Yttria-stabilized zirconia (YSZ) is a ceramic in which the cubic crystal structure of zirconium dioxide is made stable at room temperature by an addition of yttrium oxide. These oxides are commonly called "zirconia" (Zr O 2) and "yttria" (Y 2 O 3), hence the name.
Pure zirconium dioxide undergoes a phase transformation from monoclinic (stable at room temperature) to tetragonal (at about 1173 °C) and then to cubic (at about 2370 °C), according to the scheme
During these transformations, zirconia can experience volume expansion of up to 5-6%. [1] This change can induce internal stresses, leading to cracking or fracture in ceramic materials. [2]
Obtaining stable sintered zirconia ceramic products is difficult because of the large volume change, about 5%, accompanying the transition from tetragonal to monoclinic. Stabilization of the cubic polymorph of zirconia over wider range of temperatures is accomplished by substitution of some of the Zr4+ ions (ionic radius of 0.82 Å, too small for ideal lattice of fluorite characteristic for the cubic zirconia) in the crystal lattice with slightly larger ions, e.g., those of Y3+ (ionic radius of 0.96 Å). The resulting doped zirconia materials are termed stabilized zirconias. [3]
Materials related to YSZ include calcia-, magnesia-, ceria- or alumina-stabilized zirconias, or partially stabilized zirconias (PSZ). Hafnia-stabilized zirconia has about 25% lower thermal conductivity, making it more suitable for thermal barrier applications. [4]
Although 8–9 mol% YSZ is known to not be completely stabilized in the pure cubic YSZ phase up to temperatures above 1000 °C. [5]
Commonly used abbreviations in conjunction with yttria-stabilized zirconia are:
The thermal expansion coefficients depends on the modification of zirconia as follows:
By the addition of yttria to pure zirconia (e.g., fully stabilized YSZ) Y3+ ions replace Zr4+ on the cationic sublattice. Thereby, oxygen vacancies are generated due to charge neutrality: [9]
meaning that two Y3+ ions generate one vacancy on the anionic sublattice. This facilitates moderate conductivity of yttrium-stabilized zirconia for O2− ions (and thus electrical conductivity) at elevated and high temperature. This ability to conduct O2− ions makes yttria-stabilized zirconia well suited for application as solid electrolyte in solid oxide fuel cells.
For low dopant concentrations, the ionic conductivity of the stabilized zirconias increases with increasing Y2O3 content. It has a maximum around 8–9 mol% almost independent of the temperature (800–1200 °C). [3] [5] Unfortunately, 8–9 mol% YSZ (8YSZ, 8YDZ) also turned out to be situated in the 2-phase field (c+t) of the YSZ phase diagram at these temperatures, which causes the material's decomposition into Y-enriched and depleted regions on the nanometre scale and, consequently, the electrical degradation during operation. [6] The microstructural and chemical changes on the nanometre scale are accompanied by the drastic decrease of the oxygen-ion conductivity of 8YSZ (degradation of 8YSZ) of about 40% at 950 °C within 2500 hours. [7] Traces of impurities like Ni, dissolved in the 8YSZ, e.g., due to fuel-cell fabrication, can have a severe impact on the decomposition rate (acceleration of inherent decomposition of the 8YSZ by orders of magnitude) such that the degradation of conductivity even becomes problematic at low operation temperatures in the range of 500–700 °C. [10]
Nowadays, more complex ceramics like co-doped zirconia (e.g., with scandia) are in use as solid electrolytes.
YSZ has a number of applications:
Cubic zirconia (abbreviated CZ) is the cubic crystalline form of zirconium dioxide (ZrO2). The synthesized material is hard and usually colorless, but may be made in a variety of different colors. It should not be confused with zircon, which is a zirconium silicate (ZrSiO4). It is sometimes erroneously called cubic zirconium.
Zirconium dioxide, sometimes known as zirconia, is a white crystalline oxide of zirconium. Its most naturally occurring form, with a monoclinic crystalline structure, is the mineral baddeleyite. A dopant stabilized cubic structured zirconia, cubic zirconia, is synthesized in various colours for use as a gemstone and a diamond simulant.
Strontium titanate is an oxide of strontium and titanium with the chemical formula SrTiO3. At room temperature, it is a centrosymmetric paraelectric material with a perovskite structure. At low temperatures it approaches a ferroelectric phase transition with a very large dielectric constant ~104 but remains paraelectric down to the lowest temperatures measured as a result of quantum fluctuations, making it a quantum paraelectric. It was long thought to be a wholly artificial material, until 1982 when its natural counterpart—discovered in Siberia and named tausonite—was recognised by the IMA. Tausonite remains an extremely rare mineral in nature, occurring as very tiny crystals. Its most important application has been in its synthesized form wherein it is occasionally encountered as a diamond simulant, in precision optics, in varistors, and in advanced ceramics.
A regenerative fuel cell or reverse fuel cell (RFC) is a fuel cell run in reverse mode, which consumes electricity and chemical B to produce chemical A. By definition, the process of any fuel cell could be reversed. However, a given device is usually optimized for operating in one mode and may not be built in such a way that it can be operated backwards. Standard fuel cells operated backwards generally do not make very efficient systems unless they are purpose-built to do so as with high-pressure electrolysers, regenerative fuel cells, solid-oxide electrolyser cells and unitized regenerative fuel cells.
