WO2016045023A1 - 石墨烯材料的分级分离方法 - Google Patents

石墨烯材料的分级分离方法 Download PDF

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WO2016045023A1
WO2016045023A1 PCT/CN2014/087372 CN2014087372W WO2016045023A1 WO 2016045023 A1 WO2016045023 A1 WO 2016045023A1 CN 2014087372 W CN2014087372 W CN 2014087372W WO 2016045023 A1 WO2016045023 A1 WO 2016045023A1
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graphene
dispersion
different sizes
graphene material
materials
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PCT/CN2014/087372
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French (fr)
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张麟德
张明东
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深圳粤网节能技术服务有限公司
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Priority to PCT/CN2014/087372 priority Critical patent/WO2016045023A1/zh
Publication of WO2016045023A1 publication Critical patent/WO2016045023A1/zh

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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
    • C01B32/20—Graphite

Definitions

  • the present invention relates to the field of graphene materials, and in particular to a method for fractionating graphene materials.
  • the perfect graphene has an ideal two-dimensional structure. It consists of a hexagonal lattice. Each carbon atom is bonded to the other three carbon atoms in the plane of the lattice plane through the ⁇ bond. The electrons that are not ⁇ bond are used as ⁇ . The electrons form a ⁇ -orbital system perpendicular to the plane of the lattice. The ⁇ electrons can move freely on the plane, which gives the graphene excellent electrical conductivity and can withstand current densities six orders of magnitude higher than copper. Similarly, record Graphene also has thermal conductivity, the thermal conductivity of pure graphene up to 2000W • m -1 • K -1 ⁇ 4000W • m -1 • K -1.
  • graphene has excellent strength and an extremely high surface area. Moreover, the special structure of graphene also gives it a unique band structure, which has a perfect tunneling effect and a semi-integer quantum Hall effect, and its electrical conductivity that never disappears. These unique properties make it a great application prospect in materials and electronic circuits. Therefore, there is a great demand for the large-scale preparation of graphene.
  • the key parameters that measure its quality can be evaluated in terms of size, sheet thickness, and defect concentration.
  • the size of graphene determines the contact resistance
  • the thickness of the layer determines whether the electronic structure of graphene is maintained
  • the size of the defect determines the extent to which the graphene band is opened.
  • the ideal graphene has a large sheet size, a sheet thickness as thin as possible and a defect concentration close to zero, and thus has various excellent properties.
  • the electronic structure of graphene will be further changed, so that there is more possibility of application.
  • large-sized graphene sheets are used because of their large size, small contact resistance, large specific surface area, and large surface area, which can be used as a conductive agent and a negative electrode additive in lithium ion batteries.
  • the small-sized graphene sheet can be easily used as a carrier for supporting drugs because of its small size and easy penetration into cells.
  • a method for fractionating graphene materials comprising the following steps:
  • the dispersion of the graphene material is electrophoresed and sampled on the electrode side every 15 minutes to obtain a dispersion of graphene materials of different sizes; wherein the electrophoresis voltage gradient is 8V/cm ⁇ 30V/cm, electrophoresis The time is 2h ⁇ 4h.
  • the graphene material is graphene, and the dispersion of the graphene material further comprises a surfactant.
  • the surfactant is selected from the group consisting of tetramethylammonium hydrogencarbonate, tetraethylammonium hydrogencarbonate, tetrabutylammonium hydrogencarbonate, dodecyltetramethylphosphonium carbonate, hexadecyltetradecene At least one of barium methyl carbonate, cetyltrimethylammonium bromide, sodium dodecylsulfonate, sodium dodecylbenzenesulfonate, and sodium cetylbenzenesulfonate.
  • the method for preparing the dispersion of the graphene material comprises the following steps:
  • the mixed solution was ultrasonically dispersed, and then centrifuged, and the supernatant was taken to obtain a dispersion of the graphene material.
  • the surfactant in the aqueous solution of the surfactant, has a mass percentage concentration of 1% to 10%.
  • the concentration of the graphene in the mixed solution is from 0.1 mg/mL to 1 mg/mL.
  • the method further includes the step of treating the dispersion of the graphene materials of different sizes, wherein the step of treating the dispersion of the graphene materials of different sizes is specifically: The dispersion of graphene materials of different sizes is heated to 60 ° C to 80 ° C, and then filtered, and a solid is taken, and the solid is dried in a protective gas atmosphere to obtain graphene powders of different sizes.
