WO2016208884A1 - 전단 유동을 이용한 고품질 그래핀 제조 방법 및 장치 - Google Patents

전단 유동을 이용한 고품질 그래핀 제조 방법 및 장치 Download PDF

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Publication number
WO2016208884A1
WO2016208884A1 PCT/KR2016/005777 KR2016005777W WO2016208884A1 WO 2016208884 A1 WO2016208884 A1 WO 2016208884A1 KR 2016005777 W KR2016005777 W KR 2016005777W WO 2016208884 A1 WO2016208884 A1 WO 2016208884A1
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Prior art keywords
graphite
graphene
fluid
inner body
based material
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PCT/KR2016/005777
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English (en)
French (fr)
Korean (ko)
Inventor
김태영
박승준
Original Assignee
가천대학교 산학협력단
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Priority claimed from KR1020150089523A external-priority patent/KR101775610B1/ko
Priority claimed from KR1020150089522A external-priority patent/KR101775609B1/ko
Application filed by 가천대학교 산학협력단 filed Critical 가천대학교 산학협력단
Priority to CN201680028333.2A priority Critical patent/CN107624105B/zh
Publication of WO2016208884A1 publication Critical patent/WO2016208884A1/ko

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside

Definitions

  • the present invention relates to a graphene manufacturing method, and more particularly to a high quality graphene manufacturing method using a shear flow.
  • the present invention also relates to a manufacturing apparatus suitable for achieving the graphene manufacturing method.
  • Graphene is generally defined as a single layer of carbon in a hexagonal crystal structure with a two-dimensional planar structure.
  • Graphene is an carbon material that is expected to be applied to various fields, such as semiconductors and displays, because it has an advantage of showing excellent electrical conductivity, thermal conductivity, and mechanical strength compared to conventional carbon materials.
  • Such graphene is prepared by various methods.
  • Figure 1 schematically shows a graphene manufacturing method using the oxidation / reduction method.
  • graphite is oxidized to form graphite oxide, and the graphene oxide is peeled off to obtain graphene oxide, followed by reduction.
  • Graphene is prepared through.
  • Figure 2 schematically shows a graphene manufacturing method using ultrasonic waves.
  • graphene is manufactured by directly peeling graphite in a solvent to which ultrasonic waves are applied.
  • this method since it does not involve an oxidation / reduction process, graphene with few defects can be produced, and excellent electrical characteristics can be ensured.
  • this method has a disadvantage in that the graphene production rate is low due to the limitation of the exfoliation efficiency of graphite.
  • this method has a limitation in that it is difficult to continuously mass-produce graphene due to technical limitations of ultrasonic equipment.
  • Another method of preparing graphene is a method of synthesizing graphene at a high temperature using chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • Another object of the present invention to provide a graphene manufacturing apparatus that can be applied to the graphene manufacturing method.
  • Graphene manufacturing method for achieving the above object is a step of injecting a graphite-based material in a fluid containing a solvent, stored in the reaction space of the reactor; And rotating the fluid into which the graphite-based material is injected, to release the graphite-based material with a shear force generated by the rotational flow of the fluid, thereby producing graphene.
  • the reactor may include an inner body extending in a horizontal direction, and a cylindrical outer body to form a reaction space inside the inner body wrapped in the state spaced apart from the inner body.
  • a graphite-based material may be injected from one side of the cylindrical outer body, and graphene may be discharged from the other side of the cylindrical outer body.
  • the solvent may include one or more of N-methyl-2-pyrrolidinone (NMP) and N, N-dimethylformamide (DMF).
  • NMP N-methyl-2-pyrrolidinone
  • DMF N, N-dimethylformamide
  • the fluid may include at least one of sodium cholate (NaC) poly vinyl alcohol (PVA), poly vinyl pyrrolidone (PVP), polystyrenesulfonate (PSS), dodecylbenzene sulfonic acid (DBSA), and an ionic liquid (Ionic liquid). It may further include a dispersant.
  • NaC sodium cholate
  • PVA poly vinyl alcohol
  • PVP poly vinyl pyrrolidone
  • PSS polystyrenesulfonate
  • DBSA dodecylbenzene sulfonic acid
  • Ionic liquid ionic liquid
  • the fluid can be rotated in a heated state.
  • the rotational speed of the inner body can be adjusted to 500 rpm or more.
  • non-expandable graphite or expandable graphite in a compressed state may be used as the graphite-based material.
  • a graphite intercalation compound in which an intercalant is inserted between the layers of graphite may be used as the graphite-based material.
  • the intercalation species may include at least one of compounds including at least one alkali metal and alkaline earth metal, sulfuric acid, nitric acid, phosphoric acid and organic acid, and an ionic liquid.
