CN111285361A - A kind of high-efficiency liquid phase mechanical preparation method of low-defect, high-dispersion graphene - Google Patents
A kind of high-efficiency liquid phase mechanical preparation method of low-defect, high-dispersion graphene Download PDFInfo
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Abstract
一种低缺陷、高分散石墨烯的高效液相机械制备方法，属于石墨烯领域，可解决机械剥离法制备石墨烯转化率低、化学法制备石墨烯工艺复杂、缺陷多，以及石墨烯粉体难以再分散难题，制备过程包括：以石墨为原料，采用原位插层，结合原位化学反应法，在石墨层间原位产生气泡使得石墨层间距增大，制得层间范德华力较小的扩层石墨；将扩层石墨分散于含有表面活性剂的碱性水溶液中，采用高速剪切作用对扩层石墨进行机械剥离，制得高稳定石墨烯分散液；采用低温喷雾干燥法，制得可再分散的石墨烯粉体，本发明制得石墨烯不仅操作过程简单、产率高、成本低，且石墨烯缺陷少、可再分散，在功能涂料和功能高分子复合材料的等领域具有广泛应用前景。
A high-efficiency liquid-phase mechanical preparation method of low-defect and high-dispersion graphene belongs to the field of graphene, and can solve the problems of low conversion rate of graphene prepared by mechanical exfoliation method, complex process of chemical preparation of graphene, many defects, and graphene powder. It is difficult to redisperse the problem. The preparation process includes: using graphite as raw material, using in-situ intercalation, combined with in-situ chemical reaction method, in-situ generation of bubbles between graphite layers increases the spacing between graphite layers, resulting in a smaller van der Waals force between layers. The expanded graphite is dispersed; the expanded graphite is dispersed in an alkaline aqueous solution containing a surfactant, and the expanded graphite is mechanically exfoliated by high-speed shearing to obtain a highly stable graphene dispersion; a low-temperature spray drying method is used to prepare To obtain redispersible graphene powder, the graphene obtained by the present invention not only has simple operation process, high yield and low cost, but also has few graphene defects and can be redispersed, which is used in the fields of functional coatings and functional polymer composite materials Has broad application prospects.
Description
Technical Field
The invention belongs to the technical field of graphene, and particularly relates to a high-efficiency liquid-phase mechanical preparation method of low-defect and high-dispersion graphene.
Background
Due to excellent physical and chemical properties, the graphene and the derivatives thereof have great potential to play roles in a plurality of fields, for example, the outstanding electrical properties can be applied to the fields of high-performance microelectronic devices, super capacitors, novel lithium ion batteries, functional coatings and the like; the excellent mechanical property is expected to be used as a reinforced complex to play the value in the fields of military and engineering, and the market prospect is wide. Thus, the problem to be solved in the field is the first need regarding the production preparation of graphene. At present, the preparation method of graphene can be mainly divided into the following 2 types: (1) Top-Down preparation (Top-Down): preparing graphene by taking graphite or Carbon Nanotubes (CNTs) as a raw material through a physical and chemical method; (2) bottom-up preparation (Bottomup): namely, the growth of graphene is realized in space through chemical reaction by taking small molecules as basic raw materials. Compared with the two methods comprehensively, the Top-down preparation method (Top-down) requires simple equipment, is suitable for industrialization, has relatively low production stability and cost, and becomes a main preparation method of graphene powder. The current top-down preparation methods mainly comprise a mechanical stripping method and a redox chemical stripping method.
