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Metrohm Autolab

Instruments for Electrochemical Impedance Spectroscopy

Outline
The Autolab instrument
Cell connections and configurations
Basics of EIS
Practical EIS
Data analysis
Applications

The Instrument

Instrumentation requirements
for EIS
PGSTAT
Impedance analyzer
Software for data acquisition and
analysis

The instrument

FRA32M impedance analyzer module with


1 MHz 10 Hz range with PGSTAT

Analog PGSTAT with USB


connection to Windows software

FRA32M Module
Module for electrochemical impedance
spectroscopy
32 MHz to 10 Hz
1 MHz to 10 Hz in combination
with the PGSTAT
DC range: up to 10 V
Single sine and multi-sine

FRA32M
New impedance analyzer module
Replaces the FRA2
Works with Autolab PGSTAT series
Not available for AutolabIII

FRA32M
32M stands for 32 MHz
!! MAXIMUM Frequency with
PGSTAT: 1 MHz !!
Future developments to raise the limit

FRA32M
Direct DSG output

20 MHz

32 MHz

What happens above 1 MHz


PGSTAT128N/FRA32M, 500 mV (top)
Sharp decrease @ 700
kHz
~80% attenuation @ 1 MHz

~99.9 % attenuation @ 10 MHz

FRA32M
Uses on-board DSP
Crunches 1 M per channel down to
4096 points
And finally down to 1
Much faster than FRA2
No filtering

FRA2 vs FRA32M

FRA2 vs FRA32M

FRA32M: wrapping up
Very advanced module
Expected product lifetime 10+ years
All procedures are compatible!

The instrument

FRA2 impedance analyzer module


with 1 MHz 10 Hz range

Analog PGSTAT with USB


connection to Windows software

FRA2 module specifications

Frequency range from 1 MHz to 10 Hz


Applied Frequency Resolution of 0.003%
AC amplitude: 0.2mV to 0.35 V (RMS)
Input range of 10 V
Max. frequency limited by PGSTAT

Possible configurations
PGSTAT128N, 302N, 100N, 302F
Multi autolab with FRA32M module
Autolab III with built-in FRA2

Instrumental limitations
Contour plot

Not possible to measure


Z accurately at any
frequency

Cell connections

Cell connections
Autolab potentiostat / Galvanostat

Cell connections
PGSTAT provides 4
connections
CE and WE (current
measurement)
RE and S (voltage
measurement)

Cell connections (2 electrodes)

2 electrode configuration precise control of the


interfacial potential is not critical

This configuration is often used in the characterization


of energy storage and energy conversion devices
Impedance measured between RE and S

Cell connections (3 electrodes)

3 electrode configuration most common for typical


electrochemical measurements
The RE in close proximity of WE to control the interfacial
potential accurately
Impedance measured between RE and S

Cell connections (4 electrodes)

4 electrode configuration is used to study the


liquid/liquid interface (two non-miscible electrolytes or
two electrolytes separated by a membrane)
Impedance measured between RE and S

Electrochemical cell
WE/S

CE

RE

Electrochemical
interface

Electrochemical interface
Interface
Electrode
Potential
+
e-

+
+

+
+
+
+

IHP OHP

Diffusion layer Bulk Solution


1- 100 m

IHP Inner Helmoltz plane: ion adsorbed onto metal surface


OHP Outer Helholtz plane: closest ions free to move within the electrolyte

Equivalent circuit
Electrochemical interface model

Equivalent circuit

Uncompensated resistance, Ru
Solution between RE and WE
Concentration, cell setup, Temperature,
conductivity, type of ions, mass transport,

Equivalent circuit

Typical values:
up to 100 (aqueous solution)
KCl 0.1 mol/L 20C = 85.69
up to 10 k (organic solvent)
Between 1m to 1 Batteries

Equivalent circuit

Double layer capacitance, Cdl


Diffuse interfacial capacitance
Concentration, ions, electrode surface,
adsorbed species,

Equivalent circuit

Typical values:
Double layer bare metal
Fe2O3 - Ni2O5
Al2O3
Epoxy cast coating
Asphalt coating

10-50 F/cm2
2 F/cm2
0.5 F/cm2
6 pF/cm2
0.5 pF/cm2

Bernard Tribollet & Mark E. Orazem: Electrochemical Impedance Spectroscopy, Wiley-Interscience, 2008