  • the graphene material is graphene oxide, and the dispersion of the graphene material has a pH of 10-11.
  • the pH of the dispersion of the graphene material is adjusted to 10-11 by adding a lye to the dispersion of the graphene material, and the lye is a 5% by mass aqueous ammonia.
  • the method further includes the step of treating the dispersion of the graphene materials of different sizes, wherein the step of treating the dispersion of the graphene materials of different sizes is specifically: respectively The dispersion of graphene materials of different sizes is subjected to salting out, washed with water, and dried to obtain graphene oxide powders of different sizes.
  • the salting out salting-out agent is ammonium hydrogencarbonate.
  • the above-mentioned fractionation method of graphene material is based on electrophoresis technology to fractionate graphene materials, and experiments have proved that the method can separate graphene materials of different sizes to obtain graphene materials with different properties.
  • FIG. 1 is a flow chart of a method for fractionating a graphene material according to an embodiment
  • a method for fractionating graphene materials includes the following steps 10 to 20.
  • Step 10 preparing a dispersion of graphene material, which is graphene, graphene oxide or graphene quantum dots.
  • the dispersion of the graphene material further includes a surfactant. Since graphene is uncharged, the introduction of a surfactant adds a charge to the graphene. Different sizes of graphene adsorb different degrees of surfactant, and then the amount of charge is different. Separation of graphene of different sizes can be achieved by electrophoresis. Moreover, the introduction of a surfactant facilitates the dispersion of graphene and maintains the stability of the graphene dispersion.
  • the surfactant is selected from the group consisting of tetramethylammonium hydrogencarbonate, tetraethylammonium hydrogencarbonate, tetrabutylammonium hydrogencarbonate, dodecyltetramethylphosphonium carbonate, cetyltetramethylphosphonium carbonate, cetyl group. At least one of trimethylammonium bromide, sodium dodecylsulfonate, sodium dodecylbenzenesulfonate, and sodium cetylbenzenesulfonate.
  • the above surfactants are relatively easy to remove without affecting the quality of the graphene, and the quality of the isolated graphene is ensured.
  • the surfactant is at least one selected from the group consisting of tetrabutylammonium hydrogencarbonate, tetramethylammonium hydrogencarbonate, dodecyltetramethylphosphonium carbonate, and sodium dodecylbenzenesulfonate.
  • the method for preparing the dispersion of the graphene material includes the following steps 110 to 130.
  • Step 110 Formulating an aqueous solution of the surfactant.
  • the surfactant is added to deionized water and stirred uniformly to prepare an aqueous solution of the surfactant.
  • the mass concentration of the surfactant is from 1% to 10%.
  • the concentration of the surfactant is 1% ⁇ 10%, which ensures that sufficient charge is added to the graphene to facilitate electrophoresis separation.
  • the surfactant is removed to effectively reduce the effect of the surfactant on the properties of the graphene product, thereby obtaining a graphene product of various sizes of high quality and narrow size distribution.
  • Step 120 Add graphene to an aqueous solution of a surfactant and stir to obtain a mixed solution.
  • the graphene is added to the aqueous solution of the surfactant prepared in the step 110, and stirred uniformly to obtain a mixed solution.
  • the concentration of graphene in the mixed solution is from 0.1 mg/mL to 1 mg/mL.
  • Step 130 The mixture is ultrasonically dispersed, and then centrifuged, and the supernatant is taken to obtain a dispersion of graphene material.
  • the ultrasonic dispersion power is 120W ⁇ 180W
  • the ultrasonic dispersion time is 2h ⁇ 6h.
  • the centrifugal speed is 1500r/min ⁇ 3000r/min, and the centrifugation time is 1min ⁇ 3min.
  • the dispersion of the graphene material When the graphene material is graphene oxide, the dispersion of the graphene material, that is, the graphene oxide dispersion, has a pH of 10 to 11. After dispersing the graphene oxide in deionized water to prepare a dispersion of graphene oxide, the alkali solution is added to the dispersion of graphene oxide to adjust the pH to 10-11. The purpose of adjusting the pH of the dispersion of graphene oxide to 10 to 11 is to convert graphene oxide to an anion form to charge graphene oxide.
  • the anionic form of graphene oxide itself carries a charge.
  • the concentration of graphene oxide is from 0.5 mg/mL to 5 mg/mL.
