UNIVERSIT DEGLI STUDI DI CATANIA

FACOLT DI SCIENZE MATEMATICHE, FISICHE E NATURALI CORSO DI LAUREA IN CHIMICA INDUSTRIALE

DIPARTIMENTO DI SCIENZE CHIMICHE

NICO TORINO

Possible electrolytes for SOFC: synthesis and characterization of Bi3xMexTaO7 and others fluorite-related phases

M. Sc. EXPERIMENTAL THESIS

Supervisors Prof. Salvatore Scir Dr. Aurlie Rolle (ENSCL)

ACADEMIC YEAR 2010 - 2011

Abstract

How to supply the world's energy needs in a safe and clean way has become one of the most pressing task to achieve and the establishment of an electron economy seems to be a way to succeed in it. In such economy solid oxide fuel cells could play an important role in restoring electricity and to make it as much efficient as possible the basic research looks for more performing materials: this work focuses on electrolyte materials. The weberite phase La3TaO7 shows poor oxide ions conducting properties that can be increased by creating oxygen vacancies within the structure by means of the substitution of La3+ ions for Sr2+ ones. Moreover it could be stable under reducing and oxidizing conditions at once (as required for electrolyte materials suitable for SOFC) given the relatively high standard reduction potentials of the cations; however such a material has lower conducting performances than those of yttrium-doped zirconia, the main reference material for SOFC electrolytes. The aim of this research is to investigate the existence of the solid solution Bi3xSrxTaO7 and the effect of the Sr2+ ion on the oxide ions conductivity of Bi3TaO7, a phase with a structure similar to that of La3TaO7. The existence of the solid solution Bi3xLaxTaO7 was also investigated in order to find a way to solve the reducibility issues of bismuth-based materials: by dispersing the

bismuth compound in the La3TaO7 matrix, it could be created a material that can efficiently carry oxygen ions by exploiting the high polarizable 6s2 lone pair of Bi3+ ion that is the key to the high conducting properties of bismuthbased materials themselves, first of all -Bi2O3. While the existence of the solid solution Bi3xSrxTaO7 was confirmed, the existence of the Bi3xLaxTaO7 one remains questionable. Once the Sr2+-doped phase was synthesized, its oxide ions conducting properties were investigated and compared to those of Bi3TaO7, showing that the doped compound is a worst conductor. The existence of some others solid solutions with Ca2+ and Sr2+ ions was explored for compounds with fluorite-related structures, namely Y3TaO7 and Yb3TaO7, and preliminary investigations were carried out on La3TaO9 and the phases Pr3TaO7 and Pr3NbO7.

Keywords: SOFC, electrolyte, oxide ion conduction, bismuth, solid state chemistry

Contents

Preface Need to look at energy production Aim of the research work Outline

1 1 3 5

Acknowledgments

Introduction Oxide ions conducting materials The fluorite structure and YSZ Doped ceria

7 7 7 9 9 11 11 12 14 15 15 16

-Bi2O3 and BIMEVOX

Lanthanum gallate Phases derived from Ba2In2O5 Apatites Technological applications of oxide ions conductors Solid oxide fuel cells a. General overview on fuel cells b. How they work

c. About the electrolyte and the others SOFC components Oxygen pump Oxygen sensor

18 19 20

Theory

21

Experimental Sample preparation XRD characterization Data refining Thermal analyses Raman scattering spectroscopy Scanning Electron Microscopy Electron Probe Microanalyses Electrical mesurements

26 26 28 29 31 31 32 33 34

Results and discussion LaTa3O9 Pr3TaO7 and Pr3NbO7 Y3TaO7 and related phases Y3TaO7 Y2.9Ca0.1TaO6.95 Y2.9Sr0.1TaO6.95 Yb3TaO7 and related phases Yb3TaO7

37 37 40 44 44 47 48 50 50

Yb2.9Sr0.1TaO6.95 Yb3xCaxTaO7x/2 Bi3TaO7 and related phases Bi3TaO7 Bi3xLaxTaO7 Bi3xSrxTaO7x/2 How the strontium ion influences the conducting properties of Bi3TaO7

53 54 57 58 66 70 73

Conclusions

83

References

86

Preface

Need to look at energy production

The last decades have become the stage on which mankind is facing one of the most challenging trial of all times: how to supply the energy needs of the growing world population in a safe and clean way. Such an issue has arisen in recent times most likely because on the first times after the industrial revolution it was considered quite an oddity showing concernments about the finite nature of resources on the planet but that kind of attitude was drove way too far till it has become a threat to that well-being itself, that is to say, achieved thanks to that kind of exploitation. Lying mainly on fossil hydrocarbons and coal and minerals for nuclear fuel, energy supply is a geopolitical and economical issue since those resources are not widespread nor less important are the problematics connected to the environmental impact due to the use of such commodities. While being aware of the finiteness of resources has been a relatively easy task, the solution of the related problem is still to be found but it's unquestionable that it musts rely on sustainability, that is on conserving the ecological balance by avoiding the depletion of those natural resources: it means that the resources have to be renewable.

Among the various options, one of the most promising concerns the establishment of an electron economy by means of which energy would be harvested directly from physical processes e.g. photovoltaic devices replacing the chemical carriers of today's economy. In fact, with exception of biomass, all renewable energy is of physical nature: heat (solar, geotermal), solar radiation (photovoltaic) and mechanical energy (wind, waves etc.) [1]. One of the technological obstacles is the storage of the energy obtained in such ways and a practicable way could be the use of hydrogen as carrier, made by electrolysis of water. To restore, then, the electron flow the solid oxide fuel cells (SOFC) represent an efficient way to use that hydrogen, attaining at up to 60% of efficiency on electricity production and up to 80% by cogeneration of electricity and heat [2]. A SOFC is an electrochemical device that works at high temperatures, between 800C and 1000C, and allows to use the electrons coming from the oxidation of hydrogen (or hydrocarbons like methane also) as a current. The high working temperatures result in mechanical and chemical compatibility issues of the different components of such devices (anode//electrolyte//cathode) thus an important task is achieving lower working temperatures: the basic scientific research tries to answer by exploring the possibilities to obtain more performing materials. This is a pressing task even to lower prices, that range from 3500 to 15000 /kWe, to make the technology affordable for a larger market [3]. The present work focuses on the electrolyte materials for SOFCs.

Preface

Aim of the research work

An electrolyte suitable for SOFCs must be stable under reducing and oxidizing conditions at once, it must be an electronic insulator and it must have an ordered framework of defects (interstitial oxide ions and/or vacancies) through which allowing the drifting of oxygen ions. A former work by Dr. Nicolas Preux [4] studied the compound La3TaO7, having a weberite-type structure, constituted by chains of corner-sharing TaO6 octahedra, intercalated by LaO chains and isolated lanthanum atoms. Fig. 1 compares the structure of La3TaO7 and of the weberite Na2MgAlF7; the latter could be described as a defect-fluorite structure by considering only the cationic array.

Fig. 1 Strucures of La3TaO7 and of the weberite Na2MgAlF7

That compound was chosen because it showed the main features suitable for developing a new electrolyte material for SOFC applications: La3+ and Ta5+

Preface

are not so easily reduced (standard reduction potentials in water are 2.38 V and 0.81 V respectively [5]) and they are no more oxidizable; the structure of La3TaO7 is defective. Dr. Preux's work showed the existence of the solid solution La3xSrxTaO7x/2 for 0 < x 0.15 and compared the ionic conductivity of the phase with x = 0.1 to that of the non-doped La3TaO7 phase. The ionic conductivity was greatly enhanced by the substitution of lanthanum ion for the strontium one: moving from that result, the nucleus of the present research concerns the possibility of doping the phase Bi3TaO7, having a similar structure to that of La3TaO7 [6]. Because of the high polarizable 6s2 lone pair of Bi3+ ion, Bi3TaO7 presents better conducting properties than the Sr-doped La3TaO7 phase, so the purpose was to synthesize a Sr-doped Bi3TaO7 phase and to explore its conducting properties and compare them with those of the Bi3TaO7 phase. Moreover the substitution of bismuth for lanthanum was tried in order to confirm or refute the existence of the solid solution Bi3xLaxTaO7. Such investigation was useful because the reducibility of bismuth in its compounds poses limitation to their application as electrolyte for SOFC: dispersing the bismuth based compound in a lanthanum based matrix could be a way to solve such an issue. The Sr2+-doped Bi3TaO7 phase was characterized by electrochemical impedance spectroscopy and also microstructurally by Scanning Electron Microscopy.

Preface

- Yb3TaO7 to form Yb3xSrxTaO7x/2 and Yb3xCaxTaO7x/2 phases; - Y3TaO7 to form Y3xSrxTaO7x/2 and Y3xCaxTaO7x/2 phases; - LaTa3O9 by adding Zr4+ ions. The investigation looked even at the phases Pr3TaO7 and Pr3NbO7. They were chosen because of the nature of the praseodymium atom that can be oxidized from PrIII to PrIV: electronic conduction might so be added in a solid solution with other tantalates, thus introducing domains of mixed electronic/ionic conduction in a pure ionic conductor.