  • Graphene manufacturing apparatus for achieving the above object is a cylindrical outer body to form a reaction space inside the inner body extending in the horizontal direction, the inner body in a state spaced apart from the inner body Reactor comprising a; An inlet formed on one side of the cylindrical outer body and into which a graphite-based material is injected; A discharge port formed at the other side of the cylindrical outer body and discharging graphene obtained by peeling graphite by a shear force generated by a rotational flow of a fluid stored in the reaction space; And a driving unit for rotating the inner body.
  • the graphene manufacturing method according to the present invention it is possible to effectively exfoliate graphite by using the shear flow of the fluid, it is possible to continuously and mass production of graphene.
  • the intercalation species that can act to weaken the attraction between the graphene layer of the graphite is included, so that the graphite peeling efficiency, that is, the graphene production efficiency
  • the graphite peeling efficiency that is, the graphene production efficiency
  • Figure 1 schematically shows a graphene manufacturing method using the oxidation / reduction method.
  • Figure 2 schematically shows a graphene manufacturing method using ultrasonic waves.
  • Figure 3 schematically shows a graphene manufacturing method using a shear flow in accordance with the present invention.
  • Figure 4 is a perspective view schematically showing an example of a reactor that can be applied to the graphene manufacturing method according to the present invention.
  • FIG. 5 is a cross-sectional view schematically showing an example of a reactor that can be applied to the graphene manufacturing method according to the present invention.
  • Figure 6 schematically shows a graphene manufacturing apparatus according to an embodiment of the present invention.
  • Figure 3 schematically shows a graphene manufacturing method using a shear flow in accordance with the present invention.
  • the graphene manufacturing method according to the present invention uses a shear flow (shear flow). More specifically, in the present invention, graphene is manufactured by rotating a fluid to form a Taylor fluid flow and peeling the graphite-based material with a shear force generated by the rotational flow of the fluid. In this case, the shear force applied to the graphite-based material should be sufficient to overcome the strong van der Waals attractive force between the graphene layers of the graphite, which is a factor that affects the rotational flow characteristics of the fluid and increases the reactor rotation speed. , By raising the fluid temperature, or by adding an additive (interlayer species, dispersant, etc.).
  • the present invention uses a reactor such as the example shown in FIGS. 4 and 5.
  • the reactor using the taylor fluid includes an inner body 410 extending in the horizontal direction and a cylindrical outer body 420 surrounding the inner body spaced apart from the inner body.
  • the reaction space 430 is formed between the inner body 410 and the cylindrical outer body 420.
  • the inner body 410 and the cylindrical outer body 420 is sealed at both ends.
  • the inner body 410 is rotated about the horizontal axis by the rotation shaft 405, and the cylindrical outer body 420 is fixed.
  • the length of the reactor may be about 10 cm to about 1 m, and the volume of the reaction space may be about 10 mL to about 10 L.
  • the length of the reactor and the volume of the reaction space are not necessarily limited thereto.
  • the taylor fluid flow of the present invention is an external cylinder, i.e., the outer body is fixed and when the inner cylinder, i.e. the inner body is rotated, the fluid flows in the rotational direction of the inner cylinder, the force flowing from the inner cylinder side to the outer cylinder direction by centrifugal force
  • the fluid becomes unstable, and it refers to the vortex of the ring pair array that rotates in a regular and opposite direction along the axial direction.
  • Taylor fluid flow can be formed according to the rotational speed of the fluid and the radius and separation distance of the inner body and the outer body, the viscosity of the fluid, etc., the shear flow force is greatly increased as the Taylor fluid is formed.
  • the graphite-based material is added to the fluid containing the solvent, which is stored in the reaction space 430 of the reactor, and the graphite-based material is rotated to form the Taylor fluid and shear force generated by the Taylor flow.
  • Graphene is prepared by peeling the graphite-based material with a shear force.
  • the graphite-based material may be injected from one side of the cylindrical outer body 420, and the graphene may be discharged from the other side of the cylindrical outer body 420.
  • the graphite-based material used in the present invention may be general non-expandable graphite, expanded graphite in a compressed state, and the like, and these may be added alone or in combination.
