СИНТЕЗ ТА ДІЕЛЕКТРИЧНІ ВЛАСТИВОСТІ КЕРАМІКИ La0,67LixTi1-xAlxO3
Solid solutions of Al-doped lithium lanthanum titanates La0.67LixTi1-xAlxO3 system (where 0.15 ≤ x ≤ 0.3) have been synthesized by solid-state reaction technique. Light optical microscopy has shown that the grain size of La0.67LixTi1-xAlxO3 ceramic...
Saved in:
| Date: | 2020 |
|---|---|
| Main Authors: | , , , |
| Format: | Article |
| Language: | English |
| Published: |
V.I.Vernadsky Institute of General and Inorganic Chemistry
2020
|
| Online Access: | https://ucj.org.ua/index.php/journal/article/view/254 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Journal Title: | Ukrainian Chemistry Journal |
| Download file: |  |
Institution
Ukrainian Chemistry Journal| _version_ | 1871465644569919488 |
|---|---|
| author | Plutenko, Tatiana V'yunov, Oleg Khomenko, Boris Belous, Anatolii |
| author_facet | Plutenko, Tatiana V'yunov, Oleg Khomenko, Boris Belous, Anatolii |
| author_institution_txt_mv | [
{
"author": "Tatiana Plutenko",
"institution": "V.I. Vernadsky Institute of General and Inorganic Chemistry of National Academy of Sciences of Ukraine"
},
{
"author": "Oleg V'yunov",
"institution": "V. I. Vernadsky Institute of General and Inorganic Chemistry"
},
{
"author": "Boris Khomenko",
"institution": "V.I. Vernadsky Institute of General and Inorganic Chemistry of National Academy of Sciences of Ukraine"
},
{
"author": "Anatolii Belous",
"institution": "V.I. Vernadsky Institute of General and Inorganic Chemistry of National Academy of Sciences of Ukraine"
}
] |
| author_sort | Plutenko, Tatiana |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:45Z |
| description | Solid solutions of Al-doped lithium lanthanum titanates La0.67LixTi1-xAlxO3 system (where 0.15 ≤ x ≤ 0.3) have been synthesized by solid-state reaction technique. Light optical microscopy has shown that the grain size of La0.67LixTi1-xAlxO3 ceramics insignificantly increases with an increase in lithium/aluminum concentration. The materials La0.67LixTi1-xAlxO3 show very high dielectric permittivity ε΄ 104 over a relatively wide frequency range (102 ≤ f ≤ 104 Hz) with no apparent dependence on the x. The impedance spectroscopy study indicates three semicircles on Cole-Cole diagram that can be attributed to electrically different areas of ceramic’s grain. |
| doi_str_mv | 10.33609/2708-129X.86.11.2020.13-23 |
| first_indexed | 2025-09-24T17:43:35Z |
| format | Article |
| fulltext |
13
UDC: 549.641.1; 661.8; 621.315.61; 621.317 doi: 10.33609/2708-129X.86.11.2020.13-23
SYNTHESIS AND DIELECTRIC PROPERTIES
OF La0.67LixTi1-xAlxO3 (0.15≤x≤0.3) CERAMICS
T. O. Plutenko, O. I. V’yunov *, B. S. Khomenko, A. G. Belous
V. I. Vernadsky Institute of General and Inorganic Chemistry, Akademik Palladin Avenue 32/34,
Kyiv 03142 Ukraine
E-mail: vyunov@ionc.kiev.ua
ABSTRACT. Solid solutions of Al-doped lithium lanthanum titanates La0.67LixTi1-xAlxO3
system (where 0.15 ≤ x ≤ 0.3) have been synthesized by solid-state reaction technique.
Light optical microscopy has shown that the grain size of La0.67LixTi1-xAlxO3 ceramics in-
significantly increases with an increase in lithium/aluminum concentration. The materials
La0.67LixTi1-xAlxO3 show very high dielectric permittivity ε΄> 104 over a relatively wide fre-
quency range (102 ≤ f ≤ 104 Hz) with no apparent dependence on the x. The impedance spec-
troscopy study indicates three semicircles on Cole-Cole diagram that can be attributed to
electrically different areas of ceramic’s grain.
Key words: solid solution, lithium-lanthanum titanate-aluminate, complex impedance,
dielectric properties.
INTRODUCTION. Materials with per-
ovskite-related structure (ABO3) are inter-
esting candidates for a great variety of appli-
cations [1, 2]. The compounds of general for-
mula La2/3-xLi3xTiO3 the material substrate for
making good ionic conductors [3, 4] and, in
particular, lithium has been shown to move
in some perovskite systems faster than in any
other materials [5, 6]. A large amount of re-
search has been focused on the Ti cation sub-
stitution in the La2/3-xLi3xTiO3 system (in par-
ticular, at x=1/6, La0.5Li0.5TiO3) by other me
tal ions with less tendency toward reduction
against Li metal. Simultaneous lithium addi-
tion and titanium substitution by aluminum
in the system La2/3LixTi1-xAlxO3 has been in-
vestigated in work [7–10]. Crystal structure of
high temperature La2/3LixTi1-xAlxO3 phase with
0.06 ≤ x ≤ 0.2 annealed and quenched from
1273 K was determined [11–13]. Depending
on the cooling conditions, the structure can be
a perovskite-related orthorhombic or rhombo-
hedral. In the case of an orthorhombic struc-
ture, the formation of a superstructure of the
basic perovskite is due to two mechanisms: the
tilting of octahedra (Ti/Al)O6 and the ordering
of La3+ and Li+. The lithium ions are not located
at the interstitial A positions of the perovskite
structure and their coordination polyhedra is
a square pyramid with lithium ion at the apex.
