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Article history:
Available online 23 February 2015
Judicious selection of mixed ionicelectronic conducting (MIEC) perovskite oxide as oxygen transport
membrane (OTM) offers the potential to enhance overall process economics and systems performance
for a wide variety of industrial applications ranging from clean and efcient energy conversion (oxycombustion) to selective gas separation (high purity oxygen production) and value added chemicals
(syngas and liquid fuel) production with near-zero greenhouse gas emissions. Doped lanthanum
chromite perovskites have been considered as promising material of choice for oxygen transport
membrane (OTM) due to their superior thermo-chemical stability in aggressive environment (800
1000 8C, 0.211020 P O2 ) than the other mixed ionicelectronic conducting (MIEC) perovskites such as
ferrites and cobaltites. Thermo-physical properties of the lanthanum chromite, required for optimum
oxygen transport can be tuned by modifying the crystal structure, chemical bonding, and ionic and
electronic transport properties through selection of dopants type and level. A perspective on the
development of lanthanum chromite-based oxygen transport membranes is presented with an insight
based on the pertinent literature and data analysis. The role of various A- and B-site dopants on the
crystal structure, densication, thermal expansion, electrical transport, oxygen permeation, mechanical
properties, and thermochemical stability of lanthanum chromite is discussed to enlighten composition
structureproperty correlations. It has been found that: the preferred dopants are strontium at A-site
and manganese, nickel, iron, and titanium at B-site to obtain the desired thermochemoelectro
mechano properties. Challenges for long term performance and structural stability of doped lanthanum
chromite as an oxygen transport membrane are outlined for the applications under real system
exposure conditions.
2015 Elsevier B.V. All rights reserved.
Keywords:
Lanthanum chromite
Oxygen transport membrane
Perovskites
Mixed ionicelectronic conductor
Stability
Chemistrystructureproperty
relationships
Contents
1.
2.
3.
4.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Materials for oxygen transport membrane . . . . . . . . . . . . .
ABO3 perovskite . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Fabrication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Fabrication techniques . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Wet chemical methods . . . . . . . . . . . . . . .
3.1.1.
3.1.2.
Plasma spraying technique . . . . . . . . . . . .
Physical vapor deposition (PVD) . . . . . . . .
3.1.3.
Chemical vapor deposition (CVD) . . . . . . .
3.1.4.
Lanthanum chromite (LaCrO3) based perovskites for OTM
4.1.
Crystal structure and phase transition. . . . . . . . . . .
Sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.
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* Corresponding author at: University of Connecticut, Center for Clean Energy Engineering, 44 Weaver Road, Storrs, CT 06269-5233, USA. Tel.: +1 860 486 8379.
E-mail address: singh@engr.uconn.edu (P. Singh).
1
These authors contributed equally to this work.
http://dx.doi.org/10.1016/j.mser.2015.01.001
0927-796X/ 2015 Elsevier B.V. All rights reserved.
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2
6
6
9
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9
11
11
13
15
16
4.2.1.
Role of dopants . . . . . . . .
Oxygen non-stoichiometry . . . . . . .
A-site dopants . . . . . . . . .
4.3.1.
B-site dopants . . . . . . . . .
4.3.2.
A-site and B-site dopants
4.3.3.
Thermal expansion . . . . . . . . . . . . .
4.4.
A-site dopants . . . . . . . . .
4.4.1.
A and B-site dopants . . . .
4.4.2.
4.5.
Electrical conductivity . . . . . . . . . .
A-site dopants . . . . . . . . .
4.5.1.
A and B-site dopants . . . .
4.5.2.
4.6.
Mechanical behavior. . . . . . . . . . . .
Oxygen ux/permeation . . . . . . . . .
4.7.
Chemical stability . . . . . . . . . . . . . .
4.8.
Bulk stability . . . . . . . . . .
4.8.1.
4.8.2.
Surface segregation . . . . .
Interface stability. . . . . . .
4.8.3.
Challenges . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.
5.
6.
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.
