Solid State lonics 53-56 ( 1992 ) 791-797 SOLID

North-Holland STATE
IONICS

Lithium carbonate as a solid electrolyte

J u n i c h i r o M i z u s a k i l, H i r o a k i T a g a w a
Institute of Environmental Science and Technology, Yokohama National University,
156 Tokiwadai, Hodogaya-ku, Yokohama 240, Japan

K e n Saito, K e n s h i U c h i d a a n d M e g u r u T e z u k a
Department of Environmental Engineering, The Saitama Institute qf Technology, 1690 Fusatji, Okabe, Saitama 369-02, Japan

To make clear the property of Li2CO 3 as a solid electrolyte, a study was made on the electrical properties of Li2CO 3 doped with
Li3PO4,CaCO3and LiNO3 as a function of dopant concentration at 250-600°C. The sampleswere prepared by a melt-solidifying
technique. Since the crystals grew essentiallyalong the (002) plane of the monoclinic Li2CO3structure, the conductivity, 6, was
measured by impedance spectrometry both along and perpendicular to (002) using gold paste as electrodes. By the Tubandt
method, LizCO3 was a pure lithium ion conductor. The conduction along (002) was much larger than that perpendicular to
(002). The conductivity of Li2CO 3 was similar in magnitude to that of LiaSiO4, LisAIO4and Li2SO4. The conductivity increased
proportionally with the Li3PO4 concentration, and decreased with an increase in LiNO3 and CaCO3 concentration. It was con-
cluded that the conduction in LiaCO3is essentiallyby interstitial lithium ions. The Frenkel constant and the mobility of lithium
interstitial ions were calculated.

1. Introduction been no researches reported on the precise electro-

Recently, m a n y reports have been published on
solid-electrolyte CO 2 sensors. Most of them are com-
posed of non-carbonate alkali-ion conductors, such
as ~(13")-A1203 and NASICON as electrolyte, and
mixtures of alkali or alkaline-earth carbonates and
electronic conductors as electrodes [ 1-3 ]. Here, the
alkali or alkaline-earth carbonates in the electrode
work as a converter of gas-phase CO2 activity into
the activity of the metallic element of the carrier spe-
cies in the electrolyte. Our interest is if there is some
carbonate electrolyte which can be used directly as
the electrolyte of CO2 sensors.
Our preliminary research revealed that, among the
alkali and alkaline-earth carbonates, only Li2CO3
shows a fairly good conductivity and good stability
against the h u m i d i t y in the air. Although m a n y re-
searches have been made on the lithium salts such as
LiI, Li2SO4, Li3PO4, and LiC104, it seems there have
Author to whom all correspondence should be addressed.
lytic properties of Li2CO3.
In this work, in order to make clear the properties
of Li2CO 3 as a solid electrolyte for CO2 and other
chemical sensors, a study was made on the electrical
properties of Li2CO 3 doped with Li3PO4, CaCO3, and
LiNO3 as a function of dopant concentration at tem-
peratures up to 600 °C.
2. Experimental
2. 1. S a m p l e preparation a n d characterization
To prepare high-density samples of fairly homo-
geneous dopant distribution, a melt-solidifying tech-
nique was employed: Pure Li2CO3 (99.9%) and
powder mixtures of Li2CO3-Li3PO4(~<9 mol%),
Li2CO3-CaCO3 ( ~< 8 mol%) and Li2CO3-LiNO3 ( ~<2
mol%) were melted in a l u m i n a tubes and cast into
a l u m i n a rings ( 12 m m in inner diameter and 10-15
m m in length) placed at the bottom of an a l u m i n a

(1167-2738/92/$ 05.00 © 1992 ElsevierSciencePublishers B.V. All rights reserved.

