WO2013106963A1 - Process for preparing graphene dispersion - Google Patents

Process for preparing graphene dispersion Download PDF

Info

Publication number
WO2013106963A1
WO2013106963A1 PCT/CN2012/000253 CN2012000253W WO2013106963A1 WO 2013106963 A1 WO2013106963 A1 WO 2013106963A1 CN 2012000253 W CN2012000253 W CN 2012000253W WO 2013106963 A1 WO2013106963 A1 WO 2013106963A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
graphene
water
preparing
liquid phase
Prior art date
Application number
PCT/CN2012/000253
Other languages
French (fr)
Chinese (zh)
Inventor
沈志刚
易敏
麻树林
张晓静
廖锦华
Original Assignee
北京航空航天大学
格雷菲尼（北京）科技有限公司
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 北京航空航天大学, 格雷菲尼（北京）科技有限公司 filed Critical 北京航空航天大学
Publication of WO2013106963A1 publication Critical patent/WO2013106963A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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

Definitions

  • the present invention relates to a process and a process for preparing a solution for preparing graphene in a liquid phase, and more particularly to a technique for preparing graphene in a mixed solution of water and alcohol. It belongs to the technical field of graphene preparation. Background technique
  • Graphene exhibits broad application prospects in many fields such as new materials, new energy and electronic components due to its unique properties in physics, chemistry, electricity and mechanics.
  • the most important prerequisite for the true large-scale application of graphene is the development of low-cost, high-volume, non-polluting graphene preparation techniques.
  • the high-volume, low-cost, non-polluting preparation technology of graphene is one of the core issues concerning the basic research and industrial application of this material.
  • the first to produce graphene was Novoselov and Geim, winners of the 2010 Nobel Prize in Physics, who used micromechanical cleavage in 2004 to strip graphene from highly oriented pyrolytic graphite (H0PG) by tape bonding. sheet.
  • micromechanical cleavage can produce high-quality lithene with a lateral dimension of several tens of micrometers, the efficiency and yield are extremely low, and it is limited to basic research in the laboratory.
  • the mainstream method for graphene preparation belongs to the chemical technology category, mainly including substrate growth, substrate epitaxy, chemical vapor deposition and reduction of graphene oxide.
  • the first three methods show advantages in the application of electronic components, but there is temperature pressure control.
  • the method of directly stripping ordinary crystal graphite to prepare graphene in the liquid phase, the crystal graphite powder raw material, the related solvent and the mechanical stripping equipment are low in price, the solvent can be green and pollution-free, and exhibits simple green, low cost and high efficiency.
  • the advantages of preparing graphene in large quantities are low in price, the solvent can be green and pollution-free, and exhibits simple green, low cost and high efficiency.
  • the object of the present invention is to provide a preparation process and a method for preparing a solution for graphene in a liquid phase, which overcomes the deficiencies of the prior art and is a simple green low cost, high efficiency, large A good process for preparing graphene in batches.
  • the above object of the present invention is achieved by the following technical solutions:
  • the present invention relates to a process and a method for preparing a solution for preparing graphene in a liquid phase, and the specific steps of the method are as follows:
  • Step 1 directly mixing a predetermined proportion of water and alcohol to obtain a solution for preparing graphene in a liquid phase.
  • Step two dispersing graphite powder in the solution to obtain a graphite dispersion
  • Step 3 using ultrasonic cavitation or jet cavitation for treatment; '
  • Step 4 The treated solution is allowed to stand still, and then the upper layer solution is taken;
  • Step 5 The upper layer solution is further treated as a high speed poultry heart separation treatment
  • Step 6 The supernatant liquid after high-speed centrifugation is collected to obtain a stable graphene dispersion.
  • the mixed solution of water and alcohol described in the first step refers to a mixed solution of water and ethanol, and the optimum mass ratio of ethanol is 20% to 60%, and the balance is water.
  • the mixed solution of water and alcohol described in the first step means a mixed solution of water and isopropyl alcohol, and the optimum mass ratio of isopropyl alcohol is 35% to 75%, and the balance is water.
  • the graphite powder described in the second step is flaky graphite of less than 100 ⁇ m.
  • the ultrasonic cavitation treatment described in the third step is to put the mixed solution of the graphite powder and the water and ethanol or the mixed solution of water and isopropyl alcohol in the second step into the ultrasonic cavitation vessel for ultrasonication. After the cavitation treatment, after 1 hour to 10 hours of treatment, a stable dispersion containing graphene can be prepared.
