Superionic

Electrochemistry is concerned with the study of the interface between an electronic and an ionic conductor and, traditionally, has concentrated on (i) the nature of the ionic conductor, which is usually an aqueous or (more rarely) a non-aqueous solution, polymer or superionic solid containing mobile ions (ii) the structure of the electrified interface that fonns on inunersion of an electronic conductor into an ionic conductor and (iii) the electron-transfer processes that can take place at this interface and the limitations on the rates of such processes. 

Berendsen, H.J.C. Van Gunsteren, W.F. Molecular dynamics with constraints, in The Physics of Superionic Conductors and Electrode Materials ed. J.W. Perram, NATO ASI Series B 92 (1983) 221-240 (Plenum, New York). 

The most direct effect of defects on tire properties of a material usually derive from altered ionic conductivity and diffusion properties. So-called superionic conductors materials which have an ionic conductivity comparable to that of molten salts. This h conductivity is due to the presence of defects, which can be introduced thermally or the presence of impurities. Diffusion affects important processes such as corrosion z catalysis. The specific heat capacity is also affected near the melting temperature the h capacity of a defective material is higher than for the equivalent ideal crystal. This refle the fact that the creation of defects is enthalpically unfavourable but is more than comp sated for by the increase in entropy, so leading to an overall decrease in the free energy... 

The transport of charged ions in alkali halides and, later on, in (insulating) ceramics is a distinct parepisteme, because electric fields play a key role. This large field is discussed in Schmalzried s 1995 book, already mentioned, and also in a review by one of the pioneers (Nowick 1984). This kind of study in turn led on to the developments of superionic conductors, in which ions and not electrons carry substantial currents (touched on again in Chapter 11, Section 11.3.1.1). 

Crystalline ionic conductors. Superionic conductors have already been briefly introduced in Section 1.2.2.2. They have been known for quite a long time, and a major NATO Advanced Study Institute on such conductors was held as early as 1972 (van Gool 1973). Of course, all ionic crystals are to a greater or lesser extent ionically conducting - usually they are cationic conductors, because cations are smaller than anions. Superionic conductors typically have ionic conductivities lO" times higher than do ordinary ionic crystals such as KCl or AgCl. 

Electrochemistry plays an important role in the large domain of. sensors, especially for gas analysis, that turn the chemical concentration of a gas component into an electrical signal. The longest-established sensors of this kind depend on superionic conductors, notably stabilised zirconia. The most important is probably the oxygen sensor used for analysing automobile exhaust gases (Figure 11.10). The space on one side of a solid-oxide electrolyte is filled with the gas to be analysed, the other side... 

Today, the term solid electrolyte or fast ionic conductor or, sometimes, superionic conductor is used to describe solid materials whose conductivity is wholly due to ionic displacement. Mixed conductors exhibit both ionic and electronic conductivity. Solid electrolytes range from hard, refractory materials, such as 8 mol% Y2C>3-stabilized Zr02(YSZ) or sodium fT-AbCb (NaAluOn), to soft proton-exchange polymeric membranes such as Du Pont s Nafion and include compounds that are stoichiometric (Agl), non-stoichiometric (sodium J3"-A12C>3) or doped (YSZ). The preparation, properties, and some applications of solid electrolytes have been discussed in a number of books2 5 and reviews.6,7 The main commercial application of solid electrolytes is in gas sensors.8,9 Another emerging application is in solid oxide fuel cells.4,5,1, n... 

Among all semiconductor NPs, metal selenides have been the focus of great attention due to their importance in various applications such as thermoelectric cooling materials, optical filters and sensors, optical recording materials, solar cells, superionic materials, laser materials and biological labels. Many synthetic methods have been developed for the preparation of relatively monodispersed selenide nanopartides (Murray et al., 1993 Korgel... 

Voltaic cells have been used by Malov et al. to investigate several silver salts, including superionic electrolytes synthesized on the basis of Agl, such as AgRbb, AgSI, and Agf,W04l4. 

Because of the high values of conductivity which in individual cases are found at room temperature, such compounds are often called superionic conductors or ionic superconductors but these designations are unfounded, and a more correct designation is solid ionic conductors. Strictly unipolar conduction is typical for all solid ionic conductors in the silver double salts, conduction is due to silver ion migration, whereas in the sodium polyaluminates, conduction is due to sodium ion migration. 

Lindan PJD, Gillan MJ (1993) Shell-model molecular-dynamics simulation of superionic conduction in CAF2. J Phys Conden Matter 5(8) 1019—1030... 

