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Solid State Ionies 8 (1983) 159-164

North-Holland PublishingCompany

THE DETERMINATION OF HOPPING RATES AND CARRIER CONCENTRATIONS


IN IONIC CONDUCTORS BY A NEW ANALYSIS OF ac CONDUCTIVITY

D.P. ALMOND
School of Materials Science, University of Bath, Claverton Down, Bath BA2 7,4 Y, UK

and
G.K. DUNCAN, A.R. WEST
Department of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB9 2UE, Scotland, UK

Received 7 October 1982

ABSTRACT
The a.c. conductivity o(m) of ionic materials takes the form, o(m) = o(o) + Amn. The c a r r i e r
hopping rate, Up, is obtained from the new expression o(o) = Aconn and the c a r r i e r concentration is
estimated from o(o). The contribution of creation and migratio~ terms to the activation energy for
conduction may be determined from the thermal activation of o(o) and ~D and the corresponding entropy
terms quantified. D a t a have been analyzed for four widely d i f f e r e n t ibnic materials: single crystal
Na B-alumina, p o l y c r y s t a l l i n e Li4SiO~, AgTl~AsO~ glass and Ca(NO3)2/KN03 glass and melt. For each,
the c a r r i e r concentration and hopping rates have been obtained.

The conductivity of an ionic conductor is constant, T is absolute temperature and Up is


determined by both the concentration of the the hopping rate of the ions. The hopping
mobile ions and the rate at which they are able rate is thermally activated and is given by:
to hop from site to site in the material.
Experimentally, the separation of these two Up = moeXp(-AGa/kT)
terms has been found, in general, to be
= moexp(ASa/k)exp(-Ea/kT)
difficult. Methodswhich have been used with
some success include: the Hall effect [ l ] , the
doping of ionic crystals with aliovalent = meexp(-Ea/kT) (2)
impurities [2] and the electrochemical measure- where &Ga, Ea and ASa are the free energy,
ment of a c t i v i t i e s in glasses [ 3 ] . None of activation energy and entropy of the hopping
these methods appear, however, to be readily process, mQ is the vibrational frequency of
applicable to a l l ionic conductors. In this
ions in t h e l r l a t t i c e sites and me is an e f f e c t -
paper we demonstrate that c a r r i e r concentrations ive attempt frequency which includes the entropy
and hopping rates can be separated by a new term. The concentration c of mobile ions may
treatment of a.c. conductivity. The potential
or may not be temperature dependent. In the
scope of the method is i l l u s t r a t e d by the
former case,
analysis of four very d i f f e r e n t materials: a
single crystal superionic conductor (Na
B-alumina), a p o l y c r y s t a l l i n e i o n i c conductor c = CoeXp(-AGc/kT)
( L i . S i O , ) , a vitreous e l e c t r o l y t e (AgTI.AsO.
glass) and a poorly conducting n i t r a t e glass = CoeXp(ASc/k)exp(-Ec/kT)
(40 mol % Ca(NOa)2 - 60 mol % KN03) both above
and below the glass transformation temperature. = CeeXp(-Ec/kT) (3)
The d.c. c o n d u c t i v i t y of a c r y s t a l l i n e i o n i c
conductor is determined by the expression where AGc, Ec and ASc are the free energy,
activation energy and entropy for the creation
obtained from the theory of random walk [ 4 ] :
of mobile carriers and ce is the effective
a(o) = Kmp = (Ne2aZ/kT) yc(l -C)mp (l) i n f i n i t e temperature c a r r i e r concentration.
Measurements of d.c. conductivity, over a
where y is a geometrical factor that may include
range of temperatures, provide numerical values
a correlation factor, c is the concentration of
for the net activation energy and pre-exponent-
mobile ions on N equivalent l a t t i c e sites per
ial factor for the overall conduction process.
unit volume, a is the hopping distance, e is
The d i f f i c u l t i e s which often arise in c o r r e l a t -
the electronic charge, k is Boltzmann's