Equivalent circuit

Charge transfer resistance, Rct


Polarization resistance
Electron transfer kinetics, Temperature,
electrode composition, morphology,

Equivalent circuit

Typical values: whole measurable range


( m very fast kinetics up to G slow
charge transfer)
Silver 1.59 10-8 m, Copper 1.68 10-8 m
Silicon 6.40 102 m Glass1010 to 1014 m
Teflon 1022 to 1024 m

Equivalent circuit

Diffusion impedance, W (Warburg)


Related to semi infinite diffusion
T, concentration, diffusion coefficients,
viscosity, electrode area
Typical values: depends on the system

Electrochemical methods
Large number of methods available
DC: cyclic voltammetry, chrono
amperometry,
AC: electrochemical impedance
spectroscopy,

Advantage of DC methods
Ex: cyclic voltammetry
Most popular technique in
electrochemistry
Provides a complete overview of the
electrochemical interface
Immediately recognizable

Cyclic voltammetry
Platinum in HClO4 0.1 M
Immediately
recognizable

Cyclic voltammetry
Platinum in HClO4 0.1 M
Added EtOH
Anodic peaks attributed
to the oxidation of EtOH

Disadvantage of DC methods
System is driven away from equilibrium
Response is given by individual
contributions
Information about the rate determining
step can be determined
No information on the internal dynamics
of the system

Disadvantage of DC methods
Iron in sea water
No direct information about
electrochemical interface

Dummy cell case study


Assuming a simple dummy cell

Dummy cell case study


CV staircase method
Using Ohms law and a linear
regression:
Slope = 0.00014241
1/Slope = 7021.98
102 + 2230 + 4700 (7032 )

Dummy cell case study


EIS
Using direct reading of data
shown in the Nyquist plot, R1,
R2 and R3 are immediately
known
R1 = 106
R2 = 4844.1106=4738.1
R3 = 7028.74844.1=2184.6

Dummy cell case study


EIS
Using indirect reading of
data shown in the Nyquist
plot, C1, and C2 are easy to
calculate

max

1
R C

C1 = 9.95 nF using R2
C2 = 10.77 F using R3

Alternative: EIS
Electrochemical impedance
spectroscopy
Study of the variation of the impedance
of an electrochemical system with the
frequency of a small-amplitude AC
perturbation

Advantages of EIS
System remains at equilibrium
Non destructive method
Can be applied in many fields
Corrosion, biosensors, solar cells,
semiconductors, superpacitors, fuel
cells, batteries

EIS Basics

EIS Basics
Ohm's law gives a simple relation
between
dc-potential (E) and dc-current (i):

E
R
I

EIS Basics
EIS is a transfer function between
potential and current
et e sin t

Z()

it i sin t

e sin t
sin t
Z
Z0
i sin t
sin t

EIS Basics

it i sin t
et e sin t
The
current
response
leads or lags the voltage
by a phase angle

EIS Basics
When ac-signals are involved the
relation is:

Z ()=

E ()
I ()

where Z () is the complex impedance.

EIS Basics: complex number


It is common practice to express Z as
a complex function

Z() Z0e

j( )

Z0 cos jsin

Z ZRe j ZIm

EIS Basics: complex number


Real components are located on the
abscissa
Imaginary components are located on
the ordinates

EIS Basics: data presentation


Nyquist plot
Plot of Z vs Z, using iso-metric
axes

Z() Z'() j Z"()


Total impedance Real component Imaginary component

EIS Basics: data presentation


Nyquist

High frequency limit

Low frequency limit

EIS Basics: data presentation


Bode presentation
Plot of |Z| vs log F and vs log F
Phase angle

Z() Z e

j( )

Total impedance Modulus

EIS Basics: data presentation


Bode presentation

EIS Basics: data presentation


3D projection

EIS Basics: data presentation


3D projection

Circuit Element Review

Pure resistor (R)


Ohms law holds at all frequencies for a
pure resistor

Z() R
0

Pure resistor (R)


Ohms law holds at all frequencies for a
pure resistor

Z() R
0

There is no phase shift

Typical examples: Ohmic resistance,


charge transfer resistance

Resistor

Pure capacitor (C)