1. Introduction
Oxygen transport membrane offers potential for applications in
a wide variety of industrial processes ranging from high purity
oxygen separation from air to oxy-combustion of carbonaceous
and hydrocarbon fuels as well as production of syngas for
subsequent conversion to liquid fuels and hydrogen. Efcient
and clean oxy-combustion of fossil fuels enable reduction of
greenhouse gas emissions responsible for global climate change
[1,2]. In the oxy-fuel combustion process, oxygen is separated from
air and exclusively used for the fuel combustion unlike conventional combustion process where air is used as an oxidant. Use of
oxygen results in signicant increase in the process efciency
resulting in decrease in fuel consumption, heat loss, reduction in
the size of the ue gas and NOx emissions treatment. The
replacement of air to oxygen in the natural-gas red furnaces,
for example, reduced the fuel consumption and NOx emissions
from 15% to 50% and from 50% to 90% respectively [1]. The ue gas
after oxy-combustion predominantly consists of CO2 and steam.
After condensation of steam through cooling, the available CO2 gas
is easily captured, stored, and/or used for chemical production by
well-established industrial technologies. Higher ame stability,
better heat transfer characteristics, reduced gas volume and lower
particulate emissions are other advantages of the oxy-fuel
combustion process [2].
For oxy-combustion, it is to be noted that high purity oxygen
makes a difference not only by reducing the harmful gas emissions
(e.g. NOx and SOx) but also, it is important for CO2 capture from the
ue gas [3,4]. This is because, the CO2 purity level in the ue gas
decreases with decrease in O2 purity level. Lower purity oxygen
containing impurities (e.g. nitrogen) are amenable to forming NOx
as a combustion product, and be present with others (SOx, Ar, N2
etc.) in the ue gas. Lower purity oxygen used in oxy-combustion
process is also considered detrimental to compression and
liquefaction processes commonly used for the transportation of
CO2. Large scale conventional transportation process for transporting CO2 includes the use of gas pipelines, ships and vessels. For
such processes, it is required to compress CO2 to supercritical state
(80150 bar) for pipeline transport. On the other hand, CO2 needs
to be liqueed (6.5 bar and 51 8C) for ship transport [4]. It is
often found difcult to compress as well as liquefy the CO2 gas
stream if the impurities level is high (approximately greater than
4%) [4]. The impurities present in the post combustion CO2 gas
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16
18
19
20
20
21
21
22
22
23
24
25
26
28
29
30
30
30
31
33
33
Table 1
Advantages and disadvantages of various oxygen separation techniques [1,1320].
Types/methods
Principle/driving force
Advantages
Disadvantages
Applications
Pressure swing
adsorption
Adsorption/desorption
Less expensive
More efcient
Cryogenic
distillation
Fractional distillation
Ceramic oxygen
transport membrane
Electric potential/partial
pressure gradient
currently used to separate oxygen from air are: (1) cryogenic and
(2) pressure swing adsorption. In the cryogenic method, high
purity oxygen (99%) is produced on a large industrial scale by
fractional distillation of air at low temperature and pressure
[16]. First, air is compressed between 4 and 10 atm and cooled to
ambient temperature (30 8C). It is then passed over the xed bed of
adsorbents (activated alumina/molecular sieve) to remove trace
contaminants, i.e., water, carbon dioxide and hydrocarbons. The
puried air is again cooled to its liquefaction temperature
(approximately 185 8C), after which distillation occurs and the
products (nitrogen, oxygen, and argon) are obtained at low
pressure column. Oxygen which has the highest boiling point
(182.8 8C) among the components is obtained from the bottom of
the low pressure column. A simplied schematic of the cryogenic
method is shown in Fig. 2 [17]. This method is energy intensive,
less efcient, and more expensive than the pressure swing
adsorption method.
The pressure swing technique separates oxygen from air by
selectively adsorbing nitrogen from compressed air at high
pressure on active carbon or a zeolite [18]. The pressure is
reduced after the separation to desorb the nitrogen. In Fig. 3, a
schematic shows the pressure adsorption technique for air
separation [18]. The process is discontinuous and suitable only
for small-scale production when the oxygen purity (9095%) is not
an end-use concern.
