IMPEDANCE SPECTROSCOPY:

DIELECTRIC BEHAVIOUR OF POLYMER

ELECTROLYTES
By
Ri Hanum Yahaya Subban Ph. D
Faculty of Applied Sciences/Institute of Science
UiTM Shah Alam
 OUTLINE
• IMPEDANCE SPECTROSCOPY (IS) BACKGROUND
• IS PRINCIPLE
• IS TECHNIQUE
• IS PLOT OF SIMPLE CIRCUITS
• IS PLOT OF MODEL SYSTEMS
• IS PLOT OF REAL SYSTEMS
• CONSTANT PHASE ELEMENT (CPE)
• IS PLOT OF REAL SYSTEMS AND CPE
• IMPEDANCE RELATED FUNCTIONS
• Z, Y AND M PLOTS FOR SIMPLE CIRCUITS
• SOME APPLICATION OF IS
• SOME PRACTICAL DETAILS FOR IS
 IS: BACKGROUND
D. C METHOD
R=V/I cannot be used due to
polarisation of charges
- at electrode-electrolyte interface
-at defect regions inside the sample
(grain boundaries, phase boundaries
etc. )
A.C METHOD
Polarisation effects are avoided and
impedance (Z) is measured
- Since Z changes with applied signal
frequency, Z must be measured as a
function of frequency and resistance of
sample evaluated

Also known as
 AC Impedance Spectroscopy
 Complex Impedance Spectroscopy
 Electrochemical Impedance Spectroscopy
(when applied to electrochemical systems)
Popular use of IS:
 To determine electrical conductivity of ionic conductors
 To identify different processes that contribute to the total
conductivity: bulk contribution, grain boundary contribution,
diffusion, etc.
 Through identifying an equivalent circuit for the impedance
plot involved
 IS: BACKGROUND
• Resistance of sample L

R=L A

A
 = resistivity of the material
L = length of the sample
A = area of cross-section of the sample
• Conductivity  = 1 = L/A
 R
By measuring R,L and A,  can be calculated
 IS: PRINCIPLE
V(t)
Sine wave signal V(t) = Vo sin t
i(t)
of low amplitude is applied to a sample
Vo = maximum voltage
 = 2f, angular frequency

The resulting current i(t) = io (sin t + )

 = phase difference between i(t) and V(t)
: phase shift
(current is ahead of voltage by )

The impedance Z = V(t) = Vo sin (t)

i(t) io (sin t + )
Z is a function of frequency and has magnitude Z = Vo = Zo and a phase angle 
PRINCIPLE: IS
io
Both Z and  are frequency dependent quantities
 IS: PRINCIPLE
• Since ac impedances are frequency dependent quantities they are
represented by Z()

Z() can be considered as a complex quantity with a real component Z’() and
imaginary component Z”()

Z() = Z’() + j Z”() , j =-1 Im. Z Complex Impedance

plane
where real impedance = Z’ = Z cos( )
imaginary impedance = Z” = Z sin( )
Z
with a phase angle  = tan-1 (Z”/ Z’) Z”

Z’ Real Z
Magnitude of Z, Z = [(Z’)2 + (Z”)2]1/2
 IS: TECHNIQUE

Small ac signal (V  10 mV) is

Liquid Solid
applied to sample over a wide sample sample
range of frequency (mHz to MHz)

Sample holder

Electrode

Sample

Impedance spectrometer: Electrode

Computer
LCR meter/FRA
 IS: TECHNIQUE
Measure Z(f) as a function of f(=2f) over a wide range of frequency (mHz to MHz)

Plot Z(f) versus f in the form of -Z’’(f) vs Z’(f) for various f

(Cole-Cole plot/ Complex impedance plot/Nyquist plot)

Useful to evaluate :
-electrical parameters such as conductivity of ionic
conductors(solid or liquid), mixed conductors
- electrode-electrolyte interfacial effects and related phenomena
- electrochemical parameters/processes of the system under study
Also used for studying dielectric behaviour of materials
 IS PLOT OF SIMPLE CIRCUITS
a. Pure resistance R
Z”
Z”
R

Z = R for all values of  or f

Z = R and  = 0
Z’ = R and Z” =0 R Z’Z’

