Electrochemical

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

Bernard A. Boukamp

Nano-Electrocatalysis,
Research Institute
U. Leiden, 24-28 Nov. 2008. for Nanotechnology
 EIS &
Nano-El-Cat My ‘where abouts’
Nov. ‘08.

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
 EIS &
Nano-El-Cat Electrochemical techniques
Nov. ‘08.

Time domain (incomplete!):

• Polarisation, (V – I ) steady state
• Potential Step, (ΔV – I (t) ) Next slide relaxation
• Cyclic Voltammetry, (V f(t)- I(V ) ) dynamic
• Coulometric Titration, (ΔV - ∫I dt ) relaxation
• Galvanostatic Intermittent Titration (ΔQ – V (t) ) transient

Frequency domain:
• Electrochemical Impedance Spectroscopy perturbation of
(EIS) equilibrium state
 EIS &
Nano-El-Cat Time or frequency domain?
Nov. ‘08.

1.E-04

1.E-05
C u rre n t, [A ]

1.E-06

1.E-07
0 1000 2000 3000
Time, [sec]
 EIS &
Nano-El-Cat Advantages of EIS:
Nov. ‘08.

System in thermodynamic equilibrium

Measurement is small perturbation (approximately linear)
Different processes have different time constants
Large frequency range, μHz 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
 EIS &
Nano-El-Cat Black box approach
Nov. ‘08.

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 ω=2πf ,
with: 0≤ ω< ∞

Phase shift and amplitude

changes with ω!
 EIS &
Nano-El-Cat So, what is EIS?
Nov. ‘08.

Probing an electrochemical system with a small

ac-perturbation, V0⋅ejωt, over a range of frequencies.
The impedance (resistance) is given by: ω= 2πf
V (ω) V0 e jωt V0 j = √-1
Z (ω) = = j ( ωt +ϕ)
= [ cos ϕ − j sin ϕ]
I (ω) I0 e I0
The magnitude and phase shift depend on frequency.

Also: admittance (conductance), inverse of

impedance:
1 I0 e j (ωt +ϕ) I0
Y (ω) = = jωt
= [ cos ϕ + j sin ϕ]
Z (ω) V0 e V0
“real +j. imaginary”
 EIS &
Nano-El-Cat Complex plane
Nov. ‘08.

Impedance ≡ ‘resistance’
Admittance ≡ ‘conductance’:
1 Zre − jZim
Y (ω) = = 2
Z (ω) Zre + Zim2
hence:

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

Representation of impedance value,

Z = a +jb, in the complex plane
 EIS &
Nano-El-Cat
Adding impedances and
Nov. ‘08. admittances
A linear arrangement of
impedances can be added in
the impedance representation:
Ztotal = Z1 + Z2 + Z3 + ... = ∑ Zn
n

A ‘ladder’ arrangement of admittances

(inverse impedances) can be added in
the admittance representation :
Ytotal = Y1 + Y2 + Y3 + ... = ∑Yn
n
 EIS &
Nano-El-Cat Simple elements
Nov. ‘08.

The most simple element

1
is the resistance: 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’ !
 EIS &
Nano-El-Cat Capacitance?
Nov. ‘08.

Aε0ε
Take a look at the properties of a capacitor: C =
d
Charge stored (Coulombs): Q = C ⋅V
Change of voltage results dQ dV
in current, I: I= =C
dt dt

dV0 ⋅ e jωt
Alternating voltage (ac): I (ωt ) = C = jωC ⋅V0 ⋅ e jωt
dt
V (ω) 1
Impedance: ZC ( ω) = =
I (ω) jωC
Admittance: YC ( ω) = Z (ω)−1 = jωC
 EIS &
Nano-El-Cat Combination of elements
Nov. ‘08.

What is the impedance of an -R-C-

circuit?
1
Z (ω) = R + = R − j / ωC
jωC

1
Admittance? Y (ω) = =
R − j / ωC
ω2C 2 R ωC
+j
1+ ω C R
2 2 2
1 + ω2C 2 R2

Semi- ‘time constant’:

‘time constant’:
circle ττ == RC
RC
 EIS &
Nano-El-Cat A parallel R-C combination
Nov. ‘08.

The parallel combination of a resistance and a

capacitance, start in the admittance representation:
1
Y (ω) = + jωC R
R
Transform to impedance representation: C

1 1 1/ R − jωC
Z (ω) = = ⋅ =
Y (ω) 1/ R + jωC 1/ R − jωC
R − jωR2C 1 − jωτ
=R
1+ ω R C
2 2 2
1 + ω2 τ2

A semicircle in the impedance plane! Plot next slide

 EIS &
Nano-El-Cat Impedance plot (RC)
Nov. ‘08.

8.0E+04

fmax = 1/(6.3x3⋅10-9x105)=530 Hz

6.0E+04 R = 100 kΩ
518 Hz
C = 3 nF
-Zimag, [ohm]

4.0E+04

2.0E+04

1 MHz 1 Hz
0.0E+00
0.0E+00 2.0E+04 4.0E+04 6.0E+04 8.0E+04 1.0E+05 1.2E+05
Zreal, [ohm]
 EIS &
Nano-El-Cat Limiting cases
Nov. ‘08.

