulting impedance:

Z () =

RTW
2 0

4F c

~ k + j
D

12

Comparewith
withthe
the
Fractal form, n < 0.5: Z () = Z0 (k + j) n Compare

Double fractal form: Z () =

( 1)

dielectricHavriliakHavriliakdielectric
Negamifunction:
function:
Negami

Z0
n

k + ( j)

= +

1 + ( j)

SSI-17

Workshop
28 June 09

Some results for YSZ-Tb

YSZ-Tb27.3
YSZ-Tb
27.3

Lower Eact for e at higher temperatures

YSZ-Tb27.3
YSZ-Tb
27.3

X0

Eact [kJ/m]

eT
160
[SK/cm] 44
G-Y0 6.210-7 [Ssn]
-90
K
4.9107 [s-1]
125

SSI-17

Workshop
28 June 09

Polarisation dependence
Polarisation dependence of
major diffusion sub-circuit,
BiCuVOx/Ag,O2 electrode.

Slopes of
of RRdiff.
are close
close
Slopes
diff. are
to F
F//RT
RT ..
to
shows exponential
exponential
W-YY00 shows
Wdependence on
on VV..
dependence

SSI-17

Workshop
28 June 09

Electrode model for

BiCuVOx

Emerging model from data

analysis of electrode
dispersions.
Electrolyte surface is active !

SSI-17

Workshop
28 June 09

Electrode model for

BiCuVOx

Emerging model from data

analysis of electrode
dispersions.
Electrolyte surface is active !

SSI-17

Workshop
28 June 09

Praise of the time domain

Intercalation cathode.
Change of potential = change
of aA at the interface, hence
A-diffusion:

dCA ( x, t )

J (t ) = DA
dx x=0

Voltage-activity relation:

RT aA, x=0
ln 0
E(t ) =
nF
aA
Fick 1 & 2, boundary conditions
V ()
=
Z () =
+ Laplace transform:
I ()

j
coth l
D
jD

Z0

SSI-17

Workshop
28 June 09

Real cathode: LixCoO2

10.0
10.0

Measurement
Measurement
Simulation
Simulation

e
RR
e

Z"
Z"[k]
[k]

7.5
7.5
20Hz
20Hz

5.0
5.0

sl
RR
sl

ct W
RR
ct W

sl
QQ
sl

dl
CC
dl

3.78V
3.78V

27Hz
27Hz
36Hz
36Hz

3.69V
3.69V
3.84V
3.84V

2.5
2.5

63Hz
63Hz

3.88V
3.88V
4.06V
4.06V

110Hz
110Hz

0.0
0.0
0.0
0.0

LiCoO2, RF film on silicon.

Peter J. Bouwman, Thesis,
U.Twente 2002.

2.5
2.5

5.0
5.0

7.5
10.0
7.5
10.0
[k]
Z'Z'[k]

12.5
12.5

15.0
15.0

IS of a RF-film electrode: () fresh;

() charged; () intermediate SoCs.
(+) CNLS-fit. Range: 0.01 Hz 100
kHz.

Workshop
28 June 09

Diffusive part?

The lithium diffusion

process is found at lower
frequencies!
Compare the potential-step
response time with lowest
frequency of EIS
experiment:

teq. >> 3000 s (~ 0.3 mHz)

fmin ~ 10 mHz

MEASURE RESPONSE
RESPONSE IN
IN
MEASURE
THE TIME
TIME DOMAIN!
DOMAIN!
THE

10
10
99
88
-2
Current
Current[A.cm
[A.cm-2] ]

SSI-17

77

4.05V
4.05V
4.10V
4.10V

66
4.00V 4.15V
4.00V
5
4.15V
5
44

4.20V
4.20V

3.95V
33 3.95V
22

3.90V
3.90V
3.85V
11 3.85V
3.80V
3.80V
0
0
1000
2000
00
1000
2000
Time[s]
[s]
Time

3000
3000

Current response of a 0.75m RFfilm to sequential 50mV potential

steps from 3.80V to 4.20V.

