Ionics (2016) 22:2249–2262
DOI 10.1007/s11581-016-1880-1
REVIEW
A review of zirconia-based solid electrolytes
Tao Liu 1 & Xiaofang Zhang 1 & Xiangnan Wang 1 & Jingkun Yu 1 & Lin Li 2
Received: 14 June 2016 / Revised: 14 October 2016 / Accepted: 23 October 2016 / Published online: 12 November 2016
# Springer-Verlag Berlin Heidelberg 2016
Abstract Zirconia-based electrolyte is considered to be the
most reliable candidate as oxide-ion electrolyte for oxygen
sensor, oxygen pump, and solid-oxide fuel cell. The electrical
property and stability of zirconia-based electrolyte depend
strongly on dopant type and concentration. In this review,
phase diagrams, electrical properties, and the latest develop-
ments of zirconia-based electrolyte with different dopant are
discussed. The methods used to increase oxide-ion conductiv-
ity and decrease the electronic conductivity of stabilized zir-
conia are also discussed.
Keywords Stabilized zirconia . Solid electrolyte . Electrical
property . Oxide-ion conductivity
Introduction
A solid electrolyte requires that the ionic transference number
ti be larger than 0.99, the electronic transference number be
smaller than 0.01, and the energy gap be larger than 3 eV. The
oxide-ion conductivities of CeO2-, LaGaO3-, and δ-Bi2O3-
based electrolyte are higher than those of ZrO2-based electro-
lyte, but CeO2 and Bi2O3 are easily reduced at reducing con-
ditions and secondary phases often exist during the prepara-
tion of LaGaO3-based electrolyte. Zirconia-based electrolyte
* Tao Liu
liut@smm.neu.edu.cn
1
School of Metallurgy, Northeastern University, Shenyang 110819,
China
2
College of Science, Shenyang Aerospace University,
Shenyang 110136, China
is considered to be the most reliable candidate as solid elec-
trolyte for electrochemical cells operated either in an open-
circuit mode (oxygen sensor) or in a power application (oxy-
gen pump and solid-oxide fuel cell) [1]. Pure ZrO2 includes
three phases as a function of temperature: a monoclinic phase
below 1100 °C, a tetragonal phase with a distorted fluorite
below 2400 °C, and a cubic phase at higher temperature [2].
Volume changes caused by phase transformations decrease the
mechanical stability and thermal shock resistance of ZrO2. In
practical applications, ZrO2 needs to be stabilized by adding
dopant which is divided into two classes: rare-earth oxides
like Y2O3 and alkaline earth oxides like CaO. In addition to
suppressing the phase transformations, adding dopant into
ZrO2 can improve the concentration of oxide-ion vacancies,
resulting in high oxide-ion conductivity at high temperature.
The electrical properties and stability of ZrO2-based electro-
lyte depend strongly on dopant type and concentration.
The conductivities of solid electrolyte ceramics have been
reviewed in refs. [3–8]. The objective of this review is to
complement those reviews with phase diagrams, electrical
properties and the latest developments of ZrO 2 -based
electrolyte.
Y2O3-stabilized ZrO2 as solid electrolyte
Phase diagram of ZrO2-Y2O3 system
The phase diagram of ZrO2-containing system is of great sig-
nificance for material design and performance evaluation. The
phase diagrams of ZrO2-Y2O3 system drawn by different in-
vestigators are often not consistent. The causes include: (1)
oxides evaporate and/or react with crucible, especially at tem-
peratures above 2000 °C. (2) It is difficult to accurately mea-
sure liquidus in the phase diagram. (3) It is difficult to reach
2250 Ionics (2016) 22:2249–2262

equilibrium at low temperature, and there are experimental
data only at high temperature. (4) Since the problem of melt
supercooling occurs, extrapolation and interpolation methods
are used to obtain a complete curve. Therefore, the phase
diagrams of ZrO2-Y2O3 system still remain to be studied
and verified.
Figure 1 shows a phase diagram of ZrO2-Y2O3 system
[9, 10]. When the Y2O3 content is less than 1.5 mol%,
there is only a monoclinic ZrO2 at low temperatures and
a wide tetragonal phase region at high temperatures.
When the Y2O3 content is more than 1.5 mol%, the
content of cubic ZrO2 solid solution gradually increases.
Fully stabilized ZrO2 solid solution is obtained at the
Y2O3 content >9 mol%.
The Y solvus in m- and t-ZrO2 is limited to a few mole
percent and a miscibility gap is located in the ZrO2-rich region
[10]. The ratio of the two phases follows a lever rule in the
two-phase region (m + t, m + c, and t + c).
The higher the Y2O3 content, the lower the phase transfor-
mation temperature of c to c + t. The high-temperature cubic
phase is stabilized at room temperature at a sufficiently high
Y2O3 content.
High-temperature quenching of Y2O3-stabilized ZrO2
(YSZ) can prevent the diffusion-controlled reactions. C-
YSZ transforms diffusionlessly into a metastable tetragonal
phase (t′-YSZ). The lattice parameter of t-YSZ is indepen-
dent of the Y content, while the lattice parameter of t′-YSZ
is dependent on the Y content [10]. Zhou et al. [11] found a
second metastable phase (t″-YSZ) with tetragonality ct″ ¼
pffiffiffi
2at″ in 8YSZ and named c′-ZrO2.
l lower than that of materials where such short-circuit does
3000
l+c
Ionic conductivity of YSZ
Dissolution of Y2O3 in ZrO2 leads to Y3+ occupying Zr4+
sites, and an effectively positively charged oxide-ion vacancy
is created for two Y3+ present to preserve electroneutrality
according to
ZrO2 0
Y2 O3 → 2YZr þ V⋅⋅O þ3OO ð1Þ
Figure 2 shows the conductivity of YSZ depending on the
Y2O3 content and temperature [10, 12–14]. High ionic con-
ductivity is found at high temperature and the Y2O3 content
that corresponds to a maximum of conductivity is nearly in-
dependent of temperature. As the Y2O3 content increases, the
conductivity of YSZ increases to the maximum and then de-
creases. The decrease in conductivity is attributed to formation
of defect associates according to
0
 0 ⋅
YZr þ V⋅⋅O ¼ YZr −V⋅⋅O ð2Þ
0
 0 0

