KR20160100268A - Graphene having pores made by irregular and random, and Manufacturing method of the same - Google Patents
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Abstract
Description
본 발명은 비반복적이고 불규칙적인 3차원 기공을 포함하는 그래핀 및 이의 제조 방법에 관한 것이다. The present invention relates to graphenes comprising non-repeating and irregular three-dimensional pores and to a process for their preparation.
현재 탄소에 기반을 둔 재료들, 예를들어 탄소나노튜브(carbon nanotube), 다이아몬드(diamond), 그래파이트(graphite), 그래핀(graphene), 그래핀 산화물 (Graphene oxide)등이 다양한분야의 나노기술 연구 그룹에서 연구되고 있다. 이러한 재료들은 바이오센서(biosensor), 나노복합물(nanocomposite) 또는 양자소자(quantum device), 전극 소재 (Electrode) 등에 이용되거나 이용될 수 있다. 탄소기반 소재 중 하나인 그래핀은 2차원 물질로서 밴드갭이 0(zero gap)인 반도체물질이며, 최근 몇 년간 그래핀의 전기적 특성에 관하여 다양한 연구들이 발표되고 있다.Currently, materials based on carbon such as carbon nanotube, diamond, graphite, graphene, and graphene oxide are used in various fields of nanotechnology Research group. Such materials may be used or used in biosensors, nanocomposites or quantum devices, electrode materials, and the like. Graphene, one of the carbon-based materials, is a two-dimensional semiconductor material with a zero gap bandgap. In recent years, various studies have been published on the electrical properties of graphene.
그래핀(graphene)은 sp2 탄소 원자들이 6각형의 벌집 (honeycomb) 격자를 이룬 형태의 2차원 나노시트(2-D nanosheet) 단일층의 탄소 구조체를 의미한다. Graphene refers to a two-dimensional nanosheet monolayer carbon structure in which sp2 carbon atoms form a hexagonal honeycomb lattice.
일반적으로, 그래핀은 물리 내지 화학적 안정성이 우수하고, 높은 비표면적과 우수한 전자전도 특성을 가진 신소재로서 각광받고 있는 물질이다. 또한, 그래핀은 이런 물성에 의하여 나노 크기의 금속 산화물을 증착할 수 있는 효율적인 주형(template)으로 작용할 수 있다. Generally, graphene is a substance which is excellent in physical and chemical stability, and is attracting attention as a new material having a high specific surface area and an excellent electron conduction property. In addition, graphene can act as an efficient template for depositing nano-sized metal oxides with this property.
한편, 종래의 그래핀 나노 시트는 통상 용액법이라고 통칭되는 용액 내에서 그래핀을 합성하는 방법이 주로 이용되었다.On the other hand, a conventional method of synthesizing graphene in a solution commonly referred to as a solution method is mainly used for a graphene nanosheet.
상기 방법에 따르면, 먼저 그라파이트를 그라파이트 산화물로 합성한다. 그라파이트 산화물의 합성에는 통상 휴머스법(hummers method)이라고 불리는 방법이 이용된다. 상기 방법에 따르면, 상용의 그라파이트를 상온에서 고농도의 H2SO4 용액에 담지시켜 충분히 교반시킨 후, 그라파이트가 담지된 용액에 KMnO4를 투입한다. 이어서, 상기 KMnO4가 포함된 혼합 용액에 H2O2를 소정량 첨가시키면 그라파이트의 산화반응이 일어나 그라파이트 산화물이 형성된다. 이어서, 원심분리기를 이용하여 증류수와 에탄올로 수차례 세척한 후 얻어지는 분말을 오븐에서 충분히 건조시킴으로서 그라파이트 산화물의 합성 절차가 완료된다. 이어서, 상기 그라파이트 산화물을 물에 분산시킨 후 초음파 처리를 통해 낱장의 그라파이트 산화물로 박리(exfoliation)시킨다. 이어서, NaBH4와 같은 환원제를 적당량 투입하고 교반하면, 투입된 환원제는 그라파이트 산화물의 산소작용기를 분리시켜 낱장으로 환원된 그라파이트 산화물, 즉 그래핀을 얻을 수 있다.According to this method, graphite is first synthesized as a graphite oxide. A method called a hummers method is usually used for the synthesis of the graphite oxide. According to this method, commercially available graphite is supported on a high concentration H 2 SO 4 solution at room temperature and sufficiently stirred, and then KMnO 4 is added to the graphite-supported solution. Subsequently, when a predetermined amount of H 2 O 2 is added to the mixed solution containing KMnO 4 , an oxidation reaction of graphite occurs to form a graphite oxide. Subsequently, several times of washing with distilled water and ethanol using a centrifugal separator is performed, and the powder obtained is sufficiently dried in an oven to complete the synthesis procedure of the graphite oxide. Then, the graphite oxide is dispersed in water and subjected to ultrasonic treatment to exfoliate the graphite oxide into a sheet of graphite oxide. Subsequently, when a suitable reducing agent such as NaBH 4 is added and stirred, the introduced reducing agent can separate the oxygen functional groups of the graphite oxide to obtain graphite oxide, that is, graphene reduced to a sheet.