High-purity oxygen (99%) separation from air using a dense
ceramic material, an oxygen transport membrane, is a relatively
new and developing technology. In this method, oxygen from air
transports through the ion conducting ceramic material as oxygen
ions by either an electrical or chemical driving force. In comparison
to the cryogenic and pressure swing methods, oxygen production
by dense ceramic membranes has distinct advantages (Table 1): (i)
40% lower cost of oxygen generation than existing technologies,
(ii) the process is more efcient, (iii) there is lower power usage,
and (iv) the method enables heat recovery when integrated with
the power generation, and combustion units [13]. In addition,
when integrated into power or gasication combined cycle, the
oxygen gas stream need not to be heated to high temperature and
pressurized, as is needed for the cryogenic technique.
As mentioned above and in Table 1, the ceramic membranes are
more advantageous than other existing technologies for oxygen
separation especially when integrated with combustion and/or
gasication cycle for oxy-combustion and/or syngas production.
Pressure swing adsorption technique choice is eliminated for oxycombustion and/or syngas production not only because it provides
low purity oxygen, but also, the technique is only suitable for small
to medium scale plant (20100 tons/day) [21]. In addition, it is a
batch (discontinuous) process. The process is not appropriate for
integration into the combustion and/or gasication cycle. On the
other hand, even though cryogenic technique provides high purity
oxygen at large scale (beyond 100300 tons/day), the process
power consumption is high and the efciency is low [21]. For oxycombustion and syngas production, the cryogenic cycle integration
into power plant requires large volume space, high installment
capital cost ($310500/kWe), large energy consumption (245
670 kWh/tO2), and drops down the total efciency of the plant by
810% [19]. When compared to cryogenic technique, ceramic
membranes requires less installment cost ($260295/kWe), power
consumption (100655 kWh/tO2), and volume space on integration with power plants [19]. In addition, the process is single stage,
and enables heat recovery. In other words, unlike cryogenic
technique, it is a high temperature process and the permeated
oxygen gas stream need not to be heated up and pressurized when
integrated with gasication or power cycle. Overall, the ceramic
membranes are benecial (especially for oxy-combustion and
syngas production) in terms of power consumption, volume space,
heat recovery, installment cost, power production of the plant, and
efciency (Table 1).
1
O2 g VO 2e
2
(1)
s i x; t @m
i x; t
@x
zi e2
(2)
m
i x; t mi x; t zi ex; t
(3)
P O2
P 0O2
dx
kB T s ion s el L
E
ln
dx
eL
s ion s el 0
(4)
(5)
Fig. 4. Schematic of the working principle of oxygen transport membrane (OTM): (a) partial pressure driven/active (mixed ionic electronic conductor), (b) electrically driven/
passive (ionic conductor).
Table 2
Differences between active and passive oxygen transport membrane [2432].
Active
Passive
Advantages
Materials example
(La0.75Sr0.25)0.95Cr0.6Fe0.4O3d, (La0.75Sr0.25)0.95Cr0.5Mn0.5O3d,
La0.4Ca0.6Co0.2Fe0.8O3d, LaFe0.8Ni0.2O3d, Zr0.84Y0.16O1.92 + La0.8Sr0.2Cr0.5Fe0.5O3d,
and Gd0.2Sr0.8FeO3d + Ce0.8Gd0.2O1.9
Phase
Mixed ionicelectronic
Ionic
Driving force
Electric potential
Table 3
Materials key requirement for active OTM [4247].
t p
2r B r O
(6)
where rA, rB and rO are ionic radii of the respective ions. The
perovskite structure is stable for 0.77 t 1.00 [55].
The thermo-physical properties such as thermal expansion and
electrical conductivity of ABO3 perovskites depend on the
structure and the ionicity difference (Dfi) between AO and BO
bonds. Lattice distortion from the cubic symmetry (t = 1) is
associated with a high degree of anisotropy in oxygen sites, and
an increase in lattice distortion decreases the ionic conductivity. In
other words, ionic conductivity improves with higher structural
Table 4
Advantages and disadvantages of various perovskite oxides [5562].
Perovskites
Ionic/electronic/mixed
Advantages
Disadvantages
22
Chromites
Predominantly electronic
Ferrites
Mixed ionicelectronic
Manganites
Predominantly electronic
Nickelates
Predominantly electronic
Cobaltites
Mixed ionicelectronic
Fig. 6. Oxygen transport membrane conguration: (a) planar [83], (b) tubular.
