CHAPTER I INTRODUCTION

1.1 A Brief History of Fast Ionic Conductors Solid state ionics concerns properties associated with the motion of ions in solids [1]. It provides scientific support for a wide variety of advanced electrochemical devices such as batteries, fuel cells, chemical sensors, gas separation membranes and ionic switches. Numerous solids with high ionic conductivity at room temperature are extensively used in technological applications and are named as fast ionic conductors (FIC). One of the indispensable uses of FICs is as electrolytes in battery applications; hence those are referred as solid electrolytes. Longer life, high energy density, less possibilities of leak etc., are some of the advantages of using solid electrolytes in electrochemical devices against the liquid electrolytes. The study of ionic conduction in solids was initiated in 1838, when Faraday discovered PbF2 and Ag2S as good conductors of electricity. In subsequent years, a variety of solids exhibiting appreciably high ion conductivity at their operating temperature was recognized. Silver ion conducting solids of the type, RbAg4 I5, were discovered in early sixty and were used in electrochemical cells [2]. The Na-alumina was successfully used in Na/S batteries by Kummer and Weber [3]. Hong [4] and Goodenough et al., [5] reported in 1976 a high ion conducting skeleton structure having polyhedral units popularly known as NASICON (Na Super Ion CONductor). The polyhedral skeleton structure consists of rigid (immobile) subarray which provides a large number of three dimensionally connected interstitial sites suitable for long range motion of monovalent cations. In contrast to -Al2O3,3 in this mixed zirconate-phosphate compound, Na+-ions move within three dimensional channels of the structure. Analogous compounds, such as LISICON, were synthesized shortly thereafter [5]. From 1970 onwards, a number of studies focusing on the synthesis and characterisation of lithium ion conductors were reported. The enhanced interest on lithium ion conductors were driven by the small ionic radii, lower weight, ease of handling and its potential use in high energy density batteries. Li4SiO4 as well as its non-stoichiometric solid solution Li4-3xAl3SiO4 (0x0.5) were promising Li fast ionic conductors.

Otto et al., [6], was the first to report the glass compositions (M2O-SiO2-Bi2O3 with M=Li, Na) with exceptionally high alkali-ion conductivity at relatively low temperatures, thereby demonstrating that long range order was unnecessary to support the fast ion conduction. Further, important developments in solid electrolytes in this period included the discovery of fast ionic conduction in inorganic glasses [6] and polymers [7]. The general requirements for practical solid electrolytes are: (1) high ionic conductivity (2) negligible electronic conductivity (3) stability with respect to adjacent phases, thermal and electrochemical decomposition (4) suitable mechanical properties (5) ready availability of chemical constituents (6) ease of fabrication (7) reasonable cost and are particularly suitable in compact power batteries used in pacemakers, mobile telephones and laptops. Similar to electronics, progress in solid state ionics motivated major technological developments, especially in the field of energy storage and conversion. The mixed conductors-electronic and ionic-play a critical role, particularly as electrodes in electrochemical devices. Future developments in the industrialized world depend largely on the existence of sufficient energy resources. The consumption of fossil fuels, however, depletes available reserves and leads to severe environmental problems, including acid rain and global warming by emission of NOx, SO2 and CO2. Methods for decreasing these emissions include improving the efficiency of combustion engines or by converting the hydrocarbons, CO and NOx emissions into environmentally harmless products. Gas sensors operating in the feedback mode with microprocessors and fuel injectors are essential for such tasks. Indeed, one of the major successes of solid state ionics in this century is the use of sensors based on ZrO2 solid electrolyte in almost every automobile produced worldwide. One of the major challenges in solid state ionics continues to be the development of more selective electrochemical sensors capable of detecting a broader variety of gases, including NOx, SO2, CO and CO2 with response times often in the millisecond range. Besides energy conversion and storage, solid state ionics offers potential solutions for energy conservation. This is based on the development of smart electrochromic windows in which charge transferred between anode and cathode of an appropriately designed thin film battery, applied to a glass window can be used to vary the optical reflectivity of the multilayer film over wide limits. Thus, during midday, when solar absorption is normally highest, a high reflectivity can be tuned in 2

order to minimize the heat absorption, thereby decreasing the need for air conditioning. Alternatively, on cold days, the reflectivity edge can be shifted to longer wavelengths, thereby transmitting the visible spectrum, to trap the heat. Remaining challenges include means for preparation of uniform coatings over large area at low cost and continued efficient operation for long periods. Nanocrystalline materials have shown several interesting properties and are explored in different applications [8]. However, in many cases, the physical mechanisms responsible for the interesting properties are not completely known yet. One important example is the enhancement of ionic conductivity in nanostructured solid electrolytes. In fact, now a days nanoionics is one of the recent fields of research related to nanomaterials and several applications are being explored, e.g. rechargeable lithium ion batteries, gas sensors and solid oxide fuel cells. The materials in nanoscale have a large number of grain-boundaries and atoms present on the surface. These surface atoms influence the defect thermodynamics considerably.

1.2 Classifications of Ionic Conductors Electrical conduction occurs by long range migration of either electrons or ions. Usually conduction by one or other type of charge carrier dominates, but in some inorganic materials, both ionic and electronic conductions are appreciable. The specific conductivity for any charge carrier is: where, is the number of charge carriers of the species i, is its charge and is its Migration of ions does not occur to appreciable extent in most of the ionic and covalent solids. Atoms tend to be essentially fixed on their lattice sites and can move via crystal defects. Only at high temperatures the defect concentrations become quite large and conductivity becomes appreciable. The conductivity of NaCl at 800C, i.e., just below its melting point is 10-3Scm-1, whereas, at room temperature pure NaCl is an insulator [9]. There exists a small group of solids namely solid electrolytes or fast ionic conductors, in which, one set of ions can move easily. Such materials have special crystal structures, i.e., there are open tunnels or layers through which the mobile ions = (1.1)

mobility. For few of the materials other than metals, conductivity increases with temperature.

can move easily. The conductivity values of Na+ ion migration in -alumina at 25C is 10-3Scm-1, is comparable to those observed for strong liquid electrolytes. Existence of disorder or defect is necessary for ionic transport in solids; and the density of defects depends on various factors like structure, temperature, presence of impurity ions, nature of chemical bonding between the constituent ions etc. [10]. A lot of research work is being carried out in order to find the materials with improved ionic conductivity. The ion conducting materials are classified based on doping approach and structure.

