[go: up one dir, main page]

WO2014200232A1 - Stabilisant de dispersion pour exfoliation du graphène, composite graphène-sel de métal alcalin le comprenant, et procédé de préparation de graphène l'utilisant - Google Patents

Stabilisant de dispersion pour exfoliation du graphène, composite graphène-sel de métal alcalin le comprenant, et procédé de préparation de graphène l'utilisant Download PDF

Info

Publication number
WO2014200232A1
WO2014200232A1 PCT/KR2014/005057 KR2014005057W WO2014200232A1 WO 2014200232 A1 WO2014200232 A1 WO 2014200232A1 KR 2014005057 W KR2014005057 W KR 2014005057W WO 2014200232 A1 WO2014200232 A1 WO 2014200232A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
compound
group
dispersion stabilizer
alkali metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2014/005057
Other languages
English (en)
Korean (ko)
Inventor
강병남
이동현
이종찬
안자은
최지은
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongjin Semichem Co Ltd
Original Assignee
Dongjin Semichem Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongjin Semichem Co Ltd filed Critical Dongjin Semichem Co Ltd
Publication of WO2014200232A1 publication Critical patent/WO2014200232A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
    • C07C43/2055—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring containing more than one ether bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3834—Aromatic acids (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • C07F9/65586—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system at least one of the hetero rings does not contain nitrogen as ring hetero atom