Impedance (reactance) is frequency
dependent

1
Z()
C

Capacitor
Capacitor

1
1
ZC
j
jC
C
90 phase shift
Typical examples: double layer
capacitance, coating capacitance

Capacitor

Inductance
Inductance

ZL jL
90
Typical examples: instrumental
artifacts, adsorption phenomena

Inductance

RC, series
Impedance of element in series =
impedance of elements

E ER EC
i iR iC
1
Z ZR ZC R j
C

1
Z() R R
C

0
2

RC, series

RC, series

RC, parallel
Impedance of element in parallel =
1/R (1/impedance of elements)
1
1

E ER EC i iR iC

1
1
1
1

jC
Z ZR ZC R
R
Z
1 RjC

Z()

0
2

1
C
R

RC, parallel

Impedance vs admittance

Randles Cell
Electrochemical cell model
> ZCdl > 0

max

1
Zf Cdl

Capacitive
contribution

R
Pure resistive behavior,
no phase change.

R + Zf
Pure resistive behavior,
no phase change.

Randles Cell
Electrochemical cell model
R + Zf
> ZCdl > 0

Capacitive
contribution

0
Pure resistive behavior,
no phase change.

Pure resistive behavior,


no phase change.

Randles Cell
Electrochemical cell model
Fmax

R + Zf

EIS back to Basics

EIS conditions
3 fundamental conditions
Linearity
Stability
Causality

Linearity condition
The applied AC amplitude must be
small so that the response of the cell
can be assumed to be linear (in 1st
approx)
Important choice of the applied
amplitude

Linearity condition

At fixed DC potential (or current), a small amplitude sinusoidal potential


(or current) perturbation is applied. The response of the cell is a small
amplitude sinusoidal current (or potential)

Linearity condition

All systems are non


linear and the response
depends on the system

Linearity condition

Linearity condition
Potentiostatic or galvanostatic control?
Z is independent of the mode
At what DC potential or current?
Always at OCP?
Depends on the system
Requires knowledge of the system
What should the AC amplitude be?

Linearity condition
FAQ # 1
How to choose the amplitude?
Small enough to stay linear
Big enough to measure a response

Stability condition
The overall state of the system should
not change (significantly) during the
acquisition of the data
Important choice of frequency range
and measurement conditions

Stability condition
Corrosion of the electrode, adsorption
or formation of oxides, discharge of
the device, changes in the
electrochemical interface,
Electrochemical system are unstable

Stability condition
Frequency scan

Frequency scan is performed from high to low frequency


Experimental duration is dominated by the low frequency limit

Stability condition
Min. time for Z at 10 Hz: 10.000 s
Scan from 1 kHz to 1 mHz, 61
frequencies, log. distribution
2 h, 47 minutes (estimated)
Scan from 1 MHz to 1 Hz, 61
frequencies, log. Distribution
7 minutes (estimated)

Stability condition
Duration
The experiment
duration is dominated
by the low frequencies

Causality condition
The measured AC response of the
system must be directly correlated to
the applied AC stimulus
Important to shield the cell from
outside perturbations

Avoiding traps

Avoiding traps
Powerful method but not stand alone
Knowledge of the system is required
3 conditions must be respected
Instrument is not a black box

Whats wrong with this picture?

Bit of scattering in the low frequency range?

Measurement sequence
Step 1: AC signal is applied on the cell
Step 2: AC response is recorded
Step 3: signals are sent to the
impedance analyzer

Measurement sequence

Raw signals (50 Hz contamination)

Lissajous plot

Measurement sequence
FFT is computed for both signals
Impedance is calculated from
frequency domain data

Measurement sequence

Fourier transformed signals (50 Hz)

Nyquist and Bode plots


Updated in the software

Hidden information
Nyquist and Bode plots do not show
all the information
The raw signals are insteresting to
consider
Lissajous plots test the linearity

Lissajous plots
Pure R

Pure C

Real cell

Lissajous plots
Measurement of impedance
V OA
Z

1M
i
OB

D A

OD
sin
33
OA

Lissajous plots
Easy to detect non-linear behaviour
200 Hz / 25 mV AC

20 Hz / 25 mV AC

Raw signals in resolution


The raw data can be
used to verify the data
quality in terms of
limit of detection

