Lithium cobalt oxide

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Lithium cobalt oxide [1]
Lithium-cobalt-oxide-3D-balls.png
__ Li+      __ Co3+      __ O2−
Lithium-cobalt-oxide-3D-polyhedra.png
Names
IUPAC name
lithium cobalt(III) oxide
Other names
lithium cobaltite
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.032.135 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 235-362-0
PubChem CID
  • InChI=1S/Co.Li.2O/q+3;+1;2*-2
    Key: LSZLYXRYFZOJRA-UHFFFAOYSA-N
  • [Li+].[O-2].[Co+3].[O-2]
Properties
LiCoO
2
Molar mass 97.87 g mol−1
Appearancedark blue or bluish-gray crystalline solid
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
harmful
GHS labelling:
GHS-pictogram-exclam.svg GHS-pictogram-silhouette.svg
Danger
H317, H350, H360
P201, P202, P261, P272, P280, P281, P302+P352, P308+P313, P321, P333+P313, P363, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Lithium cobalt oxide, sometimes called lithium cobaltate [2] or lithium cobaltite, [3] 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.

Contents

Lithium cobalt oxide is a dark blue or bluish-gray crystalline solid, [4] and is commonly used in the positive electrodes of lithium-ion batteries.

Structure

The structure of LiCoO
2
has been studied with numerous techniques including x-ray diffraction, electron microscopy, neutron powder diffraction, and EXAFS. [5]

The solid consists of layers of monovalent lithium cations (Li+
) that lie between extended anionic sheets of cobalt and oxygen atoms, arranged as edge-sharing octahedra, with two faces parallel to the sheet plane. [6] The cobalt atoms are formally in the trivalent oxidation state (Co3+
) and are sandwiched between two layers of oxygen atoms (O2−
).

In each layer (cobalt, oxygen, or lithium), the atoms are arranged in a regular triangular lattice. The lattices are offset so that the lithium atoms are farthest from the cobalt atoms, and the structure repeats in the direction perpendicular to the planes every three cobalt (or lithium) layers. The point group symmetry is in Hermann-Mauguin notation, signifying a unit cell with threefold improper rotational symmetry and a mirror plane. The threefold rotational axis (which is normal to the layers) is termed improper because the triangles of oxygen (being on opposite sides of each octahedron) are anti-aligned. [7]

Preparation

Fully reduced lithium cobalt oxide can be prepared by heating a stoichiometric mixture of lithium carbonate Li
2
CO
3
and cobalt(II,III) oxide Co
3
O
4
or metallic cobalt at 600–800 °C, then annealing the product at 900 °C for many hours, all under an oxygen atmosphere. [6] [3] [7]

Nanometer-sized and sub-micrometer sized LCO synthesis route LCO (lithium cobalt oxide, LiCoO2) synthesis route.png
Nanometer-sized and sub-micrometer sized LCO synthesis route

Nanometer-size particles more suitable for cathode use can also be obtained by calcination of hydrated cobalt oxalate β-CoC
2
O
4
·2H
2
O
, in the form of rod-like crystals about 8 μm long and 0.4 μm wide, with lithium hydroxide LiOH, up to 750–900 °C. [9]

A third method uses lithium acetate, cobalt acetate, and citric acid in equal molar amounts, in water solution. Heating at 80 °C turns the mixture into a viscous transparent gel. The dried gel is then ground and heated gradually to 550 °C. [10]

Use in rechargeable batteries

The usefulness of lithium cobalt oxide as an intercalation electrode was discovered in 1980 by an Oxford University research group led by John B. Goodenough and Tokyo University's Koichi Mizushima. [11]

The compound is now used as the cathode in some rechargeable lithium-ion batteries, with particle sizes ranging from nanometers to micrometers. [10] [9] During charging, the cobalt is partially oxidized to the +4 state, with some lithium ions moving to the electrolyte, resulting in a range of compounds Li
x
CoO
2
with 0 < x < 1. [3]

Batteries produced with LiCoO
2
cathodes have very stable capacities, but have lower capacities and power than those with cathodes based on (especially nickel-rich) nickel-cobalt-aluminum (NCA) or nickel-cobalt-manganese (NCM) oxides. [12] Issues with thermal stability are better for LiCoO
2
cathodes than other nickel-rich chemistries although not significantly. This makes LiCoO
2
batteries susceptible to thermal runaway in cases of abuse such as high temperature operation (>130 °C) or overcharging. At elevated temperatures, LiCoO
2
decomposition generates oxygen, which then reacts with the organic electrolyte of the cell, this reaction is often seen in Lithium-Ion batteries where the battery becomes highly volatile and must be recycled in a safe manner. The decomposition of LiCoO2 is a safety concern due to the magnitude of this highly exothermic reaction, which can spread to adjacent cells or ignite nearby combustible material. [13] In general, this is seen for many lithium-ion battery cathodes.

The delithiation process is usually by chemical means, [14] although a novel physical process has been developed based on ion sputtering and annealing cycles, [15] leaving the material properties intact.

See also

Related Research Articles

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4
. It is a gray, red-grey, brown or black solid that is insoluble in water. The material has attracted attention as a component of lithium iron phosphate batteries, a type of Li-ion battery. This battery chemistry is targeted for use in power tools, electric vehicles, solar energy installations and more recently large grid-scale energy storage.

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2
, as the cathode material. They function through the same intercalation/de-intercalation mechanism as other commercialized secondary battery technologies, such as LiCoO
2
. Cathodes based on manganese-oxide components are earth-abundant, inexpensive, non-toxic, and provide better thermal stability.

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x
CoO
2
for 0 < x ≤ 1. The name is also used for hydrated forms of those compounds, Na
x
CoO
2
·yH
2
O
.

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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.

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References

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    "
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