Outline
An overview of the main oxide ions conducting materials will be given in the introduction along with the principle of SOFC functioning and some other applications. Then, a theoretical chapter will briefly survey the ionic conduction. The core of this research work will follow with the experimental section and the presentation of the results.

Preface

Acknowledgments

As part of the ERASMUS programme, the present research work was carried out with the Oxide Materials for Energy team from the Solid State Chemistry group at the UCCS (Unit de Catalyse et de Chimie du Solide) of the ENSCL (cole Nationale Suprieure de Chimie de Lille), in collaboration with Dr. Aurlie Rolle and under the supervision of Pr. Rose-Nolle Vannier and with the precious help of Dr. Nicolas Preux, assistant engineers Laurence Burylo and Nora Djelal for the analysis work (X-ray diffractions, thermal and SEM analyses), CNRS engineer Edouard Capoen during the set-up for electrical measurements and laboratory technician Maxence Vanderwalle providing and explaining everything was necessary for a happy lablife. Special thanks go to Pr. Annick Rubbens who provided Raman scattering spectra and many useful advices.

Acknowledgments

Introduction

Oxide ions conducting materials

The fluorite structure and YSZ Fluorite, CaF2, exhibits a fcc lattice of Ca2+ ions where F ions occupy all tetrahedral sites (fig. 2):

Fig. 2 The fluorite structure

This kind of structure is also shown by the main compound used as electrolyte in SOFC technology, the yttria stabilized zirconia, YSZ, of composition (ZrO2)1x(Y2O3)x with 0.08 x 0.1. ZrO2 has several polymorphs and it is a poor ionic conductor. Its cubic

Introduction

fluorite phase appears only beyond 2370C: Zr4+ ions form a fcc lattice in which oxide ions occupy the tetrahedral interstices. As a means to stabilize the fluorite phase at room temperature, ZrO2 can be added of oxides of divalent or trivalent cations such as CaO, MgO, Y2O3, Sc2O3, Yb2O3, Sm2O3 etc. Those dopant ions exactly replace part of Zr4+ ions and in turn they introduce oxygen ion vacancies for maintaining charge neutrality: through those vacancies, oxide ions can migrate and allow the material to behave as an oxide ions conductor (fig. 3).

Fig. 3 Scheme of ionic migration in YSZ

It is well understood that for zirconia, the conductivity is maximum when the dopant is just adequate to fully stabilize the cubic fluorite phase. The best conductivity results are obtained by adding Y2O3 for an 8% molar substitution of zirconium ions ( = 0.02 S/cm at 800C and 0.1 S/cm at 1000C). Zr4+ and Y3+ ions form an fcc lattice and most of the tetrahedral sites of Zr4+ ions are occupied by O2 ions. At high temperatures, oxide anions tend to vibrate in the region of their regular tetrahedral lattice sites and a few (probably equal to the number of vacancies created) migrate from one regular lattice site to the other while octahedral sites have no role to play in the

Introduction

oxygen diffusion [7, 8]. High temperatures, besides, during prolonged operations may produce cation diffusion and, as a result, the segregation of vacancies into vacancy-rich clusters that trap the mobile vacancies. This phenomenon causes a degradation of the performance of the electrolyte with time, so-called aging [9].

Doped ceria CeO2 has a stable fluorite structure from room temperature up to its melting point (2400C) and shows poor ionic conductivity, due mainly to nonstoichiometry, that can be increased by means of doping: the substitution of Ce4+ with cations of lower valence, such as Ca2+ or Y3+, creates oxygen vacancies [8]. The best results are obtained by a 10% molar substitution in Gd2O3: Ce0.9Gd0.1O1.95 has a ionic conductivity of 0.01 S/cm at 500C. Unfortunately problems in using ceria as SOFC electrolyte arise from the partial reduction of Ce4+ to Ce3+ under the reducing conditions of the anode [10].

-Bi2O3 and BIMEVOX

Bi2O3 shows a monoclinic to cubic phase transition ( ) that occurs at approximately 730C. The -phase is stable until the melting point of Bi2O3 at approximately 825C and it shows an incredibly high ionic conductivity (ca. 1 S/cm at 650C, transition temperature to the metastable -phase when cooling down from the high temperature -phase) only if pure: doping Bi2O3 by the substitution of bismuth for rare-earth dopants (such as Y, Dy or Er) or

Introduction

high valency cations (Nb5+, Ta5+) stabilizes the fluorite phase at room temperature but results in lowering its conducting properties. Moreover bismuth based compounds are unstable at high temperature under reducing conditions and undergo volatilization of bismuth oxide [9, 11]. BIMEVOX are solid solutions exhibiting high ionic conductivity at moderate temperature, 400-600C . They are based on -Bi4V2O11, stabilized by partial substitution of vanadium with transition metal cations such as Co2+, Ni2+ or Cu2+, and possess a crystal lattice belonging to the Aurivillius series that consists of alternating (Bi2O2)2+ and perovskite-like (VO3.5)2 layers (fig. 4) with oxygen vacancies allowing ion migration only in the latter ones. Solid solutions of the type Bi2V1xMexO5.5 (Me = Cu, Ni and 0.07 x 0.12) show the highest conductivities but still suffer the disadvantages of the bismuth based compounds [10, 12].

Fig. 4 Bi4V2O11 structure

Introduction

10

Lanthanum gallate Perovskite-type phases derived from LaGaO3 (fig. 5) show an ionic conductivity higher than YSZ in the temperature range 500-800C that can be even enhanced by substituting lanthanum with alkaline earth elements and/or incorporating divalent metal cations, such as Mg2+, into the gallium sublattice in order to increase oxygen vacancy concentration. The best results are obtained for the La1xSrxGa1yMgyO3 series with 0.10 x 0.20 and 0.15 y 0.20. Disadvantages of this kind of materials include possible reduction and volatilization of gallium oxide, reactivity with perovskite electrodes under oxidizing conditions and with metal anodes in reducing conditions and the relatively high cost of gallium [10].

Fig. 5 Lanthanum gallate structure

Phases derived from Ba2In2O5 Other materials with substantially high conductivity can be derived by partial substitution of brownmillerite-type Ba2In2O5. The structure of brownmillerite, A2B2O5, consists of alternating perovskite layers of cornersharing BO6 octahedra and layers of BO4 tetrahedra (fig. 6) and can be considered as an

Introduction

11

oxygen-deficient perovskite where the oxygen vacancies are ordered along (010) planes forming one dimensional diffusion pathways for oxygen ion migration. Ba2In2O5 has mixed conductivity with dominant oxygen ionic transport in dry air (the ionic transference number at 500C is ~ 0.93) but becomes a pure ionic conductor above 870-950C when it undergoes a transition to a disordered perovskite phase, stabilized at lower temperatures by substituting indium with other cations such as Zn2+, Ce4+, Sn4+ or Hf4+. Disadvantages are represented by the instability shown in humid atmospheres, the high reactivity with CO2 and the easy reducibility [10].

Fig. 6 Ba2In2O5 structure

Apatites The apatite-type phases A10x(SiO4)6O2, where A corresponds to rare earth and alkaline earth cations, possesses a significant level of oxygen ion conductivity. A-site cations are located in the cavities created by SiO4 tetrahedra with four distinct oxygen positions and additional oxygen sites forming channel through the structure (fig. 7): the ionic conduction is made by means of those isolated oxygen atoms.

Introduction

12

The oxygen ionic transport in Ln10Si6O27 (with Ln = La, Pr, Nd, Sm, Gd, Dy) increases with increasing radius of Ln3+ cations, with maximum conductivity for the La-containing phase. Due to relatively poor sintering, different processing techniques and substantial anisotropy of ionic transport in the apatite lattice, the conductivity values reported in the literature vary in a very broad range. The highest ionic transport is observed when apatite contains more than 26 oxygen ions per unit formula, suggesting a significant role of the interstitial migration mechanism. To increase ionic conductivity many other ions were tried as substituent of La3+: best results follow the scheme Ba Sr Ca Y [10, 13, 14].

Fig. 7 Apatite structure

In the next page figure 8 shows a chart in which the oxygen ionic conductivities for the mentioned materials are plotted versus the temperature.

Introduction

13

Fig. 8 Oxygen ionic conductivities of the mentioned solid electrolyte materials [10, 15, 16, 17, 18]

Technological applications of oxide ions conductors

Oxide ions conducting electrolytes are used mainly in electrochemical cells where the chemical reactants at the two electrodes are either gaseous or liquid. They are used in the form of a thin sheet of large surface area having porous electrodes on opposite surfaces for two classes of applications: power applications (solid oxide fuel cells and oxygen pump) and open-circuit applications (oxygen sensor).

Introduction

14

Solid oxide fuel cells a. General overview on fuel cells A fuel cell is an electrochemical cell. There are many types of fuel cells, all of them constituted by a stack of three elements: an anode, an electrolyte and a cathode (fig. 9).