2YZr þ V⋅⋅O ¼ YZr −V⋅⋅O −YZr ð3Þ
The ionic conductivity of polycrystalline zirconia is related
to microstructure and the grain boundaries have an important
influence on electrical properties [15–19]. As an example,
Cheikh et al. [18] reported that polycrystalline 4YSZ with
grain sizes of about 300 nm had higher ionic conductivities
of grain interior (bulk) and of grain boundaries than polycrys-
talline and monocrystalline 9.5YSZ that corresponded to the
optimum Y2O3 content (8–10 mol%) as shown in Fig. 3. The
grain boundaries cause a short-circuit around the grain interi-
or, so that the bulk conductivity, which comprises both, is
not occur.

Influence of SiO2 and Al2O3 on YSZ

2500 c

c: cubic
t: tetragonal In contrast to the above results by Cheikh et al., Guo et al. [20,
m: monoclinic 21] reported that the grain-boundary conductivity is lower
2000 l: liquid
than the grain-interior conductivity of 3YSZ and 8YSZ, re-
T/K

t+c spectively. They also reported that the grain-boundary con-

t
1500
ductivity increased as the mean grain size decreased from
28.6 to 1.6 μm and 1330 to 120 nm, respectively, which was
m+t explained by space-charge effects. The cause of blocking at
1000
grain boundary includes yttrium segregation, poor crystallin-
ity, intergranular silicate phases, and oxide-ion vacancy deple-
m+c
tion in the space-charge layers [19].
500
m Silica, which is generally considered to be deleterious to
YSZ, decreases the grain-boundary ionic conductivity
0 2 4 6 8 10 [22–25]. It is controversial whether the siliceous glassy phase
xY2O3 / mol% segregated to the grain boundary covers the grains completely,
Fig. 1 Phase diagram of the system ZrO2-Y2O3 [9, 10] partially or not at all [26–29]. HRTEM confirms that
Ionics (2016) 22:2249–2262 2251

Fig. 2 Conductivity of Y2O3-

stabilized ZrO2 (YSZ) as a
function of Y2O3 content and
temperature [10, 12–14]

amorphous SiO2 film reprecipitates around ZrO2 grains dur-
ing cooling from high temperature but is not formed at grain
boundaries [30]. Though SiO2 results in a decrease in the ionic
conductivity of ZrO 2-based electrolyte, it is helpful to
sintering, densification, and superplastic deformation.
Al2O3 is considered a cleaning agent of SiO2 impuri-
ties at the grain boundary. Adding Al2O3 into YSZ can
reduce the deleterious effects and improve the grain-
boundary conductivity. However, many controversial re-
sults show that Al2O 3 has an unfavorable impact on
grain boundary. The reason for this is that impurities
are introduced during powder synthesis and sintering
[31]. The grain-boundary resistance is also closely relat-
ed to the distribution of trace siliceous phase. In addi-
tion, trace Al2O3 cannot only reduce sintering tempera-
ture of specimens but also significantly improve the
hardness and fracture toughness of zirconia [32].
CaO-stabilized ZrO2 as solid electrolyte
CaO-stabilized ZrO2 (CaSZ) is widely used as solid electro-
lyte in solid-oxide fuel cells and electrochemical sensors.
The defect equation of CaSZ is given by
ZrO2
CaO → Ca″Zr þ V⋅⋅O þ OO ð4Þ
Figure 4 shows the experimental data and calculated
results of a ZrO2-CaO phase diagram [33]. The ZrO2-
CaO system includes a liquid phase, four solid solution
phases (cubic (c), tetragonal (t), monoclinic (m), and
periclase (p)), and four intermediate compounds (ortho-
rhombic (o-CaZrO3), cubic (c-CaZrO3), CaZr4O9 (Φ1),
3200
l

l+CaZrO3
2800
c+l
p Ruff 1927
2 c Cocco 1959
Polycrystalline 9.5YSZ grain boundary 2400 c+c-CaZrO3
c-CaZrO3 Tien 1963
Polycrystalline 9.5YSZ bulk Garvie 1968
1 Noguchi 1967
log(σT / (S·cm–1·K))

Single crystal 9.5YSZ c+o-CaZrO3 o-CaZrO3 Traverse 1969

2000 Michei 1972
YSZ : Y2O3-stabilized ZrO2 Φ2+o-CaZrO Stubican 1977
T/ K

0 3 Hellmann 1983
l: liquid Duran 1987
1600 Φ2 Yin 1993
t c+t Φ1
c: cubic
Wang 2009
t: tetragonal
–1 m: monoclinic
1200 t+m p: periclase
m o: orthorhombic
–2 Φ1: CaZr4O9
Φ2: Ca6Zr19O44
800
Polycrystalline 4YSZ bulk m+o-CaZrO3
–3 Polycrystalline 4YSZ grain boundary
400
9 10 11 12 13 14 15 16 17 18 19 20 0 20 40 60 80 100
104 / (T / K) xCaO / mol%
Fig. 3 Arrhenius plot of ionic conductivities for Y2O3-stabilized ZrO2 Fig. 4 Experimental data and calculated results of ZrO2-CaO phase
(YSZ) [18] diagram [33]
2252 Ionics (2016) 22:2249–2262

and Ca6Zr19O44 (Φ2)). Φ1 and Φ2 phases are stable over c: cubic

the temperature range 1135–1234 and 1146–1352 °C, 2200
c
t: tetragonal
m: monoclinic
respectively. The formation enthalpies of the two phases
are −1004.5 and −988.3 kJ/mol, respectively. The melt-
ing point of CaZrO3 is 2339 °C, and the transition tem- 1800
perature between o-CaZrO3 and c-CaZrO3 is 2000 °C.