792 J. Mizusaki et al. / Li:CO s as a solid electrolyte
crucible. Then the cylindrical ingot was taken off
from the alumina ring.
The samples thus prepared were more than 95% in
density. Since the crystals grew essentially along the
(002) plane of the monoclinic Li2CO3 structure, the
prepared samples were highly anisotropic. Details of
the sample characterization will be described in sec-
tion 3.1.
The samples before and after the measurements
were analyzed by XRD.
2.2. Conductivity m e a s u r e m e n t s
From the cylindrical cast ingots, pellets of 3-6 m m
in thickness and 8-10 m m in diameter were cut.
Considering the orientation (cf. section 3.1), two
types of pellets were prepared for pure and the
Li3PO4-doped compositions, so that the direction of
current would be essentially parallel to and perpen-
dicular to (002). Because the LiNO3- and CaCO3-
doped samples are quite fragile along the (002)
cleavage plane, mostly pellets perpendicular to the
(002) plane were prepared for these compositions.
A non-flux-type gold paste was applied to both
surfaces of the pellet and fired at 450°C. The imped-
ance spectra were measured in air up to 600 °C using
an impedance analyzer (mainly NF 5020, partly
Schlumberger 1260). The ac potential applied to the
cell was kept below 10 mV p-p.
2.3. Ionic transport n u m b e r
To identify the charge carrier, the Tubandt method
[4] was applied. Three Li2CO3 pellets were sand-
wiched between two silver pellets. Gold paste was
attached on the surface of the Li2CO3 pellet facing
the silver pellet, so that the reaction of Li2CO3 with
silver can be avoided. The measurement was made
at 500°C.
3. Results and discussion
3.1. Characterization o f the s a m p l e orientation
The cast cylindrical ingots were composed of sev-
eral large grains of oriented structure, as shown sche-
matically in fig. 1. In the figure, the arrows indicate
upper surface
L
1
lower surface
(T i o)
I "~ d .,F I
Fig. 1. Schematics of the cross-section of the cylindrical ingol.
The indices of the planes are determined by XRD analysis.
the growth direction of the grains. The grains tend
to cleave parallel to the arrows.
Typical X R D patterns for the upper surface and
the lower surface of the cylindrical as-grown ingots
are shown in fig. 2. The structure is monoclinic. The
lattice parameters of the doped and the pure samples
are in the range of a=8.365_+0.01 ,A., b = 4 . 9 8 0
+0.005 A, c=6.20_+0.01 /~, and fl=114.7_+0.1 '~,
which is close to the literature values of pure Li2CO3
[ 5,6 ]. The change in the lattice parameters with do-
pant concentration is smaller than the experimental
errors.
From figs. 1 and 2, we find that the upper surface
of the as-grown cylinder is essentially parallel to the
(002) plane while the lower surface is close to ( i 10 ).
The directions of grain growth and cleavage are par-
allel to (002).
3.2. D e t e r m i n a t i o n o f carriers
The cell arrangement and the result of the Tub-
andt method are shown in fig. 3 and table 1. Since
the weight loss of Li2CO3 next to the positive elec-
trode, Li2CO3(1), is considerable, the carrier must
be lithium ions. However, the increase in the total
weight of the negative electrode and the EizCO3 (Ill)
pellet next to the electrode is much smaller than the
weight loss of Li2CO3 (I). Moreover, the silica tube
near the Ag/Au/Li2CO3 interface was corroded, sug-
gesting that a reaction took place between the silica
tube and the lithium metal deposited at the interface.
 J. Mizusaki et al. /Li2CO 3 as a solid electrolyte 793

lower surface

fM CM 0"3 f¢3

0
0
upper surface
E i
Li2CO3-3m/0Li3PO 4
E CM
0

I0 20 40 60 80
20 /degree
Fig. 2. Typical XRD pattemsofan as-grownLi2CO3cylindricalingot.Sample:3 mol% Li3PO4-dopedgi2co3. X-ray:Cu Ka, 35 kV 15
mA.

Table 1

_L
Results of the Tubandt method for Li2CO3at 500°C. Electricity
of 215.1 C were passed.

Pellet Observed Calculated

weight change weight change
Ag ( i ) j Au paste
v Ag(1) }
LizCO3(I ) -78.6 mg -82.36 mg
Li2CO3 ( i ) Silica Li2CO3(II) +0.71 mg 0 mg
tube Li2CO3(III )
Li2C03 ( I I ) Ag(II) J +662 mg+°~ al + 15.47 mg

i Au paste a) O'is the unknown weight of lithium which reacted with the sil-
ica tube.