0 167-2738/83/0000-0000/$ 03.00 © 1983 North-Holland


160 D.P. A l m o n d et al. / Hopping rates and carrier concentrations in ionic conductors

ing such values w i t h the t h e o r e t i c a l expressions, whereas the f o u r t h , K/Ca n i t r a t e g l a s s , appears


( I ) , ( 2 ) , ( 3 ) , are : to have a temperature dependent c a r r i e r
c o n c e n t r a t i o n above the glass t r a n s f o r m a t i o n
a) i t is not possible t o determine,
temperature, Tg.
unambiguously, whether or not the c a r r i e r
C o n d u c t i v i t y data at several temperatures
c o n c e n t r a t i o n is t h e r m a l l y a c t i v a t e d , i . e .
f o r the f i r s t t h r e e m a t e r i a l s are shown in
whether the measured a c t i v a t i o n energy of o ( o )
Fig. I . The s o l i d l i n e s through the data are
is (E a + Ec) or Ea alone. f i t s to equation (4). The values of o(o) and
b) i t is not p o s s i b l e t o determine the A used f o r these f i t s are shown p l o t t e d in
magnitudes of me and c e since t h e y are present conventional Arrhenius format as Fig. 2. In
as a product in the p r e - e x p o n e n t i a l f a c t o r . each case, the a c t i v a t i o n energies of a(o) and
Up to now the main reasons f o r using a . c . A are in the r a t i o 1 : (I - n ) as p r e d i c t e d .
techniques to measure i o n i c c o n d u c t i v i t y have The hopping rates up c a l c u l a t e d from
been t o avoid the n e c e s s i t y of non-blocking the same data using equation (6) are shown in
e l e c t r o d e s and t o f a c i l i t a t e the s e p a r a t i o n of Arrhenius format as Fig. 3. The data were
g r a i n boundary and bulk phenomena in p o l y - f i t t e d by the s t r a i g h t l i n e s shown using l i n e a r
crystalline materials. I d e a l l y , a frequency regression and values of the a c t i v a t i o n energies
independent c o n d u c t i v i t y , equal to the d.c. and e f f e c t i v e attempt frequencies were obtained
c o n d u c t i v i t y , should be obtained a t h i g h e r from the slopes and i n f i n i t e temperature
frequencies where e l e c t r o d e and grain boundary intercepts, respectively. The a c t i v a t i o n
phenomena are i n s i g n i f i c a n t . In p r a c t i c e , such energies f o r each are w i t h i n experimental e r r o r
a frequency independent p l a t e a u is observed, the same as those found f o r a(o) in Fig. 2.
often over several decades of frequency, but is This i n d i c a t e s t h a t the thermal a c t i v a t i o n s
l i m i t e d at higher frequencies by an a d d i t i o n a l of these c o n d u c t i v i t i e s are caused by the
bulk phenomenon. This takes the form of a thermal a c t i v a t i o n s of the hopping rates alone.
power law increase in c o n d u c t i v i t y w i t h The e f f e c t i v e attempt frequency me of B-alumina
frequency. The a . c . c o n d u c t i v i t y a(m) is obtained from Fig. 3 is v e r y s i m i l a r to the
found t o v a r y w i t h angular frequency co as value 2 x 1012 Hz associated with the v i b r a t i o n -
~(co) = o(o) + A~n (4) al frequency mo obtained d i r e c t l y from i n f r a -
red a b s o r p t i o n measurements [ I 0 ] . This shows
where a(o) is the d.c. c o n d u c t i v i t y , A is a t h a t the e n t r o p y term ASa in equation (2) is
temperature dependent parameter and n is found small in t h i s p a r t i c u l a r m a t e r i a l . Several
