Ionics (2015) 21:601–610

DOI 10.1007/s11581-014-1340-8

REVIEW

Review on nanoperovskites: materials, synthesis, and applications

for proton and oxide ion conductivity
Bradha Madhavan & Anuradha Ashok

Received: 22 August 2014 / Revised: 29 November 2014 / Accepted: 2 December 2014 / Published online: 30 December 2014
# Springer-Verlag Berlin Heidelberg 2014

Abstract Perovskite materials exhibiting proton and oxide the most remarkable characteristic of nanostructured materials
ion conductivities have been utilized for various energy- is their high interfacial energy [13]. This leads to two effects:
related applications such as solid oxide fuel cells (SOFCs), trivial size effect and true size effect. In trivial size effect, as a
hydrogen production, gas sensors, etc. Nowadays, perovskites cause of the increased interface-to-bulk fraction, there is an
are being synthesized as nanoperovskites and studied for increased involvement of the interfacial effects in the overall
catalytic activity and energy-related applications. In this arti- material properties. True size effect is when the spacing of
cle, their synthesis in brief, the mechanism of proton and oxide interfaces become equivalent with the Debye length and local
ion conduction, and some specific properties and behaviors of property change as a function of distance [17–21]. Thinning
few nanoperovskites as oxide ion and proton conductors and the feature size from micrometer to nanometer scale also
applications have been reported and discussed. results in a significant change in the transport properties of
materials. Among the materials that are electrochemically
active, those which are proton and oxide ion conducting have
Keywords Perovskites . SOFCs . Proton conductors . Mixed
conductors begun to play an important role in many energy-related appli-
cations. Recently, nanostructured materials having high pro-
tonic conductivity have been employed for various applica-
tions. In certain cases, oxygen ionic conductivity is also
Introduction enhanced by synthesizing them as nanostructured materials
[22]. Ionic conduction and protonic conduction in oxides at
In recent days, improved methods of preparation of nanocrys- higher temperatures are important functional properties in
talline or nanostructured materials along with the exciting tantalizing alternative processes for a cleaner conversion of
effect of their unusual electrical and electrochemical proper- chemical energy to electricity such as in solid oxide fuel cells
ties have not only triggered the evolution of nanoelectronics (SOFCs), hydrogen gas separation membranes, solid oxide
and nanoelectrochemistry but also led to the development of a electrolyser cells (SOEC), etc. [23]. For such applications,
new size-based material system for solid-state ionics [1–15]. materials with suitable functional, chemical, and mechanical
At present, nanocrystalline materials have evolved great inter- properties for different components are therefore a prerequi-
est from chemists, physicists, and materials scientists due to site. In the midst of innovative technologies moving quickly
their unique and unusual chemical, physical, and mechanical toward smaller scales, perovskite-type materials are also in-
properties. Atoms in nanomaterials often relax to a structure creasingly being produced in nanodimensions. Nanoscale pe-
that may be different from that exhibited by their respective rovskites possess interesting properties that are comparable or
bulk, leading to a modification of the existing properties or superior to those of bulk perovskites, leading to potential
emerging of completely new properties [16]. It was reported applications in areas like energy storage, fuel cells,
that when compared with their microstructured counterparts, nanomedicine, molecular computing, nanophotonics tunable
resonant devices, catalysts, and sensors [24, 25]. Application
B. Madhavan : A. Ashok (*)
of nanomaterials in various devices mainly depends on the
Nanotech Research Facility, PSG Institute of Advanced Studies,
Coimbatore 641 004, India success in fabrication processes. The fabrication of
e-mail: [email protected] nanoperovskites is highly dependent on the synthesis
602 Ionics (2015) 21:601–610