What happens for ω << τ and for ω >> τ ?

1 − jωτ
ω << τ : Z (ω) = R ≈ R − jωRτ ≈ R − jωR 2
C
1+ ω τ
2 2

ω >> τ : Z (ω) = R
1 − jωτ R R 1 1
≈ 2 2−j ≈ 2 2−j
1+ ω τ ω τ
2 2
ωτ ω RC ωC

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
 EIS &
Nano-El-Cat Bode plot (Zre, Zim)
Nov. ‘08.

1.E+05

Zreal
1.E+04 Zimag

1.E+03
Z re a l, -Z im a g , [o h m ]

1.E+02

1.E+01
ω-1

1.E+00 ω-2
1.E-01

1.E-02
1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06
frequency, [Hz]
 EIS &
Nano-El-Cat Bode, abs(Z), phase
Nov. ‘08.

1.E+05 90

abs(Z) 75
Phase (°)

1.E+04 60
a b s (Z ), [o h m ]

P h a s e (d e g r)
45

1.E+03 30

15

1.E+02 0
1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06
Frequency, [Hz]
 EIS &
Nano-El-Cat Other representations
Nov. ‘08.

Capacitance: C(ω) = Y(ω) /jω for an (RC) circuit:

⎡1 ⎤ 1
C (ω) = Y (ω) / jω = ⎢ + jωC ⎥ / jω = C − j
⎣R ⎦ ωR
Dielectric: ε(ω) = Y(ω) /jωC0 C0 = Aε0/d
d σion d: thickness
d: thickness
ε(ω) = Y (ω) ⋅ = ε′ − j
Aε0 ωε0 A: surf.
surf. area
area
A:
Modulus: M(ω) = Z(ω) ⋅jω

ω2CR 2 + jωR
M (ω) = Z (ω) ⋅ jω =
1 + ω2C 2 R 2
 EIS &
Nano-El-Cat Simple model
Nov. ‘08.

Example: an ionically conducting solid,

e.g. yttrium stabilized zirconia,

Zr1-xYxO2-½x .
Apply two ionically blocking electrodes, Schematic
arrangement of sample
in this case thick gold. and electrodes.
Measure the ‘resistance’ (impedance)
as function of frequency:
1
Z (ω) =
1
jωCg +
1
Rion + 1
2 jωCint Equivalent circuit: (C[RC])
 EIS &
Nano-El-Cat Low & high f - response
Nov. ‘08.

Low frequency regime,

series combination Rion-Cint: Z (ω) = Rion − j / 12 ωCint

Straight vertical line in impedance plane.

High frequency regime,

parallel combination of Rion//Cgeom:
Rion ωRion
2
Cgeom
Z (ω) = −j
1 + ω RionCgeom
2 2 2
1 + ω2 Rion
2 2
Cgeom

Semicircle through the origin.

 EIS &
Nano-El-Cat ‘Debije’ model:
Nov. ‘08.

An ionic conductor between two blocking electrodes:

1
Y (ω) =
Z (ω)

Impedance representation Admittance representation

 EIS &
Nano-El-Cat Other representations
Nov. ‘08.

Different Bode
Zimag representation

Zreal

‘Bode’ representation
 EIS &
Nano-El-Cat Diffusion, Warburg element
Nov. ‘08.

Semi-infinite diffusion,
Flux (current) : J = −D ∂C
(Fick-1) ∂x x =0

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

Fick-2 :
∂C ∂ 2
C
=D 2
∂t ∂x
Boundary Redox
Li-battery
on inert
cathode
condition : C( x, t ) x→∞ = C o
electrode.

Solution through Laplace transform: next page

 EIS &
Nano-El-Cat Warburg element, cont.
Nov. ‘08.

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) = o
C( x, p)
nFC Boundary
Boundary
∂C( x, p) condition:
condition:
Transform of I (t): I ( p) = −nFD C( x, p ) x→∞ = 0
(Fick-1) ∂x x=0
 EIS &
Nano-El-Cat Warburg impedance
Nov. ‘08.

Define impedance in Laplace space!

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

RT −1/ 2 −1/ 2
Z (ω) = = Z0 (ω − jω )
(nF ) C jωD
2 o

with: In solution:
RT RT ⎛ 1 1 ⎞
Z0 = Z 0 = (σ = ) 2 2 ⎜ * + * ⎟
(nF )2 Co 2D n F A 2 ⎜⎝ CO DO CR DR ⎟
⎠
 EIS &
Nano-El-Cat Transmission line
Nov. ‘08.

Real life Warburg,

r
semi-infinite coax cable ZW (ω) =
with r Ω/m and c F/m: jωc

Combination:
• Electrolyte resistance, Re’lyte
• Double layer capacitance, Cdl Equivalent
• Charge transfer resistance, Rct circuit
• Warburg (diffusion) impedance, Wdiff
 EIS &
Nano-El-Cat Equivalent Circuit Concept
Nov. ‘08.

se
m
ic
ir
cl
e
ω

45°
 EIS &
Nano-El-Cat Instruments
Nov. ‘08.