Kramers-Kronig test
Basic test for data validation
Equations linking real and imaginary
components of complex quantities for
systems fulfilling the conditions of
linearity, causality and stability

Kramers-Kronig test
Diagnostic tool for impedance data
Test the data for consistency
Recalculates the real/imaginary part
based on the measured imaginary/real
part

Kramers-Kronig test

Invalid data can be easily detected using the KK test:


significant deviation from calculated values indicated violation
of linearity, stability or causality condition

Practical EIS

Practical EIS
Different protocols
Frequency scan: other parameters
are fixed
Single frequency: other parameters
are changed
Combination of both

Practical EIS: frequency scan


Frequency range?
Depends on the systems time constants
10 kHz to 100 mHz is a good start
(always high to low)
Above 10 kHz effects from cables,
reference electrode and connections

Practical EIS: frequency scan


Frequency scan
properties

Frequency
distribution

Amplitude
Wave type

Practical EIS: frequency scan


Direction: high to low frequency

Frequency scan is performed from high to


low frequency (stability condition)

Practical EIS: frequency scan

Practical EIS: frequency scan


# frequencies and distribution:
10/decade and logarithmic
! Duration: dominated by the low
frequency
Alternative: multisine

Multisine vs single sine


Multisine: linear combination of
single sines
5
sines signal,
contain a base
frequency and 4
higher harmonics

Multisine vs single sine


Multisine: linear combination of
single sines
15 sines signal,
contain a base
frequency and 14
higher harmonics

Multisine vs single sine


1000 Hz 0.001 Hz, 61 Freq, single:
2h, 47 min
1000 Hz 0.001 Hz, 13 Freq, 5 sine:
50 min
37 min with 15 sines
Faster but less accurate!

Data analysis

Data analysis
Analysis: crucial part of the EIS
Different tools are available
Difficult and time consuming
Pitfall: extract too much information

Analysis tools
Find circle (quick fit): used to quickly
fit a semi-circle in the Nyquist
Provides a quick estimate using a
R(RQ) circuit

Analysis tools
Find circle (quick fit)

Analysis tools
Find circle (quick fit)

Analysis tools
Fitting using equivalent circuit
User-defined equivalent circuit built
with different elements
R, C, L, Q, etc
Parallel or series
Non-linear least-squares fit

Analysis tools
Circuit description based on
B.A.Boukamp:
Solid state Ionics 20 (1986) 31-44 &
Solid State Ionics 18&19 (1986)
136-140

Analysis tools
Elements

Analysis tools
Fitting tool comes with circuit editor

Elements can be connected


using split and join elements

Analysis tools

Initial conditions,
boundaries, fixed
parameters can be
edited in the dedicated
panel

Fitting progress
Iterative process
Several iterations
required in order to
reach convergence

Report

Problems with data fitting


Non uniqueness of circuits
The 3 circuits give the
same results (identical
2 values)

Problems with data fitting


Knowledge about the system is
required
EIS never to be considered as stand
alone!

Practical examples

Case 1 coating on steel


RE
NaCl

CE

3 electrode setup
Z measured
between RE and WE

Coating
Steel
WE

Case 1 coating on steel


Pure C

Nyquist

Bode

Pure R

Case 1 coating on steel


RE

Interpretation?

CE
Ru

NaCl

Cdl

Coating
Steel
WE

Case 1 coating on steel

Poor fit

Case 1 problem?
Element Q
Used to describe an imperfect
behaviour of a reactance
ZQ

1
Y0 j

ZC

j
C

n = 1 capacitor
n = 0 resistor
n = 0.5 uniform diffusion
0.5 < n < 1 rough electrode
0 < n < 0.5 porous electrode

Case 1 Element Q

Smooth electrode: Cdl = C

Rough electrode: Cdl C Q

Case 1 Element Q

Case 1 coating on steel

Good fit

Case 2 Partially blocked


surface
Re

Electrolyte

Surface film

Csf

Cdl

Rct

Electrode

Case 2 Partially blocked


surface

Case 3 Coating revisited


RE
NaCl

CE

3 electrode setup
Z measured
between RE and WE

Coating
Steel
WE

Case 3 Coating revisited

Pure C

Two semi-circles

Nyquist

Pure R

Bode

Case 3 Coating revisited


Fitting?