3. Fabrication
10
Table 5
Advantages and disadvantages of various fabrication techniques [8691,97].
Deposition
rate/thickness
Advantages
Disadvantages
Examples of related
materials
Slip casting
120 mm
Economical/low cost
Dense/porous
microstructure
YSZ, LSM
Spraying
5100 mm
Economical/low cost
Dense/porous
microstructure
Solgel
10 nm10 mm
Economical/low cost
Dense/porous
microstructure
Atmospheric
50300 mm
Vacuum
30150 mm
Low pressure
20100 mm
In-principle, no sintering
step is required
Faster than wet chemical
technique
Controlled stoichiometry
and high purity
Dense microstructure
In-principle, no sintering
step is required
High deposition rate less
fabrication time
Faster than wet chemical
technique
Thinner layers
In-principle, no sintering
step is required
Faster than wet chemical
technique
Less thermal gradient
Thinner layers
Faster deposition
Fabrication
Techniques
Wet chemical
Plasma spraying
YSZ
YSZ, LSM
In-sight technique
Physical vapor
deposition
High cost
Micro-cracks and pores in microstructure
Thermal stress
Difcult to deposit 210 mm thick layer
YSZ
High cost
High temperature process
Decomposition of perovskites due to use of
inert/reducing gas (argon, hydrogen)
Non-uniform thickness and lower
densication
YSZ, LSM
High cost
Decomposition of perovskites due to use of
inert/reducing gas (argon, hydrogen)
YSZ
In-sight technique
Electron beam
evaporation
1.52 mm
Sputtering
1 mm
Laser ablation
A-a few mm
High cost
Tensile stress in the deposited lm
Expensive
Low deposition rate
LaCrO3-based materials,
YSZ, CGO, bilayer consisting
of Sm-doped ceria (SDC)
and lanthanum strontium,
gallate manganite (LSGM)
11
Table 5 (Continued )
Deposition
rate/thickness
Advantages
Disadvantages
Examples of related
materials
MO CVD
415 mm
Electrochemical vapor
deposition
3040 mm
Low temperature
required
Easy control of lm
composition and irregular
surface
Higher deposition rate
Long-term stability of
deposited thin lm
High cost
High deposition temperature is required
YSZ
Fabrication
Techniques
Chemical vapor
deposition
12
Fig. 8. Positions of spray gun and components to be coated: (a) horizontal/horizontal, (b) horizontal/vertical, both with tubular design and (c) vertical/horizontal with planar
design.
Reprinted from Ref. [86] with permission.
13
Fig. 11. Schematics of physical vapor deposition techniques: (a) electron beam (EB) PVD, (b) sputtering, and (c) laser ablation.
Reprinted from Ref. [90] with permission.
0
La
La CrCr !ALa CrCr
(7)
3+
3+
where La
on La3+ sites, Cr
on Cr3+
La refers to La
Cr refers to Cr
sites, A0La is single negatively (0 ) charged; A2+ is substituted on
the La3+ site and CrCr represent Cr4+ on Cr3+ site. The symbols
represent neutral and positive charges, respectively.
and
When A2+ partially substitutes La3+ at A-site, a single negative
charge is induced and compensated by the Cr3+ ! Cr4+
transition.
(2) When alkaline earth metal (A = Sr, Ca) is partially doped at Asite and/or B-site, and the material is exposed to reducing
atmosphere:
0
2La
La OO !2ALa VO
1
O2
2
1
CrCr O
O ! 2CrCr VO O2
2
(8)
(9)
14
M
M
3+
3+
(10)
4+
000
3M
M ! 3MM V M
(11)
000
3+
where M
on M3+ site leading to
M ; MM and V M denotes M
4+
3+
neutral () charge, M on M site with an extra positive ()
charge, and Mn3+ cation vacancy with three negative (0 ) charges
respectively.
