Everything about Fast Ion Conductor totally explained
Fast ion conductors, also known as
solid electrolytes and
superionic conductors, are
solid state electrical conductors which conduct due to the movement of ions through voids (or empty crystallographic positions)in their
crystal lattice. One component of the structure,
cationic or
anionic, is essentially free to move throughout the structure, acting as
charge carrier.
The important case of fast ionic conduction is one in a surface space-charge layer of ionic crystals. Such conduction was first predicted by
Kurt Lehovec (www.kurtlehovec.com) in the paper “Space-charge layer and distribution of lattice defects at the surface of ionic crystals” (J. Chem. Phys. 1953. V.21. P.1123 -1128). As a space-charge layer has nanometer thickness, the effect is directly related to
nanoionics (nanoionics-I). The Lehovec’s effect had given a basis for creation of multitude nanostructured fast ion conductors for portable lithium batteries and fuel cells.
Fast ion conductors are intermediate in nature between crystalline solids (see
crystal) which possess a regular structure with immobile ions, and liquid
electrolytes which have no regular structure and entirely mobile ions.
Solid electrolytes find use in all solid state
supercapacitors,
batteries and
fuel cells, and in various kinds of
chemical sensors.
Proton conductors are a special class of solid electrolytes, where
hydrogen ions act as charge carriers.
There is difference between solid electrolytes and superionic conductors.
In solid electrolytes (glasses or crystals), the ionic conductivity Ω
i is arbitrary value but it should be greatly large than electronic one. Usually, the solids, where electronic conductivity Ω
e is arbitrary value but Ω
i is an order of 0.0001-0.1 Ohm
-1 cm
-1 (300 K), are called by superionic conductors.
.
Superionic conductors, where Ω
i is more than 0.1 Ohm
-1 cm
-1 (300 K) and activation energy for ion transport
Ei is small (about 0.1 eV), are called by
advanced superionic conductors. The famous example of advanced superionic conductor-solid electrolyte is
RbAg4I5 where Ω
i > 0.25 Ohm
-1 cm
-1 and Ω
e ~10
-9 Ohm
-1 cm
-1 at 300 K. The Hall (drift) ionic mobility in RbAg
4I
5 is about 2x10
-4 cm
2/(V•s) at room temperatures
(Stuhrmann C.H.J., Kreiterling H., Funke K. Ionic Hall effect measured in rubidium silver iodide // Solid State Ionics 2002. V.154-155. P.109-112.).
The Ω
e – Ω
i systematic diagram distinguishing the different types of solid state ionic conductors is given on the figure
Fig. Classification of solid state ionic conductors by the
lg Ω
e -
lg Ω
i diagram (Ohm
-1 cm
-1).
2, 4 and 6 – known solid electrolytes (SEs), materials
with Ω
i >> Ω
e;
1, 3, and 5 – known mixed ion-electron conductors;
3 and 4 – superionic conductors (SICs), for example materials
with Ω
i > 0.001 Ohm
-1cm
-1, Ω
e – arbitrary value;
4 – SIC and simultaneously SE, Ω
i > 0.001 Ohm
-1cm
-1,
Ω
i >>Ω
e;
5 and 6 – advanced superionic conductors (AdSICs),
where Ω
i > 10
-1 Ohm
-1cm
-1 (300 K),
energy activation
Ei about 0.1 eV, Ω
e – arbitrary value;
6 – AdSIC and simultaneously SE, Ω
i > 10
-1 Ohm
-1cm
-1,
Ei about 0.1 eV, Ω
i >>Ω
e;
7 and 8 – hypothetical AdSIC with
Ei ≈
kBT ≈0.03 eV (300 К);
8 – hypothetical AdSIC and simultaneously SE.
Examples
Examples of fast ion conductors include
sodium chloride,
beta-alumina solid electrolyte,
beta-lead fluoride,
zirconium dioxide and
silver iodide.
- Inorganic materials:
- Sodium chloride
- Zirconium dioxide doped with calcium oxide and yttrium oxide, which is conductive for O2- ions and is used in oxygen sensors
- Beta-alumina solid electrolyte used as a membrane in several types of molten salt electrochemical cells
- Lanthanum(III) fluoride, conductive for F- ions, used in some ion selective electrodes
- Silver sulfide, conductive for Ag+ ions, used in some ion selective electrodes
- Silver iodide, conductive at higher temperatures
- Beta-lead fluoride, exhibits a continuous growth of conductivity on heating. This property was first discovered by M. Faraday
- Lead(II) chloride, conductive at higher temperatures
- Rubidium silver iodide, conductive at room temperature
- Some perovskite ceramics - strontium titanate, strontium stannate - conductive for O2- ions
- Zr(HPO4)2.nH2O - conductive for H+ ions
- UO2HPO4.4H2O - conductive for H+ ions
- Conductive ceramics - eg. NASICON (Na3Zr2Si2PO12), a sodium super-ionic conductor
Organic materials:
Further Information
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