  • the jet cavitation treatment described in the third step is that the mixed solution of the graphite powder and the water and ethanol or the mixed solution of water and isopropyl alcohol in the second step is placed in the cavitation storage tank of the jet flow. Jet After the cavitation treatment, after 10 minutes to 100 minutes of treatment, a stable dispersion containing graphene can be prepared. Note: The jet cavitation treatment process and method are described in the invention patent "A device and method for preparing graphene by jet cavitation technology", application number: 201110190763.
  • the time of the static treatment described in the fourth step is 3 hours to 50 hours;
  • the high-speed centrifugal separation treatment described in the fifth step is: the centrifuge speed is 500 rpm
  • centrifugation time is 10 minutes to 200 minutes.
  • the preparation process and method for preparing a solution for graphene in a liquid phase are particularly simple, and are easy to be realized in an experimental room and industrialized.
  • the graphene prepared in the solution has good dispersion stability, high graphene concentration and good quality.
  • Figure 1 is a flow chart of the method of the present invention
  • Example 1 Preparation of graphene by ultrasonic cavitation in a mixed solution of water and ethanol is an example, and the process steps are as follows:
  • the second step of the present invention is to disperse 4 mg of graphite powder of less than 100 ⁇ m to obtain a graphite dispersion of 0.2 mg/mL. , and put it into a 30mL container bottle; '
  • Step 3 The above-mentioned container bottle containing the graphite dispersion liquid is placed in a lOOOmL ultrasonic container containing water, ultrasonically processed for 180 min, ultrasonic output power 20 W, frequency 40 KHz;
  • Step 4 The sonicated container bottle (with graphite dispersion) is allowed to stand for 8 hours, and then the upper layer dispersion is taken out;
  • Step 5 The taken-out supernatant liquid is placed in a centrifuge tube, and then subjected to high-speed centrifugation, and the centrifuge speed is 3000 rpm (X 1008 g), and centrifuged for 30 minutes;
  • Step 6 After centrifugation, the supernatant is collected to obtain a graphene-stabilized dispersion in a mixed solution of water and ethanol.
  • Example 2 the preparation of graphene by ultrasonic cavitation in a mixed solution of water and isopropyl alcohol is taken as an example, and the process steps are as follows:
  • the second step of the mixture of water and isopropyl alcohol is 20%, the amount of isopropyl alcohol is 55%, the amount of isopropyl alcohol is 55%, the remainder is water; Graphite dispersion, and put it into a 30mL container bottle;
  • Step 3 The above-mentioned container bottle containing the graphite dispersion liquid is placed in a lOOOOmL ultrasonic container containing water, sonicated 18 (1 ⁇ 2 in, ultrasonic output power 20 W, frequency 40 KHz;
  • Step 4 The ultrasonically treated container bottle (containing the graphite dispersion) is allowed to stand for 8 hours, and then the upper layer dispersion is taken out;
  • Step 5 The taken-out supernatant liquid is placed in a centrifuge tube, and then subjected to high-speed centrifugation, the centrifuge speed is 3000 rpm (X 1008 g), and centrifugation for 30 min ;
  • Step 6 After centrifugation, collect the supernatant to obtain graphite in a mixed solution of water and isopropanol. A stable dispersion of the olefin.
  • Example 3 the preparation of graphene by jet cavitation in a mixed solution of water and ethanol is taken as an example, and the process steps are as follows:
  • Step 2 Dissolve a mixture of water and ethanol in an amount of 5,000 mL, a mass fraction of ethanol of 40%, and the balance is water; Step 2: Disperse 1000 mg of graphite powder of less than 100 ⁇ m, to obtain a graphite dispersion of 0.2 mg/mL, And install it into the 10L storage tank of the incident flow cavitation device;
  • Step 3 Set the working pressure of the plunger pump of the jet cavitation device to 20 MPa, the power of the plunger pump motor to 30 KW, and the system to run for 30 min;
  • Step 4 Remove the solution from the storage tank, pour it into the beaker and let it stand for 8 hours, then take out the upper dispersion;
  • Step 5 The taken-out supernatant liquid is placed in a centrifuge tube, and then subjected to high-speed centrifugation, and the centrifuge speed is 3000 rpm (X 1008 g), and centrifuged for 30 minutes;
  • Step 6 After centrifugation, the supernatant is collected to obtain a graphene-stabilized dispersion in a mixed solution of water and ethanol.
  • Example 4 the preparation of graphene by jet cavitation in a mixed solution of water and isopropyl alcohol is taken as an example, and the process steps are as follows:
  • the second step is to disperse 1000 mg of graphite powder of less than 100 ⁇ m, and obtain 0. 2 mg / mL of the mixture of water and isopropyl alcohol. a graphite dispersion and placed in a 10 L storage tank of the incident flow cavitation unit;
  • Step 3 Set the working pressure of the plunger pump of the jet cavitation device to 20MP a , the power of the plunger pump motor to 30KW, and the system to run for 30 minutes;
  • Step 4 Remove the solution from the storage tank, pour it into the beaker and let it stand for 8 hours, then take out the upper dispersion;
  • Step 5 The taken-out supernatant liquid is placed in a centrifuge tube, and then subjected to high-speed centrifugation, and the centrifuge is rotated at 1000 rpm (X 112 g) or 3000 rpm (X 1008 g) for 30 minutes;
  • Step 6 After centrifugation, collect the supernatant to obtain graphite in a mixed solution of water and isopropanol. A stable dispersion of the olefin.