현재 그래핀은 탄소를 기반으로 하는 나노전자 소자의 집적화를 위한 기본단위로 이용될 수 있는 물질로 각광을 받고 있으며, 전극물질로서의 그래핀의 이용성 또한 무한하다. 현재까지의 연구는 주로 2차원 그래핀 및 그래핀 산화물 나노시트에 초점을 두었는데, 왜냐하면 이러한 그래핀 산화물 구조체는 수용액에서 효과적으로 분산될 수 있고, 또한 특정 기능기를 갖는 구조체로 전환되거나, 환원될 수 있기 때문이다. Currently, graphene is widely used as a basic unit for integrating carbon-based nano-electronic devices, and the availability of graphene as an electrode material is also endless. Research to date has focused primarily on two-dimensional graphene and graphene oxide nanosheets because these graphene oxide structures can be effectively dispersed in aqueous solutions and can also be converted into structures with specific functional groups, It is because.
2차원 그래핀 나노시트의 잇점과 더불어, 3차원의 그래핀은 넓은 표면적과 기공구조를 통해 센서 및 전극 물질로서 상당한 관심을 끌고 있다. 이러한 3차원의 그래핀 구조를 제작하기 위하여, 2차원 시트 형태의 그래핀을, 중공 구조의 캡슐 또는 층간 적층 구조의 3차원 형태로 전환시키는 시도가 있었다.In addition to the advantages of two-dimensional graphene nanosheets, three-dimensional graphene has attracted considerable attention as a sensor and electrode material through its large surface area and pore structure. In order to produce such a three-dimensional graphene structure, there has been an attempt to convert graphene in the form of a two-dimensional sheet into a three-dimensional form of a hollow capsule or interlayer laminated structure.
본 발명은 비반복적이고 불규칙적인 3차원 기공을 포함하는 그래핀 및 이의 제조 방법을 제공하는 것을 목적으로 한다. It is an object of the present invention to provide a graphene containing non-repeating and irregular three-dimensional pores and a method for producing the graphene.
본 발명은 상기와 같은 과제를 해결하기 위하여 복수개의 그래 핀 시트가 접혀서 생성되고, 평균 직경이 1 내지 30 ㎛이며, 내부에 3 차원적 기공을 포함하는 그래핀 입자를 제공한다.In order to solve the above problems, the present invention provides graphene grains formed by folding a plurality of graphene sheets, having an average diameter of 1 to 30 탆, and containing three-dimensional pores therein.
입자의 평균 직경이 1um 이하일 경우 입도가 너무 낮아 그래핀이 구겨진 상태로 균일한 입자로 형성되지 않고 Flat하거나 판상 구조로 남아있어 구조적으로 잇점을 취하기 어려우며, 입자의 평균 직경이 30um 이상일 경우 구조적 특성상 부피가 커지기 때문에 충진밀도가 낮아져 상대적으로 높은 용량값을 구현하기 어렵다는 문제점이 있으므로, 본 발명의 그래핀 입자는 평균 직경이 1 내지 30 ㎛ 인 것이 바람직하다. When the average diameter of the particles is less than 1 μm, the grains are too small to form uniform particles in a wrinkled state. Therefore, grains are flat or have a plate-like structure, which makes it difficult to obtain a structural advantage. When the average diameter of the particles is more than 30 μm, The filling density is low and a relatively high capacitance value can not be realized. Therefore, the graphene particles of the present invention preferably have an average diameter of 1 to 30 mu m.
