Solid state ionics

Solid-state ionics is the study of ionic-electronic mixed conductor and fully ionic conductors (solid electrolytes) and their uses. Some materials that fall into this category include inorganic crystalline and polycrystalline solids, ceramics, glasses, polymers, and composites. Solid-state ionic devices, such as solid oxide fuel cells, can be much more reliable and long-lasting, especially under harsh conditions, than comparable devices with fluid electrolytes. The field of solid-state ionics was first developed in Europe, starting with the work of Michael Faraday on solid electrolytes Ag2S and PbF2 in 1834. Fundamental contributions were later made by Walther Nernst, who derived the Nernst equation and detected ionic conduction in heterovalently doped zirconia, which he applied in his Nernst lamp. Another major step forward was the characterization of silver iodide in 1914. Around 1930, the concept of point defects was established by Yakov Frenkel, Walter Schottky and Carl Wagner, including the development of point-defect thermodynamics by Schottky and Wagner; this helped explain ionic and electronic transport in ionic crystals, ion-conducting glasses, polymer electrolytes and nanocomposites. In the late 20th and early 21st centuries, solid-state ionics focused on the synthesis and characterization of novel solid electrolytes and their applications in solid state battery systems, fuel cells and sensors. The term solid state ionics was coined in 1967 by Takehiko Takahashi, but did not become widely used until the 1980s, with the emergence of the journal Solid State Ionics. The first international conference on this topic was held in 1972 in Belgirate, Italy, under the name "Fast Ion Transport in Solids, Solid State Batteries and Devices".

History

Foundations

In the early 1830s, Michael Faraday laid the foundations of electrochemistry and solid-state ionics by discovering the motion of ions in liquid and solid electrolytes. Earlier, around 1800, Alessandro Volta used a liquid electrolyte in his voltaic pile, the first electrochemical battery, but failed to realize that ions are involved in the process. Meanwhile, in his work on decomposition of solutions by electric current, Faraday used not only the ideas of ion, cation, anion, electrode, anode, cathode, electrolyte and electrolysis, but even the present-day terms for them. Faraday associated electric current in an electrolyte with the motion of ions, and discovered that ions can exchange their charges with an electrode while they were transformed into elements by electrolysis. He quantified those processes by two laws of electrolysis. The first law (1832) stated that the mass of a product at the electrode, Δm, increases linearly with the amount of charge passed through the electrolyte, Δq. The second law (1833) established the proportionality between Δm and the "electrochemical equivalent" and defined the Faraday constant F as F = (Δq/Δm)(M/z), where M is the molar mass and z is the charge of the ion. In 1834, Faraday discovered ionic conductivity in heated solid electrolytes Ag2S and PbF2. In PbF2, the conductivity increase upon heating was not sudden, but spread over a hundred degrees Celsius. Such behavior, called Faraday transition, is observed in the cation conductors Na2S and Li4SiO4 and anion conductors PbF2, CaF2, SrF2, SrCl2 and LaF3. Later in 1891, Johann Wilhelm Hittorf reported on the ion transport numbers in electrochemical cells, and in the early 20th century those numbers were determined for solid electrolytes.

First theories and applications The voltaic pile stimulated a series of improved batteries, such as the Daniell cell, fuel cell and lead acid battery. Their operation was largely understood in the late 1800s from the theories by Wilhelm Ostwald and Walther Nernst. In 1894 Ostwald explained the energy conversion in a fuel cell and stressed that its efficiency was not limited by thermodynamics. Ostwald, together with Jacobus Henricus van 't Hoff, and Svante Arrhenius, was a founding father of electrochemistry and chemical ionic theory, and received a Nobel prize in chemistry in 1909. His work was continued by Walther Nernst, who derived the Nernst equation and described ionic conduction in heterovalently doped zirconia, which he used in his Nernst lamp. Nernst was inspired by the dissociation theory of Arrhenius published in 1887, which relied on ions in solution. In 1889 he realized the similarity between electrochemical and chemical equilibria, and formulated his equation that correctly predicted the output voltage of various electrochemical cells based on liquid electrolytes from the thermodynamic properties of their components. Besides his theoretical work, in 1897 Nernst patented the first lamp that used a solid electrolyte. Contrary to the existing carbon-filament lamps, Nernst lamp could operate in air and was twice more efficient as its emission spectrum was closer to that of daylight. AEG, a lighting company in Berlin, bought the Nernst's patent for one million German gold marks, which was a fortune at the time, and used 800 of Nernst lamps to illuminate their booth at the world's fair Exposition Universelle (1900).

Ionic conductivity in silver halides

Among several solid electrolytes described in the 19th and early 20th century, α-AgI, the high-temperature crystalline form of silver iodide, is widely regarded as the most important one. Its electrical conduction was characterized by Carl Tubandt and E. Lorenz in 1914. Their comparative study of AgI, AgCl and AgBr demonstrated that α-AgI, is thermally stable and highly conductive between 147 and 555 °C; the conductivity weakly increased with temperature in this range and then dropped upon melting. This behavior was fully reversible and excluded non-equilibrium effects. Tubandt and Lorenz described other materials with a similar behavior, such as α-CuI, α-CuBr, β-CuBr, and high-temperature phases of Ag2S, Ag2Se and Ag2Te. They associated the conductivity with cations in silver and cuprous halides and with ions and electrons in silver chalcogenides.

Point defects in ionic crystals

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