T / ºC
t c+t
CaSZ goes through a degradation process in the tempera-
ture range 900–1100 °C and its ionic conductivity decreases, 1400
1240 ºC t + MgO
but it can restore to its original level at 1400 °C.
The typical chemical composition of a commercial
CaSZ electrolyte (ZR23, Friedrichsfeld AG, Germany) is 1000 m + MgO
CaO (4.5–5 wt.%), MgO (0.5 wt.%), Al 2 O 3 (0.5–
0 5 10 15 20
0.7 wt.%), SiO2 (0.30 wt.%), Fe2O3 (0.15 wt.%), and
xMgO / mol%
TiO2 (0.20 wt.%) [34]. The composition in ZR23 can be
classified into oxidizable (such as Fe and Ti) and non- Fig. 5 Phase diagram of the system ZrO2-MgO [35]
oxidizable (such as Al and Mg) cationic species, which
can either segregate at grain boundary or replace Zr4+ in Rare-earth oxide-stabilized ZrO2 (ScSZ) as solid
the host lattice, depending on their solubilities in ZrO2. electrolyte
For the oxidizable cationic species such as Fe, if it segre-
gates at grain boundary, oxidation reactions may occur Figure 6 shows the highest conductivity of rare-earth
(FeO → Fe3O4 → Fe2O3) at a certain oxygen activity; if oxide-stabilized ZrO2 at 1000 °C, the oxide-ion migra-
it replaces Zr4+, Fe2+ may be oxidized to Fe3+ [34]. tion enthalpies and association enthalpies as a function of
1 dopant cation radius [39]. The authors believed that the
2Fe″Zr þV⋅⋅O þ O2 →2Fe″Zr þOO ð5Þ association enthalpy was the differences between the
2
slopes of the Arrhenius conductivity plots in lower and
For the non-oxidizable cationic species, if they segre- higher temperature ranges. The more similar the radii,
gate at grain boundary, they do not affect point defect the larger the maximum ionic conductivity. However,
concentrations of commercial ZrO2, but if they dissolve the association enthalpies decrease with increasing the
into the cation sublattice, they may change the defect dopant ionic radius as shown in Fig. 6, which contradicts
formation energies of intrinsic defects and/or form the the widely held view of dopant-vacancy interactions [3].
defect associates. This may be due to an oversimplified analysis of
Arrhenius conductivity plots.
Scandia-stabilized ZrO2 (ScSZ) exhibits the highest
oxide-ion conductivity among rare-earth oxide-stabilized
MgO-stabilized ZrO2 as solid electrolyte
0.4
110 Sc3+
There are significant differences between the reported Eu3+

ZrO2-MgO phase diagrams. Nowadays, a phase diagram, 80

∆HA
as shown in Fig. 5, has been universally accepted [35]. 100 Association enthalpy ∆ HA / (KJ·mol–1)
Migration enthalpy ∆Hm / (KJ·mol-1)

The shaded region in the figure represents the composi- 0.3

Gd3+
tion range of commercial MgO-stabilized ZrO2 (MgSZ) 60
σ1000 ºC / (S·cm–1)

90
electrolyte. Fluorite-type MgSZ solid solution undergoes Yb3+ ∆
∆

σ
eutectoid decomposition to form tetragonal phase and Er3+ Dy3+
0.2 80 40
MgO at 1400 °C over a MgO content of 13 mol%. The Y3+

phase interface of fluorite-type solid solution, the solid

70
solubility of MgO in monoclinic ZrO2, and the eutectoid
∆Hm 20
reaction in tetragonal phase at high temperature still re- 0.1 Zr4+
main uncertain. Fluorite-type Mg2Zr5O12 and metastable 60

MgZr6O13 phases have been reported [36]. 0.85 0.90 0.95 1.00 1.05
The solid solution limit of MgO is much smaller than that Dopant cation radius / Å
of CaO in tetragonal and monoclinic phases. MgSZ that has Fig. 6 Maximum conductivity of rare-earth oxide-stabilized ZrO2 at
better thermal shock resistance than CaSZ is widely used to 1000 °C, the oxygen-ion migration enthalpies and association
measure oxygen activity in molten steel [37, 38]. enthalpies as a function of dopant cation radius [39]
Ionics (2016) 22:2249–2262 2253

T /°C
ZrO 2. Figure 7 shows a common binary ZrO 2-Sc2O 3
1200 1000 800 600 400
phase diagram [40]. Cubic phase with high conductivity 3
does not extend to room temperature. When the doping
2
amount of Sc2O3 is greater than 10 mol%, ZrO2-Sc2O3 is
cubic phase at high temperature and is transformed into 1

log(σT / (S· cm · K))

the rhombohedral phase at low temperature. Since the
0

-1
conductivity of the rhombohedral phase is lower than 8ScSZ [7]
that of cubic phase, Arrhenius plot of ionic conductivi- 9ScSZ [41]
-1
ties is broken as shown in Fig. 8 [4, 7, 41–46]. The 9.3ScSZ [42]
-2 10ScSZ [43]
phase transformation causes a volume change, leading
10ScSZ [44]
to a crack in electrolyte and a shedding of electrode from -3 10ScSZ [45]
electrolyte surface. This is overcome by adding a small 11ScSZ [46]
amount of oxides such as Bi2O3, Y2O3, Yb2O3, Mn2O3, -4
ScSZ: Sc2O3-stabilized ZrO2
CeO2,and Al2O3. In addition, the substitution of Bi2O3,
-5
Y2O3, Yb2O3, Mn2O3, or CeO2 for Sc2O3 in ZrO2 solid 0.8 1.0 1.2 1.4 1.6 1.8
solution can decrease the degradation but adding Al2O3 3
10 / (T / K)
can accelerate the degradation [47–53]. Fig. 8 Arrhenius plot of ionic conductivities for Sc2O3-stabilized ZrO2
(ScSZ) [4]