1.2.1 Doping Strategies Homogeneous doping with appropriate elements is one approach to obtain materials with high ionic conductivity. These types of compounds contain an ion with different valency to maintain the bulk electrical neutrality and the supplementary defects are created. Depending on the types of defects different materials are investigated.

1.2.1.1 Fluorite-Type Compounds Oxides with fluorite-type structure (e.g. ZrO2, CeO2, ThO2) can form solid solutions with lower valence cations like CaO, Y2O3 and other rare earth oxides resulting in 10%-15% oxygen deficiencies. These materials find application in cathode materials, gas sensors, catalysts and in oxygen storage materials. Fluoride ion conduction is common in materials with fluorite structure; where PbF2 shows significant conductivity, but CaF2, SrF2 and BaF2 are moderate fluoride ion conductors [11]. Aliovalent doping is used to enhance the low temperature ionic conductivity in these materials [12].

1.2.1.2 Perovskites Compounds in perovskite or related structures have many applications in high performance electroceramics, including high-TC superconductors, dielectrics,

piezoelectrics and ferroelectrics [13]. The chemical formula of these compounds is ABO3, few of these materials show mixed conductivity. It can accommodate dopant cations in A and B sites, which improve its electronic or oxygen ion conductivity [14]. Depending on the cation radii, ideal cubic structure may deform to lower symmetry.

(i) Solid Oxide Fuel Cell Electrode Materials Oxygen ion conduction in perovskite like La1xCaxAlO3 and CaTi1xAlxO3 is 3x10-2Scm-1 at 1000C. The ability of perovskite structures to accommodate multivalent titanium ion contributes to the mixed ionic and electronic conductivity. Goodenough et al.,[15] examined highly oxygen deficient perovskite related brownmillerite structures of the form A2B2O5, at elevated temperatures that change to perovskite structure.

(ii) Proton Conductors Most of the proton conductors discovered initially were hydrates and were thermally unstable [16]. Iwahara and coworkers [17] did pioneering investigations on proton conduction at high temperatures in perovskite oxides, ABO3, where A=Ba, Sr and B=Ce, Zr. 1.2.2 Structurally Disordered Materials 1.2.2.1 Crystalline Compounds with Disordered Sub-Lattice In this type of materials, highly disordered sub-lattice exists, where the number of equivalent sites is greater than the number of ions to fill it [18]. This results in exceptionally high mobile carrier concentrations (1022cm3) and diffusion coefficients are comparable to those in liquids (typically ~10-5cm2 s-1). The carrier concentrations are much higher than in classical solid ionic conductors (typically 10 15 to 1018cm-3) where, the causes of point defects are thermal activation, deviations from stoichiometry or doping.

(i) Noble metal Halides and Chalcogenides High ionic conductivity and low activation energy of -AgI is due to the presence of many randomly accessible almost equivalent sites with small energy barriers in the body centered cubic structure. The -CuBr is structurally analogous to -AgI, exhibits high ionic conductivity. Major work was done to stabilize the structure to the room temperature.

(ii) Bismuth Oxide and BIMEVOX Compounds The Bi2O3 and mixed bismuth oxides exhibit high oxide ion conductivity. The low temperature semiconducting -modification transforms to -phase at 730C [19] 5

and is accompanied by an oxide ion conductivity jump of almost three orders of magnitude. -Bi2O3 presents disordered fluorite type structure, where a quarter of the oxygen sites are intrinsically empty. The polarizability of bismuth cation is responsible for its high anion conductivity and is one to two orders of magnitude higher than doped ZrO2. Attempts to stabilize -phase to the lower temperature, led to a new family called BIMEVOX compounds [20], in which vanadium is partially substituted by low valence cations like Cu, Ni or Co. These compounds present high mixed conductivity with remarkable oxygen ion conductivity at moderate temperatures. These are promising compounds for use in oxygen separation membranes with high permeation rates [21].

(iii) Pyrochlores These compounds have the general formula, A(III)2B(IV)2O6X, where X is an anion that can be oxygen. It is a superstructure of defect fluorite lattice with exactly twice the lattice parameters. This materials degree of disorder can be varied almost continuously from low to high values using solid solution systems. Two types of disorders are important in pyrochlores i.e., Frenkel like disorder on anion sub-lattice and anti-site disorder on cation sub-lattice where A and B cations switch positions [22].

(iv) NASICON Type Compounds NASICON is a family of compounds of general formula, Na1+xZr2(P1xSixO4)3 (0<x<3), where excess charge of the dopant is counter balanced by sodium ions. The NASICON frame-work is built of (Si,P)O4, tetrahedra and ZrO6, octahedra, which provide relatively open three dimensional network of sites for Na+ ions. This material presents an unusually high ionic conductivity (optimized at x=2) and relatively low activation energy. G. Govindaraj et al., studied the ac electrical properties of glassy NASICON materials in detail [23]. NASICON has been proposed as the sensitive membrane of Na+ ion selective electrode with better selectivity than classical glass electrodes [24].

1.2.2.2 Layered Compounds (i) Lithium Insertion Compounds Lithium insertion is essential for the development of rechargeable lithium batteries. The first layered compound with Li+ ion conductivity is Li3N. Doping with hydrogen, Li3-xH xN, is essential because the substitutional hydrogen leaves vacancies for Li+ ion conduction. However, low decomposition voltage limits its use as solid electrolyte in batteries. (ii) -Alumina Crystal structure of this compound is related to that of Al2O3. In -Al2O3 structure, planes with sodium ions are intercalated between blocks with the normal spinel structure, hence a general formula NaAl11O17 is obtained. However, this compound is not stable and can be stabilized by partial substitution of Al by divalent cations like Mg giving "-alumina. Sodium ions are mobile in the planes producing anisotropic ionic conductivity in -alumina [25]. The conductivity depends on ionic radius and is best for ion size intermediate between sodium and potassium.

1.2.2.3 Tunnel Compounds Tunnel compounds support ionic conduction along one dimensional channel. Basic limitations are due to the anisotropy of ionic conduction. Examples are hollandites, with general composition BaxMn8O16(x<2), with tunnels parallel to the crystallographic c-axis. The priderites have the chemical formula, Ax(B,Ti)8O 16 (A=alkali metal, B=Mg, Zr and Ga), which have the same structure and show alkali ion conduction along the tunnels. Higher conductivities at high alternating current frequency may relay on alkali ion oscillation between bottlenecks in the tunnels.