Abstract

Disclosed is a process for preparing a graphene dispersion, comprising the following steps: (1) directly mixing water and an alcohol at a pre-determined ratio to obtain a solution used for the preparation of graphene; (2) dispersing the graphite into this solution to obtain a graphite dispersion; (3) treating same by ultrasound cavitation or jet cavitation; (4) allowing the treated solution to stand, and taking the solution in the upper layer; (5) subjecting the solution in the upper layer to separation by a high speed centrifuge; and (6) collecting the supernatant after the treatment by the high speed centrifuge, so as to obtain a stabilized graphene dispersion.

Description

一种石墨烯分散液的制备方法 技术领域  Method for preparing graphene dispersion liquid
本发明涉及一种在液相中制备石墨烯所用溶液的制备工艺及方法， 具体是 一种在水和醇的混合溶液中制备石墨烯的技术。 属于石墨烯制备技术领域。 背 景 技 术  The present invention relates to a process and a process for preparing a solution for preparing graphene in a liquid phase, and more particularly to a technique for preparing graphene in a mixed solution of water and alcohol. It belongs to the technical field of graphene preparation. Background technique
石墨烯以其在物理、 化学、 电学、 力学等各方面的独特优异性能， 在新材 料、 新能源和电子元器件等诸多领域展现出了广阔的应用前景。 然而， 从长远 来看， 实现石墨烯真正大规模应用的最重要前提是， 开发出低成本、 大批量、 无污染的石墨烯制备技术。 同样， 石墨烯的大批量低成本无污染制备技术也是 关于该材料基础研究与产业化应用的核心问题之一。  Graphene exhibits broad application prospects in many fields such as new materials, new energy and electronic components due to its unique properties in physics, chemistry, electricity and mechanics. However, in the long run, the most important prerequisite for the true large-scale application of graphene is the development of low-cost, high-volume, non-polluting graphene preparation techniques. Similarly, the high-volume, low-cost, non-polluting preparation technology of graphene is one of the core issues concerning the basic research and industrial application of this material.
首次制备出石墨烯的是 2010年诺贝尔物理学奖获得者 Novoselov和 Geim, 他们在 2004年采用微机械解理， 即以胶带黏贴技术从高定向热解石墨 （H0PG) 中剥离出石墨烯片。 微机械解理虽然可制备出横向尺寸达几十微米的高质量石 墨烯， 但效率和产量极低， 仅限于实验室的基础研究。 目前石墨烯制备的主流 方法属于化学技术范畴， 主要包括基底生长、 基底外延、 化学气相沉积和还原 氧化石墨烯等方法， 前三种方法在电子元器件应用上展现出优势， 但存在温度 压强控制要求高、 高质量基片、 石墨烯与基片分离难以控制等苛刻条件， 很难 以达到大量简易生产石墨烯的目的， 尤其无法满足石墨烯材料的产业化应用需 求。 另外， 基于液相工艺的氧化石墨烯还原方法， 虽然是宏量制备石墨烯的有 效途径， 但该方法工艺复杂， 条件不易控制， 制备成本较高，. 还原的氧化石墨 烯与纯石墨烯在性能上还是有所差别， 且还原效率较低， 所用化学试剂大多有 毒， 难以满足低成本绿色应用需要。 而在液相中直接剥离普通晶体石墨制备石 墨烯的方法， 以其晶体石墨粉原料、 相关溶剂及机械剥离设备价格低廉， 溶剂 可以绿色无污染的特点， 展现出简易绿色、 低成本、 高效率、 大批量制备石墨 烯的优势。  The first to produce graphene was Novoselov and Geim, winners of the 2010 Nobel Prize in Physics, who used micromechanical cleavage in 2004 to strip graphene from highly oriented pyrolytic graphite (H0PG) by tape bonding. sheet. Although micromechanical cleavage can produce high-quality lithene with a lateral dimension of several tens of micrometers, the efficiency and yield are extremely low, and it is limited to basic research in the laboratory. At present, the mainstream method for graphene preparation belongs to the chemical technology category, mainly including substrate growth, substrate epitaxy, chemical vapor deposition and reduction of graphene oxide. The first three methods show advantages in the application of electronic components, but there is temperature pressure control. High-quality, high-quality substrates, difficult conditions such as difficult separation of graphene and substrate are difficult to control, and it is difficult to achieve a large number of simple production of graphene, especially for the industrial application of graphene materials. In addition, the graphene oxide reduction method based on the liquid phase process is an effective way to prepare graphene in a macroscopic manner, but the method is complicated, the conditions are not easy to control, and the preparation cost is high. The reduced graphene oxide and the pure graphene are The performance is still different, and the reduction efficiency is low. Most of the chemical reagents used are toxic, which is difficult to meet the needs of low-cost green applications. The method of directly stripping ordinary crystal graphite to prepare graphene in the liquid phase, the crystal graphite powder raw material, the related solvent and the mechanical stripping equipment are low in price, the solvent can be green and pollution-free, and exhibits simple green, low cost and high efficiency. The advantages of preparing graphene in large quantities.
I 发 明 内 容 I Summary of the invention