to take values between 0 and I . Jonsche~ [ 5 ] authors [4, I I ] have iTnd,~ed suggested t h a t
has suggested t h a t t h i s power law is a these e n t r o p y terms should be small in f a s t ion
' u n i v e r s a l ' p r o p e r t y of m a t e r i a l s t h a t is conductors such as B-alumina.
r e l a t e d t o the dynamics of hopping conduction. For L i , S i O , and the Ag+ g l a s s , the e f f e c t -
R e c e n t l y , we have shown [ 6 ] t h a t t h e r e is a ive attempt f r e q u e n c i e s , I0 zsHz Fig. 3, are
simple r e l a t i o n s h i p between a(o) and A. The c o n s i d e r a b l y higher than l i k e l y values of
c o n d u c t i v i t y o(co) can then be expressed as corresponding v i b r a t i o n a l f r e q u e n c i e s , ~1013Hz.
, l-n n This r a i s e s the question o f the magnitude o f
• o(co) = K~p + ~CJp co (5) the e n t r o p y of a c t i v a t i o n ASa in these, and
where K was defined in equation (1). By o t h e r , i o n i c conductors. Some i n s i g h t may be
combining equations (4) and (5) the hopping obtained by using the formula f o r ~Sa which
rate cop is given by was d e r i v e d by Wert and Zener [12] in t h e i r
t h e o r y of i n t e r s t i t i a l d i f f u s i o n in m e t a l s :
co = ( ~ ( o ) / A ) I / n (6) AS - BEa (7)
P
This provides a p a r t i c u l a r l y sir.lple way of a T
m
quantifying m . The t h e o r e t i c a l temperature
dependences of p o(o) and A may be obtained by where Tm is the m e l t i n g temperature and B is
s u b s t i t u t i n g f o r K and cod from ( I ) , (2) and (3) a dimensionless number, ~ 0 . 4 , which is r e l a t e d
in ( 5 ) . For m a t e r i a l s 'in which the c a r r i e r to the temperature dependence of the shear
c o n c e n t r a t i o n is independent of temperature, modulus of the m a t e r i a l . Estimates of the
o n l y mo is t h e r m a l l y a c t i v a t e d and the magnitude of the term exp(ASa/k) in me,
a c t i v a t i o n energies of a(o) and A are Ea and obtained using equation (7) are 40, I I and 1.3
(I - n ) E a, r e s p e c t i v e l y . For m a t e r i a l s in which f o r the Ag+ g l a s s , Li4SiO, and B-alumina
the c a r r l e r c o n c e n t r a t i o n is a l s o t h e r m a l l y respectively. These e n t r o p y values match,
a c t i v a t e d , K is t h e r m a l l y a c t i v a t e d and to w i t h i n a f a c t o r of f i v e or b e t t e r , those
consequently, the a c t i v a t i o n energies of ~(o) determined using equation (2) and Fig. 3 and
and A become Ec + Ea and E + (I - n ) E a, assuming wo ~ 1013 Hz f o r L i , S i 0 4 and the Ag+
respectively, c glass. In view of the e r r o r s in e s t i m a t i n g me,
The above r e l a t i o n s h i p s have been used to 8 and mo ( e s p e c i a l l y f o r Li4Si04 and the Ag+
analyse a.c. c o n d u c t i v i t y data from f o u r glass) t h i s is a l l t h a t can be expected at
d i f f e r e n t i o n i c conductors. The f i r s t three : t h i s stage.
s i n g l e c r y s t a l Na B-alumina, p o l y c r y s t a l l i n e A f t e r the hopping rates have been
L i , S i 0 4 and AgTI,AsO, g l a s s , appear t o have determined, i t is p o s s i b l e to estimate the
temperature independent c a r r i e r c o n c e n t r a t i o n s carrier concentrations. For B-alumina, however
D.P. A l m o n d et al. / Hopping rates and carrier concentrations in ionic conductors 161

