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Ionic Conduction in the Solid State

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Ionic Conduction in the Solid State J. Chem. Sci., Vol. 118, No. 1, January 2006, pp. 135–154. © Indian Academy of Sciences. Ionic conduction in the solid state P PADMA KUMAR and S YASHONATH Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012 e-mail: [email protected] Abstract. Solid state ionic conductors are important from an industrial viewpoint. A variety of such conductors have been found. In order to understand the reasons for high ionic conductivity in these sol- ids, there have been a number of experimental, theoretical and computational studies in the literature. We provide here a survey of these investigations with focus on what is known and elaborate on issues that still remain unresolved. Conductivity depends on a number of factors such as presence of interstitial sites, ion size, temperature, crystal structure etc. We discuss the recent results from atomistic computer simula- tions on the dependence of conductivity in NASICONs as a function of composition, temperature, phase change and cation among others. A new potential for modelling of NASICON structure that has been proposed is also discussed. Keywords. Ionic conduction; solid state; atomistic computer simulations; NASICON structure. 1. Introduction 2. A brief history of superionic conductors There exist many solids with high ionic conductivity The study of ionic conduction in solid state origi- (>10–4 W–1 cm–1) and they are of immense use in di- nated way back in 1838 when Faraday discovered verse technological applications. Some of these solids that PbF2 and Ag2S are good conductors of electri- which are also good electronic conductors are often city.2,3 These solids are, the first ever discovered referred to as ‘mixed conductors’, while the term solid electrolyte and intercalation electrode respecti- ‘superionic conductor’ or ‘fast ion conductor’ is re- vely. The discovery of good Na+ mobility in glass by served for good ionic conductors with negligible Warburg4 as well as the first transference number electronic conductivity.1 One of the most important measurements by Warburg and Tegetmeier5 are im- use of superionic conductors is, as electrolytes in portant contributions in the study of solid ionic con- battery applications and hence, often, they are re- ductors. Yttria (Y2O3) stabilized zirconia (ZrO2), ferred to as ‘solid electrolytes’ as well. There are after Nernst6 in 1900, as well as AgI, after Tubandt many advantages in electrochemical devices using and Lorenz7 in 1914, are among the other superionic solid electrolytes instead of liquid electrolytes. conductors discovered in the early days. Katayama8 These include, among others, longer life, high energy in 1908 demonstrated that fast ionic conduction can density, no possibility of leak etc., and are particu- be made use of in potentiometric measurements. larly suitable in compact power batteries used in Another important discovery is that of the first solid pace-makers, mobile telephones, laptops etc. Mixed oxide fuel cell by Baur and Preis9 in 1937 using yttria- ion conductors find application in electrochemical stabilized zirconia as the electrolyte. The field of devices as electrode materials. solid electrolytes did not seem to have gained much Here we provide a survey of the literature of the in the later years until in 1957 Kiukkola and Wag- solids with high ionic conductivity. Some of the de- ner10 carried out extensive potentiometric measure- velopments in the past 3–5 years may not be dis- ments using solid electrolyte based electrochemical cussed here. sensors. 11 Silver ion conducting solids, such as Ag3SI and 12,13 RbAg4I5, were discovered in the 1960s. The use 14 of Ag3SI, by Takahashi and Yamamoto, and 15 RbAg4I5, by Argue and Owens, in electrochemical Dedicated to Prof J Gopalakrishnan on his 62nd birthday cells were demonstrated soon after this. There was a *For correspondence burst of enthusiasm following the discovery of high 135 136 P Padma Kumar and S Yashonath ion mobility in b-alumina (M2O.xAl2O3, where M = conductors are motivated by the small ionic radii of + Li, Na, Ag, K, Rb, NH4 etc.) by Yao and Kummer in Li , its lower weight, ease of handling and its poten- 16 1967. Na-b-alumina was successfully used in Na/S tial use in high energy density batteries. Li2SiO4 is cell by Kummer and Weber.17 The discovery of b- one of the earliest superionic solids known.26 alumina, an excellent solid electrolyte with a fairly Li2SiO4 as well as many solid solutions involving it rigid framework structure, boosted searches for shows high ionic conductivity and has been the sub- 27–29 30 newer superionic conductors with skeleton structures. ject of many interesting studies. Li2SiO4 as This led to the synthesis of gallates, by Kuwabara well as its non-stoichiometric solid solution Li4–3x 18 19 31 and Takahashi and Boilot et al, and