Therefore, there is a large amount of non-oc-
cupied interstitial positions of this kind for the
INORGANIC CHEMISTRY SYNTHESIS AND DIELECTRIC PROPERTIES OF LA0.67LIXTI1-XALXO3 (0.15≤X≤0.3) CERAMICS
14 ISSN 2708-129X. Укр. хім. журн., 2020
lithium ions to move to, and this is likely to be
the reason for the very high ionic conductivity
of these kinds of materials (~ 8·105 S/cm for the
oxide with x = 0.25) [12]. In the case of a rhom-
bohedral structure [11, 14] twisting of TiO6 oc-
tahedra is observed in the structure in order
to optimize the distances between oxygen and
lanthanum ions. Lithium ions are bonded to
four oxygen atoms in a square configuration.
This environment for Li is different from the
tetrahedral-like coordination.
Another interesting property of the La2/3Lix-
Ti1-xAlxO3 oxides is their dielectric beha
vior. The authors recently reported a “giant”
barrier layer capacitance effect in La0.67Li0.25
Ti0.75Al0.25O3 [9]. It has been demonstrated
that the origin of the high dielectric constant
(ε = 2·105, tg δ=0.5 for La0.67Li0.2Ti0.8Al0.2O3 and
ε =5·105, tg δ=0.5 for La0.67Li0.25Ti0.75Al0.25O3 at
10 ≤ f ≤ 103 Hz) can be attributed to a barrier
layer capacitor associated with grain boundary
effects in the ion-conducting material [8].
However, dielectric behavior was investigat-
ed only for an orthorhombic structure sintered
with subsequent quenching. While for the
practically important case, when the material
is obtained by slow cooling and has a rhombo-
hedral structure, dielectric behavior remains
unexplored.
Therefore, in this work for the first time die-
lectric properties of partially substituted com-
plex low-temperature phase La0.67LixTi1-xAlxO3
(where 0.15 ≤ x ≤ 0.3) solid solutions with
rhombohedral crystal structure have been in-
vestigated. For this, impedance spectroscopy
data, recorded at room temperature, have been
analyzed. Light optical microscopy has been
finally used to analyze the influence of lithi-
um/aluminum concentration on the micro-
structure of these perovskites. For comparison,
La0.5Li0.5TiO3 sample, which has a larger num-
ber of lithium ions in the structure was inves-
tigated.
EXPERIMENTAL SECTION. Samples
were obtained from stoichiometric amounts
of dried Li2CO3 (Merck), Al2O3 (Merck), La2O3
(Aldrich 99.99%), and TiO2 (Aldrich 99 %)
by solid-state reaction technique. Li2CO3 was
dried at 300 ºC, La2O3 at 800 ºC and Al2O3,
TiO2 at 600 ºC. The mixtures were ground in
an agate mortar with acetone, and calcined in
air for 6 h at 1200 ºC. The rate of temperature
increase was 200 ºC/hour. The phases were
characterized by X-ray powder diffractometry
(XRPD) using DRON-4-07 diffractometer (Cu
Kα radiation, λ = 1.54178 Å; 40 kV, 20 mA).
The unit cell parameters of the samples were
determined using FullProf software by the
whole-pattern profile-matching Le Bail proce-
dure [15]. The calcined powders were ground
and pressed into pellets with a diameter of
8 mm and a thickness of 2 mm under a pres-
sure of 500 kg/cm2 (50MPa). The pellets were
sintered at 1270–1300 ºC depending on Li/Al
content (6 h) and were cooled to air tempera-
ture with a cooling rate 200 ºC/h. Finally, sam-
ples with 1 mm thickness were cut out from
prepared raw ceramic.
Grain sizes of ceramic samples of La0.67Lix-
Ti1-xAlxO3 (0.15 ≤ x ≤ 0.3) system were deter-
mined using an optical microscope LOMO
MBS-10. Using a semi-automatic computer pro-
gram imageJ [16] the area of the grain was meas-
ured, mathematically found the nominal diam-
eter, equating the resulting area to the area of the
circle. The average value of the measured nom-
inal grain diameters was considered the nomi-
nal diameter of the characteristic grain. At least
50 grains were measured from three different
areas [17]. Sintered cylindrical pellets 8 mm in
UCJ № 11 / Vol. 86T. O. Plutenko, O. I. V’yunov, B. S. Khomenko, A. G. Belous
15https://ucj.org.ua
diameter and 2 mm thick, with evaporated me
tal electrodes, were used for electrical measure
ments. Impedance spectroscopy measurements
were conducted using a 1260 Impedance /
Gain phase Analyzer (Solartron Analytical).
RESULTS AND DISCUSSION. It has been
shown that single-phase solid solutions
La0.67LixTi1-xAlxO3 (where 0.15 ≤ x ≤ 0.3) are
formed at temperatures above 1200 ºC using
solid-state reaction technique.
Fig. 1. Experimental (dots)
and calculated (line) room-tem-
perature powder X-ray powder
diffraction patterns of ceramic
samples La0.67Li0.3Al0.3Ti0.7TiO3
sintered at 1300 ºC for 2 h. Bars
indicate the peak positions.