Measurement methods
Bulk, conductivity:
• two electrodes
• pseudo-four electrodes
• true four electrodes

Electrode properties:
• three electrodes
 EIS &
Nano-El-Cat
Frequency Response
Nov. ‘08. Analyser
Multiplier:
Vx(ωt)×sin(ωt) &
Vx(ωt)×cos(ωt)
Integrator:
integrates
multiplied signals
Display result:
a + jb = Vsign/Vref
Impedance:
But be aware of the input
impedance of the FRA! Zsample = Rm (a + jb)
 EIS &
Nano-El-Cat Potentiostat, electrodes
Nov. ‘08.

Vpwr.amp = A Σk Vk
A= amplification
Vwork – Vref =
Vpol. + V3 + V4

Current-voltage
converter
provides virtual
ground for
Work-electrode.

Source of
General schematic inductive effects
 EIS &
Nano-El-Cat Data validation
Nov. ‘08.

Kramers-Kronig relations (old!)

Real and imaginary parts are linked
through the K-K transforms:

Kramers-Kronig
conditions: Response only
• causality Response
due to input
State
scales of
linearly
• linearity signalmay
system
with input
• stability notsignal
change
• (finiteness) during
measurement
 EIS &
Nano-El-Cat Putting ‘K-K’ in practice
Nov. ‘08.

Relations,
∞
2ω Z re ( x) − Z re (ω)
Real → imaginary: Z im (ω) =
∫
π 0 x −ω
2 2
dx

not a singularity!
∞
2 xZ im ( x) − ωZ im (ω)
Imaginary → real: Z re (ω) = R∞ + ∫ dx
π0 x −ω
2 2

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.
 EIS &
Nano-El-Cat Linear KK transform
Nov. ‘08.

Linear set of parallel RC circuits:

τk = Rk⋅Ck

Create a set of τ values: τ1 = ωmax-1 ; τM = ωmin-1

with ~7 τ-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

 EIS &
Nano-El-Cat Actual test
Nov. ‘08.

Fit function simultaneously to

real and imaginary part:
1 − jωi ⋅ τ k
M
Z KK (ωi ) = R∞ + ∑ Rk
Shortcut to KKtest.lnk

k =1 1 + ω 2
i ⋅ τ 2
k

Set of linear equations in Rk,

only one matrix inversion! It works like a
‘K-K compliant’
flexible curve
Display relative residuals:

Zre,i − Z KK, re (ωi ) Zim,i − Z KK,im (ωi )

Δreal = , Δimag =
Zi Zi
 EIS &
Nano-El-Cat Example ‘K-K check’
Nov. ‘08.

Impedance of a sample, not in

equilibrium with the ambient.

χ2KK = 0.9·10-4
χ2CNLS = 1.4 ·10-4
 EIS &
Nano-El-Cat Finite length diffusion
Nov. ‘08.

Particle flux at x=0:

~ dC( x, t )
J (t ) = −D
dt x=0

Fick’s 2nd law:

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

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
 EIS &
Nano-El-Cat Finite length diffusion
Nov. ‘08.

Replace concentration
by its perturbation:
c( x, t ) = C( x, t ) − C 0
Impermeable
dC( x, t )
boundary at x =L: = 0 FSW
dx x=l

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

General expression
for permeable
boundary:
dC( x, t )
dx
[
= −k C( x, t ) x=l − Cl ] General!
x =l
 EIS &
Nano-El-Cat FLD, continued
Nov. ‘08.

Voltage with respect to reference C0 (a0):

RT ax=0 RT ⎡ d ln a ⎤
E(t ) = ln 0 = 0 ⎢ ⎥ c( x, t ) x=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

a a0 + Δa ⎛ Δa ⎞ Δa
Assumption: Δa << a0: ln 0 = ln
a a 0
= ln⎜1 + 0 ⎟ ≈ 0
⎝ a ⎠ a
Relation a ⇔ C from da a0 dln a Δa Δa
‘titration curve’: = 0 ≈ =
dC C dln C ΔC Δc( x, t ) x=0
 EIS &
Nano-El-Cat Up to the Frequency Domain!
Nov. ‘08.

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

gives the complex impedance (with p=jω): with:
R T Vm ⎡ d ln a ⎤
E(ω) Z0 jω Z0 = 2 2 ⎢ ⎥ =
FSW Z (ω) = = ~ cothl D~ n F S ⎣ d ln c ⎦
I (ω) jωD Vm ⎡ d E ⎤
= ⎢ ⎥
nFS ⎣ d δ ⎦

FLW
E(ω) Z0 jω
Z (ω) = = ~ tanhl D~
I (ω) jωD

Laplace space p p
solution of Fick-2: C( p) = A cosh x ~ + B sinh x ~
D D
 EIS &
Nano-El-Cat Dispersions
Nov. ‘08.

High frequencies:
Z(ω) = Z0 (j ω)-1/2
−1
Vs nF ⎡ d E ⎤
Cint = = Warburg diffusion
VM ⎢⎣ d δ ⎥⎦

Low frequency limit:

FSW = capacitive
FLW = dc-resistance

Impedance representation of
FSW and FLW.
 EIS &
Nano-El-Cat
General finite length
Nov. ‘08. diffusion

Generic finite Z0 jωD%⋅ coth l jω

D%
+k
length diffusion: Z (ω) =
jωD% k coth l jω
D%
+ jωD%

If k =0 then
blocking interface
⇒ FSW
If k = ∞ then ideal
passing interface
⇒ FLW

Å Plot for different

values of k.
 EIS &
Nano-El-Cat A Simple Example
Nov. ‘08.

