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-CONDUCTING MATERIALS
F. Kremer
D
H j
t
j E
D 0 E
(Ohms law)
i 0
Dielectric spectroscopy
electric field E
Debye relaxation
s
(1 i )
3.6
3.2
'= s
'
2.8
2.4
2.0
= s-
'=
0.8
polarization P
''max
0.6
''
PS
0.4
0.2
max
0.0
P D( )
10
10
10
10
10
10
-1
[rad s ]
( )
( )
2
1
10
10
10
235 K
220 K
10
10
10
10
10
205 K
10
10
-2
-1
10
10
10
10
10
10
10
frequency [Hz]
10
10
190 K
10
10
-2
10
10
-1
10
10
frequency [Hz]
10
10
10
10
10
4
4
4
4
4
7
7
7
8
8
4
4
4
4
4
K
K
K
K
K
5
6
7
8
9
8
8
8
8
1
K
K
K
K
K
-1
l o g ( [ S c m ] )
-7
0
1
2
3
4
-8
-9
-1 0
1
lo g ( [H z ])
100 mol%
-1
-7
-8
396 K
391 K
382 K
373 K
364 K
355 K
346 K
-9
-10
-11
5
log( [rad/s])
-1
lo g ( [ S c m ] )
T [K ]
295
285
-4
262
250
236
223
-6
210
lo g ( [H z ])
0 .1 0 0
0 .0 7 5
0 .0 5 0
-1
-2
0 .0 3 0
-3
0 .0 2 0
0 .0 1 5
-4
0 .0 1 2 5
-5
-6
-7
-8
0 .0 1 0
-9
-1 0
2
lo g ( [H z ])
4
- 396 K
- 391 K
- 382 K
- 372 K
- 364 K
- 355 K
log( '/ o)
3
2
1
0
-2
2
log()
lo g
3
2
1
0
-1
-1 2
-8
-1 0
lo g
-6
e
kT 0
2
-4
0
2
lo g ( a p [H z ])
10
12
-2
-1
log( 0 [Scm ])
-4
-6
-8
-10
-12
-1
log(1/e [Hz])
Experimental findings
In all examined materials the conductivity shows a similar
frequency and temperature (resp. concentration) dependence
There is no principle difference between electron and ion
conducting materials
CH
H 3C
CH
COO
x
(C H 2)m
CH
(C H 2)3
3
SO
'
10
10
396 K
391 K
382 K
373 K
364 K
355 K
346 K
10
10
10
"
396 K
391 K
382 K
373 K
364 K
355 K
346 K
10
10
1
10
-1
log( [rad/s])
10
5
log( [rad/s])
-5,0
-5,5
-6,0
-6,5
-7,0
-7,5
-8,0
-8,5
-9,0
-9,5
-5
-6
-1
-1
-7
-8
-9
5
log( [rad/s])
5
6
log( [rad/s])
396 K
391 K
382 K
373 K
364 K
355 K
346 K
7
0.04
0.08
0.03
0.02
0.04
M"
M'
0.06
0.01
0.02
0.00
0.00
3
5
6
Log (Rad/s)
log( [rad/s])
0 e arctan e
1 2
2
2 2
ln 1 e arctan e
4
0 e ln 1 2 e2
1 2
2
2 2
ln 1 e 2 arctan e
2
-1
5
6
log( [rad/s])
log( c, M, 1/e)
c
M
1/e
4
3
2
340
350
360
370
T [K]
380
390
400
- 0 mol%
- 100 mol%
- 200 mol%
-1
log( 0 [Scm ])
-7
-8
-9
-10
-11
-12
-13
-1
1
2
3
4
log(1/e [Hz])
Summary
The dielectric properties of the zwitterionic poly-methacrylate:
poly{3-[N-[-oxyalkyl)-N,N-dimethylammonio]propane
sulfonate} are characterized by a pronounced frequency and temperature dependence.
