KR20160088097A - Method for Purifying Graphene Oxide - Google Patents
Method for Purifying Graphene Oxide Download PDFInfo
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- KR20160088097A KR20160088097A KR1020150007358A KR20150007358A KR20160088097A KR 20160088097 A KR20160088097 A KR 20160088097A KR 1020150007358 A KR1020150007358 A KR 1020150007358A KR 20150007358 A KR20150007358 A KR 20150007358A KR 20160088097 A KR20160088097 A KR 20160088097A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims description 22
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000000746 purification Methods 0.000 claims description 15
- 229910001385 heavy metal Inorganic materials 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- 238000005191 phase separation Methods 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 7
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 230000005484 gravity Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- -1 engineering plastics Chemical compound 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- 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
- C01B32/198—Graphene oxide
-
- C01B31/043—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- C01B31/0492—
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- 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
- C01B32/196—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
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- Organic Chemistry (AREA)
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Abstract
Description
본 발명은 산화 그래핀의 정제방법에 관한 것으로, 보다 상세하게는 고순도의 산화 그래핀을 간단한 공정에 의해 효율적으로 정제하는 방법에 관한 것이다. TECHNICAL FIELD The present invention relates to a method for purifying graphene oxide, and more particularly, to a method for efficiently purifying high-purity graphene oxide by a simple process.
산화그래핀(Graphene Oxide)은 환원(reduction) 공정 이후에 그래핀과 유사한 전기화학적 특성을 보이면서 대량 생산이 용이하기 때문에, 산업적으로 그래핀을 대량 생산하기 위한 출발 물질로 사용된다. 최근에는 산화그래핀 자체가 가지는 우수한 기계적, 화학적 특이성을 이용한 엔지니어링 플라스틱, 유기합성 촉매, 산화그래핀-금속 복합체, 산화그래핀-고분자 복합체와 같은 산화그래핀 자체를 이용한 기능성 첨단 신소재에 대한 연구가 활발하게 이루어지고 있다. 산화그래핀은 다양한 산업 분야에서 쉽게 응용될 수 있기 때문에 산화그래핀의 산업적 중요성과 관련 시장은 매우 크다 할 수 있다.Graphene Oxide is used as a starting material for the mass production of graphene in industry because it is easy to mass-produce with electrochemical characteristics similar to graphene after the reduction process. Recently, research on advanced functional materials using functionalized graphene such as engineering plastics, organic synthesis catalysts, oxidized graphene-metal composites, and oxidized graphene-polymer composites using the excellent mechanical and chemical specificity of oxidized graphene itself . Since oxidized graphene can be easily applied in various industrial fields, the industrial importance of oxidized graphene and the related market can be very large.
일반적으로 산화그래핀을 제조하는 방법은 과량의 강산과 산화력이 강한 중금속 산화제를 이용하는 방법이 이용된다[대한민국 공개특허 제10-2014-0045851호 참조]. 산화 공정 이후에 반드시 거쳐야 하는 중요한 공정이 산화 공정에서 발생하는 산폐액과 중금속 이온들을 제거하는 정제공정인데, 이러한 정제공정은 산화그래핀의 순도와 물성을 결정하기 때문에 매우 중요한 공정이다. 특히 중금속 이온 물질은 반드시 완전히 제거되어야 본래의 산화그래핀의 특성을 가지면서 사용될 수 있기 때문에 과량의 증류수를 이용한 반복 세정 작업이 요구된다.Generally, a method of producing an oxidized graphene is a method using an excessive oxidizing agent and a strong oxidizing agent [see Korean Patent Publication No. 10-2014-0045851]. An important process that must be performed after the oxidation process is a purification process that removes acidic wastewater and heavy metal ions generated in the oxidation process. This purification process is an important process because it determines the purity and physical properties of the oxidized graphene. In particular, heavy metal ion materials must be completely removed to use the graphene grains with the characteristics of the original graphene grains.