Li&SiO4 n : 0.68 AgTILAs~ n :0.68


Z
E
f184K
u

..(Z
0

b
~ 4 8 0 K ~ 1 4 0 K ~

2 3 A 5 6 2 3 4 5 6 2 3 4 5 6 7
log f(Hz)

FIG. 1
Conductivity data for single crystal Na 6-alumina (ref. 6,7), polycrystalline Li,SiO, (ref. 8)
and Ag~l,AsO4 glass (ref. 9) at a selection of temperatures. Solid curves are f i t s of equation (4)
to the experimental data. Errors in n are estimated as ±0.03. The experimental data for
6-alumina and AgTI,AsO, at the highest temperatures and low frequencies show a conductivity dispersion
associated with electrode polarisation effects.

4t Na /B-alumina Li/.Si 04

n:O-60 n :0.68

1 o-(olT
log o'(o)T 0 -~Eo = 17± 2 kJ moL-1
or - ~ 80±2
1
log AT }

26±2 tl
§
0, 2 4 6 8 10 0 2 Z. 0 4 6 8 10
1000IT (K '1)

FIG. 2
Arrhenius plots of o(o)T and AT.
16 2 D.P. Almond et al. /Hopping rates and carrier concentrations in ionic conductors

161 I
i Na /~-alumine T Liz.Si04 " Ag71 z.A sO4
15 i
14

13

li

Iog~(secP)1(119~ =15-+2kJrnO[-1 / 78-*4 I \ 25±2

7 •

1000/T ( K4 )

FIG. 3
Arrhenius plots of ion hopping rates, Up.
equation ( I ) may be used only semiquantitatively ratio~. However, in the Ag+ glass, the density
because of uncertainties in y, a and N : the of Ag- ions is about 4 times greater than the
mechanism of conduction is an interst~t~alcy one density of Na+ ions in B-alumina and therefore,
involving several Na+ ions and two types of the ionic c a r r i e r density difference between the
l a t t i c e s i t e , the Beevers-Ross and mid-oxygen, two materials is only a factor of ~5. This
are involved in the conduction. Further + difference is offset by the higher (~7 fold)
d i f f i c u l t i e s arise with Li,SiO, and the Ag hopping rate in the Ag+ glass at room temperat-
glass because the conduction mechanisms are not ure as shown in Fig. 3. This enhanced hopping
known and in the Ag+ glass, the structure is rate can be a t t r i b u t e d , almost e n t i r e l y , to the
completely unknown. We estimate the net c a r r i e r large entropy of activation of the Ag+ glass.
concentration c' using the approximation: The estimated room temperature conductivity of
c' = c ( l - c ) N (8) Li,SiO, is some I0 decades less than that of
the other two materials. This is largely due
and substituting into equation (I) wish assumed to the much reduced hopping rate in Li,Si04,
average values for a and y of 3 A and Fig. 3, which in turn is a consequence of i t s
0.33 respectively. The net a l k a l i ion c a r r i e r much higher activation energy.
concentrations, c ' , are then calculated to be Conductivity data for the fourth material
22%~(Na B-alumina) 0.5% (Li,SiO,) and I . I % the K/Ca n i t r a t e glass, are shown in Fig. 4a.
(Ag" glass). The data f a l l into two groups, above and below
The composition of the Na B-alumina crystal the glass t r a n s i t i o n temperature, Tg, ~60°C.
was ~ 1.2 Na20.IIA~203 and the high conductivity These data were analysed in the same way and i t
of B-alumina has been attributed to the 0.2 is evident that the q u a l i t y of some of the f i t s ,
excess soda content. Our estimate of the solid lines Fig. 4a, is not so good as that for
c a r r i e r concentration of ~22% is in f a i r agree- the other three materials, Fig. I. The reasons
ment with t h i s . The room temperature conduct- for this are not understood. Nevertheless,
i v i t y of the Ag÷ glass is comparable to that of reasonable estimates of o(o) and A were obtained
Na B-alumina despite i t s lower c e r r i e r concent- from the low and high frequency l i m i t i n g regions
D.P. A l m o n d et al. / Hopping rates and carrier concentrations in ionic conductors 163

