WO2014175449A1 - Nouvelle nanodispersion de graphène et procédé de préparation associé - Google Patents

Nouvelle nanodispersion de graphène et procédé de préparation associé Download PDF

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Publication number
WO2014175449A1
WO2014175449A1 PCT/JP2014/061787 JP2014061787W WO2014175449A1 WO 2014175449 A1 WO2014175449 A1 WO 2014175449A1 JP 2014061787 W JP2014061787 W JP 2014061787W WO 2014175449 A1 WO2014175449 A1 WO 2014175449A1
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ionic liquid
graphene
mixed
carbon atoms
compound
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PCT/JP2014/061787
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English (en)
Japanese (ja)
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相田　卓三
道生 松本
雄介 斉藤
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国立大学法人 東京大学
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Priority to JP2015513860A priority Critical patent/JP6122949B2/ja
Publication of WO2014175449A1 publication Critical patent/WO2014175449A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/61—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms not forming part of a nitro radical, attached to ring nitrogen atoms
    • 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
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms

Definitions

  • the present invention relates to a novel ionic liquid capable of dispersing graphene at a high concentration, a graphene nano-dispersion using the ionic liquid, and a method for preparing the dispersion.
  • Graphite a carbon material
  • Graphene has a layered structure, one of which is called graphene.
  • Graphene consists only of hexagonal network-bonded carbon atoms, with a thickness of only one carbon atom, extremely high thermal conductivity, and excellent electrical properties such as electrical conductivity. Expected as a nanosheet.
  • Non-Patent Document 1 The Nobel Prize-winning Geim et al. Stuck graphene on a cellophane tape, folded it so that the flake was sandwiched by the adhesive surface of the tape, and then peeled off the tape again to peel off the graphene. Obtained (Non-Patent Document 1).
  • Non-patent Document 2 a method of obtaining graphene oxide by oxidizing graphite and then exfoliating it in water.
  • the other method is a method of exfoliating graphite in a solvent or a surfactant solution by ultrasonic treatment or the like (liquid phase exfoliation) to obtain graphene dispersed in the liquid.
  • Non-patent Document 2 Non-patent Document 2
  • the level of dispersibility at the present time is about 2 mg / mL, which is still insufficient for developing a wide range of applications.
  • An object of the present invention is to provide a novel ionic liquid capable of dispersing graphene at a high concentration.
  • the present inventors have developed a novel ion that gives an extremely high concentration of graphene dispersion by linking an ionic liquid portion of an imidazolium salt with an alkylene oxide core portion. It was found that a liquid could be provided, and a patent application was filed (Japanese Patent Application No. 2012-111019 currently pending). The present inventors further examined a solvent capable of further enhancing the dispersibility of graphene. By connecting the ionic liquid portion of the imidazolium salt with alkylene or arylene, the graphene dispersibility exceeding the above ionic liquid is achieved. Was found and the present invention was completed.
  • R 1 and R 5 may be the same or different and each independently represents a substituted or unsubstituted C1-C7 linear or branched alkyl group
  • R 2 is (i) an alkylene group having 1 to 10 carbon atoms, (ii) -R 6a -Ar-R 6b- , or (iii) Selected from
  • Ar represents an arylene group
  • R 6a and R 6b may be the same or different, and each independently represents an alkylene group having 1 to 4 carbon atoms
  • R 7a and R 7b may be the same or different and each independently represents an alkylene group having 1 to 4 carbon atoms
  • R 8a and R 8b may be the same or different and each independently represents an alkylene group having 1 to 4 carbon atoms
  • m and m ′ represent an integer of 1 to 10
  • R 3 and R 4 may be the same or different and each independently represents a hydrogen atom, a
  • a graphene dispersion liquid comprising graphene and the ionic liquid according to any one of [1] to [7] or the mixed ionic liquid according to [8].
  • a method for preparing a graphene dispersion which comprises the step of applying ultrasonic waves or microwaves to the mixed liquid.
  • the preparation method according to [10] further including a step of centrifuging the mixed solution after application of ultrasonic waves.
  • a graphene dispersion liquid having an extremely high concentration compared to the prior art can be obtained.
  • a graphene dispersion liquid having an extremely high concentration compared to the prior art can be obtained.
  • high dispersibility is obtained by the ionic liquid of the present invention, graphene can be applied to a wide range of applications, for example, many electronic components such as lithium ion secondary batteries and energy storage appliances.
  • the method for preparing a graphene dispersion of the present invention can obtain a high-concentration graphene dispersion by a one-step exfoliation process of graphite without going through graphene oxide. High value.