1、 目的： 本发明的目的在于提供一种在液相中制备石墨烯所用溶液的制备工 艺及方法， 该方法克服了现有技术的不足， 是一种简易绿色的低成本、 高效率、 大批量制备石墨烯的好工艺方法。  1. Purpose: The object of the present invention is to provide a preparation process and a method for preparing a solution for graphene in a liquid phase, which overcomes the deficiencies of the prior art and is a simple green low cost, high efficiency, large A good process for preparing graphene in batches.
2、 技术方案： 本发明的上述目的是通过如下的技术方案予以实现的： 本发明一种在液相中制备石墨烯所用溶液的制备工艺及方法，该方法具体步 骤如下：  2. Technical Solution: The above object of the present invention is achieved by the following technical solutions: The present invention relates to a process and a method for preparing a solution for preparing graphene in a liquid phase, and the specific steps of the method are as follows:
步骤一：把预定比例的水和醇直接混合， 即可获得在液相中制备石墨烯所用的溶Step 1: directly mixing a predetermined proportion of water and alcohol to obtain a solution for preparing graphene in a liquid phase.
、―、_> , ―, _>
涖； Responsible
步骤二:将石墨粉分散于该溶液中， 得到石墨分散液； Step two: dispersing graphite powder in the solution to obtain a graphite dispersion;
步骤三：采用超声空化或射流空化进行处理； ' Step 3: using ultrasonic cavitation or jet cavitation for treatment; '
步骤四：把处理后的溶液进行静置处理， 然后取上层的溶液； Step 4: The treated solution is allowed to stand still, and then the upper layer solution is taken;
步骤五：把上层溶液再作高速禽心分离处理； Step 5: The upper layer solution is further treated as a high speed poultry heart separation treatment;
步骤六：把高速离心分离处理后的上层清液收集出来， 即得到稳定的石墨烯分散 液。 Step 6: The supernatant liquid after high-speed centrifugation is collected to obtain a stable graphene dispersion.
其中， 步骤一中所述的水和醇的混合溶液是指水和乙醇的混合溶液， 乙醇 最佳质量比例为 20%- 60%， 其余为水。  Wherein, the mixed solution of water and alcohol described in the first step refers to a mixed solution of water and ethanol, and the optimum mass ratio of ethanol is 20% to 60%, and the balance is water.
其中， 步骤一中所述的水和醇的混合溶液是指水和异丙醇的混合溶液， 异 丙醇最佳质量比例为 35%- 75%， 其余为水。  Among them, the mixed solution of water and alcohol described in the first step means a mixed solution of water and isopropyl alcohol, and the optimum mass ratio of isopropyl alcohol is 35% to 75%, and the balance is water.
其中， 步骤二中所述的石墨粉为小于 100微米的鳞片状石墨。  Wherein, the graphite powder described in the second step is flaky graphite of less than 100 μm.
其中， 步骤二中所述的石墨粉与乙醇 /水混合溶液的质量比为 0. 001%-10%， 石墨粉与异丙醇 /水混合溶液的质量比为 0. 001%- 10%。  001%至 10%。 The mass ratio of the graphite powder to the mixed solution of the isopropyl alcohol / water is 0. 001% - 10%.
其中， 歩骤三中所述的超声空化处理是把步骤二中所述的石墨粉与水和乙 醇的混合溶液或者水和异丙醇的混合溶液放到超声空化的容器中， 进行超声空 化处理， 处理 1小时至 10小时后， 就可制备出含有石墨烯的稳定分散液。  Wherein, the ultrasonic cavitation treatment described in the third step is to put the mixed solution of the graphite powder and the water and ethanol or the mixed solution of water and isopropyl alcohol in the second step into the ultrasonic cavitation vessel for ultrasonication. After the cavitation treatment, after 1 hour to 10 hours of treatment, a stable dispersion containing graphene can be prepared.
其中， 步骤三中所述的射流空化处理是把步骤二中所述的石墨粉与水和乙 醇的混合溶液或者水和异丙醇的混合溶液放到射流空化的储料罐中， 进行射流 空化处理， 处理 10分钟至 100分钟后， 就可制备出含有石墨烯的稳定分散液。 注： 射流空化处理工艺及方法见发明专利 "一种射流空化技术制备石墨烯的装 置及方法"， 申请号为： 201110190763. 3。 The jet cavitation treatment described in the third step is that the mixed solution of the graphite powder and the water and ethanol or the mixed solution of water and isopropyl alcohol in the second step is placed in the cavitation storage tank of the jet flow. Jet After the cavitation treatment, after 10 minutes to 100 minutes of treatment, a stable dispersion containing graphene can be prepared. Note: The jet cavitation treatment process and method are described in the invention patent "A device and method for preparing graphene by jet cavitation technology", application number: 201110190763.
其中， 步骤四中所述的静置处理的时间是 3小时至 50小时；  Wherein, the time of the static treatment described in the fourth step is 3 hours to 50 hours;
其中， 步骤五中所述的高速离心分离处理是： 离心机转速为 500 转 /分至 Among them, the high-speed centrifugal separation treatment described in the fifth step is: the centrifuge speed is 500 rpm
10000转 /分； 离心处理时间是 10分钟至 200分钟。 10,000 rpm; centrifugation time is 10 minutes to 200 minutes.
3、 本发明的有益效果是：  3. The beneficial effects of the present invention are:
( 1 ) 在液相中制备石墨烯所用溶液的制备工艺及方法特别简单， 易于实验 室和工业化实现。  (1) The preparation process and method for preparing a solution for graphene in a liquid phase are particularly simple, and are easy to be realized in an experimental room and industrialized.