1.2.2.4 Amorphous Materials Amorphous materials intrinsically exhibit three dimensional disorders. The transport mechanisms in glasses are substantially less understood than in crystalline materials. Advantages of glassy fast ionic conductors over crystalline include isotropic conduction, absence of highly resistive and corrosion sensitive grain boundaries, wide compositional flexibility and ease of fabrication. Fast ionic conductivity is observed in many glasses, especially those with small cations like Ag, 7

Cu, Li and Na [26]. Ternary glasses contain a network former (e.g. SiO2, B2O3, P2O5 and GeS2), network modifier (e.g. Ag2O, Li2O, Cu2O and Ag2S) and dopant compound, mostly a halide (e.g. AgI, CuI and LiCl). As the term implies, the glass network structure and its physical and chemical properties can be substantially modified by addition of modifier. Dopant salts apparently do not interact strongly with network; cation and anion dissolve into interstices of the glass structure. Increased ion conductivity can be resulted from the carrier density and/or carrier mobility. According to the weak electrolyte model, enhanced conduction is primarily due to dissociation between alkali and halide ions. Others believe that the additives induce major changes in the glass structure, and it has a significant effect on ion mobility. In this model, a large fraction of carriers are assumed to be non associated and free to move in the glass.

1.2.2.5 Composite Solid Electrolytes The development of composite solid electrolytes gives a new degree of freedom in solid state ionics. Mixtures can provide enhanced conductivity together with other useful characteristics such as improved mechanical strength. The conductivity enhancement in numerous ceramic composites was reported. Besides Al2O3, other oxides such as MgO, SiO2, CeO2, TiO2 and ferroelectric BaTiO3 was found to be the effective second phases for ionic conductivity improvement. More recently, the composite effect was also observed in anion conductors, such as lead or calcium fluoride and even in inorganic solids with trivalent cation conductivity, such as aluminium and rare-earth wolframates [27].

1.3 Technological Applications of Fast Ion Conducting Materials 1.3.1 Batteries Power storage devices require high energy density batteries. The highest possible energy density is achieved using reactants with high free energy of reaction and low mass such as lithium or sodium. This requires that the solid electrolytes remain stable under highly reducing or highly oxidizing conditions. Silver and copper fast ion conductors were initially used to design advanced solid state batteries. The anisotropic conductivity of layered compounds led to the development of improved solid electrolytes such as NASICON. There is an increasing demand for microbatteries compatible with microelectronics technology related 8 to the

development of laptop computers or portable telephones. This led to the development of a high energy density and long cycle life rechargeable lithium batteries. Suitable solid electrolytes for lithium batteries should have the requirements: (1) high Li+ ion conductivity (2) compatibility with lithium metal or high lithium activity electrodes (3) high decomposition voltage and (4) ease of thin film fabrication. Many systems based on metallic lithium suffered from problems due to metal oxidation and poor rechargeability due to the formation of metallic dendrites. The alternative is based on lithium insertion compounds LixWO2 and LiyTiS2, but was unable to provide sufficiently high energy density. Improved rechargeable lithium ion batteries were based instead on nongraphitic carbons as the lithium insertion anodes [28]. The insertion of lithium into normal graphite was unsuccessful and other materials tested include certain zinc blende structure materials. The successful association of hard carbon insertion anodes with the high voltage LiCoO 2 insertion cathode was a major breakthrough [28]. Because of the relatively high cost of cobalt, alternative systems based on other cathode materials such as LiNiO2 or LiMn2O4 are currently under investigation. The three dimensional spinel LiMn2O4 is

environmentally friendly and inexpensive, but it suffers from several drawbacks, especially storage losses [29]. Presently, electrolytes are nonaqueous liquids, such as ethylene carbonate or propylene carbonate with dissolved metal salts, including LiPF6. Hybrid electrolytes based on polymers impregnated with liquid electrolytes is in the development stage [29].

1.3.2 Solid Oxide Fuel Cells Solid oxide fuel cells provide many advantages over traditional energy conversion systems. It include s high energy conversion efficiency, fuel flexibility because of internal reforming, very low levels of NOx, SOx emissions and long lifetime because of the elimination of corrosive liquids [30]. Operation at an elevated temperature is necessary because the solid electrolytes have relatively low ionic conductivities and slow electrode processes at low temperatures. Furthermore, mechanical stability and compatibility of the materials require improvement and costs need to be decreased. It consists of two porous electrodes separated by a dense oxygen ion electrolyte. Several important material requirements must be satisfied for the optimal operation of solid oxide fuel cells: (1) suitable electrical properties (high oxygen ion conductivity and low electronic conductivity for electrolyte material and 9

mixed conduction for electrodes) (2) adequate chemical and structural stability under conditions of operation (3) minimal reactivity and inter diffusion between components and (4) matching thermal expansion coefficients.

1.3.3 Sensors Monitoring of chemical processes in real time enables closer quality control of the products. Electrochemical microsensors transform a chemical signal into an electrical signal that is easy to measure, monitor and process. Ionic and mixed conducting solids are basic materials for its development because they can be easily miniaturized, for instance, in thin film form and can be operated at elevated temperatures or in an aggressive environment. Sensor development is largely driven by the following requirements: high sensitivity, selectivity, short response time, reproducibility, long term stability, lifetime, reversibility, size and low cost. The three major types of electrochemical sensors are [31]:

(i) Potentiometric Sensors In this type, the concentration or partial pressure of a species is determined by measuring emf of solid electrolyte. The potentiometric sensors are categorized in to three groups: (a) Oxygen Sensors: The most successful commercial sensor is the oxygen sensor using stabilized ZrO2 as solid electrolyte. (b) Gas Sensors: These sensors detect the atmospheric pollution gases using cation conducting metal salts as solid electrolytes like Ba(NO3)2 for NO2, K2SO4 for SO2, and K2CO3 for CO2. (c) Ion Sensors: An ion sensor (selective electrode) measures ion concentrations in solution. It contains an ion conducting membrane in contact with solution, an internal reference and a metal connector. The measured membrane potential depends on ion activity according to Nernsts law. Sodium and lithium ions have been detected with NASICON type membranes. (ii) Amperometric Sensors The amount of excess oxygen or fuel in an exhaust can be determined by measuring the limiting electrochemical current of amperometric oxygen sensors. (iii) Conductometric Sensors It uses the dependence of electrical conductivity of a material on the chemical potential of gaseous species. 10

1.3.4 Electrochromic Windows Electrochromic light transmission modulators called smart windows, using solid ionic conductors, are significant in energy savings by regulation of thermal insulation. In such a system, the window is maintained transparent in the visible and reflecting in the infrared during the winter, allowing penetration of sunshine but blocking loss of interior heat. On the other hand, the window is rendered partially opaque during hot summer days, decreasing the amount of radiations entering the building. The electrochromic elements that color or bleach on insertion/deinsertion of lithium or hydrogen ions, are sandwiched between two transparent thin film electrodes and separated by solid electrolyte [32]. The transparent electrodes are generally indium tin dioxide. Glass electrolytes appear as promising choices.