Fig. 9 Schematic representation of a fuel cell

At the anode an oxidation reaction provides the electron flow and at the cathode a reduction one uses the same electrons that pass through the circuit to occur; the electrolyte is responsible for the ionic current that must balance the electronic current in the external circuit. Being the principle of functioning the same for all types of fuel cell devices, they differ mainly for the working temperatures range, the electrolyte and the nature of the ionic species involved. Table 1 summarizes the different kinds of fuel cells: Alkaline Fuel Cell (AFC), Proton Exchange Membrane Fuel Cell (PEMFC) and Phosphoric Acid Fuel Cell (PAFC) belong to the low temperature devices whereas Molten Carbonate Fuel Cell (MCFC) and Solid Oxide Fuel Cell (SOFC) belong to the high temperature ones.

Introduction

15

low temperature fuel cells type of fuel cell electrolyte working temperature charge carrier application domains
AFC KOH solution 25 - 90C OH spacial transportation PEMFC water 70 - 90C H+ transportation stationary PAFC H3PO4 200C H+ stationary

high temperature fuel cells

MCFC Li2CO3/K2CO3 600 - 650C CO32 stationary SOFC solid oxide 800 - 1000C O2 transportation stationary

Tab. 1 The different kinds of fuel cells [19, 20]

Today's research is oriented mostly towards PEMFC technology, where water through a proton exchange polymeric membrane (a sulfonated polytetrafluoroethylene based copolymer) can deliver hydrogen ions from the anode to the cathode [7], and towards SOFC where a ceramic oxide (mainly yttria-doped zirconia) conducts oxyde ions from the cathode to the anode.

b. How they work A schematic drawing of a SOFC is shown in fig. 10. While air is supplied at the cathode, the oxide ions resulting from the reduction of oxygen molecules diffuse through the conducting ceramic membrane to react with hydrogen, at the anode, forming water as byproduct along with heat since the reaction is exothermic: H2 + 1/2 O2 H2O (g) with H < 0

Introduction

16

Fig. 10 Functioning scheme of a solid oxide fuel cell

The electrons provided by the oxidation reaction occurring at the anode can so be used to power electrical devices. The Nernst potential for the reaction, for a fuel cell operating at atmospheric pressure, is given by:
0 E th = E Ox /R.ed + 1/2 P PO RT H ln 2 2 2F PH2O

The migration of oxide ions through the electrolyte membrane is a thermally

! activated process thus high temperatures are needed (800 - 1000C), limiting

indeed the applications only to big stationary and transportation systems. Such high temperatures even imply aging problems to overcome which many efforts are addressed to the development of technologies working at lower temperatures (500 - 600C), the so-called Intermediate Temperature-SOFC, namely by researching materials that can conduct oxide ions at milder conditions without significant dropping in conductivity.

Introduction

17

There this work looks, focusing on phases with a defect-fluorite structure and trying to enhance their conduction properties by introducing oxygen vacancies within the structure.

c. About the electrolyte and the others SOFC components The electrolyte in a SOFC performs three critical functions: a. separation of reactants; b. blockage of internal electronic current between the cell electrodes, thus forcing any electronic current to flow in an external circuit; c. conduction of ions responsible for the internal ionic current that must balance the electronic current in the external circuit. To be suitable for SOFC applications it must satisfy several requirements: - it must be an electronic insulator but a good ionic conductor; - it must be as denser and thinner as possible to limit the ohmic resistance; - it must be stable under oxidant and reductive atmosphere; - it must display good mechanical properties; - it must be chemically and mechanically compatible with the other components of the cell (cathode and anode). Nowadays, the main material used in SOFC application is the yttria stabilized zirconia (YSZ). At the cathode oxygen molecules from air dissociate and are reduced to oxide ions. The cathode is a porous structure (20 - 40% of porosity) that must allow rapid mass transport of reactant and product gases. Strontium-doped lanthanum manganite (LSM), a p-type semiconductor, is the most commonly used cathode material.

Introduction

18

At the anode hydrogen is oxidized to water. Similarly to the cathode, the anode has a high porosity so that mass transport of reactant and product gases is not inhibited. The anode of state-of-art SOFCs is a cermet made of metallic nickel and a YSZ skeleton [7].

Oxygen pump At the negative electrode of an oxygen pump, the reaction O2 + 4 e 2 O2 provides oxide ions that flow through the electrolyte membrane driven by the application of a voltage Vapp across the electrodes. Once on the opposite side, at the positive electrode, the reverse reaction gives back oxygen molecules (fig. 11) [21]. The technique is used for the separation of oxygen from air or for industrial scale oxygen separation in the conversion of natural gas to syngas.

Fig. 11 Oxygen pump

Introduction

19

Oxygen sensor In an oxygen sensor (fig. 12), the difference between the oxygen partial pressure of a standard gas, p0O , and of an unknown pO is obtained by
2 2

measuring the open-circuit voltage VOC between the electrodes. The voltage is related to the difference in the oxygen free energies on opposite sides of the electrolyte. Such sensors are extensively used to measure oxygen content in molten metals particularly liquid steel and also to measure the oxygen content of gaseous atmospheres like furnace flue gas or car exhaust helping to maintain air-fuel ratio at an optimum level [9, 22].

Fig. 12 Oxygen sensor

Introduction

20

Theory

The electrical conductivity, , the proportionality constant between the current density j and the electric field E, is given by j/E = = ci Zi q i
i

where: ci i Zi q
3 is the carrier density (number/cm );

is the mobility (cm2/V s); is the charge of the ith charge carrier (q = 1.6 10-19 C).

The differences in between metals, semiconductors and insulators generally result form differences in c rather than . On the other hand, the higher conductivities of electronic versus ionic conductors are usually due to the higher mobilities of electronic versus ionic species. Typical ionic solids possess limited numbers of mobile ions, hindered in their motion because of being trapped in relatively stable potential walls (fig. 13) so that ionic conduction easily falls below 10-10 S/cm between room temperature and 200C.

Theory

21

Fig. 13 Example of potential energy variation along diffusion path

An activated jump process describes the motion of ions, for which the diffusion coefficient D is given by D = D0 e G/k where:
B

= (1 c) Z a2 0 e S/k e E
B

/kB T

c Z a

is a constant including geometric and correlation factors; is the fractional occupation; is the number of nearest neighbours, so that the (1 c) Z factor defines the number of neighbouring unoccupied sites; is the jump distance; is the attempt frequency; is the migration energy.

0
Em

Since the ion mobility is defined by i = Zi q Di / kB T

Theory

22

and ci, the density of carriers of Zi q charge, is N c, with N density of ion sites in the sublattice of interest, the ionic conductivity becomes

(Z i q) 2 ion = N c (1 c) Z a2 0 e S/k e E kB T
B

/kB T

This expression shows that ion is nonzero only when the product c (1 c) is nonzero. Since in a perfect crystal all normal sites are fully occupied (c = 1) and all interstitial sites are empty (c = 0), this is expected to lead to insulating characteristics. The classical theory of ionic conduction in solids is thus described in terms of creation and motion of atomic defects, that is vacancies and interstitial sites. The oxygen ion conductivity is therefore given by the sum of oxygen vacancy and interstitial partial conductivities, though in all oxygen ion electrolytes of interest the interstitial one does not appear to make significant contribution. Consequently ionic conductivity can be expressed by

ion [V ] 2q V O
with [V ] concentration of oxygen vacancies doubly positive charged. O

Optimized levels of conductivity hence require a combination of high charge carrier density and mobility without neglecting a continuous pathway of
partially occupied and energetically equivalent ionic sites through the structure. Ionic mobilities are greatly enhanced by doping with an aliovalent ion that introduces mobile vacancies into the occupied sites: this is the method that has classically been used to induce high charge carrier density in solids. Another method consists in introducing oxygen atoms in interstitial position where oxide ions can diffuse.

Theory

23

Furthermore migration energy Em must be minimized. To achieve this task it should be considered the barrier energy required for a mobile ion to move from an occupied site to the common interface (fig. 14) between donor and acceptor sites, respectively occupied site and vacancy.

Fig. 14 Interface between occupied site and vacancy

This energy is minimal where the sum of the ionic radii of the mobile and an interface ion matches the distance Rb from the centre of the interface to an interface ion; the effective bottleneck distance Rb is enlarged where the interface ions are easily polarized and/or the mobile ion can also change its shape to a prolate ellipsoid. It must be said that solid oxide electrolytes are purely ionic conductors only within a specific range of temperatures, oxygen partial pressures and compositions, beyond which electronic (n- or p- type) contribution becomes significant. For that reason another important parameter used to describe their properties is the transport number, a measure of the fraction of the total

Theory

24

current carried by ions: to consider a solid electrolyte useful it must be 0.99 over a wide range of oxygen partial pressures and temperatures. It has been observed that at high dopant concentration, which is usually the case for oxygen ion conductors, the transport number is relatively insensitive to composition. On the other hand, it is strongly dependant on temperature and oxygen partial pressure [9, 22, 23].