Definitions

  • the present invention relates to a dispersion stabilizer for graphene peeling, a graphene-alkali metal salt composite including the same, and a method for preparing graphene using the same, and more particularly, graphene capable of efficiently peeling graphene from graphite.
  • the present invention relates to a dispersion stabilizer for peeling, a graphene-alkali metal salt composite including the same, and a method of preparing graphene using the same.
  • Graphene is a carbon crystal in which carbon atoms are connected in a hexagonal honeycomb shape to have a two-dimensional sheet shape, and a plurality of graphene sheets are stacked to form graphite. Therefore, when the graphite is exfoliated, a sheet-like graphene composed of one or more layers can be obtained.
  • Graphene is a material having both metal and nonmetal properties, and has good electrical and thermal conductivity as metals, and has high thermal stability and chemical inertness as nonmetals. Graphene can be applied to various applications such as electric devices, batteries, fuel cells, refractory materials, and the like.
  • the mechanical peeling method is a method of mechanically grinding or using an adhesive tape, in which graphite is simply mechanically crushed, or an adhesive tape is attached to the graphite and then peeled off to obtain graphene that is attached to the adhesive tape and peeled off.
  • graphite is prepared by oxidizing graphite with an oxidizing agent, and then a solvent such as water is inserted between the surfaces of the graphite oxide to increase the spacing between the layers, stirring or ultrasonic grinding, After peeling off the graphene oxide, it is reduced again to prepare a graphene.
  • a solvent such as water
  • the vinol sodium salt improves the dispersity of graphene oxide in water, and the two naphthalene groups improve the separation properties of graphene, as well as due to weak ⁇ - ⁇ interaction, And by washing with an organic solvent, it can be easily removed from the graphene without affecting the properties of the reduced graphene.
  • the method of manufacturing the graphene excellent in solubility by adding a dispersing agent to the graphite peeled by the mechanical peeling method is also studied.
  • a method of separating graphite using ⁇ - ⁇ interaction by mixing graphite and a metal salt aqueous solution, intercalation of metal salts between graphite, or intercalation of aromatic cyclic compounds between graphite has been studied (patent publication). 10-2012-0095907 et al.).
  • the metal salt or aromatic compound dissolved in the aqueous solution is intercalated between the layers of graphite, thereby increasing the interlayer distance of graphite.
  • An object of the present invention is not only excellent dispersibility in aqueous and organic solvents, but also graphene peeling dispersion stabilizer and graphene containing the same, which can improve the intercalation and dispersion characteristics of alkali metal salts in graphite. It provides an alkali metal salt complex.
  • Another object of the present invention is to provide a method for producing graphene, which is easy to mass-produce graphene, and can stably and easily prepare graphene.
  • the present invention provides a dispersion stabilizer for graphene peeling having a structure of the formula (1).
  • Ar is an aromatic group having 4 to 100 carbon atoms
  • M is an alkali metal
  • X is an oxide group (-O-), carboxylate group (-COO-) capable of ion bonding with the alkali metal M
  • Y is -CH 2 -or -CF 2-
  • n is 0 to 10
  • m is an integer from 1 to 3
  • Z is absent, or -CH 2- , -NH-, -O-, -S-, -SO 2- , -CO- or -CF 2-
  • E is -H, -CH 3 , -SH, -OH, -NH 2 or -CH 2 NH 2
  • p is an integer from 1 to 100
  • l is 1 or 2.
  • the present invention provides a graphene-alkali metal salt complex having a graphene peeling dispersion stabilizer represented by Chemical Formula 1 interposed between the layer and the layer of graphene.
  • the present invention by mixing the graphite stabilizer dispersion stabilizer and graphite in the presence of a solvent, so that the graphene release dispersion stabilizer is inserted between the graphite layer and the layer, the interlayer of graphite Increasing the interval; Dispersing the graphite having the graphene peeling dispersion stabilizer inserted therein to prepare a graphene-alkali metal salt composite having a graphene peeling dispersion stabilizer inserted between the graphene layer and the layer; And by washing the graphene-alkali metal salt complex with a solvent, to provide a graphene manufacturing method comprising the step of removing the dispersion stabilizer for graphene peeling from the graphene-alkali metal salt complex.
  • the dispersion stabilizer for graphene peeling according to the present invention may not only have excellent dispersion in aqueous and organic solvents, but also improve insertion and dispersion characteristics of alkali metal salts in graphite. Hydrophobic graphite is agglomerated due to the strong attraction between each other, the dispersion stabilizer having a hydrophilic group according to the present invention can prevent the agglomeration of the graphite, it can be easily dispersed in various solvents by modifying the dispersion stabilizer . In addition, according to the method for producing graphene according to the present invention, it is possible to stably produce a large amount of graphene.
  • FIG. 1 is a schematic diagram showing a process of peeling off the graphene using the dispersion stabilizer for graphene peeling according to the present invention.
  • Figure 2 is a photograph showing the long-term stability of the graphene-graphene peeling dispersion stabilizer composite prepared using NaOH and the dispersion stabilizer for graphene peeling of the present invention.
  • Figure 3 is an electron scanning micrograph of the graphene prepared using NaOH and the dispersion stabilizer for graphene peeling of the present invention.
  • Dispersion stabilizer for graphene peeling according to the present invention is inserted between the layer and the layer of graphite, by increasing the interlayer distance of the graphite, as a material to promote the peeling of the graphene from graphite, having a structure of formula (1).
  • Ar is an aromatic group having 4 to 100 carbon atoms, preferably 5 to 50 carbon atoms, for example, 6 to 20 carbon atoms
  • M is an alkali metal such as Li, Na, K
  • X is an alkali metal M
  • Oxide groups (Oxide, -O-), carboxylate groups (Carboxylate, -COO-), sulfonate groups (Sulfonate, -SO 3- ), sulfonyl groups (Sulfonyl, -SO 2- ) Or a phosphite group (Phosphite, -PO 3- )
  • Y is -CH 2 -or -CF 2-
  • n is 0 to 10, preferably 0 to 5, for example an integer of 1, 2 or 3
  • m is the number of functional groups containing alkali metal M connected to aromatic group Ar, which is an integer of 1 to 3.
  • Z is absent or is -CH 2- , -NH-, -O-, -S-, -SO 2- , -CO- or -CF 2-
  • E is -H, -CH 3 ,- SH, -OH, -NH 2 or -CH 2 NH 2
  • p is an integer from 1 to 100, preferably from 1 to 25, for example from 2 to 10
  • l is an ethylene glycol chain linked to the aromatic group Ar As the number of, 1 or 2.
  • the aromatic group Ar may include one or more hydrocarbon aromatic groups or heterocyclic aromatic groups, preferably an aromatic group having a planarity, for example, Aromatic groups, such as these, may be sufficient.
  • A is each independently O, S, Se or NH
  • n is an integer from 0 to 10, preferably 0 to 5, for example 1, 2 or 3
  • v and w is an integer of 0 to 1
  • each R is independently a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, for example, an alkyl group having 1 to 20 carbon atoms or an alkoxy group, having 2 to 50 carbon atoms,
  • an alkene or alkyne having 3 to 20 carbon atoms
  • an aryl or heteroaryl group having 4 to 50 carbon atoms for example, 5 to 20 carbon atoms.
  • the alkyl group, alkene group or alkyne group may have a branched (branched chain) or cyclic structure, such as linear, iso alkyl (iso alkyl).
  • the said R may be substituted by substituents, such as an amine.
  • binding salts of the alkali metals M, X, and Y may be exemplified.