  • Ionic liquid One embodiment of the present invention relates to a novel ionic liquid represented by the following formula (1).
  • R 1 and R 5 may be the same or different, and each independently represents a substituted or unsubstituted C1-C7 linear or branched alkyl group.
  • R 1 and R 5 are each independently preferably a C1-C6 linear alkyl group, ie methyl, ethyl, n-propyl, n-butyl, n-pentyl or n-hexyl, Particularly preferred is n-butyl.
  • R 2 is (i) an alkylene group having 1 to 10 carbon atoms, (ii) -R 6a -Ar-R 6b- , or (iii) Selected from.
  • R 2 is an alkylene group having 1 to 10 carbon atoms.
  • the alkylene group includes linear, branched and cyclic alkylene, and preferably has 4 to 10 carbon atoms, more preferably 6 to 8 carbon atoms.
  • Preferable alkylene includes, for example, hexene and octene.
  • Ar represents an arylene group.
  • the arylene group include a phenylene group and a naphthylene group.
  • R 6a and R 6b may be the same or different and each independently represents an alkylene group having 1 to 4 carbon atoms.
  • R 6a and R 6b are the same and are alkylene groups having 1 to 2 carbon atoms.
  • R 7a and R 7b may be the same or different and each independently represents an alkylene group having 1 to 4 carbon atoms.
  • R 7a and R 7b are the same and are alkylene groups having 1 to 2 carbon atoms.
  • R 8a and R 8b may be the same or different and each independently represents an alkylene group having 1 to 4 carbon atoms.
  • R 8a and R 8b are the same and are alkylene groups having 1 to 2 carbon atoms.
  • m and m ′ represent an integer of 1 to 10, preferably an integer of 1 to 2.
  • Ar is a phenylene group
  • the two oxygen atoms in R 6a and R 6b and formula (2) may be bonded to the phenylene group so as to be in any of the ortho, meta, and para arrangements. It is preferable to combine so that.
  • an imidazo it is considered that the lithium-based salt interacts with graphene and the alkylene oxide core does not interact with graphene.
  • the alkylene or arylene core also has graphene. It is thought that it contributes to the interaction.
  • R 3 and R 4 may be the same or different and each independently represents a hydrogen atom, a substituted or unsubstituted C1-C4 linear or branched alkyl group. In the present invention, both R 3 and R 4 are preferably hydrogen.
  • X ⁇ represents a counter ion, preferably PF 6 ⁇ , (CF 3 SO 2 ) 2 N ⁇ (abbreviated herein as TSFI ⁇ ), BF 4 ⁇ , Cl ⁇ . or Br - is selected from.
  • n represents 0-30.
  • n is an integer of 0 to 2
  • the imidazolium salt portion is a dimer, trimer or tetramer.
  • the synthesis of the ionic liquid of formula (1) uses a continuous synthesis method instead of the sequential synthesis method.
  • the ionic liquid of formula (1) consists of several types of n. It is a mixture of compounds, and n is the average of these.
  • the present invention includes the case where the ionic liquid represented by the formula (1) is such a mixture.
  • 1-Butylimidazole is added to an acetonitrile solution of 1,8-dichlorooctane, heated and mixed.
  • the reaction mixture is concentrated to dryness under reduced pressure, methylene chloride or the like is added to the viscous residue, and two-layer separation is performed using ethyl acetate or the like.
  • the ionic liquid layer is dried by a rotary evaporator and a vacuum oven, Compound 1a, which is a reddish brown viscous liquid, is obtained.
  • any of the ionic liquids represented by the formula (1) can be used as A.
  • R 2 in the formula (1) is an octene group or a p-xylylene group (ie, In (ii), Ar is a phenylene group and R 6a and R 6b are methylene groups), and n is preferably an ionic liquid having 0-2.
  • the content of A in the mixed ionic liquid of the present invention can vary depending on the type of the ionic liquid of A.
  • A can be 35 to 55% by weight.
  • the mixed ionic liquid of the present invention contains A and B or C as essential components, but can contain other solvents such as methanol and water as appropriate in addition to these components.
  • a further embodiment of the present invention relates to a graphene dispersion comprising graphene and the ionic liquid or mixed ionic liquid of the present invention.
  • graphene is dispersed at a high concentration.
  • the graphene dispersion of the present invention preferably contains 10 mg or more, more preferably 20 mg or more, and further preferably 40 mg or more of graphene per 1 ml of the dispersion.
  • graphene has a layer number distribution and is often a mixture of a single layer of graphene and a plurality of layers of graphene.
  • graphene includes not only single-layer graphene but also one in which a plurality of graphene layers, preferably 9 layers or less, are stacked.
  • the graphene dispersion of the present invention is prepared, for example, by the following method, but is not limited thereto.
  • the method for preparing a graphene dispersion in the present invention includes an ionic liquid represented by the formula (1) or a mixed ionic liquid of the ionic liquid and butylmethylimidazolium hexafluorophosphate or butylmethylimidazolium bis (trifluoromethanesulfonyl) imide.
  • the graphite particles that can be used in the preparation method of the present invention have an average particle size of 100 ⁇ m or less, preferably 1 ⁇ m or more and 100 ⁇ m or less.