( 2 )在该溶液中所制备的石墨烯， 分散稳定性好， 石墨烯浓度高， 质量好。 (2) The graphene prepared in the solution has good dispersion stability, high graphene concentration and good quality.
( 3 ) 与文献报道的沸点高、 价格贵、 有毒的有机溶剂相比， 水和乙醇混合 溶液、 水和异丙醇混合溶液沸点低， 无毒无污染， 制造成本低， 完全可以满足 工业生产中安全性和绿色环保的要求。 (3) Compared with the organic solvent with high boiling point, high price and toxic content reported in the literature, the mixed solution of water and ethanol, water and isopropanol have low boiling point, no toxicity, no pollution, low manufacturing cost, and can fully meet industrial production. Safety and green requirements.
( 4 ) 使用本发明方法生产的石墨烯， 经原子力显微镜统计分析表明， 单层 石墨烯占 6%Γ10%，三层及其以下石墨烯占 36%~50%，十层以下石墨烯占 79%〜92%， 石墨烯片的大小为几百纳米至几微米。  (4) Graphene produced by the method of the present invention, statistical analysis by atomic force microscopy shows that single layer graphene accounts for 6% Γ 10%, graphene with three layers and below accounts for 36% to 50%, and graphene accounts for less than ten layers. %~92%, the size of the graphene sheets is several hundred nanometers to several micrometers.
附 图 说 明 Attachment
图 1为本发明方法的流程框图  Figure 1 is a flow chart of the method of the present invention
图 2为本发明方法所制备石墨烯分散液的自由沉降曲线 （超声空化处理） ， 纵坐标 C/C,为石墨烯分散液瞬时浓度与其初始浓度的比值， 横坐标 t为超声空 化处理时间； W-IPA指水和异丙醇混合溶液 （异丙醇的质量分数为 55%， 水的质 量分数为 45%) ， W-E指水和乙醇混合溶液 （乙醇的质量分数为 40%, 水的质量 分数为 60%) 。 具 体 实 施 方 式 下面结合实施例对本发明做进一步说明。  2 is a free sedimentation curve of the graphene dispersion prepared by the method of the present invention (ultrasonic cavitation treatment), the ordinate C/C is the ratio of the instantaneous concentration of the graphene dispersion to its initial concentration, and the abscissa t is the ultrasonic cavitation treatment. Time; W-IPA refers to a mixed solution of water and isopropyl alcohol (55% of isopropanol, 45% of water), WE refers to a mixed solution of water and ethanol (40% by mass of ethanol, water) The quality score is 60%). DETAILED DESCRIPTION OF THE INVENTION The present invention will be further described below in conjunction with the embodiments.
见图 1， 本发明一种在液相中制备石墨烯所用溶液的制备工艺及方法， 该方法 具体实施如下： ' 1 is a process and a method for preparing a solution for preparing graphene in a liquid phase, the method The specific implementation is as follows: '
实施例 1， 以在水和乙醇混合溶液中超声空化制备石墨烯为实施例， 详述 工艺步骤如下：  Example 1 Preparation of graphene by ultrasonic cavitation in a mixed solution of water and ethanol is an example, and the process steps are as follows:
步骤一：配置水和乙醇的混合溶液 20mL， 乙醇质量比例为 40%， 其余为水，； 步骤二:将小于 100微米的石墨粉 4 mg分散于其中， 得到 0. 2mg/mL的石墨分散 液， 并将其装入一个 30mL容器瓶中； ' The second step of the present invention is to disperse 4 mg of graphite powder of less than 100 μm to obtain a graphite dispersion of 0.2 mg/mL. , and put it into a 30mL container bottle; '
步骤三：把上述装有石墨分散液的容器瓶放置在盛有水的 lOOOmL的超声容器中， 超声处理 180min， 超声输出功率 20W、 频率 40KHz ; Step 3: The above-mentioned container bottle containing the graphite dispersion liquid is placed in a lOOOmL ultrasonic container containing water, ultrasonically processed for 180 min, ultrasonic output power 20 W, frequency 40 KHz;
步骤四：把经过超声处理后的容器瓶 （内装有石墨分散液） 静置 8小时， 然后把 上层分散液取出来； Step 4: The sonicated container bottle (with graphite dispersion) is allowed to stand for 8 hours, and then the upper layer dispersion is taken out;
步骤五：把取出来的上层分散液装入离心管中， 然后作高速离心分离处理， 离心 机转速为 3000rpm ( X 1008g)， 离心处理 30分钟； Step 5: The taken-out supernatant liquid is placed in a centrifuge tube, and then subjected to high-speed centrifugation, and the centrifuge speed is 3000 rpm (X 1008 g), and centrifuged for 30 minutes;
步骤六：离心分离处理后， 收集上层清液， 即得到水和乙醇混合溶液中的石墨烯 稳定分散液。 Step 6: After centrifugation, the supernatant is collected to obtain a graphene-stabilized dispersion in a mixed solution of water and ethanol.
石墨烯的沉降曲线如图 2所示。  The sedimentation curve of graphene is shown in Fig. 2.
实施例 2， 以在水和异丙醇混合溶液中超声空化制备石墨烯为实施例， 详述 工艺步骤如下：  Example 2, the preparation of graphene by ultrasonic cavitation in a mixed solution of water and isopropyl alcohol is taken as an example, and the process steps are as follows:
步骤一：配置水和异丙醇的混合溶液 20 mL， 异丙醇质量比例为 55%， 其余为水，； 步骤二:将小于 100微米的石墨粉 4mg分散于其中， 得到 0. 2mg/mL的石墨分散 液， 并将其装入一个 30mL容器瓶中； 2mg/mL。 2mg/mL. 2mg/mL。 The second step of the mixture of water and isopropyl alcohol is 20%, the amount of isopropyl alcohol is 55%, the amount of isopropyl alcohol is 55%, the remainder is water; Graphite dispersion, and put it into a 30mL container bottle;