Ag ( I i ) ~partially
corroded Au or L i - A u - A g alloy a n d / o r s i l i c a - L i - O solid
solutions.
In table 1, the theoretical weight loss of the
Li2CO3(I) pellet was calculated from eq. ( 1 ), while
Fig. 3. Schematics of the Tubandt cell. The part of the corroded the theoretical weight gain of the Li2CO3 (III) pellet
area of the silica tube is indicated. - A u / A g electrodes was calculated based on eq. (2).
The calculated weight changes essentially agreed with
The reaction at the positive electrode may be writ- the observed weight changes. It was shown that
ten as Li2CO3 was essentially a pure lithium-ion conductor.

I-,i2CO3 ~ 2 L i + + 2 e + C O 2 ( g ) + ½02(g) ,
while the reaction at the negative electrode is only
the deposition of lithium, i.e.
Ii+ +e~Li •
The deposited lithium was incorporated into the
electrode metals a n d / o r the silica tube to form L i -
( 1)
3.3. Conductivity
3.3.1. Conductivity and its anisotropy
(2) Fig. 4 shows the conductivity along and perpen-
dicular to (002) as a function of temperature for pure
LizCO3 and 3 mol% Li3PO4-doped Li2CO3. In the
figure, the conductivity of Li4SiO4 [ 7 ], LisA104 [ 8 ]
794 J. Mizusaki et al. /Li:CO~ as a solid Heclrolyte

t/°C
t/°C
600 500 400 300 600 500 400 300
-2 I I I I I I I I

I Li 3PO4-d°ped Li2C03
?
~E 3
o

g~
L/ / °'sm°l

-5 \ Li5AIO 4
-

6 4 • : pure
'k"ko' te

hi3P04 \ \ " ' i x°"x Li4SiO 4

-6
] I [ \ I I x I l e~: O.5molZ X ' I ~
1.2 1.4 1.6 1.8
103T-1/K 1 I\
Fig. 4. Conductivity of pure (~ and • ) and 3 tool% ki3PO4-
doped ( O and • ) Li2CO3.Solid lines and open symbols: paral- /
lel to (002): broken lines and closed symbols: perpendicular to | I i I I I I ",
(002). The conductivity of Li2SO4, LisAIO4,Li4SiO4,and ki3PO4 -6 1.2 1.4 1.6 1.8
are indicated by the thin lines. 103T-I/K l

and Li2SO 4 [9] are also shown for comparison. As t/°C

shown in fig. 4, the conductivity, 0, along the (002) 600 500 400 300
i i I I i r I

plane was much larger than that perpendicular to 2' ~ , , , , , , Li3P04_doped Li2C03
(002). The conductivity of Li2CO3 is found to be of
the same order as that o f Li4SiO4, LisA104 and
Li:S04.

3.3.2. l{ffect o f d o p a n t
Figs. 5, 6 and 7 show the effect of the dopant on
the conductivity. With Li3PO4 doping, the conduc-
tivity increases and the activation energy decreases.
On the other hand, with slight LiNO3 and CaCO3 • : pure ~ z<,
doping, the conductivity decreases and the activa- a : 3 tool% pure~
tion energy increases slightly. o : 5 mol% xll
Figs. 8 and 9 show the change in ~ with dopant
-6 m : 9 molZ X
concentration at 400 and 500°C, respectively. The
k
conductivity increased proportionally with Li3PO4 ± (002) ~_
concentration. On the other hand, with the increase I I I I I 1 •
1.2 1.4 1.6
in LiNO3 and CaCO3 concentration, a decreased,
]03T-1/K -1
then showed a m i n i m u m , and increased slightly.
When the concentration of LiNO~ or CaCO3 ex- Fig. 5. Conductivity parallel and perpendicular to (002) of
ceeded 2-3 tool%, a was constant for further in- Li3PO4-doped Li2C()~.
crease in the dopant concentration. The solubility
limit of LiNO3 and CaCO3 was considered to be 2 - no phase study seems to have been reported relevant
3 tool%. Since a of the Li3PO4-doped Li2CO3 in- to the solubility of these dopants in LieCO~.
creases up to 9 tool% doping, the solubility limit of
Li~PO4 is considered to be more than 9 tool%. So tar
 J. Mizusaki et al. /Li2COs as a solid electrolyte 795

t/°C t/°C
-2
600
i I
500
i I
400
I I
300
1
600 500 400 300
-2 dg, I 1 I I I I
~.. Li NO3-doped Li2C03 CaCO3-doped Li2C03