  • the average particle diameter is the particle size d 50 at an accumulation of 50%.
  • any ultrasonic disperser can be used, but a horn type ultrasonic disperser is preferably used.
  • the frequency of the ultrasonic wave is about 10 kHz to 1 MHz.
  • the amplitude of the ultrasonic wave is about 1 ⁇ m or more and 100 ⁇ m or less (zero-to-peak value).
  • the application time of the ultrasonic wave is not particularly limited, but is usually 1 minute or longer, preferably 1 minute or longer and 6 hours or shorter.
  • any microwave oven can be used.
  • a general microwave oven of 500 W and 2.4 GHz can be used.
  • the microwave application time is not particularly limited, but is usually 10 seconds or longer, preferably 10 seconds to 10 minutes.
  • the method for preparing a graphene dispersion of the present invention may include a step of centrifuging the liquid after application of ultrasonic waves, and may further include a step of recovering the liquid layer from the mixed solution after centrifugation.
  • the graphene dispersion is obtained by, for example, centrifuging the whole or part of the obtained mixture with a centrifuge and collecting the supernatant. Centrifugation conditions can be appropriately adjusted depending on the desired graphene concentration.
  • the ionic liquid layer is dried over Na 2 SO 4 , concentrated on a rotary evaporator, and dried in a vacuum oven overnight at 100 ° C. using P 2 O 5 to give compound 1, a reddish brown viscous liquid. (43.2 g, 46.89 mmol, yield: 72%).
  • Example 1 Compound 2 was added to butyl methyl imidazolium hexafluorophosphate (BMIPF 6 ) so as to have a concentration of 0, 15 wt%, 26 wt%, 35 wt%, and 55 wt% to prepare a mixed ionic liquid. In each of these mixed ionic liquids, graphene was dispersed by the above procedure, and the graphene concentration was calculated.
  • BIPF 6 butyl methyl imidazolium hexafluorophosphate
  • Table 1 shows the measurement results of the graphene concentration of the dispersions according to Example 1 and Reference Example 1.
  • FIG. 1 shows the graphene layer number distribution of graphite obtained by adding a graphite to acetonitrile and measuring the Raman spectrum without sonication and centrifugation. From FIG. 1, it can be seen that in graphite not subjected to special dispersion treatment, the number of graphene layers larger than 9 accounts for 60% or more. In the following examples, the graphene layer number distribution was examined using the mixed ionic liquid of the present invention.
  • Example 2 Compound 2 was added to BMIPF 6 to prepare a mixed ionic liquid having a concentration of the compound of 35% by weight. To this mixed ionic liquid, graphite was added so as to be 70 mg / mL, and sonication and centrifugation were performed under the following conditions.
  • a Raman spectrum was measured for the dispersion obtained by processing under the conditions (a) and (b), and the graphene layer number distribution was examined.
  • FIGS. 2a and 2b The results are shown in FIGS. 2a and 2b. From FIG. 2a and FIG. 2b, it can be seen that when the mixed ionic liquid of the present invention is used, the ratio of the number of graphene layers is 9 or less is about 90% of the whole.
  • Example 3 (4) Dispersion only by ultrasonic treatment Compound 1 was added to BMITFSI to prepare a mixed ionic liquid having a concentration of 35% by weight. Graphite is added to this mixed ionic liquid so as to be 70 mg / mL, ultrasonic waves are applied for 5 minutes, 30 minutes, and 60 minutes, the Raman spectrum is measured for the dispersion at each time point, and the graphene layer number distribution I investigated. The results are shown in FIG.
  • Example 4 The same test as in Example 3 was performed using Compound 3. The results are shown in FIG.
  • FIG. 3 shows that by using the mixed ionic liquid of the present invention, the proportion of graphene layers of 9 or less is increased only by ultrasonic treatment.
  • a high-concentration graphene dispersion can be provided by using the novel ionic liquid of the present invention.
  • the dispersibility is obtained by the ionic liquid of the present invention, it becomes easy to form a graphene film, and the graphene is applied to many electronic components such as lithium ion secondary batteries and energy storage appliances. It becomes possible to do.
  • the manufacturing method of this invention can obtain a high concentration graphene dispersion by the one-step exfoliation process of graphite, without going through a graphene oxide, production efficiency is high and industrially high.
  • the ionic liquid of the present invention it is possible to obtain a dispersion with a high graphene content with 9 or less graphene layers only by ultrasonic treatment, and the production efficiency of the graphene dispersion can be improved. It can be expected to increase.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Le problème décrit par la présente invention est d'obtenir un nouveau liquide ionique dans lequel du graphène peut être dispersé à une concentration élevée. La solution selon l'invention consiste en un liquide ionique représenté par la formule générale (1).
PCT/JP2014/061787 2013-04-26 2014-04-25 Nouvelle nanodispersion de graphène et procédé de préparation associé WO2014175449A1 (fr)