본 발명의 그래핀 입자는 내부에 3차원으로 연결된 기공을 포함하며, 상기 기공은 폐쇄형 또는 개방형인 것을 특징으로 한다. 본 발명에 있어서, 상기 3차원으로 연결된 기공은 복수개의 그래핀 시트가 적층되어 접히면서 복수개의 그래핀 시트 사이에 형성되거나, 그래핀 시트가 마치 종이가 구겨진 상태로 형성되면서 내부에 형성되는 기공을 의미한다. The graphene particle of the present invention includes pores connected three-dimensionally therein, and the pores are characterized by being closed or open. In the present invention, the three-dimensionally interconnected pores may be formed by stacking a plurality of graphene sheets and folding the same between a plurality of graphene sheets, or the graphene sheet may be formed in a state where the graphene sheets are formed in a wrinkled state, it means.
상기 기공이 폐쇄형이라는 것은 내부에 기공이 생기나 입자 외부와 연결되지 않는 것을 의미하며, 상기 기공이 개방형이라는 것은 입자 외부와 연결되는 기공을 의미한다. When the pores are closed, it means that pores are formed in the inside but are not connected to the outside of the particles. The open pores mean pores connected to the outside of the particles.
본 발명의 그래핀 입자는 코튼 볼, 솜사탕, 또는 종이가 구형으로 구겨진 형상이 가능하며, 내부에 3차원 기공이 포함되는 형상이면 이와 같은 형상으로 한정되는 것은 아니다. The graphene particles of the present invention can be formed into a shape in which a ball, cotton candy, or paper is crumpled into a spherical shape, and the shape of the graphene particle is not limited to this shape as long as the shape includes three-dimensional pores therein.
본 발명의 그래핀 입자는 입자를 구성하는 구겨진 상태의 그래핀 단위 시트의 말단부가 내부로 향하는 구조인 것을 특징으로 한다. 즉, 본 발명의 그래핀 입자는 입자를 구성하는 그래핀 입자의 말단이 내부로 향함으로써, 내부로 향하여 접히거나 구부러짐으로써 표면에 말단이 형성하는 단부, 즉, 에지(edge)가 노출되지 않는 구조인 것을 특징으로 한다. The graphene particle of the present invention is characterized in that the graphene unit sheet in a crumpled state constituting the grains has a structure in which the end portion of the graphene unit sheet faces inward. That is, the graphene grains of the present invention have a structure in which the ends of the graphene grains constituting the grains are oriented inwardly and folded or bent toward the inside, .
본 발명의 그래핀 입자는 비표면적이 300 내지 900 ㎡/g 인 것을 특징으로 한다. 본 발명의 그래핀 입자의 비표면적은 700 내지 900 ㎡/g 인 것이 더욱 바람직하다. 비표면적이 300 ㎡/g 이하일 비표면적이 너무 낮아 전극 재료로 사용시 전해질들이 침투하여 물리적으로 흡탈착 할 수 있는 면적이 적어 고용량을 구현하기 어려우며, 비표면적이 900 ㎡/g 이상일 경우 물리적인 흡탈착이 가능한 면적은 늘어나지만 기공에 증가에 따른 입도의 크기 및 부피가 늘어나 전극 1셀당 용량률은 오히려 줄어들 수 있기 때문에 적정 부피와 입도를 유지하는 것이 중요하다. The graphene particles of the present invention have a specific surface area of 300 to 900 m < 2 > / g. The specific surface area of the graphene particles of the present invention is more preferably 700 to 900 m < 2 > / g. When the specific surface area is less than 300 m < 2 > / g, the specific surface area is too low. Therefore, when the electrode material is used as the electrode material, the electrolytic materials penetrate and the physical absorption / It is important to maintain the proper volume and size because the size and volume of the pore increases and the capacity rate per cell of the electrode may be reduced.
본 발명의 그래핀 입자는 탭밀도가 0.3 내지 1.5 g/cc 인 것을 특징으로 한다. 탭 밀도가 0.3 g/cc 이하인 경우 입자 고유 특성인 고비표면적을 구현하기 어렵고, 탭 밀도가 1.5 g/cc 이하인 경우 단위 면적당 무게가 많이 나가기 때문에 좋은 전극특성을 유지하기 어려워진다. The graphene particle of the present invention is characterized by having a tap density of 0.3 to 1.5 g / cc. When the tap density is 0.3 g / cc or less, it is difficult to realize a high specific surface area, which is a particle specific characteristic. When the tap density is 1.5 g / cc or less, the weight per unit area becomes large.