~ p u r e
~ 0.5 moI%
~mol%
I~
X\~X~------8 mol%

I E --~ ~-4 -
"~.~ ' ~ I mol%
(9
v~ re

C~ • .'pure

m: 0"5mo]~ ~ X
m: p u r e X
0 : 1 mol% \~.~
zx: 0 , 5 mo]~ ~ X
~ 6
o: l mol
±(002)
I:]: 8 mol% \~'
z (002) %
I I I I I I I I I I I I
1.2 1.4 1.6 1.8 1.2 1.4 1.6 1.8
103T-1/K -1 I03T-I/K -I
Fig. 6, Conductivity perpendicularto (002) of LiNO3-doped Fig. 7. Conductivity perpendicular to (002) of CaCO3-doped
Li2COs. LizCO3.

3.3.3. D e f e c t m o d e l
In lithium carbonate crystal, large plenary CO I - o • : L i 3 P 0 4 doped /
ions compose the (002) planes and small lithium ions 8 It, A:LiN03 doped f
are placed in between the oxygens of the neighboring
CO 2- ions [6]. Therefore, Frenkel defects in lith-
~-E ~-. :CaC03 doped ] / , O,
ium sites may be easier to form than Schottky-type ~ 4 ]open symbol: ,1002] / 4"
or anion-cation interstitial defects.
The Frenkel constant, KF, is given by the equation r / ~ . " • 400°C
0 l*-~-..-'-ge~'" 7 " , Li~ C03,
KF= [VL] [Li[] . (3)
8 4 0 4 8
dopand concentration/mol%
In this paper, we use the Kr6ger-Vink type of no-
lation for defects [ 10]. For pure Li2CO3, Fig. 8. Conductivity of Li2CO3as a function of dopant concen-
tration at 400°C. Open symbols and solid curve: t~ parallel to
IV[,] = [Li[] = K ~ -/2 . (4) (002): closed symbols and broken curve: o- perpendicular to
(OO2).
With Li3PO 4 doping, PO 3- may replace the C O ] - ,
and the number of interstitial lithium ions, Lil, in- Similarly, with CaCO3 or LiNO3 doping, V}_ i in-
creases by the equation creases according to the equations

Li3 PO4 ~ 2Li~i + PO ;,co3 + Lil. (5) CaCO3 -+ CaLi+ Vii + C0~,co3 (7)
or
The electroneutrality is expressed by
LiNO3 ~ L i ( / + V L + NO3.co3. (8)
[Lil] = [VL] + [P04,co,] • (6)
796 J. Mizusaki et al. / L t e C O 3 as a solid electrolyte

a, = (N,~/G,~)yell (14)
o•:Li3P04 doped

o//-
where y is in the unit of mole fraction, e is 1.6 X 10 t,~
A :LiN03 doped
~E C,/, is the mobility of Lil in cm 2 s-~ V - ~, N.x is the
. • :CaC03 doped Avogadro constant, I;,, is the molar volume of Li2CO,
open symbol: lID02 which is 35.00 cm 3. Using eqs. (13) and (14), we
2 closed symbol:z002
have