ferrites, by Al3SiO4 (0 £ x £ 0×5) are promising Li superionic Takahashi et al,20,21 which are b-alumina type com- conductors. Some of the important Li ion conductors 32,33 pounds with the Al replaced by Ga and Fe respecti- that have attracted investigations are Li3N, Li- 34 35 vely. Lamellar structures of the kind K0×72L0×72M0×28O2, b-alumina, NASICON type, LiZr2(PO4)3, 35 where L = Se or In and M = Hf, Zr, Sn, and LiHf2P3O12 etc., ternary chalcogenides like Li- 36 37 Na0×5In0×5Zr0×5S2 or Na0×8Zr0×2S2 having high electrical InS2, Li4B7O12X (X = Br, Cl or S). conductivities were also synthesized following While most of the superionic conductors dis- this.22,23 cussed above are crystalline, many glassy38–40 as Another advance in the tailored making of superi- well as polymer41–44 electrolytes are also being studied onic solids was when Hong24 and Goodenough et extensively. al25 reported high conductivity in ‘skeleton’ struc- tures involving polyhedral units. The skeleton struc- ture consists of a rigid (immobile) subarray (sub- 3. Conduction mechanisms lattice) of ions which render a large number of For ionic conductivity, transport of one or more three-dimensionally connected interstitial sites suit- able for long range motion of small monovalent types of ions across the material is necessary. In an cations.25 Hong reported synthesis and characteriza- ideal crystal all constituent ions are arranged in regular periodic fashion and are often stacked in a tion of Na1+xZr2SixP3–xO12, where 0 £ x £3, now pop- ularly known as NASICONs.25 It is observed that close-packed form. Thus there is little space for an ion to diffuse. Often, the available space is just the best conductor of the series is Na3Zr2Si2PO12 (x = 2). Its conductivity is comparable to Na-b- enough for vibration around its equilibrium position. However, at any non-zero temperature there exist alumina above 443 K. Na3Zr2Si2PO12 is the first re- ported Na+ ion conductor with three dimensional defects. These could, for example, be positional dis- conductivity. Hong24 reported the synthesis and order due to deviation from ideal stacking. The de- structure of Li, Ag and K counterparts of NASI- gree of such disorder can vary from one material to another or even from one temperature or pressure to CONs as well. LiZr2(PO4)3 is yet another superionic conductor at high temperature. The enormous ionic another in the same material. At zero temperature the free energy is dominated by the potential energy. substitutions possible in NaZr2(PO4)3 led to the syn- thesis of a very large number of compounds which Hence the arrangement of ions in an ideal crystal at now find applications in diverse fields of materials zero temperature is such that the total potential en- science. ergy of the system is the lowest. As the temperature Goodenough et al25 investigated the possibility of of the system increases, the contributions to free en- fast ion transport in various other skeleton structures ergy from entropy becomes more and more promi- as well. The other skeleton structures examined in- nent. The entropy, as it is often described, is a cludes that of the high-pressure-stabilized cubic Im3 measure of the degree of disorder. Thus the origin of phase of KSbO3 and NaSbO3, defect-pyrochlore the crystal defect arises from the system attempting structure of the kind AB2X6, carnegieite structure of to minimize the free energy through an increase in high-temperature NaAlSiO4 as well as the NASI- the entropy. 25 CONs. While the Na3Zr2Si2PO12 is found to be the Two types of defects important in the context of best in the series, NaSbO3 is also a promising mate- ion mobility in crystals are ‘Schottky’ and ‘Frenkel’ rial for solid electrolyte applications.25 defect. These belong to the class of ‘point defects’ Since 1970, a good number of studies focusing on in crystals. Schottky defect refers to the crystal im- the synthesis and characterization of lithium ion perfection in which a pair of ions, one cation and the conductors appeared. Search for the lithium ion other an anion, disappears leaving their positions Ionic conduction in the solid state 137 vacant. A single ion missing from its regular posi- These are generally poor ionic conductors like, tion and wandering in interstitial sites results in NaCl, KCl etc. Frenkel defect. Interstitial sites have different envi- Type II: Ionic solids with high concentration of ronments, in terms of the number or type of their defects, typically, ~1020 cm–3 at room temperature neighbours or its separation from the neighbours, belong to this category. These are generally good than the regular sites. Interstitial sites, or simply in- ionic conductors at room temperature and, often, terstitials, are not energetically favourable for ions; fast ion conductors at high temperatures. Stabilized their occupancy, though, is driven by entropy en- ZrO2, CaF2 etc. are examples. hancement discussed earlier.
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