The unit cell parameters were deter-
mined from the XRPD patterns using a rapid
whole-pattern profile-matching Le Bail proce-
dure (Fig. 1). La0.67LixTi1-xAlxO3 solid solutions
(where 0.15 ≤ x ≤ 0.3) materials have a rhom-
bohedral perovskite-related structure (space
group R-3c, № 167). In XRPD spectra addi-
tional lines of small amount La0.67LixTi1-xAlxO3
with tetragonal phase symmetry (space group
P4/mmm, № 123) are observed. The phases
observed do not differ in chemical composi-
tion. The main difference between these phases
is in the crystal structure. Unit cell parameters
depend on Li/Al concentration (Fig. 2).
Fig. 2 shows the dependence of the unit cell
volume of the samples La0.67LixTi1-xAlxO3 sys-
tem sintered at 1300 ºC for 2 h. For the sam-
ple x = 0 the data given in [18] was used. The
dependence is linear and obeys Vegard’s law,
which indicates the formation of a continuous
series of solid solutions in La0.67LixTi1-xAlxO3
(0.15 ≤ x ≤ 0.3). Unit cell volume decreases
with an increase in x, due to the difference in
ionic radii of aluminum and titanium.
Fig. 2. Unit cell volume of La0.67LixTi1-xAlxO3
solid solutions sintered at 1300 ºC for 2 h.
INORGANIC CHEMISTRY SYNTHESIS AND DIELECTRIC PROPERTIES OF LA0.67LIXTI1-XALXO3 (0.15≤X≤0.3) CERAMICS
16 ISSN 2708-129X. Укр. хім. журн., 2020
Fig. 3. Optical microscope imag-
es of La0.67LixTi1-xAlxO3 ceramics,
where x=0.15 (a), 0.2 (b), 0.25 (c),
0.3 (d).
The ceramic’s size and morphology of
La0.67LixTi1-xAlxO3 were studied by light optical
microscopy (Fig. 3). It has been shown in Fig. 3
that with an increase in x, the average grain
size slightly increases from 6.1 μm (x=0.15) to
7.7 μm (x=0.3). This fact can be attributed to an
increase in sintering temperature with an in-
crease in Li/Al content. The boundary between
one grain and another is a defect in the crystal
structure and so it is associated with a certain
amount of energy [19]. As a result, there is a
thermodynamic driving force for the total area
of boundary to be reduced. With sintering tem-
perature growth in La0.67LixTi1-xAlxO3 grain size
UCJ № 11 / Vol. 86T. O. Plutenko, O. I. V’yunov, B. S. Khomenko, A. G. Belous
17https://ucj.org.ua
increases accompanied by a reduction in the
number of grains, therefore the total area of the
grain boundary is reduced.
a
b
Fig. 4. Complex impedance diagram of La0.67Li0.2
Ti0.8Al0.2O3 (a) and La0.5Li0.5TiO3 (b) at room tem-
perature.
The results of the frequency investigation
of La0.67LixTi1-xAlxO3 ceramics can be analyzed
as four types of dependencies: complex impe
dance (Z*), complex admittance (Y*), com-
plex permittivity (ε*), and complex electric
modulus (M*) [20–22]. These complex quan-
tities are interrelated: M* = 1/ε* = jωCoZ* =
jωCo(1/Y*), where ω is the angular frequency
and Co is the capacitance of empty cell (where
j = -1). Initially, the results of the frequency in-
vestigation of PTCR materials were obtained as
Z’’ = f(Z’) relations (Fig. 4a). There are three sem-
icircles on the complex impedance diagram at
room temperature for La0.67Li0.2Ti0.8Al0.2O3 solid
solution.
For comparison, we present impedance dia-
grams of La0.5Li0.5TiO3. Fig. 4b shows the com-
plex impedance diagram at room temperature
for the La0.5Li0.5TiO3. One semicircle depressed
below the real axis, part of a second semicir-
cle, and a spike at the lowest frequencies are
observed. The arc at the highest frequencies is
presented in the inset of Fig. 4b.
The appearance of three semicircles in the
Cole-Cole plots indicates that there are three
relaxation mechanisms, which may be due to
grain, grain boundary, and electrode polar-
ization. Generally, the arc at high frequen-
cy refers to bulk, at low frequency refers to
electrode polarization, and middle-frequency
area - to grain boundary. The good separa-
tion of these semicircles in La0.67LixTi1-xAlxO3
is ascribed to the small pore size. If the pore
size is greater than 1 µm, it would lead to the
overlapping of the semicircles like in La0.5Li0.5
TiO3 [8].
The dielectric constant was calculated from
an impedance measurement. Fig. 5 shows di-
electric constant (Fig. 5a) and dielectric loss
(Fig. 5b) versus frequency at room tempe
rature. All La0.67LixTi1-xAlxO3 samples have
a high dielectric constant value ε′ > 105 at
low frequencies (f ≤ 10 Hz). These values are
close for ones of the samples of the orthor-
hombic high-temperature phases La0.67Li0.2
Ti0.8Al0.2O3 and La0.67Li0.25Ti0.75Al0.25O3 [9, 10].
Whereas it has been shown that La0.5Li0.5TiO3
sample has a high ε′ > 104 at low frequencies
(f ≤ 10 Hz).
INORGANIC CHEMISTRY SYNTHESIS AND DIELECTRIC PROPERTIES OF LA0.67LIXTI1-XALXO3 (0.15≤X≤0.3) CERAMICS
18 ISSN 2708-129X. Укр. хім. журн., 2020
Fig. 5. Dielectric constant (a) and dielectric
loss tangent (b) of La0.67LixTi1-xAlxO3 at x = 0.15 (1),
0.20 (2), 0.25 (3), 0.3 (4) and La0.5Li0.5TiO3 (5).