0 4Ca{NO3}2 0.6KNO3 Tg~ 3 ~ 0 6 3 of these data. Results are shown plotted in


Arrhenius format in Fig. 4b. In the low
353.3K~ : :~ ~ _ . w ~ 0'63 temperature region, below Ta, the activation
energies of o(o) and A are Tn the r a t i o l :
(l - n ) as with the other three materials, Fig. 2.
Above Tg, however, this relationship does not
"T hold. The activation energies are in the r a t i o
E
of I:0.5 whereas a r a t i o I:0.37 might be
expected since in this region n ~ 0.63. The
b --
o', 11
hopping rates, uD, calculated using equation
o (6) and the values of ~(o) and A shown in
Fig. 4b, are plotted in Arrhenius format as
&3 (a} Fig. 4c. In the low temperature region,
T~_ below Ta, the activation energy for ~n is very
0 1 2 3 L 5 6 s i m i l a r ~ t o t h a t of o ( o ) , Fig. 4b. Ab6ve Tn,
log f IHz) however, the a c t i v a t i o n energy of ~(o) is
s i g n i f i c a n t l y higher than t h a t of Up. This is
i n t e r p r e t e d as being due to a temperature
dependent c a r r i e r concentration above TO. The
(b)
temperature dependence of o ( o ) , equati6ns ( I ) ,

~
( 2 ) , ( 3 ) , is in g e n e r a l , caused by the thermal
a c t i v a t i o n of both the c a r r i e r c o n c e n t r a t i o n , c,
328_t 17 kJ mo[ 4 and the hopping rate u D. Thus the a c t i v a t i o n
energy f o r o ( o ) , Fig. ~b, above TQ is taken to
log o-(o)T be Ea + Ec whereas t h a t of Up is ~ Ea alone,
or cr(o)T i.e. Ea = 257 kJ mol "I and Ec = 71 kJ mol " I ,
In the presence of a t h e r m a l l y a c t i v a t e d
IogAT c a r r i e r concentration i t was shown e a r l i e r t h a t
o(o) and A should have a c t i v a t i o n energies in
the r a t i o (E c + Ea) _~c(EC + ( I - n ) E ~ ) . _ Using
i5 the above values OT and Ea with = 0.63 t h i s
r a t i o becomes 1:0.5 which i.s e s s e n t i a l l y the
, ;g , 36_.5, same as the observed r a t i u , Fig. 4b. The
T~ c a r r i e r concentration in the n i t r a t e glass was
2.8 3-0 3.2 3.4 estimated in the same way as f o r the other three
systems. Assuming that only K+ ions c o n t r i b u t e
1000IT (K -1) to the c o n d u c t i v i t y , the concentration of mobile
K+ tons is ~ 0.1% below Tg.
7 Using the new method of analysis proposed
(c) here we are able to u t i l i s e the dynamical
c h a r a c t e r i s t i c s of a.c. c o n d u c t i v i t y to separate
6 the c o n t r i b u t i o n s made by the m o b i l i t y and
concentration of ions to d.c. c o n d u c t i v i t y . The
5 57_.1/., kJ mot -1 method has been used successfully on four
log 0 m a t e r i a l s of widely d i f f e r i n g s t r u c t u r e s and
P4 conductivities and each with a d i f f e r e n t
(sec -1) mobile c a t i o n : Li +, Na+, K+ and Ag+: In the
3 evaluation of ion hopping r a t e s , the c o n t r i b u t -
ion of the associated entropy term has become
e v i d e n t . The q u a n t i f i c a t i o n of t h i s term raises
2 i n t e r e s t i n g questions as to i t s physical o r i g i n
in i o n i c conductors. The a b i l i t y to separate
1 Tg the c o n t r i b u t i o n s of c a r r i e r c o n c e n t r a t i o n , with
! i t s possible temperature dependence, and hopping
0 i i i~ i i i i
rates providesa powerful new way of studying
2.8 3.0 3.2 3-4 ionic transport.
10001T (K ~ ) ACKNOWLEDGEMENT
We thank Dr. M.D. Ingram f o r providing
FIG. 4 (a, b, c) o r i g i n a l c o n d u c t i v i t y data f o r the Ag+ glass.
Conductivity data f o r K/Ca n i t r a t e glass and
supercooled melt a) c o n d u c t i v i t y data ( r e f . 13)
and f i t t e d curves, b) Arrhenius p l o t s of o(o) T
and AT, c) Arrhenius p l o t of Up.
164 D.P. Almond e# al. /Hopping rates and carrier concentrations in ionic conductors

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Electrochim. Acta 22 (1977) 811. and unpublished results.
(2) L.W. Barr and A.B. Lidiard, in
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Ed. W. Jost, Academic Press, 1970,
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