Theory

25

Experimental

Sample preparation
All phases were prepared by solid-state reaction in air, starting from oxide precursor or carbonate ones: Bi2O3 (Riedel - De Haen, 99.5%), Ta2O5 (Aldrich, 99%), SrCO3 (Sigma Aldrich, 98%), La2O3 (Alfa Aesar, 99.9%), Yb2O3 (Alfa Aesar, 99.9%), CaCO3 (Sigma Aldrich, 99.95%), Y2O3 (Sigma Aldrich, 99.99%), Pr6O11 (Alfa, 99.9%), Nb2O5 (Aldrich, 99.9%). Before starting the syntheses, every single reactant was characterized by X-ray diffraction and, when necessary, thermally treated to obtain the pure compound. The appropriate stoichiometric amounts were mixed in an agate mortar, then put into a crucible and heated up with a heating rate of 200C/h and intermediary grinding between the heating steps. Table 2 summarizes the experimental conditions for every phase.

Experimental

26

reaction
3/2 Bi2O3 + 1/2 Ta2O5 Bi3TaO7 (3x)/2 Bi2O3 + x SrCO3 + 1/2 Ta2O5 Bi3xSrxTaO7x/2 + x CO2 (3x)/2 Bi2O3 + x La2O3 + 1/2 Ta2O5 Bi3xLaxTaO7 3/2 Yb2O3 + 1/2 Ta2O5 Yb3TaO7 2.9/2 Yb2O3 + 0.1 SrCO3 + 1/2 Ta2O5 Yb2.9Sr0.1TaO6.95 + 0.1 CO2 2.95/2 Yb2O3 + 0.05 CaCO3 + 1/2 Ta2O5 Yb2.95Ca0.05TaO6.975 + 0.05 CO2 2.9/2 Yb2O3 + 0.1 CaCO3 + 1/2 Ta2O5 Yb2.9Ca0.1TaO6.95 + 0.1 CO2 3/2 Y2O3 + 1/2 Ta2O5 Y3TaO7 2.9/2 Y2O3 + 0.1 CaCO3 + 1/2 Ta2O5 Y2.9Ca0.1TaO6.95 + 0.1 CO2 2.9/2 Y2O3 + 0.1 SrCO3 + 1/2 Ta2O5 Y2.9Sr0.1TaO6.95 + 0.1 CO2 1/2 Pr6O11 + 1/2 Ta2O5 Pr3TaO7 + 1/2 O2 1/2 Pr6O11 + 1/2 Nb2O5 Pr3NbO7 + 1/2 O2 1/2 La2O3 + 3/2 Ta2O5 LaTa3O9 1/2 La2O3 + 3/2 Ta2O5 LaTa3O9 [x = 0.05 and 0.1]

type of crucible
alumina alumina alumina alumina alumina alumina alumina alumina alumina alumina alumina alumina alumina platinum

temperature (C)*
900 900 900 1600 1600 1550 1600 1600 1550 1550 1250 1250 1600 1700

reaction time (h)

130 274 106 164 58 104 130 164 118 118 480 480 164 78

[x = 0.05 and 0.1]

Tab. 2 Sample preparation: experimental conditions * it represents the maximum temperature reached for the syntheses

XRD characterization
X-ray powder diffraction (XRD) is an analytical technique primarily used for phase identification of a crystalline material that can also provide information on unit cell dimensions. X-ray diffraction is based on the interaction of the incident X-rays with a crystalline sample that produces constructive interference (and a diffracted ray) when conditions satisfy Bragg's Law n = 2d sin being the wavelength of incident radiation, the diffraction angle, d the lattice spacing in a crystalline sample. These diffracted X-rays are then detected, processed and counted. By scanning the sample through a range of 2 angles (the geometry of an X-ray diffractometer is such that the sample rotates in the path of the collimated X-ray beam at an angle while the detector is mounted on an arm to collect the diffracted rays and rotates at an angle of 2), all possible diffraction directions of the lattice should be attained due to the random orientation of the powdered material. Conversion of the diffraction peaks to dspacings allows identification of the crystalline compound because each compound has a unique set of d-spacings. On all phases XRD analyses were performed using a D8 Advance diffractometer (Bruker AXS), using CuK radiation (1 = 1.5406 and 2 = 1.54439 ). Data were collected in the 2 range 10-100, with a step of 0.02 and a scan time of 0.2 s per step. The diffractometer was equipped with a - goniometer and a LynxEye linear detector.

Experimental

28

For Bi3TaO7 and Yb3TaO7 data were even collected at various temperatures in air, from 50C to 900C and 1100C respectively, every 25C in order to follow the evolution of the cubic lattice parameter, in the 2 range 25-95, with a step of 0.02 and a scan time of 0.2 s per step, with a Pt sample holder. XRD characterizations of reactants were performed on a Guinier G670 HUBER automated diffractometer. It was equipped with an image plate and a monochromator acting on the source radiation, hence irradiating the samples with a nearly pure CuK1 light ( = 1.5406 ). That instrument was also equipped with a multiple sample-holder and worked on transmission. All diffraction diagrams were evaluated using the software DIFFRACplus EVA (Bruker AXS).

Data refining
The refining of the collected XRD data was made by the Rietveld method, a quantitative analysis method that takes into account the contribution of all diffraction planes for every considered phase. It was performed the full pattern matching, that is the determination of a mathematical XRD pattern profile in order to justify the experimental one. To obtain such profile the parameters taken into account were: 1. the sample displacement; 2. the lattice parameters;

Experimental

29

3. the profile function (a pseudo-Voigt type), defined by the FWHM of the Braggs peaks; 4. the mixing factor of the pseudo-Voigt profile function and the asymmetry. That is the sequence by which the refining is carried out. Five refinement cycles were performed with the refined parameters considered as the starting ones in the next cycle. By the Rietveld method refining means to minimize the so-called reduced 2, the weighted square difference between the observed and the calculated pattern, respectively yi and yci, divided by the number of degree of freedom:
2 v =

wi ( y i y ci )
i

N P +C

with wi = 1 i2 , i2 being the variance of the observed intensity yi and

N
P C

the number of the points on the diagram; the number of parameters taken into account; the number of constrained parameters (distance, angle, etc).

The quality of the agreement between observed and calculated profile is measured by a set of conventional factors: Profile factor
y i y ci R p = 100
i

yi
i

Weighted profile factor

wi y i y ci Rwp = 100
i

wi yi2
i

Expected weighted profile factor

Rexp = 100

N P +C wi yi2
i

Experimental

30

Thus, the reduced 2 can be expressed as:

R 2 wp 2 = Rexp

Thermal analyses
Heat flow differential scanning calorimetry analyses were performed using a SETARAM TAG 2400 instrument in air with a heating rate of 5C/min. Differential scanning calorimetry (DSC) is a technique by means of which the difference between the heat flow through a sample and a reference (air, alumina, SiC, glass etc.) is measured, during a temperature programme. It is used to study the thermal behaviour of organic and inorganic compounds and one of the most important applications concerns the study of phase transitions.

Raman scattering spectroscopy

Raman scattering spectra were obtained using a DYLOR XY800 instrument with a Kr-ion laser light source, equipped with a CCD (charge-coupled

Experimental

31

device) detector. Samples were irradiated with a light of wavelength equals to 647.1 nm and 10 mW of power. Raman spectra have their origin in the electronic polarization caused by ultraviolet, visible, and near-IR light and are obtained by measuring the radiation scattered at a certain angle, usually 90. This spectroscopic technique is used to observe the vibrational transitions occurring as a consequence of the interaction between light and matter, and is a powerful means for theoretical and structural studies of inorganic systems as well as organic ones. All spectra were evaluated by means of the software LABSPEC.

Scanning Electron Microscopy

SEM images were obtained by using a HITACHI S-3800N instrument on gold-sputtered samples. By means of the scanning electron microscope (SEM), images of surfaces can be obtained exploiting the interaction of an electron beam with matter. Thermoionically emitted electrons are accelerated by means of an applied voltage (experimental images were obtained with accelerating voltages of 5 kV and 7 kV) and focalised on a sample through a system of electrostatic lenses. While the electron beam scans the surface of the sample, from the latter are emitted secondary, backscatterd and Auger electrons along with X

Experimental

32

photons. The secondary electrons are produced at a depth ranging from 50 to 500 and they are, thus, sensible to the topography of the sample's surface: by detecting those ones it can be built an image of the surface.

Electron Probe Microanalyses

The electron probe microanalyzer is used to determine, locally (irradiating volume ~ 1 m3), the chemical composition of a sample. The X photons emitted by means of the interaction of a highly accelerated electron beam (20 kV) with matter are characteristic of the chemical element constituting the sample that emits them. Analyses were performed using a CAMECA SX100 instrument equipped with three wavelength dispersive spectrometers.