(4) When transition metal (M = Mn, Co, Fe, Ni, Ti, Cu, and Al)
is partially doped at B-site and/or alkaline earth metal (A) at
A-site, and the material is exposed to oxidizing atmosphere:
1
O2 VO 2M
M OO 2MM
2
(12)
1
O2 VO 2M0M O
O 2MM
2
(13)
3+
3+
on M3+ sites, MM refers to M4+ on M3+
where M
M refers to M
0
2+
sites, MM refers to M on M3+ sites, and VO refers to oxygen
vacancy with two positive charges. In reducing atmosphere, the
oxygen vacancies formation occur for charge compensation when
M4+ ! M3+ and M3+ ! M2+.
0
La
La CrCr !SrLa CrCr
where Sr0La
3+
15
0
2La
La OO !2SrLa VO
1
O2
2
(15)
(16)
where r AE2 is the ionic radius of alkaline earth metal ions (Sr/Ca).
The average ionic radius of La0.9Sr0.1CrO3 is 0.1368 nm and the
rhombohedral phase transition temperature is 42 8C. For
La0.9Ca0.1CrO3, the average ionic radius is 0.1342 nm and the
transition temperature is 307 8C due to the smaller ionic radii of
Ca2+ (0.134 nm) compared to Sr2+ (0.144 nm). The transition
temperature shifts below room temperature (173 8C) for
La1xSrxCrO3 (x 0.2) [104]. Smaller the average ionic radius,
higher is the transition temperature of alkaline earth doped LaCrO3
as shown in Fig. 13. Substitution of La3+ with Ca2+/Sr2+ alkaline
earth ions changes oxidation state of chromium ion (Cr3+ ! Cr4+)
to maintain charge neutrality, leading to rearrangement of
constituent ions in the crystal structure of La1x(Ca/Sr)xCrO3 with
decreasing (Cr4+/Cr3+)O2 and O2O2 ionic distances [104,105].
The ionic distances decrease and [CrO6]6 octahedral units shrink
with increase in the Ca/Sr-content; leading toward the orthorhombic to rhombohedral phase transformation [104].
In addition to A-site dopants, the B-site dopants can also effect
the phase transformation of LaCrO3. However, the knowledge of
B-site dopants effects on the phase transformation and transition
temperatures is limited in the literature as mentioned here. For
(14)
0
2+
16
Pm3m
formation. This indicates co-existence of cubic phase with
rhombohedral. The fraction of cubic phase is calculated as 85.5% at
! Pm3m
Fig. 14. Tolerance factor of La0.9Sr0.1Cr0.9M0.1O3 (M = Mg, Al, Ti, Mn, Fe, Co, Ni). The
broken line corresponds to La0.9Sr0.1CrO3 tolerance factor.
Reprinted from Ref. [111] with permission.
(17)
17
Fig. 15. Microstructures of LaCrO3 sintered at 1450 8C in air for 10 h: (a) lower
magnication to show the porosity, (b) higher magnication with Cr2O3 deposition
at inter-particle neck [112].
18
Fig. 18. Relative density of A-site (Sr) and B-site (Ni, Co and Cu) doped LaCrO3 vs
temperature [125,128].
000
3Mn
Mn ! 3MnMn VMn
(19)
000
3+
where Mn
on Mn3+ site leading to
Mn ; MnMn and VMn denotes Mn
4+
3+
neutral () charge, Mn on Mn site with an extra positive ()
charge, and Mn3+ cation vacancy with three negative (0 ) charges
respectively.
19
Fig. 20. Oxygen non-stoichiometry of La1-xAxCr1-yByO3-d: (a) A-site doping (b) variation with temperature, (c) B-site doping, and (d) simultaneous A and B-site doping at
1000 8C, (e) simultaneous A (Sr) and B-site (Ti/Mn/Fe) at 1000 8C [137141].
20
(20)
1
O2 VO 2Fe0Fe O
O 2FeFe
2
(21)
3+
on Fe3+ sites, FeFe refers to Fe4+ on Fe3+
where Fe
Fe refers to Fe
sites, Fe0Fe refers to Fe2+ on Fe3+ sites, and VO refers to oxygen
vacancy with two positive charges.