본 발명은 또한, The present invention also relates to
그래핀 또는 산화 그래핀을 제조하는 단계; Producing graphene or oxide graphene;
상기 그래핀 또는 산화 그래핀을 용매에 분산시켜서 분산액을 제조하는 단계; 및Dispersing the graphene or the oxide graphene in a solvent to prepare a dispersion; And
상기 분산액을 분무 건조하여 입자를 형성하는 단계; 를 포함하는 그래핀 입자의 제조 방법을 제공한다. Spray-drying the dispersion to form particles; Wherein the graphene grains are grafted onto the graphene grains.
본 발명의 제조 방법에 있어서, 상기 그래핀 또는 산화 그래핀을 용매에 분산시켜서 분산액을 제조하는 단계에서는 용매로서 증류수 등을 100 중량부를 기준으로, 상기 그래핀 또는 산화 그래핀을 1 내지 10 중량부를 포함하는 것을 특징으로 한다.In the manufacturing method of the present invention, in the step of dispersing the graphene or the oxidized graphene in a solvent to prepare a dispersion, 1 to 10 parts by weight of the graphene or the oxidized graphene is dissolved in 100 parts by weight of distilled water as a solvent .
본 발명의 제조 방법에 있어서, 상기 그래핀 또는 산화 그래핀을 용매에 분산시켜서 분산액을 제조하는 단계에서 상기 분산액의 농도는 0.01 내지 50 mg/ml 인 것을 특징으로 한다. In the production method of the present invention, the concentration of the dispersion in the step of dispersing the graphene or the oxidized graphene in a solvent is 0.01 to 50 mg / ml.
본 발명의 제조 방법에 있어서, 상기 분무 건조시 온도는 100 내지 250 ℃ 인 것을 특징으로 한다. In the production method of the present invention, the spray drying temperature is 100 to 250 ° C.
본 발명의 제조 방법에 있어서, 상기 그래핀 또는 산화 그래핀을 용매에 분산시켜서 분산액을 제조하는 단계에서는 NaBH4등의 환원제를 첨가하는 것을 특징으로 한다.In the production method of the present invention, a step of adding a reducing agent such as NaBH 4 is added to the step of preparing the dispersion by dispersing the graphene or the oxide graphene in a solvent.
본 발명은 또한, 본 발명의 그래핀 입자를 포함하는 전기 화학 소자용 전극활물질을 제공한다. The present invention also provides an electrode active material for an electrochemical device comprising the graphene particles of the present invention.
본 발명에 있어서, 상기 전기 화학 소자는 리튬이온이차전지, 리튬황전지, 마그네슘 전지, 연료 전지 또는 커패시터, 전기이중층커패시터,슈퍼커패시터 등 당업자에게 자명한 전기 화학 소자가 모두 가능하다. In the present invention, the electrochemical device may be any electrochemical device known to those skilled in the art such as a lithium ion secondary battery, a lithium sulfur battery, a magnesium battery, a fuel cell or a capacitor, an electric double layer capacitor, and a super capacitor.
본 발명의 전기 화학 소자는 음극활물질로서 본 발명의 그래핀 입자를 포함하는 것이 가능하다. The electrochemical device of the present invention can contain the graphene particles of the present invention as an anode active material.
본 발명에 의한 비반복적이고 불규칙적인 3차원 기공을 포함하는 그래핀은 산화 그래핀 용액에 환원제를 첨가한 상태에서 분무 건조함으로써 비표면적이 넓으면서도 일정 강도를 나타내는 새로운 구조의 코튼 타입의 비반복적이고 불규칙적인 3차원 기공 구조를 갖는 그래핀으로 제조된다. The graphene containing non-repetitive irregular three-dimensional pores according to the present invention is a non-repetitive type of cotton type of new structure exhibiting a constant specific strength while having a large specific surface area by spray drying with addition of a reducing agent to the oxidized graphene solution And is made of graphene having an irregular three-dimensional pore structure.
도 1 내지 도 6 은 본 발명의 일 실시예에 의하여 제조된 코튼 타입의 비반복적이고 불규칙적인 3차원 기공 구조를 갖는 그래핀의 SEM 사진을 측정한 결과이다. FIGS. 1 to 6 are SEM photographs of graphene having a non-repetitive, irregular three-dimensional pore structure of the cotton type produced according to an embodiment of the present invention.