Ternary YSZ as solid electrolyte of defect associates. Fonseca et al. [57, 58] reported that the
solubility limit of MgO in 8YSZ was 10 mol%. 3YSZ added
The grain conductivity in the (ZrO2)0.88(Y2O3)x(CaO)0.12–x with more than 15 mol% MgO consists of MgO and stabilized
system increased with the x value from 0 to 4 mol%, and then ZrO2. Since MgO reacts with the SiO2 and Al2O3 impurities to
decreased slightly with increasing x [54]. Gong et al. [55, 56] form discrete Mg2SiO4 and MgAl2O4 grains in the electrolyte,
reported that the conductivity of the (ZrO 2 ) 0 . 8 8 – respectively, the zirconia grain boundary is very clean which
0.04×(Y2O3)0.08×(CaO)0.12(1–x) system increased at high tem- avoids the current blocking. The conductivity of composite
perature but decreased at low temperature due to the formation electrolyte is closely related to the phase continuity. The
higher the phase continuity, the higher the conductivity [59].
2500 Kaneko et al. [60] reported that the conductivity of 8 mol%
c: cubic
Sc2O3- and Y2O3-stabilized ZrO2 increased with increasing
t: tetragonal Sc2O3 content at temperatures above 370 °C, while it de-
m: monoclinic
creased below this temperature. De Souza et al. [61] reported
2000 that the conductivity of impure zirconia stabilized by
6.5 mol% Y2O3 and RE2O3 (rare-earth) was very close or
higher than that of high-purity electrolytes with low silica
t+c
level. The improvement of the conductivity is attributed to
1500 the segregation of impurities.
Adding 5–20 mol% CeO2 into YSZ improves the struc-
T / ºC

tural stability but decreases the ionic conductivity [62,

c 63]. According to composition, temperature, and synthesis
1000 method, Y2O3- and CeO2-stabilized ZrO2 can be oxide-
ion conductor [64, 65] or oxide-ion/electron conductor
t [63, 66]. The electronic conductivity of ZrO2-based mate-
Rhombohedral

rial increases with increasing the CeO2 content.

Sc2Zr5O13(γ)

500 The addition of a small amount of Fe2O3 in 8YSZ can

Rhombohedral

m
promote the densification and reduce the sintering temper-
Sc2Zr7O12 (β)

