Graphite intercalation compound

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Space-filling model of potassium graphite KC8.

In the area of solid state chemistry. graphite intercalation compounds are materials prepared by intercalation of diverse guests into graphite. The materials have the formula (guest)Cn where n can range from 8 to 40's. The distance between the carbon layers increases significantly upon insertion of the guests. Common guests are reducing agents such as alkali metals. Strong oxidants, such as arsenic pentafluoride also intercalate into graphite. Intercalation involves electron transfer into or out of the host. The properties of these materials differ from those of the parent graphite. [1] [2]

Contents

Preparation and structure

These materials are prepared by treating graphite with a strong oxidant or a strong reducing agent:

C + m X → CXm

The reaction is reversible.

The host (graphite) and the guest X interact by charge transfer. An analogous process is the basis of commercial lithium-ion batteries.

In a graphite intercalation compound not every layer is necessarily occupied by guests. In so-called stage 1 compounds, graphite layers and intercalated layers alternate and in stage 2 compounds, two graphite layers with no guest material in between alternate with an intercalated layer. The actual composition may vary and therefore these compounds are an example of non-stoichiometric compounds. It is customary to specify the composition together with the stage. The layers are pushed apart upon incorporation of the guest ions.

Examples

Alkali and alkaline earth derivatives

Potassium graphite under argon in a Schlenk flask. A glass-coated magnetic stir bar is also present. Potassium graphite.jpg
Potassium graphite under argon in a Schlenk flask. A glass-coated magnetic stir bar is also present.

One of the best studied graphite intercalation compounds, KC8, is prepared by melting potassium over graphite powder. The potassium is absorbed into the graphite and the material changes color from black to bronze. [3] The resulting solid is pyrophoric. [4] The composition is explained by assuming that the potassium to potassium distance is twice the distance between hexagons in the carbon framework. The bond between anionic graphite layers and potassium cations is ionic. The electrical conductivity of the material is greater than that of α-graphite. [4] [5] KC8 is a superconductor with a very low critical temperature Tc = 0.14 K. [6] Heating KC8 leads to the formation of a series of decomposition products as the K atoms are eliminated:[ citation needed ]

3 KC8 → KC24 + 2 K

Via the intermediates KC24 (blue in color), [3] KC36, KC48, ultimately the compound KC60 results.

The stoichiometry MC8 is observed for M = K, Rb and Cs. For smaller ions M = Li+, Sr2+, Ba2+, Eu2+, Yb3+, and Ca2+, the limiting stoichiometry is MC6. [6] Calcium graphite CaC6 is obtained by immersing highly oriented pyrolytic graphite in liquid Li–Ca alloy for 10 days at 350 °C. The crystal structure of CaC6 belongs to the R3m space group. The graphite interlayer distance increases upon Ca intercalation from 3.35 to 4.524 Å, and the carbon-carbon distance increases from 1.42 to 1.444 Å.

Structure of
CaC6 CaC6structure.jpg
Structure of CaC6

With barium and ammonia, the cations are solvated, giving the stoichiometry (Ba(NH3)2.5C10.9(stage 1)) or those with caesium, hydrogen and potassium (CsC8·K2H4/3C8(stage 1)).[ clarification needed ]

In situ adsorption on free-standing graphene and intercalation in bilayer graphene of the alkali metals K, Cs, and Li was observed by means of low-energy electron microscopy. [7]

Different from other alkali metals, the amount of Na intercalation is very small. Quantum-mechanical calculations show that this originates from a quite general phenomenon: among the alkali and alkaline earth metals, Na and Mg generally have the weakest chemical binding to a given substrate, compared with the other elements in the same group of the periodic table. [8] The phenomenon arises from the competition between trends in the ionization energy and the ion–substrate coupling, down the columns of the periodic table. [8] However, considerable Na intercalation into graphite can occur in cases when the ion is wrapped in a solvent shell through the process of co-intercalation. A complex magnesium(I) species has also been intercalated into graphite. [9]

Graphite bisulfate, perchlorate, hexafluoroarsenate: oxidized carbons

The intercalation compounds graphite bisulfate and graphite perchlorate can be prepared by treating graphite with strong oxidizing agents in the presence of strong acids. In contrast to the potassium and calcium graphites, the carbon layers are oxidized in this process:

48 C + 0.25 O2 + 3 H2SO4 → [C24]+[HSO4]·2H2SO4 + 0.5 H2O[ clarification needed ]

In graphite perchlorate, planar layers of carbon atoms are 794 picometers apart, separated by ClO4 ions. Cathodic reduction of graphite perchlorate is analogous to heating KC8, which leads to a sequential elimination of HClO4.