parameters such as temperature, pH, the nature and the con- materials, our focus is on perovskites that are proton and oxide
centration of the precursor, etc. They influence the heteroge- ion conducting. Oxide ions and protons are the repre-
neity setting of the reacting mixture. All these constraints sentative conducting ions in a group of perovskite ox-
establish the nuclei formations, crystallite growth, and aggre- ides. Proton conduction, resulting from the ability to
gation and hence determine the final particle size. At this time, dissolve protons from water vapor or hydrogen, is no
research is paying attention to synthesis and characterization exception. In some perovskites, suitable defects for pro-
of nanostructured perovskites include interesting topics with ton incorporation may be absent and they are the bar-
size-dependent electronic, magnetic, optical, thermal, me- riers for hydrogen, water vapor, and protons. Other
chanical, and chemical properties [26–28]. In this article, we perovskites are dominated by defects such as oxygen
discuss the important methods to synthesize nanoperovskites, vacancies at high temperatures, and they are predomi-
recent studies on the nanoperovskite materials, proton and nantly proton and/or oxide ion conductors. At lower
oxide ion conduction in nanostructured materials and their temperatures in water atmosphere, these vacancies can
applications. incorporate protons in the form of OH•O. Thus, presence
of oxygen vacancies is an important requirement for this
property.

Common perovskite oxides

Significance of nanoperovskites
Pervoskites are a type of materials that have the flexibility of
altering the effective negative charges by performing doping/ Nanostructured materials have established immense consider-
substitution on the cationic sites, thereby producing vacancies ation from scientific and industrial communities due to their
for various properties. The typical chemical formula of a exclusive properties in physics and chemistry. Based on the
perovskite is ABX3, where A and B denote two different type of dopants and number and arrangement of defects, the
cations and X can be oxygen, halogen, etc. A basic perovskite crystal symmetry of perovskites may vary from cubic which is
structure is shown in Fig. 1. A perovskite structure is lenient in the ideal perovskite structure to other symmetries having
incorporating foreign atoms of a certain difference in size or similar atomic arrangement. Their properties strongly depend
valence. Heterovalent cation substitution in perovskites can on the crystal structure. At nanoscale, defects at the surface
result not only in anion vacancy formation but also in mixed become predominant contributors to the properties when com-
valence state of other cations. In fact, several kinds of ions pared to the bulk defects produced by dopants. Table 2 is a list
have been made mobile in perovskite and perovskite-related of some nanoperovskites and their properties and crystal
compounds during the past four decades [29–37]. This class structures. For applications where property enhancement is
of compounds can also undergo a wide range of structural due to activities on the surface such as catalysis or conductiv-
phase transitions, which can strongly affect their physical and ity (in cases where conductivity is predominant through grain
chemical properties. Table 1 shows some of the properties and boundaries), substantial enhancement of the properties could
applications of commonly used perovskites. Among such be expected from nanoperovskites. So far, many studies have
been carried out on perovskites in micron size range and
predominantly their bulk properties were being studied.
Nanoperovskites are able to reduce the sintering temperature
significantly for pellet densification because of their high
surface energy, which is beneficial for applications such as
in ceramic oxygen separation membranes. For some applica-
tions, the perovskite should form a highly porous layer to
minimize the diffusion polarization. For example, a high
porosity of an electrode is critical for application as a cathode
in solid oxide fuel cells. Alternatively, a high electrode surface
area is critical in order to minimize the oxygen activation
polarization. The pores in an electrode are created from the
packing of particles, while the surface area is contributed by
the external surface area of particles. A porous cathode built
up of nanoparticles then has the advantage of high surface area
and therefore low activation polarization [45]. According to
Fig. 1 A basic perovskite unit cell having a B atom at the corners of the
cube, an A atom at the center, and O atoms on the centers of ref. [22], in nanocrystalline materials, interfacial protonic
edges of the cube conduction is more considerable. As the grain size reaches
Ionics (2015) 21:601–610 603

Table 1 List of some perovskites which were synthesized and studied earlier along with their basic properties and possible applications

Perovskite material Property Applications

LaCaCoNiO3–δ [38] Mixed conductivity Solid oxide fuel cell electrodes

La,SrTiO3 [39] Mixed conductivity Electrodes for symmetrical fuel cells (SOFCs)
BaTiO3 [40] Mixed conductivity Ferroelectric, dielectric, optical, pyroelectric, piezoelectric,
thermistors, multilayer ceramic capacitors, pressure sensors, etc.
SrLaTiO3 [41] Thermoelectric properties Exhausting heat from power plant and steel works
LaCoMnO3 [42] Electrical conductivity Magnetism and catalytic activity
LaCoO3 [43] Optical, electrical, and magnetic properties Gas sensors, thermal electric batteries, chemical sensors, fuel
cells, and catalyst
SrCeO3, BaCeO3 [44] Proton conductivity Fuel cells, hydrogen sensors

nanoscale, the portion of the grain boundaries will be in- physical and chemical characteristics resulting from its small
creased significantly in order that the overall ionic conduction particle size and large specific surface area. The performance
of the nanocrystallite is controlled by electrical charge carrier is expected to improve with decrease of particle size and
concentrations and mobilities at the interface [22]. The increase of specific surface area in favor of specific
nanoperovskite is a kind of promising material with particular applications.