m+t
ature. The occupied position of Fe in YSZ lattice depends
on phase and oxygen vacancy content at room tempera-
0 ture. The densification and grain growth behavior of
0 5 10 15
Y 2 O 3 - and Fe 2 O 3 -stabilized ZrO 2 are explained by a
xSc2 O / mol%
3 Fe3+ interstitial diffusion mechanism. Fe3+ segregation at
Fig. 7 Phase diagram of the system ZrO2-Sc2O3 [40] grain boundary prevents grain growth [67].
2254
Nitrogen-stabilized YSZ as solid electrolyte
Cubic and tetragonal nitrogen-stabilized YSZ (N-YSZ) is a
mixed oxide-ion/nitride-ion conductor. Table 1 summarizes
the activation energies and diffusion coefficients for N-YSZ
at 1000 K [68]. The activation energies for nitride-ion conduc-
tivity, which are approximately 2 eV, are approximately twice
as large as those for oxide-ion conductivity. The diffusion
coefficients of nitride-ion, which range from 10 −13 to
10−11 cm2 S−1, are three to four orders of magnitude lower
than those of oxide-ion. However, it is inferred that they are
comparable at high temperature (>1200 °C) according to the
experimental data at low temperature [68–70].
In order to reveal the charge transport property in solid, we
need to select a proper defect model. Valov [68] plotted four
Kroeger-Vink diagrams for N-YSZ (Fig. 9). The nitrogen de-
fect obtained at high nitrogen activity and low oxygen activity
increases with increasing nitrogen content.
Vacancy ordering is strongly dependent on N/O ratio and
dopant cation in the system Y-Zr-O-N, Ca–Zr–O–N and Mg–
Zr–O–N [71–73]. Quaternary zirconium oxide nitrides can be
prepared by skull-melting method, microwave irradiation, ion
implantation, pulsed laser deposition, electrochemical meth-
od, and laser treatment under nitrogen atmosphere [74].
The ionic conductivity of solid electrolyte can be obtained
by electrochemical impedance spectrum (EIS). Figure 10
shows Arrhenius representation of the ionic conductivities
for N-YSZ (111) single crystal [75]. The ionic conductivity
decreases with increasing the nitrogen content, which is evi-
dent at lower temperature.
The introduction of nitrogen into YSZ further improves the
oxide-ion vacancy concentration according to
0 3
N2 ðgÞþ3OO →2NO þ V⋅⋅O þ O2 ðgÞ ð6Þ
2 method.
N-YSZ shows a high ionic conductivity at above 1000 °C,
while it shows a low ionic conductivity at lower temperature
due to the formation of defect associates.
The N3− transference number measured by a concentra-
tion cell technique ranges from 0 to 0.1 at 750 < T < 850 °C
and −20 < logaO2 < −14 (Fig. 11 [76]). Since the nitrogen-
Table 1 Activation energies and diffusion coefficients for nitrogen-
stabilized Y2O3-stabilized ZrO2 (N-YSZ) at 1000 K [62]
Materials Experimental method Ea (eV) DN (cm2 S−1)
Tetragonal N-YSZ Diffusion (AES) 1.92 1.63 × 10−11
Tetragonal N-YSZ EIS (Raman) 1.76 5.24 × 10−12
Cubic N-YSZ 15
N diffusion 2.1 2.084 × 10−11
N-YSZ nitrogen- and Y2O3-stabilized ZrO2, Ea activation energy, DN
diffusion coefficient of nitride-ion, AES Auger electron spectrum, EIS
electrochemical impedance spectrum
Ionics (2016) 22:2249–2262
containing compounds are easily oxidized and lose nitrogen,
they should be used in reducing atmospheres.
ZrO2-based eutectic oxides as solid electrolyte
Eutectic oxide is an in-situ composite material. The eutectic
reaction occurs in eutectic melt during solidification, forming
a crystal with unique characteristic of eutectic microstructure.
The reduced interphase spacing, homogeneous microstructure
and clean interphase with large surface area make eutectic
have excellent mechanical properties.
The thermo-mechanical stresses at high operation temper-
atures are one of the key factors that influence the durability of
ZrO2-based electrolyte. To a certain extent, this was overcome
by using ZrO2-based directionally solidified eutectic (DSE).
Since DSE shows good thermo-mechanical property, corro-
sion resistance, and ionic conductivity, it is a potential solid
electrolyte material for SOFC, electrochemical sensor, Nernst
glower elements and high temperature heating elements
[77–80]. Though YSZ Nernst lamp is stable at high tempera-
ture, porous YSZ needs to be used due to poor thermal shock
resistance of YSZ. However, dense YSZ/Al2O3 DSE grown
by a laser floating zone method can glow at 1600 °C for long
term without degradation of ionic conductivity and mechani-
cal property [77, 81]. A coarser microstructure was observed
at 1500 °C for 340 h but the interpenetrating microstructure
remained unchanged (Fig. 12) [82].
Table 2 shows the experimental data and theoretical predic-
tions of ionic conductivity of some DSE oxides containing
stabilized zirconia at 1000 K [77]. The σ|| value is higher than
the σ⊥ value in CaZrO3/CaSZ DSE oxide, while the σ|| of
lamellar CaZrO3/CaSZ DSE oxide is higher than that of gran-
ular CaZrO3/CaSZ eutectic grown by conventional sintering
The anisotropy of lamellar CaZrO3/CaSZ DSE oxide and
the differences between conductivities of granular and lamel-
lar CaZrO3/CaSZ DSE oxide can be explained by a mean-
field approximation. The conductivity of CaZrO3/CaSZ DSE
oxide prepared by directional-solidification follows the pre-
diction for a simple microstructure consisting of an ordered
stacking of oxide-ion conductor (cubic CaSZ with a conduc-
tivity of 3.5 × 10−4 Ω cm−1 at 1000 K) and non-conductor
(CaZrO 3 with a conductivity of 1.7 × 10 −9 Ω cm −1 at
1000 K) [77]. Some misorientation in the lamellae leads to
the difference between theoretical value and experimental val-
ue in vertical direction. The conductivities of granular
CaZrO3/CaSZ DSE oxide obtained by theoretical calculation
and experiment are coincident. For fibrous MgO/MgSZ DSE
oxide, prediction based on an effective medium approxima-
tion exhibits a weak anisotropy, while the experimental value
does not show anisotropy, which can be explained by the
microstructural disorder associated with the eutectic grains.
Ionics (2016) 22:2249–2262 2255

[ N'O] 2[ VO ] [YZr' ] 2[VO ] '

[h ] [YZr ] 2[Oi'' ] [ h ]
'
2[VO ] [e'] 2[ VO ] [YZr ] [ h ] [YZr' ]
-1/2
[ N 'O ]
-1/6 1/6
-1/2 1/6
[YZr' ] -2/3 -1/2
-1/4 1/4
-1/2 [YZr' ] [ VO ]
1/4 1/2

log X
log X

1/2 -1/6 h
-3/4 [Oi'' ] 1/6 e' -1/6
h [VO ] 1/2
1/2
[Oi'' ] -1/4 -3/4
e' -1/6 1/6 -1/6
-1/2 -1/2
-2/3
-2/3

logaO2 logaO2

(a) (b)
log X
[YZr' ] 2[VO ] [ N'O ] 2[VO ]
aN 2

1/3 2[ VO ] [N'O ] 2[VO ]

'
[Y ] Zr [e'] [VO ]
log X

1/2 O2 h
1/6 [YZr' ] 2[VO ]

[N 'O ] -1/6
e' [YZr' ] [ h ]
''
[O ] i

1/2 -1/3 [Oi'' ] 2[h ]

logaN2 aO2

(c) (d)
Fig. 9 Kroeger-Vink diagrams for nitrogen- and Y2O3-stabilized ZrO2 (N-YSZ): a at constant nitrogen activity and aN2 ≥ aO2 , b at constant nitrogen
activity and aN2 ≤ aO2 , c at constant oxygen activity, and d at different aN2 and aO2 [68]

The ionic conductivity of Al2O3/YSZ DSE with three- conductivity of YSZ is one order of magnitude higher than
dimensional interpenetrating microstructure was measured at that of Al2O3/YSZ DSE. If the connectivity between the YSZ
300–1600 °C (Fig. 13) [81]. The activation energies are 1.04 domains increases, the conductivity of Al2O3/YSZ DSE can
and 0.76 eVat lower and higher temperature, respectively. The

1.0 1.0
T / ºC
1000 800 600 400

Y0.17Zr0.83O1.91
0.8 0.8
6 V0.0868
Y0.17Zr0.83O1.89N0.015 V0.0958
tO2- tN3-
4 Y0.17Zr0.83O1.81N0.068 V0.1209 0.6 0.6
Y0.17Zr0.83O1.70N0.139
tN3-

V0.1562
tO2-

2 850 ºC
ln (σ T / (S·cm–1·K))