Impedance plot is a point on the real axis at Z’ = R

 IS PLOT OF SIMPLE CIRCUITS
b. Pure capacitance C
Z” -ve Z”
C

Z = 1 = -j 
jC C
Z’Z’
Z’ = 0 and Z” = -1
C
Impedance plot is a
Z = Z” varies with frequency straight line lying on
As  increases, Z decreases the Z” axis
Z points lie along the Z” axis
 IS PLOT OF SIMPLE CIRCUITS
c. R and C connected in series
-ve Z”
C
R


The total impedance
Z=R- j
C Z’
R Z’

With Z’ = R and Z” = -1
C
On complex plane the graph becomes
a straight line at Z’ = R, parallel to the Z” axis
 IS PLOT OF SIMPLE CIRCUITS
d. R and C connected in parallel
R
1 = 1 + 1 = 1 + jC
Z R 1/j C R
C
Z= R
1 + j RC
= R(1 - jRC) = R(1 - jRC)
(1 + jRC) (1 - jRC) 1 + (RC)2
= R - jR2C
1 + 2R2C2 1 + 2R2C2
= Z’ - jZ” with Z” = RC
Z’
On eliminating  : (Z’- R/2)2 + (Z”)2 = (R/2)2  Equation of a circle
 IS PLOT OF SIMPLE CIRCUITS

d. R and C connected in parallel

-ve Z”
Impedance plot is a semicircle with
centre (R/2, 0) on the Z’ axis m

Maximum point on the semicircle

corresponds to mRC = 1 

 m = 1 R/2 R Z’
RC
where RC =   Time constant or Note: Z’ and Z” axes must have
the same scales to see the
Relaxation time semicircle

From m , C can be calculated for an unknown circuit

 IS PLOT OF SIMPLE CIRCUITS
e. Combined circuits
R1 R1 R2

Rs
C1 C1 C2

-ve Z” -ve Z”

2 = R2C2
1 = R1C1 1 = R1C1

Rs Rs + R1 Z’ R1 R1+ R2 Z’
due to internal resistance of electrolyte/electrode interface
 IS PLOT OF MODEL SYSTEMS
a. Ionic solid with two non-blocking electrodes
Eg: Ag/AgI/Ag (Ag+ mobile, I- immobile)
No ion accumulation at the electrodes
Cell arrangement  R and C connected in parallel (equivalent circuit)
(assume no electrode resistance)
Electrodes

Sample  Rb
Rb= bulk resistance

Cb Cb (Cg) bulk capacitance

Expected impedance plot
-ve Z” m
Cb is related to vacuum capacitance Co;
Cb = Co


And Co = oA
Z’ d
A - area of cross section  - dielectric constant
Rb/2 Rb d - thickness of sample o – permittivity of free space
 IS PLOT OF MODEL SYSTEMS
a. Ionic solid with two non-blocking electrodes: experimental results

Rb

Cb

Cb(Cg) bulk capacitance

(a) Li6SrLa2Ta2O12 with Li electrodes

 (b) Li6BaLa2Ta2O12
Thangadurai and Weppner Ionics 12 (2006) 81-92

Note: depressed/distorted semicircles

 IS PLOT OF MODEL SYSTEMS
b. Ionic solid with two blocking electrodes
Egs: AgI with Pt electrodes, Ag+ mobile and I- immobile
Ions cannot enter the electrodes , get accumulated at the electrodes
+ - + -
two double layer of charges at electrode/electrolyte interfaces - + - + -
+
two double layer capacitances at the interfaces ( C’dl) + - + -

Equivalent circuit Expected impedance plot

-ve Z”
R
m

C’dl 
R/2
C’dl
C
R R Z’

Cdl C
Cdl will add a spike to the
Impedance plot
Cdl= effective double layer capacitance
 IS PLOT OF MODEL SYSTEMS
b. An ionic solid with two blocking electrodes: experimental
results

Au/Li6BaLa2Ta2O12/Au
Thangaduarai and Weppner
Ionics 12 ( 2006) 81-92
SS/PVC-LiCF3SO3/SS
Subban and Arof, Journal of New Materials for
Electrochemical Systems 6 (2003) 197-203

Note: depressed/distorted semicircles and slanted/curved spikes

 IS PLOT OF MODEL SYSTEMS
c. Polycrystalline solid with two blocking electrodes
Conduction will occur inside the grain (intra grain-bulk conduction) and along the grain
boundaries (inter grain conduction)
System = crystalline grain + grain boundaries + electrode/electrolyte interface
Expected impedance plot Grain Electrode/electrolyte
interface
-ve
Z”  Pt Pt