  • M, Y and n are as described in the formula (1).
  • graphene peeling dispersion stabilizer represented by Formula 1 may include a compound represented by the following formula (1a) to 1j.
  • FIG. 1 is a schematic diagram showing a process of peeling off the graphene using the dispersion stabilizer for graphene peeling according to the present invention.
  • the dispersion stabilizer for graphene peeling according to the present invention is inserted between the layer of graphite (A of Figure 1) and the layer (B of Figure 1), by increasing the interlayer distance of graphite, graphite The graphene is peeled off (FIG. 1C).
  • the dispersion stabilizer for graphene peeling according to the present invention is an aromatic compound having an alkali metal salt and a hydrophilic alkyl chain in the form of ethylene glycol, and has excellent dispersity and solubility in aqueous and organic solvents, and graphite It can be effectively penetrated (inserted) between layers of and.
  • an alkali metal salt is intercalated between the layer and the layer of graphite to increase the interlayer distance of the graphite, and also has excellent planarity of the dispersion stabilizer.
  • an oxide group (-O-), a carboxylate group (-COO-), a sulfonate group (-SO 3- ), a sulfonyl group (-SO 2- ), and a phosphate at one end of the graphene peeling dispersion stabilizer By introducing a fighter group (-PO 3- ) and the like and stably coordinating the metal salt using the same, the stability of the metal salt can be improved.
  • the dispersion stabilizer for peeling graphene since the oxygen atoms constituting the alkyl chain in the form of ethylene glycol have unshared electron pairs, the oxygen atoms surround some alkali metal salts (Li + , Na + , K +, etc.). As a result, metal salts can be stably coordinated in a form similar to crown ethers. In this case, since the metal salt is located at both ends of the graphene peeling dispersion stabilizer, when the graphene peeling dispersion stabilizer penetrates between the graphite layer and the layer, the dispersibility of the graphite can be further improved.
  • the dispersion stabilizer for graphene peeling according to the present invention can be prepared by reacting an aromatic compound having a hydroxy group with ethylene glycol and a metal salt, as shown in the following examples.
  • a graphene peeling dispersion stabilizer represented by the formula (1) and graphite are mixed, The interlayer spacing of graphite is increased by inserting a dispersion stabilizer for peeling graphene between layers.
  • the amount of the graphene peeling dispersion stabilizer represented by the formula (1) is 10 to 90% by weight, preferably 50 to 90% by weight, more preferably based on the total content of the graphene peeling dispersion stabilizer and graphite. 80 to 90% by weight.
  • the amount of the dispersion stabilizer for peeling graphene may be 2 to 10 times by weight.
  • the amount of the graphene peeling dispersion stabilizer is too small, there is a concern that the peeling of graphite may be insufficient.
  • the amount of the graphene peeling dispersion stabilizer is too large, the electrical conductivity of the resulting graphene is lowered. There is a risk of becoming unfavorable and economically undesirable without any particular benefit.
  • a conventional aqueous or organic solvent may be used without particular limitation, and for example, water, ethanol, isopropyl alcohol, dimethyl sulfoxide, dichloromethane, carbon disulfide , Acetone, chloroform, carbon tetrachloride, 1,4-dioxane, methyl acetate, pyridine, m-cresol, phenol, dimethylformamide, dimethylacetamide, sulfuric acid, N-methyl-2-pyrrolidone and pyridine
  • One or more solvents selected may be used.
  • the amount of the solvent is not particularly limited and may be set as needed.
  • 500 to 9900 parts by weight preferably 2000 to 9900, based on 100 parts by weight of the dispersion stabilizer for graphene and the total graphite. Parts by weight. If the amount of the solvent is too small, the dispersion stabilizer for graphene peeling and graphite may not be sufficiently dissolved. If the amount of the solvent is too high, the production efficiency of graphene may be lowered.
  • the mixing temperature of the solvent, the dispersion stabilizer for graphene peeling, and graphite may also be appropriately set as necessary, for example, 0 to 200 ° C, preferably 25 to 50 ° C.
  • a graphene-alkali metal salt composite having a graphene peeling dispersion stabilizer is inserted between the graphene layer and the layer.
  • the dispersing step may be performed by peeling and pulverizing graphite into which the dispersion stabilizer for graphene peeling is inserted, by stirring or ultrasonically pulverizing the graphite solution into which the dispersion stabilizer for graphene peeling is inserted.
  • the content of the dispersion stabilizer for graphene peeling is 10 to 90% by weight, preferably 50 to 90% by weight, and more, based on the total content of the graphene-alkali metal salt composite. Preferably it is 80 to 90 weight%.
  • the composite in which the dispersion stabilizer for graphene peeling is inserted between the layer and the layer of graphene thus prepared is referred to as "graphene-alkali metal salt complex" or "graphene-graphene dispersion stabilizer composite".
  • the solution containing the graphene-alkali metal salt composite is referred to as "graphene-alkali metal salt composite ink.”
  • the graphene-alkali metal salt composite is washed with a solvent to remove the graphene peeling dispersion stabilizer from the graphene-alkali metal salt composite, thereby obtaining pure graphene.
  • a solvent used in the washing step, one or more of the solvent used for mixing the graphene peeling dispersion stabilizer and graphite may be appropriately selected and used as necessary, and water may be preferably used.
  • the method for producing graphene according to the present invention as an organic-inorganic complex compound having a safe and inexpensive alkali metal salt and a hydrophilic alkyl chain, using a graphene peeling dispersion stabilizer represented by the formula (1), By peeling the pins, it is possible to produce graphene easily, stably, and inexpensively as compared to a method of simply peeling graphite using an alkali metal.
  • the method for producing graphene according to the present invention it is possible to mass-produce graphene without undergoing an environmentally undesirable chemical reduction process.
  • the graphene prepared according to the present invention may be used as various electrical and electronic materials such as electrostatic discharge (ESD) devices such as antistatic films, electromagnetic interference (EMI) devices such as electromagnetic shielding films, electrodes, and heat radiating materials.
  • ESD electrostatic discharge
  • EMI electromagnetic interference
  • reaction solution was raised to 60 ° C., stirred for 2 hours, and then cooled to room temperature to obtain a white solid material.
  • 2.50 g (4.62 mmol) of the obtained compound (35) were dissolved in 16 ml of acetonitrile (MeCN), cooled to 0 ° C., and 0.53 ml (3.99 mmol) of bromotrimethylsilane was added thereto. , And reacted at room temperature for 17 hours to synthesize compound (36). While slowly adding 2M aqueous NaOH solution (aq) to the synthesized compound (36), the pH was adjusted to 8, and then precipitated with ethanol to obtain a phosphate type compound (37).
  • the graphene-graphene peeling dispersion stabilizer composite ink obtained in Example 8 was filtered under reduced pressure, and then washed several times with water to remove the graphene peeling dispersion stabilizer from the graphene-graphene peeling dispersion stabilizer composite. Pins were prepared.
  • the remaining powder (graphene without dispersion stabilizer) was added to water, ethanol, isopropyl alcohol, dimethyl sulfoxide, dichloromethane, carbon disulfide, acetone, chloroform, carbon tetrachloride, 1,4-dioxane , Methyl acetate, pyridine, m-cresol, phenol, dimethylformamide, dimethylacetamide, sulfuric acid, N-methyl-2-pyrrolidone and pyridine was prepared.
  • SEM scanning electron microscope, Hitachi S-4800