이하에서는 본 발명을 실시예에 의하여 더욱 상세히 설명한다. 그러나, 본 발명이 이하의 실시예에 의하여 더욱 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited by the following examples.
실시예 1. 코튼볼 형태의 환원 그래핀 옥사이드 제조EXAMPLE 1 Preparation of Reduced Grafting Oxide in Cotton Ball Form
1-1. 그래핀 옥사이드 분산액(분무액) 제조1-1. Preparation of graphene oxide dispersion (spray solution)
흑연 분말(Bay Carbon, SP-1)을 보정된 Hummers의 방법에 의해 산화시켜 그래핀 옥사이드를 제조하였다. Graphite powder (Bay Carbon, SP-1) was oxidized by the method of Hummers to prepare graphene oxide.
20L 이중 자켓 반응기의 내부온도를 0℃로 설정한 후 흑연 76g을 황산(H2SO4, 8L)에 투입 후 1시간 동안 250rpm의 속도로 교반하면서 혼합했다. 그 다음 이 현탁액에 과망간산칼륨(KMnO4) 380g을 10분 간격으로 50g씩 서서히 가하고, 현탁액이 청녹색으로 변하는 것을 확인 후 1시간 동안 교반했다. 1시간 교반 후 0.5℃/min의 속도로 35°C까지 승온 시킨 후 2시간동안 다시 교반하였다. 현탁액에 탈이온수(DI)(12L)를 서서히 가하고, 탈이온수(DI) 첨가시 온도가 60℃가 넘지않도록 주의하며 첨가하였다. 과산화수소 용액(H2O2, 50wt%, 20mL)를 서서히 가하고 밝은 갈색의 그래핀 옥사이드 용액으로 변하면 반응을 종결시킨다. 반응이 끝난 혼합액을 여과하고 원심분리기를 통해 탈이온수로 20~30회 세척 한 다음, 건조 단계를 거쳐 "그래핀 옥사이드 분말"을 수득하였다. After setting the internal temperature of the 20 L double jacket reactor to 0 캜, 76 g of graphite was added to sulfuric acid (H 2 SO 4 , 8 L) and mixed at a rate of 250 rpm for 1 hour while stirring. 380 g of potassium permanganate (KMnO 4 ) was then gradually added to the suspension in an amount of 50 g at intervals of 10 minutes, and after confirming that the suspension turned blue, the mixture was stirred for 1 hour. After stirring for 1 hour, the temperature was raised to 35 ° C at a rate of 0.5 ° C / min and then stirred again for 2 hours. To the suspension was slowly added deionized water (DI) (12 L) and added with caution so that the temperature did not exceed 60 ° C when deionized water (DI) was added. A hydrogen peroxide solution (H 2 O 2 , 50 wt%, 20 mL) is slowly added and the reaction is terminated when the solution is changed to a light brown graphene oxide solution. The reaction mixture was filtered, washed with deionized water for 20 to 30 times through a centrifuge, and then subjected to a drying step to obtain a "graphen oxide powder ".
탈이온수 1000ml에 15g의 그래핀 옥사이드를 첨가한 후 호모게나이저를 이용하여 4500rpm의 속도로 100분간 분산시킨다.(15mg/ml) 상기 방법을 통해 수용액상 담지된 그래핀 옥사이드는 전단응력을 통해 단일 또는 수층으로 박리되며, 균일한 그래핀 옥사이드 분산 용액을 형성하였다. 15 g of graphene oxide was added to 1000 ml of deionized water and dispersed at a rate of 4500 rpm for 100 minutes using a homogenizer (15 mg / ml). Through this method, the graphene oxide supported on an aqueous phase was subjected to single Or water layer to form a homogeneous graphene oxide dispersion solution.
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1-2. 코튼볼 타입의 그래핀 옥사이드 제조 및 환원1-2. Manufacture and reduction of cotton ball type graphene oxide
상기 실시예 1-1에서 제조된 그래핀 옥사이드 분산 용액을 액적으로 분무시키기 위한 분무장치로서 스프레이 드라이어(디스크 타입)을 이용하였으며, 분무량은 분당 15 ml 회전속도는 12000rpm으로 분산액을 분사시켜 분무건조를 진행하였다. 상기 그래핀 옥사이드 분산액이 마이크로 액적 상태로 분무되는 오븐의 내부온도는 100 ℃로 설정하였다. A spray drier (disc type) was used as a spray apparatus for spraying the graphene oxide dispersion solution prepared in Example 1-1 with droplets. Spray was sprayed by spraying the dispersion at a rate of 15 ml per minute at a rotation speed of 12,000 rpm . The internal temperature of the oven in which the graphene oxide dispersion was sprayed in a microdroplet state was set at 100 캜.