  • the lye is an aqueous solution having a mass percentage concentration of 5%, an aqueous ammonia having a mass concentration of 10%, an aqueous solution of sodium hydroxide having a mass percentage of 10%, an aqueous solution of potassium hydroxide having a mass percentage of 10%, An aqueous solution of saturated sodium carbonate or an aqueous solution of saturated ammonium hydrogencarbonate.
  • the alkali solution is an aqueous solution of 5% by mass aqueous ammonia, 10% by mass aqueous ammonia or saturated ammonium hydrogencarbonate.
  • the volume ratio of the volume of the graphene oxide dispersion to the lye is 1:0.5-2.
  • the dispersion of the graphene material ie, the graphene oxide dispersion
  • the dispersion of the graphene material is placed on a shaker for 3 min to 5 min, and then subjected to subsequent treatment.
  • the graphene quantum dots When the graphene material is a graphene quantum dot, since the graphene quantum dots generally have residual functional groups such as a carboxyl group, a hydroxyl group, an amino group, a carbonyl group and the like, the graphene quantum dots are dispersed in deionized water to prepare graphene.
  • the dispersion of quantum dots directly uses the dispersion of graphene quantum dots for subsequent electrophoresis.
  • the graphene quantum dots with large size have more electric charges and faster moving speed, and the graphene quantum dots with smaller size have less charge and slower moving speed, thereby realizing the separation of graphene quantum dots of different sizes.
  • the concentration of graphene quantum dots in the dispersion of graphene quantum dots is from 0.1 mg/L to 1 mg/L.
  • Step 20 electrophoresis is carried out by electrophoresing a dispersion of graphene material by electrophoresis and sampling on the electrode side every 15 minutes to obtain a dispersion of graphene materials of different sizes; wherein the electrophoretic voltage gradient is 8 V/cm to 30 V/cm. The time is 2h ⁇ 4h.
  • the dispersion of the graphene material obtained in the step S10 is poured into the overflow tank of the electrophoresis device, and the power source is connected to adjust the voltage gradient to 8 V/cm to 30 V/cm, so that the graphene material can move at a uniform speed under the action of the electric field.
  • the electrophoresis time was 2 h to 4 h, and the solution near the electrode side was taken out every 15 min. The larger the size of the graphene material, the faster the movement speed, the first to follow the electrophoresis; the smaller the size, the later the arrival. In this way, fractionation of graphene materials of different sizes is achieved.
  • the electrode side is the positive electrode side or the negative electrode side.
  • the graphene material moves toward the negative electrode, collecting the dispersion near the negative electrode side; when the charge on the surface of the graphene material is negative, the graphene material moves toward the positive electrode, in the vicinity The dispersion was collected on the positive electrode side.
  • Sampling on the electrode side is to take the solution near the electrode side.
  • the electrophoresis tank is close to the 1/10 volume of the electrode portion as the sampling area, that is, the volume of the capacitor groove is 1/10 as the sampling area, and the sampling area is close to the electrode side from the capacitor groove.
  • the edge extends toward the inside of the capacitor slot.
  • the sampling zone is generally brown.
  • the electrophoresis device used is a conventional electrophoresis device, for example, an electrophoretic coating device.
  • the electrophoresis time is 2h ⁇ 4h, which refers to the time from the start of electrophoresis to the stop of electrophoresis.
  • a step of treating a dispersion of graphene materials of different sizes is further included. This step is specifically as follows:
  • the dispersion of graphene materials of different sizes is heated to 60 ° C to 80 ° C, and then filtered, and a solid is taken, and the solid is dried in a protective gas atmosphere to obtain graphene powders of different sizes.
  • the dispersion of graphene materials of different sizes is heated to 60 ° C ⁇ 80 ° C to destroy the surfactant on the graphene.
  • the shielding gas may be nitrogen or an inert gas such as helium, argon or the like.
  • the temperature at which the solid is dried in a protective gas atmosphere is preferably 200 ° C, and the drying time is 0.5 h to 1 h. Drying the solid on the one hand gives dry graphene powder and on the other hand removes the undestroyed surfactant to obtain high quality graphene powder.
  • a step of treating a dispersion of graphene materials of different sizes is further included. This step is specifically as follows:
  • the dispersions of graphene materials of different sizes are respectively salted out, washed with water, and dried to obtain graphene oxide powders of different sizes.
  • the salting-out agent is preferably ammonium hydrogencarbonate.
