EXPERIMENT- 1

Ionic Conductivity in Fluorite-Structured Oxides

Aim:
• To measure ionic conductivity as a function of temperature in doped
fluorite-structured solids.
• To determine enthalpy for migration of oxygen ions in fluorite oxides.

Background:

Fluorite-structured oxides such as CeO2 and ZrO2 have found wide applications in high-
temperature energy devices such as solid oxide fuel cells (SOFCs), oxygen transport membrane
and chemical sensors. With a relatively large interionic open space, fluorite structure allows for
high levels of point defect disorder. A relatively small concentration of point defects (<1020 cm-
3
) may affect the physical properties of these oxides in a very significant ways. For example,
ionic conductivity, electronic conductivity, optical absorption, and diffusion can be tailored and
modified by the precise control of these zero-dimensional defects. In the present experiment,
the ionic conductivity of CeO2 and ZrO2 based materials is evaluated as a function of
temperature.

Figure 1. Cubic fluorite structure of Figure 2. Oxygen ion jump in Gd doped CeO2
CeO2

Figure 1 shows the cubic fluorite structure of CeO2. In this Ce4+ cations form the face-centered
cubic sub-lattice while O2- anions occupy the tetrahedral positions. There are effectively 4 Ce4+

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cations and 8 anions in one unit cell. Thus, there are 4 molecules of CeO2 in a single unit cell.
The co-ordinates of Ce4+ and O2- are given as following,

Ce4+: (0 0 0), (1/2 1/2 0), (0 1/2 1/2), (1/2 0 1/2)

O2-: ( 1/4 1/4 1/4), (3/4 1/4 1/4), (1/4 3/4 1/4), (1/4 1/4 3/4), (3/4 3/4 1/4), (3/4 1/4 3/4), (1/4 3/4
3/4), (3/4 3/4 3/4)

Typically for fluorite structure oxides, anion Frenkel disorder is a favoured type of intrinsic
ionic disorder. Thus, O2- may leave its parent site to occupy the vacant octahedral interstitial
positions. The intrinsic disorder reaction can be given as following (in a Kröger Vink notation):

OO× → Oi// + VO•• [1]

Although these intrinsic ionic defects are present at all temperatures in equilibrium, their
concentration decreases considerably on lowering temperature. In fact, oxygen ion conductivity
which is a function of concentration of ionic defects and their respective mobility becomes
almost negligible at lower temperatures (below 900oC). Thus, oxygen ion conductivity in pure
CeO2 and ZrO2 is quite poor.

Oxygen ion conduction in these materials takes place via vacancy diffusion mechanism.
Thus, an oxygen ion (which is initially occupying the tetrahedral site in the unit cell) can
diffuse by moving into an adjacent vacant tetrahedral site of the same kind (see Figure 2).
These vacant oxygen ion sites are introduced into the lattice by replacing host cations with
acceptor dopant cations. The extrinsic defect reaction when B2O3 is doped in AO2 can be given
as,

B2 O 3 → 2 B A/ + VO•• + 3OO×

AO2
[2]

Pure zirconium dioxide undergoes a phase transformation from monoclinic (stable at room
temperature) to tetragonal (at about 1173 °C) and then to cubic (at about 2370 °C). Stabilization
of the cubic polymorph of zirconia over wider range of temperatures is accomplished by
substitution of some of the Zr4+ ions in the crystal lattice with slightly larger ions, e.g., those of
Y3+. Substitution of Zr4+ ion with Y3+ ion creates vacant oxygen ion site.

Diffusion of ion is a thermally activated process and can be given as,

 ∆G m 
Di = γλ 2ν [VO•• ] exp  −  [3]
 kT 
where [VO•• ] , γ, λ, ν, ∆Gm, k, and T are the site fraction of oxygen vacancy, orientation factor,
jump distance, jump frequency, Gibb’s free energy change for migration, Boltzmann’s constant
and the absolute temperature, respectively. It is important to note that the oxygen ion jumps
from one tetrahedral site to another in this material. The ionic conductivity is related to
diffusion coefficient as follows,