AgxNbS2 is a layered structure,

consisting of two-dimensional NbS2
layers. Insertion and extraction of Ag+
ions goes in an ideal manner (see graph).
H.J.M. Bouwmeester
Isostatically pressed and sintered
sample. Some preferential orientation
(in the proper direction!) will occur.

Simple cell
design for EIS
measurements.
 EIS &
Nano-El-Cat Circuit Description Code
Nov. ‘08.

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 ω)n (Adm.) Z0(j ω)-n (Imp.)
 EIS &
Nano-El-Cat The CPE
Nov. ‘08.

Constant Phase Element:

YCPE = Y0 ωn {cos(n π/2) + j sin(n π/2)}
n=1 Î Capacitance: C = Y0
• n=½ Î Warburg: σ = Y0
• n=0 Î Resistance: R = 1/Y0
• n = -1 Î Inductance: L = 1/Y0
All other values, ‘fractal?’

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

 EIS &
Nano-El-Cat Non-ideal behaviour
Nov. ‘08.

General observations:
• Semicircle (RC ) ⇒ depressed
• vertical spur (C ) ⇒ inclined
• Warburg ⇒ less than 45°

Deviation from ‘ideal’ dispersion:

Constant Phase Element (CPE),
(symbol: Q )

⎡ nπ nπ ⎤ nn == 1,1, ½,
½,
YCPE = Y0 ( jω) = Y0ω ⎢cos + j sin ⎥
n n

⎣ 2 2⎦ 0, -1,
0, -1, ??
 EIS &
Nano-El-Cat The Fractal Concept
Nov. ‘08.

How to explain this non-ideal behaviour?

1980’s: ‘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 (
 EIS &
Nano-El-Cat Fractals
Nov. ‘08.

Fractal line

Self similarity!
Self similarity!

‘Sierpinski carpet’
 EIS &
Nano-El-Cat ‘Fractal electrode’
Nov. ‘08.

‘Cantor bar’
arrangement

Impedance of the network:

a 1a
Z⎛(ω)⎞= R + a Z (ω)
Z⎜ ⎟ = R+ 2 22 R aR a2R a3R
⎝a⎠ jω CC+Z+(ω) + 2
jωaC
Z (ω) 1
R+
aR
22
jωC aC++ 2
aaRR + ...
 EIS &
Nano-El-Cat Arriving at the ‘CPE’
Nov. ‘08.

⎛ ω⎞ a Z (ω)
Frequency scaling relation: Z ⎜ ⎟ = R +
⎝a⎠ jωC Z (ω) + 2

In the low frequency

limit this reduces to:
⎛ ω⎞ a
Z ⎜ ⎟ = Z (ω)
⎝a⎠ 2
Which is satisfied by
the formula: Z (ω) = A( jω)−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.
 EIS &
Nano-El-Cat CDC
Nov. ‘08.

CDC = ‘instruction string’ for response calculation

Uses brackets:
• [ … ] series combination, e.g.: [RC]

• ( … ) parallel combination, e.g. (RC)

Randles circuit: R(C[RW])

W
 EIS &
Nano-El-Cat Determining the CDC
Nov. ‘08.

(C[(Q[R(RQ)])(C[RQ])])
 EIS &
Nano-El-Cat CNLS data analysis
Nov. ‘08.

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

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

{ 2
S = ∑ wi Zre,i − Zre (ωi ) + Zim,i − Zim (ωi )
i =1
2
}
2 2
with: wi = Zi ≈ Z (ωi , ak ) (weight factor)

d
for k = 1 ..M S =0
dak
Non-linear, complex model function!
Effect of minimisation
 EIS &
Nano-El-Cat Non-linear systems
Nov. ‘08.

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

[
Z (ω) = Z0 ⋅ k + ( jω) ]
β −α
= Z (ω, Z0 , k , α, β) (‘Gerischer’)

Linearisation: Taylor development around ‘guess values’, ajo:

∂Y ( x, a1..aM )
Y ( x, a1..aM ) = Y ( x, a ..a ) + ∑
ο
1
ο
M ⋅ δa j + ....
j ∂a j
a1ο..aM
ο

Derivative of error sum with respect to δaj :

∂S ⎡ ∂Y ( xi , a1..M ) ⎤ ∂Y ( xi , a1..M )
= 0 = 2∑ wi ⎢ yi − Y ( xi , a1..M ) + ∑
ο
δak ⎥
∂a j i ⎣ k ∂ak ⎦ ∂a j
 EIS &
Nano-El-Cat NLLS-fit
Nov. ‘08.

A set of M simultaneous equations, in matrix form:

α ⋅ δa = β , solution: δa = α-1⋅ β = ε ⋅ β

∂Y ( xi , a1..M ) ∂Y ( xi , a1..M )
With: α j,k = ∑ wi ⋅
i ∂a j ∂ak
∂Y ( xi , a1..M )
and: βk = ∑ wi [ yi − Y ( xi , a1..M )]
i ∂ak
Derivatives are taken in point ao1..M.