Table 2 Properties and crystal

structures of some Chemical formula of the nanoperovskites Properties Crystal structure
nanoperovskites
BaZr0.8Y0.2 O3–δ [46] Proton conducting Cubic
LaFeO3 [47, 48] Photo catalytic hydrogen generation Orthorhombic
La0.8Pb0.2FeO3 [49] Electrical and sensing properties to H2 gas Orthorhombic
SrRuO3 [50] Catalytic activity for hydrogen evolution Orthorhombic
reaction
NaATiMO6 (A=Ca or Sr; M=Nb or Ta) Electrical conductivity Orthorhombic
[51]
BaCe0.9Y0.1O2.9 [52] Oxide ion conducting Orthorhombic
La0.6Sr0.4Co0.2Fe0.8O3−δ, Electro catalytic activity Rhombohedral
La0.8Sr0.2MnO3−δ [53] Rhombohedral
BaTiO3 Photocatalysis Cubic
CaTiO3 Cubic
SrTiO3 [54, 55] Cubic
La0.8Sr0.2MnO3 Electrochemical applications Rhombohedral
La0.6Sr0.4Co0.2Fe0.8O3 Rhombohedral
Ba0.5Sr0.5Co0.8Fe0.2O3 [56] Cubic
BaIn0.3Ti0.7O2.85 Electrolyte and anode Cubic
La0.58Sr0.4Co0.2Fe0.8O3–δ [57] Cathode Rhombohedral
La1−xSrxMO3−δ (M=Co, Mn; x=0, 0.4) [58] Catalytic activity Rhombohedral
YSZ combined with WO3, LaFeO3, Sensing electrodes Orthorhombic
La0.8Sr0.2FeO3 [59]
La0.67Ca0.33Mn1−xMexO3 (Me=Al; Magnetic property Orthorhombic
La0.7Ca0.3MnO3 [60, 61] Orthorhombic
La0.8Ba0.2MnO3 [62] Microwave-absorbing properties Cubic
La0.8Sr0.2Mn1−xFexO3−δ [63] Catalytic and redox properties Rhombohedral
LaCoO3 [64] Catalyst Orthorhombic
Nanodispersed Ag in La0.6Sr0.4Cox SOFC applications Orthorhombic
Fe1−xO3−δ [65]
La0.6Sr0.4CoO3−δ and Sm0.5Sr0.5CoO3−δ [66]
BaCe0.9Y0.1O3−δ [67] Ceramic membrane for hydrogen Orthorhombic
separation
604 Ionics (2015) 21:601–610