종래의 산화그래핀 정제 방법으로는 원심 분리, 투석(Dialysis), 필터와 같은 방법이 사용되어 왔다. 하지만 이러한 방법들은 정제의 시간이 길고, 과량의 중금속 산폐액이 발생하기 때문에 대량 생산이 어렵고 환경적인 측면에서도 문제가 된다. 또한, 기존의 산화그래핀 정제 방법은 내산성 고가 장비의 사용이 반드시 요구되기 때문에 경제적으로 산화그래핀을 대량 생산하는데 어려운 점이 있다. Conventional graphene oxide graphene purification methods include centrifugal separation, dialysis, and filtration. However, these methods are difficult to mass-produce and environmental problems because of the long purification time and excessive heavy metal acid waste solution. In addition, since the existing graphene oxide graphene refining method is required to use acid-resistant high-priced equipment, it is difficult to economically produce graphene oxide in a large quantity.
본 발명자들은 산화그래핀의 정제에 있어서 상기한 문제점을 해결하고자 예의 연구 검토한 결과, 친수성 입자로 물에 잘 분산되는 산화그래핀이 놀랍게도 유기용매층으로 이동되어 중금속 산폐액으로부터 분리 정제될 수 있음을 알아내고, 본 발명을 완성하게 되었다. DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies to solve the above problems in the purification of graphene oxide, and as a result, it has been found that the graphene oxide which is dispersed well in water as hydrophilic particles can be surprisingly moved to the organic solvent layer and can be separated and purified from the heavy metal acid waste solution And the present invention has been completed.
따라서, 본 발명의 목적은 고순도의 산화그래핀을 유기용매를 이용하여 효율적으로 간단하게 정제하는 방법을 제공하는 것이다.Accordingly, an object of the present invention is to provide a simple and efficient method for purifying high-purity oxide graphene using an organic solvent.
본 발명의 일 실시형태는 그라파이트를 산과 중금속 산화제를 이용하여 산화시켜 생성되는 산화그래핀 수용액을 유기용매를 이용하여 상 분리(phase separation)하는 단계를 포함하는 산화그래핀의 정제방법에 관한 것이다.One embodiment of the present invention relates to a method for purifying graphene oxide comprising the step of phase separation using an organic solvent in an aqueous solution of an oxidized graphene produced by oxidizing graphite with an acid and a heavy metal oxidizing agent.
본 발명의 일 실시형태에서, 상기 산화그래핀 수용액은 그라파이트를 산과 중금속 산화제를 이용하여 산화시켜 생성되는 것으로, 당해 기술분야에서 통상적으로 사용되는 방법에 의해 제조할 수 있다.In one embodiment of the present invention, the graphene oxide aqueous solution is produced by oxidizing graphite with an acid and a heavy metal oxidizing agent, and can be produced by a method commonly used in the art.
상기 산으로는 황산, 인산, 질산 등을 사용할 수 있으며, 상기 중금속 산화제로는 과망간산칼륨(potassium permanganate: KMnO4), 크롬산(Chromic acid: H2CrO4) 등을 사용할 수 있다.As the acid, sulfuric acid, phosphoric acid, nitric acid and the like can be used. As the heavy metal oxidizing agent, potassium permanganate (KMnO 4 ), chromic acid (H 2 CrO 4 ) and the like can be used.
상기 방법에 의해 제조된 산화그래핀 수용액에는 과량의 폐산과 금속 이온이 포함되어 있다.The graphene oxide aqueous solution prepared by the above method contains excessive amounts of waste acid and metal ions.
본 발명의 일 실시형태에 따르면, 극성(relative polarity) 차로 인하여 산화그래핀 수용액과 혼합되지 않으면서 비중(density) 차로 인해 상 분리가 되는 유기용매를 사용하여 산화그래핀을 유기용매층으로 이동시키고, 폐산과 금속 이온이 포함된 수용액층을 상 분리한다.According to one embodiment of the present invention, graphene grains are moved to an organic solvent layer using an organic solvent that is phase-separated due to a density difference without being mixed with an aqueous solution of graphene due to a relative polarity difference Phase separation of the aqueous solution layer containing the spent acid and the metal ion.
구체적으로, 상기 산화그래핀 수용액에 유기용매를 혼합하고 교반한 후, 상 분리(phase separation)가 되도록 일정 시간 방치한 다음, 분별 깔대기를 이용하여 유기용매층으로 이동한 산화그래핀을 폐산과 금속 이온이 포함된 수용액층으로부터 분리한다.Specifically, an organic solvent is mixed and stirred in the aqueous solution of the oxidized graphene, and the solution is allowed to stand for a predetermined time for phase separation. Then, the graphene oxide transferred to the organic solvent layer by using a separating funnel is mixed with the waste acid Ions are separated from the aqueous solution layer containing the ions.
