Mixed conductor

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Cerium oxide is a potent mixed conductor. Cerium(IV) oxide.jpg
Cerium oxide is a potent mixed conductor.

Mixed conductors, also known as mixed ion-electron conductors(MIEC), are a single-phase material that has significant conduction ionically and electronically. [1] [2] [3] 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.

Contents

They are used as catalysts (for oxidation), permeation membranes, sensors, and electrodes in batteries and fuel cells, because they allow for rapidly transducing chemical signals and permeating chemical components. [3]

Strontium titanate (SrTiO3), titanium dioxide (TiO2), (La,Ba,Sr)(Mn,Fe,Co)O
3−d
,La2CuO
4+d
, cerium(IV) oxide (CeO2), lithium iron phosphate (LiFePO4), and LiMnPO4 are examples of mixed conductors. [1]

Introduction

MIEC materials tend to be nonstoichiometric oxides, many of which have perovskite structures with rare earth metals on the A-site and transition metals on the B-site. [4] Substituting various ions into the lattice of such an oxide can result in increased electronic conductivity through the formation of holes and introduce ionic conductivity by developing oxygen vacancies. [4] This mechanism is known as defect theory, which states that defects like these offer additional pathways that favor fast diffusion. [5] Other promising materials include those with pyrochlore, brownmillerite, Ruddlesden-Popper, and orthorhombic K2NiF4-type structures. [5]

However, true (single-phase) MIECs that are compatible with other design parameters can be difficult to find, so many researchers have turned to heterogeneous MIEC materials (H-MIECs). An H-MIEC is a composite mixture of two phases: one for conducting ions, and another conducting electrons or holes. [6] These materials are desirable for the ability to tune their properties for specific applications by adjusting concentration levels to achieve optimal electron and ion transport. [7] Porous H-MIECs also incorporate a third phase in the form of pores, which allow the formation of triple phase boundaries (TPBs) between the three phases that provide high catalytic activity. [7]

Applications

SOFC/SOEC

Schematic of a solid oxide fuel cell. Note that the cathode material must conduct both oxygen ions and electrons. Solid oxide fuel cell.svg
Schematic of a solid oxide fuel cell. Note that the cathode material must conduct both oxygen ions and electrons.

Current state-of-the-art solid oxide fuel cells (SOFCs) and electrolysis cells (SOECs) frequently incorporate electrodes made of MIEC materials. SOFCs are unique among fuel cells in that negatively charged ions (O2-) are transported from the cathode to the anode across the electrolyte, making MIEC cathode materials critical to achieving high performance. These fuel cells operate with the following oxidation-reduction reaction:

Anode Reaction: 2H2 + 2O2− → 2H2O + 4e
Cathode Reaction: O2 + 4e → 2O2−
Overall Cell Reaction: 2H2 + O2 → 2H2O

MIECs like lanthanum strontium cobalt ferrite (LSCF) are frequently the subject of modern fuel cell research, as they enable the reduction reaction to occur over the entire cathode surface area instead of only at the cathode/electrolyte interface. [8]

One of the most commonly used oxygen electrode (cathode) materials is the H-MIEC LSM-YSZ, consisting of lanthanum strontium manganite (LSM) infiltrated onto a Y2O3-doped ZrO2 scaffold. [9] The LSM nanoparticles are deposited on the walls of the porous YSZ scaffold to provide an electronically conductive pathway and a high density of TPBs for the reduction reaction to occur. [9]

See also

Related Research Articles

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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.

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<span class="mw-page-title-main">Solid oxide fuel cell</span> Fuel cell that produces electricity by oxidization

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<span class="mw-page-title-main">Bismuth(III) oxide</span> Chemical compound

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<span class="mw-page-title-main">Fast-ion conductor</span>

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Lanthanum strontium cobalt ferrite (LSCF), also called lanthanum strontium cobaltite ferrite is a specific ceramic oxide derived from lanthanum cobaltite of the ferrite group. It is a phase containing lanthanum(III) oxide, strontium oxide, cobalt oxide and iron oxide with the formula La
x
Sr
1-x
Co
y
Fe
1-y
O
3
, where 0.1≤x≤0.4 and 0.2≤y≤0.8.

<span class="mw-page-title-main">Lanthanum strontium manganite</span>

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<span class="mw-page-title-main">Lithium cobalt oxide</span> Chemical compound

Lithium cobalt oxide, sometimes called lithium cobaltate or lithium cobaltite, is a chemical compound with formula LiCoO
2
. The cobalt atoms are formally in the +3 oxidation state, hence the IUPAC name lithium cobalt(III) oxide.

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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" (ZrO2) and "yttria" (Y2O3), hence the name.

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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.

<span class="mw-page-title-main">Solid state ionics</span>

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.

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<span class="mw-page-title-main">NASICON</span> Class of solid materials

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.

A triple phase boundary (TPB) is a geometrical class of phase boundary and the location of contact between three different phases. A simple example of a TPB is a coastline where land, air and sea meet to create an energetic location driven by solar, wind and wave energy capable of supporting a high level of biodiversity. This concept is particularly important in the description of electrodes in fuel cells and batteries. For example for fuel cells, the three phases are an ion conductor (electrolyte), an electron conductor, and a virtual "porosity" phase for transporting gaseous or liquid fuel molecules. The electrochemical reactions that fuel cells use to produce electricity occur in the presence of these three phases. Triple phase boundaries are thus the electrochemically active sites within electrodes.

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.

A polymer electrolyte is a polymer matrix capable of ion conduction. Much like other types of electrolyte—liquid and solid-state—polymer electrolytes aid in movement of charge between the anode and cathode of a cell. The use of polymers as an electrolyte was first demonstrated using dye-sensitized solar cells. The field has expanded since and is now primarily focused on the development of polymer electrolytes with applications in batteries, fuel cells, and membranes.

<span class="mw-page-title-main">Lithium aluminium germanium phosphate</span> Chemical compound

Lithium aluminium germanium phosphate, typically known with the acronyms LAGP or LAGPO, is an inorganic ceramic solid material whose general formula is Li
1+x
Al
x
Ge
2-x
(PO
4
)
3
. LAGP belongs to the NASICON family of solid conductors and has been applied as a solid electrolyte in all-solid-state lithium-ion batteries. Typical values of ionic conductivity in LAGP at room temperature are in the range of 10–5 - 10–4 S/cm, even if the actual value of conductivity is strongly affected by stoichiometry, microstructure, and synthesis conditions. Compared to lithium aluminium titanium phosphate (LATP), which is another phosphate-based lithium solid conductor, the absence of titanium in LAGP improves its stability towards lithium metal. In addition, phosphate-based solid electrolytes have superior stability against moisture and oxygen compared to sulfide-based electrolytes like Li
10
GeP
2
S
12
(LGPS) and can be handled safely in air, thus simplifying the manufacture process. Since the best performances are encountered when the stoichiometric value of x is 0.5, the acronym LAGP usually indicates the particular composition of Li
1.5
Al
0.5
Ge
1.5
(PO
4
)
3
, which is also the typically used material in battery applications.

References

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