Brief comparison of the important methods of preparation and the oxides are expected to have different characteristics at
of nanoperovskites hetero-interfaces where space charges are generated and affect
these defect equilibria [81–86]. H+ is the only ion of chemical
Vast interest has been shown in the synthesis methods of significance that does not have an electron shell of its own.
nanoperovskite materials due to their influence on the properties Therefore, it strongly polarizes its environment, which leads
of these materials. The structure and properties of perovskites can to high binding energies. Considering in terms of transport
be engineered/tailored by suitably adopting the preparation route. mechanism, according to Kruer [87], this corresponds to a
The techniques used for the synthesis of nanoperovskites include high degree of self-localization and implies a strong coupling
mainly solid-state reaction and wet chemical methods. In fact, the of long-range proton motion to the dynamics of the proton
preparation of perovskite-type oxides with sufficiently high sur- environment. This is one common feature of all proton con-
face areas is a big challenge since it involves solid-state reaction duction mechanisms in quite diverse families of compounds
of the precursor oxides to form the characteristic ABO3−δ struc- [87]. For proton-conducting perovskites, oxide ion vacancies
••
ture. This requires significant exposure time at high temperatures, VO are very important as they are needed for the incorporation
leading to a low-surface-area catalyst. In order to prevent such a of protonic defects by the dissociative absorption of water.
limitation, a number of alternative preparation strategies have These vacancies are usually formed extrinsically with a lower-
been tried with the aim of reducing the calcination temperature valent cation substituting on the A or B site. If a trivalent rare
necessary for perovskite phase formation. The recently evolved earth cation is used as a substituent on the A site, then the
high energy ball milling technique is popularly known to activate original cation in the parent structure would have to be tetra-
the solid-state reactions at much lower temperatures due to valent in order to invoke oxygen vacancy formation.
increased surface area and formation of different crystal lattice Transport of hydrogen as H2 or H+ also would require defects,
defects in the milled powder particles. It can be carried out in two namely oxygen vacancies. Through these structural defects,
different forms, wet milling and dry milling. The precursor there are two main routes to hydrogen transport in such
powder materials are broken and fused repeatedly, forming pow- materials. One method is to dissolve protons compensated
ders with nanoscale particle size. But in the case of perovskites, by electrons originating from the H2 gas as follows:
generally, subsequent calcination after ball milling is necessary to
obtain a single phase. Nevertheless, solid-state reaction routes are H2 →2Hþ þ 2e0
time consuming and they produce microcrystalline materials Hþ þ Oxo →OH•o ð1Þ
0
often with heterogeneous phases on heat treatment at elevated H2 ðgÞ þ 2Oxo ↔2OH•o þ 2e
temperatures. To overcome heterogeneity especially when syn-
In the above equations, the Kröger-Vink notation has been
thesizing multielement-substituted compositions and to achieve
used to denote the species: the subscript and superscript
nanocrystalline phase pure powder, solution-based precursor
denote the lattice site and charge of the species, respectively.
techniques are adopted. Some of the well-known solution-based
The charge notation, the dot, x, and the superscript denote the
techniques are (i) hydroxide/carbonate/oxalate co-precipitation,
charge of the species, positive, neutral, and negative, respec-
(ii) metal-carboxylate gel decomposition, and (iii) urea, tartarate,
tively. Thus, for example, Oxo denotes a neutral oxygen atom at
and citrate combustion. The solution-based techniques provide
an oxygen lattice site, where “neutral” means the negative
homogeneous mixing in atomic scale and allow the reactants to
“2−” charge of O is compensated by a positive “2+” charge of
form the product at relatively low temperatures. The metal
the surrounding ions. Here, hydrogen gets attached with the
nitrate-carboxylic acid complexes help in bringing all the reactant
oxygen atoms at the oxygen lattice site. This method has a risk
ions into a single complex, which decomposes at a specific
of the total reduction of the perovskite to elemental metals or
temperature facilitating the formation of the product. The regen-
binary oxides. The second method is to expose the material to
erative sol-gel technique improves the sintering behavior of the
water vapor. The acceptors are compensated by oxygen va-
material. Solution precursor via regenerative sol-gel or ••
cancies, denoted by VO in the reactions below. When the
microwave-assisted synthesis can yield homogeneous products
doped oxide is exposed to water vapor, the following reaction
with lower processing costs and desired material properties
occurs as shown in Eq. (2).
[68–80].
H2 O→Hþ þ OH−
Hþ þ Oxo →OH•o
ð2Þ
Mechanism of proton and oxide ion conductors OH− þ V••o →OH•o
H2 O ðgÞ þ V••o þ Oxo ↔2OH•o
Proton-conducting oxides contain protonic charge carriers that
••
originate from the dissolution of ambient water molecules into where VO is the Kröger-Vink notation for an oxygen vacancy,
the oxide ion vacancies in their crystal lattices. Protons in Oo is an oxide ion, and OH•o is a proton attached to an oxide
x

these oxides will be in equilibrium with holes and electrons, ion. The protons will move around in the crystal by jumping
Ionics (2015) 21:601–610 605