건조기에서 100℃의 온도 조건하에서 6시간 동안 추가로 건조시킨 후 그래핀 옥사이드 분말 15g을 증류수 1L에 첨가하고 1시간동안 교반 시켜 분산시킨 후 분산된 용액에 하이드라진(35wt% in H2O) 15ml를 투입하여 100℃에서 12hr동안 가열 교반하였다. 반응 종료 후 상온건조 시킨 후 멤브레인 필터를 이용하여 용매를 제거하고 증류수로 3~5회 수세하였다. After further drying for 6 hours at a temperature of 100 ° C. in a drier, 15 g of graphene oxide powder was added to 1 L of distilled water and stirred for 1 hour to disperse. 15 ml of hydrazine (35 wt% in H 2 O) And the mixture was heated and stirred at 100 ° C for 12 hours. After completion of the reaction, the reaction mixture was dried at room temperature, and then the solvent was removed using a membrane filter, followed by washing with distilled water three to five times.
수득한 분말을 증류수로 수세한 이후 100℃의 온도 조건하에서 건조시켜 직경이 10 내지 15 마이크로인 "코튼 볼 타입의 환원 그래핀 옥사이드"를 제조하였다. The obtained powder was washed with distilled water and then dried under a temperature condition of 100 ° C to produce a "cotton ball type reduced graphene oxide" having a diameter of 10 to 15 μm.
도 1 내지 도 3에 제조된 "코튼 볼 타입의 환원 그래핀 옥사이드"의 SEM 사진을 나타내었다. 도 1 내지 도 3 에서 보는 바와 같이 본 발명의 실시예에 의하여 제조된 그래핀 옥사이드는 코튼 볼 타입이고, 그래핀 시트 말단이 내부로 향하도록 접혀진, 폴딩된 상태인 것을 확인할 수 있다. SEM photographs of "cotton ball type reduced graphene oxide" produced in Figs. 1 to 3 are shown. As shown in FIGS. 1 to 3, it can be seen that the graphene oxide prepared according to the embodiment of the present invention is a cotton ball type, and the folded state of the graphene sheet end is folded toward the inside.
실시예 2. 코튼볼 형태의 환원 그래핀 옥사이드 제조Example 2. Preparation of reduced graphene oxide in the form of a cotton ball
2-1. 그래핀 옥사이드 분산액(분무액) 제조2-1. Preparation of graphene oxide dispersion (spray solution)
상기 실시예 1-1과 동일한 방법으로 수행하여 산화된 그래핀 옥사이드 분말을 얻은 후 그래핀 옥사이드 혼합액의 농도를 5mg/ml로 변화하여 실험을 진행하였다.The oxidized graphene oxide powder was obtained in the same manner as in Example 1-1, and the concentration of the graphene oxide mixed solution was changed to 5 mg / ml.
2-2. 코튼볼 타입의 그래핀 옥사이드 제조 및 환원2-2. Manufacture and reduction of cotton ball type graphene oxide
실시예 1-2과 동일한 방법으로 수행하여 직경이 5 내지 30 마이크로인 "코튼 타입의 환원 그래핀 옥사이드"를 제조하였다. Was carried out in the same manner as in Example 1-2 to prepare a "cotton type reduced graphene oxide" having a diameter of 5 to 30 micrometers.
도 4에 제조된 "코튼 타입의 환원 그래핀 옥사이드"의 SEM 사진을 나타내었다. 도 4 에서 보는 바와 같이 본 발명의 실시예에 의하여 제조된 그래핀 옥사이드는 코튼 볼 타입이고, 그래핀 시트 말단이 내부로 향하도록 접혀진, 폴딩된 상태인 것을 확인할 수 있다. SEM photographs of the "cotton-type reduced graphene oxide" produced in Fig. 4 are shown. As shown in FIG. 4, it can be seen that the graphene oxide prepared according to the embodiment of the present invention is a cotton ball type and the folded state of the graphene sheet end is folded toward the inside.