It should be analysed in terms of the complex dielectric
function T), the complex conductivity T) and the
complex electrical modulus M*T) =1/ T)
The data can be well described by Dyres random free
energy barrier model
The BNN-relation is fulfilled
At low frequencies electrode polarisation effects show up
1-butyl-3-methylimidazolium
tetrafluoroborate
BMIM SCN
1-n-butyl-3-methylimidazolium
thiocyanate
Temperature dependence
9
10
BMIM BF4
BMIM BF4
"
'
10
10
280 K
270 K
260 K
250 K
240 K
230 K
10
10
10
10
10 -1
10
280 K
270 K
260 K
250 K
240 K
230 K
10
-1
10
10
Frequency (Hz)
10
10
10
10
-1
10
10
10
Frequency (Hz)
10
Temperature dependence
BMIM BF4
280 K
270 K
260 K
250 K
240 K
230 K
-3
10
-4
10
-5
10
(S/cm)
-5
10
"
'
(S/cm)
-4
10
-6
BMIM BF4
-3
10
-6
10
280 K
270 K
260 K
250 K
240 K
230 K
-7
10
-8
10
10
-1
10
10
10
10
Frequency (Hz)
10
-9
10
10
-1
10
10
10
Frequency (Hz)
10
MMIM Me2PO4
6
10
268 K
258 K
248 K
238 K
10
'
268 K
258 K
248 K
238 K
"
10
6
10
5
10
4
10
3
10
2
10
1
10
0
10
-1
10
-2
10 -2
10
10
Thickness= 50m
0
10
10
10
10
Frequency (Hz)
10
10 -2
10
10
10
10
10 10 10 10
Frequency (Hz)
10
10
MMIM Me2PO4
-3
MMIM Me2PO4
10
-4
10
10
-4
10
-5
10
-6
10
-7
10
10
-8
10
"
(S/cm)
'
(S/cm)
10
268 K
258 K
248 K
238 K
-5
10
268 K
258 K
248 K
238 K
-6
10
-7
-8
-2
10
10
10
10
10
Frequency (Hz)
10
10
10
10
-2
10
10 10 10 10
Frequency (Hz)
10
10
10
MMIM Me2PO4
MMIM Me2PO4
10
10
10
10
10
10
'
268 K
258 K
248 K
238 K
"
10
268 K
258 K
248 K
238 K
10
10
10
10 -10 -8
-6
-4
-2
0
2
4
10 10 10 10 10 10 10 10
e
-2
10 -10 -8
-6
-4
-2
0
2
4
10 10 10 10 10 10 10 10
e
10
10
MMIM Me2PO4
MMIM Me2PO4
268 K
258 K
248 K
238 K
-3
10
-5
10 -10 -8 -6 -4 -2
0
2
4
10 10 10 10 10 10 10 10
e
10
"
-1
10
/ 0
10
'
/ 0
10
268 K
258 K
248 K
238 K
-2
10
-4
10 -10 -8
-6
-4
-2
0
2
4
10 10 10 10 10 10 10 10
e
10
NaCl
10
10
"
10
10
10 -5
10
-3
10
-1
10
10
10
'
317 mg/ml
44.63 mg/ml
4.09 mg/ml
0.52 mg/ml
317 mg/ml
44.63 mg/ml
4.09 mg/ml
0.52 mg/ml
10
10
10
10 -5
10
-3
10
10
-1
10
10
10
(S/cm)
-2
10
317 mg/ml
44.63 mg/ml
4.09 mg/ml
0.52 mg/ml
-4
10
10
-5
10
-3
-1
10
10
10
-1
10
"
'
/ 0
10
10
317 mg/ml
44.63 mg/ml
4.09 mg/ml
0.52 mg/ml
-2
10
-5
10
-3
10
-1
10
10
10
10
0 e arctan e
1 2
2
2 2
ln 1 e arctan e
4
0 e ln 1 2 e2
1 2
2
2 2
ln 1 e 2 arctan e
2
10 -2
10
10
10
10
10
Frequency (Hz)
10
10
10
7
5
10
"
10
268 K
258 K
248 K
238 K
228 K
218 K
208 K
198 K
188 K
10
10
268 K
258 K
248 K
238 K
228 K
218 K
208 K
198 K
188 K
'
10
10
10
10
10
-1
10
-3
10
-2
10
10
10
10
Frequency (Hz)
10
10
10
The Dyre model describes the observed frequencyand temperature dependence; additionally electrode
polarization effects show up
-2
-3
10
-4
-5
10
-6
10
-8
10
'
(S/cm)
10
-9
10
-11
10
-13
10
-15
10
-2
10
10
10 10 10
Frequency (Hz)
10
10
10
"
268 K
258 K
248 K
238 K
228 K
218 K
208 K
198 K
188 K
-7
(S/cm)
10
268 K
258 K
248 K
238 K
228 K
218 K
208 K
198 K
188 K
-10
10
-12
10
-14
10
-2
10
10
10 10 10
Frequency (Hz)
10
10
10
10
-6
0(S/cm)
10
-8
10
-10
10
MMIM Me2PO4
-12
10
EMIM Et2PO4
-14
10
-2
10
10
10
10
10
1/e(Hz)
10
10
-7
10
-9
220
210
200
190
180
170
-11
'
10
-13
10
-15
10
'
10
-2
10
10
10
10
e4
0(T3)
e3
0(T2)
0(T1)
e5
0(T4)
'
(S /c m )
0(T5)
K
K
K
k
K
K
(S /c m )
e2
e1
Frequency (Hz)
Activation plots
-4
10
10
10
-6
-8
1/e(Hz)
0(S/cm)
10
10
10
-10
10
-12
10
-14
10
MMIM Me2PO4
10
EMIM Et2PO4
10
MMIM Me2PO4
EMIM Et2PO4
-2
10
Final Summary
The dielectric properties of Ionic Liquids are similar to
other ion - conducting systems
They should be analysed in terms of the complex dielectric
function T), the complex conductivity T) and the
complex electrical modulus M*T) =1/ T)
The data can be well described by Dyres random free
energy barrier model but as well a superposition a
thermally activated d.c.conductivity,a power law and a
nearly constant loss contribution
The BNN-relation is fulfilled
At low frequencies electrode polarisation effects show
up
A.
A.Serghei