Transport of Li ions in La0.5Li0.5TiO3 occurs
via vacancies in the A-site of the perovskite
ABO3 structure. Lithium ions are believed to
move transport through the so-called struc-
tural conduction channels, i.e. “bottlenecks”
formed by oxygen ions. Li ions are located at
the center of the square planar windows con-
necting contiguous oxygen sites (Fig. 6). [14].
The high value of the dielectric constant for
the La0.67LixTi1-xAlxO3 is attributed to the mo-
tion of charge carriers (Li ions) both inside
and between unit cells. It should be noted
that lithium ion’s movement can contribute
to both ionic conductivity and polarization.
When lithium ions move from one electrode
to another, such motion contributes to ionic
conductivity. At the same time, if the motion
of lithium ions in structural channels is limit-
ed, for example by lanthanum ions, then such
displacements of lithium ions contribute to
polarization.
In complex perovskites, the A-sites are
shared by ions of very different sizes such as
La3+ and Li+ and vacancies whereas the B-sites
are also shared by ions of different charges and
sizes (Fig. 6).
Fig. 6. Schematic representation of the dif-
ference in the rhombohedral and orthorhombic
La0.67LixTi1xAlxO3 structure.
La ions occupy A sites, while Li ions are lo-
cated at the A-cage faces of the perovskite. The
Li+ ions present a distorted square planar coor-
dination and are located in interstitial positions
of the structure, which could explain the very
high ionic conductivity of this type of material
[11]. The very high dielectric constant of this
type of material seems to be related to the loca-
tion of the lithium atoms within the interstitial
positions, providing a great number of sites for
the atoms to move through. Compared with
the La0.5Li0.5TiO3, compositions of the La0.67Lix-
UCJ № 11 / Vol. 86T. O. Plutenko, O. I. V’yunov, B. S. Khomenko, A. G. Belous
19https://ucj.org.ua
Ti1-xAlxO3 system have a lower number of Li+
and a bigger number of structural vacancies.
These conditions cause a lower possibility for
Li+ - VLi+ interactions and enhanced opportu-
nities for Li+ movement. That is why materials
synthesized have a higher dielectric constant
than the conventional La0.5Li0.5TiO3.
It should be noted that the dielectric con-
stant and dielectric loss tangent slightly de-
pends on the content of lithium and aluminum
in La0.67LixTi1-xAlxO3 system.
CONCLUSIONS. It has been shown that
single-phase solid solutions La0.67LixTi1-xAlxO3
(0.15 ≤ x ≤ 0.3) synthesized by solid-state re-
action technique are formed at temperatures
higher than 1200 °C. The dielectric properties
of ceramic materials have been studied by im-
pedance spectroscopy. Using light optical mi-
croscopy shown that the grain size of ceramics
in La0.67LixTi1-xAlxO3 system slightly increases
from 6.1 μm (x=0.15) to 7.7 μm (x=0.3). Ma-
terials exhibit high dielectric constant values
(ε ~ 4·105 at 1 Hz) in all ceramic samples that
can be explained by the high ionic conduc-
tivity of this material. The materials synthe-
sized in La0.67LixTi1-xAlxO3 system have a high-
er dielectric constant than the conventional
La0.5Li0.5TiO3. The dielectric losses increase
with increasing lithium concentration that
can be attributed to the fact that the size of the
structural domains decreases with increasing
the annealing temperature.
ACKNOWLEDGEMENTS. The work
was supported by the Research program
of the Ukrainian National Academy of Scienc-
es “New functional substances and materials
for chemical production” (Fine Chemicals),
project № 0119U101351.
СИНТЕЗ ТА ДІЕЛЕКТРИЧНІ ВЛАСТИВОСТІ
КЕРАМІКИ La0,67LixTi1-xAlxO3
Т. О. Плутенко, О. І. В’юнов *,
Б. С. Хоменко, А. Г. Білоус
Інститут загальної та неорганічної хімії
ім. В. І. Вернадського
* e-mail: vyunov@ionc.kiev.ua
Показано, що однофазні тверді розчини
в системі La0,67LixTi1-xAlxO3 в концентрацій-
ному інтервалі 0,15 ≤ x ≤ 0,3, синтезовані
методом твердофазних реакцій, утворю-
ються за температур вище 1200 ºC. Тверді
розчини La0,67LixTi1-xAlxO3 (де 0,15 ≤ x ≤ 0,3)
мають ромбоедричну структуру перовскі-
ту. Параметри елементарної комірки зале-
жать від концентрації Li/Al.
Із ростом концентрації х об’єм елемен-
тарної комірки лінійно зменшується через
різницю в іонних радіусах алюмінію та
титану. Ця залежність підпорядковуєть-
ся закону Вегарда, що вказує на утворен-
ня неперервного ряду твердих розчинів
La0,67LixTi1-xAlxO3 (де 0,15 ≤ x ≤ 0,3).