1.4 Polyanionic Frame-work Polyanion compounds containing compact tetrahedral anion structural units (XO4)n- (X=P, Mo, W and S) with strong covalent bonding[33]. These units networked to produce higher coordination sites such as oxygen octahedral, that are occupied by other metal ions. Among the family of (PnO3n+1)(n+2)- polyanions, the polyphosphates can be classified into: (1) orthophosphates (n=1) characterized by (PO4)3- isolated units (2) pyro or diphosphates (n=2) in which P2O7 groups are formed by corner sharing of two (PO4)3- units and (3) triphosphates (n=3) where three (PO4)3units from (P3O10)5- anions. The polyanionic compounds considered under the present study are NASICON and olivine type orthophosphates, which show great interest in rechargeable batteries.

1.5 Review of NASICON 1.5.1 Structure of NASICON Polymorphs Phosphates having NASICON structure are unique due to their properties determined by structure and composition. These properties include high ion conductivity, low (sometimes, negative) thermal expansion coefficient and low thermal conductivity. Its hardness, chemical and thermal stability are also significant. In addition, NASICON phosphates have catalytic activity or luminescent properties and most attractive property is its high ionic conductivity. The general form of NASICON (Na Super Ionic CONductor) type materials is Na3Zr2(SiO4)2(PO4) [34]. 11

The mixed frame-work, [T2(XO4)3]n- has an important role in crystal chemistry of compounds with tetrahedral anions. In this frame-work, all oxygen atoms are shared between XO4 tetrahedra and TO6 octahedra. The element T can be in different oxidation states like +2, +3, +4, +5 and X=Si, P, As, S, Mo and W. Usually monovalent cations compromise negative charges in the frame-work; even multivalent cations are also suitable [35]. In the general, these compounds exist in different polymorphs i.e., rhombohedral, orthorhombic, monoclinic and triclinic with c, P21/n and Cc. Figs. 1.1(a)-(d) show structural polymorphs different space groups R3 of NASICON.

c) Figure 1.1: Structure of NASICON polymorphs: (a) Rhombohedral symmetr ( R3 ) symmetry. (b) Orthorhombic (Pbna) (c) Monoclinic (P21/c) and (d) Triclinic (C 1 (Courtesy: J. Gopalakrishnan et al., and N. Anantharamulu et al.,) available for monovalent alkali atoms i.e., M1 sites surrounded by six oxygen atoms and located at an inversion centre and M2 sites surrounded by ten oxygens and disposed symmetrically around the ternary axis. If the octahedral M1(6b) site is fully occupied, tenfold coordinated M2(18e) site is empty. In Fig. 1.1(a) red circles denote 12 c space group, two different sites are In rhombohedral symmetry with R3

M1 and M2 positions in the interconnected channels within the frame-work. A pair of near lying octahedra is linked through PO4 tetrahedra. Both these sites are arranged in alternating way along the conducting channels. LiGe2(PO4)3 and LiTi2(PO4)3 are crystallized in this symmetry and privileged occupancy of M1 site is deduced from the neutron diffraction experiments [36]. Particular attention has been given to titanium based materials having NASICON structure like Li1+xTi2-xN x(PO4)3, LiTi2xM x(PO4)3

and Li1-xTi2-xR x(PO4)3, where, N, M and R stand for tri, tetra and

pentavalent cations respectively [37]. Various methods are used to increase the conductivity of parent LiTi2(PO4)3 for practical applications, which include addition of Li2O or Li4P2O7 as a binder to increase the density of pellets [38]. Even though, high energy ball-milling is widely used as a method for preparation of samples, few literatures are available about the synthesis of nanocrystalline NASICON materials by this technique. Attempts have been made to increase the conductivity of parent materials by substitution of P in the frame by V or Sb [39]. The ball-milling technique is used to enhance the electrical properties in LiTi2(PO4)3 and in Al and V substituted LiTi2(PO4)3 materials. The crystal structure and conductivity are determined by size of guest (or mobile) cation in the frame-work. The MIIZr2(PO4)3 (MII= Mg, Ca, Sr, Ba, Mn, Co, Ni, Zn, Cd and Pb) crystallize in NASICON or -Fe2(SO4)3 type structure depending on the ionic radii of M2+ [40]. Mg, Co, Ni and Zn are crystallized in -Fe2(SO4)3 type structure and showed an order-disorder transition between 600C-720C. But, Ca, Sr, Ba, Cd and Pb compounds crystallize in NASICON type structure and the phase is stable from room temperature to 1000C. The Mn based compounds sinter at 900 C crystallize in -Fe2(SO4)3 type structure and those sinter above 900C crystallize in NASICON structure. LiZr2(PO4)3 shows change in crystal structure with sintering temperature; those sinter between 1000C-1100C is crystallized as mixture of two phases [41]. The Li3Fe2(PO4)3 synthesized by Masquelier et al., [42] is crystallized in three different forms, i.e., -monoclinic (P21/n), -monoclinic (P21/n) and -rhombohedral c). Li3Fe2(PO4)3 is crystallized in Fe2(SO4)3 form of monoclinic symmetry (P21/n) (R3 by solid-state reaction. The monoclinic cell results from small distortion of the orthorhombic frame-work due to lithium ion ordering at room temperature. dYvoire et al., and Bykov et al., [43] showed that monoclinic Li3Fe2(PO4)3 transforms 13

reversibly to orthorhombic structure on heating above 270C due to progressive breaking of long range ordering of Li+ ions in the interstitial space. Na3Fe2(PO4)3 has monoclinic C2/c structure with two formula units, i.e., Z=2 at room temperature [44]. The monoclinic -phase is formed (C2/c) at 368K and above 418K rhombohedral c). phase exist ( R3