According to the above oxygen non-stoichiometry discussion, it
would be benecial to dope lanthanum chromite based material
with Sr and Ti dopants at A-site and B-site respectively for higher
redox stability of OTM. On the other hand, it is known that oxygen
ion conductivity increases with increase in oxygen vacancies or
decrease in P O2 : For example, (La0.75Sr0.25)0.95Cr0.5Mn0.5O3d ionic
conductivity increases from 3.1 105 to 2.2 104 when PO2
decrease from 0.21 to 1015 atm at 950 8C, respectively [148]. The
corresponding transference number (the fraction of the total
current carried by a given ion (O2) in OTM, tion = sion/sel) also
increases from 8.9 107 to 5.6 105 S cm1 with increase in
oxygen ion conductivity, respectively. The oxygen vacancies also
increase with increase in dopant level. For instance, the ionic
conductivity of (La0.75Sr0.25)0.95Cr1xFexO3d is 0.056 S cm1
(x = 0.3, d = 0.16) and 0.079 S cm1 (x = 0.4, d = 0.19) at 950 8C
and PO2 1017 atm [32]. Similarly, the transference number
increases from 0.04 to 0.15, respectively. With increase in Fedoping level, the ionic conductivity increases due to increase in
oxygen vacancy concentration. It is noted that higher ionic
conductivity and transference number is obtained for Fe-doping.
This could be due to the variation in the disproportion of valence
state of Mn/Fe and oxygen vacancies formation. This suggests that
Fe doping at B-site would be more benecial over Mn-doping to
induce mixed ionicelectronic conductivity in lanthanum chromite based materials. However, Ti-doping would be suitable from
redox stability point of view. From authors perspective, it is
suggested to use co-doping of transition metal (e.g. Fe) at B-site
with Ti to obtain mixed conductivity and redox stability at the
same time. However, an in-depth study is required to understand
the co-doping effect and optimize doping level.
Microscopic level change in crystal lattice due to oxygen nonstoichiometry signicantly affects LaCrO3 properties such as
thermal expansion, electronic and ionic conductivity, catalytic
property for oxygen reduction, and thermo-mechanical and
E
DaT T 0
1#
(22)
1
O2 g VO 2Ce0Ce
2
(23)
4+
on Ce4+ site, Ce0Ce refers to Ce3+ on Ce4+
where Ce
Ce refers to Ce
site, and VO refers to oxygen vacancy with two positive charges.
It indicates that GDC is not very stable in reducing atmosphere
due to the oxygen vacancies formation leading to signicant
increase in lattice expansion. This generates micro-cracks as well
as pin holes on the surface and at the fracture of GDC electrolyte
[160]. Yttria-stabilized zirconia (YSZ) is one of the most common
oxygen ion conductive and stable material which can be used as a
uorite phase in oxygen separation membrane and the other layers
[41,161,162].
For the above reason, the lanthanum chromite based membranes are expected to have similar thermal expansion coefcient
(TEC) as uorite phase (YSZ). However, the average TEC of LaCrO3
was measured in the range of 8.18.6 106 8C1 in both air and
H2 atmosphere in the temperature range of 501000 8C
[98,111,133,163]. The thermal expansion coefcient of LaCrO3 is
4.6 106 8C1 and 9.4 106 8C1 in the temperature range of
40275 8C and 2901050 8C respectively [164]. Recently, the
change in TEC due to high temperature cubic phase formation at
1300 8C is reported as 9.8 106 8C1 in the temperature range
of 11001395 8C [112].
21
Fig. 21. Thermal expansion coefcient of A-site (Sr, Ca) doped LaCrO3 vs x in La1x(Sr/Ca)xCrO3 in air and H2. The broken line corresponds to the TEC of 8YSZ
[111,128,133,168].
22
Fig. 22. Subtracted TEC of La0.9Sr0.1Cr1-xMxO3 (x = 0.05; M = Mg, Al, Ti, Mn, Fe, Co, Ni) with La0.9Sr0.1CrO3 versus ionic radii of B-site dopant in: (a) air and (b) H2 atmosphere.
The subtracted zero TEC values correspond to the broken line.
Reprinted from Ref. [111] with permission.
Fig. 23. Comparison of thermal expansion coefcient of A-site (Sr) and B-site
(M = Mg, Al, Ti, Mn, Fe, Co, Ni, Cu) doped LaCrO3 with () 8YSZ in air and H2 (50
1000 8C) [111,128,170].