Методом оптичної спектроскопії було
показано, що розмір зерен кераміки
La0,67LixTi1-xAlxO3 незначно зростає зі збіль-
шенням концентрації літію/алюмінію. Цей
факт можна пояснити підвищенням тем-
ператури спікання зі збільшенням. Зі зрос-
танням температури спікання в La0,67LixTi1-x
AlxO3 збільшується розмір зерен, що су-
проводжується зменшенням кількості зе-
рен, отже, загальна площа границь зерен
зменшується. Дослідження за допомогою
методу комплексного імпедансу продемон-
стрували три півкола на діаграмі Коул –
INORGANIC CHEMISTRY SYNTHESIS AND DIELECTRIC PROPERTIES OF LA0.67LIXTI1-XALXO3 (0.15≤X≤0.3) CERAMICS
20 ISSN 2708-129X. Укр. хім. журн., 2020
Коула, які можна віднести до електрично
неоднорідних за властивостями ділянок зе-
рен кераміки. Поява трьох напівкіл на діа-
грамах Коул – Коула вказує на те, що існує
три механізми релаксації. Напівколо за ви-
сокої частоти належить до об’ємної частини
зерна, на низькій частоті – до поляризації
електродів, а область середньої частоти –
до властивостей границі зерен. Діелектрич-
ну проникність розраховували за даними
вимірювань комплексного імпедансу. По-
казано, що зразки системи La0,67LixTi1-xAlxO3
мають велике значення діелектричної
проникності ε΄> 105 на низьких частотах
(f ≤ 10 Hz). Водночас зразок La0,5Li0,5TiO3 має
високий значення діелектричної проник-
ності ε΄> 104 на низьких частотах (f ≤ 10 Гц),
що можна пояснити високою іонною про-
відністю цього матеріалу. Синтезовані мате-
ріали, леговані алюмінієм La0,67LixTi1-xAlxO3,
мають вищу діелектричну проникність,
ніж La0,5Li0,5TiO3. Діелектричні втрати зро-
стають зі збільшенням концентрації літію у
La0,67LixTi1-xAlxO3, що можна пояснити змен-
шенням розмірів структурних доменів зі
збільшенням температури відпалу.
Ключові слова: твердий розчин, тита-
нат-алюмінат літію-лантану, комплексний
імпеданс, діелектричні властивості.
ЛИТЕРАТУРА
1. Оксидные литийпроводящие твердые
электролиты. / Белоус А. Г., Кобилян
ская С. Д. ‒ К.: Наукова думка, 2018. ‒
319 с. ISBN: 978-966-00-1614-9.
2. Belous A. G. Synthesis and electrophysical
properties of novel lithium ion conduct-
ing oxides // Solid State Ionics. ‒ 1996. ‒
V. 90, № 1–4. – P. 193–196. https://doi.
org/10.1016/S0167-2738(96)00406-7.
3. Белоус А. Г., Бутко В. И., Новицкая Г. Н.,
Полянецкая С. В., Поплавко Ю. М.,
Хоменко Б. С. Электропроводность пе
ровскитов La2/3-xM3xTiO3 // Украинский
физический журнал. – 1986. – T. 31. –
C. 576–581. https://doi.org/10.5281/zeno-
do.4091576.
4. Белоус А. Г., Новицкая Г. Н., Поляне
цкая С. В., Горников Ю. И. Исследование
сложных оксидов состава La2/3-xLi3x
TiO3 // Изв. АН СССР. Неорган. мате
риалы. – 1987. – T. 23, № 3. – C. 470.
https://doi.org/10.5281/zenodo.4074927.
5. Stramare S., Thangadurai V., Weppner W.
Lithium lanthanum titanates: a re-
view // Chemistry of materials. – 2003. –
V. 15, № 21. ‒ P. 3974–3990. https://doi.
org/10.1021/cm0300516.
6. Mehrer H. Fast ion conductors // Diffusion
in Solids: Fundamentals, Methods, Mate
rials, Diffusion-Controlled Processes, 2007. –
P. 475–490. ISBN: 3540714863. https:// doi.
org/10.1007/978-3-540-71488-0_27.
7. Morata-Orrantia A., García-Martín S.,
Morán E., Alario-Franco M. Á. A New
La2/3LixTi1-xAlxO3 Solid Solution: Structure,
Microstructure, and Li+ Conductivity //
Chemistry of materials. ‒ 2002. ‒ V. 14,
№ 7. – P. 2871–2875. https://doi.org/10.1021/
cm011149s.
UCJ № 11 / Vol. 86T. O. Plutenko, O. I. V’yunov, B. S. Khomenko, A. G. Belous
21https://ucj.org.ua
8. Morata-Orrantia A., García-Martín S.,
Alario-Franco M. A. Optimization of
lithium conductivity in La/Li titana
tes // Chemistry of materials. ‒ 2003. ‒
V. 15, № 21. ‒ P. 3991–3995. https://doi.
org/10.1021/cm0300563.
9. García-Martín S., Morata-Orrantia A.,
Aguirre M. H., Alario-Franco M. Á.
Giant barrier layer capacitance effects
in the lithium ion conducting material
La0.67Li0.25Ti0.75Al0.25O3 // Applied Physics
Letters. ‒ 2005. ‒ V. 86, № 6. ‒ P. 043110.
https://doi.org/10.1063/1.1852717.
10. García-Martín S., Morata-Orrantia A.,
Alario-Franco M. Á. Influence of the crystal
microstructure on the dielectric response of
the La0.67Li0.2Ti0.8Al0.2O3 // Journal of applied
physics. ‒ 2006. ‒ V. 100, № 7. ‒ P. 054101.
https://doi.org/10.1063/1.2221528.
11. Rivera A., León C., Santamaría J., Várez
A., V’yunov O., Belous A., Alonso J., Sanz
J. Percolation-Limited Ionic Diffusion in
Li0.5-xNaxLa0.5TiO3 Perovskites (0 ≤ x ≤ 0.5)
// Chemistry of materials. ‒ 2002. ‒ V. 14,
№ 12. ‒ P. 5148–5152. https://doi.org/
10.1021/CM0204627.