1
el, --~, = ( N~\/ l~m )e lt(_)cG ) ( 15 )

where q . is the conductivity due to Lil of pure

/// , ee°c. Li2CO). For most of the composition in this work.
Li2C03 base O'i m O""
[ I I I I I I I From the slope of the plot of ~2 vs. xe. we can de-
8 4 0 4 8
dopant c o n c e n t r a t i o n / m / o termine I*. Since eq. (4) holds for pure Li2CO~. we
have
Fig. 9. Conductivity of Li2CO3 as a function of dopant concen-
tration at 500°C. Open symbols and solid curve: c; parallel to ( & , = K I / 2 ( N~,/ [],,)e l l . (16)
(002), closed symbols and broken curve: cr perpendicular to
(002). Thus we can determine Kv from the conductivity of
pure LizCO~ and ,u. The calculated it and K~: are
Electroneutrality in the respective cases is main- shown in fig. 10.
rained by the equations The mobility parallel to (002) is about three times
as large as that perpendicular to (002). The acti-
[Li]] + [Ca;.,] = [V~,] (9)
vation energy is about 0.6 eV (60 kJ mol '). Al-
and though the calculated K~ shows the scattering due to
the exaggeration of experimental errors during the
[Lil] + [NO;.~,,,] = [ V L , ] . (10) calculation procedures, o" parallel to (002) and per-
Since the Frenkel equilibrium, eq.(3), holds, an
increase in [Vk,] by the CaCO3 or LiNO3 doping ac- t/o C
companies the decrease in [Lil]. The change in 600 500 400 300
[ Lil ] agrees with the observed conductivity changes I I I I -~
A L~2C03
for the Li3PO4-doped and slightly LiNO3- and
CaCOs-doped samples. It was concluded that the
lithium-ion conduction in pure and doped Li2CO3 is
essentially by Lil.
r> -4 • -6 Y

3.3.4. Calculations,lbr KF and mobilRy

Here, we put the dopant concentration as --.~ -5 - -8
[PO;,c,,,] - [NOiv< o~] - [CaL,] = x . ( 11 )

and [Lil] as -6 k 002 xx XCX

\
[Lil]=y. (12) IN
-7 l J I
using eq. (3). eqs. (4), (6), (9) and (10) are sum- .2 1.4 l .6 I.
marized as 103T-1/K 1

y = Kv-/y+ x . ( 13 ) Fig. 10. Calculated mobility of Ell and Frenkel constant. ()pen
symbols: calculated from ~ parallel to (002): closed symbols: cal-
The conductivity by [Lil] can be expressed by culated from o- perpendicular to (002).
 z Mizusaki et al./Li2C03 as a solid electrolyte
pendicular to (002) give essentially the same KF val-
ues. The formation energy for the Frenkel defects is
about 110 kJ m o l - ~.
4. Conclusions
(1) Li2CO3 was found to be a lithium ion con-
ductor. The conductivity is of the same order to that
of other lithium ion conductors, Li4SiO4, LisAIO4 and
Li2SO4.
(2) Lithium ion conduction takes place essen-
tially along the (002) plane.
(3) Interstitial lithium ions contribute the ionic
conduction, while the c o n t r i b u t i o n of lithium va-
cancies is small.
(4) The conductivity increases proportionally to
the Li3PO4 doping concentration.
797
References
[ 1] Y. Saito and T. Maruyama,Solid State lonics 28-30 (1988)
1644.
[2] N. Imanaka, T. Kawasato and G. Adachi, Chem. Lett.
(1990) 497.
[3] M. Gauthier, A. Belanger and D. Fauteux, Proc. Intern.
Meeting on Chemical Sensors (Fukuoka, 1983)
(Kodansha/ Elsevier, Tokyo, Amsterdam, l 983 ) p. 353.
[4] C. Tubandt, Handb. Exp. Phys. XII (Berlin, 1932) p. 404.
[ 5] Powder Diffraction File Inorganic ~22-1141, JCPDS.
[ 6 ] R.W.G.Wyckoff,Crystal Structure, 2nd Ed., Vol. 2 (Krieger,
Florida, 1986) pp. 463-464.
[ 71 R.A. Huggms, Electrochim. Acta 22 ( 1977 ) 773.
[8] R.M. Biefeld and R.T. Johnson, J. Solid State Chem. 29
(1979) 393.
[9] V.K. Deshpande, F.C. Raghuwanshi and K. Singh, Solid
State lonics 18/19 (1986) 378.
[ t 0 ] F.A. Kr~Sger,The Chemistry of Imperfect Crystals (North-
Holland, Amsterdam, 1974).