Electrical Properties of Lithiumbased Electroceramics

Peter M. K. Hanafi Jamal GS34083

M.Sc Materials Chemistry
Committee members: Dr Tan KB, Dr Tan YP and Dr Khaw CC

Introduction
Electronic ceramics are classified as technical ceramics
They are high technological materials
properties and applications depend on a complex interplay of structural,
processing and compositional variables

Applications of electronic ceramics are

Hybrid/chip carriers
Insulators
Functional ceramics i.e dielectric, piezoelectric or pyroelectric

Literature Review
Li+ ion conductivity has been found in several dierent systems and
structural families, such as perovskites, LISICON, Li4SiO4,
NASICON and Li2SO4 (Kawai and Kuwano, 1994; Hong. 1978;
Bruce and West, 1980)
In general, stoichiometric materials have low conductivity and
increased conductivity is associated with the introduction of nonstoichiometry, especially with the creation of either Li+ ion
interstitials or Li+ ion vacancies (West et al, 2004)

Literature Review
Li+ ion conduction in rock salt-based oxides, there are a number of
materials that have rock salt superstructures and that contain other
multivalent cations in addition to Li+, for example, Li3NbO4,
Li2TiO3, LiFeO2, and Li2CuZrO4 (Dorrian and Newnham, 1969; Cox
et al, 1962; Mather et al, 2001)
Lithium vacancy creation by substitution of Ni exclusively onto the
lithium sites according to the mechanism: 2Li+ Ni2+. The general
formula of these solid solutions may be written as Li3-2xNixNbO
(West et al, 2004)

Objectives
1. To synthesise the Li3NbO4 phase
2. To dope divalent, trivalent and penta-valent in order to obtain an
extensive range of solid solution
3. To characterize the pure phase sample using various techniques
4. To perform electrical properties on pure phase samples

Li3+xNbO4 series of solid solution

The Doping of Pb2+, Er3+, and V5+

Synthesis Methodology
Li2CO3 (dried at 180oC), Nb2O5 and the dopants i.e PbO were weighed
out to give 23 g totals in an agate mortar and pestle with acetone,
Dried and red in Alumina boats at 600oC then to its final firing of
900, 925 and 950oC for over 24 hours
Ground samples were characterised by;
Purity:
X-ray powder diraction
Conductivity: AC Impedance Spectroscopy.
Pellets were cold-pressed and sintered. Opposite pellet faces were coated with gold paste
to form electrodes which were then dried and hardened by gradually raising the
temperature to 800C. Pellets with electrodes attached were then inserted into a
conductivity jig and placed inside a tube furnace, controlled and measured to 3 oC.

Pure Phase Samples

1. Parent Li3NbO4 phase;

044

235
244

242

32300

ICDD 01-075-0902
Cubic rock salt structured
Body centred
Space group I23
White powder

2. Doping Mechanisms

343

521
413

330
024

213

222

200

130

400

011

121

Divalent: Li3-2xMxNbO4
Trivalent Li3-3xMxNbO4
Pentavalent: Li3Nb1-xMxNbO4
Where M is the cation to be doped

Chemical dopants result in low extended limit

XRD patterns of Pb2+ doped sample

PbO

Solid solution up to x = 0.2 can only be

obtained at 900oC over 48h
PbO was remain unreacted at the same firing
parameters with x = 0.3 indicating it
reaches the limit of the solid solution.
x = 0.3 and 0.4 samples were also subjected
to a higher and longer firing similar
patterns were observed.
Phase present:

Li3NbO4
PbO

x = 0.1

x = 0.2

x = 0.3

x = 0.4

XRD patterns of Er3+ doped sample

Firing at 900oC and 925oC
for 48 hours are both giving
the similar result no solid
solution can be obtained
Phase present:
Li3NbO4
Er2O3
LiNbO3

Er2O3
LiNbO3

x=0
900oC

x = 0.1
900oC

x = 0.1
925oC

XRD patterns of V5+ doped sample

Li3VO4
LiNbO3
V2O5

Solid solution up to x = 0.1 can only be obtained at

900oC over 48h
X = 0.1

Binary Li3VO4 phase was formed at the same firing

parameters with x = 0.2 indicating it reaches the
limit of the solid solution
Both x = 0.2 and 0.3 samples were also subjected to
a higher and longer firing similar patterns were
observed