Experimental

33

Electrical measurements
Electrical parameters were determined by impedance spectroscopy using a Solartron 1260 frequency response analyzer in the frequency range 1 Hz to 1 MHz, under a 500 mV voltage. Samples for impedance measurement were tablets (5 mm diameter, 2-3 mm thickness) sintered at 800C for 12 hours, with gold-coated parallel faces: the coating was made in two steps, by sputtering and by brushing using an organic suspension of gold powder. Pellets were shaped by uniaxial pressing and compacted by a 5 minutes isostatic hydraulic pressing at 1700 bars. Impedance spectra were recorded in air during heating and cooling ramps between 200C and 800C at stabilized temperatures separated by 20C steps. The impedance spectroscopy technique is based on the characterization of the samples response to an alternative tension of variable frequency. The electric impedance of a system, denoted by Z(), represents the ratio between the applied sinusoidal tension, U(), and the resulting electrical current, I(), where

= 2
and is the frequency. Z(), U() and I() are complex quantities that can be represented on a Cartesian plot: Z() = ZR + j ZI = |Z| e j with ZR representing the real part of Z(), ZI its imaginary part, |Z| its modulus and its argument. There are many ways impedance spectroscopy data may be plotted. Conventionally one plots ZI = (ZR)

Experimental

34

to give a complex-plane impedance plot (Cole-Cole plot). Through Z the resistivity R of a material can be determined by modelling the physicochemical processes occurring while applying the tension, by means of an appropriate equivalent electrical circuit. In the simplest case of an homogeneous tablet of 100% of relative density or a monocrystalline solid, perfectly in contact with the electrodes, the sample itself can be described as a resistor in parallel with a capacitor (fig. 15):

Fig. 15 a. Electrical circuit equivalent to the sample; b. related impedance plot

The total impedance of such circuit is:

Z(" ) = R 1+ j R C "

Multiplying it for its complex conjugate, we obtain:

!
Z R ( ) = R 1+ ( j C )2

()

and

Z I ( ) =

R 2 C 1+ ( j C ) 2

Combining these two expressions, we get:

(Z

R 2 + Z I2 = R 2

( )

Experimental

35

That is the equation of a circumference centred in (R/2 ; 0) and of diameter R. From () it can be seen that Z approaches to the intrinsic resistivity of the material R as the frequency approaches to zero and that Z approaches to zero as the frequency approaches to infinity. The amplitude maxima for Z is obtained when

= 0 = 2 0 = 1 R C
where 0 is the characteristic resonance frequency of the system. Conductivity is defined by:

= lRS
where:

l
S R

is the thickness of the sample tablet; is its surface area; is the resistivity.

Given the Arrhenius law

E/N T e

kB T

E 1000 2.3 1000 NA kB T

log (T) = log 0

by plotting log (T) versus 1000/T one can get macroscopic data about the

sample, the activation energy related to the oxygen ions drifting E. Every impedance plot obtained is evaluated by means of software through which data are collected and transformed in order to get a table of log versus T.

Experimental

36

Results and discussion

The first task of the merely laboratory work was, once collected the bibliographic references about the compounds to synthesize, trying to obtain the pure phases by means of a solid-state reaction. As always, when facing to experimental experiences, it is hard to fulfil every task. It will be shown, first, the results of the experiences that didn't give positive answers or, at least, not the hoped ones. Then the struggle for bringing order from chaos started giving better results, upon which continuing the investigation was therefore possible.

LaTa3O9
The LaTa3O9 phase is orthorhombic with space group Pnma. In the structure (fig. 16), ribbons of pentagonal TaO7 bipyramids are recognizable parallel to the a-direction. These ribbons are connected with each other by TaO6 octahedra: the tunnels formed in this way are occupied by lanthanum atoms [24]. This structure was taken into account because such tunnels might

Results and discussion

37

represent a path through which oxygen ions could flow: the substitution of lanthanum for zirconium might provide some interesting clues about such possibility by introducing oxygen vacancies within the structure.

Fig. 16 La3TaO9 structure

Unfortunately it was impossible to obtain that phase with a simple solid-state reaction in air since other phases are formed. By using an alumina crucible at 1600C the phase obtained was La0.33TaO3, primitive tetragonal with space group P4/mmm. Then it was tried to carry out the reactionin a platinum crucible: by heating the mixed powders at 1700C, different phases coexist, mainly La0.33TaO3 and LaTa5O14, besides La4.67Ta22O62. Figures 17 and 18 show the XRD diagrams related to the two samples.

Results and discussion

38

Fig. 17 XRD diagram of the Al2O3/1600C sample constituted by La0.33TaO3

Results and discussion

39

Fig. 18 a. XRD digram of the Pt/1700C sample; b. particular of the diagram showing the phases La0.33TaO3 (x), LaTa5O14 (v) and La4.67Ta22O62 (o)

Pr3TaO7 and Pr3NbO7

Both phases are described in the literature [25] as fluorite-related orthorhombic structures with space group Cmcm: for that reason it was interesting to investigate the possibility of doping them by substituting Pr3+ ions with lower valence cations, such as Sr2+, therefore creating oxygen vacancies and allowing so oxide ions conduction. Morevover PrIII can be

Results and discussion

40

oxidized to PrIV and this might add mixed electronic/ionic conducting properties. During the synthesis processes it was observed the persistent presence of grains of unreacted praseodymium (III, IV) oxide which required a 20 hours ball milling treatment and a following heating step to disappear: a preliminary reduction of the particles size is therefore desirable before starting the syntheses. The XRD diagrams of the niobate phase and of the tantalate one are very similar as it can be expected by the resemblance of the ionic radius of the two ions (Nb+5, 69 pm; Ta5+, 68 pm). Figures 19 and 20 show the XRD diagram and the refined profile for the phase Pr3TaO7 while figures 21 and 22 show the diagrams related to Pr3NbO7. Unfortunately the lack of time made the carrying on of the investigation impossible to fulfil so the report on these phases stops with the definition of a procedure for the syntheses.

Fig. 19 XRD diagram of Pr3TaO7 at room temperature

Results and discussion

41

Fig. 20 Fitted profile for Pr3TaO7, orthorhombic, base-centered, space group Cmcm Lattice parameters a = 10.97392(12) , b = 7.51560(4) , c = 7.67241(4) Rp = 16.7%; Rwp = 23.4%; Rexp = 8.00%; 2 = 8.56

Fig. 21 XRD diagram of Pr3NbO7 at room temperature

Results and discussion

42

Fig. 22 Fitted profile for Pr3NbO7, orthorhombic, base-centered, space group Cmcm Lattice parameters a = 10.96504(10) , b = 7.51192(3) , c = 7.66809(3) Rp = 15.3%; Rwp = 20.6%; Rexp = 8.41%; 2 = 5.99

Results and discussion

43

Y3TaO7 and related phases

Y3TaO7 Y3TaO7 phase is said to be cubic above 1600C and orthorhombic at 1400C [26], but many essays showed that the cubic defect-fluorite phase at 1600C is in equilibrium with a small quantity of orthorhombic phase. In fig. 23 the experimental XRD diagram and in fig. 24 an enlargement showing the pattern of the orthorhombic phase.

Fig. 23 X-ray powder diffraction pattern for Y3TaO7 at room temperature

Results and discussion

44

Fig. 24 XRD pattern for Y3TaO7; enlargement showing the orthorhombic phase pattern

This first positive result allowed to continue for the second step, the substitution of Y3+ ion for a lower valence one in order to create oxygen vacancies in the fluorite-related phase, therefore enhancing the conditions for conducting oxide ions. Calcium and strontium were tried, attempting at obtaining a Y3xMexTaO7 solid solution with x = 0.1. A very first sign of a successful substitution is a change in the lattice parameters, compared to those of the non-doped compound: in accordance with Vegard's law, it exists a linear relation between the crystal lattice parameters of a solid solution and the concentration of the doping agent. It must be said that this is an empirical rule so it is not sufficient to confirm the substitution but it is anyway a good start.

Results and discussion

45

The experimental pattern was therefore refined in order to find a value for the cubic lattice parameter that was influenced to a lesser extent by the experimental conditions. For Y3TaO7 both phases were considered by imposing the Fm 3 m space group for the cubic one and the C2221 space group for the orthorhombic one; fig. 25 shows the refined pattern while results are displayed in legend.

Fig. 25 Fitted profile for Y3TaO7: cubic, space group Fm 3 m and orthorhombic, space group C2221. Cubic phase - Lattice parameter a = 5.25739(4) Orthorhombic phase - Lattice parameters a = 10.42639(36) , b = 7.42912(12) , c = 7.42020(12) Rp = 14.8%; Rwp = 23.5%; Rexp = 6.05%; 2 = 15.1 !

Results and discussion

46

Y2.9Ca0.1TaO6.95 For the Y2.9Ca0.1TaO6.95 phase some results were positive but further investigations are needed because although the Ca2+ ion seems to be entered within the structure, since the cubic lattice parameter has changed (from 5.25739 to 5.25814 ), an unexplained reflection occurred in the XRD pattern. The XRD pattern of the Ca2+-added Y3TaO7 phase was refined considering only the cubic phase since it is the one to consider in discussing the cubic lattice parameter variation; the fitted profile is shown in fig. 26. Figure 27 shows an enlargement of the experimental XRD diagram with the unexplained peak.