Case 3 Coating revisited


Knowledge of the system is required
Not the same coating as case 1
What would happen if the coating
fails?

Case 3 Failing coating


RE

CE
Ru

NaCl

Cdl

Coating
Steel

Pores
WE

Case 3 Failing coating


Ru

Cdl

Coating + pores
Steel

Case 3 Failing coating


Fit result

Case 3 Failing coating


Knowledge of the system is required
when fitting the data

Case 4 Coating with


blisters
Electrolyte
Re

Surface film
Rep
Blister with electrolyte

Csf

Cdl

Zwa
Rct
Electrode

Case 4 Coating with


blisters

Case 5 Two layer coating


Electrolyte

Re
Csf1

Rsf1

Surface
film 1

Rsf2
Surface film 2

Csf2

Cdl

Rct
Electrode

Case 5 Two layer coating

Case 6 Mass transfer


Semi infinite diffusion
Platinum working electrode
[Fe(CN)6]4-/[Fe(CN)6]3-

Case 6 Mass transfer


Semi infinite diffusion
Platinum working electrode
[Fe(CN)6]4-/[Fe(CN)6]3-

Angle of 45
Indication of semiinfinite diffusion
Randles-like
behavior

Case 6 Mass transfer


Warburg diffusion element, W
|ZW| = |ZW|
45
- = /4
W depends on the concentration,
diffusion coefficient and temperature

ZW
j

RT
1
1
2 2

n F A 2 DO CO
DRCR

Case 6 Mass transfer


Semi infinite diffusion
Platinum working electrode
[Fe(CN)6]4-/[Fe(CN)6]3-

Semi-infinite diffusion
contribution

Case 7 Forced convection


Finite diffusion
Platinum working electrode
[Fe(CN)6]4-/[Fe(CN)6]3Hydrodynamic conditions
Falls off towards a
finite impedance

Angle of 45
Indication of semiinfinite diffusion

Case 7 Mass transfer


through a thin layer, a coating
Finite diffusion layer
Typically used for:
O element
ZO

ZO

1
Y0 j

1
Y0 j

tanh B j

ZW

- Diffusion through thin layer


- Ion selective electrodes
- Diffusion through a coating

O element is identical to W
when tanh argument >

Case 7 Fuel Cell

Electrode poisoning by the presence of CO


in the H2 Stream

Typical for fuel cells finite diffusion represented by O

Case 7 Fuel Cell

Red O2
Blue Air

Case 7 Fuel Cell

Air

O2

Case 7 Forced convection


Finite diffusion layer
O element

B
D

1.61 D1/3 1/6

RDE

For a rotating disc


electrode

Case 7 Forced convection


Finite diffusion
Platinum working electrode
[Fe(CN)6]4-/[Fe(CN)6]3-

Finite diffusion contribution

Case 7 Forced convection


Variation of rotation rate
Platinum working electrode
[Fe(CN)6]4-/[Fe(CN)6]3At higher rotation rates
diffusion layer thickness,
decreases ZO decreases

Case 7 Forced convection


Variation of rotation rate
Platinum working electrode
[Fe(CN)6]4-/[Fe(CN)6]3-

ZO

1
Y0 j

tanh B j

YO600RPM YO1200RPM YO2400RPM


B600RPM B1200RPM B2400RPM

Case 8 Bounded diffusion


Tangent hyperbolic diffusion
Impedance of finite-length diffusion
with reflective boundary
Typical of film with electro-active
species, porous electrodes, Li Batteries

Y Y0 j th B j

Z ( )=

1
Y0 j

coth B j

Case 8 Bounded diffusion


Tangent hyperbolic diffusion
B = time (second) take for a reactant to
diffuse from one side of the layer to the
other.
Thickness of the thin layer

Diffusion coefficient D

B=
D

Case 8 Bounded diffusion


Tangent hyperbolic diffusion
T element

>45

Case 8 Bounded diffusion


Tangent hyperbolic diffusion

Case 9 Gerischer impedance


Chemical reaction in bulk solution
Model for porous electrodes
Lithium batteries

1
k j

Y Y0 k j

Case 9 Gerischer impedance


Model for porous electrodes

Case 9 Gerischer impedance


Li-Thionyl battery

Summary of mass transport


elements
T, bounded Warburg,
linear finite diffusion
W, semi-infinite
linear diffusion