X = 0.2

X = 0.3
900oC

Phase present:

Li3NbO4
Li3VO4
V2 O 5
LiNbO3

X = 0.3
950oC

Phase crystallises at high temperature

Sintering temperature determination of parent
Li3NbO4 at 700 900oC shows the phase
evolution
Optimal sintering temperature is 900oC
- Non-crystallised phase formed at 850oC
and lower temperature

Li3NbO4

900oC

850oC

800oC

700oC

Li3+xNbO4 Series
LiNbO3 peak appear at lower Li2CO3 introduction
Li3+xNbO4 solid solution ranges 0 x 0.3
Sintering temperature is 900oC over 24 hours
Indexed XRD pattern of Li3NbO4 sintered at 900oC
for 24 hours. Unit cell parameters; a = b = c =
8.4338; = = = 90o, cell volume = 599.89
more introduction of Li in the system such that
x=0.4 and 0.5 have reached the limit for the
formation of the desired binary system. In these
samples, the -Li2O remain unreacted and co-exist
with -3Li2O-Nb2O5 binary phase supports the
binary phase diagram reported by Svaasand et al

Strain size Li series

Using formula;
Sherrer method

Value was calculated from peak 121

Williamson-Hall method

Value was calculated from 5 most

intense peaks

Strain size Li series

High strain value at
both end series
indicates its limit
i.e x = 0 and x = 0.3

Dislocation of 121 indexed peak in Li series

(121)

The peak position of (1 2 1)

shown in sample x = 0, 0.2
and 0.3 have high value
Peak dislocated towards
higher angle with higher x
composition
Cause by the lattice strain
defects

x=0
x = 0.1
x = 0.2
x = 0.3

Thermal Analysis
The Li3+xNbO4; 0 x 0.3
samples are thermally
stable

x=0
x = 0.1

x = 0.2

x = 0.3

Neither weight loss nor phase

transition were detected
x=0
x = 0.1

x = 0.2

x = 0.3

Electrical properties of Li3+xNbO4 series

Modest conduction was observed by Li3NbO4

Arrhenius Plot Li3NbO4

Activation energy
Heat = 0.67 eV
Cool = 0.69 eV

Reversible cooling and

heating ramps

-3.00
0.80

0.90

1.00

1.10

1.20

-3.50

-4.00

-4.50

-5.00

-5.50

-6.00

-6.50

-7.00

f(x) = - 3.47x - 0.3

f(x)
R ==1 - 3.38x - 0.49
R = 1

1.30

1.40

1.50

1.60

1.70

1.80

Conductivity of Li3+xNbO4; 0 x 0.3

Insignificant decrease in conductivity
is observed from x = 0.1 to x = 0.2
Two overlapping lines indicated the
varies amount of Li+ in the system
does not affect the conductivity
The activation energy range falls
between 0.6 0.75eV typical for a
modest Li+ phase

Conductivity of Li3+xNbO4; 0 x 0.3

Conductivity is temperature dependent

-500000

1e11

1.32 decade

-250000

M''

Electrically homogenous with average FWHM =

1.32 decade

Z''

More conductive at higher temperature

Increase number of thermally activated charge carrier

Deviates from 1.14 decade of an ideal Debye response

No grain was observed in cole-cole plots at all

studied temperatures
Perfect semi-circle started at T ~ 300 - 350 oC at lower
x composition i.e x = 0.1 and 0.2

0 0
10

101

102

103

104

105

Frequency (Hz)

106

107

0
108

Conductivity of Li3+xNbO4; 0 x 0.3

The conductivity, Y is temperature
dependent and similar response at 100,
1000KHz and 1MHz with value in order of
10-7 at ~25oC
The capacitance value is temperature and
frequency dependent where at frequency
100 KHz, the plot showing increment with
the temperature whereas the 1000KHz and
1MHz shown no significant increment
which the values are in order of 10 -12

Conductivity of Li3+xNbO4; 0 x 0.3

At 100KHz, the dielectric loss os
a function of temperature shows
higher values
Similar function and trend were
shown in permittivity vs
temperature plot

Conductivity of Li3+xNbO4; 0 x 0.3

Electrical data for capacitance, permittivity,
dielectric loss and admittance values for
Li3+xNbO4 series
At higher Li composition, the Y value is
relatively lower. Possibly because of low
defects concentration in the lattice