12. Amador U., García-Martín S., Morata-
Orrantia A., Rodríguez-Carvajal J., Alario-
Franco M. Á. Structure and Microstructure
Study of Oxides of the La2/3xLi3xTiO3-
family // MRS Online Proceedings
Library Archive. ‒ 2008. ‒ V. 1126. ‒
P. S14–06.
13. García-Martín S., Morata-Orrantía A.,
Alario-Franco M., Rodríguez-Carvajal J.,
Amador U. Beyond the structure-proper-
ty relationship paradigm: influence of the
crystal structure and microstructure on
the Li+ conductivity of La2/3LixTi1xAlxO3
oxides // Chemistry. A European Journal. ‒
2007. ‒ V. 13, № 19. ‒ P. 5607. https://doi.
org/10.1002/chem.200700235.
14. Alonso J. A., Sanz J., Santamaría J., León C.,
Várez A., Fernández‐Díaz M. T. On the
location of Li+ cations in the fast Li‐cati-
on conductor La0.5Li0.5TiO3 perovskite //
Angewandte Chemie. ‒ 2000. – V. 112,
№ 3. – P. 633–635. https://doi.org/10.1002/
( S I C I ) 1 5 2 1 - 3 7 7 3 ( 2 0 0 0 0 2 0 4 ) 3 9 : 3 <
619::AID-ANIE619>3.0.CO;2-O.
15. Le Bail A. Whole powder pattern de-
composition methods and applications:
A retrospection // Powder Diffraction. ‒
2005. ‒ V. 20, № 4. ‒ P. 316–326. https://doi.
org/10.1154/1.2135315.
16. Collins T. J. High-content screening //
BioTechniques. ‒ 2007. ‒ V. 43, № 1. ‒ P. 25–
29. https://doi.org/10.2144/000112517.
17. ISO 13383-1:2016 Fine ceramics (advanced
ceramics, advanced technical ceramics) -
Microstructural characterization - Part 1:
Determination of grain size and size dis-
tribution (ISO 13383-1:2012). ‒ Geneva,
Switzerland: International Organization
for Standardization, 2016. ‒ 29 p.
18. Yokoyama M., Ota T., Yamai I., Takahashi J.
Flux growth of perovskite-type La2/3TiO3-x
crystals // Journal of crystal growth. ‒
1989. ‒ V. 96, № 3. ‒ P. 490–496. https://doi.
org/10.1016/0022-0248(89)90043-2.
19. Rahaman M. N. Ceramic processing //
Kirk‐Othmer Encyclopedia of Chemical
Technology. ‒ 2014. ‒ P. 1–98. https://doi.
org/10.1002/0471238961.03051801052319
21.a01.pub2.
20. Morrison F. D., Sinclair D. C., West A. R.
Characterization of lanthanum‐doped bar-
ium titanate ceramics using impedance
spectroscopy // Journal of the American
Ceramic Society. ‒ 2001. ‒ V. 84, № 3. ‒
INORGANIC CHEMISTRY SYNTHESIS AND DIELECTRIC PROPERTIES OF LA0.67LIXTI1-XALXO3 (0.15≤X≤0.3) CERAMICS
22 ISSN 2708-129X. Укр. хім. журн., 2020
P. 531–538. https://doi.org/10.1111/j.1151-
2916.2001.tb00694.x.
21. Morrison F. D., Sinclair D. C., West A. R.
An Alternative Explanation for the Origin
of the Resistivity Anomaly in La‐Doped
BaTiO3 // Journal of the American Ceramic
Society. ‒ 2001. ‒ V. 84, № 2. ‒ P. 474–76.
https://doi.org/10.1111/j.1151-2916.2001.
tb00684.x.
22. Abram E. J., Sinclair D. C., West A. R. A
strategy for analysis and modelling of im-
pedance spectroscopy data of electroce-
ramics: doped lanthanum gallate // Journal
of Electroceramics. ‒ 2003. ‒ V. 10, № 3. ‒
P. 165–177. https://doi.org/10.1023/B:-
JECR.0000011215.56084.87.
23. Gangadharudu D., Babu Y. N. C. R., Rao
B. V., Rao K. S. Dielectric Spectroscopy
Studies on Lead Sodium Bismuth Potasium
Neobate (PNBKN) Ceramic // International
Journal of Advanced Research in Physical
Science. ‒ 2015. ‒ V. 2, № 3. ‒ P. 7–21.
REFERENCES
1. Belous, A. G.; Kobylianska, S. D., Lithium
conducting solid oxide electrolytes. Nauko-
va Dumka: Kyiv, 2018; p 318. [in Russian].
ISBN: 978-966-00-1614-9.
2. Belous, A. G., Synthesis and electrophysical
properties of novel lithium ion conducting
oxides. Solid State Ionics 1996, 90 (1-4),
193–196. https://doi.org/10.1016/S0167-
2738(96)00406-7.
3. Belous, A. G.; Butko, V. I.; Novitskaya, G. N.;
Polyanetskaya, S. V.; Poplavko, Y. M.; Kho-
menko, B. S., Electrical conductivity of the
perovskites La2/3‑xM3xTiO3. Ukrainian Jour-
nal of Physics 1986, 31, 576-581. [in Rus-
sian].
4. Belous, A. G.; Novitskaya, G. N.; Polya-
netskaya, S. V.; Gornikov, Y. I., Investiga-
tion into complex oxides of La2/3-xLi3xTiO3
composition. Izv. Akad. Nauk SSSR, Neorg.
