Mixed ions-electrons conducting membranes

The process that is the subject of this article consists of the use of high temperature ceramic membranes that selectively transport oxygen. They are referred to with several acronyms of which ITM (Ion Transport Membranes), OTM (Oxygen Transport Membranes) and MIEC (Mixed Ionic Electronic Conducting) membranes prevail. We will use ITM throughout this article. 

Figure 7.9 A schematic of H2 production by H2O dissociation with a mixed oxygen-ion-electron conducting membrane.

Spallina, V., Melchiori, T., Gallucci, F., and van Sint Annaland, M. (2015) Auto-thermal reforming using mixed ion-electronic conducting ceramic membranes for a small-scale H2 production plant. Molecules, 20 (3), 4998-5023. 

Ceramic electrochemical reactors are currently undergoing intense investigation, the aim being not only to generate electricity but also to produce chemicals. Typically, ceramic dense membranes are either pure ionic (solid electrolyte SE) conductors or mixed ionic-electronic conductors (MIECs). In this chapter we review the developments of cells that involve a dense solid electrolyte (oxide-ion or proton conductor), where the electrical transfer of matter requires an external circuitry. When a dense ceramic membrane exhibits a mixed ionic-electronic conduction, the driving force for mass transport is a differential partial pressure applied across the membrane (this point is not considered in this chapter, although relevant information is available in specific reviews). 

Solid-state electrochemistry is an important and rapidly developing scientific field that integrates many aspects of classical electrochemical science and engineering, materials science, solid-state chemistry and physics, heterogeneous catalysis, and other areas of physical chemistry. This field comprises - but is not limited to - the electrochemistry of solid materials, the thermodynamics and kinetics of electrochemical reactions involving at least one solid phase, and also the transport of ions and electrons in solids and interactions between solid, liquid and/or gaseous phases, whenever these processes are essentially determined by the properties of solids and are relevant to the electrochemical reactions. The range of applications includes many types of batteries and fuel cells, a variety of sensors and analytical appliances, electrochemical pumps and compressors, ceramic membranes with ionic or mixed ionic-electronic conductivity, solid-state electrolyzers and electrocatalytic reactors, the synthesis of new materials with improved properties and corrosion protection, supercapacitors, and electrochromic and memory devices. 

Generally, the activation layer is a functionally graded porous structure made of the same composition as the membrane layer. A second case is when the two porous interfaces, acting as mixed ionic/electronic-conducting electrodes, are made of materials different from the membrane (a purely ion-conducting electrolyte), as shown in Figure 9.10c. In this case, the oxygen flux can be precisely controlled by the... 

However, for mixed oxygen ion-electron conducting materials the surface processes can become rate limiting for oxygen transport through the membrane rather than bulk diffusion. Under surface reaction we understand the... 

Solid mixed ionic-electronic conductors (MIECs) exhibit both ionic and electronic (electron-hole) conductivity. Naturally, in any material there are in principle nonzero electronic and ionic conductivities (a i, a,). It is customary to limit the use of the term MIEC to those materials in which a, and 0, 1 do not differ by more than two orders of magnitude. It is also customary to use the term MIEC if a, and Ogi are not too low (o, a i 10 S/cm). Obviously, there are no strict rules. There are processes where the minority carriers play an important role despite the fact that 0,70 1 exceeds those limits and a, aj,i< 10 S/cm. In MIECs, ion transport normally occurs via interstitial sites or by hopping into a vacant site or a more complex combination based on interstitial and vacant sites, and electronic (electron/hole) conductivity occurs via delocalized states in the conduction/valence band or via localized states by a thermally assisted hopping mechanism. With respect to their properties, MIECs have found wide applications in solid oxide fuel cells, batteries, smart windows, selective membranes, sensors, catalysis, and so on. 

The fluoride electrode is a typical example of an ion selective electrode. Its sensitive element is a crystal of lanthanum trifluoride that allows fluorine atoms to migrate into the network formed by lanthanum atoms (Fig. 18.3). Other electrodes use a mineral membrane obtained as agglomerates of crystalline powders (for measurement of Cl-, Br-, I , Pb++, Ag+ and CN ). Generally, the internal electrolyte can be eliminated (by dry contact). However, it is preferable to insert a polymer layer with a mixed-type conductivity to ensure the passage of electrons from the ionic conductivity membrane to the electronic conductivity electrode (Fig. 18.3). 

In contrast, in most ion-selective membranes the charge conduction is done by ions. Thus, a mismatch between the charge-transfer carriers can exist at the noble metal/membrane interface. This is particularly true for polymer-based membranes, which are invariably ionic conductors. On the other hand, solid-state membranes that exhibit mixed ionic and electronic conductivity such as chalcogenide glasses, perovskites, and silver halides and conducting polymers (Lewenstam and Hulanicky, 1990) form good contact with noble metals. 

---