실시예 3. 코튼볼 형태의 환원 그래핀 옥사이드 제조Example 3. Preparation of reduced graphene oxide in the form of a cotton ball
3-1. 그래핀 옥사이드 분산액(분무액) 제조3-1. Preparation of graphene oxide dispersion (spray solution)
실시예 1-1과 동일한 방법으로 수행하여 산화그래핀옥사이드 분말을 얻은 후 그래핀 옥사이드 혼합액의 농도를 10 mg/ml로 변화시켜서 실험을 진행하였다.The procedure of Example 1-1 was repeated to obtain graphene oxide powder, and the concentration of the graphene oxide mixture was changed to 10 mg / ml.
3-2. 코튼볼 타입의 그래핀 옥사이드 제조 및 환원3-2. Manufacture and reduction of cotton ball type graphene oxide
실시예 1-2와 동일한 방법으로 수행하여 직경이 5 내지 10 마이크로인 "코튼 타입의 환원 그래핀 옥사이드"를 제조하였다. Was carried out in the same manner as in Example 1-2 to prepare a "cotton type reduced graphene oxide" having a diameter of 5 to 10 m.
도 5에 제조된 "코튼 타입의 환원 그래핀 옥사이드"의 SEM 사진을 나타내었다. 도 5 에서 보는 바와 같이 본 발명의 실시예에 의하여 제조된 그래핀 옥사이드는 코튼 볼 타입이고, 그래핀 시트 말단이 내부로 향하도록 접혀진, 폴딩된 상태인 것을 확인할 수 있다. SEM photographs of the "cotton-type reduced graphene oxide" produced in Fig. 5 are shown. As shown in FIG. 5, it can be seen that the graphene oxide prepared according to the embodiment of the present invention is a cotton ball type and folded so that the end of the graphene sheet is inwardly folded.
실시예 4. 코튼볼 형태의 환원 그래핀 옥사이드 제조Example 4. Preparation of reduced graphene oxide in the form of a cotton ball
4-1. 그래핀 옥사이드 분산액(분무액) 제조4-1. Preparation of graphene oxide dispersion (spray solution)
상기 실시예 1-1과 동일한 방법으로 수행하여 산화그래핀옥사이드 분말을 얻은 후 그래핀 옥사이드 혼합액의 농도를 20mg/ml로 변화하여 실험을 진행하였다.The graphen oxide oxide powder was obtained in the same manner as in Example 1-1, and the concentration of the graphene oxide mixed solution was changed to 20 mg / ml.
4-2. 코튼볼 타입의 그래핀 옥사이드 제조 및 환원4-2. Manufacture and reduction of cotton ball type graphene oxide
실시예 1-2 와 동일한 방법으로 수행하여 직경이 10 내지 35 마이크로인 "코튼볼 타입의 환원 그래핀 옥사이드"를 제조하였다. Was carried out in the same manner as in Example 1-2 to prepare a "cotton ball type reduced graphene oxide" having a diameter of 10 to 35 microns.
도 6에 제조된 "코튼 타입의 환원 그래핀 옥사이드"의 SEM 사진을 나타내었다. 도 6 에서 보는 바와 같이 본 발명의 실시예에 의하여 제조된 그래핀 옥사이드는 코튼 볼 타입이고, 그래핀 시트 말단이 내부로 향하도록 접혀진, 폴딩된 상태인 것을 확인할 수 있다. SEM photographs of the "cotton-type reduced graphene oxide" produced in Fig. 6 are shown. As shown in FIG. 6, it can be seen that the graphene oxide prepared according to the embodiment of the present invention is a cotton ball type and folded so that the end of the graphene sheet is inwardly folded.
비교예. 편평한 타입의 환원그래핀옥사이드 제조Comparative Example. Production of flat type reduced graphene oxide
비교예 1-1. 그래핀 옥사이드 분말 제조Comparative Example 1-1. Preparation of graphene oxide powder
실시예 1-1과 동일한 방법으로 수행하여 산화그래핀옥사이드 분말을 얻었다.Was carried out in the same manner as in Example 1-1 to obtain an oxide graphene oxide powder.
비교예 1-2. 편평한 환원그래핀옥사이드 제조Comparative Example 1-2. Manufacture of flat reduction graphene oxide
상기 그래핀 옥사이드를 15g을 탈이온수 1000ml에 첨가한 후 호모게나이저를 이용해 4500rpm의 속도로 100분간 분산시킨다. 15 g of the graphene oxide was added to 1000 ml of deionized water and dispersed at a speed of 4500 rpm for 100 minutes using a homogenizer.