  • An aqueous solution of ammonium hydrogencarbonate is prepared, and an aqueous solution of ammonium hydrogencarbonate is added to a dispersion of graphene materials of different sizes to separate the graphene oxide from the salt, and then washed with water until no bicarbonate ions, and then at 60 ° C to 80 ° Drying at ° C to obtain different sizes of graphene oxide powder.
  • the concentration of the aqueous solution of ammonium hydrogencarbonate is from 0.5 mg/mL to 5 mg/mL.
  • the step of treating a dispersion of graphene materials of different sizes is further included. This step is specifically as follows:
  • the dispersions of graphene quantum dots of different sizes are evaporated to dryness, and solids are obtained to obtain graphene quantum dot powders of different sizes.
  • the above-mentioned fractionation method of graphene material is based on electrophoresis technology to fractionate graphene materials, and experiments have proved that the method can separate graphene materials of different sizes to obtain graphene materials with different properties.
  • the above-mentioned fractionation method of graphene material has simple process and short separation time; and the degree of separation is uniform, and the separated graphene materials of different sizes have a narrow size distribution and a complete structure, and the graphene material has high quality.
  • Graphene is added to the aqueous solution of the above surfactant, and uniformly stirred to obtain a mixed solution in which the concentration of graphene is 0.1 mg/mL.
  • the mixture was ultrasonically dispersed under ultrasonic waves of 120 W for 6 h, then centrifuged at 1500 r/min for 3 min, and the supernatant was taken to obtain a dispersion of graphene; the precipitate obtained by centrifugation was repeated for the above steps 2 and 3, and continued.
  • a dispersion of graphene is prepared for subsequent electrophoretic separation.
  • the graphene dispersion was subjected to electrophoresis.
  • the voltage gradient of electrophoresis was 8 V/cm, and the electrophoresis time was 4 h.
  • the electrode side was sampled every 15 min, and 10 mL was sampled each time to obtain a dispersion of graphene of different sizes. .
  • Fig. 2(a), Fig. 2(b) and Fig. 2(c) Different sizes of graphene powders were characterized by atomic force microscopy (AFM) as shown in Fig. 2(a), Fig. 2(b) and Fig. 2(c).
  • the graphene powder shown in Fig. 2(a) has a size of 0.380 ⁇ m
  • the graphene powder shown in Fig. 2(b) has a size of 0.311 ⁇ m
  • the size is 0.092 ⁇ m, and the above dimensions all refer to the size of the selection. It can be seen from Fig. 2(a) to Fig. 2(c) that the fractionation method of the above graphene material can effectively fractionate graphene to obtain graphene of different sizes.
  • the mixture was ultrasonically dispersed under ultrasonic waves of 180 W for 2 h, then centrifuged at 3000 r/min for 1 min, and the supernatant was taken to obtain a dispersion of graphene; the precipitate obtained by centrifugation was repeated for the above step 2 and the step 3, and continued.
  • a dispersion of graphene is prepared for subsequent electrophoretic separation.
  • Electrophoresis of the graphene dispersion was carried out.
  • the voltage gradient of electrophoresis was 30 V/cm, and the electrophoresis time was 2 h. Among them, the electrode side was sampled every 15 min, and 10 mL was sampled each time to obtain a dispersion of graphene of different sizes. .
  • Graphene is added to the aqueous solution of the above surfactant, and uniformly stirred to obtain a mixed solution in which the concentration of graphene is 0.5 mg/mL.
  • the mixture was ultrasonically dispersed under ultrasonic waves of 150 W for 4 h, then centrifuged at 2000 r/min for 2 min, and the supernatant was taken to obtain a dispersion of graphene; the precipitate obtained by centrifugation was repeated for the above steps 2 and 3, and continued.
  • a dispersion of graphene is prepared for subsequent electrophoretic separation.
  • the graphene dispersion was electrophoresed, the electrophoresis voltage gradient was 20V/cm, and the electrophoresis time was 3h. Among them, the electrode side was sampled every 15 minutes, and 10 mL was taken each time to obtain a dispersion of graphene of different sizes. .
  • the pH of the dispersion was 10.
  • the volume ratio of the volume of the dispersion of graphene oxide to the lye is 1:0.5.
  • a dispersion of graphene oxide having a pH of 10 was placed on a shaker for 3 min.
  • the above-mentioned oscillating dispersion of graphene oxide having a pH of 10 is subjected to electrophoresis.
  • the voltage gradient of the electrophoresis is 15 V/cm, and the electrophoresis time is 3.5 h.
  • the electrode side is sampled every 15 min, each time taken. 5 ml, a dispersion of graphene oxide of different sizes was obtained.
