North-Holland, Amsterdam
136
1. INTRODUCTION
Impedance spectroscopy is frequently used in
the
c i r c u i t parameters.
immittance diagram.
diffusion, etc..
are located f i r s t
analysis program.
w i l l y i e l d a s u i t a b l e equivalent c i r c u i t ,
diate and f i n a l f i t
dispersion.
The interme-
Both
137
This results in a
program can f i t
The f i t t i n g
An ana-
litical
drawn.
tion f i t s
(1)
response.
(2)
(3)
Otherwise,
(5)
C = I / wI (Z~' - ml n. s i n - ~ / Y o )
representation.
wi = I / IZ*
-i i 2 ,
c r i p t i o n Code (CDC)12'13, which uniquely represents the equivalent c i r c u i t . The CDC, which is
in t e r p r e t e d by the program, acts as a set of
pointers to a corresponding set of subroutines
which calculate the i n d i v i d u a l responses of the
d i f f e r e n t types of c i r c u i t elements.
The par-
t i a l d e r i v a t i v e s of the e r r o r function with respect to the adjustable parameters, are calculated in the same subroutines and at the same
time.
code f o r the f i t
procedure.
To t h i s purpose, the
138
T<
O
O3
O
,~2
In t h i s p l o t
1
-
Arei -
i Z*i I
For a good f i t
and Aim.=1
Z' , (*103ohm)
I Z;i
(6
FIGURE 2
Impedance diagram showing the tangential l i n e
f o r the estimation of the interface parameters.
first
(Warburg or CPE).
The
lysis.
CPE parameters, f i g .
kHz.
T2
Ago.9CrogSno.lS2
i.
From
T = 298 K
2.
The r e s u l t i n g dispersion is
given in f i g . 3.
l y represents two i n t e r f e r i n g s u b c i r c u i t s .
The parameters of the high frequency (bulk)
CPE are estimated using the tangential l i n e
option in the admittance representation ( f i g .
65535o Hz
o
oooOO o
,~o-g~T55.35imHz i
Y'
Oooo o
3).
( x1 mho}
A c i r c l e is f i t t e d by
139
-S
CDC
0.5
(IRP) ( R P ) P
FIGURE 5
Schematic representation of the equivalent
c i r c u i t used in the dispersion analysis.
ooOOOOoo
0
I
35
2.5
Y'
, ( xlO - 3 m h o )
>
FIGURE 3
Admittance diagram of the modified data set
showing the tangential l i n e used in the e s t i mation of the parameters of the bulk CPE.
In t h i s case the
The r e s u l t of a complete
fit
CPE.
5. DISCUSSION
The c i r c u i t used in t h i s f i t
is
(RP)(RP).
The i n t e r a c t i v e dispersion
From
t'
O.1
0
c-
Are
Aim
'='",~o
o
o
x
-1
!.,
4/
iI
2.4
2.5
y' , { x 10-3 mho )
2.6
~-
FIGURE 4
Admittance diagram of the r e s u l t i n g (grain
boundary) dispersion.
-20
1
2
3
Iogca , (u in rod/s)
4
)
FIGURE 6
FQ-plot f o r the f i n a l parameter set obtained
with the dispersion analysis program.
140
TABLE 1
Parameter r e s u l t s obtained with the data analysis
program and the general immittance f i t program
or Pascal.
R
~Yo
~n
~Yo
)n
391
9.00.55xI0 -7
38
7 . 1 x 10-s
O.84
6.66x I0 -s
0.502
NLLSF-prog.
"EQIVCT":
rel.
err:
389
8.2 x i0 -~
0.56
0.3%
0.7%5
%
62
12 %
1.5 x 10-" 18 %
O.7O
5 %
6.64x 10-s 0.1%
0.505
0.2%
I t s use requires,
Also
1 / / IZ~l
Z~
I hI
(7)
This may be
REFERENCES
1. P.H. Bottelberghs, Low-frequency measurements on s o l i d e l e c t r o l y t e s and t h e i r
i n t e r p r e t a t i o n s , in: Solid E l e c t r o l y t e s , eds.
P. Hagenmuller and W. van Gool (Academic
Press, New York, 1978) pp. 145-172.
2. J.R. Macdonald and J.A, Garber, J. Electrochem. Soc. 124 (1977) 1022.
3. I.D. R a i s t r i c k and R.A. Huggins, in: Proc.
Symposium and Workshop on Advanced Battery
Research and Design, Argonne National
Laboratory 76-8 (1976) B277.
4. J.R. Macdonald, in: Electrode Processes in
Solid State l o n i c s , eds. M. K l e i t z and
J. Dupuy (D. Reidel, Dordrecht, 1976)
p. 149,
5. D.R. Franceschetti, J. Schoonman and J.R.
Macdonald, Solid State lonics 5 (1981) 617.
6. B.A. Boukamp and G.A. Wiegers, Solid State
lonics 9/10 (1983) 1193.
f a c t o r , fsc:
fsc
accordingly.
I t is often possible t h a t , w i t h i n the error
The