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention porte sur un stabilisant de dispersion pour exfoliation du graphène, capable d'exfolier efficacement le graphène à partir du graphite, sur un composite graphène-sel d'un métal alcalin le comprenant, et sur un procédé de préparation du graphène l'utilisant. Le stabilisant de dispersion pour exfoliation du graphène a la structure de la formule chimique 1. Dans la formule chimique 1, Ar est un groupe aromatique C4-100 ; M est un métal alcalin ; X est un groupe oxyde (-O-), un groupe carboxylate (-COO-), un groupe sulfonate (-SO3-), un groupe sulfonyle (-SO2-) ou un groupe phosphite (-PO3-) pouvant se lier au métal alcalin M par une liaison ionique ; Y est -CH2- ou -CF2- ; n est un entier de 0-10 ; m est un entier de 1-3 ; Z n'existe pas, ou est -CH2-, -NH-, -O-, -S-, -SO2-, -CO- ou -CF2- ; E est -H, -CH3, -SH, -OH, -NH2 ou -CH2NH2 ; p est un entier de 1-100 ; et l vaut 1 ou 2.
PCT/KR2014/005057 2013-06-10 2014-06-10 Stabilisant de dispersion pour exfoliation du graphène, composite graphène-sel de métal alcalin le comprenant, et procédé de préparation de graphène l'utilisant Ceased WO2014200232A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20130065707 2013-06-10
KR10-2013-0065707 2013-06-10