Single and mixed oxides synthesised using these procedures are widely probed as cathode materials, superionics, magnetic materials, catalysts, and other multipurpose materials [4-20],... 

Volume 26 III-V Compound Semiconductors and Semiconductor Properties of Superionic Materials... 

Superionic conducting glass systems, 12 586 Superior vena cava, 5 80 Super iron cells, 3 431t Superlattice(s), 13 499, 19 166 via MOCVD, 22 158-160 Superleaks, 17 354 Super Lewis acids, 12 191 Superluminscent LEDs, 22 176 Supermilling acid dyes, 26 396 Super milling dyes, 9 184, 185 Super-moire pattern, 17 428 Supermolecular organization, of polyamide fibers, 19 740... 

More recent quantum-based MD simulations were performed at temperatures up to 2000 K and pressures up to 30 GPa.73,74 Under these conditions, it was found that the molecular ions H30+ and OH are the major charge carriers in a fluid phase, in contrast to the bcc crystal predicted for the superionic phase. The fluid high-pressure phase has been confirmed by X-ray diffraction results of water melting at ca. 1000 K and up to 40 GPa of pressure.66,75,76 In addition, extrapolations of the proton diffusion constant of ice into the superionic region were found to be far lower than a commonly used criterion for superionic phases of 10 4cm2/s.77 A great need exists for additional work to resolve the apparently conflicting data. 

The superionic phase has been explored with more extensive CPMD simulations.69 Calculated power spectra (i.e., the vibrational density of states or VDOS) have been compared with measured experimental Raman spectra68 at pressures up to 55 GPa and temperatures of 1500 K. The agreement between theory and experiment was very good. In particular, weakening and broadening of the OH stretch mode at 55 GPa was found both theoretically and experimentally. 

Figure 8 The phase diagram of H20 as measured experimentally68 (black solid) and through first principles simulations of the superionic phase (gray dash).68,69 The estimated ZND state of HMX is shown as a square for reference.

The calculated diffusion constants of hydrogen and oxygen atoms are shown in Figure 9. The inset plot shows the equation of state for this isotherm for both L and S simulations. The two results are virtually identical up until 2.6 g/cc. At 34 GPa (2.0 gIcc), the hydrogen atom diffusion constant has achieved values associated with superionic conductivity (greater than... 

In contrast, the O diffusion constant drops to zero at 75 GPa (2.6 g/cc) for both L and S initial configurations. The surprisingly small hysteresis in the fluid to superionic transition allows us to place the transition point between 70 GPa (2.5 g/cc) and 77 GPa (2.6 g/cc). The small hysteresis is most likely caused by the weak O-H bonds at the conditions studied, which have free energy barriers to dissociation comparable with kBT (see below). Simulations that start from the L initial configurations are found to quench to an amorphous solid upon compression to 2.6 g/cc. 

Concomitant with the change in the oxygen coordination number is a shift of the first minimum of the O-H RDF from 1.30 A at 34 GPa to 1.70 A at 115 GPa. We observe a similar structural change in the H-H RDF in which the first peak lengthens from 1.63 A (close to the result for ambient conditions) to 1.85 A. These observations bear a strong resemblance to the ice VII to ice X transition in which the covalent O-H bond distance of ice becomes equivalent to the hydrogen bond distance as pressure is increased.82 However, the superionic phase differs from ice X, in that the position of the first peak in g(RoH) is not half the distance of the first 0-0 peak.82 We analyze the effect... 

Given the above definition of a bond distance, we can analyze species lifetimes. The lifetime of all species is less than 12 fs above 2.6g/cc, which is roughly the period of an O-H bond vibration (ca. 10 fs). Hence, water does not contain any molecular states above 75 GPa and at 2000 K but instead forms a collection of short-lived transient states. The L simulations at 2.6g/cc (77 GPa) and 2000 K yield lifetimes nearly identical to that found in the S simulations (within 0.5 fs), which indicates that the amorphous states formed from the L simulations are closely related to the superionic bcc crystal states found in the S simulations. 

S. Hull, Rep. Prog. Phys., 67, 1233 (2004). Superionics Crystal Structures and Conduction... 

Science, 283, 44 (1999). Superionic and Metallic States of Water and Ammonia at Giant Planet Conditions. 

NASICON, the acronym for Na superionic conductor, is a non-stoichio-metric framework zirconophosphosilicate (Kreuer et al, 1989). It is... 

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