Grain Bulk
boundary Thickness of grain boundary is small
Z’  large Cgb
Rb Rb+ Rgb Rgb is large - larger semicircle for GB
The overall σ :
is determined by Rb +Rgb
Rb Rgb

Cb Cgb Cdl

Equivalent circuit
 IS PLOT OF MODEL SYSTEMS
c. A polycrystalline solid with two blocking electrodes: experimental
results

High frequency semicircle (small C) bulk conduction

100 Hz
Low frequency semicircle (large C)  grain boundary
10 kHz
conduction
From the values of the capacitances
different semicircles can be associated
R1 R2 with different conduction process in the
sample
Cdl
C1 C2
SS/ Li1+xCrxSn2-xP3-yVyO12/SS
Norhaniza, Subban and Mohamed, Journal
of Power Sources 244 (2013) 300-305
Note: Slanted/curved spike and
depressed/distorted semicircles
 IS PLOT OF MODEL SYSTEMS
TYPICAL C VALUES
In general, a number of processes can contribute to the total conduction and an ideal equivalent circuit
(hypothetical ) may be represented by the following simple circuit (various circuits possible)

R1 R2 R3

C1 C2 C3 Cdl
Bulk Different phases or Orientation Double layer capacitance
Grain boundary of crystal planes at the electrode

• R and C values ,particularly C values differ for different processes

• Each transport process may give a semicircle to the Impedance plot
• From the approximate C values different processes may be identified

Approximate C values Phenomenon responsible

Actual identification
2-20 pF Bulk(main phase) of different
 10 pF Second phase, orientation etc. processes must be
based on
1-10 nF Grain boundary
dependence on
0.1-10 Fcm-2 Double layer/surface charge temperature,
0.2 mFcm-2 Surface layer at electrode/adsorption pressure, etc.
 IS PLOT OF REAL SYSTEMS
IS plot of real systems and devices are usually complicated
• Deviate from ideal behaviour due to :

• Distorted semicircles may arise due to

- Overlap of semicircles with various time constants

• Depressed semicircles may arise due to

- Electrolyte is not homogeneous
- Distributed microscopic properties of the electrolyte

• Slanted or curved spikes may arise due to

- Unevenness of electrode/electrolyte interfaces
- Charge transfer across the electrode/electrolyte interface, diffusion of
species in the electrolyte or electrode

The deviation from ideal behaviour of Impedance plot is explained in

terms of a new circuit parameter called Constant Phase Element (CPE)
 CONSTANT PHASE ELEMENT (CPE)
In general CPE has the properties of R and C (equivalent to a leaky capacitor)

Mathematically impedance of a CPE is given by the

Complex quantity:
ZCPE = 1 = Zo (jω)-n , 0 ≤ n ≤ 1

Y0(jω) n

When n = 0, Z is frequency independent and Zo  R, CPE ≅ pure Resistance

When n = 1, Z = 1 /jωY0 . Hence Yo  C, CPE ≅ pure Capacitance

 CPE
When 0 < n < 1, CPE acts as intermediate between R and C
Can show that R and CPE in parallel gives a circular arc in the impedance plane
as shown
Usually CPE is denoted by the circuit element Q

-Z” R
• CPE alone gives an inclined
-Q- Q straight line (pink) at angle (n=90)

R • CPE // R gives a tilted semicircle

with its centre (C) depressed so
that the plot appears as an arc
n= 90° Z’ (green)
- The diameter of the semicircle
(1-n)= 90° is inclined at (1-n) = 90 
C
 IS PLOT OF REAL SYSTEMS AND CPE
The general equivalent circuit of a solid electrolyte with non perfect
blocking electrodes may take the form

R1 R2 R3
CPE4
CPE1 CPE2 CPE3

-Z”
Resulting impedance plot will have depressed
semicircles and a slanted spike
Here processes are assumed to be well separated

Z’
R1 R1 + R 2 R1 + R2 + R3
 IMPEDANCE RELATED FUNCTIONS
There are several other measured or derived
quantities related to impedance (Z) which often play
important role in IS:
- Admittance (Y)
- Dieletric/Permittivity (ε)
- Modulus (electric) (M)
Generally referred to as ‘immitances’