Publications (1)

Publication Number Publication Date
WO2014200232A1 true WO2014200232A1 (fr) 2014-12-18

Family

ID=52022468

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2014/005057 Ceased WO2014200232A1 (fr) 2013-06-10 2014-06-10 Stabilisant de dispersion pour exfoliation du graphène, composite graphène-sel de métal alcalin le comprenant, et procédé de préparation de graphène l'utilisant

Country Status (2)

Country Link
KR (1) KR102253512B1 (fr)
WO (1) WO2014200232A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019054931A1 (fr) * 2017-09-14 2019-03-21 Taher Mamoun Nanocomposite de graphène ionique hybride à structure en couches
CN114744195A (zh) * 2022-03-18 2022-07-12 西安近代化学研究所 一种石墨烯-冠醚-金属三元复合材料和制备方法及应用
CN115124562A (zh) * 2022-07-05 2022-09-30 辽宁大学 一种萘基高反应活性石墨烯分散剂及其制备方法和应用

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101750935B1 (ko) 2014-12-12 2017-06-27 주식회사 엘지화학 블록 공중합체, 및 이를 이용한 그래핀의 제조 방법
KR101912294B1 (ko) * 2016-05-09 2018-10-26 울산과학기술원 그래핀 제조방법, 그래핀 분산 조성물, 및 그 제조방법
KR102178358B1 (ko) * 2016-12-14 2020-11-12 주식회사 엘지화학 기능화된 그래핀의 제조 방법
KR102654623B1 (ko) * 2021-12-15 2024-04-04 (주)플로우테크 고품질의 그래핀을 대량으로 제조하는 방법
CN117836265A (zh) * 2022-05-27 2024-04-05 宁德时代新能源科技股份有限公司 有机化合物及其应用、钝化膜、太阳能电池及用电装置
KR102819989B1 (ko) * 2022-07-12 2025-06-12 (주)플로우테크 대량으로 제조된 고품질의 그래핀을 이용한 케이블형 누액감지센서 및 이를 이용한 원격 모니터링 시스템
KR102819991B1 (ko) * 2022-07-27 2025-06-12 (주)플로우테크 대량으로 제조된 고품질의 그래핀을 이용한 누액감지센서 및 이를 이용한 원격 모니터링 시스템
KR102819990B1 (ko) * 2022-07-27 2025-06-12 (주)플로우테크 대량으로 제조된 고품질의 그래핀을 이용한 누액감지센서
KR102740213B1 (ko) * 2022-10-25 2024-12-10 주식회사 제이앤씨머트리얼즈 수분산성 및 재 분산성을 갖고 이종재료와 복합화할 수 있는 환원그래핀 제조방법
KR102881686B1 (ko) * 2023-06-12 2025-11-06 (주)플로우테크 고품질의 그래핀을 대량으로 제조하는 방법

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009052933A1 (de) * 2009-11-12 2011-05-19 Bayer Technology Services Gmbh Verfahren zur Herstellung von Graphen-Lösungen, Graphen-Alkalimetallsalzen und Graphen-Verbundmaterialien
EP2585403A4 (fr) 2010-06-25 2016-07-13 Univ Singapore Procédés de formation de graphène par exfoliation de graphite