  • the pH of the liquid is 11.
  • the volume ratio of the volume of the graphene oxide dispersion to the lye is 1:2.
  • a dispersion of graphene oxide having a pH of 11 was placed on a shaker for 5 min.
  • the above-mentioned oscillating dispersion of graphene oxide having a pH of 11 is subjected to electrophoresis.
  • the voltage gradient of the electrophoresis is 25 V/cm, and the electrophoresis time is 2.5 h.
  • the electrode side is sampled every 15 min, each time taken. 5 mL, a dispersion of graphene oxide of different sizes was obtained.
  • the above-mentioned dispersion of graphene quantum dots is subjected to electrophoresis.
  • the voltage gradient of electrophoresis is 18 V/cm, and the electrophoresis time is 3 h. Among them, sampling is performed on the electrode side every 15 min, and 5 mL is taken each time to obtain graphene of different sizes.

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Abstract

石墨烯材料的分级分离方法，包括制备石墨烯材料的分散液，所述石墨烯材料为石墨烯、氧化石墨烯或石墨烯量子点及将所述石墨烯材料的分散液进行电泳，并每隔15min在电极侧取样，得到不同尺寸的石墨烯材料的分散液；其中，所述电泳的电压梯度为8V/cm～30V/cm，电泳的时间为2h～4h的步骤。上述石墨烯材料的分级分离方法基于电泳技术对石墨烯材料进行分级分离，经实验证明，该方法能够将不同尺寸的石墨烯材料分开，得到不同性能的石墨烯材料。

Description

石墨烯材料的分级分离方法
【技术领域】
本发明涉及石墨烯材料技术领域，特别是涉及一种石墨烯材料的分级分离方法。
【背景技术】
自从2004年英国曼彻斯特大学的Andre Geim及Konstantin Novoselof首次成功剥离热解石墨并观测到石墨烯以来，学界内对于新型碳材料的研究热度就一直没有消退过。石墨烯的成功分离意味着理论对于二维晶体热力学不稳定的预言被破除，也就带来了许多新领域研究的可能。
完美的石墨烯具有理想的二维结构，它由六边形晶格组成，每个碳原子通过σ键在晶格平面方向上与其他的三个碳原子结合，未成σ键的电子则作为π电子，组成了垂直于晶格平面的π轨道体系。π电子可在平面上任意移动，这赋予了石墨烯极好的导电性，能够承受比铜高六个数量级的电流密度。同样，石墨烯也具有创纪录的导热性，纯净石墨烯的导热率高达2000W•m-1•K-1~4000W•m-1•K-1。并且，石墨烯具有极好的强度和极高的表面积。不仅如此，石墨烯的特殊结构也赋予其独特的能带结构，使其具有完美的隧穿效应和半整数的量子霍尔效应、以及它从不消失的电导率。这些独特的性能使其在材料和电子电路等方面有着极大的应用前景。也因此，对石墨烯的大量制备有极大的需求。