SSI-17

Workshop
28 June 09

Fourier transform

Fourier transform of a temporal function X (t):

X () = X (t ) e jt dt
0

Impedance:

V ()
Z () =
I ()

E.g. with a voltage step, V0:

V0
V () =
j

Model function: Laplace transform of transport equations

and boundary conditions, with p = s +j . Set s = 0:
impedance

SSI-17

Fourier Transform

Workshop
28 June 09

X(t )=at + b

Two problems with F-T:

Data is discrete:
approximate by summation (X =at + b)

Xi -1

Data set is finite (next slide)

Xi

Very Simple Summation Solution (VS3):

N

LM
N

X () = Xi sin ti Xi 1 sin ti 1 +
i =1

L
j M X cost X
N
N

i =1

ti -1 ti

OgP
Q

a
costi costi 1 1 +

gOPQ

a
1
cos

sin

sin

i 1
i 1
i
i 1

SSI-17

Simple exponential extension

Workshop
28 June 09

Assume finite value, Q0, for t ,

this value can be subtracted before total FT.
Fit exponential function to
selected data set in end range: Q(t ) = Q0 + Q1 et /
Full Fourier Transform:

tN

Q0
jt
X () = [ X (t ) Q0 ] e dt j
+ Q1 e t / e jt dt

0
t
N

Analytical transform of exponential extension:

Q1 e
tN

t /

jt

dt = Q1 e

t N /

R S
T

cos t N sin t N
cos t N + 1 sin t N
+j
2
2
+
2 + 2

UV
W

SSI-17

Workshop
28 June 09

Simple exponential decay

The effects of truncation can be studied using a simple

exponential decay:

I (t ) = exp(t / )
V (t < 0) = 0 and V (t 0) =1
Fourier transform (from t = 0 to t = ):

1 j
1
1
, V () = , Z () = 1 j
I () =
2 2

1+
j
Compare with truncated transform at tmax.

SSI-17

Effect of truncation

Workshop
28 June 09
10

Delta-Real
Delta-Imag

tmax
tmax
= 100
= 100
s, s,
= 20
= 30
sec,
sec,
Y Y(t(max
tmax
) =) 0.67%
= 3.6%

Delta-Real
Delta-Imag

re, im , [%]

4
2

tmax = 100 s, = 40 sec, Y (tmax) = 8.2%

0
-2
-4
-6
-8
-10
0.01

im =

0.1

Zimag () Zim,tr ()
Z ()

Frequency, [Hz]

10

re =

100

Zreal () Zre,tr ()
Z ()

SSI-17

Workshop
28 June 09

Fourier transformed data

Simple discrete Fourier transform:

tN

X () = X (t ) e jt dt
0

X (tk ) X (tk 1 )
(cost j sin t )

tk tk 1
k =1
N

Correction / simulation for t:

X (t ) = X 0 + X 1e t /
X 0 = leakage current.

V (t )
Impedance: Z () =
I (t )

SSI-17

Workshop
28 June 09

V-step experiment

Sequence of 10 mV step Fourier transformed impedance spectra,

from 3.65 V to 4.20 V at 50 mV intervals. Fmin = 0.1 mHz

SSI-17

Workshop
28 June 09

CNLS-fit of FT-data
Circuit Description R1
R2
Code:

R(RQ)OT

*)

Fit result:
2CNLS = 3.710-5
*) O

= FLW

T = FSW

Q3, Y0
,, n
O4, Y0
,, B
T5, Y0
,, B

:
:
:
:
:
:
:
:

550
49
6.810-3
0.96
0.047
30
0.028
5.9

0.5 %
10 %
12 %
8 %
1.5 %
2.4 %
2.9 %
2.9 %

SSI-17

Workshop
28 June 09

Bode Graph
Double
logarithmic
display
almost
always
gives
excellent
result !

Bode plot, Zreal and Zimag versus frequency in double log plot

SSI-17

More Fourier transform

Workshop
28 June 09

Method Martijn Lankhorst:

fit polynomials to small sets
m
t
of data points (sections): Pm (t ) t = Ak t k

piece wise
wise
piece
integration
integration

k =0

analytical transformation to frequency domain:

m i +1

P () t = Ai
tr

i = 0 k =1

(i 1)!
(i 1 k )!

i 1 k
q

jt q

i 1 k
r

jt r

( j) k +1

More general extrapolation function (stretched exponential):

Q(t ) = Q0 + Q1 e

(t / )

, 0 1

(Fourier transform complicated, can be done numerically)

Workshop
28 June 09

Non linear effects

Electrode response based on

Butler-Vollmer:
RTa F (1RTa ) F
e
I = I0 e

When the voltage amplitude is

too large, the current response
will contain higher harmonics (i.e.
is not linear with V).
Substituting
a = aF/RT,
b = (1-c)F/RT
and a serial
expression for
exp(), we obtain:

0.05
0.05

Current, [A]
Current, [A]

SSI-17

I0 = 1 mA
a = 0.4
T = 23C

-0.05
-0.05

-0.1
-0.1
-0.2
-0.2

-0.1
-0.1

0
0
Polarisation, [V]
Polarisation, [V]

0.1
0.1

0.2
0.2

a22 a33
b22 b33
+
+ ... 1 + b
+
+ ...
I = I0 1 + a+
2!
3!
2!
3!