from one oxygen atom to another. The formation of protonic BaCe0.4Zr0.4Sc0.2O2.90·xD2O by neutron powder diffraction.
defects according to reaction (2) is accompanied by a signif- The structural refinements performed for both nondeuterated
icant weight increase. By thermogravimetric analysis (TGA), and deuterated phases revealed that the oxygen sites strongly
the concentration of protonic defects is usually measured as a favor anisotropic atomic displacement parameters. The rotations
function of temperature and water partial pressure. The oxide and/or tilts of the BO6 octahedra, implicit from the anisotropic
and/or hydroxide ions move by jumping from one vacancy oxygen displacement components, were expected to influence
site to another, simultaneously bringing about the vacancy proton transport in BaCe0.4Zr0.4Sc0.2O2.90·xD2O [91].
••
(VO ) movement in the opposite direction. Figure 2 reveals The oxide ion and proton conduction mechanisms in the
the calculated proton conductivities of oxides having gallate La1−xBa1+xGaO4−x/2 were studied by Kendrick et al.
perovskite- or fluorite-type structures as calculated from data [92] using neutron diffraction and DFT calculations. Through
on proton concentrations and mobilities, by Norby and these simulations, oxide ion vacancies are shown to be ac-
Larring [88]. Mobility of the H+ ion depends upon the lattice commodated in the structure through the formation of Ga2O7
and is probably accompanied by large, basic atoms on the A site defects, which are also integral to the mechanism of oxide ion
of the perovskite such as Ba. The perovskite oxides have an conduction. In particular, oxide ion conduction occurs via an
exothermic reaction with steam; the enthalpy for this reaction lies unusual cooperative “cog-wheel”-type process involving the
between −50 and −250 kJ/mol. This implies that the oxides will breaking and re-formation of Ga2O7 units, as well as the
be dominated by proton transport at lower temperature and start relatively facile rotation of the GaO4 units. According to the
to lose protons at around 500–900 °C; this is likely an irreversible authors [92], in contrast to the anisotropic oxide ion conduc-
process and the proton conductivity must be recovered only by tion mechanism, the proton conduction process is expected to
vapor treatment. At higher temperatures, oxygen vacancies are be isotropic. In this case, the rate-determining step has been
getting more energetically preferable so that oxygen permeation identified as proton migration around a gallate tetrahedron,
may become dominating at these temperatures [89]. Ahmed et al. with the activation barrier for transfer between tetrahedra
studied the structural refinements and proton conductivity for the being low owing to mediation through hydrogen-bonding
dried and deuterated BaZr0.5In0.5O3−y and revealed that the interactions. Similar mechanistic aspects may feature in the
oxygen sites strongly favor anisotropic atomic displacement ionic conduction characteristics of related oxide systems con-
parameters. They concluded that the smaller, short-range corre- taining tetrahedral moieties. Kruth et al. [93] investigated the
lated distortions present in deuterated BaZr0.5In0.5O2.5 are re- combined neutron diffraction and atomistic modeling for
sponsible for the proton conductivity [90]. Azad et al. reported doped BaCe1−xYxO3−x/2. Defect energy calculations suggest
the location of deuterium positions in the proton-conducting a possible replacement of La and Y dopants at high dopant
contents in Ba1−xLaxCe0.9−xY0.1+xO2.95. After doping struc-
tural change was observed, the doping has no influence on the
oxygen vacancy concentration. The results suggest that the
reduced protonic defect concentration was observed within
the compositional range, where the structural irregularity
might be caused by less-favorable water incorporation
energies.

Proton and oxide ion conduction in nanostructured oxides

Recently, some perovskites have been synthesized as nano-

structured materials for conductivity applications. It was
proved that in certain cases oxygen ionic conductivity is
enhanced by nanostructures [22, 94–98]. A move toward
new ionic conductors for conductivity applications would be
by making use of their active areas such as the grain boundary
and surface. A feature specific to the grain boundary is the
space charge layer, which develops to compensate for a sta-
tionary positive charge at the grain boundary core. It was
formerly well demonstrated for ZrO2- and CeO2-based oxide
Fig. 2 Proton conductivities of oxides having perovskite- or fluorite-type
ion conductors that the depletion of oxide ion vacancy in the
structures as calculated from data on proton concentrations and mobilities space charge layer is responsible for grain boundary resistance
[88] during oxide ion conduction [98, 99]. The same theory has
606 Ionics (2015) 21:601–610