Iteration process yields new, improved values: a’j = aoj + δaj.

 EIS &
Nano-El-Cat Marquardt-Levenberg
Nov. ‘08.

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! Successfuliteration:
Successful iteration:
SSnew Sold
new<<S
Multiply diagonal terms with (1+λ). Î decrease λ
Î decrease λ (=
old
(=λ/10).
λ/10).
Otherwiseincrease
Otherwise increase
• λ << 1, analytical search (=λ×10)
λλ(= λ×10)
• λ >> 1, gradient search
Bottom line: good starting parameter estimates are essential!
 EIS &
Nano-El-Cat Error estimates
Nov. ‘08.

For proper statistical analysis the weight factors, wi,

should be established from experiment.
Other (dangerous) method:
Step 1: set weight factors, wi = g ⋅ σi-2
Step 2: assume variances can be replaced by parent
distribution, hence χν2 ≈ 1 (with ν = N –M – 1)
Step 3:
χ 1 [ yi − Y ( xi , a1..M )] 1
2 2
1 S
χ = = ∑
2
ν = S∑ = ≅1
ν ν i σi 2
ν i wi ⋅ σi g ⋅ ν
2

Hence proportionality factor, g = S/ν.

 EIS &
Nano-El-Cat Error analysis NLLS-fit
Nov. ‘08.

Based on this assumption we can derive

[ ]
the variances of the parameters: σ a2k = g ⋅ αk , k
−1
= g ⋅ εk ,k
Error matrix, ε, also contains the covariance of the
parameters: σ ⋅σ = g ⋅ ε
aj ak j ,k

g⋅ εj,k ≅ 0, no correlation between aj and ak.

g⋅ εj,k ≅ 1, strong correlation between aj and ak.

Only acceptable for many data points AND

random distribution of the ‘residuals’
 EIS &
Nano-El-Cat
Weight factors and error
Nov. ‘08. 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!
Zre,i − Zre (ωi ) Zim,i − Zim (ωi )
Residuals graph: Δre = , Δim =
Z (ωi ) Z (ωi )
Large error estimates:
strongly correlated
parameters (+ noise).
Option: modification of
weight factors.
 EIS &
Nano-El-Cat Two different CNLS-fits
Nov. ‘08.

Example of correct
error estimates: R(RC)(RC)

CDC: R(RQ)(RQ)
χ2 2.4⋅10-5
R1 999 0.8%
R2 4000 1.7% χ2 3.8⋅10-3
And of incorrect
Q3 1.03⋅10-9 7% error estimates: R1 1290 4%
-n3 0.898 0.6% R2 4650 2.7%
R4 8020 0.9% CDC: R(RC)(RC)
Values seem O.K. C3 2.38⋅10-103.8%
Q5 1.03⋅10-7 3.6% but look at the R4 6580 2.6%
-n5 0.697 0.7% residuals!
C5 6.07⋅10-9 7.3%
 EIS &
Nano-El-Cat Residuals plot!
Nov. ‘08.

Systematic deviation,
‘Trace’, bad fit

Good fit (not bad for

a straight simulation!)
 EIS &
Nano-El-Cat ‘Fingerprinting’
Nov. ‘08.

Classification of capacitance
source approximate value

geometric 2-20 pF (cm-1)

grain boundaries 1-10 nF (cm-1)
double layer / space charge 0.1-10 μF/cm2
surface charge /”adsorbed species” 0.2 mF/cm2
(closed) pores 1-100 F/cm3
“pseudo capacitances”
“stoichiometry” changes large !!!!
Modified after: Peter Holtappels, TMR symposium ‘Alternative anodes...’,
Jülich, March 2000.
 EIS &
Nano-El-Cat Gas phase capacitance
Nov. ‘08.

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

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

2 Example:
Combination: C = ⎛ 4F ⎞ V ⋅ P air, 700°C, Vol. = 10 mm3
ox ⎜ ⎟
⎝ RT ⎠ Cox = 0.456 F !
 EIS &
Nano-El-Cat Conclusions on ‘fitting’
Nov. ‘08.

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!

It’s human to err, its dumb not to include

an error estimate with a number result
 EIS &
Nano-El-Cat ‘Molecular Printboard’
Nov. ‘08.

ferrocenyl (Fc) decorated poly(propylene imine) dendrimer

β-cyclodextrin

Christian A. Nijhuis, B.A. Boukamp, B-J. Ravoo,

J. Huskens and D.N. Reinhoudt J. Phys. Chem. C 111 (2007) 9799
 EIS &
Nano-El-Cat Electrochemical response
Nov. ‘08.

Impedance graphs of
an aqueous solution of 1
mM (in Fc
functionality) of G4-
PPI-(Fc)32-(β-CD)32
at a β-CD SAM.
(10 mM β-CD at pH = 2)

Potential: -0.15 V to 0.15 V

Frequency: 10 kHz to 10 mHz
KK-test: < 10 × 10-6
 EIS &
Nano-El-Cat Subtraction procedure
Nov. ‘08.

• Partial CNLS-fit of recognizable structure

ƒ Semicircle
ƒ 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
 EIS &
Nano-El-Cat Impedance G-4 at 0.105 V
Nov. ‘08.