Ion exchange method has been explored for synthesis of NASICON

compounds that cannot be prepared by conventional techniques. The rhombohedral form of Li3Fe2(PO4)3 is prepared by ion exchange method from Na3Fe2(PO4)3. The room temperature -Na3Fe2(PO4)3 has an ordered distribution of Na+ ions, that resulted in a slight distortion of rhombohedral frame-work to monoclinic symmetry (C2/c) [45]. The substitution of Na+ by Li+ through ion exchange leads to disordered c) -Li3Fe2(PO4)3. This technique is used to prepare Li3Fe2(AsO4)3 rhombohedral (R3

from Na3Fe2(AsO4)3, and the material is crystallized in rhombohedral symmetry [42]. Similar observations are reported by Delmas et al., [46] for ATi2(PO4)3 (A=Li, Na), attributed to vacant M1 sites along C axis, resulting in higher electrostatic repulsion between TiO6 octahedra. In general, an insignificant distortion of hexagonal lattice reduces the symmetry to monoclinic with P21/n or C2/c symmetries with one angle close to 120. The monoclinic distortion (C2 /c or Cc) splits M2 sites to: 3(M2) hex(M3+2M4)mon and octahedral M1 site shares faces with two adjacent TO6 octahedra. The formed groups

O3TO3M1O3TO3 are mutually linked along the hexagonal c axis by XO4 tetrahedra. The infinite ribbons resulting from the linking are connected together normally to c axis by XO4 tetrahedra and M2 sites are situated between these ribbons. In rhombohedral phase, building blocks are aligned parallel to hexagonal c-axis, while in monoclinic phase; these are aligned perpendicular to one another. In some cases, the symmetry is deteriorated to triclinic, as reported by M. Catti et al., in LiZr2(PO4)3 [47]. In this case, unit cell may be chosen with one angle close to 120 and the other two close to 90. Thus, the structural resemblance to the above mentioned phases is quite evident. The rhombohedral and monoclinic structural modifications differ in three dimensional connectivity between T2(XO4)3 lantern units. There is a significant difference between monovalent cation sites between two phases. In orthorhombic symmetry (Pcan), cations fully occupy three distinct crystallographic sites; M2 and M3 are in five fold coordination and M1 is in four fold coordination. 14

1.5.2 Phase Transition in NASICON Polymorphs The Na3Fe2(PO4)3 showed phase transitions at 368K and 418K [43]. The hysteresis is observed in transition temperatures, i.e., there is a shift in the transition temperatures while heating and cooling. The low temperature phase has weak monoclinic distortion induced by interstitial occupancy of sodium ions and its ordering [48]. The cation order disappears upon transition. In the case of Na3Cr2(PO4)3 material, calorimetry experiments showed the phase transitions at 348K, 411K and 439K [49]. X-ray diffraction indicates that the unit cell symmetry is improved upon these transitions and structural aspects of the transitions are discussed by Genkina et al., [50]. The Na3Zr2PSi2O12 phase undergoes a single monoclinic to rhombohedral phase transition unlike the above mentioned compounds [51]. However, this transition occurs over a wide temperature range of about 70K. For lithium double phosphates, phase transition data are less abundant. Monoclinic to rhombohedral phase transition is observed in LiZr2(PO4)3 and transition temperature depends on annealing [52]. Later, another phase was discovered [53]; monoclinic to rhombohedral phase transition in that phase was observed only at 573K. The phase transitions in sodium scandium phosphate Na3Sc2(PO4)3 are studied in detail by L. Boehm et al., [54].

1.5.3 Conductivity in NASICON Polymorphs The maximum conductivity of Na3Zr2Si2PO12 composition falls in the region 0.06 to 0.036Scm-1. The activation energy for conduction in this composition is 1730kJmol-1 and the best conductivity of NASICON family reached 10-1Scm-1 at 570K [55]. The spread in activation energy is due to existence of minor phases, different densities of samples and different techniques used for synthesis. The Na3Sc2(PO4)3 showed dc conductivity of 3x10-6 to 5x10-3Scm-1 at 300K. Activation energy for conduction in -phase is less compared to -phase because more energy is required to transfer cation between M1 and M2 sites [56]. The sodium ion has to pass through a triangular face of trigonal anti-prism and size of face changes in course of phase transition or with temperature. The key parameter that determines anti-prism size is the nature of T and alkali ions. The indium analogue has even lower conductivity at almost all temperature ranges but slightly higher than iron and chromium compounds [57]. NaZr2(PO4)3 shows still lower conductivity even though its unit cell volume is 15

larger than scandium compounds [58]. In this material M1 site is fully occupied and M2 sites are vacant; hence mobile charge carrier concentration is lower in this material compared to Na3A2(PO4)3 type materials, where only two-third of M2 positions are occupied. While, LiZr2(PO4)3 is having higher conductivity in spite of its lower cell volume compared to Na analogue. It is because of the smaller size of Li+ ions, it can overcome the narrow triangular faces of coordination polyhedra easily [59]. Lithium phosphates of trivalent elements like Li3Sc2(PO4)3, Li3Cr2(PO4)3 and Li3Fe2(PO4)3 are in orthorhombic structure in the high temperature phases [60]. Activation energy for conduction decreases for to -phase transition; hence conductivity is more at high temperature phases. But dvoire et al., did not find this tendency [43]. Neutron diffraction is a valuable tool to determine the structural information on lithium ion transport. Powder neutron diffraction of Li1+xFexTi2-x(PO4)3 with x=0.5, at room and high temperatures give the complex pattern of lithium disorder, involving sites lying within both M1and M2 cavities. This suggests high mobility of Li+ ions, in contrast with results obtained for LiM2(PO4)3 and Li3M2(PO4)3 NASICON compounds, where Li is located in one of the sites. On raising the temperature, Li distribution within M1 cavity changes substantially, leaving the M1 site and moving towards peripheral positions [61]. Ion transport in a solid occurs through the transfer of defects; ionic conductivity is the product of defect concentration and mobility. Hence, heterovalent doping increases the ion mobility in NASICON. Materials containing various univalent cations show the minimum conductivity with composition independent of temperature [62]. One of the high ion conducting NASICONs is prepared by partial substitution of phosphorous by silicon in 1:2 ratio [63]. Compounds in which B, As, Al or V partially substitutes for phosphorous are explored and optimization of the conducting properties is achieved for Na1.8Ti2B1.2P1.8O12 [64]. Attempt is made to explore the conductivity studies in Ti based materials, where phosphorous is replaced by pentavalent elements like vanadium, antimony etc. [65]. Ti cation is substituted by trivalent and pentavalent elements and the overall charge is less than five. In Na1+xAlxTi2-x(PO4)3 and Na1+xEu xTi2-x(PO4)3 series, conductivity increases with doping due to increase in charge carrier density [66].