• The four different formalisms give the same information in different ways
• However each formalism highlights different features of the system
• Thus it may be worthwhile to plot the data in more than one formalism in
order to extract all possible information from the results

• Z plot gives prominence to most resistive elements

• M plot gives prominence to smallest capacitance
Eg: To study grain boundary effects , Z plot is good
To study bulk effects M plot is good
 IMPEDANCE RELATED FUNCTIONS
A.C voltage applied to a sample v = Zi
Generally impedance Z = R + j X; R = resistance, X = reactance

1
Hence the current , i  v  Yv
Z
Immitance Symbol Relation Complex Form
Impedance Z - Z’ – jZ”
Admittance Y Y = Z-1 Y’ + j Y”
Permittivity   = 1/jCoZ = Y/ jCo ’ - j ”
Electric M M =  -1 = jCo Z M’ + j M”
modulus

Where Co   o A
d
 IMPEDANCE RELATED FUNCTIONS
Complex Admittance
1 1 Z' jZ "
Y ( )    
Z ( ) Z ' ( )  jZ " ( ) Z '2  Z "2 Z '2  Z "2

Z' Z"
Y' Y" 2 2
Z '2  Z "2 (Z '  Z " )

Complex Permittivity
Z" Z'
 
'
2 2 "
C o ( Z '  Z " ) 2
C o ( Z '  Z " )
2

Complex Electrical Modulus M ( )  Z ( )  Co Z  jCo Z

" '

M '  Co Z "

M "  C o Z '

" "
M'  M 
"
2 2
'2 "2
(   ) ( '   " )
Z, Y AND M PLOTS FOR SIMPLE CIRCUITS

C
R

M”
-ve Z”
Y” m

 
Y’ 

1/Rb

C0/2C M’
R Z’
 Z, Y AND M PLOTS FOR SIMPLE CIRCUITS
R

Y”
M” m

-ve Z” m

R/2
 M’

Co/2C
Z’
R/2 R 1/R Y’
 u 
 
 s  v
SOME APPLICATION OF IS
DETERMINATION OF DC IONIC CONDUCTIVITY
: - Z” vs Z’
OF IONIC CONDUCTORS

PVC-NH4CF3SO3-Bu3MeNTf2N In general IS plot consists of a depressed

1.20E+03
semicircle with a tilted spike and intercept
on the real axis corresponds to Rb
1.00E+03

Rb may be determined graphically by

8.00E+02 drawing the best semicircle OR by fitting
R R//C circuit with suitable values of R and
i (Ω)
-Zi()

C. Here the value R= Rb

Z

6.00E+02
Note: both Z‘ and Z‘’ axes must have the
same scale in order to see the semicircle .
4.00E+02
If only spike is present , it can be extended
R to obtain the intercept
2.00E+02
 is calculated from R by using
p2
 =LA/Rb
0.00E+00 2
0.00E+00 2.00E+02 4.00E+02 6.00E+02 8.00E+02 1.00E+03 1.20E+03
Zr (Ω)
L - thickness of sample
p1 
2
A - area of contact

S.K. Deraman Ph.D thesis UiTM 2014

 SOME APPLICATION OF IS
DETERMINATION OF DC IONIC CONDUCTIVITY : - Z’’ vs. Z’ plot
OF IONIC CONDUCTORS

PVA-NH4x (x = Cl, Br, I)

Equivalent circuit of PVA-NH4x
at low NH4x concentration
R1

CPE2

CPE1
A0 A5

Semi-circle disappears
Only resistive component A5
prevails at higher frequency as
NH4Br/I content increases
Equivalent circuit of PVA-NH4x
at high NH4x concentration

A25 A30 CPE3

Hema et. al J. Non Crystalline Solids 355
(2009) 84-90
 SOME APPLICATION OF IS
ANALYSIS OF IS PLOT: CHOOSING EQUIVALENT
CIRCUITS
Choosing the correct equivalent circuit can be difficult

Softwares do not give a unique

Some possible equivalent circuits
equivalent circuit (model) for a
particular IS plot but may A
suggest a number of
complicated circuits (multiple
models)

An example: B
Two time-constant impedance spectrum

-Z”