Y0.17Zr0.83O1.69N0.146 V0.1598
0.4 0.4
0
800 ºC

N-YSZ <111> 750 ºC

-2 0.2 0.2
YSZ <100>
rising temperature
-4
bulk conductivity
0.0 0.0
-6 YSZ: Y2O3-stabilized ZrO2
N-YSZ: nitrogen- and Y2O3-stabilized ZrO2 -20 -19 -18 -17 -16 -15 -14
-8
0.8 1.0 1.2 1.4 1.6 1.8
log a
O2
3
10 /(T/ K)
Fig. 11 Transference number of O2− and N3− in nitrogen- and 9.5 mol%
Fig. 10 Arrhenius plot of ionic conductivities for nitrogen- and Y2O3- Y2O3-stabilized ZrO2 (N-9.5YSZ) as a function of oxygen partial
stabilized ZrO2 (N-YSZ) (111) single crystal [75] pressure and temperature [76]
2256 Ionics (2016) 22:2249–2262

Fig. 12 Coarsening process of (a)

Y2O3-stabilized ZrO2 (YSZ)/
Al2O3 directionally solidified
eutectic (DSE) grown by a laser
floating zone method after
heating at 1500 °C for a 0, b 100,
and c 340 h [82]

(b) (c)

be increased by a factor of two times, reaching the theoretical
values of mean-field approximation (Table 2).
Nanocrystalline ZrO2-based solid electrolyte
Unlike microcrystalline oxides, nanocrystalline oxides
have unique electrical property and chemical reactivity.
However, the earlier studies revealed that there was no
significant change in the conductivity of nanocrystalline
materials compared with microcrystalline materials. For
example, Mondal and Hahn [83] prepared the YSZ ceram-
ic with grain sizes range of 35–49 nm and found no en-
hancement of conductivity. This is because the grain sizes
are not small enough.
Kosacki et al. [84, 85] reported that the 16YSZ thin films
with thickness of about 1 μm were prepared on sapphire and
alumina substrates by a polymer spin coating procedure. They
found that the conductivity increased with decreasing grain
size of YSZ, and the conductivity of nanocrystalline YSZ
films was one to two orders of magnitude higher than that of
single crystalline and bulk microcrystalline YSZ (see Fig. 14).
The authors suggested that the grain-boundary resistance de-
termined the high-frequency resistance of nanocrystalline
YSZ and dramatic decrease in the grain-boundary resistance
was attributed to a reduction in the content of impurities seg-
regating to boundaries [8].
Subsequently, Kosacki et al. [86] reported that the highly
textured 9.5YSZ thin films were prepared on MgO substrates
by pulsed laser ablation, of which the in-plane conductivity

Table 2 Experimental data and

theoretical predictions of ionic Materials Processing E (eV) σ|| (S · cm−1) σ⊥ (S · cm−1)
conductivity of some
directionally solidified eutectic Experiment Theory Experiment Theory
(DSE) at 1000 K [71]
Al2O3/YSZ DSE 1.04 2.0 × 10−3 4.0 × 10−3 2.0 × 10−3 4.0 × 10−3
Fibrous MgO/MgSZ DSE 1.5 1.5 × 10−3 2.8 × 10−3 1.5 × 10−3 3.5 × 10−3
Lamellar CaZrO3/CaSZ DSE 1.3 1.5 × 10−4 1.45 × 10−4 2.0 × 10−5 0
Granular CaZrO3/CaSZ Sintered 1.3 5.0 × 10−5 4.1 × 10−5 5.0 × 10−5 4.1 × 10−5

σ|| the ionic conductivity along the lamella or fiber direction, σ⊥ the ionic conductivity along the perpendicular
direction, YSZ Y2O3-stabilized ZrO2, MgSZ MgO-stabilized ZrO2, CaSZ CaO-stabilized ZrO2
Ionics (2016) 22:2249–2262 2257

2 Electronic and protonic conduction in electrolyte

high-temperature
1 before treatment The ionic transference number of solid electrolyte is higher
log (σT / (S·cm–1·K))

0.76 eV after treatment than 0.99 in a certain range of temperature and oxygen pres-
0 sure. Outside this range, n- or p-type electronic conductivity
becomes noticeable [88, 89].
–1 The equilibrium reaction at high temperature under high
oxygen partial pressure is given by
–2
1
–3 1.04 eV O2 þV⋅⋅O ¼ OO þ 2h⋅ ð7Þ
2
–4 As the oxygen partial pressure increases, p-type (hole) con-
ductivity increases.
0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 The reaction (8) occurs at high temperature under low ox-
3
10 /(T / K) ygen partial pressure.
Fig. 13 Arrhenius plot of ionic conductivity for Y2O3-stabilized ZrO2 1
(YSZ)/Al2O3 directionally solidified eutectic (DSE) before and after heat OO ¼ O2 þV⋅⋅O þ 2e0 ð8Þ
treatment at 1600 °C [81] 2
The n-type (electron) conductivity increases with decreas-
ing the oxygen partial pressure.
were enhanced at a thickness below 60 nm. They suggested The Nernst emf is given by [90]:
that the enhancement of conductivity was related to a signif-
Z μ″O
icant contribution from MgO/YSZ interfacial conductivity. 1 2

The interfacial conductivity of interface layer that was estimat- E¼ t i dμO2 ð9Þ
4F 0
μO
ed to be about 1.6-nm thick was more than three orders of 2

magnitude greater than that of lattice. where ti is the ionic transference number, t i ¼ σi þσσ0i þσh⋅ , σi,
Peters et al. [87] reported that the specimens of 8.7CaSZ/ e