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 [i ]Di z i2 e 2 [i ]z i2 e 2 γλ 2ν [VO•• ]  ∆G m 
σ= = exp − 
kT kT  kT 
[i ]z i2 e 2 γλ 2ν [VO•• ] [4]
 ∆S   ∆H m 
= exp − m  exp − 
kT  k   kT 

where zi, e, ∆Sm and ∆Hm are the charge of ion, columbic charge of electron, entropy change in
migration and enthalpy change in migration, respectively. Here [i] is the site fraction of ions
related to [VO•• ] as,
[VO•• ] + [i] = 1 [5]

Thus the equation [4] can be written as,

 ∆H m 
σT = α [VO•• ](1 − [VO•• ]) exp −  [6]
 kT 

where α is a constant depending upon the dimensions of the unit cell and the entropy change during
migration. The equation [6] will eventually takes the following form, which is also termed as
Arrhenius relationship for ionic conduction.
 ∆H m 
σT = σ o exp −  [7]
 kT 
Equation [7] indicates the extrinsic nature of the conductivity in which carrier concentration is
fixed by doping, where σo is a pre-exponential coefficient given by,

σ o = α [VO•• ](1 − [VO•• ]) [8]

In the present experiment, student will be given either Y0.148Zr0.852O1.926 or
Gd0.10Ce0.90O1.95. Due to the larger unit cell of ceria than cubic ZrO2, the ease of oxygen anion
diffusion is higher in ceria case (aCeO2 = 5.4114 Å and a8YSZ = 5.1339 Å). By measuring the
ionic conductivity of an electroded polycrystalline ceramic pellet at various temperatures,
student is required to determine ∆Hm and σo. Further, using the obtained σo and the respective
[VO•• ] value in the composition, the value of α needs to be estimated for a given material
composition.

Requirements for the experiment:

A. Electrical equipment
1. Tube furnace
2. Sample holder for ionic conductivity measurement. (Schematic of the sampler
holder is shown in Figure 3)
3. Dual Digit Measurement Multimeter (GwINSTEK, model-GDM 8261A, 6½ digits)

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 Figure 3. Schematic representation of the sample holder

B. Other requirements
1. Sintered pellets for Gd0.10Ce0.90O1.95 (GDC10) or Y0.148Zr0.852O1.926 (8YSZ)
2. Silver conductive paste
3. Painting brush
4. Acetone
Brief Description of the Experimental procedure
1. As it takes approx. 1 h to reach 400oC, the temperature of the internal thermocouple
inside the tube furnace will be preset to this temperature.
2. The sample holder containing the Ag-electroded cylindrical pellet of either GDC10 or
8YSZ will be already kept inside the tube furnace.
3. It is expected from the student to carefully study the sample holder and draw an
equivalent analog electric circuit.
4. The information related to material composition, thickness and diameter of the sintered
sample will be provided to the student.
5. Student should connect both the connecting Ag wires coming out from the sample
holder to the multimeter and measure the two-probe resistance
6. Once the temperature reading is stable for at least 2 min, measure the temperature of the
external thermocouple. At the same time, measure the resistance from the multimeter.
The resistance value in the multimeter may fluctuate but student should report an
appropriate value at the stable temperature.
7. Manually increase the temperature of the internal thermocouple by 25°C and wait at
least for 20 min. for the temperature to get stabilize. Again, take the reading from the
external thermocouple and multimeter.
8. Continue to take the reading of external thermocouple and multimeter for at least 5
different temperatures.
9. Determine the conductivity (σ) using the geometrical aspect ratio of the sample and the
resistance value obtained at a given temperature.
10. Plot log σT versus 1000/T, and estimate the slope by fitting with linear least-square
algorithm. From the slope, determine the activation energy (in eV) and σo.
11. Using the obtained σo value, estimate and report the value of α for a given material
composition.
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Expectations from the Students:
1. What is the value of [VO•• ] and [i] in GDC10 and 8YSZ?
2. What is the jump distance of oxygen ion during diffusion in fluorite structure oxide?
3. Why 8YSZ exhibits higher activation energy than GDC10?
4. Why do oxygen vacancies (and not cation interstitial or holes) are formed on doping
with acceptor oxides?
5. What would be the effect on conductivity of both GDC10 and 8YSZ on changing the
environment from air to H2?

References:
1. D.M. Smythe, “The Defect Chemistry of Metal Oxides”, Oxford University Press, 2000.
2. M. W. Barsoum, “Fundamentals of Ceramics” McGraw-Hill, 2000.
3. C. B. Carter and M. G. Norton, “Ceramic Materials: Science & Engineering”, Springer
2nd Edition, 2013.