been reported to be working on protonic conduction in The protonic conduction on silica surfaces was explained
BaZrO3-based perovskites having a grain boundary in nano- by Anderson and Parks [110] is due to adsorption isotherms
meters [100]. The occurrence of a positive impact of the that are formed by freely vibrating hydroxyl groups offering
interface on ionic conduction is the enhancement of fluoride the strongest surface adsorption sites. This behavior has often
ion conductivity in hetero-layered BaF2/CaF2 films, which been shown in materials having a layer structure by containing
originates from accumulation of anti-Frenkel defect pairs in water itself, such as WO3·n(H2O) and MoO3·2H2O [111, 112].
the space charge region [101]. On the other hand, the oxide
surface may involve mass transport behaviors which are not
inherent to the bulk. For example, according to Nawroki et al. Proton and oxide ion conductivity in nanostructured
[102], ZrO2-based oxides are reviewed as high-temperature perovskites deposited as thin films
oxide ion conductors. Studies have been carried out on the
surface chemistry and reactivity of ZrO2-based oxides. It has When deposited as thin films, nanoperovskites are expected to
been found that in the presence of water, zirconium and be more effective as ion conductors due to the presence of a
oxygen atoms on the bare surface of ZrO2-based oxides larger area of active sites. The nanostructured barium cerate-
dissociatively adsorb water molecules to form hydroxyl based film (BaCe0.5Zr0.4Y0.1O3−δ) was prepared by Ma et al.
groups which act as Bronsted acid sites. The enthalpy of this [113] from nanograin feedstock using an air plasma spray.
hydroxylation reaction was reported to be rather high, indicat- They measured its protonic conductivity and found that the
ing the instability of the bare surface. On the hydroxyl groups, conductivity was low. Guo et al. [114] tried to investigate
H 2 O molecules are bound by hydrogen bonding. The whether there was a water effect on conduction in nanostruc-
adsorbed H2O molecules are thermally unstable and easily tured YSZ film, a famous oxygen ionic conductor, and con-
desorbed at low temperatures. On the other hand, it has also cluded that protonic defects were found to form on the surface
been pointed out that it is in some cases difficult to remove the and diffuse along the grain boundaries into the interior of the
water molecules [103–105]. Such chemistry of hydroxyls and specimen in boiling water [114]. The electrical transport of
H2O molecules on the ZrO2-based oxide surface would facil- SrCe0.95Yb0.05O3 films is determined by its grain boundary
itate protonic transport along it. On a simple thought, such a conductivity. When compared between microstructure and
transport property may come to appear as a macroscopic one, nanostructure [115], the nanostructure of SrCe0.95Yb0.05O3
when the oxides are fabricated in a small-grained structure to films posed greatly enhanced conductivity and faster kinetic
increase the population of interfaces. Furthermore, in contrast reactions with ambient atmosphere due to grain boundary and
to micrometer grains with a well-relaxed surface, nanograins surface-controlled diffusion rates than do microcrystalline
are considered to involve a disordered surface structure and specimens of the same composition.
resultant dangling bonds, which lead to increased instability of
the bare surface. This will modify the Lewis/Bronsted acidity
of the hydroxyls and H2O molecules on the surface, leading to Grain boundary conductivity in nanoperovskites
particular protonics behavior of such nanograined materials
[22]. Miyoshi et al. [106] measured the water uptake and Many researchers have carried out comparative studies of
conductivity property of nanograined yttria-doped zirconia grain boundary and bulk conductivities of nanoperovskites.
fabricated by ultra-high pressure compaction at room temper- Several nanoperovskites have exhibited larger conductivities
ature. In dry atmospheres, oxide ion governs the total electri- at the grain boundaries than in bulk. The grain boundary
cal conductivity as usually observed for yttria-stabilized zir- conductivities of CaZr0.9In0.1O3−δ synthesized by both the
conia (YSZ). Below about 800 K, the electric conduction in citric acid complexation method and solid-state reaction meth-
humidified atmospheres is dominated essentially by proton od were found to be higher than their respective bulk conduc-
hopping, which has been signified by its H/D isotope effect tivities. The complete diffusion of indium into zirconium sites
and pH2O dependence. And this shows a good feasibility of also resulted in a higher oxygen deficiency in the perovskite
fabricating proton-conducting materials based on nanograined CaZr0.9In0.1O3−δ. The higher oxygen defect density along the
oxides, even if the bulk property involves negligible proton grain boundary of CaZr0.90In0.10O3−δ perovskites synthesized
solubility and conductivity [106, 107] reported the protonic by the citric acid complexation method was useful for proton
conduction in the porous YSZ with a surface conduction transfer and higher grain boundary conductivity [116] .
mechanism. The physisorption reaction dominantly takes Tuller et al. [117] performed a comparative study of the
place at lower temperatures (<100 °C), and the chemisorption bulk and grain boundary conductivities of nano- and micro-
reaction dominantly takes place at higher temperatures crystalline YSZ. The bulk as well as the total grain boundary
(>100 °C). This behavior has been reported in many metal conductivity of the nanocrystalline samples was more or less
oxides, including Al2O3, TiO2, SiO2, and Fe2O3, by forming in the same range as compared with the microcrystalline
single or multiobserved water layers [108–110]. sample. The grain size is smaller by a factor of 10–25; the
Ionics (2015) 21:601–610 607