3.E+04
3.E+04

SAM cap.//resist.
Randles response
[ohm]
Zimag,[ohm]

2.E+04
2.E+04
--Zimag,

1.E+04
1.E+04

0.E+00
0.E+00
0.E+00
0.E+00 1.E+04
1.E+04 2.E+04
2.E+04 3.E+04
3.E+04 4.E+04
4.E+04
Zreal,[ohm]
Zreal, [ohm]
 EIS &
Nano-El-Cat Subtract Rel’lyte, CSAM
Nov. ‘08.

3.E+04
3.E+04

Fit of Randles circuit: R(C[RW])

[ohm]
Zimag,[ohm]

2.E+04
2.E+04
--Zimag,

1.E+04
1.E+04

0.E+00
0.E+00
0.E+00
0.E+00 1.E+04
1.E+04 2.E+04
2.E+04 3.E+04
3.E+04 4.E+04
4.E+04
Zreal,[ohm]
Zreal, [ohm]
 EIS &
Nano-El-Cat First CNLS-result
Nov. ‘08.

-Z-ima g x 1e 5

4
Re a l,Ima g-e rror x 1e -2 EqCWIN analysis
3

2
Full circuit
1

-1

0.2 -2

-3

-4

1e -1 1 1e 1 1e 2 1e 3
Fre que ncy

Re a l,Ima g-e rror x 1e -2

Residuals plot(R[RC])
4
0.1 3

2
Circuit without
1

-1

-2

-3

-4

1e -1 1 1e 1 1e 2 1e 3
Fre que ncy

0
0 0.1 0.2 0.3 0.4
Z-re a l x 1e 5
G4-ferrocene, 0.105 V
 EIS &
Nano-El-Cat Subtract Rel’lyte, CSAM
Nov. ‘08.

3.E+04
3.E+04

Fit of Randles circuit: R(C[RW])

[ohm]
Zimag,[ohm]

2.E+04
2.E+04
--Zimag,

1.E+04
1.E+04

0.E+00
0.E+00
0.E+00
0.E+00 1.E+04
1.E+04 2.E+04
2.E+04 3.E+04
3.E+04 4.E+04
4.E+04
Zreal,[ohm]
Zreal, [ohm]
 EIS &
Nano-El-Cat Subtract Randles
Nov. ‘08.
[ohm]
Zimag,[ohm]

100
100
--Zimag,

00
3800
3800 3900
3900 4000
4000
Zreal,[ohm]
Zreal, [ohm]
 EIS &
Nano-El-Cat Small difference, but …
Nov. ‘08.

-Z-ima g x 1e 5

4
Re a l,Ima g-e rror x 1e -2 EqCWIN analysis
3

2
Full circuit
1

-1

0.2 -2

-3

-4

1e -1 1 1e 1 1e 2 1e 3
Fre que ncy

Re a l,Ima g-e rror x 1e -2

4
0.1 3

2
Circuit without (R[RC])
1

-1

-2

-3

-4

1e -1 1 1e 1 1e 2 1e 3
Fre que ncy

0
0 0.1 0.2 0.3 0.4
Z-re a l x 1e 5
G4-ferrocene, 0.105 V
 EIS &
Nano-El-Cat Equivalent Circuit
Nov. ‘08.

+
Au
 EIS &
Nano-El-Cat Consistency of Circuit!
Nov. ‘08.

R2 CSAM

R1
C2

Tentative model
 EIS &
Nano-El-Cat Modelling of diffusion
Nov. ‘08.

Modelling diffusion:
1
Qdiff = Q0
⎛ 1 ⎞ ⎛ DO ⎞
⎜1+ ⎟ + ⎜⎜ 1 + K θ ⎟⎟
⎝ K θ ⎠ ⎝ DR ⎠

n 2F 2 A 2 0
with: Q0 = CFc ,tot DO
RT
for right hand side only.

Actually: Qdiff= Qconst + Qdiff(V)

Modelling of double- nF
RT
( η−η ) 0
e
layer capacitance: Cdl = Cdl ,1θ + Cdl ,2 (1 − θ) , with: θ = nF
( η−η0 )
1+ e RT
 EIS &
Nano-El-Cat Diffusion & generation
Nov. ‘08.

Generation 1 to 4 measured at the same βCD SAM:

■ : G1
▼: G2
100 ▲: G3

●: G4
σ (μF)

RT ⎛ 1 1 ⎞
σ= 2 2 ⎜ + * ⎟
n F A 2 ⎜⎝ CO DO C R DR ⎟
10
*
⎠
-0.02 0.00 0.02 0.04 0.06 0.08 0.10
Polarization (V)
 EIS &
Nano-El-Cat Stokes-Einstein
Nov. ‘08.

Stokes-Einstein relation:
kT
D=
6ηπr

Qdiff ÷ √D
and r ÷ Generation nr.
Hence: Qdiff ÷ (Gx)-1/2

The Warburg admittance corrected for the

concentration of dendrimers and the number
of electrons involved per molecules plotted vs
the (square root of generation)-1.
 EIS &
Nano-El-Cat Reaction Pathways
Nov. ‘08.