对于石墨烯而言，主要衡量其品质的关键参数可以从尺寸、片层厚度、缺陷浓度等几个方面去评估。其中，石墨烯的尺寸大小决定了其接触电阻的大小，片层厚度则决定了石墨烯的电子结构是否得到保持，而缺陷浓度的大小则决定了石墨烯能带被打开的程度大小。理想的石墨烯具有大的片层尺寸，尽可能薄的片层厚度与接近零的缺陷浓度，从而也就具有了各种不同的优异性能。然而当其片层尺寸与厚度发生变化后，石墨烯的电子结构也将进一步改变，从而有更多应用的可能。实际上，大尺寸的石墨烯片层正因为其尺寸大而接触电阻小，比表面积中非孔比表面积大，能够很好的在锂离子电池中作为导电剂和负极添加剂来使用；另外一方面，小尺寸的石墨烯片层则由于其尺寸小，能够轻易的渗透入细胞当中，因而可以作为负载药品的载体来使用。
然而，目前的石墨烯的分离方法中，由于石墨烯尺寸小、密度低，无法通过传统的离心和过筛的方式有效分离不同尺寸的石墨烯；而膜过滤技术又耗时过长，且石墨烯不能溶解，也难以分离不同尺寸的石墨烯。因此，目前的石墨烯的分离方法很难将不同尺寸的石墨烯进行分开，从而难以发挥不同尺寸的石墨烯的作用。
【发明内容】
基于此，有必要提供一种石墨烯材料的分级分离方法，用于将不同尺寸的石墨烯材料分开。
一种石墨烯材料的分级分离方法，包括如下步骤：
制备石墨烯材料的分散液，所述石墨烯材料为石墨烯、氧化石墨烯或石墨烯量子点；及
将所述石墨烯材料的分散液进行电泳，并每隔15min在电极侧取样，得到不同尺寸的石墨烯材料的分散液；其中，所述电泳的电压梯度为8V/cm~30V/cm，电泳的时间为2h~4h。
在其中一个实施例中，所述石墨烯材料为石墨烯，所述石墨烯材料的分散液中还包含表面活性剂。
在其中一个实施例中，所述表面活化剂选自四甲基碳酸氢铵、四乙基碳酸氢铵、四丁基碳酸氢铵、十二烷基四甲基碳酸胍、十六烷基四甲基碳酸胍、十六烷基三甲基溴化铵、十二烷基磺酸钠、十二烷基苯磺酸钠及十六烷基苯磺酸钠中的至少一种。
在其中一个实施例中，所述石墨烯材料的分散液的制备方法包括如下步骤：
配制表面活性剂的水溶液；
将石墨烯加入所述表面活性剂的水溶液中，搅拌均匀得到混合液；及
将所述混合液进行超声分散后再进行离心，取上清液，得到所述石墨烯材料的分散液。
在其中一个实施例中，所述表面活性剂的水溶液中，所述表面活性剂的质量百分比浓度为1%~10%。
在其中一个实施例中，所述混合液中，所述石墨烯的浓度为0.1mg/mL~1mg/mL。
在其中一个实施例中，还包括对所述不同尺寸的石墨烯材料的分散液进行处理的步骤，所述对所述不同尺寸的石墨烯材料的分散液进行处理的步骤具体为：将所述不同尺寸的石墨烯材料的分散液加热至60℃~80℃，然后过滤，取固体，在保护气体氛围中对所述固体进行干燥，得到不同尺寸的石墨烯粉体。
在其中一个实施例中，所述石墨烯材料为氧化石墨烯，所述石墨烯材料的分散液的pH值为10~11。
在其中一个实施例中，通过向所述石墨烯材料的分散液加入碱液调节所述石墨烯材料的分散液的pH值为10~11，所述碱液为质量百分比浓度为5%的氨水、质量百分比浓度为10%的氨水、质量百分比浓度为10%的氢氧化钠的水溶液、质量百分比浓度为10%的氢氧化钾的水溶液、饱和碳酸钠的水溶液或饱和碳酸氢铵的水溶液。
在其中一个实施例中，还包括对所述不同尺寸的石墨烯材料的分散液进行处理的步骤，所述对所述不同尺寸的石墨烯材料的分散液进行处理的步骤具体为：分别将所述不同尺寸的石墨烯材料的分散液进行盐析，水洗后干燥，得到不同尺寸的氧化石墨烯粉体。
在其中一个实施例中，所述盐析的盐析剂为碳酸氢铵。
上述石墨烯材料的分级分离方法基于电泳技术对石墨烯材料进行分级分离，经实验证明，该方法能够将不同尺寸的石墨烯材料分开，得到不同性能的石墨烯材料。
【附图说明】
图1为一实施方式的石墨烯材料的分级分离方法的流程图；
图2（a）~图2（c）为实施例1的不同尺寸的石墨烯的原子力显微镜（AFM）图。
【具体实施方式】
