Professional Documents
Culture Documents
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
(V I )
steady state
Next slide
relaxation
dynamic
relaxation
SSI-17
Workshop
28 June 09
1.E-04
C u rre n t, [A ]
1.E-05
1.E-06
1.E-07
1000
2000
Time, [sec]
3000
SSI-17
Workshop
28 June 09
1.E-04
C u rre n t, [A ]
1.E-05
1.E-06
1.E-07
1000
2000
Time, [sec]
3000
SSI-17
Workshop
28 June 09
Advantages of EIS:
SSI-17
Workshop
28 June 09
SSI-17
Workshop
28 June 09
V0
V () V0 e jt
=
= [ cos j sin ]
Z () =
j ( t +)
I () I0 e
I0
= 2f
j = -1
SSI-17
Workshop
28 June 09
Complex plane
Impedance resistance
Admittance conductance:
Zre jZim
1
= 2
Y () =
Z () Zre + Zim2
Zre jZim
1
=
Yre jYim
1
Z () =
= 2
Y () Yre + Yim2
SSI-17
Workshop
28 June 09
A linear arrangement of
impedances can be added in
the impedance plane:
Ztotal = Z1 + Z2 + Z3 + ... = Zn
n
Ytotal = Y1 + Y2 + Y3 + ... = Yn
n
SSI-17
Workshop
28 June 09
Simple elements
1
ZR = R ; YR =
R
SSI-17
Workshop
28 June 09
Capacitance?
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
SSI-17
Combination of elements
Workshop
28 June 09
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
SSI-17
Workshop
28 June 09
1
Y () = + jC
R
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!
SSI-17
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
SSI-17
Limiting cases
Workshop
28 June 09
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
Next slides
SSI-17
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
SSI-17
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
SSI-17
Workshop
28 June 09
Other representations
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
SSI-17
Simple model
Workshop
28 June 09
Zr1-xYxO2-x .
Apply two ionically blocking electrodes,
in this case thick gold.
Schematic
arrangement of sample
and electrodes.
Z () =
jCg +
1
1
Rion + 1
2 jCint
SSI-17
Workshop
28 June 09
2
Rion
Cgeom
Rion
Z () =
j
2 2
2
2
2
1 + RionCgeom
1 + 2 Rion
Cgeom
Semicircle through the origin.
SSI-17
Workshop
28 June 09
Debije model:
1
Y () =
Z ()
Impedance representation
Admittance representation
SSI-17
Workshop
28 June 09
Other representations
Zimag
Zreal
Bode representation
Different Bode
representation
SSI-17
Workshop
28 June 09
Other representations
Zimag
Zreal
Bode representation
Different Bode
representation
SSI-17
Workshop
28 June 09
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
SSI-17
Workshop
28 June 09
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.
SSI-17
Workshop
28 June 09
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
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
SSI-17
Workshop
28 June 09
Transmission line
ZW () =
r
jc
Combination:
Electrolyte resistance, Relyte
Equivalent
Double layer capacitance, Cdl
circuit
Charge transfer resistance, Rct
Warburg (diffusion) impedance, Wdiff
SSI-17
Workshop
28 June 09
se
m
ic
ir
cl
e
45
SSI-17
Workshop
28 June 09
Instruments
Measurement methods
Bulk, conductivity:
two electrodes
pseudo-four electrodes
true four electrodes
Electrode properties:
three electrodes
SSI-17
Workshop
28 June 09
R1
Zsample = Zcomp.
R2
Very accurate,
but limited
range
& time
consuming!
SSI-17
Workshop
28 June 09
I+
V+
VII+
V+
VI-
SSI-17
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
SSI-17
Workshop
28 June 09
SSI-17
Workshop
28 June 09
SSI-17
Workshop
28 June 09
Data validation
Response only
Response
due
to input
State
of
scales
linearly
signalmay
system
with input
notsignal
change
during
measurement
SSI-17
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.
SSI-17
Workshop
28 June 09
Linear KK transform
k = RkCk
SSI-17
Actual test
Workshop
28 June 09
1 ji k
Z KK (i ) = R + Rk
2
2
1
+
k =1
i
k
M
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
SSI-17
Workshop
28 June 09
No information in Rk values
SSI-17
Workshop
28 June 09
SSI-17
Workshop
28 June 09
2KK = 0.910-4
2CNLS = 1.4 10-4
SSI-17
Workshop
28 June 09
SSI-17
Workshop
28 June 09
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!
SSI-17
Workshop
28 June 09
FLD, continued
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
SSI-17
Workshop
28 June 09
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
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
SSI-17
Workshop
28 June 09
Cothyp (Imp.)
Tanhyp (Imp.)
SSI-17
The CPE
Workshop
28 June 09
Capacitance: C = Y0
n=
Warburg:
n=0
Resistance: R = 1/Y0
n = -1
Inductance: L = 1/Y0
= Y0
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,
SSI-17
Workshop
28 June 09
) Self similarity (
SSI-17
Fractals
Workshop
28 June 09
Fractal line
Self similarity!
similarity!