본 발명의 일 실시형태에서, 상기 유기용매는 상기 산화그래핀 수용액을 기준으로 50 내지 150 부피%, 바람직하게는 80 내지 120 부피%로 사용할 수 있다.In one embodiment of the present invention, the organic solvent may be used in an amount of 50 to 150% by volume, preferably 80 to 120% by volume, based on the aqueous solution of the oxidized graphene.
본 발명의 일 실시형태에서, 상기 유기용매는 디메틸 에테르, 에틸 아세테이트, 2-부탄온, 1-헵탄올, 1-펜탄올 및 1-부탄올로 구성된 군으로부터 선택된 하나 이상일 수 있다.
In one embodiment of the present invention, the organic solvent may be at least one selected from the group consisting of dimethyl ether, ethyl acetate, 2-butanone, 1-heptanol, 1-pentanol and 1-butanol.
본 발명의 일 실시형태에 따른 정제방법은 상기 상 분리 단계 이후에 산화그래핀을 건조 및 분쇄하는 단계를 추가로 포함할 수 있다.
The purification method according to an embodiment of the present invention may further include drying and crushing the oxidized graphene after the phase separation step.
본 발명의 일 실시형태에 따른 정제방법에 의해 정제된 산화그래핀은 물에 분산시킬 경우 침전 없이 반투명 상태를 유지하며, pH가 3 내외로 폐산이 거의 제거되고 금속 이온이 거의 완벽히 제거된 고순도 산화그래핀이다.The graphene oxide purified by the purification method according to an embodiment of the present invention maintains a translucent state without precipitation when dispersed in water and has a high purity oxidation state in which almost no spent acid is removed and the metal ion is almost completely removed It is grapina.
본 발명에 따르면, 고가의 특별한 장치 없이 교반기와 분별 깔대기만을 이용하여 짧은 시간 내에 폐산과 금속 이온 물질을 분리할 수 있다. 또한, 기존 반복 작업이 필요한 원심분리나 필터 그리고 투석과 같은 방법에 비해 정제 시간이 매우 짧고 간편하기 때문에 경제성이 매우 우수하며, 산 폐액 발생이 크게 줄어들어 친환경적이다. 아울러, 단 한번의 공정만으로도 산과 금속 이온을 거의 완벽하게 제거할 수 있어 고품질의 산화그래핀을 생산하는 데 매우 효과적이다.According to the present invention, the spent acid and the metal ion material can be separated in a short time by using only the stirrer and the separating funnel without expensive special apparatus. In addition, since the purification time is very short and simple compared with centrifugal separation, filter and dialysis, which require the conventional repetitive operation, the economical efficiency is excellent, and the generation of acid waste is greatly reduced, thereby being environmentally friendly. In addition, it is very effective in producing high quality graphene oxide because it can almost completely remove acid and metal ions by a single process.
이하, 실시예에 의해 본 발명을 보다 구체적으로 설명하고자 한다. 이들 실시예는 오직 본 발명을 설명하기 위한 것으로 본 발명의 범위가 이들 실시예에 국한되지 않는다는 것은 당업자에게 있어서 자명하다.
Hereinafter, the present invention will be described in more detail with reference to Examples. It should be apparent to those skilled in the art that these embodiments are for illustrative purpose only and that the scope of the present invention is not limited to these embodiments.
제조예 1: Preparation Example 1:
그라파이트 분말 1g에 황산(H2SO4) 90ml와 인산(H3PO4) 10ml를 넣고 1시간 가량 교반하여 그라파이트 분말이 산에 충분히 풀리도록 한 후, 혼합물이 5℃ 내외가 되도록 얼음 중탕 환경에서 과망간산칼륨(KMnO4) 6g을 천천히 넣은 후 24시간 교반하여 그라파이트 산화 반응을 실시하였다. 산화 반응된 반응물을 다시 얼음 중탕하여 냉각시킨 후, 2% 과산화수소 100ml를 넣어 산화그래핀 용액을 얻어내었다. 수득한 산화그래핀 용액에는 산화 공정에서 사용된 강산과 금속 이온이 과량으로 포함되어 있다.