분산된 용액에 하이드라진(35wt% in H2O) 15ml를 투입하여 100℃에서 12시간동안 가열 교반하였다. 15 ml of hydrazine (35 wt% in H 2 O) was added to the dispersed solution, and the mixture was heated and stirred at 100 ° C for 12 hours.
반응 종료 후 멤브레인 필터를 이용하여 용매를 제거한 후 탈이온수로 수세하였다. 100℃의 온도 조건하에서 건조시켜 편평한 환원 그래핀옥사이드를 제조하였다.After completion of the reaction, the solvent was removed using a membrane filter, followed by washing with deionized water. And dried under a temperature condition of 100 DEG C to prepare a flat reduced graphene oxide.
Claims (12)
Graphene particles produced by folding a plurality of graphene sheets and having an average diameter of 1 to 30 mu m and three-dimensional pores therein.
상기 기공은 폐쇄형 또는 개방형인 것인 그래핀 입자
The method according to claim 1,
Wherein the pores are closed or open,
상기 그래핀 입자는 구겨진 상태의 그래핀 시트의 말단부가 내부로 향하는 구조인 것인 그래핀 입자
The method according to claim 1,
Wherein the graphene grains are graphene sheets having a structure in which a distal end portion of the graphene sheet in a wrinkled state faces inwardly
상기 그래핀 입자는, 코튼 볼, 솜사탕, 또는 종이가 구형으로 구겨진 형상인 것인 그래핀 입자
The method according to claim 1,
The graphene particles may be selected from the group consisting of cotton balls, cotton candy, or graphene particles,
상기 그래핀 입자의 비표면적은 300 내지 900 ㎡/g 인 것인 그래핀 입자
The method according to claim 1,
Wherein the graphene particles have a specific surface area of 300 to 900 m < 2 > / g.
상기 그래핀 입자의 탭밀도는 0.3 내지 1.5 g/cc 인 것인 그래핀 입자
The method according to claim 1,
Wherein the tap density of the graphene grains is 0.3 to 1.5 g / cc.
상기 그래핀 또는 산화 그래핀을 용매에 분산시켜서 분산액을 제조하는 단계;
상기 분산액을 분무 건조하여 입자를 형성하는 단계; 를 포함하는
제 1 항에 의한 그래핀 입자의 제조 방법.
Producing graphene or oxide graphene;
Dispersing the graphene or the oxide graphene in a solvent to prepare a dispersion;
Spray-drying the dispersion to form particles; Containing
A method for producing graphene particles according to claim 1,
상기 그래핀 또는 산화 그래핀을 용매에 분산시켜서 분산액을 제조하는 단계에서는 용매 100 중량부당 상기 그래핀 또는 산화 그래핀을 1 내지 10 중량부를 포함하는 것인
그래핀 입자의 제조 방법.
8. The method of claim 7,
In the step of dispersing the graphene or the oxidized graphene in a solvent, the graphene or the oxidized graphene is contained in an amount of 1 to 10 parts by weight per 100 parts by weight of the solvent
A method for producing graphene grains.
상기 그래핀 또는 산화 그래핀을 용매에 분산시켜서 분산액을 제조하는 단계에서 상기 분산액의 농도는 0.01 내지 50 mg/ml 인 것인
그래핀 입자의 제조 방법.
8. The method of claim 7,
The concentration of the dispersion in the step of dispersing the graphene or the oxidized graphene in a solvent is 0.01 to 50 mg / ml
A method for producing graphene grains.
상기 분무 건조시 온도는 100 내지 250 ℃ 인 것인
그래핀 입자의 제조 방법.
8. The method of claim 7,
Wherein the spray drying is carried out at a temperature of 100 to 250 DEG C
A method for producing graphene grains.
상기 그래핀 또는 산화 그래핀을 용매에 분산시켜서 분산액을 제조하는 단계에서는 환원제를 첨가하는 것을 특징으로 하는 주름진 표면을 갖는 그래핀의 제조 방법.
8. The method of claim 7,
Characterized in that a reducing agent is added in the step of dispersing the graphene or the oxidized graphene in a solvent to prepare a dispersion.
An electrode active material for electrochemical devices comprising graphene particles according to any one of claims 1 to 5.
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