  • the graphite-based material may be a graphite intercalation compound.
  • the graphite intercalation compound it is a graphite-based material in which an intercalant, which is a heterogeneous material, is inserted between layers of graphite, that is, between layers of graphene. Since intercalation species may act to lower the interlayer energy of graphite by weakening the attraction between each layer of graphene of graphite, in the case of the graphite intercalation compound, the exfoliation efficiency of graphene may be greatly improved during shear flow.
  • intercalation species of the graphite intercalation compound compounds containing at least one alkali metal and alkaline earth metal, for example, potassium sodium tartrate, can be given.
  • organic acids including sulfuric acid, nitric acid and phosphoric acid may be used.
  • ionic liquids such as ammonium or imidazolium may also be used as intercalation species. These intercalation species can be used alone or in combination of two or more.
  • the solvent contained in the fluid may include one or more of N-methyl-2-pyrrolidinone (NMP) and N, N-dimethylformamide (DMF).
  • NMP N-methyl-2-pyrrolidinone
  • DMF N, N-dimethylformamide
  • the fluid may further include a dispersant to improve the peeling efficiency of the graphite-based material.
  • the dispersant may include at least one of sodium cholate (NaC) poly vinyl alcohol (PVA), poly vinyl pyrrolidone (PVP), polystyrenesulfonate (PSS), dodecylbenzene sulfonic acid (DBSA), and an ionic liquid.
  • a method of further improving the fluidity of the fluid is a method of adjusting the rotational speed of the inner body 410 to 500 rpm or more, more specifically 500 rpm or more and 5,000 rpm.
  • the rotational speed is less than 500 rpm, the formation of the Taylor fluidized bed is limited and the shear efficiency of the fluidized bed may be deteriorated.
  • Figure 6 schematically shows a graphene manufacturing apparatus according to an embodiment of the present invention.
  • the graphene manufacturing apparatus includes the reactor, the inlet 601, the outlet 602, and the driving unit 610.
  • the reactor includes an inner body 410 extending in the horizontal direction and a cylindrical outer body 420 surrounding the inner body while being spaced apart from the inner body.
  • the reaction space 430 is formed between the inner body 410 and the cylindrical outer body 420, and the fluid is stored in the reaction space.
  • the inner body 410 is rotated by the rotating shaft 405 and the cylindrical outer body 420 is fixed.
  • the inlet 601 is formed on one side of the cylindrical outer body 420, the graphite-based material is injected. Only the graphite-based material may be added, the graphite-based material and the fluid may be added together, and the adding may be performed continuously or periodically.
  • the discharge port 602 is formed on the other side of the cylindrical outer body 420, and discharges the graphene obtained by the graphite is peeled off by the shear force generated by the rotational flow of the fluid stored in the reaction space 430.
  • the discharged product may be separated into graphene, other graphite-based materials, solvents, and the like having a layer number of less than about 10 layers, that is, 1 to 9 layers, by centrifugation.
  • layer number of less than about 10 layers, that is, 1 to 9 layers, by centrifugation.
  • more than 10 layers of graphite-based materials, solvents, and the like may be introduced back into the reactor through the inlet 601.
  • the driving unit 610 rotates the inner body 410 and the cylindrical outer body 420 through the rotation shaft 405.
  • the heater 620 and the support 630 may be included.
  • the heater 620 may contribute to facilitate the rotational flow by heating the fluid, and may be formed to surround the cylindrical outer body 420.
  • the support 630 serves to enable the reactor including the rotating shaft 405 to rotate about the horizontal axis.
  • the graphene manufacturing method according to the present invention which does not involve oxidation / reduction, can produce high quality graphene, and corresponds to an economical and eco-friendly method without generating strong acid or acid waste in the manufacturing process. do.
  • the graphene to be manufactured may be utilized in various fields such as electrode material fields of energy storage devices such as conductive graphene ink and supercapacitors for manufacturing printed electronic devices, heat dissipation, and composite materials.
  • energy storage devices such as conductive graphene ink and supercapacitors for manufacturing printed electronic devices, heat dissipation, and composite materials.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Carbon And Carbon Compounds (AREA)
PCT/KR2016/005777 2015-06-24 2016-05-31 전단 유동을 이용한 고품질 그래핀 제조 방법 및 장치 WO2016208884A1 (ko)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201680028333.2A CN107624105B (zh) 2015-06-24 2016-05-31 利用剪切流动的高品质石墨烯制备方法及制备装置