步骤三:把上述装有石墨分散液的容器瓶放置在盛有水的 lOOOmL的超声容器中， 超声处理 18(½in， 超声波输出功率 20W、 频率 40KHz ; Step 3: The above-mentioned container bottle containing the graphite dispersion liquid is placed in a lOOOOmL ultrasonic container containing water, sonicated 18 (1⁄2 in, ultrasonic output power 20 W, frequency 40 KHz;
步骤四：把经过超声处理后的容器瓶 （内装有石墨分散液） 静置 8小时， 然后把 上层分散液取出来； ， Step 4: The ultrasonically treated container bottle (containing the graphite dispersion) is allowed to stand for 8 hours, and then the upper layer dispersion is taken out;
步骤五：把取出来的上层分散液装入离心管中， 然后作高速离心分离处理， 离心 机转速为 3000rpm ( X 1008g)， 离心处理 30min; Step 5: The taken-out supernatant liquid is placed in a centrifuge tube, and then subjected to high-speed centrifugation, the centrifuge speed is 3000 rpm (X 1008 g), and centrifugation for 30 min ;
步骤六：离心分离处理后， 收集上层清液， 即得到水和异丙醇混合溶液中的石墨 烯稳定分散液。 Step 6: After centrifugation, collect the supernatant to obtain graphite in a mixed solution of water and isopropanol. A stable dispersion of the olefin.
石墨烯的沉降曲线如图 2所示。  The sedimentation curve of graphene is shown in Fig. 2.
实施例 3， 以在水和乙醇混合溶液中射流空化制备石墨烯为实施例， 详述工 艺步骤如下：  Example 3, the preparation of graphene by jet cavitation in a mixed solution of water and ethanol is taken as an example, and the process steps are as follows:
步骤一：配置水和乙醇的混合溶液 5000mL， 乙醇质量分数为 40%， 其余为水； 步骤二:将小于 100微米的石墨粉 1000 mg分散于其中， 得到 0. 2mg/mL的石墨 分散液 ， 并将它装入射流空化装置的 10L的储料罐中； Step 2: Dissolve a mixture of water and ethanol in an amount of 5,000 mL, a mass fraction of ethanol of 40%, and the balance is water; Step 2: Disperse 1000 mg of graphite powder of less than 100 μm, to obtain a graphite dispersion of 0.2 mg/mL, And install it into the 10L storage tank of the incident flow cavitation device;
步骤三：设定射流空化装置的柱塞泵的工作压力为 20MPa， 柱塞泵电机功率为 30KW, ***运行 30min; Step 3: Set the working pressure of the plunger pump of the jet cavitation device to 20 MPa, the power of the plunger pump motor to 30 KW, and the system to run for 30 min;
步骤四：从储料罐中取出溶液， 倒入烧杯并静置 8小时， 然后把上层分散液取出 来； Step 4: Remove the solution from the storage tank, pour it into the beaker and let it stand for 8 hours, then take out the upper dispersion;
步骤五：把取出来的上层分散液装入离心管中， 然后作高速离心分离处理， 离心 机转速为 3000rpm ( X 1008g)， 离心 30分钟； Step 5: The taken-out supernatant liquid is placed in a centrifuge tube, and then subjected to high-speed centrifugation, and the centrifuge speed is 3000 rpm (X 1008 g), and centrifuged for 30 minutes;
步骤六：离心分离处理后， 收集上层清液， 即得到水和乙醇混合溶液中的石墨烯 稳定分散液。 Step 6: After centrifugation, the supernatant is collected to obtain a graphene-stabilized dispersion in a mixed solution of water and ethanol.
实施例 4， 以在水和异丙醇混合溶液中射流空化制备石墨烯为实施例， 详述 工艺步骤如下：  Example 4, the preparation of graphene by jet cavitation in a mixed solution of water and isopropyl alcohol is taken as an example, and the process steps are as follows:
步骤一：配置水和异丙醇的混合溶液 5000mL，异丙醇质量比例为 55%，其余为水; 步骤二:将小于 100微米的石墨粉 1000 mg分散于其中， 得到 0. 2mg/mL的石墨 分散液， 并将它装入射流空化装置的 10L的储料罐中； The second step is to disperse 1000 mg of graphite powder of less than 100 μm, and obtain 0. 2 mg / mL of the mixture of water and isopropyl alcohol. a graphite dispersion and placed in a 10 L storage tank of the incident flow cavitation unit;
步骤三：设定射流空化装置的柱塞泵的工作压力为 20MPa， 柱塞泵电机功率为 30KW, ***运行 30min; Step 3: Set the working pressure of the plunger pump of the jet cavitation device to 20MP a , the power of the plunger pump motor to 30KW, and the system to run for 30 minutes;
步骤四：从储料罐中取出溶液， 倒入烧杯并静置 8小时， 然后把上层分散液取出 来； Step 4: Remove the solution from the storage tank, pour it into the beaker and let it stand for 8 hours, then take out the upper dispersion;
步骤五：把取出来的上层分散液装入离心管中， 然后作高速离心分离处理， 离心 机转速为 lOOOrpm ( X 112g) 或 3000rpm ( X 1008g)， 离心 30分钟； Step 5: The taken-out supernatant liquid is placed in a centrifuge tube, and then subjected to high-speed centrifugation, and the centrifuge is rotated at 1000 rpm (X 112 g) or 3000 rpm (X 1008 g) for 30 minutes;
步骤六：离心分离处理后， 收集上层清液， 即得到水和异丙醇混合溶液中的石墨 烯稳定分散液。 Step 6: After centrifugation, collect the supernatant to obtain graphite in a mixed solution of water and isopropanol. A stable dispersion of the olefin.
显然， 本发明的上述实施案例仅仅是为了清楚说明本发明所作的举例， 而 并非对本发明的实施方式的限定。 对于所述领域的普通技术人员来说， 在上述 说明的基础上还可以做出其他不同形式的变化或变动。 这里无法对所有的实施 方式予以穷举， 凡是属于本发明的技术方案所引申出的显而易见的变化或变动 仍处于本发明的保护范围之列。  It is apparent that the above-described embodiments of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Other variations or modifications of the various forms may be made by those skilled in the art in light of the above description. It is to be understood that the various changes and modifications may be made without departing from the scope of the invention.