90 ml of sulfuric acid (H 2 SO 4 ) and 10 ml of phosphoric acid (H 3 PO 4 ) were added to 1 g of the graphite powder and stirred for about 1 hour to sufficiently dissolve the graphite powder in the acid. 6 g of potassium permanganate (KMnO 4 ) was slowly added thereto, followed by stirring for 24 hours to carry out graphite oxidation reaction. The oxidized reaction product was cooled again by ice bathing, and then 100 ml of 2% hydrogen peroxide was added to obtain an oxidized graphene solution. The obtained oxidized graphene solution contains excessive amounts of strong acid and metal ions used in the oxidation step.
실시예 1: Example 1:
제조예 1에서 수득한 산화그래핀 용액 30ml에 디메틸 에테르(극성 = 0.117, 비중 = 0.713 g/ml) 30ml를 혼합하였다. 10분간 교반한 후 혼합 용액을 상 분리가 되도록 15분간 고정하였다. 상 분리되어 아래로 가라앉은 중금속 산폐액을 분별 깔대기를 이용하여 분리하여 정제하였다. 한편, 디메틸 에테르층으로 이동한 산화그래핀은 상온에서 건조한 후 분쇄하여 산화그래핀 분말을 제조하였다.
30 ml of the oxidized graphene solution obtained in Production Example 1 was mixed with 30 ml of dimethyl ether (polarity = 0.117, specific gravity = 0.713 g / ml). After stirring for 10 minutes, the mixed solution was fixed for 15 minutes to allow phase separation . The heavy metal acid waste which has been phase separated and settled down was separated and purified by using a separating funnel. On the other hand, the oxidized graphene moved to the dimethyl ether layer was dried at room temperature and then pulverized to prepare an oxidized graphene powder.
실시예 2: Example 2:
디메틸 에테르 대신에 에틸 아세테이트 (극성 = 0.228, 비중 = 0.894 g/ml)를 사용하는 것을 제외하고는, 실시예 1과 동일한 방법으로 산화그래핀 분말을 제조하였다.
Oxidized graphene powder was prepared in the same manner as in Example 1, except that ethyl acetate (polarity = 0.228, specific gravity = 0.894 g / ml) was used instead of dimethyl ether.
실시예 3: Example 3:
디메틸 에테르 대신에 2-부탄온 (극성 = 0.327, 비중 = 0.805 g/ml)를 사용하는 것을 제외하고는, 실시예 1과 동일한 방법으로 산화그래핀 분말을 제조하였다.
Oxide graphene powder was prepared in the same manner as in Example 1, except that 2-butanone (polarity = 0.327, specific gravity = 0.805 g / ml) was used instead of dimethyl ether.
실시예 4:Example 4:
디메틸 에테르 대신에 1-헵탄올 (극성 = 0.549, 비중 = 0.819 g/ml)를 사용하는 것을 제외하고는, 실시예 1과 동일한 방법으로 산화그래핀 분말을 제조하였다.
Oxidized graphene powder was prepared in the same manner as in Example 1, except that 1-heptanol (polarity = 0.549, specific gravity = 0.819 g / ml) was used instead of dimethyl ether.
실시예 5:Example 5:
디메틸 에테르 대신에 1-펜탄올 (극성 = 0.568, 비중 = 0.814 g/ml)를 사용하는 것을 제외하고는, 실시예 1과 동일한 방법으로 산화그래핀 분말을 제조하였다.
Oxide graphene powder was prepared in the same manner as in Example 1, except that 1-pentanol (polarity = 0.568, specific gravity = 0.814 g / ml) was used instead of dimethyl ether.
실시예 6:Example 6:
디메틸 에테르 대신에 1-부탄올 (극성 = 0.586, 비중 = 0.81 g/ml)를 사용하는 것을 제외하고는, 실시예 1과 동일한 방법으로 산화그래핀 분말을 제조하였다.
Oxidized graphene powder was prepared in the same manner as in Example 1, except that 1-butanol (polarity = 0.586, specific gravity = 0.81 g / ml) was used instead of dimethyl ether.