1 e2 a2
E
Cr3
Cr4
exp
T 6K B t O
kB T
3x/2
23
(24)
(a)
(b)
Fig. 25. Electrical conductivity of A-site (Sr, Ca) doped LaCrO3 as a function of
temperature with various dopant levels: (a) air, (b) H2 atmosphere [133,166,181
183].
24
Fig. 26. Electrical conductivity of A-site (Sr) and B-site (Ni, Mn, Co, Fe) doped LaCrO3
as a function of temperature with various dopant levels [32,128,130,133,188].
25
and
(25)
Table 6
Mechanical properties of various doped lanthanum chromite materials [109,154,192196].
Composition
Temperature
(8C)
8 YSZ
RT
800
900
RT
800
600
600
1400
RT
RT
RT
RT
RT
RT
RT
RT
RT
1400
RT
1000
RT
1000
RT
RT
RT
RT
10 CGO
La0.9Sr0.1CrO3
La0.8Sr0.2CrO3
La0.7Sr0.3CrO3d
La0.85Ca0.15CrO3
La0.8Ca0.2CrO3
La0.8Ca0.2CrO3d
La0.75Ca0.25CrO3
La0.7Ca0.3CrO3
La0.7Ca0.3CrO3d
La0.8Sr0.2Cr0.92Co0.08O3
La0.7Sr0.3Cr0.9Co0.1O3
La0.2Sr0.8Fe0.8Cr0.2O3d
La0.8Ca0.2Cr0.9Al0.1O3d
La0.8Ca0.2Cr0.9Co0.1O3d
La0.8Ca0.2Cr0.9Cu0.1O3d
La0.8Ca0.2Cr0.9Fe0.1O3d
Oxygen
partial
pressure (atm)
0.21
0.21
0.21
0.21
0.21
0.21
0.21
0.21
0.21
0.21
0.21
0.21
1010
1016
0.21
1010
1016
0.21
0.21
0.21
0.21
0.21
0.21
0.21
0.21
0.21
Elastic
modulus (GPa)
Poissons
ratio
Fracture
toughness
(KIC-MPa m1/2)
Flexure
strength (MPa)
Mean
fracture
strength (MPa)
Micro
hardness (GPa)
190
157
200
200
73.5 7.9
180
180
175
181
178
175
91.5 10.3
143.6 17.6
371.2 36.2
99.8 10.3
0.308
0.313
0.328
1.61
1.02
3.52 0.11
2.1
2
1.4
0.50.8
4.02 0.12
4.23 0.14
4.33 0.15
4.02 0.12
416
80
105
98
61 11.5
96 14.4
131.3
122.7 26
145
15
107.4 5.9
107.4 5.9
15
220
62
103
98.9
170.5
356.9
154.3
214
146
120
169
91.2 11
167
108
80.8 8.7
148.9 14.6
339.2 16.2
133.6 12.3
4.33 0.24
5.98
5.2
7.35 0.42
9.04 0.54
9.85 0.34
7.35 0.42
Weibull
modulus
5.7
8.6
3.8
5.7
10
8.7
11.3
9.7
5.2
9.4
9.3
36.9
12.9
26
EN LN
1@N
PN E j L j
j1 1# j
1
y
ed
dy=LN
LN
0
(26)
O2 g ! Oads
(27)
(28)
(29)
Membrane
(d) Lattice and grain boundary diffusion of Oinc due to chemical
0
potential gradient of oxygen P 0O2 > > P 0 O2
(e) Oxygen transport through oxygen vacancy VO
Fig. 27. Oxygen transport steps during oxygen permeation through a dense MIEC
[203].
Fig. 28. Schematic of different steps involved in surface exchange for oxygen
reduction and its diffusion in OTM.
27
Fig. 29. Schematic of bulk diffusion path of oxygen in an OTM with closed pores
[205].
Interface II
(f) Desorption of oxygen
O2 ! Odes 2e
(30)
(31)
jO2
RT
42 F 2 L
ln P0 O
ln P 0O
s el s ion
dln P O2
s el s ion
(32)
28
Fig. 31. Oxygen ux of various perovskite phases (lanthanum chromites/manganites/ferrites/cobaltites) as a function of temperature (7001000 8C) [31,32,37,212218].