Fig. 26 Fitted profile for Y2.9Ca0.1TaO6.95, cubic, space group Fm 3 m. Lattice parameter a = 5.25814(9) ; Rp = 15.0%; Rwp = 22.1%; Rexp = 6.06%; 2 = 13.3
!

Results and discussion

47

Fig. 27 XRD pattern for Y2.9Ca0.1TaO6.95. Enlargement showing the unexplained peak

Y2.9Sr0.1TaO6.95 For the Y2.9Sr0.1TaO6.95 phase something can instead be stated: the solid solution was not obtained because during the synthesis a phase separation occurred and the Y(Sr0.5Ta0.5)O3 phase was formed (fig. 28 and 29), polluting the main fluorite-type compound. For the experimental conditions in which the reaction was carried out the substitution was impossible so the solid solution doesn't exist or, at least, a change in the experimental conditions is needed.

Results and discussion

48

Fig. 28 XDR patterns for Y3TaO7 (black) and the Sr2+-added phase (red, up-shifted); a. entire dagrams and b. enlargement showing some of the reflections due to the Y(Sr0.5Ta0.5)O3 phase

Fig. 29 Reflections due to the Y(Sr0.5Ta0.5)O3 phase

Results and discussion

49

Yb3TaO7 and related phases

Yb3TaO7 The Yb3TaO7 phase has a cubic fluorite-type structure, an fcc lattice with fully occupied anion sites. Fig. 30 and 31 show the experimental XRD pattern and the fitted profile, respectively. In fig 32 the XRD diagrams with raising temperature, in fig. 33 the DSC performed on the compound and in fig. 34 the thermal variation of the cubic lattice parameter. Data collected show that the phase is stable at least until 1300C with no phase transition occurring and that it has a lattice parameter that changes linearly with the raising temperature. Proofs of its stability until 1700C can be found in the literature [27]. Having a pure compound opens the door on the possibility of doping the phase with lower valence cations, such as Sr2+ and Ca2+.

Fig. 30 X-ray powder diffraction pattern for Yb3TaO7 at room temperature

Results and discussion

50

Fig. 31 Fitted profile for Yb3TaO7, cubic, space group Fm 3m. Lattice parameter a = 5.19448(4) ; Rp 10.2%; Rwp 13.6%; Rexp 6.57%; 2 = 4.1
!

Fig. 32 a. XRD diagrams for Yb3TaO7 with raising temperature in air; b. enlargement of the red highlighted Braggs peaks (the firsts on the left)

Results and discussion

51

34 29 24 Heat flow (V) 19 14 9 4 -1 0 200 400 600 800 1000 1200 1400 Temperature (C)
Fig. 33 DSC performed on Yb3TaO7 in air, heating rate 5C/min

5.25 5.24 Lattice parameter () 5.23 5.22 5.21 5.20 5.19 0 200 400 600 Temperature (C) 800 1000 1200

Fig. 34 Thermal variation of the cubic lattice parameter, a, in Yb3TaO7

Results and discussion

52

Yb2.9Sr0.1TaO6.95 In the same attempt at creating oxygen vacancies, it was tried to make the strontium ion enter the structure of Yb3TaO7 by replacing the Yb3+ ion. What happened is that even for Yb2.9Sr0.1TaO6.95 a phase separation occurred during the synthesis and the SrYb0.5Ta0.5O3 phase was formed (fig. 35 and 36), polluting the main fluorite-type compound: the solid solution Yb3xSrxTaO7x/2 cannot exist if one adopts the experimental conditions that were successful for the synthesis of the non-doped Yb3TaO7.

Fig. 35 XDR patterns for Yb3TaO7 (black) and the Sr2+-added phase (red, up-shifted); a. entire diagrams and b. enlargement showing some of the reflections due to the SrYb0.5Ta0.5O3 phase

Results and discussion

53

Fig. 36 Reflections due to the SrYb0.5Ta0.5O3 phase

Yb3xCaxTaO7x/2 To replace Yb3+ ions for the Ca2+ ones a change in the experimental conditions was tried. Two degree of substutition were tried: for x = 0.05 the temperature raises between the heating steps were made smaller and the phase was formed at 1550C; for the x = 0.1 compound the same conditions used for the Sr-doped one gave a positive answer. Fig. 37 shows the XRD diagrams of the three phases: x = 0, x = 0.05 and x = 0.1. Data were, then, refined and the results are shown in fig. 38 and 39.

Results and discussion

54

Fig. 37 XRD patterns for the Yb3xCaxTaO7x/2 solid solution; x = 0 in black, x = 0.05 in red, x = 0.1 in blue

Fig. 38 Fitted profile for Yb2.95Ca0.05TaO6.975, cubic, space group Fm 3m. Lattice parameter a = 5.19672(9) ; Rp = 12.2%; Rwp = 15.9%; Rexp = 8.52%; 2 = 3.5
!

Results and discussion

55

Fig. 39 Fitted profile for Yb2.9Ca0.1TaO6.95, cubic, space group Fm 3m. Lattice parameter a = 5.19662(4) ; Rp = 10.8%; Rwp = 14.2%; Rexp = 6.68%; 2 = 4.5
!

From the XRD diagrams of the Ca2+ doped phases it cannot be seen any phase separation but the variation of the lattice parameter as the presence of calcium ions becomes higher doesn't follow the Vegard's law (fig. 40). Anyway the Vegard's law is only an empirical rule so further investigations are needed. What the experiments with the yttrium and the ytterbium phases show is that the Sr-doped compounds are harder to obtain than the Ca-doped ones. This can be explained by the larger ionic radius of the Sr2+ ion compared to that of the Ca2+ ion, 112 pm versus 99 pm. While calcium ion seems to replace the yttrium ion (ionic radius 89.3 pm), with which the diagonal relationship also might be invoked, and the ytterbium one (85.8 pm) in the fluorite-related lattice, the strontium ion seems too big to fit their place.

Results and discussion

56


Fig. 40 Evolution of the cubic lattice parameter a with increasing Ca2+ presence. Error is reported as 3

Bi3TaO7 and related phases

-Bi2O3 has a disordered cubic fluorite structure and exhibits one of the highest known oxide ion conductivities, 2.3 S cm1 at 800C. The reasons for that relatively high conductivity are [28]: a. 1/4 of the oxygen sites are vacant in the fluorite-type lattice; b. the electronic structure of Bi3+ is characterized by the presence of 6s2 lone pair electrons, leading to high polarizability of the cation network, which in turn leads to oxide ion mobility; c. the ability of the Bi3+ to accommodate highly disordered surroundings.

Results and discussion

57

This phase is stable only between 730C and 825C but the substitution of bismuth cations by others can lead to its room temperature stabilization. Ta5+ is such a cation, giving, by a 25% molar substitution, the phase Bi3TaO7, a yellow compound with a fcc fluorite-type structure belonging to the Fm 3 m space group. Abrahams et al. [6] proposed a structure in which there are chains of apical sharing TaO6 octahedra, explaining that as a consequence of the presence of tantalum: such chains would make the structure similar to a weberite (fig. 41), at which we can look as a defect-fluorite by considering only the cationic array.

Fig. 41 The structure of the weberite Na2MgAlF7

Bi3TaO7 Figure 42 shows the X-ray diffraction pattern for Bi3TaO7 at room temperature while figure 43 shows the refined diffraction diagram: red dots for the experimental diagram, black profile for the calculated one and blue profile for the difference between them.

Results and discussion

58

Fig. 42 X-ray powder diffraction pattern for Bi3TaO7 at room temperature

Fig. 43 Fitted profile for Bi3TaO7, cubic, space group Fm 3m. Lattice parameter a = 5.45761(9) ; Rp 16.0%; Rwp 21.0%; Rexp 7.53%; 2 = 7.8
!

Results and discussion

59

The difference between the experimental diagram and the calculated one, represented by the blue profile on the refined pattern, might seem not negligible but such difference arises from the presence of preferential orientations due to the preparation of the sample for the XRD analysis. The teflon sample holder gives a parasite reflection at 2 18: given the absence of Braggs reflections related to the main phase in those proximities, the refinement was made by excluding the region around that peak; the blank space in the diagram is due to that reason. The X-ray powder diffraction profile reveals a superlattice ordering (fig. 44), better shown by the neutron diffraction pattern (fig. 45), arising from a threedimensionally modulated incommensurate structure:

Fig. 44 X-ray powder diffraction for Bi3TaO7. Enlargement showing a superlattice reflection (green mark)

Results and discussion

60

Fig. 45 Neutron diffraction pattern for Bi3TaO7 at room temperature in air. Black marks indicate the first order Bragg reflections, green ones the second order reflections due to the superlattice structure

The second order Bragg peaks were indexed by using a single modulation parameter, = 0.3780(3) (courtesy of Pascal Roussel). Considering that the reflections due to that incommensurate structure are observed with greater intensity on the neutron diffraction profile, we can say that most likely this kind of structure involves oxygen atoms. Such incommensurately modulated structure, with an underlying average fluorite unit cell that has the space group symmetry Fm 3 m, is known in the literature as Type II [29]. A careful analysis of the diffraction profile reveals, besides, the presence of ! another phase (fig. 46a and 46b), Bi7Ta3O18, with peaks of slight intensity that grow as temperature rises (fig. 47).