Both graphite bisulfate and graphite perchlorate are better conductors as compared to graphite, as predicted by using a positive-hole mechanism. [4] Reaction of graphite with [O2]+[AsF6] affords the salt [C8]+[AsF6]. [4]

Metal halide derivatives

A number of metal halides intercalate into graphite. The chloride derivatives have been most extensively studied. Examples include MCl2 (M = Zn, Ni, Cu, Mn), MCl3 (M = Al, Fe, Ga), MCl4 (M = Zr, Pt), etc. [1] The materials consists of layers of close-packed metal halide layers between sheets of carbon. The derivative C~8FeCl3 exhibits spin glass behavior. [10] It proved to be a particularly fertile system on which to study phase transitions.[ citation needed ] A stage n magnetic graphite intercalation compounds has n graphite layers separating successive magnetic layers. As the stage number increases the interaction between spins in successive magnetic layers becomes weaker and 2D magnetic behaviour may arise.

Halogen- and oxide-graphite compounds

Chlorine and bromine reversibly intercalate into graphite. Iodine does not. Fluorine reacts irreversibly. In the case of bromine, the following stoichiometries are known: CnBr for n = 8, 12, 14, 16, 20, and 28.

Because it forms irreversibly, carbon monofluoride is often not classified as an intercalation compound. It has the formula (CF)x. It is prepared by reaction of gaseous fluorine with graphitic carbon at 215–230 °C. The color is greyish, white, or yellow. The bond between the carbon and fluorine atoms is covalent. Tetracarbon monofluoride (C4F) is prepared by treating graphite with a mixture of fluorine and hydrogen fluoride at room temperature. The compound has a blackish-blue color. Carbon monofluoride is not electrically conductive. It has been studied as a cathode material in one type of primary (non-rechargeable) lithium batteries.

Graphite oxide is an unstable yellow solid.

Properties and applications

Graphite intercalation compounds have fascinated materials scientists for many years owing to their diverse electronic and electrical properties.

Superconductivity

Among the superconducting graphite intercalation compounds, CaC6 exhibits the highest critical temperature Tc = 11.5 K, which further increases under applied pressure (15.1 K at 8 GPa). [6] Superconductivity in these compounds is thought to be related to the role of an interlayer state, a free electron like band lying roughly 2 eV (0.32 aJ) above the Fermi level; superconductivity only occurs if the interlayer state is occupied. [11] Analysis of pure CaC6 using a high quality ultraviolet light revealed to conduct angle-resolved photoemission spectroscopy measurements. The opening of a superconducting gap in the π* band revealed a substantial contribution to the total electron–phonon-coupling strength from the π*-interlayer interband interaction. [11]

Reagents in chemical synthesis: KC8

The bronze-colored material KC8 is one of the strongest reducing agents known. It has also been used as a catalyst in polymerizations and as a coupling reagent for aryl halides to biphenyls. [12] In one study, freshly prepared KC8 was treated with 1-iodododecane delivering a modification (micrometre scale carbon platelets with long alkyl chains sticking out providing solubility) that is soluble in chloroform. [12] Another potassium graphite compound, KC24, has been used as a neutron monochromator. A new essential application for potassium graphite was introduced by the invention of the potassium-ion battery. Like the lithium-ion battery, the potassium-ion battery should use a carbon-based anode instead of a metallic anode. In this circumstance, the stable structure of potassium graphite is an important advantage.

See also

Related Research Articles

<span class="mw-page-title-main">Alkali metal</span> Group of highly reactive chemical elements

The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), and francium (Fr). Together with hydrogen they constitute group 1, which lies in the s-block of the periodic table. All alkali metals have their outermost electron in an s-orbital: this shared electron configuration results in their having very similar characteristic properties. Indeed, the alkali metals provide the best example of group trends in properties in the periodic table, with elements exhibiting well-characterised homologous behaviour. This family of elements is also known as the lithium family after its leading element.

<span class="mw-page-title-main">Boron nitride</span> Refractory compound of boron and nitrogen with formula BN

Boron nitride is a thermally and chemically resistant refractory compound of boron and nitrogen with the chemical formula BN. It exists in various crystalline forms that are isoelectronic to a similarly structured carbon lattice. The hexagonal form corresponding to graphite is the most stable and soft among BN polymorphs, and is therefore used as a lubricant and an additive to cosmetic products. The cubic variety analogous to diamond is called c-BN; it is softer than diamond, but its thermal and chemical stability is superior. The rare wurtzite BN modification is similar to lonsdaleite but slightly softer than the cubic form.

<span class="mw-page-title-main">Chlorine</span> Chemical element, symbol Cl and atomic number 17

Chlorine is a chemical element with the symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine is a yellow-green gas at room temperature. It is an extremely reactive element and a strong oxidising agent: among the elements, it has the highest electron affinity and the third-highest electronegativity on the revised Pauling scale, behind only oxygen and fluorine.

<span class="mw-page-title-main">Carbide</span> Inorganic compound group

In chemistry, a carbide usually describes a compound composed of carbon and a metal. In metallurgy, carbiding or carburizing is the process for producing carbide coatings on a metal piece.

<span class="mw-page-title-main">Graphite</span> Allotrope of carbon, mineral, substance

Graphite is a crystalline form of the element carbon. It consists of stacked layers of graphene. Graphite occurs naturally and is the most stable form of carbon under standard conditions. Synthetic and natural graphite are consumed on large scale for uses in pencils, lubricants, and electrodes. Under high pressures and temperatures it converts to diamond. It is a good conductor of both heat and electricity.