Conductivity
4.50E-04
4.00E-04
3.50E-04
3.00E-04
2.50E-04

Admittance
Y' (-1cm-1)
2.00E-04

x=0
x=0.
1
x=0.
2

1.50E-04
1.00E-04
5.00E-05
0.00E+00

100

200

300

400

500

Temperature (oC)

600

700

800

900

Conductivity of Li3+xNbO4; 0 x 0.3

The hopping of Li+ ion is suggested as the influential behaviour
of the conducting mechanism for this system
The Cp plot showing positive temperature coefficient of
capacitance starting from T = approx. 400oC
Capacitance

dielectric loss
0

14

12

x=0.
1
x=0.
2

10
8

tan

0
0
0
Capacitance (F/cm)

x= 0

x = 0.1

x = 0.2

x = 0.3

100

200

300

400

500

-2

Temperature (oC)

600

700

800

900

100

200

300

400

500

Temperature (oC)

600

700

800

900

Impedance Analysis of Li3+xNbO4

a) log E' vs log F

b) log E' vs log F

10-6

10-5

H400.Z
H450.Z
H500.Z
H550.Z
H600.Z
H650.Z

10-7

10-7

10-9

10-8

E'

E'

10-8

Permittivity reduces with

frequency
Higher temperature has exhibits
higher permittivity

H300.Z
H350.Z
H400.Z
H450.Z
H500.Z
H550.Z
H600.Z
H650.Z
H700.Z

10-6

10-10

10-9

10-11

10 -10

10-12

102

103

104

105

Frequency (Hz)

106

107

108

10 -12
100

101

102

10 3

104

105

10 6

107

108

tan d vs log freq

Frequency (Hz)

c)

The tand vs freq plot shows the

phase undergone relaxation process
Return to equilibrium at low and
high freq

d)

-7.5

tan d vs log freq

-20

H400.Z
H450.Z
H500.Z
H550.Z
H600.Z
H650.Z

H400.Z
H450.Z
H500.Z
H550.Z
H600.Z
H650.Z

-5.0

tan d

101

tan d

10-13
100

10 -11

-10

-2.5

0
100

10 1

102

10 3

104

10 5

Frequency (Hz)

106

107

108

0
100

101

102

103

104

105

Frequency (Hz)

106

107

108

-1000000

Conductivity of Li2.8Pb0.1NbO4

Real Center: 3.7077E5

C450.Z
Imag. Center: 1.0302E5
Diameter: 7.7305E5
Deviation: 3298.2
Low Intercept: -1773.9
High Intercept: 7.4332E5
Depression Angle: 15.457
w_max: 1.5643E5
Estimated R(ohms): 7.4509E5
Estimated C(farads): 8.2691E-12

Z''

-750000

-500000

The perfect semi-circle started to appear at T =

400oC onwards

-250000

No grain was observed over the range of

temperatures studied

0
0

-1.5e6

750000

1000000

Arrhenius plot Pd2+ doped x = 0.1

-4.20
-4.70

-2.0e6
H401.Z
H453.Z
H500.Z
H551.Z
H600.Z
H651.Z
H700.Z
H750.Z

500000

Z'

The conductivity showing a reversible plots with

activation of 0.66 eV and 0.63 eV for heating and
cooling respectively
-2.0e6

250000

C403.Z
C450.Z
C501.Z
C553.Z
C600.Z

-1.5e6

-5.20

log conductivity (-1 cm-1)

f(x) = - 3.15x - 1.45

f(x)
- 3.35x - 1.39
R ==0.99
R = 0.96

-5.70

Z''

-1.0e6

Z''

-6.20

-5.0e5

-5.0e5

-1.0e6

-6.70
-7.20
0.90 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80

T X 1/1000 (K)
0

5.0e5

1.0e6

Z'

1.5e6

2.0e6

5.0e5

1.0e6

Z'

1.5e6

2.0e6

Heati
ng

Conductivity of Li2.8Pb0.1NbO4
The sample is temperature dependent

-160000
400H.Z

More conductive at higher T

More thermally activated charge carriers
present as T increases

Modulus spectroscopic plot of

Li2.8Pb0.1NbO4 show that the sample is
electrically homogenous with FMHW
M= 1.36 decade
Deviates from 1.14 decades of ideal
Debye response

M''

Z''