Results and discussion

61

Fig. 46a X-ray powder diffraction for Bi3TaO7 and enlargement showing the Braggs peaks related to the Bi7Ta3O18 phase

Fig. 46b Enlargement showing a portion of the diffraction pattern of Bi7Ta3O18

Results and discussion

62

Fig. 47 Growing of the peaks related to the phase Bi7Ta3O18 as temperature rises: syntesized compound (black), 3 hours sintering at 950C (red) and 3 hours sintering at 1000C (blue)

The presence of the phase Bi7Ta3O18 can be attributed to the sublimation of Bi2O3 (melting point 825C) as suggested by the lowering of the Bi/Ta molar ratio, equals to 3 in Bi3TaO7 and to 2.3 in Bi7Ta3O18. The Bi7Ta3O18 phase is labelled in the literature as a Type II* structure, a commensurately modulated -Bi2O3-related phase. This is not, anyway, the right way to refer at it strictu sensu. The space group symmetry is triclinic C1 but is very close to monoclinic C2/m. The metal atom array is approximately face-centred cubic, punctuated by regularly spaced displacement faults. The coordination environments of the Bi atoms appear to be related to the cubic (eightfold) coordination found in fluorite, distorted by the presence of TaO6 octahedra: this leads to pyramidal and trigonal prismatic coordination

Results and discussion

63

environments, typically observed around cations with stereochemically active electron lone pairs, such as Bi3+ [30]. Bi3TaO7 reveals so its instability with rising temperature; conversely it can be said that both phases and their relative abundances are stable from room temperature up to 900C (the synthesis temperature) being the diffraction diagrams the same after every further thermal treatment: they do not make Bi2O3 to sublime any more nor any phase transition occurs as it is shown by the thermal analysis (fig. 48). The XRD diagrams (fig. 49a and 49b) show that the Bi7Ta3O18 phase is still there, though its main reflection is progressively hidden by the left shift of the Bi3TaO7 phase's peak at 2 28.2, produced by the raise of temperature. Fig. 50 shows the thermal variation of the cubic lattice parameter, that reveals a small degree of non-linearity above ca. 500C.

16 14 12 Heat flow (V) 10 8 6 4 2 0 -2 -4 0 200 400 600 Temperature (C) 800 1000

Fig. 48 DSC performed on Bi3TaO7 in air, heating rate 5C/min

Results and discussion

64

Fig. 49a a. XRD diagrams for Bi3TaO7 with raising temperature in air; b. enlargement of the red highlighted Braggs peaks (the first on the left)

Fig. 49b The phase Bi7Ta3O18 is still visible from room temperature up to 900C

Results and discussion

65

5.52 5.51 Lattice parameter () 5.50 5.49 5.48 5.47 5.46 5.45 0 100 200 300 400 500 600 700 800 900 1000

Temperature (C)

Fig. 50 Thermal variation of the cubic lattice parameter, a, in Bi3TaO7

Bi3xLaxTaO7 Despite the presence of the Bi7Ta3O18 phase, whose presence is almost negligible but still identifiable, the substitution of the bismuth ion with the other cations was tried. The results for the solid solutions with La2O3 were conflicting: although the XRD diagrams don't show any phase separation and furthermore the increasing presence of lanthanum seems to inhibit the formation of Bi7Ta3O18 (fig. 51), the evolution of the lattice parameter with the increasing lanthanum presence doesn't follow the Vegard's law (fig. 52). In figures 53 and 54 the refined diffraction profiles for Bi2.95La0.05TaO7 and Bi2.9La0.1TaO7

respectively.

Results and discussion

66

Fig. 51 a. XRD patterns for the Bi3xLaxTaO7 solid solution; x = 0 in black, x = 0.05 in red, x = 0.1 in blue b. enlargement showing the disappearing of the main reflection due to Bi7Ta3O18 while lanthanum presence increases

Fig. 52 Evolution of the cubic lattice parameter a with increasing La3+ presence. Error is reported as 3

Results and discussion

67

Fig. 53 Fitted profile for Bi2.95La0.05TaO7, cubic, space group Fm 3m. Lattice parameter a = 5.45901(6) ; Rp 13.7%; Rwp 17.2%; Rexp 7.38%; 2 = 5.4
!

Fig. 54 Fitted profile for Bi2.9La0.1TaO7, cubic, space group Fm 3m. Lattice parameter a = 5.45821(9) ; Rp 18.1%; Rwp 23.3%; Rexp 7.28%; 2 = 10.2
!

Results and discussion

68

Other evidences that would confirm or refute that the substitution had actually taken place can be provided by the examination of the Raman scattering spectra and, in particular, of the band at ca. 748 cm1 that can be related to the TaO bond stretching. Fig. 55 compares the portion of interest of the spectra of the La-doped compounds with that of Bi3TaO7 (courtesy of Annick Rubbens). The change of the tantalum surroundings, as a result of the introduction of La3+ cations within the structure, would cause a shift of the emitting frequencies of the band but none seems to have occurred, thus most likely the substitution has not taken place.

Fig. 55 Raman scattering spectra of the Bi3xLaxTaO7 solid solutions

Results and discussion

69

Bi3xSrxTaO7x/2 The data collected in the case of the Sr-doped compounds suggest that a solid solution exists for 0 < x 0.1: no phase separation has occurred (fig. 56); there is a linear relation between the strontium concentration and the evolution of the lattice parameter (fig. 57); a slight lower frequencies shift of the band at ca. 748 cm1, ascribable to the TaO bond stretching, is observed while increasing molar substitution (fig. 58). It was observed also that the Bi7Ta3O18 phase does not appear in the Sr-doped phases (fig.59), despite the preparation was almost the same than that of Bi3TaO7 (up to 900C). In figures 60 and 61 the refined diffraction profiles for Bi2.95Sr0.05TaO6.975 and Bi2.9Sr0.1TaO6.95 respectively.

Fig. 56 XRD patterns for the Bi3xSrxTaO7x/2 solid solution; x = 0 in black, x = 0.05 in red, x = 0.1 in blue

Results and discussion

70

Fig. 57 Evolution of the cubic lattice parameter a with increasing Sr2+ presence. Error is reported as 3

Fig. 58 Raman scattering spectra for the Bi3xSrxTaO7x/2 solid solution

Results and discussion

71

Fig. 59 XRD diagrams for the Bi3xSrxTaO7x/2 solid solution: x = 0 in blue, x = 0.05 in red, x = 0.1 in green. The Bi7Ta3O18 phase (dark blue marks) is not present in the Sr2+-doped compounds

Fig 60 Fitted profile for Bi2.95Sr0.05TaO6.975, cubic, space group Fm 3m. Lattice parameter a = 5.45631(4) ; Rp 10.5%; Rwp 13.4%; Rexp 7.87%; 2 = 2.9
!

Results and discussion

72

Fig. 61 Fitted profile for Bi2.9Sr0.1TaO6.95, cubic, space group Fm 3m. Lattice parameter a = 5.45474(8) ; Rp 14.7%; Rwp 18.4%; Rexp 8.13%; 2 = 5.12
!

How the strontium ion influences the conducting properties of Bi3TaO7

Once verified the existence of the Bi3xSrxTaO7x/2 solid solution, the second step was the preparation of the samples for the electrical measurements, that is making the tablets. Tablets must be compact and their relative density has to approach as much as possible the theoretical one, in the case of Bi3TaO7 equals to 9.478 g/cm3 [6].

Results and discussion

73

Attaining the maximum relative density is important because conductivity is inversely proportional to resistance and the unfilled space within the tablet gives a contribution to the latter. Anyway since the objective was to investigate how the strontium ion influences the conducting properties of Bi3TaO7, powders were grounded only manually in the agate mortar, then pressed and shaped as tablets. In table 3 the relative densities of the tablets are summarized.

sample
Bi3TaO7 Bi2.95Sr0.05TaO6.975 Bi2.9Sr0.1TaO6.95

relative density
78.8 % 78.8 % 78.5 %

Tab. 3 Relative densities of the tablets used for the electrical measurements

The size of particles ranged from few m up to 20 m. Fig. 62 shows some SEM images of the particles of the Bi3TaO7 phase while in fig. 63 is shown the surface of the tablet .

Fig. 62 SEM images of Bi3TaO7 particles

Results and discussion

74

Fig. 63 Bi3TaO7; SEM images of the tablet's surface. Scratches and holes keep the tablet from being in perfect contact with the electrodes

By looking at the tablet surface, it can be noticed that there is plenty of scratches and holes. Another contribution to the resistance is given by the imperfect contact between the tablet and the electrode, and it seemed unlikely that the imperfections were formed as a consequence of the size of particles. Even if the contribution to the resistance related to those imperfections could have been negligible, since within the first heating cycle the contact becomes better as the gold-coated surface of the tablet welds to the electrode, by trying to look for the cause of the phenomenon it was discovered an heterogeneity in the appearance of the tablet: the scratches were actually produced during the polishing of the surface by little grains (diameter up to 100 m) dispersed in the tablet matrix, formed during the sintering step. In figure 64 those grains are showed as they appear at the microscope. An XRD analysis was then performed on a sample of a grounded tablet but showed no differences. To investigate the nature of those little grains an analysis with the electron probe microanalyzer was carried out (courtesy of Sverine Bellayer).