29
Fig. 32. Oxygen ux of various dual phase (perovskite-uorite) OTM (lanthanum chromites/manganites/ferrites/cobaltites and YSZ/CGO/CSO) as a function of temperature
(6001000 8C) [30,36,219224].
Fig. 33. Solid solubility limit of A-site (Sr, Ca) dopants in LaCrO3 with P O2 and
temperature: (a) Sr-dopant level, (b) Ca-dopant level.
Reproduced from Refs. [230,233] with permission.
30
31
32
Table 7
Summary properties of A and/or B-site doped lanthanum chromite materials [31,32,37,109,111114,119,122,125,127130,133,138141,148,182184,192,193].
Composition
Relative
density (%)
Thermal
Oxygenexpansion
nonstoichiometry
(106 8C1)
(Dd) (T = 1000 8C,
PO2 0:211015 atm)
Electrical
conductivity
(S cm1)
LaCrO3
La0.9Ca0.1CrO3d
0.0112
La0.7Ca0.28CrO3
La0.7Ca0.3CrO3d
0.07
La0.7Ca0.32CrO3
(La0.6Ca0.4)1.02CrO3
La0.9Sr0.1CrO3d
0.0114
(La0.85Sr0.15)0.95CrO3
La0.7Sr0.3CrO3d
58 (T = 1600 8C
65 (T = 1400 8C)
0.082
(La0.85Sr0.15)1.02CrO3
154.3 (T = 25 8C)
La0.8Sr0.2Cr0.9Fe0.1O3d
La0.75Sr0.25Cr0.7Fe0.3O3d
(La0.75Sr0.25)
0.95Cr0.7Fe0.3O3d
(La0.75Sr0.25)0.95Cr0.6Fe0.4O3d
0.1266
La0.8Sr0.2Cr0.5Fe0.5O3d
La0.9Sr0.1Cr0.5Mn0.5O3
La0.75
Sr0.25Cr0.5Mn0.5O3d
(La0.75Sr0.25)
0.95Cr0.5Mn0.5O3d
La0.9Sr0.1Cr0.3Mn0.7O3
0.1468
170.5 (T = 25 8C)
356.9 (T = 25 8C)
33
20 mol% level. The stability for the B-site doping is not studied well.
The solubility of the B-site dopants in the lanthanum chromite
decreases in reducing atmosphere and tend to reduce to metallic
form. Considering the positive role on the thermo-physical
properties of the lanthanum chromite, B-site dopants can be used
at lower level ( 30 mol%). However, cobalt doping should be
avoided because it undesirably increases the TEC attributed to the
change in valance state.
From the above discussions, it can be suggested that strontium
as A-site dopant and transition metals (Mn, Ni and Fe) as B-site
dopants can be considered for compositional design to achieve all
the required properties simultaneously. From the thermomechanical stability point of view, titanium as B-site dopant
can be considered because of reduced chemical expansion. In
addition, Ti-based La0.7Sr0.3Cr0.7Ti0.3O3d composition provides
least oxygen-nonstoichiometry (d) at 1000 8C and PO2 1
1015 atm (Table 7). Overall, La1xSrxCr1yzMyTizO3 (M = Ni,
Fe, Mn; x < 0.2, y, z 0.3) composition would be the best
perovskite composition for OTM. For higher oxygen ux and
performance, it is suggested to combine perovskite phase with
uorite phase (e.g. 8YSZ) to obtain higher ionic conductivity.
More fundamental research needs to be conducted in the areas of
transport behavior and electrochemical activity, in particular, for
doped lanthanum chromites, to fully exploit the material for
active OTM application.
0.048
0.005
La0.7Sr0.3Cr0.9Ti0.1O3d
La0.7Sr0.3Cr0.7Ti0.3O3d
La0.9Sr0.1Cr0.95Ti0.05O3
La0.8Ca0.2Cr0.9Cu0.1O3d
La0.85Sr0.15Cr0.95Cu0.05O3
Acknowledgements
La0.8Ca0.2Cr0.9Co0.1O3d
La0.85Sr0.15Cr0.95Co0.05O3
La0.9Sr0.1Cr0.95Co0.05O3
La0.9Sr0.1Cr0.95Ni0.05O3
34
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