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Cited By (7)

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WO2015159635A1 (fr) * 2014-04-17 2015-10-22 株式会社Adeka Liquide contenant une substance en couches et son procédé de fabrication
WO2016088753A1 (fr) * 2014-12-02 2016-06-09 大日本印刷株式会社 Graphite lamellaire, matériau à base de graphite, et dispersion de graphite lamellaire
WO2016158842A1 (fr) * 2015-03-27 2016-10-06 株式会社カネカ Hydrocarbure saturé à chaîne aliphatique résistant à la chaleur ayant des paires d'ions aux deux extrémités et composition l'utilisant
WO2017014310A1 (fr) * 2015-07-22 2017-01-26 国立大学法人 東京大学 Solution électrolytique non aqueuse
CN107189493A (zh) * 2017-04-10 2017-09-22 桂林理工大学 一种离子液体改性石墨烯的制备方法
WO2019074109A1 (fr) 2017-10-12 2019-04-18 国立大学法人東京工業大学 Composite à particules inorganiques, sa méthode de production et dispersion de composite à particules inorganiques
CN110229107A (zh) * 2018-08-07 2019-09-13 中国农业大学 一种疏水性双核咪唑类离子液体及其制备方法

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015159635A1 (fr) * 2014-04-17 2015-10-22 株式会社Adeka Liquide contenant une substance en couches et son procédé de fabrication
WO2016088753A1 (fr) * 2014-12-02 2016-06-09 大日本印刷株式会社 Graphite lamellaire, matériau à base de graphite, et dispersion de graphite lamellaire
WO2016158842A1 (fr) * 2015-03-27 2016-10-06 株式会社カネカ Hydrocarbure saturé à chaîne aliphatique résistant à la chaleur ayant des paires d'ions aux deux extrémités et composition l'utilisant
CN107531643A (zh) * 2015-03-27 2018-01-02 株式会社钟化 两末端具有离子对的耐热性脂肪族链式饱和烃以及使用其的组合物
WO2017014310A1 (fr) * 2015-07-22 2017-01-26 国立大学法人 東京大学 Solution électrolytique non aqueuse
JPWO2017014310A1 (ja) * 2015-07-22 2018-06-14 国立大学法人 東京大学 非水系電解液
CN107189493A (zh) * 2017-04-10 2017-09-22 桂林理工大学 一种离子液体改性石墨烯的制备方法
WO2019074109A1 (fr) 2017-10-12 2019-04-18 国立大学法人東京工業大学 Composite à particules inorganiques, sa méthode de production et dispersion de composite à particules inorganiques
KR20200068670A (ko) 2017-10-12 2020-06-15 고쿠리츠다이가쿠호진 토쿄고교 다이가꾸 무기 입자 복합체 및 그의 제조 방법, 그리고 무기 입자 복합체 분산액
CN110229107A (zh) * 2018-08-07 2019-09-13 中国农业大学 一种疏水性双核咪唑类离子液体及其制备方法

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