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DIELECTRIC PROPERTIES OF ION

-CONDUCTING MATERIALS

F. Kremer

Coauthors: J. Rume, A. Serghei,

The relationship between the complex dielectric function


and the complex conductivity

Phenomenology of the conductivity of charge conducting


materials
The dielectric properties of zwitterionic polymethacrylate
The dielectric properties of Ionic Liquids
Theoretical descriptions of the observed frequency
and temperature dependemce of the complex conductivity

The spectral range of Broadband Dielectric


Spectroscopy (BDS) and its information content
for studying dielectric relaxations and charge
transport.

The linear interaction of electromagnetic fields


with matter is described by Maxwells equations
curl

D
H j
t

j E

D 0 E

(Ohms law)

Current-density and the time derivative of D are equivalent

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 ]

complex dielectric function

( )

( )

2
1

10

Analysis of the dielectric spectra


propylene glycol
5

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

The spectral range (10-3 Hz to 1011 Hz)


of Broadband Dielectric Spectroscopy (BDS)

(sample amount required < 5 mg)

Brief summary concerning Broadband Dielectric


Spectroscopy (BDS)
1. The spectral range of BDS ranges from 10-3 Hz to 1011 Hz.
2. Orientational polarisation of polar moieties and
charge transport are equivalent and observed both.
3. The main information content of dielectric spectra
comprises for fluctuations of polar moieties the
relaxation- rate, the type of its thermal activation,
the relaxational strength and the relaxation-time
distribution function.
For charge transport the mean attempt rate to overcome
the largest barrier determining the d.c.conductivity and
its type of thermal activation can be deduced

Phenomenology of the conductivity of


charge conducting materials

Frequency and temperature dependence of the conductivity


of a mixed alkali-glass 50LiF-30KF-20Al(PO3)3
-6

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 ])

Frequency and temperature dependence of the conductivity


of a zwitterionic polymer
-6

100 mol%

-1

log( ' [Scm ])

-7
-8

396 K
391 K
382 K
373 K
364 K
355 K
346 K

-9
-10
-11

5
log( [rad/s])

Frequency and temperature dependence of the electronic


conductivity of poly(methyl-thiophene)
-2

-1

lo g ( [ S c m ] )

T [K ]
295
285

-4

262
250
236
223

-6

210

lo g ( [H z ])

Frequency and concentration dependence of the electronic


conductivity of composites of carbonblack
and poly(ethylene terephthalate)
1

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 ])

Mixed alkali-glass: Scaling with temperature is possible

4
- 396 K
- 391 K
- 382 K
- 372 K
- 364 K
- 355 K

log( '/ o)

3
2
1
0
-2

2
log()

poly(methyl-thiophene): Scaling with temperature is possible


5
4

lo g

3
2
1
0
-1
-1 2

-8

-1 0

lo g

-6

e
kT 0
2

-4

composites of carbonblack and poly(ethylene terephthalate):


Scaling with concentration is possible
3

0
2

lo g ( a p [H z ])

10

12

The Barton-Nakajima-Namikawa (BNN) relationship holds


for all materials examined:
- 0 mol%
- 100 mol%
- 200 mol%
- conductor-polymer composite
- mixed alkali glasses
- polymer

-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

The conductivity scales with the number of effective


charge-carriers as determined by temperature or concentration
A characteristic frequency exists where the frequency
dependence of the conductivity sets in
With increasing number of effective charge-carriers the
conductivity increases.
The BNN-relationship is fulfilled

The dielectric properties of zwitterionic polymethacrylate: poly{3-[N-[-oxyalkyl)-N,Ndimethylammonio]propanesulfonate}

CH
H 3C

CH

COO
x

(C H 2)m

CH

(C H 2)3
3

SO

Dielectric data as displayed for the complex


dielectric function T)

'

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

log( " [Scm ])

-1

log( ' [Scm ])

Dielectric data as displayed for the complex


conductivity T)

-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

Dielectric data as displayed for the complex


electrical modulus M*T) =1/ T)
0.10

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])

Dyres random free energy barrier model


Hopping Conduction in a spatially randomly varying
energy barrier :

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

log( ' [Scm ])

Fits using the Dyre theory work well


-5,0
-5,5
-6,0
-6,5
-7,0
-7,5
-8,0
-8,5
-9,0
-9,5
3

5
6
log( [rad/s])

The rates c, M and 1/ e nearly coincide and have


- over 5 decades - a similar temperature dependence
7

log( c, M, 1/e)

c
M

1/e

4
3
2
340

350

360

370
T [K]

380

390

400

The BNN-relationship holds for varying the


charge carrier concentration
-6

- 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

The dielectric properties of Ionic Liquids


BMIM BF4

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

Imaginary and real part of the complex dielectric


function are strongly temperature dependent

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

The complex conductivity of the ionic liquid BMIM


BF4 is also strongly temperature dependent

Broadband dielectric measurements displayed


for the complex dielectric function T)
MMIM Me2PO4

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

Broadband dielectric measurements displayed


for the complex conductivity T)
-3

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

Scaling with temperature possible


7

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

Scaling with temperature as displayed in terms of


the complex conductivity T)
3

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

All data collapse into a single characteristic curve

Scaling with concentration for NaCl solutions as


displayed for the complex dielectric function
NaCl
8

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

Scaling possible but deviations on the low


frequency side

Scaling with concentration for NaCl solutions as


displayed for the complex conductivity
NaCl
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

s is the angular frequency of the minimum in

10

Dyres random free energy barrier model


Hopping Conduction in a spatially randomly varying
energy barrier :

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

Fits using the Dyre-model of conduction


9

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

Fits using the Dyre-model


10

-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

Electrode polarization effects show up already


at 100 kHz

10

10

The BNN Relation is fulfilled for 0 and e as


obtained from Dyre-fits
-4

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

:Near constant loss


contribution

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 )

Alternative approach: Superposition of a thermally


activated d.c. conductivity and nearly constant
loss contribution.

e2
e1

Frequency (Hz)

The BNN relation is a


trivial consequence

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

3,6 3,8 4,0 4,2 4,4 4,6 4,8 5,0


1000 K/Temperature

MMIM Me2PO4
EMIM Et2PO4

-2

10

3,6 3,8 4,0 4,2 4,4 4,6 4,8 5,0


-1
1000/Temperature (K )

Both 0 and 1/e show a VFT - dependence

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

Thanks to Joshua Rume


and

A.

A.Serghei

and financial support through the DFG

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