The mechanical stripping method belongs to a typical physical preparation method, and takes highly oriented pyrolytic graphite as a raw material to realize the stripping of the graphite under the physical action condition. The Geim subject group of the university of Manchester successfully obtains graphene sheets with 1-3 layers for the first time by using a tape stripping method and taking graphite as a raw material in 2004. Although the method can obtain high-quality graphene with a complete structure, the method is not suitable for large-scale preparation of graphene due to overlarge workload and low conversion rate. In addition to the tape stripping method, the mechanical stripping method includes a wet mechanical stripping method, i.e., mechanical stripping of graphite by a shear force supplied by a high-speed stirrer, a ball mill, or a sand mill. Although the process is simple, and the graphene sp hybridized structure remains relatively complete, the mechanical exfoliation efficiency and conversion rate are low due to van der waals force existing between graphites, and how to separate graphene or graphene-like from graphite which is not exfoliated or is exfoliated to a relatively low degree is also difficult. Thus, such methods are difficult to implement large-scale preparation of graphene. The oxidation-reduction chemical stripping method comprises the steps of using graphite as a raw material, firstly pretreating the graphite to obtain a precursor, namely, expanding the distance between graphite layers through acidification and an enhancer action and an intercalation principle to further reduce van der waals force between the graphite layers, then thoroughly destroying the van der waals acting force between the graphite layers under an ultrasonic action or a mechanical force to realize stripping of the graphite to prepare graphene oxide, and further reducing the graphene oxide through a chemical or physical method. The redox method is a main method for the industrial preparation of graphene at present because of high preparation efficiency and high conversion rate, and numerous patents and documents are published and reported. However, the product prepared by the method is graphene oxide, graphene can be obtained only by further reduction, the preparation process and the process are complex, the batch stability is poor, and the cost is high; in addition, some irreparable defects are inevitably introduced in the graphite pretreatment process, so that the graphene loses many due characteristics, and the problems greatly limit the industrial application of the graphene.
It is known that graphene prepared by a physical method or a chemical method is generally prepared in an aqueous phase, and the graphene cannot exist in the aqueous phase in many applications, so that how to extract the graphene from the aqueous phase and disperse the graphene again is a common problem in research and application in the field. At present, the simplest and commonly adopted method is to remove water by a thermal drying method to obtain graphene powder, and then the graphene powder is applied to various downstream fields, but unrecoverable aggregates are easily formed in the graphene drying process, so that the physical characteristics of graphene are greatly reduced, and the problem of poor stability of downstream product structures and performance batches due to uneven dispersion caused by the aggregates is solved. This problem is also one of the bottleneck problems that graphene is difficult to be industrially applied.
Disclosure of Invention
Aiming at the problems of low conversion rate, complex chemical graphene preparation process, more defects and difficult redispersion of graphene powder, the invention newly develops a novel preparation process, namely a gas layer expansion-mechanical liquid phase stripping method, namely, the water solubility and the interlayer spacing of graphite are increased through simple acidification pretreatment, and the interlayer spacing (larger than 0.5nm) of the graphite is further expanded by further adopting a method for generating bubbles in situ, so that the van der Waals force of the graphite interlayer spacing is greatly reduced; and finally, in the presence of a surface modifier with a specific structure, mechanically stripping the expanded graphite in an in-situ liquid phase to directly obtain the high-dispersity graphene, and obtaining the redispersible graphene powder by combining a low-temperature drying process, thereby laying a solid foundation for accelerating and expanding the industrial application of the graphene.
The invention adopts the following technical scheme:
a high-efficiency liquid-phase mechanical preparation method of low-defect and high-dispersion graphene comprises the following steps:
firstly, adding potassium permanganate (with the purity of more than 98%) into concentrated sulfuric acid (with the concentration of more than 98%) at room temperature, mechanically stirring the potassium permanganate to completely dissolve the potassium permanganate to form a homogeneous mixed solution, adding graphite powder into the mixed solution, stirring the mixed solution at the temperature of 25-35 ℃ for 0.5-1h at the speed of 500 plus materials and 1000 revolutions/min, then adding a layer expanding material at the speed of 500 plus materials and 1000 revolutions/min to 10g/min, then adding acid, reacting the acid and the layer expanding material to form a viscous mixed system at the speed of 1000 plus materials and 2000 revolutions/min, finally continuously stirring the mixed system at the temperature of 25-35 ℃ for 2-6h to obtain layer expanding graphite slurry, adding the layer expanding graphite slurry into 2L deionized water, adding hydrogen peroxide into the layer expanding graphite slurry at the speed of 10mL/min, stirring and mixing at the temperature of 25-35 ℃ and the rotating speed of 100-;
second, liquid phase mechanical stripping
Adding a surfactant into an alkaline aqueous solution with the pH value of 14, stirring at room temperature until the surfactant is dissolved, adding the expanded graphite obtained in the first step, and mechanically stripping in a sand mill or a high-speed stirrer to obtain a graphene dispersion liquid;
third, spray drying at low temperature
And (3) carrying out low-temperature spray drying on the graphene dispersion liquid with the concentration of 0.1-2.0 wt% obtained in the second step to obtain the redispersible graphene powder, wherein the inlet temperature is room temperature, the outlet temperature is 40-50 ℃, the temperature of a drying chamber is 60-70 ℃, and the feeding speed is 1.0-5L/h.