σe0 , and σh⋅ are the ionic, n-type (electron), and p-type (hole)
Al2O3 multilayers were prepared by pulsed laser deposition
and the conductivity parallel to heterophase boundaries in- conductivities, respectively; μO2 is the oxygen chemical po-
creased by two orders of magnitude for a layer thickness from tential. n- and p-type electronic conductivities lower the
0.78 μm down to 40 nm due to a much higher ionic mobility Nernst emf. Compared with other solid electrolyte, ZrO2-
in the disordered core regions of incoherent interfaces than in based electrolytes generally have higher ionic transference
the bulk. number in oxygen partial pressures ranging from 100 to 200
to 10−25–10−20 atm [3].
By integrating right side of Eq. (9), the cell voltage is given
by [91]:
-1
″1=4 1=4 0
1=4 1=4
!
RT pO 2 þ pe 0 pO 2 þ ph ⋅
E¼ ln 0 1=4 þ ln ″1=4 ð10Þ
-2 0.93 eV
F p þp 0
1=4
p
1=4
þp ⋅
O2 e O2 h

-3 where R is the gas constant, T the absolute temperature, F the

log(σ / (S·cm–1))

dg =
Faraday constant, pe0 the oxygen partial pressure at which the
-4
0.01 μm
0.02 μm ionic conductivity is equal to the n-type conductivity, and ph⋅
1.15 eV 0.20 μm the oxygen partial pressure at which the ionic conductivity is
equal to the p-type conductivity. p-type conduction does not
-5
appear for ZrO2-based electrolyte under normal conditions.
1.3 μm
2.4 μm Figure 15 illustrates pe0 of Zr1–xCaxO2–x [92]. There are
-6 6.5 μm
single crystal significant differences, reaching six orders of magnitude at
11 12 13 14 15 16 17 18 19
1500 °C. This may be caused by measurement methods, dop-
4
10 / (T / K)
ant concentration, raw material purity and synthesis proce-
dures. Since pe0 decreases with decreasing temperature, the
Fig. 14 Electrical conductivity for single crystalline, bulk
microcrystalline, and nanocrystalline 16 mol% Y2O3-stabilized ZrO2 electrolytes should be operated at lower temperature (600–
(16YSZ) [84, 85] 800 °C) [88, 93].
2258 Ionics (2016) 22:2249–2262

Stoichiometric CaZrO3 is not only a p-type semiconducting
material but also a ferroelectric material [94, 95]. Trivalent
cations (such as In3+, Ga3+, and Sc3+) doped CaZrO3 exhibit
protonic conduction under hydrogen-containing atmosphere
[96] and it is used successfully for measurement of hydrogen
in molten metal [97, 98]. Excess CaO- or ZrO2-doped CaZrO3
shows pure oxide-ion conduction over a wide range of oxygen
partial pressure.
When there is an excess of CaO, the defect reaction is as
shown in Eq. (4) [99].
When ZrO2 is present in excess, the probable defect reac-
tion is [99]
ð1−xÞCaO þ ZrO2 →ð1−xÞCaCa þ xV″Ca þZrZr
þ ð3−xÞOO þ xV⋅⋅O þ ðCaO−ZrO2 Þss
In addition to doped CaZrO3, perovskite structured oxides
such as doped SrZrO3, BaZrO3, SrCeO3, and BaCeO3 exhibit
appreciable protonic conduction with low activation energy at
temperatures above 700 °C in steam and hydrogen atmo-
spheres [100–104].
Measurement of conductivity
Measurement of electrical conductivity
The total electrical conductivity of electrolyte is the sum of
ionic and electronic (electron/hole) conductivity. The DC
four-probe method has been used to measure the electrical
conductivity but the method can cause errors due to the influ-
of high-frequency semicircle, intermediate-frequency semicir-
cle and low-frequency semicircle, corresponding to grain-
interior (grain-interior capacitance Cgi and resistance Rgi),
grain-boundary (grain-boundary capacitance Cgb and resis-
tance Rgb) and electrode response (double-layer capacitance
Ce and electrode resistance Re), respectively. For isotropic
electrolyte only electrode response is found due to the effect
of relaxation behavior at high temperature. The high-
frequency intercept on the real axis represents the electrolyte
resistance, while the low-frequency intercept on the real axis
represents the sum of electrolyte resistance and area-specific
resistance (ASR). The complete impedance spectrum can be
observed only at a certain temperature. In addition, the imped-
ð11Þ ance spectrum is also influenced by electrode materials and its
synthesis method, connection method of electrode, and instru-
ment performance.
Measurement of electronic conductivity
(1) DC polarization technique.
The electronic conductivity can be measured by a Hebb-
Wagner ion-blocking method. The cell can schematically be
represented by:
Reversible electrode|ZrO2-based electrolyte|oxide-ion-
blocking electrode 12.
By applying a constant DC voltage to the polarization cell,
oxide-ion and electron are transferred in the beginning. Since
oxygen is completely blocked, the steady-state current is pure-
ly electronic. When the migrating charge is anion, the steady-
state current density, i∞, is given by:
        

RT jE jF jE jF
ence of electrodes and grain boundaries which may mask the i∞ ¼ σh⋅ 1−exp − þ σe0 exp −1 ð13Þ
FL RT RT
true behavior of bulk. This is overcome by using the EIS
[105–107]. Figure 16 shows the idealized equivalent circuit where E is the polarization voltage, L the ratio of thickness of
and impedance spectrum for a polycrystalline ZrO2-based sample to geometrical area of electrode, and σe0 and σh⋅ the n-
electrolyte [108]. The impedance spectrum usually consists type (electron) and p-type (hole) conductivity, respectively.

