Beruflich Dokumente
Kultur Dokumente
Institutslogo
Lecture Series at Fritz-Haber-Institute Berlin
„Modern Methods in Heterogeneous Catalysis“
7.12.2012
Impedance Spectroscopy
Cornelia Breitkopf
o it is a linear technique and results are interpreted in terms of Linaer Systems Theory
o if measured of an infinite frequency range, the impedance delivers all information
from a system by linear electrical pertubation/response techniques
o high experimental efficiency
o validation of data is quite easy via integral transform techniques (Kramers-Kronig)
that are independent of the physical processes
…. some examples
Electrochemistry basics behind….
…. some examples
Introduction to impedance
Black Box
Sinusoidal Response
Excitation Analysis
Principle – Representation of Complex Impedance
E
o Ohm´s law R= R resistance
I
E voltage
I current
• ideal resistor
valid at all E, I levels
R independent of frequency
AC current and voltage are in phase
• ideal capacitor
AC current and voltage are completely out of
phase, current follows voltage
Principle – Representation of Complex Impedance
𝑑
o ideal resistor 𝑅 = 𝐴
R resistance []
electrical resistivity [ cm]
d distance [cm]
A area [cm2]
conductivity 1/
0 𝐴
o ideal capacitor 𝐶= 𝑑
C capacitance [F]
0 electrical permittivity of vacuum (8.85 *10-14 F/cm)
relative electrical permittivity of material [-]
water = 80,1
polymers = 2…8
vacuum = 1
Principle – Representation of Complex Impedance
o definition of linear systems (by Oppenheim and Willsky in Signals and Systems):
…A linear system ….is one that possesses the important property of
superposition: if the input consists of the weighted sum of several signals, then
the output is simply the superposition (weighted sum) of the responses of the
system to each of the signals
in case of an electrochemical cell: input is potential, output is current
o electrochemical cells are not linear (doubling voltage = double the current)
Pseudo-linearity of electrochemical systems
o for small excitations a pseudo-linear response results with characteristic phase shifts
Z impedance
Z0 magnitude
𝐸𝑡
Z () = 𝐼𝑡
Et Eo .exp( jt )
Z ( ) Z o (cos j sin ) Z Re jZ Im
I t I o .exp( jt )
Principle – Representation of Complex Impedance
impedance is represented as
vector with length IZI
negative!
log frequency
phase shift
log frequency
Models and analogs interpretation
tools to
analogs interprete physical models
impedance data
o analogs which always take the form o aim to reproduce the phenomena
of electrical equivilant circuits of interest
o existance of electrical double layer on the interface between an electrode and its
surrounding electrolyte
o double layer forms by "sticking" ions on the electrode surface charged electrode
is separated from charged ions formation of a capacitor
R2
R1
demonstration examples
Physical Electrochemistry – Examples
demonstration examples
Physical Electrochemistry - Diffusion
o Warburg impedance is the diffusional impedance for the diffusion layer of infinite
thickness which is characterized for the macroelectrode
o W is given by
o RANDLES cell: equivalent circuit with mixed kinetic and charge transfer/diffusion control
Physical Electrochemistry - Diffusion
demonstration examples
o de LEVIE
373 K
30 Methan
Neon
Deff [cm /s]
25 Ethan
2
Propan
20
Butan
14
3*10 Moleküle/Puls
15 14
1.5*10 Moleküle/Puls
o equivilant circuit
Example: gas diffusion in porous systems
o aim of study:
evaluation of adsorption rate of hydrogen in presence of iodine in solution
on the surface of crystal Pt(111) and polycrystalline Pt by EIS
o why interesting?:
- former investigation of adsorption of hydrogen on Pt, Rh in acid solution
- using iodine can increase adsorption of hydrogen on the surface
Sample
- single-crystall Pt(111) and polycrstalline Pt with 10mm
in diameter
- electrolyte: alkaline: KOH addition KI with pH= 13; 14
Set up of experiment
- carrying out in standard electrochemical cell
- using 3 electrodes: counter- (Pt sheet), working (Pt or
Pt (111))-, and reference electrode
Method
- cyclic voltammetry (CV): check the surface orientation
- electrochemical impedance: evaluation of hydrogen
and iodine adsorption
1. Single-crystal Pt(111)
2. Polycrystalline Pt
Aim of study
- general model to fit electrochemical impedance spectra experimental data considering
adsorption of species at the electrode’s surface of lithium-ion batteries
Reasons
- essential information about processes at graphite electrodes from electrochemical
impedance: charge transfer at interface, diffusion inside, adsorption at the interface,
geometric limitation.
- understanding of limitations in order to obtain maximum performance of electro-active
materials
Fabio La Mantia, Jens Vetter, Petr Novak. Electrochimica Acta 53 (2008) 4109–4121
Literature example:
Impedance spectroscopy on porous materials: A general model of lithium-ion
batteries (experiment)
2. Approach
EIS: using a Potentiostatic/Galvanostat by Princeton
Applied Reseach at 25oC, DC potential of 1.5V,
frequency 100kHz down to 10mHz, amplitude 2mV Table 1
3. Materials (Table 1)
Fabio La Mantia, Jens Vetter, Petr Novak. Electrochimica Acta 53 (2008) 4109–4121
Literature example:
Impedance spectroscopy on porous materials: A general model of lithium-ion
batteries (results)
Fabio La Mantia, Jens Vetter, Petr Novak. Electrochimica Acta 53 (2008) 4109–4121
Literature example:
Impedance spectroscopy on porous materials: A general model of lithium-ion
batteries (expressions of model)
d ln Ap RT Cw S E
x dx x FC (1 2t ) x a. A (6)
S p
Fabio La Mantia, Jens Vetter, Petr Novak. Electrochimica Acta 53 (2008) 4109–4121
Literature example:
Impedance spectroscopy on porous materials: A general model of lithium-ion
batteries (Fitting experimental data with model)
Fabio La Mantia, Jens Vetter, Petr Novak. Electrochimica Acta 53 (2008) 4109–4121
Applications of EIS (current and future)
o corrosion monitoring
o AC voltammetry
o potentiodynamic and (fast) Fourier-transform impedance spectroscopy
o non-linear higher-harmonics impedance analysis
o local EIS
o scanning photo-induced impedance microscopy (SPIM)
Cornelia.Breitkopf@tu-dresden.de