Fast ion conductor

In materials science, fast ion conductors are solids in which ions are highly mobile. These materials are important in the area of solid-state ionics, and are also known as solid electrolytes and superionic conductors. These materials are useful in batteries and various sensors. Fast ion conductors are used primarily in solid oxide fuel cells. As solid electrolytes they allow the movement of ions without the need for a liquid or soft membrane separating the electrodes. The phenomenon relies on the hopping of ions through an otherwise rigid crystal structure.

Mechanism

Fast ion conductors are intermediate in nature between crystalline solids which possess a regular structure with immobile ions, and liquid electrolytes which have no regular structure and fully mobile ions. Solid electrolytes find use in all solid-state supercapacitors, batteries, and fuel cells, and in various kinds of chemical sensors.

Classification

In solid electrolytes (glasses or crystals), the ionic conductivity Ω_i can be any value, but it should be much larger than the electronic one. Usually, solids where Ω_i is on the order of 0.0001 to 0.1 Ohm⁻¹ cm⁻¹ (300 K) are called superionic conductors.

Proton conductors

Proton conductors are a special class of solid electrolytes, where hydrogen ions act as charge carriers.

Superionic conductors

Unlike conventional solid electrolytes and superionic conductors.

Superionic conductors where Ω_i is more than 0.1 Ohm⁻¹ cm⁻¹ (300 K) and the activation energy for ion transport E_i is small (about 0.1 eV), are called advanced superionic conductors. The most 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 RbAg₄I₅ is about 2×10⁻⁴ cm²/(V•s) at room temperatures.^[1] The Ω_e – Ω_i systematic diagram distinguishing the different types of solid-state ionic conductors is given in the figure.^[2]

Classification of solid-state ionic conductors by the lg (electronic conductivity, Ω_e) – lg (ionic conductivity, Ω_i) diagram. 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), i.e. 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 E_i 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 ≈ k_BT ≈0.03 eV (300 К); 8 – hypothetical AdSIC and simultaneously SE.

Today, we don’t know yet the examples of fast ion conductors belonging to the class of the hypothetical AdSIC (7 and 8 areas on the classification plot). However, in crystal structure of several SICs, e.g. in the minerals of the pearceite-polybasite group, the large structural fragments with activation energy of ion transport Ei < k_BT (300 К) had been discovered in.^[3]

Examples

Zirconia-based materials

A common solid electrolyte is yttria-stabilized zirconia, YSZ. This material is prepared by doping Y₂O₃ into ZrO₂. Oxide ions typically migrate only slowly in solid Y₂O₃ and in ZrO₂, but in YSZ, the conductivity of oxide increases dramatically. These materials are used to allow oxide to move through the solid in certain kinds of fuel cells. Zirconium dioxide can also be doped with calcium oxide to give an oxide conductor that is used in oxygen sensors in automobile controls. Upon doping only a few percent, the diffusion constant of oxide increases by a factor of ~1000.^[4]

Other conductive ceramics function as ion conductors. One example is NASICON, (Na₃Zr₂Si₂PO₁₂), a sodium super-ionic conductor

beta-Alumina

Another example of a popular fast ion conductor is beta-alumina solid electrolyte.^[5] Unlike the usual forms of alumina, this modification has a layered structure with open galleries separated by pillars. Sodium ions (Na₊) migrate through this material readily since the oxide framework provides an ionophilic, non-reducible medium. This material is considered as the sodium ion conductor for the sodium–sulfur battery.

Fluoride ion conductors

Lanthanum trifluoride (LaF₃) is conductive for F⁻ ions, used in some ion selective electrodes. Beta-lead fluoride exhibits a continuous growth of conductivity on heating. This property was first discovered by Michael Faraday.

Iodides

A textbook example of a fast ion conductor is silver iodide (AgI). Upon heating the solid to 146 °C, this material adopts the alpha-polymorph. In this form, the iodide ions form a rigid cubic framework, and the Ag+ centers are molten. The electrical conductivity of the solid increases by 4000x. Similar behavior is observed for copper(I) iodide (CuI), rubidium silver iodide (RbAgI₂), and Ag₂HgI₄.

Other Inorganic materials

• Silver sulfide, conductive for Ag⁺ ions, used in some ion selective electrodes
• Lead(II) chloride, conductive at higher temperatures
• 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

Organic materials

• Many gels, such polyacrylamides, agar, etc. are fast ion conductors^[6][7]
• A salt dissolved in a polymer – e.g. lithium perchlorate in polyethylene oxide^[8]
• Polyelectrolytes and Ionomers – e.g. Nafion, a H⁺ conductor

History

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.^[9] As a space-charge layer has nanometer thickness, the effect is directly related to nanoionics (nanoionics-I). Lehovec's effect is used as a basis for developing nanomaterials for portable lithium batteries and fuel cells.

References

1. Stuhrmann C.H.J., Kreiterling H., Funke K (2002). "Ionic Hall effect measured in rubidium silver iodide". Solid State Ionics. 154–155: 109–112. doi:10.1016/S0167-2738(02)00470-8.
2. Александр Деспотули, Александра Андреева (2007). Высокоёмкие конденсаторы для 0,5 вольтовой наноэлектроники будущего. Современная Электроника (Portable Document Format) (in Russian) (http://www.nanometer.ru/2007/10/17/nanoionnie_superkondensatori_4879/PROP_FILE_files_1/Despotuli_Andreeva_Modern_Electronics_2007.pdf) (7): 24–29. Alexander Despotuli, Alexandra Andreeva (2007). "High-capacity capacitors for 0.5 voltage nanoelectronics of the future". Modern Electronics (Portable Document Format) (http://www.nanometer.ru/2007/10/17/nanoionnie_superkondensatori_4879/PROP_FILE_files_2/Despotuli_Andreeva_Modern_Electronics_2007(ENG).pdf) (7): 24–29.
3. Bindi, L.; Evain M. (2006). "Fast ion conduction character and ionic phase-transitions in disordered crystals: the complex case of the minerals of the pearceite– polybasite group". Phys Chem Miner 33 (-): 677–690. Bibcode:-. doi:10.1007/s00269-006-0117-7.
4. Shriver, D. F.; Atkins, P. W.; Overton, T. L.; Rourke, J. P.; Weller, M. T.; Armstrong, F. A. “Inorganic Chemistry” W. H. Freeman, New York, 2006. ISBN 0-7167-4878-9.
5. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 0-08-037941-9.
6. "The Roll-to-Roll Battery Revolution". Ev World. Retrieved 2010-08-20.
7. Perzyna, K.; Borkowska, R.; Syzdek, J. A.; Zalewska, A.; Wieczorek, W. A. A. (2011). "The effect of additive of Lewis acid type on lithium–gel electrolyte characteristics". Electrochimica Acta 57: 58. doi:10.1016/j.electacta.2011.06.014.
8. Syzdek, J. A.; Armand, M.; Marcinek, M.; Zalewska, A.; Żukowska, G. Y.; Wieczorek, W. A. A. (2010). "Detailed studies on the fillers modification and their influence on composite, poly(oxyethylene)-based polymeric electrolytes". Electrochimica Acta 55 (4): 1314. doi:10.1016/j.electacta.2009.04.025.
9. Lehovec, Kurt (1953). "Space-charge layer and distribution of lattice defects at the surface of ionic crystals". Journal of Chemical Physics 21 (7): 1123–1128. Bibcode:1953JChPh..21.1123L. doi:10.1063/1.1699148.