Schematic of the potential-dependent surface coverage of the

dendrimers (left), and a scheme of adsorption and desorption kinetics
(right), Redsol = reduced dendrimers in solution, Redads = dendrimers
adsorbed at the βCD SAM, Oxsol = oxidized dendrimers in solution,
Oxads = oxidized dendrimers at the surface; kdr, kar, kdo and kao are
adsorption (a) and desorption (d) rates of oxidized (o) and reduced (r)
dendrimers; kb and kf are electrochemical rate constants.
 EIS &
Nano-El-Cat Praise of the time domain …
Nov. ‘08.

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
E(t ) = ln 0
nF aA
Fick 1 & 2, boundary conditions V (ω) Z0 jω
+ Laplace transform: Z (ω) = = coth l
I (ω) jωD% D%
 EIS &
Nano-El-Cat Real cathode: LixCoO2
Nov. ‘08.

10.0
10.0
Measurement
Measurement RR sl RR ct W
ct W
Simulation
Simulation RR e
sl
e
7.5 QQ
sl
sl CC
dl
dl
7.5
20Hz
20Hz
3.78V

[kΩ]
3.78V

Z"[kΩ]
5.0
5.0 27Hz
27Hz

Z"
36Hz
3.69V
3.69V
36Hz
3.84V
3.84V
2.5
2.5
63Hz
63Hz 3.88V
3.88V
110Hz
110Hz
4.06V
4.06V
0.0
0.0
0.0
0.0 2.5
2.5 5.0
5.0 7.5
7.5 10.0
10.0 12.5
12.5 15.0
15.0
Z'Z'[kΩ]
[kΩ]

LiCoO2, RF film on silicon. IS of a RF-film electrode: (○) ‘fresh’;

(□) charged; (‘) intermediate SoC’s.
Peter J. Bouwman, Thesis, (+) CNLS-fit. Range: 0.01 Hz – 100
U.Twente 2002. kHz.
 EIS &
Nano-El-Cat Diffusive part?
Nov. ‘08.
10
10
The lithium diffusion 99
process is found at lower 88
4.05V
4.05V

frequencies! 77
4.10V
4.10V

[μA.cm-2] ]
Compare the potential-step

-2
66

Current[μA.cm
response time with lowest
4.00V 4.15V
4.00V
55 4.15V

Current
frequency of EIS 44 4.20V
4.20V
experiment: 33 3.95V
3.95V

22
teq. >> 3000 s (~ 0.3 mHz) 3.90V
3.90V
11 3.85V
3.85V

fmin ~ 10 mHz 00
3.80V
3.80V

00 1000
1000 2000
2000 3000
3000
MEASURE RESPONSE
MEASURE RESPONSE IN
IN Time[s]
Time [s]

THE TIME
THE TIME DOMAIN!
DOMAIN! Current response of a 0.75μm RF-
film to sequential 50mV potential
steps from 3.80V to 4.20V.
 EIS &
Nano-El-Cat Fourier transform
Nov. ‘08.

Fourier transform of a temporal function X (t):

∞
X (ω) = ∫ X (t ) ⋅ e− jωt dt
0

V (ω)
Impedance: Z (ω) =
I (ω)
V0
E.g. with a voltage step, V0: V (ω) =
jω

Model function: Laplace transform of transport equations

and boundary conditions, with p = s +j ω. Set s = 0: ⇒
impedance
 EIS &
Nano-El-Cat Fourier Transform
Nov. ‘08.

Two problems with F-T: X(t )=at + b

• Data is discrete:
approximate by summation (X =at + b) Xi -1
• Data set is finite (next slide) Xi

Very Simple Summation Solution (VS3): ti -1 ti

N
L
M
X (ω) = ∑ Xi sin ωti − Xi −1 sin ωti −1 +
a
b O
gP
cosωti − cosωti −1 ω −1 +
N
i =1 ω Q
LX cosωt − X
− j∑ M
N

i −1 cosωti −1 − b
a O
sin ωt − sin ωt g
Pω −1

N i =1
i i
ω
i i −1
Q
 EIS &
Nano-El-Cat Simple exponential extension
Nov. ‘08.

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 e−t /τ
Full Fourier Transform:

z z
tN ∞
− jωt Q0
X (ω) = [ X (t ) − Q0 ] e dt − j + Q1 e −t / τ e − jωt dt
0
ω t N

Analytical transform of exponential extension:

R U
z
∞ −1
τ cos ωt − ω sin ωt ω cos ωt N + τ −1 sin ωt N
Q1 e −t / τ
e − jωt
dt = Q1 ⋅ e −t N / τ
⋅S N N
+j V
tN T ω +τ 2 −2
ω 2 + τ −2 W
 EIS &
Nano-El-Cat Fourier transformed data
Nov. ‘08.

Simple discrete Fourier transform:

tN

X (ω) = ∫ X (t ) e− jωt dt ≈
0
N
X (tk ) − X (tk −1 )
∑ (cosωt − j sin ωt )
k =1 tk − tk −1
Correction / simulation for t→∞:
X (t ) = X 0 + X 1e −t / τ
X 0 = leakage current.

V (t )
Impedance: Z (ω) =
I (t )
 EIS &
Nano-El-Cat V-step experiment
Nov. ‘08.