A solid oxide fuel cell is an electrochemical conversion device that produces electricity directly from oxidizing a fuel. Fuel cells are characterized by their electrolyte material; the SOFC has a solid oxide or ceramic electrolyte.
Cerium(IV) oxide, also known as ceric oxide, ceric dioxide, ceria, cerium oxide or cerium dioxide, is an oxide of the rare-earth metal cerium. It is a pale yellow-white powder with the chemical formula CeO2. It is an important commercial product and an intermediate in the purification of the element from the ores. The distinctive property of this material is its reversible conversion to a non-stoichiometric oxide.
Yttrium oxide, also known as yttria, is Y2O3. It is an air-stable, white solid substance.
Electroceramics are a class of ceramic materials used primarily for their electrical properties.
Bismuth(III) oxide is a compound of bismuth, and a common starting point for bismuth chemistry. It is found naturally as the mineral bismite (monoclinic) and sphaerobismoite, but it is usually obtained as a by-product of the smelting of copper and lead ores. Dibismuth trioxide is commonly used to produce the "Dragon's eggs" effect in fireworks, as a replacement of red lead.
A ceramic knife is a knife with a ceramic blade typically made from zirconium dioxide (ZrO2; also known as zirconia), rather than the steel used for most knives. Ceramic knife blades are usually produced through the dry-pressing and firing of powdered zirconia using solid-state sintering. The blades typically score 8.5 on the Mohs scale of mineral hardness, compared to 4.5 for normal steel and 7.5 to 8 for hardened steel and 10 for diamond. The resultant blade has a hard edge that stays sharp for much longer than conventional steel blades. However, the blade is brittle, subject to chipping, and will break rather than flex if twisted. The ceramic blade is sharpened by grinding the edges with a diamond-dust-coated grinding wheel.
In materials science, fast ion conductors are solid conductors with highly mobile ions. 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.
Lanthanum strontium manganite (LSM or LSMO) is an oxide ceramic material with the general formula La1−xSrxMnO3, where x describes the doping level.
A solid oxide electrolyzer cell (SOEC) is a solid oxide fuel cell that runs in regenerative mode to achieve the electrolysis of water by using a solid oxide, or ceramic, electrolyte to produce hydrogen gas and oxygen. The production of pure hydrogen is compelling because it is a clean fuel that can be stored, making it a potential alternative to batteries, methane, and other energy sources. Electrolysis is currently the most promising method of hydrogen production from water due to high efficiency of conversion and relatively low required energy input when compared to thermochemical and photocatalytic methods.
Solid-state ionics is the study of ionic-electronic mixed conductor and fully ionic conductors 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.
Gadolinium-doped ceria (GDC) (known alternatively as gadolinia-doped ceria, gadolinium-doped cerium oxide (GCO), cerium-gadolinium oxide (CGO), or cerium(IV) oxide, gadolinium-doped, formula Gd:CeO2) is a ceramic electrolyte used in solid oxide fuel cells (SOFCs). It has a cubic structure and a density of around 7.2 g/cm3 in its oxidised form. It is one of a class of ceria-doped electrolytes with higher ionic conductivity and lower operating temperatures (<700 °C) than those of yttria-stabilized zirconia, the material most commonly used in SOFCs. Because YSZ requires operating temperatures of 800–1000 °C to achieve maximal ionic conductivity, the associated energy and costs make GDC a more optimal (even "irreplaceable", according to researchers from the Fraunhofer Society) material for commercially viable SOFCs.
NASICON is an acronym for sodium (Na) super ionic conductor, which usually refers to a family of solids with the chemical formula Na1+xZr2SixP3−xO12, 0 < x < 3. In a broader sense, it is also used for similar compounds where Na, Zr and/or Si are replaced by isovalent elements. NASICON compounds have high ionic conductivities, on the order of 10−3 S/cm, which rival those of liquid electrolytes. They are caused by hopping of Na ions among interstitial sites of the NASICON crystal lattice.
Ceria-zirconia is a solid solution of cerium(IV) oxide (CeO2, also known as ceria) and zirconium oxide (ZrO2, also known as zirconia).
Mixed conductors, also known as mixed ion-electron conductors(MIEC), are a single-phase material that has significant conduction ionically and electronically. Due to the mixed conduction, a formally neutral species can transport in a solid and therefore mass storage and redistribution are enabled. Mixed conductors are well known in conjugation with high-temperature superconductivity and are able to capacitate rapid solid-state reactions.
Yttralox is a transparent ceramic consisting of yttria (Y2O3) containing approximately 10% thorium dioxide (ThO2). It was one of the first transparent ceramics produced, and was invented in 1966 by Richard C. Anderson at the General Electric Research Laboratory while sintering mixtures of rare earth minerals.
Lithium lanthanum zirconium oxide (LLZO, Li7La3Zr2O12) or lithium lanthanum zirconate is a lithium-stuffed garnet material that is under investigation for its use in solid-state electrolytes in lithium-based battery technologies. LLZO has a high ionic conductivity and thermal and chemical stability against reactions with prospective electrode materials, mainly lithium metal, giving it an advantage for use as an electrolyte in solid-state batteries. LLZO exhibits favorable characteristics, including the accessibility of starting materials, cost-effectiveness, and straightforward preparation and densification processes. These attributes position this zirconium-containing lithium garnet as a promising solid electrolyte for all-solid-state lithium-ion rechargeable batteries.
