Method for exfoliating carbonaceous materials containing graphite, assisted by a Diels-Alder reaction

Patent metadata

Field	Value
Publication number	US-9718692-B2
Application number	US-201414909012-A
Country	US
Kind code	B2
Filing date	Jul 30, 2014
Priority date	Jul 31, 2013
Publication date	Aug 1, 2017
Grant date	Aug 1, 2017

Abstract

The present invention relates to a process for exfoliating graphite in carbonaceous materials facilitated by a Diels-Alder reaction, and the applications of same, in particular for producing electronic or microelectronic components such as transparent conductive electrodes. The inventive method comprises a Diels-Alder reaction between a material containing graphite and an anthrone compound represented by formula (I), wherein X, R 1 , R 2 , R 3 and R 4 are as defined in the description, in an organic solvent, in the presence of a base, and subjected to sonication, ball-milling and/or high-shear mixing, at a temperature of between 15° C. and 65° C., to obtain the corresponding graphene Diels-Alder adduct.

First claim

The invention claimed is:

1. A process for the exfoliation of graphite in a graphite-containing material, comprising
subjecting the graphite-containing material to a Diels-Alder reaction with a compound of formula (I):

wherein:
X represents O or S;
R 1 , R 2 , R 3 and R 4 independently represent a hydrogen atom, —NR A R B , —N + R A R B R C , —OR, —CO 2 M or —SO 3 M; or else R 1 and R 2 , on the one hand, and R 3 and R 4 , on the other hand, together form an optionally substituted unsaturated C 6 cycloalkyl group to result in a pentacenone-type compound of formula (II) having the following structure:

wherein:
X represents O or S;
R′ 1 , R′ 2 , R′ 3 and R′ 4 independently represent a hydrogen atom, —NR A R B , —N + R A R B R C , —OR, —CO 2 M or —SO 3 M;
where M represents a hydrogen atom or an alkali metal atom; and each occurrence of R, R A , R B and R C independently represents a hydrogen atom or a linear or branched C 1 to C 16 alkyl; wherein the R radical can also represent, independently for each occurrence of R, a polyethylene glycol radical of formula:

 wherein n represents an integer from 1 to 6;
in an organic solvent, in the presence of a base, and under sonication, ball-milling and/or high-shear mixing, at a temperature of between 15° C. and 65° C., to obtain the corresponding graphene Diels-Alder adduct.

2. The process of claim 1 , wherein the compound of formula (I) has one of the following structures:

3. The process of claim 1 , wherein the organic solvent is selected from the group consisting of a saturated or unsaturated aliphatic or alicyclic hydrocarbon, an aromatic hydrocarbon, an alcohol, a glycol, a halogenated hydrocarbon, a ketone, an ester, an ether, a glycol ether or another suitable organic solvent, and a mixture of two or more thereof.

4. The process of claim 1 , wherein the organic solvent is selected from the group consisting of tetrahydrofuran (THF), acetonitrile, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), 2-propanol, toluene, benzene, chlorobenzene, and 1,2-dichlorobenzene.

5. The process of claim 1 , wherein the base is di- or trialkylamine.

6. The process of claim 1 , wherein the Diels-Alder reaction is carried out at a temperature of 20-65° C.

7. The process of claim 1 , further comprising a centrifuging step.

8. The process of claim 7 , further comprising a step of filtering the supernatant obtained from the centrifuging step, to isolate the Diels-Alder adduct of graphene sheets obtained by the process.

9. The process of claim 1 , wherein the graphite-containing material is carbon black or graphite.

10. The process of claim 1 , further comprising a step of annealing the Diels-Alder adduct of graphene sheets under vacuum, to obtain monolayer graphene, or multilayer graphene of 2 to 5 graphene sheets, or a mixture of these.

11. A Diels-Alder adduct of graphene sheets obtainable by a process according to claim 1 .

12. The process of claim 3 , wherein the organic solvent is an alcohol comprising at least 3 carbon atoms.

13. The process according to claim 1 , wherein n represents an integer from 1 to 3.

14. The process according to claim 5 , wherein the di- or trialkylamine is selected from the group consisting of diethylamine, dimethylamine, aza-crown ether, diisopropylamine, diisopropylethylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, N-methylcyclopentylamine, and N-ethylcyclopentylamine.

Assignees

• Univ Bordeaux
• Inst Polytechnique Bordeaux
• Centre Nat De La Rech Scientifique—Cnrs
• Centre Nat Rech Scient

Inventors

• Bassani Dario
• Verlhac Jean-Baptiste
• Bares Hugo Florian

Classifications

• C01B2204/02

  Single layer graphene · CPC title

• C01B31/0423

  Chemistry & Metallurgy · mapped topic

• H01L2251/301

  Electricity · mapped topic

• H01L51/5203

  Electricity · mapped topic

• C01B2204/04

  Specific amount of layers or specific thickness · CPC title