Claims

权利 要 求 书 Claim
1、 一种在液相中制备石墨烯所用溶液的制备工艺及方法， 其特征在于： 该方 法具体步骤如下： 步骤一：把预定比例的水和醇直接混合， 获得在液相中制备石墨烯所用的溶液； 步骤二:将石墨粉分散于该溶液中， 得到石墨分散液； . 步骤三：采用超声空化或射流空化进行处理； 步骤四：把处理后的溶液进行静置处理， 然后取上层的溶液； 步骤五：把上层溶液再作高速离心分离处理； 步骤六：把高速离心分离处理后的上层清液收集出来， 得到稳定的石墨烯分散 液。 A process and a method for preparing a solution for preparing graphene in a liquid phase, characterized in that: the specific steps of the method are as follows: Step 1: directly mixing a predetermined proportion of water and an alcohol to obtain a graphene in a liquid phase The solution used; Step 2: Disperse the graphite powder in the solution to obtain a graphite dispersion; Step 3: treatment by ultrasonic cavitation or jet cavitation; Step 4: The treated solution is allowed to stand still, then Take the upper layer solution; Step 5: The upper layer solution is further subjected to high-speed centrifugation; Step 6: The supernatant liquid after high-speed centrifugation is collected to obtain a stable graphene dispersion.
2、 根据权利要求 1所述的一种在液相中制备石墨烯所用溶液的制备工艺及方 法， 其特征在于： 步骤一中所述的水和醇的混合溶液是指水和乙醇的混合溶液， 乙醇最佳质量比例为 20%-60%， 其余为水。  2 . The preparation process and method for preparing a solution for graphene in a liquid phase according to claim 1 , wherein: the mixed solution of water and alcohol in step 1 refers to a mixed solution of water and ethanol; The best mass ratio of ethanol is 20%-60%, and the rest is water.
3、 根据权利要求 1所述的一种在液相中制备石墨烯所用溶液的制备工艺及方 法， 其特征在于： 步骤一中所述的水和醇的混合溶液是指水和异丙醇的混合溶 液， 异丙醇最佳质量比例为 35%-75%， 其余为水。  3 . The preparation process and method for preparing a solution for graphene in a liquid phase according to claim 1 , wherein: the mixed solution of water and alcohol described in step 1 refers to water and isopropyl alcohol. The mixed solution, the optimal mass ratio of isopropyl alcohol is 35%-75%, and the rest is water.
4、 根据权利要求 1所述的一种在液相中制备石墨烯所用溶液的制备工艺及方 法， 其特征在于： 步骤二中所述的石墨粉为小于 100微米的鳞片状石墨。  4. The process and method for preparing a solution for preparing graphene in a liquid phase according to claim 1, wherein the graphite powder in the second step is flaky graphite of less than 100 μm.
5、 根据权利要求 1所述的一种在液相中制备石墨烯所用溶液的制备工艺及方 法， 其特征在于： 步骤二中所述的石墨粉与乙醇 /水混合溶液的质量比为 0. 001%- 10%， 石墨粉与异丙醇 /水混合溶液的质量比为 0. 001%- 10%。  5 . The preparation process and method for preparing a solution for graphene in a liquid phase according to claim 1 , wherein: the mass ratio of the graphite powder to the ethanol/water mixed solution in step 2 is 0. 001%至 10%。 001% - 10%, the mass ratio of graphite powder to isopropyl alcohol / water mixed solution is 0. 001% - 10%.
6、 根据权利要求 1所述的一种在液相中制备石墨烯所用溶液的制备工艺及方 法， 其特征在于： 步骤三中所述的超声空化处理是把步骤二中所述的石墨粉与 水和乙醇的混合溶液或者水和异丙醇的混合溶液放到超声空化的容器中， 进行 超声空化处理， 处理 1小时至 10小时后， 就制备出含有石墨烯的稳定 ;分散液。6. The process and method for preparing a solution for preparing graphene in a liquid phase according to claim 1, wherein: the ultrasonic cavitation treatment described in the third step is the graphite powder described in the second step. Mixing with water and ethanol or a mixture of water and isopropyl alcohol in an ultrasonic cavitation vessel Ultrasonic cavitation treatment, after treatment for 1 hour to 10 hours, a stable ; dispersion containing graphene was prepared.
7、 根据权利要求 1所述的一种在液相中制备石墨烯所用溶液的制备工艺及方 法， 其特征在于： 步骤三中所述的射流空化处理是把步骤二中所述的石墨粉与 水和乙醇的混合溶液或者水和异丙醇的混合溶液放到射流空化的储料罐中， 进 行射流空化处理， 处理 10分钟至 100分钟后， 就制备出含有石墨烯的稳定分散 液。 7. The process and method for preparing a solution for preparing graphene in a liquid phase according to claim 1, wherein: the jet cavitation treatment described in the third step is the graphite powder described in the second step. A mixed solution of water and ethanol or a mixed solution of water and isopropyl alcohol is placed in a jet cavitation storage tank to perform jet cavitation treatment, and after 10 minutes to 100 minutes, a stable dispersion containing graphene is prepared. liquid.
8、 根据权利要求 1所述的一种在液相中制备石墨烯所用溶液的制备工艺及方 法， 其特征在于： 步骤四中所述的静置处理的时间是 3小时至 50小时。  8. The process and method for preparing a solution for preparing graphene in a liquid phase according to claim 1, wherein the time of the standing treatment described in the fourth step is from 3 hours to 50 hours.
9、 根据权利要求 1所述的一种在液相中制备石墨烯所用溶液的制备工艺及方 法， 其特征在于： 步骤五中所述的高速离心分离处理是： 离心机转速为 500转 / 分至 10000转 /分； 离心处理时间是 10分钟至 200分钟。  9. The process and method for preparing a solution for preparing graphene in a liquid phase according to claim 1, wherein: the high-speed centrifugal separation treatment described in the fifth step is: the centrifuge speed is 500 rpm. Up to 10,000 rpm; centrifugation time is 10 minutes to 200 minutes.
PCT/CN2012/000253 2012-01-17 2012-02-28 Process for preparing graphene dispersion WO2013106963A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2012100148902A CN102583332B (en) 2012-01-17 2012-01-17 Technology and method for preparing solution used for preparing graphene in liquid phase
CN201210014890.2 2012-01-17

Publications (1)

Publication Number Publication Date
WO2013106963A1 true WO2013106963A1 (en) 2013-07-25

Family

ID=46472697

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2012/000253 WO2013106963A1 (en) 2012-01-17 2012-02-28 Process for preparing graphene dispersion

Country Status (2)

Country Link
CN (1) CN102583332B (en)
WO (1) WO2013106963A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10304937B2 (en) 2013-03-14 2019-05-28 The Provost, Fellows, Foundation Scholars, And The Other Members Of Board, Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth Near Dublin Scalable process for producing exfoliated defect-free, non-oxidised 2-dimensional materials in large quantities
US10843145B2 (en) 2015-08-11 2020-11-24 Graphenest, S.A. Method and device for production of graphene or graphene-like materials