specific grain boundary conductivity of the nanocrystalline conducting capabilities, has two advantages over their bulk
sample is 1–2 orders of magnitude higher than that of the counterparts:
microcrystalline sample [117]. Tamburini et al. [118] also
measured the protonic conduction in highly dense nanostruc- 1. An increase in their surface area may provide more sites
tured YSZ with a grain size of ∼15 nm, made by spark plasma for proton incorporation/oxygen vacancies at the surfaces.
sintering (SPS) at low temperature. They observed conductiv- This will contribute to the increase in conductivity by
ity values in hydrated nanometric zirconia which are almost increasing the carrier concentration.
comparable to the other typical protonic conductors [118]. 2. The temperature range at which the proton and oxide ion
conductivities are maximum may be brought down due to
their nanosize.

Effect of doping or adding a co-catalyst to nanoperovskites A good number of the attempts to obtain enhanced prop-
on conductivity erties by doping the nanoperovskites with suitable cations
have been successful. But some perovskites showed a de-
Adding more dopants to the existing proton- and oxide ion- crease in conductivity due to the higher resistance shown by
conducting nanoperovskites or addition of a co-catalyst for the grain boundaries. By incorporating a threshold amount of
enhancing the conductivity has shown mixed results. metals like platinum, it was observed that the electrical con-
Nanocrystalline La0.9Sr0.1Al0.85Co0.05Mg0.1O3 (LSAMC) pe- ductivity of protonic and oxide ionic conductors could be
rovskite was synthesized by citrate nitrate auto-ignition pro- brought down significantly [120]. In certain cases, additional
cess by [119]. Phase pure-sintered active material was formed doping has also improved the conductivity [121–125].
at a lower temperature of around 900 °C. The sintered
LSAMC perovskite exhibited a conductivity of 2.42 ×
10−2 S/cm in air at 1000 °C compared with 4.91×10−3 S/cm Conclusion
exhibited by the La0.9Sr0.1Al0.85Mg0.15O3 (LSAM) composi-
tion without cobalt. Thus, an order of magnitude increase in This article demonstrates the advantages of nanoperovskites
conductivity was observed with Co incorporation into the and their proton- and oxide ion-conducting properties over
composition. In addition, both LSAM and LSAMC samples their bulk forms. There is an observable effect because of their
exhibited a higher conductivity in air than argon, consistent small particle size and reduced grain boundary resistivity
with the p-type conduction mechanism. through decreased operating temperature and larger carrier
There are reports of a decrease in protonic conductivity due concentration, respectively. As a result, research has been
to the nanocrystalline nature of the perovskite or addition of a focused on materials development, into the search for new
certain catalyst. Cerversa et al. [46] have compared the pro- materials; the driving forces are higher conductivity and lower
tonic conduction of nanostructured BaZr0.8Y0.2O3 − δ and operating temperature.
found a contradictory effect when comparing with the overall
conduction for the bulk conductivity of BaZr0.8Y0.2O3 − δ
Acknowledgments The authors wish to acknowledge the UGC-DAE
which was already reported by Kreuer [85]. Matsumoto Consortium for Scientific Research for providing the financial support to
et al. [120] made an experimental observation and established carry out this research work.
a marked change in the electrical properties in the proton
conductor SrZr0.9Y0.1O3−δ by dispersing fine platinum parti-
cles. An experimental comparative study was made with pure References
SrZr0.9Y0.1O3−δ and Pt/ SrZr0.9Y0.1O3−δ. They concluded that
the fine platinum particles dispersed in the proton-conducting
1. Maier J (2000) Point defect thermodynamics: macro- vs
oxide show a decrease in electrical conductivity of the Pt/ nanocrystals. Electrochem 68(6):395–402
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