Results and discussion

75

Despite the different colour, the analysis confirmed the same composition for the grains and the matrix (fig. 65 a and b).

Fig. 64 Images of the tablet's surface showing the grains dispersed in the tablet matrix

Fig. 65a EPMA analysis of grains

Results and discussion

76

Fig. 65b EPMA analysis of the tablet matrix

Figure 66 a and b and figure 67 a and b show the particles size and the tablet surface of Bi2.95Sr0.05TaO6.975 and Bi2.9Sr0.1TaO6.95, respectively. The size of the particles ranged for both phases from few m to 20 m and the surfaces are scratched in the same manner as the Bi3TaO7 tablet. Even in those tablets the same grains were present and, by induction, it was concluded that they had the same composition as the matrix. All the tablets, thus, presented the same characteristics: their relative densities were very similar, their particles had similar size, their surfaces displayed the same imperfections. Given that, the electrical measurements were performed. Results are shown in the form of an Arrhenius plot in fig. 68 along with -Bi2O3 and YSZ as general terms of comparison.

Results and discussion

77

Fig. 66 SEM images of the Bi2.95Sr0.05TaO6.975 phase; a. particles and b. tablet surface

Fig. 67 SEM images of the Bi2.9Sr0.1TaO6.95 phase; a. particles and b. tablet surface

Results and discussion

78

Fig. 68 Arrhenius plot of total conductivity for the Bi3xSrxTaO7x/2 solid solution and some terms of comparison

The slope change in the x = 0 curve, at around 525C, is reflected in the temperature variation of the cubic lattice parameter of Bi3TaO7 (fig. 50). The conductivity exhibited by Bi3TaO7 is lower than that of -Bi2O3, as expected, for the concentration of vacancies decreases when doping Bi2O3 with a pentavalent oxide like Ta2O5. In fact by expressing the unit cell of Bi2O3 as Bi4O62 (where represents oxygen vacancy) the resulting composition is: 2 [(Bi2O3)1x (Ta2O5)x] Bi4(1x)Ta4xO6+4x24x It may be considered that while the vacancy concentration of pure Bi2O3 is too high for the phase to be stable at low temperature, the filling up of vacancies with the added oxide stabilizes the phase at room temperature [9]. Doping Bi3TaO7 by adding Sr2+ ions within the structure should have been, therefore, a way to enhance its conductivity by introducing oxygen vacancies,

Results and discussion

79

whose concentration is directly proportional to the conductivity itself but the results showed the contrary. In fig. 69 is shown the high temperature portion of the Arrhenius plot of total conductivity for the Bi3xSrxTaO7x/2 solid solution, that is the portion beyond the point where the slope change is observed.

1000/T (K-1) 0.9 0.7 0.95 1 1.05 1.1 1.15 1.2 1.25 1.3

0.2 log ( T) (S cm-1 K)

E0 = 1.18 eV E0.05 = 1.211 eV E0.1 = 1.198 eV

-0.3

-0.8 x=0 -1.3 x = 0.05 x = 0.1 -1.8

Fig. 69 Arrhenius plot of total conductivity for the Bi3xSrxTaO7x/2 solid solution (high temperatures)

It is taken for granted that the observed conductivities are due mainly to mobile O2 ions whose drifting, in Bi3TaO7, has an activation energy of 1.18 eV, in good accordance with the value reported in the literature, 1.16 eV [6]. The lower conductivity showed by the doped samples can partly be explained with the shrinking of the lattice parameter, which influences the migration energy of the oxide ions. However more important seems the fundamental difference between the electronic structure of the Sr2+ ion and of the Bi3+ one:

Results and discussion

80

the Bi3+ has a 6s2 lone pair that confers to the ion a high polarizability, crucial to the conducting properties [31]. The role of the latter is even more highlighted at lower temperatures (fig. 70) in the phase with higher substitution degree. In fact the higher concentration of vacancies, created by means of the strontium ion, means also a higher hindrance to the mobility of the oxide ions since that privileged path provided by the Bi3+ ions becomes more limited. Here, at low temperatures, the loss of polarizability play a more important role whereas as temperature raises the contribution of the increasing concentration of vacancies (the intrinsic ones that arise as temperature is increased) tends to erase the initial disadvantage.

1000/T (K1) 1.2 0 -1 log ( T) (S cm1 K) -2 -3 -4 -5 -6 -7 x=0 x = 0.05 x = 0.1 E0 = 0.95 eV E0.05 = 1.04 eV E0.1 = 1.08 eV 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1

Fig. 70 Arrhenius plot of total conductivity for the Bi3xSrxTaO7x/2 solid solution (low temperatures)

Results and discussion

81

The measurements performed on Bi3TaO7 also showed the possible aptitude of the phase at conducing protons: in the chart of fig. 71 it can be observed the difference between the curve of total conductivity recorded during the first heating cycle and that recorded during the last one, the fourth. The two curves rejoin at ca. 400C, probably when all the water leaves the tablet. Given that the phenomenon is observed only during the first heating cycle while the other three give the same curves, protons might give some contribution to the total conductivity, as they do in La3TaO7 [4].

Fig. 71 Arrhenius plot of total conductivity for Bi3TaO7. Curves related to the first heating cycle and to the fourth one

Results and discussion

82

Conclusions

This scientific research explored the possibility to develop new electrolyte materials for solid oxide fuel cells. The basic research deals with the synthesis and the characterization of new oxide ions conductors starting from the former experiences in this domain and trying to answer to the need for more performing materials mainly for what concerns the lowering of operating temperatures. This work looked at several phases starting from the synthesis and coming to the substitution of cations for lower valence ones to obtain new doped phases. Some syntheses did not succeed, as in the case of LaTa3O9, for which a different method must be tried since a classic solid-state reaction cannot lead to the desired compound. For some others, as in the case of the niobate Pr3NbO7 and the tantalate Pr3TaO7, the lack of time did not allow to continue through the substitution step and the investigation stopped with the definition of a procedure for the syntheses which must involve an accurate reduction of the size of the reagents' particles in order to obtain the desired phases. Some other syntheses were successful: for Y3TaO7 and Yb3TaO7 the second step followed, the attempt at substituting the Y3+ ion and the Yb3+ one, respectively, for lower valence cations such as Sr2+ and Ca2+. Unfortunately

Conclusions

83

all the substitutions involving the Sr2+ ion did not succeed since phase separations occurred whereas on the XRD diagram of the phase Y2.9Ca0.1TaO6.95 a peak has remained unexplained . The only solid solution that seems to exist is Yb3xCaxTaO7x/2 although further investigations are needed to confirm it. What seems to be a preference for the calcium ion can be explained by considering its size that is smaller than that of the strontium one, therefore it can enter within the structure. A deeper investigation was carried out on the Bi3TaO7 phase, a yellow compound with a fluorite-type structure. Abrahams et al. [6] proposed a structure in which there are chains of TaO6 octahedra that would make the structure similar to a weberite, at which we can look as a defect-fluorite by considering only the cationic array. Preux [4] investigated the weberite-related phase La3TaO7 and its solid solution La3xSrxTaO7x/2, showing that for x = 0.1 we get a material with substantially enhanced conducting properties. Two substitution, thus, were tried: Bi3+ for La3+, to explore the possibility to obtain a solid solution in order to find an answer to the compatibility issues of Bi-based compounds in the reducing conditions of SOFC devices; Bi3+ for Sr2+, to see if the latter could enhance the conducting properties of Bi3TaO7 as it does for the La3TaO7 phase. While the existence of the Bi3xLaxTaO7 solid solution is questionable, the data collected by means of the X-ray diffraction and the Raman scattering spectroscopy confirmed the existence of a Bi3xSrxTaO7x/2 solid solution for 0 < x 0.10.

Conclusions

84

Such result allowed to go into the next step: how the presence of the strontium ion influences the conducting properties of Bi3TaO7. By means of the impedance spectroscopy technique it was discovered that doping the Bi3TaO7 phase by adding Sr2+ ions within the structure doesn't lead, as hoped, to a material with enhanced oxide ions conducting properties. In fact, despite the increase of oxygen vacancies concentration, the doped phases are worst conductors. This is due mainly to the differences in the electronic structure between the strontium ion and the bismuth one: the latter has a 6s2 lone pair, high polarizable, which is of central importance for the conducting properties of the non-doped phase and, in general, of all -Bi2O3 related phases. The electrical measurements performed on Bi3TaO7 also showed the possible property of the phase at conducing protons, therefore further investigations in this direction might be carried out.

Conclusions

85

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