(a2 b2 )2 (a3 + b3 )3
= I0 (a + b)+
+
+ ...
2!
3!

SSI-17

Higher-order terms

Workshop
28 June 09

At zero bias, with the perturbation voltage, ejt, this

equation yields:

I (t )

2
2
3
3

+
(
a
b
)
(
a
b
) j 3t
jt
j 2t
= I0 (a + b)e +
e +
e + ...
2!
3!

This clearly shows the occurrence of higher-order terms.

When the polarization current is symmetric the even terms
will drop out as a = b. At a dc-polarization the response is
more complex:
3
3
2

jt
(
a
b
)
+

2
2
I (t ) = I0 (a + b) + (a b )+
+ ... e +
2!

a2 b2 (a3 + b3 ) j 2t a3 + b3
j 3t
+
+
+ ... e +
+ ... e + ...
2!
2!

3!

SSI-17

Workshop
28 June 09

Conclusions

Electrochemical Impedance Spectroscopy:

Powerful analysis tool
Subtraction procedure reveals small contributions
Presents more visual information than time domain
Almost always analytical expressions available
Equivalent Circuit approach often useful
Data validation instrument available (KK transform)
Also applicable to time domain data
(FT: ultra low frequencies possible)
Able to analyse complex systems

Unfortunately, analysis requires experience!

SSI-17

Workshop
28 June 09

Not just electrochemistry!

Data analysis strategy is applicable to any system where:

a driving force
a flux
can be defined/measured.
Examples:
mechanical properties, e.g. polymers: G () or J () &
catalysis, pressure & flux, e.g. adsorption
rheology
heat transfer, etc.

No need to measure in the frequency domain!

SSI-17

Workshop
28 June 09

Last slide

SSI-17

Active shielding

Workshop
28 June 09

I+

I-

coax

1x

coax

1x

Diff.
Amp.

System to eliminate added

capacitances from cables.
Used by e.g. Solartron 1286/1287

SSI-17

Workshop
28 June 09

Frequency Response
Analyser
Multiplier:
Vx(t)sin(t) &
Vx(t)cos(t)
Integrator:
integrates
multiplied signals
Display result:
a + jb = Vsign/Vref

But be aware of the input

impedance of the FRA!

Impedance:
Zsample = Rm (a + jb)

SSI-17

Workshop
28 June 09

Influence of input
impedances
Input impedances can seriously
influence the measurements.
For the Solartron FRA:
R = 1 M
C = 47 pF (add cable
capacitance to this!)

SSI-17

Workshop
28 June 09

Alternate set-up
Simple set-up for high
impedance samples.
Improvement: use preamplifiers / impedance
transformers.
Assignment:
Work out expression
for Zsample in terms of:
a + jb = V1/V2
(assume R1 = R2)

Match cable length for left and right

SSI-17

Workshop
28 June 09

Dealing with x =

Develop in Taylor series around x = , e.g. for Zreal:

xZim ( x) Zim ()
=
2
2
x
dZim ( x)
( x )2 d 2 Zim ( x)
xZim () + x( x )
+x
+ (...) Zim ()
2
2!
dx
dx
( x + )( x )
In the limit of x this reduces to:

xZim ( x) Zim () 1 Zim () dZim ( x)

=
+
lim

2
2
x
x
2
dx x=
In discrete KK transforms, just ignore the point x =

SSI-17

Workshop
28 June 09

Uses for NLS-fit

Virtually all non-linear functions, provided that good

initial guesses are available:

Complex impedance/admittance (CNLS-fit)

Conductivity relaxation

Polarisation (I-V ) measurements

Permeation measurements

What ever you can think of

SSI-17

Workshop
28 June 09

Mixed conductivity Tb-YSZ

0.9bar
bar
ppOO22==0.9

Zr0.909-xY0.091TbxO2-
gold electrodes
Act. energies (kJmol-1):
x = 0.091

126 (ionic)
67 (electr.)

x = 0.182 130 (ionic)

64 (electr.)

x = 0.273
x = 0.364

56 (electr.)
52 (electr.)

Eact for electronic

conduction drops at high
temperatures

SSI-17

Results YSZ-Tb36.4

Workshop
28 June 09

YSZ-Tb364
YSZ-Tb364

YSZ-Tb364
YSZ-Tb364

X0

Eact [kJ/m]

eT
460
[SK/cm] 39
G-Y0 910-3 [Ssn]
-33
K
1.3106 [s-1]
82

SSI-17

Workshop
28 June 09

Determining the CDC

(C[(Q[R(RQ)])(C[RQ])])