In the first step, the mass ratio of the graphite powder to the potassium permanganate is 2:1-4:1, and the mass ratio of the graphite powder to the concentrated sulfuric acid is 1:6-1: 10.
In the first step, the layer expanding substance comprises one or two of sodium carbonate and sodium bicarbonate, and the mass ratio of the graphite powder to the layer expanding substance is 1:2-1: 3.
In the first step, the acid reacting with the layer expanding substance comprises any one or two of sulfuric acid (> 90%), phosphoric acid (> 70%) and nitric acid (> 40%), and the mass ratio of the acid to the layer expanding substance is 3: 1-10: 1.
In the second step, the surfactant is water-soluble imidazole ionic liquid, and the mass ratio of the graphite powder to the surfactant is 150:1-20: 1.
In the second step, the surfactant includes any one of 1, 3-dimethylimidazole methanesulfonate, 1-ethyl-3-methylimidazole methanesulfonate, 1-propyl-3-methylimidazole acetate and 1-propyl-3-methylimidazole acetate.
In the second step, the rotational speed of the sand mill is 2000-2500 rpm, the sand milling time is 10-24h, the rotational speed of the high-speed stirrer is 15000-20000 rpm, and the stirring time is 0.5-2 h.
According to the method, graphite is intercalated in a mixed solution of concentrated sulfuric acid and potassium permanganate, sulfate radicals can enter between graphite layers to obtain pre-intercalated graphite, the water solubility of the graphite is improved, the graphite layer spacing is enlarged, compared with the traditional acidification treatment, less concentrated sulfuric acid and potassium permanganate are used, the oxidation degree of the graphite is extremely low, and the excellent structural integrity is maintained. In the process of adding the layer expanding substance into the acid-containing intercalated graphite, because the acid-containing intercalated graphite is viscous, the layer expanding substance (sodium carbonate and sodium bicarbonate) is uniformly mixed in the acid-containing intercalated graphite at a high rotating speed and is diffused among graphite layers before reacting with residual acid. After acid which reacts with the layer expanding substance is added, the acid between the graphite layers reacts with sodium carbonate or sodium bicarbonate under high-speed stirring to generate gas, the gas is slowly and continuously generated to further expand the interlayer of the graphite to be increased to more than 0.5nm (according to calculation simulation, the interlayer spacing of the graphite is more than 0.5nm, the interlayer spacing acting force is small), the van der Waals force between the graphite layers is greatly reduced, and the efficient mechanical stripping of the subsequent graphene is facilitated. In addition, water-soluble imidazole ionic liquid is added in the liquid-phase mechanical stripping, and the water-soluble imidazole ionic liquid can form a physical adsorption effect with carbon atoms in graphite or graphene, so that the dispersion stability of the graphite and the graphene in water is improved, and the mechanical stripping efficiency is improved; in addition, the ionic liquid with a larger anion ratio is selected to prevent the ionic liquid from forming an ion pair, so that the surface of the ionic liquid modified on the surface of the graphene is positively charged, the generation of the graphene and the formation of unrecoverable aggregates in the drying process can be effectively prevented through the electrostatic repulsion, and meanwhile, the ionic liquid has higher temperature stability and further prevents the unrecoverable aggregates caused by the winding or bonding of the surface modifier in the drying process of the graphene. Through the control of the process, the beneficial effects of the invention are as follows:
1. according to the method, carbon dioxide is generated by reacting water-soluble carbonate with acid, the graphite layer is expanded by the generation of gas, compared with the traditional method for increasing the graphite layer spacing by an intercalation principle, the method is simpler, green and environment-friendly, the layer expansion effect is better (the layer spacing is increased more), compared with the traditional mechanical stripping method, the mechanical stripping time is shortened, the energy consumption is reduced, the preparation efficiency and the conversion rate of graphene are improved, and the application pace of the mechanical method in the field of graphene preparation is accelerated.
2. According to the method, the graphite after layer expansion is used as a raw material, a mechanical stripping method is combined, the situation that a large amount of concentrated sulfuric acid and strong oxidant are used in a traditional chemical method and a high-energy ultrasonic microwave stripping method is avoided, the process flow is simplified, and the structural defects of the graphene are reduced.