16

The Na1-xNbxZr2-x(PO4)3 and Na1+2xMgxZr2-x(PO4)3 solid solutions are studied by nuclear magnetic resonance spectroscopy and showed that Na atoms are in M1 positions. Partial substitution of Zr causes some of Na+ ion to move from these positions to lower symmetry M2 positions [67]. The substitution of Mg or Zr for chromium i.e., Na3+xCr2-xMgx(PO4)3 and Na3-xCr2-xZr x(PO4)3 decreases the

conductivity. The maximum conductivity is evidenced in NASICON phases containing three sodium ions per formula unit [68]. For lithium systems, the disorder in cation sub-lattice increases the defect concentration. The substitution of tetravalent ion for a trivalent ion generates lithium site vacancies and conductivity increases by several orders of magnitude. Cation mobility and disorder suppress the phase transition temperature. The phase transition temperature is shifted by heterovalent substitution of Zr in LiZr2(PO4)3. 50% of low temperature triclinic phase transforms into high temperature rhombohedral phase when trivalent or pentavalent cations substitute for one percent of zirconium and 5% 10% doping stabilizes the rhombohedral phase at room temperature [69]. The Li NMR spectra and conductivity measurements at low temperatures signify an increase in cation mobility due to generation of extra vacancies and insertion of extra lithium interstitials at low dop ing levels. However, charge carrier concentration decreases at higher pentavalent doping concentration and conductivity decreases [70]. With high chromium concentration, intrinsic rhombohedral phase of LiHf2(PO4)3 is changed to orthorhombic phase [71]. Lithium titanium phosphate crystallizes in rhombohedral symmetry and Ti doping by heterovalent elements are investigated [72]. The compound crystallizes in orthorhombic or monoclinic symmetry at higher doping concentrations. The conductivity passes through a maximum with doping level and is reported for Li1+xTi2-xAlx(PO4)3 (x=0.3) at 570K is 10-2 to 10-3Scm-1. The Li+ ions are disordered between positions of M1 and M2 [73]. Moreover, total electrical conductivity strongly depends on density of the compound and nature of grain-boundaries [74]. Nanostructured materials attracted great interest due to their enhanced properties. Important property is the enhancement in ionic conductivity in nanocrystalline form. In conventional polycrystalline solid electrolytes, grainboundaries partially block the ionic transport, an extra contribution to total conductivity. But in nanostructured materials, grain-boundary diffusion is much

faster than grain diffusion and its volume fraction is more in nanomaterials [75]. 17

Alternate synthesis techniques like wet chemical synthesis and sol-gel procedures are explored for the synthesis of NASICON materials in nanocrystalline form [76]. Solution combustion synthesis is an effective low cost method for the production of ceramic materials in nanocrystalline form, but this technique is rarely used for the synthesis of NASICON materials [77].

1.6 Review of Olivine Based Lithium Metal Phosphates 1.6.1 Structure of Olivine Olivine compounds exhibit high redox potential, fast Li+ ion transport, excellent thermal stability and energy density comparable to that of conventional lithium metal oxides. Moreover, anion substitution can alter the redox potential due to two effects: (i) an inductive effect due to changes in the metal ion energy levels resulting from the changes in the anion group and (ii) production of fewer or more electrons shift the lithium concentration at which given redox reaction takes place. Lithium orthophosphates, LiMPO4, where M=Ni, Fe, Mn and Co assume an olivine related structure, consists of hexagonal closed packing of oxygen atoms with Li+ and M2+ cations located in half of the octahedral sites and P5+ cations in 1/8 of the tetrahedral sites [78]. The LiMPO4 olivine structure consists of PO4 tetrahedra with M2+ ions on the corner sharing octahedral positions and Li+ ions on the edge sharing octahedral positions, the latter running parallel to the b-axis. Figs. 1.2(a)-(b) show the structure of LiNiPO4 in different orientations. Fig. 1.2(a) shows the chains (along the c direction) of the corner sharing NiO6 octahedral layers. Fig. 1.2(b) shows edge sharing LiO6 octahedral chains, which are cross linked by PO4 groups forming the three dimensiona l network. In the hexagonal close packing array of oxide ions Li resides in octahedral sites. Li+ ions on the edge sharing octahedral positions, it is running parallel to the b-axis. These compounds generally crystallize in orthorhombic (Pnma) symmetry, which accommodates four units of LiMPO4. The co-valence of MO bond differs with the degree of co-valence in the P-O bond. In the ordered olivine structure, M3+/M2+ level lies lower than NASICON like frame-work, giving a higher voltage versus lithium. Out of the olivine members, weak ferromagnetism is found for LiNiPO4, LiMnPO4 and LiCoPO4 but not for LiFePO4 [79].

18

Figure 1.2: Olivine structure of LiNiPO4 showing Li ions (yellow spheres), PO4 tetrahedra (red) and NiO6 octahedra (blue) (a) Shows the chains (along the cdirection) of corner sharing NiO6 octahedral layers (b) Shows edge sharing LiO6 octahedral chains which are cross linked by PO4 groups forming the three dimensional network. (Courtesy: J. Gopalakrishnan et al.) Atomistic simulation studies suggest that most favourable intrinsic defect in bulk LiNiPO4 is the anti-site defect, for which a small population (less than 2%) of Li+ and Ni2+ ions are expected to exchange sites [80]. This defect would be temperature dependent and sensitive to experimental synthesis conditions. Structural analysis of hydrothermally synthesized LiFePO4 suggests 3mol% Fe on the lithium sites, while scanning transmission electron microscopy study observed anti-site defects in LiFePO4, quoting a concentration of around 1%. Nickel based olivine has low capacities, less than 125mAhg-1; extremely low conductivities and high oxidation potential of 5V make it unsuitable for use with known electrolytes. The potentials of LiFePO4 and Li3Fe2(PO4)3 in lithium cells range from around 2.5 to 3.5V. This larger difference between Fe2+/Fe3+ and Li/Li+ relative to iron oxides is explained by the inductive effect [81]. The more electronegative the central atom in PO4 groups, higher the cell potential. The presence of PO4 group in the structure causes flow of electron density away from the MO bond.