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似改进，因此本发明不受下面公开的具体实施的限制。
请参阅图1，一实施方式的石墨烯材料的分级分离方法，包括如下步骤10至步骤20。
步骤10：制备石墨烯材料的分散液，石墨烯材料为石墨烯、氧化石墨烯或石墨烯量子点。
当石墨烯材料为石墨烯时，石墨烯材料的分散液还包括表面活性剂。由于石墨烯不带电荷，引入表面活性剂给石墨烯附加上电荷。不同尺寸的石墨烯对表面活性剂的吸附程度不同，随即所带的电荷量亦不同，通过电泳能够实现不同尺寸的石墨烯的分离。并且，引入表面活性剂有利于石墨烯的分散，能够维持石墨烯分散液的稳定性。
表面活性剂选自四甲基碳酸氢铵、四乙基碳酸氢铵、四丁基碳酸氢铵、十二烷基四甲基碳酸胍、十六烷基四甲基碳酸胍、十六烷基三甲基溴化铵、十二烷基磺酸钠、十二烷基苯磺酸钠及十六烷基苯磺酸钠中的至少一种。上述表面活性剂较易除去而不会影响石墨烯的品质，保证分离得到的石墨烯的质量。
优选地，表面活性剂选自四丁基碳酸氢铵、四甲基碳酸氢铵、十二烷基四甲基碳酸胍及十二烷基苯磺酸钠中的至少一种。
当石墨烯材料为石墨烯时，石墨烯材料的分散液的制备方法包括如下步骤110至步骤130。
步骤110：配制表面活性剂的水溶液。
将表面活性剂加入去离子水中，搅拌均匀，配制得到表面活性剂的水溶液。优选地，表面活性剂的水溶液中，表面活性剂的质量百分比浓度为1%~10%。选用表面活性剂的质量百分比浓度为1%~10%，一方面保证在石墨烯上附加足够的电荷，以便于电泳分离；另一方面，保证分离后能够较方便地将不同尺寸的石墨烯上的表面活性剂除去，以能够有效地降低表面活性剂对石墨烯产品性能的影响，从而获得高品质、尺寸分布窄的各种尺寸的石墨烯产品。
步骤120：将石墨烯加入表面活性剂的水溶液中，搅拌均匀得到混合液。
将石墨烯加入步骤110制备得到的表面活性剂的水溶液中，搅拌均匀，得到混合液。
优选地，石墨烯在混合液中的浓度为0.1mg/mL~1mg/mL。
步骤130：将混合液进行超声分散后再进行离心，取上清液，得到石墨烯材料的分散液。
优选地，超声分散的功率为120W~180W，超声分散的时间为2h~6h。
离心的转速为1500r/min~3000r/min，离心的时间为1min~3min。
将混合液进行超声分散并离心后，取上清液，得到石墨烯材料的分散液。离心后的沉淀不废弃，而是重复上述步骤120，继续制备石墨烯材料的分散液用于后续电泳分离，以提高收率。
当石墨烯材料为氧化石墨烯时，石墨烯材料的分散液即氧化石墨烯的分散液的pH值为10~11。将氧化石墨烯分散于去离子水中配制得到氧化石墨烯的分散液后，向氧化石墨烯的分散液中加入碱液调整pH值为10~11。将氧化石墨烯的分散液的pH值调整为10~11的目的是将氧化石墨烯转换为阴离子形式，以使氧化石墨烯带电荷。
阴离子形式的氧化石墨烯本身带有电荷。氧化石墨烯的尺寸越大，所带的电荷越多，电泳时的运动速度越快；氧化石墨烯的尺寸越小，所带的电荷越少，电泳时的运动速度越慢，从而能够实现不同尺寸的氧化石墨烯的分级分离。
优选地，氧化石墨烯的分散液中，氧化石墨烯的浓度为0.5mg/mL~5mg/mL。
优选地，碱液为质量百分比浓度为5%的氨水、质量百分比浓度为10%的氨水、质量百分比浓度为10%的氢氧化钠的水溶液、质量百分比浓度为10%的氢氧化钾的水溶液、饱和碳酸钠的水溶液或饱和碳酸氢铵的水溶液。进一步优选地，碱液为质量百分比浓度为5%的氨水、质量百分比浓度为10%的氨水或饱和碳酸氢铵的水溶液。
氧化石墨烯的分散液的体积与碱液的体积比为1:0.5~2。
调节好pH值后，将石墨烯材料的分散液即氧化石墨烯的分散液放置于摇床上震荡3min~5min后，再进行后续的处理。
当石墨烯材料为石墨烯量子点时，由于石墨烯量子点一般会存在残留官能团，例如羧基、羟基、氨基、羰基等而带电荷，因此将石墨烯量子点分散于去离子水中制备得到石墨烯量子点的分散液，直接将石墨烯量子点的分散液用于后续的电泳即可。尺寸大的石墨烯量子点上的电荷较多，运动速度较快，尺寸小的石墨烯量子点上的电荷较少，运动速度较慢，从而实现不同尺寸的石墨烯量子点的分离。