Mater 1987, 23 (3), 470-472. [in Russian].
https://doi.org/10.5281/zenodo.4074927.
5. Stramare, S.; Thangadurai, V.; Weppner, W.,
Lithium lanthanum titanates: a review.
Chem. Mater. 2003, 15 (21), 3974-3990.
https://doi.org/10.1021/cm0300516.
6. Mehrer, H., Fast ion conductors. In Diffu-
sion in Solids: Fundamentals, Methods, Ma-
terials, Diffusion-Controlled Processes, 2007;
pp 475-490. ISBN: 3540714863. https://doi.
org/10.1007/978-3-540-71488-0_27.
7. Morata-Orrantia, A.; García-Martín, S.;
Morán, E.; Alario-Franco, M. Á., A New
La2/3LixTi1-xAlxO3 Solid Solution: Struc-
ture, Microstructure, and Li+ Conductivi-
ty. Chem. Mater. 2002, 14 (7), 2871-2875.
https://doi.org/10.1021/cm011149s.
8. Morata-Orrantia, A.; García-Martín, S.;
Alario-Franco, M. A., Optimization of lith-
ium conductivity in La/Li titanates. Chem.
Mater. 2003, 15 (21), 3991-3995. https://
doi.org/10.1021/cm0300563.
9. García-Martín, S.; Morata-Orrantia, A.;
Aguirre, M. H.; Alario-Franco, M. Á., Gi-
ant barrier layer capacitance effects in the
lithium ion conducting material La0.67Li0.25
Ti0.75Al0.25O3. Appl. Phys. Lett. 2005, 86 (6),
043110. https://doi.org/10.1063/1.1852717.
10. García-Martín, S.; Morata-Orrantia, A.;
Alario-Franco, M. Á., Influence of the
crystal microstructure on the dielectric re-
sponse of the La0.67Li0.2Ti0.8Al0.2O3. J. Appl.
Phys. 2006, 100 (7), 054101. https://doi.
org/10.1063/1.2221528.
11. Rivera, A.; León, C.; Santamaría, J.; Vá
rez, A.; V’yunov, O.; Belous, A.; Alonso, J.;
UCJ № 11 / Vol. 86T. O. Plutenko, O. I. V’yunov, B. S. Khomenko, A. G. Belous
23https://ucj.org.ua
Sanz, J., Percolation-Limited Ionic Diffu-
sion in Li0.5-xNaxLa0.5TiO3 Perovskites (0 ≤
x ≤ 0.5). Chem. Mater. 2002, 14 (12), 5148-
5152. https://doi.org/10.1021/CM0204627.
12. Amador, U.; García-Martín, S.; Mor-
ata-Orrantia, A.; Rodríguez-Carvajal,
J.; Alario-Franco, M. Á., Structure and
Microstructure Study of Oxides of the
La2/3-xLi3xTiO3-family. MRS Online Proceed-
ings Library Archive 2008, 1126, S14-06.
13. García-Martín, S.; Morata-Orrantía, A.;
Alario-Franco, M.; Rodríguez-Carvajal, J.;
Amador, U., Beyond the structure-proper-
ty relationship paradigm: influence of the
crystal structure and microstructure on the
Li+ conductivity of La2/3LixTi1-xAlxO3 ox-
ides. Chemistry. A European Journal 2007,
13 (19), 5607. https://doi.org/10.1002/
chem.200700235.
14. Alonso, J. A.; Sanz, J.; Santamaría, J.;
León, C.; Várez, A.; Fernández‐Díaz, M. T.,
On the location of Li+ cations in the fast Li‐
cation conductor La0.5Li0.5TiO3 perovskite.
Angew. Chem. 2000, 112 (3), 633-635.
https://doi.org/10.1002/(SICI)1521-3773
(20000204)39:3<619::AID-ANIE619>3.0.
CO;2-O.
15. Le Bail, A., Whole powder pattern decom-
position methods and applications: A ret-
rospection. Powder Diffr. 2005, 20 (4), 316-
326. https://doi.org/10.1154/1.2135315.
16. Collins, T. J., High-content screening. Bio-
Techniques 2007, 43 (1), 25-29. https://doi.
org/10.2144/000112517.
17. AENOR, ISO 13383-1:2016 Fine ceramics
(advanced ceramics, advanced technical
ceramics) - Microstructural characteriza-
tion - Part 1: Determination of grain size
and size distribution (ISO 13383-1:2012).
International Organization for Standardi-
zation: Geneva, Switzerland, 2016; p 29.
18. Yokoyama, M.; Ota, T.; Yamai, I.; Taka-
hashi, J., Flux growth of perovskite-type
La2/3TiO3‑x crystals. J. Cryst. Growth 1989, 96
(3), 490-496. https://doi.org/10.1016/0022-
0248(89)90043-2.
19. Rahaman, M. N., Ceramic processing.
Kirk‐Othmer Encyclopedia of Chemical
Technology 2000, 1-98. https://doi.org/10.
1002/0471238961.0305180105231921.a01.
pub2.
20. Morrison, F. D.; Sinclair, D. C.; West, A. R.,
Characterization of lanthanum‐doped ba
rium titanate ceramics using impedance
spectroscopy. J. Amer. Ceram. Soc. 2001,
84 (3), 531-538. https://doi.org/10.1111/
j.1151-2916.2001.tb00694.x.
21. Morrison, F. D.; Sinclair, D. C.; West, A. R.,
An Alternative Explanation for the Origin
of the Resistivity Anomaly in La‐Doped
BaTiO3. J. Amer. Ceram. Soc. 2001, 84 (2),
474-76. https://doi.org/10.1111/j.1151-2916.