비교예 1: Comparative Example 1:
제조예 1에서 수득한 산화그래핀 용액을 1차 원심분리하여 고형분만을 얻어내고, 에탄올을 1000ml 혼합하여 1시간 동안 교반해 준 후 5마이크로 포어 크기를 갖는 필터를 이용하여 진공펌프를 이용한 감압조건 하에서 필터하였다. 필터된 산화그래핀 고형분을 다시 에탄올 1000ml에 분산하여 진공 필터하는 정제 과정을 추가로 3회 반복한 후, 얻어진 산화그래핀 고형분을 건조, 분쇄하여 분말로 제조하였다.
The oxidized graphene solution obtained in Preparation Example 1 was subjected to primary centrifugation to obtain only a solid component. 1,000 ml of ethanol was mixed and stirred for 1 hour, and then, using a filter having a size of 5 micro pores, under a reduced pressure condition using a vacuum pump Filtered. The filtered graphene graphene solids were again dispersed in 1000 ml of ethanol and subjected to a vacuum filtration process. The obtained graphene graphene solids were dried and pulverized to prepare powders.
비교예 2: Comparative Example 2:
제조예 1에서 수득한 산화그래핀 용액을 6000rpm에서 1시간 동안 원심분리하여 폐산 용액과 산화그래핀을 분리하였다. 이후 얻어진 산화그래핀 고형분을 다시 증류수 1000ml에 교반하면서 분산시키고 다시 6000rpm에서 1시간 원심분리하였다. 이러한 원심분리 공정을 총 3회 반복 실시하였다. 마지막으로 원심분리하여 얻어진 산화그래핀 고형분을 건조, 분쇄하여 분말로 제조하였다.
The graphene oxide solution obtained in Production Example 1 was centrifuged at 6000 rpm for 1 hour to separate the waste acid solution and the oxidized graphene. The resulting graphene oxide grains were dispersed in 1,000 ml of distilled water with stirring and centrifuged again at 6000 rpm for 1 hour. This centrifugation process was repeated three times in total. Finally, the grafted oxide grains obtained by centrifugal separation were dried and pulverized to prepare powders.
실험예 1: Experimental Example 1:
실시예 1 및 2에서 건조, 분쇄 공정 후 얻어진 최종 산화그래핀 분말을 각각 물에 1mg/ml 농도로 분산 시킨 후 pH를 측정하여, 유기용매를 이용한 분리정제 공정 이후 잔류하는 산의 함량을 비교 분석하였다.In Examples 1 and 2, the final graphene grains obtained after the drying and pulverizing processes were each dispersed in water at a concentration of 1 mg / ml, and the pH was measured. The residual acid content after the separation and purification process using an organic solvent was compared Respectively.
산화그래핀 분산용액의 pH는 각각 2.6 그리고 3.0으로, 산이 거의 제거되었음을 확인할 수 있었다.
The pH of the graphene dispersion solution was 2.6 and 3.0, respectively, indicating that the acid was almost removed.
실험예 2: Experimental Example 2:
실시예 1-6 및 비교예 1-2에서 수득한 산화그래핀 분말의 XPS(X-ray photoelectron spectroscopy)를 분석하여 그 결과를 하기 표 1에 나타내었다.X-ray photoelectron spectroscopy (XPS) of the oxidized graphene powders obtained in Examples 1-6 and 1-2 was analyzed and the results are shown in Table 1 below.
상기 표 1에서 보듯이, 본 발명에 따른 정제방법에 의해 정제된 산화그래핀 분말은 단 한번의 공정만으로, 정제 후 잔류하는 산에 의해 검출되는 원소성분(S)이 낮게 나오면서, 중금속 산화제의 사용에 의해 잔류하는 금속 이온 성분(Mn)이 거의 완벽히 검출되지 않으므로, 고품질(고순도)의 산화그래핀이 생성됨을 확인할 수 있었다. As shown in Table 1, the graphene oxide fine particles purified by the purification method according to the present invention show only a small amount of elemental component (S) detected by the residual acid after purification, (High purity) graphene grains were generated because the remaining metal ion component (Mn) was almost completely not detected by the catalyst.
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