<span class="mw-page-title-main">Electrolysis</span> Technique in chemistry and manufacturing

In chemistry and manufacturing, electrolysis is a technique that uses direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of elements from naturally occurring sources such as ores using an electrolytic cell. The voltage that is needed for electrolysis to occur is called the decomposition potential. The word "lysis" means to separate or break, so in terms, electrolysis would mean "breakdown via electricity".

<span class="mw-page-title-main">High-temperature superconductivity</span> Superconductive behavior at temperatures much higher than absolute zero

High-temperature superconductors are defined as materials with critical temperature above 77 K, the boiling point of liquid nitrogen. They are only "high-temperature" relative to previously known superconductors, which function at even colder temperatures, close to absolute zero. The "high temperatures" are still far below ambient, and therefore require cooling. The first break through of high-temperature superconductor was discovered in 1986 by IBM researchers Georg Bednorz and K. Alex Müller. Although the critical temperature is around 35.1 K, this new type of superconductor was readily modified by Ching-Wu Chu to make the first high-temperature superconductor with critical temperature 93 K. Bednorz and Müller were awarded the Nobel Prize in Physics in 1987 "for their important break-through in the discovery of superconductivity in ceramic materials". Most high-Tc materials are type-II superconductors.

A period 2 element is one of the chemical elements in the second row of the periodic table of the chemical elements. The periodic table is laid out in rows to illustrate recurring (periodic) trends in the chemical behavior of the elements as their atomic number increases; a new row is started when chemical behavior begins to repeat, creating columns of elements with similar properties.

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<span class="mw-page-title-main">Intercalation (chemistry)</span> Reversible insertion of an ion into a material with layered structure

In chemistry, intercalation is the reversible inclusion or insertion of a molecule into layered materials with layered structures. Examples are found in graphite and transition metal dichalcogenides.

<span class="mw-page-title-main">Chalcogenide</span>

A chalcogenide is a chemical compound consisting of at least one chalcogen anion and at least one more electropositive element. Although all group 16 elements of the periodic table are defined as chalcogens, the term chalcogenide is more commonly reserved for sulfides, selenides, tellurides, and polonides, rather than oxides. Many metal ores exist as chalcogenides. Photoconductive chalcogenide glasses are used in xerography. Some pigments and catalysts are also based on chalcogenides. The metal dichalcogenide MoS2 is a common solid lubricant.

An organic superconductor is a synthetic organic compound that exhibits superconductivity at low temperatures.

<span class="mw-page-title-main">Carbon monofluoride</span> Chemical compound

Carbon monofluoride (CF, CFx, or (CF)n), also called polycarbon monofluoride (PMF), polycarbon fluoride, poly(carbon monofluoride), and graphite fluoride, is a material formed by high-temperature reaction of fluorine gas with graphite, charcoal, or pyrolytic carbon powder. It is a highly hydrophobic microcrystalline powder. Its CAS number is 51311-17-2. In contrast to graphite intercalation compounds it is a covalent graphite compound.

Bromine compounds are compounds containing the element bromine (Br). These compounds usually form the -1, +1, +3 and +5 oxidation states. Bromine is intermediate in reactivity between chlorine and iodine, and is one of the most reactive elements. Bond energies to bromine tend to be lower than those to chlorine but higher than those to iodine, and bromine is a weaker oxidising agent than chlorine but a stronger one than iodine. This can be seen from the standard electrode potentials of the X2/X couples (F, +2.866 V; Cl, +1.395 V; Br, +1.087 V; I, +0.615 V; At, approximately +0.3 V). Bromination often leads to higher oxidation states than iodination but lower or equal oxidation states to chlorination. Bromine tends to react with compounds including M–M, M–H, or M–C bonds to form M–Br bonds.

A potassium-ion battery or K-ion battery is a type of battery and analogue to lithium-ion batteries, using potassium ions for charge transfer instead of lithium ions. It was invented by the Iranian/American chemist Ali Eftekhari in 2004.

<span class="mw-page-title-main">Titanium disulfide</span> Inorganic chemical compound

Titanium disulfide is an inorganic compound with the formula TiS2. A golden yellow solid with high electrical conductivity, it belongs to a group of compounds called transition metal dichalcogenides, which consist of the stoichiometry ME2. TiS2 has been employed as a cathode material in rechargeable batteries.

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<span class="mw-page-title-main">Fulleride</span> Chemical compound

Fullerides are chemical compounds containing fullerene anions. Common fullerides are derivatives of the most common fullerenes, i.e. C60 and C70. The scope of the area is large because multiple charges are possible, i.e., [C60]n (n = 1, 2...6), and all fullerenes can be converted to fullerides. The suffix "-ide" implies their negatively charged nature.

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<span class="mw-page-title-main">Hexafluoroarsenate</span> Chemical compound

The hexafluoroarsenate anion is a chemical species with formula AsF−6. Hexafluoroarsenate is relatively inert, being the conjugate base of the notional superacid hexafluoroarsenic acid.

References

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Further reading