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
 EIS &
Nano-El-Cat CNLS-fit of FT-data
Nov. ‘08.

Circuit Description R1 : 550 0.5 %

Code: R2 : 49 10 %
Q3, Y0 : 6.8⋅10-3 12 %
R(RQ)OT *)
,, n : 0.96 8 %
Fit result: O4, Y0 : 0.047 1.5 %
,, B : 30 2.4 %
χ2CNLS = 3.7⋅10-5 T5, Y0 : 0.028 2.9 %
,, B : 5.9 2.9 %

*) O = ‘FLW’
T = ‘FSW’
 EIS &
Nano-El-Cat Bode Graph
Nov. ‘08.

Double
logarithmic
display
almost
always
gives
excellent
result !

‘Bode plot’, Zreal and Zimag versus frequency in double log plot
 EIS &
Nano-El-Cat Conclusions
Nov. ‘08.

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!
 EIS &
Nano-El-Cat Not just electrochemistry!
Nov. ‘08.

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 (ω) or J (ω) & γ
• catalysis, pressure & flux, e.g. adsorption
• rheology
• heat transfer, etc.
No need to measure in the frequency domain!
 EIS &
Nano-El-Cat Last slide
Nov. ‘08.
 EIS &
Nano-El-Cat
Nov. ‘08.
 EIS &
Nano-El-Cat Effect of truncation
Nov. ‘08.
10
Delta-Real
8
Delta-Imag tmax
tmax
= 100
= 100
s, s,
τ =τ 20
= 30
sec, Y Y(t(max
sec, tmax
) =) 0.67%
= 3.6%
6
Delta-Real
4 Delta-Imag
Δre, Δim , [%]

2
tmax = 100 s, τ = 40 sec, Y (tmax) = 8.2%
0

-2

-4

-6

-8

-10
0.01 0.1 1 10 100

Zimag (ω) − Zim,tr (ω) Frequency, [Hz] Zreal (ω) − Zre,tr (ω)
Δim = Δre =
Z (ω) Z (ω)
 EIS &
Nano-El-Cat More Fourier transform
Nov. ‘08.

Method Martijn Lankhorst: piece wise

wise
piece
¾ fit polynomials to small sets integration
integration
m
of data points (sections): Pm (t ) t = ∑ Ak t k
t r

q
k =0
¾ analytical transformation to frequency domain:
i −1− k − jωt q i −1− k − jωt r
m i +1
(i − 1)! t ⋅e −t ⋅e
P (ω) t = ∑ ∑ Ai
tr q r
⋅
q
i = 0 k =1 (i − 1 − k )! ( jω) k +1

More general extrapolation function (stretched exponential):

−(t / τ )α
Q(t ) = Q0 + Q1 ⋅ e , 0 ≤ α ≤1
(Fourier transform complicated, can be done numerically)
 EIS &
Nano-El-Cat Non linear effects
Nov. ‘08.

Electrode response based on 0.05

0.05

Butler-Vollmer:
⎡ αRTa F η − (1−αRTa ) F η ⎤
I = I0 ⎢e −e ⎥ 0
0

Current, [A]
⎣ ⎦

Current, [A]
When the voltage amplitude is -0.05
I0 = 1 mA
αa = 0.4
-0.05

too large, the current response

T = 23°C
will contain higher harmonics (i.e. -0.1

is not linear with V).

-0.1
-0.2 -0.1 0 0.1 0.2
-0.2 -0.1 0 0.1 0.2
Polarisation, [V]
Polarisation, [V]

Substituting
a = αaF/RT, ⎡ a2η2 a3η3 b2η2 b3η3 ⎤
I = I0 ⎢1 + aη+ + + ... −1+ bη− + + ...⎥
b = (1-αc)F/RT ⎣ 2! 3! 2! 3! ⎦
and a serial
expression for ⎡ (a2 − b2 )η2 (a3 + b3 )η3 ⎤
exp(), we obtain:
= I0 ⎢(a + b)η+ + + ...⎥
⎣ 2! 3! ⎦
 EIS &
Nano-El-Cat Higher-order terms
Nov. ‘08.

At zero bias, with the perturbation voltage, ∆·ejωt, this

equation yields:
⎡ jωt (a 2
− b2
) j 2ωt (a3
+ b3
) j 3ωt ⎤
I (t ) = I0 ⎢(a + b)Δe + Δe + Δe + ...⎥
⎣ 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:
⎧⎪⎡ (a3
+ b3
)η2
⎤ jωt
I (t ) = I0 ⎨⎢(a + b) + (a − b )η+
2 2
+ ...⎥ Δe +
⎪⎩⎣ 2! ⎦
⎡ a2 − b2 (a3 + b3 )η ⎤ j 2ωt ⎡ a3 + b3 ⎤ j 3ωt
+⎢ + + ...⎥ Δe + ⎢ + ...⎥ Δe + ... }
⎣ 2! 2! ⎦ ⎣ 3! ⎦
 EIS &
Nano-El-Cat The derivatives!
Nov. ‘08.

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 + Δa j ,..aM ) − F ( xi , a1.., a j − Δa j ,..aM )
F ( xi , a1..M ) =
∂a j 2Δa j

* This is actually an approximation