3. According to the invention, in the preparation process, the water-soluble imidazole ionic liquid is used as a dispersing agent, the structure of the dispersing agent is controlled, the interaction force with graphite or graphene is given, the dispersing agent has excellent water solubility and temperature stability, and the formation of ion pairs of positive ions and negative ions in an aqueous solution is avoided, so that the efficiency and the conversion rate of graphene liquid phase stripping are further improved, and the redispersible graphene powder can be prepared by combining a low-temperature spray drying process, thereby providing a new process for preparing the graphene composite material with uniform structure and performance by adopting a direct addition method in the downstream.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of exfoliated graphite prepared in example 1 of the present invention.
Fig. 2 is a Scanning Electron Microscope (SEM) image of exfoliated graphene prepared in example 1 of the present invention.
Fig. 3 is a Raman (Raman) spectrum of the exfoliated graphene prepared in example 1 of the present invention.
Fig. 4 is an X-ray diffraction (XRD) pattern of the exfoliated graphene prepared in example 1 of the present invention.
Fig. 5 is a projection electron microscope (TEM) image of exfoliated graphene prepared in example 1 of the present invention.
Fig. 6 is an Atomic Force Microscope (AFM) image of exfoliated graphene prepared in example 1 of the present invention.
Detailed Description
Example 1
A low-defect and high-dispersion graphene and a high-efficiency liquid-phase mechanical preparation method thereof comprise the following steps:
in the first step, 20 g of graphite is added into a mixed solution containing 10g of potassium permanganate (purity >98%) and 120 ml of concentrated sulfuric acid (concentration >98%) at room temperature, and stirred for 1h at 35 ℃, then 40 g of sodium bicarbonate is added into the acid-containing intercalated graphite at the speed of 5g/min at the speed of 1000 rpm, the sodium bicarbonate is uniformly mixed and inserted into the acid-containing intercalated graphite, then 250 ml of phosphoric acid (concentration > 70%) is added into the acid-containing intercalated graphite, and stirring is continued for 6h at the speed of 2000 rpm, so that the acid-containing exfoliated graphite is obtained. Adding the acid-containing expanded graphite into 2 liters of deionized water, removing redundant sodium bicarbonate, adding 10 milliliters of hydrogen peroxide (30%) solution, removing redundant potassium permanganate, standing, removing supernatant, continuing to add deionized water, standing, removing supernatant, repeating the steps for several times until the pH value is 7, and obtaining the acid-free expanded graphite.
In the second step, 0.2 g of 1, 3-dimethylimidazole methanesulfonate was added to 800 ml of an aqueous sodium hydroxide solution with pH =14, and stirred at room temperature until dissolved. And adding the layer-expanded graphite in the first step into the alkaline solution containing the surfactant, and emulsifying at 15000 rpm for 2h to obtain the graphene dispersion liquid.
The graphene dispersion liquid prepared by the process is stably dispersed in an alkaline aqueous solution, the yield of the single-layer or multi-layer graphene is more than 90%, and the prepared graphene is thin like cicada's wing, has the thickness of 0.858 nanometer and is about 2-3 layers as can be seen from fig. 5 and 6.
And thirdly, adding 1.0L of 0.2wt% graphene solution into a container of a dryer, wherein the inlet temperature is room temperature, the outlet temperature is set to be 40 ℃, the temperature of a drying chamber is 60 ℃, the feeding speed is 1.0L/h, and the graphene powder can be prepared by spraying for 1 h.
Example 2
In the first step, 20 g of graphite is added into a mixed solution containing 10g of potassium permanganate (purity >98%) and 120 ml of concentrated sulfuric acid (concentration >98%) at room temperature, and stirred for 1h at 35 ℃, then 40 g of sodium bicarbonate is added into the acid-containing intercalated graphite at a speed of 5g/min at a speed of 1000 rpm, the sodium bicarbonate is uniformly mixed and inserted into the acid-containing intercalated graphite, then 250 ml of phosphoric acid (concentration > 70%) is added thereto, and stirring is continued for 6h at a speed of 2000 rpm, and the acid-containing exfoliated graphite is obtained. Adding the acid-containing expanded graphite into 2 liters of deionized water, removing excessive sodium bicarbonate, adding 10 milliliters of hydrogen peroxide (30%) solution, removing excessive potassium permanganate, standing, removing supernatant, continuing to add deionized water, standing, removing supernatant, repeating the steps for several times until the pH value is 7, and obtaining the acid-free expanded graphite.