1.6.2 Conductivity in Olivine Compounds In olivine form of lithium metal phosphates, octahedra are connected to form the tunnel structure. These tunnels are along the b axis but are not connected, so the 19

lithium ions residing in the tunnels cannot readily jump from one tunnel to another. Thus, lithium ion diffusion is one dimensional and any blockage in the tunnel prevents movement of lithium ions [82]. Any attempt to dope these materials with aliovalent ions must ensure that these ions do not reside in the lithium sites, but rather in M sites. The exact mechanism of lithium ion motion in olivine type structures is still not known, but an idea about the magnitude can be obtained from conductivity measurements. The electrical conductivity of pure LiFePO4, synthesized from the non-carbon containing reactants, is less than 10-9Scm-1 [83]. Assuming the conductivity is solely due to lithium ions and all the lithium ions are mobile. In pure LiFePO4, no electronically conducting species is present, so that the total conductivity is as low as 10-11Scm-1[84] and the conductivity is due to motion of lithium ions. Many LiFePO4 samples are prepared using carbon containing precursors such as oxalates, acetates or carbonates, which resulted in some residual carbon in the reducing atmospheres. These samples typically have much higher conductivities, around 10-5 to 10-6Scm-1 but still too low for high power battery applications [85]. Addition of magnesium or titanium resulted in poorer electrochemical performance, perhaps because of occupancy of the lithium sites. Julien et al., reported the electrical conductivity and micro structural properties of LiMPO4 system synthesized by solid-state reaction [86]. The strong covalent bonding between oxygen and P5+ to form (PO4)3- units allow for greater stabilization of the structure compared to layered oxides, e.g. LiCoO2, where, the oxide layers are more weakly bound. This strong co-valency stabilizes the anti-bonding Fe3+/Fe2+ state through Fe-O-P inductive effect. Li intercalation potential for LiNiPO4 is close to 5.1V, which is above the maximum potential that can be tolerated by Li electrolytes and delithiation of LiNiPO4 is not observed.

1.7 Computational Methods The occurrence of fast and inexpensive microcomputers during the past decade has made computational techniques widely available and major progress is seen in last years. The most common computational technique is the finite element calculation: it has been applied to simulate the influence of various experimental parameters on the impedance spectra of electroceramics, including nonhomogeneous 20

contacts and variation of grain-boundary properties. The dynamic and electronic properties of mobile ions in the superionic solids are studied using molecular dynamics simulation [87]. Numerical simulation techniques have been used to model the conductivity of ionic conductor-insulator composites, especially near the percolation threshold [88] and fractal decomposition structures are observed after solid state electrolysis of CuBr films at large direct current voltage [89]. One major goal of computational material science is the predictive capability. Ceder et al., [90] gave an example to calculate the significant enhancement in the open circuit voltage of LixCoO2 cathode materials by the addition of Al2O3. An overview on atomistic computational material science based on quantum chemical concepts can be found in an article by Hafner. Such techniques have been used recently to determine the oxygen migration energies in CeO2 based oxides [91].

1.8 Ionic Conduction in the Bulk: Hopping Model Ionic conductivity is due to the thermally activated ion hopping. D is the diffusion coefficient, a is function of jump distance, 0 is the characteristic attempt frequency, Eh is the free energy of migration and the diffusion coefficient is given by: D=a2 0 exp - k hT
B

(1.2)

The factor takes into account geometrical and correlation effects. The backward jump has higher probability than forward jump and cooperative motion may lead to higher diffusion coefficients than isolated jumps. The mobility, , is related to diffusion coefficient, D as: = k
Dq
BT

(1.3)

Using Eqs. (1.2) & (1.3), the ionic conductivity can be expressed as: dc =ncq=n0 q2 a2 0 exp - k fT exp - k hT /k BT
B B

(1.4)

The creation of charge carriers is thermally activated and carrier density, nc, is of the form: nc=n0 exp - k fT
B

(1.5)

The general form of ionic conductivity, dc, then becomes dc=

0 T

exp k T
B

(1.6) 21

where, is the sum of the migration and formation energies i.e., =f+h. Most of the crystalline and amorphous fast ionic conductors satisfy the Eq. (1.6), where f is negligible.

1.9 Different Relaxation Functions for Understanding the ac Electrical Relaxation Process in Ion Conducting Materials One of the important characteristic properties of electrical conduction in disordered solids is dispersion in ac conductivity. In many non-metallic ionic conductors dc or ac electrical conductivity is the result of diffusion of ions through the conductors. As Almond et al., pointed out, very often the dispersive behavior of ac conductivity of (disordered solids) ion conducting materials can be expressed in the form [92]: ' ()=dc +An (1.7) where, the first term dc is the frequency independent dc conductivity and the second

term is purely dispersive component of the ac conductivity, depends on the measurement frequency, , in a characteristic power law fashion. The frequency

exponent n lies in the range 0.5 to 1 and the parameter A is frequency independent, but may be temperature dependent. The concept of dipoles giving rise to polarization was introduced by Debye and Debye response is obtained for an assembly of non-interacting ideal dipoles. Solid electrolyte materials show a non-Debye dielectric response, characterized by a broad loss peak and constant phase angle behaviour at frequencies above the loss peak [93]. Hence, it is essential to have a proper theoretical understanding of rather general behaviour. In literature, relaxation functions like Cole-Cole, Cole-Davidson, HavriliakNegami, Kohlrausch-William-Watts functions are widely used for the analysis of electrical relaxation process [94]. In general, non-Debye relaxation behaviour can be regarded as arising from the elongation of time scale, i.e., a single effective relaxation time is no longer sufficient to describe the entire relaxational behaviour. The various empirical forms of different relaxation functions are [95]: Cole-Cole function: Z* ()= [1+() cc ] Cole-Davidson function: Z*()=
1 1

(1.8) (1.9)