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR1020150089523A KR101775610B1 (ko) 2015-06-24 2015-06-24 전단 유동을 이용하여 흑연층간삽입화합물로부터 고품질의 그래핀을 제조하는 방법
KR10-2015-0089523 2015-06-24
KR10-2015-0089522 2015-06-24
KR1020150089522A KR101775609B1 (ko) 2015-06-24 2015-06-24 전단 유동을 이용한 고품질 그래핀 제조 방법 및 장치

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CN106976870A (zh) * 2017-03-29 2017-07-25 天津工业大学 高效剥离石墨粉制备大尺寸石墨烯的方法
CN107265445A (zh) * 2017-07-06 2017-10-20 东南大学 一种高质量石墨烯的绿色高效制备法
CN110540193A (zh) * 2019-09-20 2019-12-06 上海大学 加压石墨化的石墨烯薄膜的制备方法
WO2020022839A1 (ko) * 2018-07-27 2020-01-30 주식회사 하윤 화학적으로 개질된 그래핀의 제조방법
WO2020077004A1 (en) * 2018-10-10 2020-04-16 Cornell University Continuous manufacture of graphenic compounds
US10953380B1 (en) * 2019-10-21 2021-03-23 Global Graphene Group, Inc. Continuous production of 2D inorganic compound platelets

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CN109205601A (zh) * 2018-10-20 2019-01-15 安徽省彤歌碳纳米材料有限公司 一种通过零距离剪切制备少层均匀石墨烯的方法及其装置
CN110042284A (zh) * 2019-05-08 2019-07-23 东南大学 一种高强度铝合金的制备方法
CN111484006A (zh) * 2020-01-17 2020-08-04 北京清烯科技有限公司 一种大面积石墨烯的制备方法
CN111484005A (zh) * 2020-01-17 2020-08-04 北京清烯科技有限公司 一种用于高效率制造大面积石墨烯的装置
CN111807354A (zh) * 2020-01-17 2020-10-23 北京清烯科技有限公司 一种大面积石墨烯的高效制备方法

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106976870A (zh) * 2017-03-29 2017-07-25 天津工业大学 高效剥离石墨粉制备大尺寸石墨烯的方法
CN106976870B (zh) * 2017-03-29 2018-12-25 天津工业大学 高效剥离石墨粉制备大尺寸石墨烯的方法
CN107265445A (zh) * 2017-07-06 2017-10-20 东南大学 一种高质量石墨烯的绿色高效制备法
WO2020022839A1 (ko) * 2018-07-27 2020-01-30 주식회사 하윤 화학적으로 개질된 그래핀의 제조방법
KR20200012621A (ko) * 2018-07-27 2020-02-05 주식회사 하윤 화학적으로 개질된 그래핀의 제조방법
KR102277797B1 (ko) * 2018-07-27 2021-07-15 주식회사 하윤 화학적으로 개질된 그래핀의 제조방법
WO2020077004A1 (en) * 2018-10-10 2020-04-16 Cornell University Continuous manufacture of graphenic compounds
CN110540193A (zh) * 2019-09-20 2019-12-06 上海大学 加压石墨化的石墨烯薄膜的制备方法
US10953380B1 (en) * 2019-10-21 2021-03-23 Global Graphene Group, Inc. Continuous production of 2D inorganic compound platelets

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