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
ARTUR CIESIELSKI ET AL.: "Graphene via sonication assisted liquid-phase exfoliation", CHEMICAL SOCIETY REVIEWS, vol. 43, 3 September 2013 (2013-09-03), pages 381 - 398 *
JI-HOON JANG ET AL.: "Direct preparation of 1-PSA modified graphene nanosheets by supercritical fluidic exfoliation and its electrochemical properties", JOURNAL OF MATERIALS CHEMISTRY, vol. 21, 2 December 2010 (2010-12-02), pages 3462 - 3466 *
MIN SOO KANG ET AL.: "Direct exfoliation of graphite using a non-ionic polymer surfactan for fabrication of transparent and conductive graphene films", JOURNAL OF MATERIALS CHEMISTRY C, vol. 1, 8 January 2013 (2013-01-08), pages 1870 - 1875 *
XIAO HUANG ET AL.: "Graphene-based composites", CHEMICAL SOCIETY REVIEWS, vol. 41, 28 July 2011 (2011-07-28), pages 666 - 686 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019054931A1 (fr) * 2017-09-14 2019-03-21 Taher Mamoun Nanocomposite de graphène ionique hybride à structure en couches
CN111344143A (zh) * 2017-09-14 2020-06-26 石墨烯材料科技公司 具有分层结构的混合离子型石墨烯纳米复合材料
US11607866B2 (en) 2017-09-14 2023-03-21 Graphmatech Ab Hybrid ionic graphene nanocomposite with layered structure
CN111344143B (zh) * 2017-09-14 2023-04-04 石墨烯材料科技公司 具有分层结构的混合离子型石墨烯纳米复合材料
CN114744195A (zh) * 2022-03-18 2022-07-12 西安近代化学研究所 一种石墨烯-冠醚-金属三元复合材料和制备方法及应用
CN114744195B (zh) * 2022-03-18 2023-12-12 西安近代化学研究所 一种石墨烯-冠醚-金属三元复合材料和制备方法及应用
CN115124562A (zh) * 2022-07-05 2022-09-30 辽宁大学 一种萘基高反应活性石墨烯分散剂及其制备方法和应用
CN115124562B (zh) * 2022-07-05 2024-02-20 辽宁大学 一种萘基高反应活性石墨烯分散剂及其制备方法和应用

Also Published As

Publication number Publication date
KR20140144148A (ko) 2014-12-18
KR102253512B1 (ko) 2021-05-18

Similar Documents

Publication Publication Date Title
WO2014200232A1 (fr) Stabilisant de dispersion pour exfoliation du graphène, composite graphène-sel de métal alcalin le comprenant, et procédé de préparation de graphène l'utilisant
WO2020027415A1 (fr) Procédé de production d'un cristal de difluorophosphate de lithium de pureté élevée et électrolyte non aqueux pour batterie secondaire l'utilisant
CA2470423A1 (fr) Procede de preparation de derives de phosphonooxymethyle d'alcool et de phenol
CN104496979A (zh) 一种噁唑烷酮类化合物及其中间体的制备方法
WO2009139579A9 (fr) Préparation de dérivés d'anthracène asymétriques et dispositif électroluminescent organique utilisant lesdits dérivés
WO2016043462A2 (fr) Procédé de préparation de calcobutrol
WO2010030132A2 (fr) Procédé de purification d'adefovir dipivoxil
CN109689626B (zh) 合成近红外、闭链磺基-花青染料的方法
CN111233947A (zh) 一类呋喃糖环状磷酸酯阻燃剂的结构及其制备方法
KR102065710B1 (ko) 많은 가교 작용기를 가지는 아지드 유형의 가교제
WO2023195774A1 (fr) Sel de diphényliodonium pour photoinitiateur et son procédé de préparation
WO2009099291A2 (fr) Dérivé d'organotrifluoroborate de potassium et procédé de production
WO2019199013A1 (fr) Méthode de préparation de sel de bis(fluorosulfonyl)imide de lithium
WO2009128631A2 (fr) Procédé de préparation d'une α-glycérophosphorylcholine racémique ou optiquement active et d'un dérivé de cette dernière
JP2009263316A (ja) 不完全縮合オリゴシルセスキオキサンの製造方法
WO2023277207A1 (fr) Procédé de préparation d'un composé ester propargylique de phosphate utile en tant que composé ignifuge pour batterie au lithium-ion
WO2019151644A1 (fr) Kznsb stratifié, znsb stratifié, nanofeuille de kznsb, nanofeuille de znsb, et leurs procédés de préparation
WO2014065560A1 (fr) Composé de cristaux liquides sous la forme d'un dendron et son procédé de préparation
WO2022080812A1 (fr) Procédé de préparation d'intermédiaire pour la synthèse d'un agoniste du récepteur de sphingosine-1-phosphate
WO2012015269A2 (fr) Composé électroluminescent organique à base de phosphaphénanthrène-carbazole et dispositif électroluminescent organique comprenant ce dernier
WO2020040617A1 (fr) Procédé de production de gadobutrol
WO2022092835A1 (fr) Procédé de préparation d'un composé symétrique à base de phosphate
WO2017082541A1 (fr) Précurseur de métal, procédé de préparation associé, et procédé de formation de film mince au moyen de celui-ci
WO2024014637A1 (fr) Procédé de préparation d'un dérivé de pérampanel comprenant un procédé d'écoulement en continu
KR102758936B1 (ko) 탄화수소고리 화합물의 제조방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14811585

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14811585

Country of ref document: EP

Kind code of ref document: A1