G, bulk chemical reaction


O, finite-length diffusion

WT= Zinc Air battery


T>450
W 450

Case 10 Inductance
High frequencies inductance
Low frequencies inductance

Z=jL

High frequencies Inductance


Wrong frequencies range, electrode
inductance, connecting wire

Low frequencies Inductance


Adsorption process at electrode surface,
surface reaction or chemical modification

Low frequencies Inductance


Adsorption process at electrode surface,
surface reaction or chemical modification

Case 11 Bisquert2
Transmission line element

Model for a porous or mixed-phase


electrode of thickness L

Case 11 Bisquert2

X3X

X3X

X1X
X3X

X1X

X1X
X3X

X1X

X2

X2
XX

X2

Case 11 Bisquert2

ZB2

X1X 2
2
12 22
L

cot anh
1 2
1 2

sinh

Where is given by

X3
1 2

Case 11 Bisquert2
DSSC V@MaxPP

Case 11 Bisquert2
DSSC V@ OCP

Summary of all elements


Resistance

Capacitance

Inductance

Constant Phase element Q

Y0 and n

Summary of all elements


Warburg diffusion

Y0

Finite diffusion

Y0 and B

Bound diffusion

Y0 and B

Gerischer impedance

Y0 and Ka

Summary of all elements


Transmission line
B2
R1 Q1 n1, R2 Q2 n2, R3 Q3 n3, L

If R or Q is 0 means that is not available

Conclusions

Summary
Potentiostat setting
FRA setting

Summary Potentiostat setting


OCP?
Potentiostat or Galvanostat?
Fix DC potential (current) or potential
scan?

Potential scan
Potential Scan: Mott Schottky plot of a
semiconductor

Slope gives number


of dopants.
Intercept gives Flat Band Potential

Summary FRA setting


Frequency range?
Amplitude value?
Single sine or Multi sine?

Example of frequency range:


1MHz -100mHz

Example of frequency range:


10KHz -1mHz

Summary FRA setting


Amplitude value?

Summary FRA setting


Amplitude value?

50 mV = 42.1A
10 mV = 6.4A

Summary FRA setting


Amplitude value?
100mV = 0.18A

200mV = 0.39A

Summary FRA setting


Amplitude value?

Z=1 GOhm
10 mV leads to I=10 pA!!

Take home message


Modern electrochemical
instrumentation and software allows
easy and fast data acquisition
Powerful data handling and analysis
tools are available
Data analysis remains a difficult task

High current density


measurement

Control of programmable electronic loads


or power supplies for high current or
high voltage measurements

PEM fuel cell stack at 200 A


DC current

DSSC devices measurements


IMPS and IMVS measurement on
photovoltaic device through modulation
of light intensity
DSC IMVS measurement at 625 nm,
OCP, E = 1.652 mW/cm2, DE = 10 %

DSSC devices measurements


DSSC charge transfer TiO2/dye/electrolyte
Diffusion process of I-/I3-

DSSC devices measurements


DSSC charge transfer TiO2/dye/electrolyte
Diffusion process of I-/I3-

Monitoring of impedance in
function of time

Fuel cell measurement, Z measured for


1800 seconds

Battery (LiPo)

Take home message


! System knowledge is always required
! Impedance cannot be considered as a
stand alone
! Careful attention to the data
acquisition settings

EIS only one form of many


Electrochemical impedance
spectroscopy one form of impedance
Rotation rate, mass, temperature,
light intensity, charge, etc

References
The reference handbook on impedance
spectroscopy

Evgenij Barsoukov & J. Ross Macdonald: Impedance


Spectroscopy: Theory, Experiment, and Applications,
Wiley-Interscience, 2005

References
Good reference book, specifically
focussed on Electrochemical
Impedance Spectroscopy

Bernard Tribollet & Mark E. Orazem: Electrochemical


Impedance Spectroscopy, Wiley-Interscience, 2008

References
The reference handbook on
electrochemistry, also covers
impedance spectroscopy

Allen J. Bard and Larry R. Faulkner,


Electrochemical Methods: Fundamentals and
Applications, Wiley, 2001

www.metrohm-autolab.com

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factory warranty

Metrohm Autolab
Instruments for Electrochemistry