1e11

1.36
decades

-10000
100

101

102

103

104

105

Frequency (Hz)

106

107

0
108

10-3

Conductivity of Li2.8Pb0.1NbO4
Y'

10-4

10-5

10-6

10-7
100

101

102

103

104

105

106

107

108

Frequency (Hz)
50
C403.Z
C450.Z
C501.Z
C553.Z
C600.Z
C650.Z
C701.Z
C750.Z

tan d

High dielectric loss at low frequency might due to

the time availability for the displacement of defects
Energy loss through the against the applied
field
Lower temperature exhibit similar dielectric loss to
the parent compound Li3NbO4

C403.Z
C450.Z
C501.Z
C553.Z
C600.Z
C650.Z
C701.Z
C750.Z

0
100

101

102

103

104

105

Frequency (Hz)

106

107

108

Conductivity of Li2.8Pb0.1NbO4

107
C403.Z
C450.Z
C501.Z
C553.Z
C600.Z
C650.Z
C701.Z
C750.Z

10

105

The maximum curves decrease with increase of

temperature
They are displaced towards higher
frequency region as T increases

Z''

104

103

102

101

100
100

101

102

103

104

105

106

107

108

Frequency (Hz)
10-7

10-9
10-10
10-11

E'

The single peak for each studied temperature

indicates that polarisation has taken place
during the heating and cooling of the
measurement

C403.Z
C450.Z
C501.Z
C553.Z
C600.Z
C650.Z
C701.Z
C750.Z

10-8

10-12
10-13
10-14
10-15
100

101

102

103

104

105

Frequency (Hz)

106

107

108

Conductivity of Li2.8Pb0.1NbO4
The heating and cooling plots are showing that the sample gave a
reversible response for heating and cooling
107

10-3
H401.Z
H453.Z
H500.Z
H551.Z
H600.Z
H651.Z
H700.Z
H750.Z

106

H401.Z
H453.Z
H500.Z
H551.Z
H600.Z
H651.Z
H700.Z
H750.Z

H401.Z
H453.Z
H500.Z
H551.Z
H600.Z
H651.Z
H700.Z
H750.Z

10

10-9

tan d

10-5

10-11

E'

104

10-12

103

10-13

10-6

102

101
100

H401.Z
H453.Z
H500.Z
H551.Z
H600.Z
H651.Z
H700.Z
H750.Z

-8

10-10

Y'

Z''

10

10-4

10-7

50

10-14

101

102

103

104

105

Frequency (Hz)

106

107

108

10-7
100

101

102

103

104

105

Frequency (Hz)

106

107

108

0
100

101

102

103

104

105

Frequency (Hz)

106

107

108

10-15
100

101

102

103

104

105

Frequency (Hz)

106

107

108

Conclusion
Li3+xNbO4 series extended in range 0 x 0.3 exhibit Li+ conductivity properties
To date, pure doped samples are;

Ni2+ up to x = 0.1 (prepared) and x < 0.12 (A. R. West, 2008)

Mg2+ up to x = 0.15
Pb2+ up to x = 0.2
V5+ up to x = 0.1

Ni2+ doped Li3NbO4 sample exhibit the highest electrical conductivity with value
in order of 10-5
All synthesized samples are a modest conductor with conductivity average is 10 -6
with activation energy ranging 0.6 0.7 eV

References
Y. Inaguma, C. Liquan, M. Itoh, T. Makamura, T. Uchida, H. Ikuta and M.
Wakihara, Solid State Commun., 1993, 86, 689.
H. Kawai and J. Kuwano, J. Electrochem. Soc., 1994, 141, L78.
H. Y-P. Hong, Mater. Res. Bull., 1978, 13, 117.
P. G. Bruce and A. R. West, J. Solid State Chem., 1980, 15, 117.
A. R. West, J. Appl. Electrochem., 1973, 3, 327.
J. F. Dorrian and R. F. Newnham, Mater. Res. Bull., 1969, 4, 179. 15 D. E. Cox,
W. J. Takei and G. Shirane, American Crystallography Association: Programme
and Abstracts, 1962, L6. 16 G. C. Mather, C. Dussarat, J. Etourneau and A. R.
West, J. Mater. Chem., 2001, 11, 153159. 17 M. Castellanos, M. Chavez Martinez
and A. R. West, Z. Kristallogr., 1990, 190, 161.