B Z’
R1 R1 + R2
 SOME APPLICATION OF IS
ANALYSIS OF IS PLOT: CHOOSING EQUIVALENT
CIRCUITS
The model chosen should not only fit the IS data but also must be verifiable through
other experiments, theories and justifiable through other known facts , etc.
An example: The circuits below can give 3 distinct semi-circles in the IS plot if
their time constants are well separated

b
a
Cg
C1 C2 C3
Can be
CR
equivalent
R1 R2 R3 to
Rg C2

RR
R2

a is more suitable for a polycrystalline sample

b is more suitable for a homogeneous material
 SOME APPLICATION OF IS
DETERMINATION OF DIELECTRIC : ’ vs log f (permittivity/
PARAMETERS OF IONIC CONDUCTORS dielectric constant,
transport processes )
Low frequency:
Static dielectric
constant  10 4
ε’ :
• a measure of a material’s polarisation
• associated with capacity to store charge and
High frequency: •represents the amount of dipole alignment in
Optical dielectric a given volume
constant at 104Hz 
between 3.5 and 5 • related to dielectric relaxation
Compared to pure
PVC film = 3

In ionic conductors:
Relaxation peaks usually not observed due to
large electrode polarisation effects
Alternative is M’ /M” or ac conductivity
PVC(1-x)LiCF3SO3xLiPF6
Subban and Arof Ionics 9
(2003) 375-381
 SOME APPLICATION OF IS
DETERMINATION OF DIELECTRIC : ’ vs concentration
PARAMETERS OF IONIC CONDUCTORS

Same trend: variation with concentration

PCL-NH4SCN

Woo et. al
Materials Chemistry and Physics 134
(2012) 755-761
 SOME APPLICATION OF IS
DETERMINATION OF DIELECTRIC : M” vs log f (relaxation
PARAMETERS OF IONIC CONDUCTORS time , transport
processes )
PEO- AgCF3SO3

Relaxation peaks

Relaxation peak is responsible

for fast segmental motion which
reduces the relaxation time and
increase the transport properties

fmax Relaxation time  =1/2fmax

Gondaliya et.al Materials Sciences

and Applications 2 (2011) 1639-
1643
 SOME APPLICATION OF IS
DETERMINATION OF DIELECTRIC Tan  vs log f
:
PARAMETERS OF IONIC CONDUCTORS (relaxation time and
nature of conductivity
Tan  = ”/‘ relaxation)
•Single well defined resonance peak is an indication of long range conductivity
relaxation in good ionic conductors
•From FWHM value can find out Debye conformation (=1.14) or otherwise.
t 1.14
 (t )  exp[( )  ],  
M FWHM
Effect of temperature
Effect of concentration

MG30-LiCF3SO3

Yap et. al, Physica B 407(20120 2421-2428

 SOME APPLICATION OF IS
Number density of charge
DETERMINATION OF IONIC
carriers , mobility ,
TRANSPORT PARAMETERS IN IONIC :
diffusion coefficient D,
CONDUCTORS
transference number t ion etc,
s =h em Chitosan-LiClO4-TiO2-DMC

æ2(Ze2 ) ö
s =ç ÷h Eat exp(- Ea / kT)
è 3kTm ø

  Ea 
   o exp 
 kT 
 Ea
gradient 
k
Muhammad et. al, Key Engineerinhg
Materials 594-595 (2014) 608-612
 SOME APPLICATION OF IS
Number density of charge
DETERMINATION OF IONIC
carriers , mobility ,
TRANSPORT PARAMETERS IN IONIC :
diffusion coefficient D,
CONDUCTORS
transference number t ion etc,
1/ 2 l  v
 2 Ea 
v  l CMC-NH4Br
 m   
v
Eg. For CMC
 kT 
D
 e 2 

l  1.5nm  

H+

CMC Sample with

optimised Samsudin and Isa, J. of Applied Sciences
conductivity 12 (2012) 174-179
 SOME APPLICATION OF IS
DETERMINATION OF IONIC
: log () -  dc vs. log () (exponent
CONDUCTION MODEL s)

 ac   o r
      dc   ac
 ac  A s Gradient = s

Small Polaron Hopping

(SPH ) model

Samsudin and Isa, J. of Current

Engineering Research 1(2) (2011)
7-11
SOME PRACTICAL DETAILS FOR IS
Frequency window limitation: the available equipment have
limited frequency range: fl to fh

•Only part of IS spectrum is obtained (depends on R and C value)

•Changing the temperature may show different parts of the full

spectra provided no new conduction processes comes into play at
different temperatures

•Curve fitting is needed to see full spectrum