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103350995B (en) * 2013-07-12 2015-04-22 北京航空航天大学 Turbulence method for preparing high-quality graphene
CN104085886B (en) * 2014-07-28 2015-11-04 嵇天浩 Graphene and preparation method thereof
CN104560347A (en) * 2014-12-29 2015-04-29 北京航空航天大学 In-situ preparation method of water-based lubricant containing molybdenum disulfide nanosheet
ITUB20155920A1 (en) * 2015-11-26 2017-05-26 Fondazione St Italiano Tecnologia Exfoliation of layered materials using wet-jet milling techniques.
CN105836737B (en) * 2016-05-06 2018-11-09 上海利物盛企业集团有限公司 A method of it is combined with jet stream stripping using ultrasound stripping and prepares graphene
CN106219534A (en) * 2016-08-10 2016-12-14 吉林吉大地球科学与地质开发股份有限公司 A kind of multistage graphene powder segregation apparatus
CN108658062A (en) * 2017-03-28 2018-10-16 纳米石墨烯股份有限公司 Method and apparatus for manufacturing non-oxidized graphite alkene plate
CN107055520B (en) * 2017-04-26 2019-01-18 大连理工大学 A kind of method that carbon dioxide packet ion liquid type microemulsion collaboration impinging jet prepares graphene
GB2575827A (en) * 2018-07-24 2020-01-29 Npl Management Ltd Method of an apparatus for producing nanomaterials
CN108975321A (en) * 2018-09-04 2018-12-11 浙江工业大学 A kind of method that the removing of Hydrodynamic cavitation liquid phase prepares graphene
CN110120499B (en) * 2019-05-10 2021-06-29 华瑞墨石丹阳有限公司 Graphite nanosheet and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101746755A (en) * 2009-12-14 2010-06-23 重庆大学 Method for preparing multi-layer graphene
CN102173414A (en) * 2011-03-18 2011-09-07 中国地质大学（武汉） Method for preparing graphene oxide by chemical peeling
CN102249222A (en) * 2011-07-08 2011-11-23 北京航空航天大学 Apparatus and process for preparing graphene by the technology of cavitating jet

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7892514B2 (en) * 2007-02-22 2011-02-22 Nanotek Instruments, Inc. Method of producing nano-scaled graphene and inorganic platelets and their nanocomposites
US7824651B2 (en) * 2007-05-08 2010-11-02 Nanotek Instruments, Inc. Method of producing exfoliated graphite, flexible graphite, and nano-scaled graphene platelets
CN101671015B (en) * 2009-10-13 2011-07-20 南昌航空大学 Method of producing graphene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101746755A (en) * 2009-12-14 2010-06-23 重庆大学 Method for preparing multi-layer graphene
CN102173414A (en) * 2011-03-18 2011-09-07 中国地质大学（武汉） Method for preparing graphene oxide by chemical peeling
CN102249222A (en) * 2011-07-08 2011-11-23 北京航空航天大学 Apparatus and process for preparing graphene by the technology of cavitating jet

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHEN, ZHIGANG ET AL.: "Sheliukonghua Fangfa Zhibei Shimoxi Yanjiu", SYMPOSIUM ON RECENT PROGRESS IN PARTICUOLOGY-10TH NATIONAL CONFERENCE ON PARTICLE PREPARATION AND TREATMENT, November 2011 (2011-11-01), pages 54 - 56 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10304937B2 (en) 2013-03-14 2019-05-28 The Provost, Fellows, Foundation Scholars, And The Other Members Of Board, Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth Near Dublin Scalable process for producing exfoliated defect-free, non-oxidised 2-dimensional materials in large quantities
US10843145B2 (en) 2015-08-11 2020-11-24 Graphenest, S.A. Method and device for production of graphene or graphene-like materials

Also Published As

Publication number Publication date
CN102583332A (en) 2012-07-18
CN102583332B (en) 2013-11-06

Similar Documents

Publication Publication Date Title
WO2013106963A1 (en) Process for preparing graphene dispersion
CN101513998B (en) Method for preparing ordered graphene oxide films
WO2015109916A1 (en) Method for preparing graphene
US10472243B2 (en) Industrial method for preparing large-sized graphene
CN103350995B (en) Turbulence method for preparing high-quality graphene
CN102732966B (en) Method for preparing two-dimensional atomic crystal new material by supercritical fluid
CN102719803A (en) Method for preparing and transferring graphene transparent film
CN103613095B (en) A kind of method of purifying and classifying Graphene
CN107555423B (en) Stripping solution for preparing two-dimensional nano material and application thereof
CN103253659A (en) Method for preparing graphene through carrying out ultrasonic stripping on graphite
CN102910624A (en) Preparation method of high-yield graphene without defects
CN108411267B (en) Method for preparing free-state polyhedral nano Ag particles
CN103864137B (en) Flower shape zinc oxide nano material and preparation method thereof
CN102581267A (en) Silver-graphene composite material and method for conveniently producing silver-graphene composite material
CN104944392A (en) Mass preparation method of graphite-phase carbon nitride nanosheets
CN102704190A (en) Method for preparing polyvinylidene fluoride and titanium dioxide (PVDF/TiO2) compounded nanofiber membrane
CN102701190A (en) Process and method for preparing graphene in mixed solution of water and acetone
CN105314623A (en) Graphene synthesis method
CN110171815A (en) A kind of preparation method of the high-purity carbon nano-tube film of low cost
CN103489532A (en) Czochralski method for preparing graphene transparent conducting thin films
CN103864059A (en) Graphene high-efficiency preparation method based on extraction purification technology
CN111825085A (en) CO regulated by ionic liquid2System and method for preparing graphene by stripping through high-entropy solution induced cavitation field
CN106672951A (en) Environment-friendly, high-efficiency and large-scale graphene preparation method
CN105776200B (en) A kind of photo catalytic reduction continuously prepares the device and method of graphene
CN104843677A (en) Porous graphene and preparation method therefor

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: 12865637

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: 12865637

Country of ref document: EP

Kind code of ref document: A1