Self
Sierpinski carpet
SSI-17
Workshop
28 June 09
Fractal electrode
Cantor bar
arrangement
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
SSI-17
Workshop
28 June 09
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
SSI-17
Workshop
28 June 09
Different presentation
Sometimes useful to
rephrase the CPE:
PZT, dielectric
response:
d Y0
r =
0 A
SSI-17
Workshop
28 June 09
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])])
SSI-17
Workshop
28 June 09
SSI-17
Workshop
28 June 09
Equivalencies
Ra = RdRe/(Rd + Re)
Rb = Re2/(Rd + Re)
Cc = Cf [Rd/(Rd + Re)]2
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
Workshop
28 June 09
with: wi = Zi
for k = 1 ..M
Z (i , ak )
(weight factor)
d
S =0
dak
Effect of minimisation
SSI-17
Workshop
28 June 09
Non-linear systems
Z () = Z0 k + ( j)
= Z (, Z0 , k , , )
Y ( x, a1..aM )
Y ( x, a1..aM ) = Y ( x, a ..a ) +
a j
j
D
1
a j + ....
D
M
D
a1D ..aM
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 =
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
SSI-17
Workshop
28 June 09
The derivatives!
F ( xi , a1..M ) =
a j
2a j
* This is actually an approximation
SSI-17
Workshop
28 June 09
Marquardt-Levenberg
Hence, combination!
Multiply diagonal terms with (1+).
Successfuliteration:
iteration:
Successful
Sold
new<<S
SSnew
old
decrease
(=/10).
/10).
decrease (=
Otherwiseincrease
increase
Otherwise
(=10)
10)
(=
SSI-17
Workshop
28 June 09
Error estimates
(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
SSI-17
Workshop
28 June 09
[ ]
= g k ,k
ak
j ,k
SSI-17
Workshop
28 June 09
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
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
SSI-17
Workshop
28 June 09
Subtraction procedure
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)
SSI-17
Workshop
28 June 09
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
SSI-17
Workshop
28 June 09
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
SSI-17
Workshop
28 June 09
SSI-17
Workshop
28 June 09
SSI-17
Workshop
28 June 09
SSI-17
Workshop
28 June 09
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
-n5
0.668
1.0
C6
1.74 10-8 F
0.5
R7
68100
1.7
W8
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
SSI-17
Workshop
28 June 09
Discretisation of
transport in solid and
across interfaces
Transport coordinate
Reaction coordinate
Chemical capacitance
SSI-17
Workshop
28 June 09
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
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
Fick-2:
electrolyte
electrolyte
#)
OHadad
OOadad,,HHadad,,OH
Slow adsorption
& diffusion *)
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
Zs
r1
Z0
Z () =
=
=
1 / r2 + jc
Yp
k + j
With k = (r2c)-1 and Z0 = (r1/c)1/2
SSI-17
Workshop
28 June 09
YSZ-Tb example
[V
Y = 3 +, hence oxygen vacancies:
O ] = 2[Y ]
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
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
[VO MZr]
[MZr VO MZr] ,
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
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
Z () =
RTW
2 0
4F c
~ k + j
D
12
Comparewith
withthe
the
Fractal form, n < 0.5: Z () = Z0 (k + j) n Compare
dielectricHavriliakHavriliakdielectric
Negamifunction:
function:
Negami
Z0
n
k + ( j)
= +
1 + ( j)
SSI-17
Workshop
28 June 09
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
SSI-17
Workshop
28 June 09
SSI-17
Workshop
28 June 09
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
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
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
Workshop
28 June 09
Diffusive part?
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
SSI-17
Workshop
28 June 09
Fourier transform
X () = X (t ) e jt dt
0
Impedance:
V ()
Z () =
I ()
V0
V () =
j
SSI-17
Fourier Transform
Workshop
28 June 09
X(t )=at + b
Xi -1
Xi
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
Workshop
28 June 09
tN
Q0
jt
X () = [ X (t ) Q0 ] e dt j
+ Q1 e t / e jt dt
0
t
N
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
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
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
X () = X (t ) e jt dt
0
X (tk ) X (tk 1 )
(cost j sin t )
tk tk 1
k =1
N
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
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
Workshop
28 June 09
piece wise
wise
piece
integration
integration
k =0
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
Q(t ) = Q0 + Q1 e
(t / )
, 0 1
Workshop
28 June 09
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
I (t )
2
2
3
3
+
(
a
b
)
(
a
b
) j 3t
jt
j 2t
= I0 (a + b)e +
e +
e + ...
2!
3!
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
SSI-17
Workshop
28 June 09
SSI-17
Workshop
28 June 09
Last slide
SSI-17
Active shielding
Workshop
28 June 09
I+
I-
coax
1x
coax
1x
Diff.
Amp.
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
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)
SSI-17
Workshop
28 June 09
Dealing with x =
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:
2
2
x
x
2
dx x=
In discrete KK transforms, just ignore the point x =
SSI-17
Workshop
28 June 09
Conductivity relaxation
Permeation measurements
SSI-17
Workshop
28 June 09
Zr0.909-xY0.091TbxO2-
gold electrodes
Act. energies (kJmol-1):
x = 0.091
126 (ionic)
67 (electr.)
x = 0.273
x = 0.364
56 (electr.)
52 (electr.)
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
(C[(Q[R(RQ)])(C[RQ])])