[1+()] CD

22

Havriliak-Negamai function: Z* ()= [1+()cc ]CD

(1.10)
ww

Williams-Watts stretched exponential function: ww (t)= exp[-

where, 0cc <1, 0<CD 1 , these parameters accommodates the distribution of

(1.11)

relaxation times. The is angular frequency of applied electric field, is the mean

relaxation time. The position of dielectric loss peak is shifted to high frequency (above Debye loss peak) with asymmetry in the loss peak curve in these relaxation functions. In time domain relaxation function, the exponent, 0<ww 1 , ww (t) is
t t

deviating from exponential decay for

non-Debye functions are either inadequate to explain the ac conductivity features or fails to satisfy the linear response theory. Acquiring motivation from this inadequacy of non-Debye functions, an anomalous relaxation function is proposed by Govindaraj et al., [96]. The recently proposed model is capable of explaining the dispersion in electrical relaxation, while satisfying the linear response theory criteria. 1.10 Present Work With the outlook of available literatures, present study explored high energy ball-milling and solution combustion technique for the synthesis of NASICON type materials in nanocrystalline form. The olivine type materials are prepared in nanocrystalline form by solution combustion technique. The following NASICON: (i) LiTi2(PO4)3 Li1.3Al0.3Ti1.7(PO4)2.9(VO4)0.1 Li1.0Al0.4Ti1.7(PO4)2.88(VO4)0.12 Li1.6Al0.2Ti1.7(PO4)2.94(VO4)0.06 (ii) Na3Cr2(PO4)3: Glycine, urea and citric acid in 1:1, 1:2 and 1:3 molar ratios. Li3Fe2(PO4)3: Glycine in 1:2 molar ratio and citric acid-ethylene glycol in 1:1 molar ratio. Na3Fe2(PO4)3: Citric acid-ethylene glycol in 1:1 molar ratio. Li3Fe2-xCr x(PO4)3, where x=0.1, 0.2, 0.3, 0.4, 0.5: Citric acid-ethylene glycol in 1:1 molar ratio. Li3+xFe2-xMgx(PO4)3, where x=0.1, 0.2, 0.3, 0.4, 0.5: Citric acid-ethylene glycol in 1:1 molar ratio.

1 and 1 as ww decreases. The existing

23

and the following olivine: (iii) LiNiPO4: Citric acid in 1:2 molar ratio. LiNi1-xCu xPO4, where x=0.1, 0.2, 0.3, 0.4, 0.5: Citric acid in 1:2 molar ratio. LiNi1-xMgxPO4, where x=0.1,0.2, 0.3, 0.4, 0.5: Citric acid in 1:2 molar ratio. systems are synthesised in the present study. In NASICONs, Li3Fe2-xCr x(PO4 )3, Li3+xFe2-xMgx(PO4)3 and in olivine, LiNi1-xCu xPO4, LiNi1-xMgxPO4 are new series and are not reported in the literature. LiTi2(PO4)3 is one of the well studied NASICON type material because of its reasonably high ion conductivity at room temperature. In the present study, high energy ball-milling technique is explored to increase the conductivity of microcrystalline material by reducing crystallite size. The nanocrystalline material shows one order increase in conductivity compared to the microcrystalline material, due to feasible conduction through grain-boundaries [97, 98]. The average crystallite size decreases with milling duration and the volume fraction of grain-boundaries increases. The Al and V substituted LiTi2(PO4)3 material is ball-milled at different durations and physical and electrical properties are investigated. The Na3Cr2(PO4)3 and Li3Fe2(PO4)3 materials showed reversible structural phase transitions in the microcrystalline form. The present study synthesizes these materials in thermally stable nanocrystalline form by solution combustion technique. Effects of nature of the fuel/chelating agent and its molar ratio on physical and electrical properties of Na3Cr2(PO4)3 are investigated in detail. The electrical properties are found to be dependent on physical properties of the material [99,100]. Nanocrystalline Li3Fe2(PO4)3 is synthesized using glycine and citric acid-ethylene glycol mixture and is crystallized in orthorhombic crystal system with Pcan space group. The improved dc conduction in Li3Fe2(PO4)3, synthesized using glycine, is explained through enhanced hopping rate and unit cell volume. The dc conductivity of Na3Fe2(PO4)3 is higher than Li3Fe2(PO4)3 due to rattling of ions within the large interstitial space available. Li3Fe2(PO4)3 and Na3Fe2(PO4)3 are crystallized in monoclinic symmetry i.e., -Fe2(SO4)3 type structure. In this structure, mobile ions occupy four co-ordination sites which are preferable to six co-ordination sites of NASICON for ion conduction.

24

The effects of B-site ion radius and polarization on the conductivity are investigated by substitution of Fe3+ in Li3Fe2(PO4)3 by Cr3+ and Mg2+ in different compositions. The mobile ion density of Li3Fe2-xCr x(PO4)3 is almost same in the series, but dc conductivity shows increasing trend with Cr3+ substitution, reaching a maximum at x=0.3, owing to its high mobility. The Mg2+ substitution increases Li+ ion occupation rate and the carrier density is apparently the same for all compositions. The substitution of Fe3+ by electropositive Mg2+ increases the ionic character of the skeleton and as a consequence the Li-O bonds are strengthened; hence mobility decrease with composition. The highest conductivity of x=0.1 composition is attributed to its mobility. LiNiPO4 based olivine materials are synthesized using citric acid in 1:2 molar ratio. Solution combustion technique reduces the crystallite size to nanometer range and the electrical conductivity of the sample is improved in nanocrystalline phase. To investigate the effect of octahedral metal ion substitution; LiNi1-xMgxPO4 and LiNi1-xCu xPO4 are (where x=0.1, 0.2, 0.3, 0.4 and 0.5) synthesized. In Mg and Cu substituted series, highest conductivity is exhibited by x=0.1 composition. But compared to the parent material, these compositions didnt show any improvement in conductivity. The decrease in conductivity in other compositions is due to the antisite defect, where a small population of Li+ and Ni2+ ions exchange their sites on the substitution of aliovalent ions for Ni2+. Even though, ac electrical data are analyzed using constant phase element, power law and modulus formalism, the physical picture for the dispersion in ac conductivity still needs further interpretation or an alternate approach. Recently proposed alternate model [96] clearly discerns the fast process from slow relaxation and extracts dc, P and the exponent g. Slow and fast relaxation processes are related

to each other through the parameter g, which quantify the dispersion process in ion conducting solids. Due to the trapping and correlated motions of charge carriers, fast process is getting delayed. The extracted dc and ac electrical parameters of ion conducting solids show good agreement with the experimental observation. The model is successful in explaining the fast and slow relaxation process in glassy systems. As a first attempt, this is demonstrated by analysing the NASICON glassy systems like Li2.6+xTi1.4-xCd(PO4)3.4-x and K2.6+xTi1.4-xCd(PO4)3.4-x (where x=0.4, 0.8

and 1.0) [23].

25

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