Fig. 15 Oxygen partial pressure T / °C

at which ionic conductivity is 1800 1700 1600 1500 1400 1300
equal to n-type conducitivity (pe0 –6 No. Authors x
) of Zr1–xCaxO2–x [92] 9 1 Baker, West 0.11···0.15
–8 2 Fischer, Janke 0.12
5
3 Etsell, Flengas 0.10
–10 Ramana Rao,
6 7 4 0.12
log (pe / Pa)

1 11 Tare
–12 10 2 5 Janke, Fischer 0.14
8 6 Scaife, et al 0.13···0.17
–14 7 Iwase, Mori 0.12
4 8 Gilderman, et al 0.15
9 Cales,Baumard 0.10
–16
3 10 Gozzi, et al 0.15
11 Iwase, et al 0.11···0.15
–18
4.8 5.0 5.2 5.4 5.6 5.8 6.0 6.2 6.4
104 / (T / K)
Ionics (2016) 22:2249–2262 2259

Fig. 16 a Idealized equivalent grain-interior grain-boundary electrode

circuit and b impedance spectrum resistance (Rgi) resistance (Rgb) resistance (Re)
for a polycrystalline ZrO2-based
electrolyte [108]

grain-interior grain-boundary double layer

capacitance (Cgi) capacitance (Cgb) capacitance (Ce)

(a)

Rgi Rgb Re
–Z" / (Ω·cm2)

0
Z ' / (Ω·cm2)
(b)

Let μ be jERTj F , then Eq. (13) becomes: oxygen partial pressure in melt is reduced to extremely low
0
  levels and meets the condition: pe′ >> pO2 . Moreover, the
i∞ RT
¼ ðσh⋅ þ σe0 expμÞ ð14Þ oxygen partial pressure of air, 0.21 atm, fulfills the condition:
1−expð−μÞ FL
p″O2 >> pe0 .
There is a linear relationship between 1−expi∞ð−μÞ and exp μ.
The slope and the intercept of the straight line are RT
FL σe and
0

RT
FL σh , respectively. Therefore, we can obtain the σe and σh
⋅ 0
values.
(2) Coulometric oxygen extraction technique.
0
When ph ≫p″O2 ≫pe0 ≫pO2 , Eq. (10) is simplified as:
RT p″O2
E¼ ln
4F pe0
At a given temperature, if E and p″O2 are known, pe′ can be
calculated.
In order to meet the above conditions, the structure of the
cell was designed as follows:
  0     [111]. Since the impedance spectrum measurement
W ½OðAg or SnÞ pO2 ZrO2 ‐basedelectrolyteair p″O2 Pt ð16Þ
ph⋅ >> 105 Pa for ZrO2-based electrolyte, which meets ph⋅
>> p″O2 . By applying a voltage to the cell, oxygen in melt is
transferred to air. When the voltage reaches a certain value, the
⋅
Degradation of conductivity
Long-term exposure to high temperatures leads to a sig-
nificant decrease in oxide-ion conductivity of ZrO2-based
electrolyte [10, 76, 83–86], which affects the accuracy
and stability of sensor [10]. This phenomenon is com-
ð15Þ
monly found in YSZ with an yttria content of less than
9 mol% at temperatures of about 1000 °C. For example,
the conductivity degradation of 8YSZ is reduced by
>50 % after annealing at 1000 °C for 1000 h [109, 110].
Such a degradation effect decreases with increasing the
yttria content and disappears in the case of 10YSZ
showed that the grain-boundary impedance remained un-
changed and the bulk impedance increased after annealing
at about 1000 °C [10, 87, 105], the degradation of highly
pure 8YSZ was attributed to bulk mechanisms. A de-
crease in concentration of mobile minority charge carriers
2260
and/or their mobility results in the degradation of conduc- References
tivity. The mechanisms of bulk conductivity degradation
have been proposed, including continual phase transfor- 1.
mations to less-conductive phases [112–115], and vacancy 2.
trapping or “short-range ordering” whereby the charge
3.
carriers in the electrolyte are not transferred under cou-
lombic attraction between the positive charge field of va- 4.
0
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6.
However, experimental proof is still lacking and the most
of proposed reasons remain controversial. The reason is 7.
due in part to complex phase behavior and formation of
multiple, structurally similar, metastable phases in the 8.
9.
ZrO2-based electrolyte such as YSZ and ScSZ, which
are difficult to differentiate [117, 118]. 10.
11.
12.
Conclusion and future trends
13.
14.
The phase diagrams, the electrical properties, and the latest 15.
developments of zirconia-based electrolyte with different dop-
ant are discussed in this review.
16.
The phase diagram of ZrO2-containing system can be
used to guide material design and performance evaluation. 17.
The phase diagrams of ZrO2-based system drawn by dif- 18.
ferent investigators are often not consistent, and they still
19.
remain to be studied and verified. The oxide-ion conduc-
tivity of stabilized zirconia can be improved by the fol- 20.
lowing methods: (1) Addition of three dopant in zirconia, 21.
which optimizes the average size of dopant cations. (2) 22.
Addition of small amounts of highly dispersed alumina in 23.
zirconia, which decreases the grain-boundary resistance 24.
due to “scavenging” of silica-rich impurity phases into
new phases that do not wet the grain boundaries. (3) 25.
26.
Preparation of nanocrystalline stabilized zirconia, which
27.
decreases the activation energy for grain-boundary migra-
tion. (4) Preparation of hetero-interface, which has excel-
lent conductive properties. 28.
29.
ZrO2-based electrolytes require high operating temperature
such as 1000 °C but this can lead to the problems of high 30.
temperature sealing, component compatibility, and high oper-
ating costs. A decrease in the electrolyte thickness can de- 31.
crease operating temperature. Thin-film ZrO2-based electro-
32.
lyte is still an important research field in the future. In addi-
tion, densification, mechanical properties and aging resistance 33.
of ZrO2-based electrolyte need to be further improved.
34.
35.
36.
Acknowledgements The authors acknowledge the financial support
from the National Natural Science Foundation of China (51274059, 37.
51374055 and 61403260), the Fundamental Research Funds for the
Central Universities of China (N130502003).
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