In the second step, 0.2 g of 1, 3-dimethylimidazole methanesulfonate was added to 800 ml of an aqueous sodium hydroxide solution with pH =14, and stirred at room temperature until dissolved. And adding the layer-expanding graphite in the first step into the alkaline solution containing the surfactant, and sanding for 24 hours at 2400 revolutions per minute to obtain the graphene dispersion liquid.
And thirdly, adding 1.0L of graphene solution with the concentration of 1.0wt% into a dryer container, setting the inlet temperature to be room temperature, the outlet temperature to be 50 ℃, the drying chamber temperature to be 70 ℃, and the feeding speed to be 1.0L/h, and obtaining the graphene powder after 1 h.
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| CN112892473A (en) * | 2021-01-15 | 2021-06-04 | 神美科技有限公司 | Preparation method of heavy metal removing material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103950927A (en) * | 2014-05-21 | 2014-07-30 | 苏州斯迪克新材料科技股份有限公司 | Preparation method of graphene |
| CN105585005A (en) * | 2014-10-24 | 2016-05-18 | 江阴碳谷科技有限公司 | A production device and a method for preparing graphene by adopting a mechanical stripping manner |
| CN105776187A (en) * | 2016-01-27 | 2016-07-20 | 复旦大学 | Method for green environmental-protection preparation of high-concentration ultra-clean graphene dispersion liquid |
| CN108314022A (en) * | 2018-03-27 | 2018-07-24 | 广东聚石化学股份有限公司 | A kind of method that the direct stripping of ionic liquid prepares graphene |
| WO2018152755A1 (en) * | 2017-02-23 | 2018-08-30 | 深圳先进技术研究院 | Secondary battery and preparation method therefor |
| CN109575642A (en) * | 2019-01-21 | 2019-04-05 | 中北大学 | It is a kind of can again oiliness dispersion modified graphene raw powder's production technology |
| CN110203913A (en) * | 2019-05-30 | 2019-09-06 | 广东聚石化学股份有限公司 | A method of preparing graphene |
| CN110330012A (en) * | 2019-07-24 | 2019-10-15 | 上海烯望材料科技有限公司 | The preparation method of high concentration graphene aqueous liquid dispersion and self-dispersing graphene powder |
-
2020
- 2020-04-14 CN CN202010289142.XA patent/CN111285361B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103950927A (en) * | 2014-05-21 | 2014-07-30 | 苏州斯迪克新材料科技股份有限公司 | Preparation method of graphene |
| CN105585005A (en) * | 2014-10-24 | 2016-05-18 | 江阴碳谷科技有限公司 | A production device and a method for preparing graphene by adopting a mechanical stripping manner |
| CN105776187A (en) * | 2016-01-27 | 2016-07-20 | 复旦大学 | Method for green environmental-protection preparation of high-concentration ultra-clean graphene dispersion liquid |
| WO2017128929A1 (en) * | 2016-01-27 | 2017-08-03 | 复旦大学 | Method for preparing graphene dispersion and article thereof |
| WO2018152755A1 (en) * | 2017-02-23 | 2018-08-30 | 深圳先进技术研究院 | Secondary battery and preparation method therefor |
| CN108314022A (en) * | 2018-03-27 | 2018-07-24 | 广东聚石化学股份有限公司 | A kind of method that the direct stripping of ionic liquid prepares graphene |
| CN109575642A (en) * | 2019-01-21 | 2019-04-05 | 中北大学 | It is a kind of can again oiliness dispersion modified graphene raw powder's production technology |
| CN110203913A (en) * | 2019-05-30 | 2019-09-06 | 广东聚石化学股份有限公司 | A method of preparing graphene |
| CN110330012A (en) * | 2019-07-24 | 2019-10-15 | 上海烯望材料科技有限公司 | The preparation method of high concentration graphene aqueous liquid dispersion and self-dispersing graphene powder |
Non-Patent Citations (3)
| Title |
|---|
| WENCHENG DU, ET AL: "From graphite to graphene:direct liquid-phase exfoliation of graphite to produce single- and few- layered pristine graphene", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 刘厅: "石墨烯的常温少酸制备及其在超级电容器中的应用研究", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技I辑》 * |
| 申路严: "石墨烯水相机械剥离制备及在涂层中的防腐性能研究", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112892473A (en) * | 2021-01-15 | 2021-06-04 | 神美科技有限公司 | Preparation method of heavy metal removing material |
| CN112892473B (en) * | 2021-01-15 | 2022-08-09 | 神美科技有限公司 | Preparation method of heavy metal removing material |
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