2001.tb00684.x.
22. Abram, E. J.; Sinclair, D. C.; West, A. R.,
A strategy for analysis and modelling of
impedance spectroscopy data of electroce-
ramics: doped lanthanum gallate. J. Electro-
ceram. 2003, 10 (3), 165-177. https://doi.
org/10.1023/B:JECR.0000011215.56084.87.
23. Gangadharudu, D.; Babu, Y. N. C. R.; Rao,
B. V.; Rao, K. S., Dielectric Spectroscopy
Studies on Lead Sodium Bismuth Potasium
Neobate (PNBKN) Ceramic. International
Journal of Advanced Research in Physical
Science 2015, 2 (3), 7-21.
Стаття надійшла 28.10.2020
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-254 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:05:19Z |
| publishDate | 2020 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/76/f6249bc6299afa47223c00d7545e5576.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-2542026-07-22T08:23:45Z SYNTHESIS AND DIELECTRIC PROPERTIES OF La0.67LixTi1-xAlxO3 (0.15≤x≤0.3) CERAMICS СИНТЕЗ ТА ДІЕЛЕКТРИЧНІ ВЛАСТИВОСТІ КЕРАМІКИ La0,67LixTi1-xAlxO3 Plutenko, Tatiana V'yunov, Oleg Khomenko, Boris Belous, Anatolii solid solution, lithium-lanthanum titanate-aluminate, complex impedance, dielectric properties. Solid solutions of Al-doped lithium lanthanum titanates La0.67LixTi1-xAlxO3 system (where 0.15&nbsp;≤&nbsp;x&nbsp;≤&nbsp;0.3) have been synthesized by solid-state reaction technique. Light optical microscopy has shown that the grain size of La0.67LixTi1-xAlxO3 ceramics insignificantly increases with an increase in lithium/aluminum concentration. The materials La0.67LixTi1-xAlxO3 show very high dielectric permittivity ε΄&nbsp;104 over a relatively wide frequency range (102&nbsp;≤&nbsp;f&nbsp;≤&nbsp;104&nbsp;Hz) with no apparent dependence on the x. The impedance spectroscopy study indicates three semicircles on Cole-Cole diagram that can be attributed to electrically different areas of ceramic’s grain. V.I.Vernadsky Institute of General and Inorganic Chemistry 2020-12-15 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/254 10.33609/2708-129X.86.11.2020.13-23 Ukrainian Chemistry Journal; Vol. 86 No. 11 (2020): Ukrainian Chemistry Journal; 13-23 Украинский химический журнал; ##issue.vol## 86 ##issue.no## 11 (2020): Украинский химический журнал; 13-23 Український хімічний журнал; Том 86 № 11 (2020): Український хімічний журнал; 13-23 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/254/139 Copyright (c) 2020 Tatiana Plutenko, Oleg V'yunov, Boris Khomenko, Anatolii Belous https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Plutenko, Tatiana V'yunov, Oleg Khomenko, Boris Belous, Anatolii СИНТЕЗ ТА ДІЕЛЕКТРИЧНІ ВЛАСТИВОСТІ КЕРАМІКИ La0,67LixTi1-xAlxO3 |
| title | СИНТЕЗ ТА ДІЕЛЕКТРИЧНІ ВЛАСТИВОСТІ КЕРАМІКИ La0,67LixTi1-xAlxO3 |
| title_alt | SYNTHESIS AND DIELECTRIC PROPERTIES OF La0.67LixTi1-xAlxO3 (0.15≤x≤0.3) CERAMICS |
| title_full | СИНТЕЗ ТА ДІЕЛЕКТРИЧНІ ВЛАСТИВОСТІ КЕРАМІКИ La0,67LixTi1-xAlxO3 |
| title_fullStr | СИНТЕЗ ТА ДІЕЛЕКТРИЧНІ ВЛАСТИВОСТІ КЕРАМІКИ La0,67LixTi1-xAlxO3 |
| title_full_unstemmed | СИНТЕЗ ТА ДІЕЛЕКТРИЧНІ ВЛАСТИВОСТІ КЕРАМІКИ La0,67LixTi1-xAlxO3 |
| title_short | СИНТЕЗ ТА ДІЕЛЕКТРИЧНІ ВЛАСТИВОСТІ КЕРАМІКИ La0,67LixTi1-xAlxO3 |
| title_sort | синтез та діелектричні властивості кераміки la0,67lixti1-xalxo3 |
| topic_facet | solid solution lithium-lanthanum titanate-aluminate complex impedance dielectric properties. |
| url | https://ucj.org.ua/index.php/journal/article/view/254 |
| work_keys_str_mv | AT plutenkotatiana synthesisanddielectricpropertiesofla067lixti1xalxo3015x03ceramics AT vyunovoleg synthesisanddielectricpropertiesofla067lixti1xalxo3015x03ceramics AT khomenkoboris synthesisanddielectricpropertiesofla067lixti1xalxo3015x03ceramics AT belousanatolii synthesisanddielectricpropertiesofla067lixti1xalxo3015x03ceramics AT plutenkotatiana sinteztadíelektričnívlastivostíkeramíkila067lixti1xalxo3 AT vyunovoleg sinteztadíelektričnívlastivostíkeramíkila067lixti1xalxo3 AT khomenkoboris sinteztadíelektričnívlastivostíkeramíkila067lixti1xalxo3 AT belousanatolii sinteztadíelektričnívlastivostíkeramíkila067lixti1xalxo3 |