优选地，石墨烯量子点的分散液中，石墨烯量子点的浓度为0.1mg/L~1mg/L。
步骤20：将石墨烯材料的分散液进行电泳，并每隔15min在电极侧取样，得到不同尺寸的石墨烯材料的分散液；其中，电泳的电压梯度为8V/cm~30V/cm，电泳的时间为2h~4h。
将步骤S10得到的石墨烯材料的分散液倒入电泳装置的溢流槽，接上电源，调节电压梯度为8V/cm~30V/cm，在电场作用下，使石墨烯材料能够匀速运动。电泳时间为2h~4h，其中，每隔15min将靠近电极侧的溶液取出。石墨烯材料尺寸越大，运动速度越快，越先随电泳泳出；尺寸越小，则越后到达。如此，实现不同尺寸的石墨烯材料的分级分离。
其中，电极侧为正极侧或负极侧。当石墨烯材料表面的电荷为正电荷时，石墨烯材料向负极方向运动，在靠近负极侧收集分散液；当石墨烯材料表面的电荷为负电荷时，石墨烯材料向正极方向运动，在靠近正极侧收集分散液。
在电极侧取样是取电极侧附近的溶液，一般以电泳槽靠近电极部分的1/10体积处为取样区，即电容槽的体积1/10为取样区，该取样区自电容槽靠近电极侧的边缘起往电容槽内部延伸。对于石墨烯电泳分离而言，取样区一般呈棕色。
其中，所用的电泳装置即常规的电泳装置，例如，电泳涂装装置。可以用移液管或移液枪在靠近电极侧处取样，每次取5mL~10mL。在大规模分离时，每次取样的体积为电泳槽体积的1/10。
电泳的时间为2h~4h是指开始电泳至停止电泳的时间。
优选地，当石墨烯材料为石墨烯时，还包括对不同尺寸的石墨烯材料的分散液进行处理的步骤。该步骤具体为：
将不同尺寸的石墨烯材料的分散液加热至60℃~80℃，然后过滤，取固体，在保护气体氛围中对该固体进行干燥，得到不同尺寸的石墨烯粉体。
将不同尺寸的石墨烯材料的分散液加热至60℃~80℃，以破坏石墨烯上的表面活性剂。
保护气体可以为氮气或惰性气体，如氦气、氩气等。在保护气体氛围中对固体进行干燥的温度优选为200℃，干燥的时间为0.5h~1h。对固体进行干燥一方面得到干燥的石墨烯粉体，另一方面脱除未被破坏的表面活性剂以得到高品质的石墨烯粉体。
优选地，当石墨烯材料为氧化石墨烯时，还包括对不同尺寸的石墨烯材料的分散液进行处理的步骤。该步骤具体为：
分别将不同尺寸的石墨烯材料的分散液进行盐析，水洗后干燥，得到不同尺寸的氧化石墨烯粉体。
盐析剂优选为碳酸氢铵。配制碳酸氢铵的水溶液，分别向不同的尺寸的石墨烯材料的分散液加入碳酸氢铵的水溶液，使氧化石墨烯被盐析析出，然后水洗至无碳酸氢根离子，再于60℃~80℃下烘干，得到不同尺寸的氧化石墨烯粉体。
优选地，碳酸氢铵的水溶液的浓度为0.5mg/mL~5mg/mL。
于60℃~80℃下烘干，确保进一步脱除未洗出的碳酸氢铵，得到高品质、不同尺寸的氧化石墨烯粉体。
优选地，当石墨烯材料为石墨烯量子点时，还包括对不同尺寸的石墨烯材料的分散液进行处理的步骤。该步骤具体为：
分别将不同尺寸的石墨烯量子点的分散液蒸干，取固体，得到不同尺寸的石墨烯量子点粉体。
上述石墨烯材料的分级分离方法基于电泳技术对石墨烯材料进行分级分离，经实验证明，该方法能够将不同尺寸的石墨烯材料分开，得到不同性能的石墨烯材料。
上述石墨烯材料的分级分离方法工艺简单，分离时间短；并且，分离程度均一，分离得到的不同尺寸的石墨烯材料的尺寸分布窄，且结构完整，石墨烯材料的品质较高。
以下通过具体实施例对上述石墨烯材料的分级分离方法进一步阐述。
实施例1
1、将四甲基碳酸氢铵加入去离子水中，搅拌均匀，配制成质量百分比浓度为1%的表面活性剂的水溶液。
2、将石墨烯加入上述表面活性剂的水溶液中，搅拌均匀得到混合液，其中，石墨烯的浓度为0.1mg/mL。
3、将上述混合液于120W的超声波下超声分散6h，然后于1500r/min下离心3min，取上清液，得到石墨烯的分散液；离心所得的沉淀重复上述步骤2和该步骤3，继续制备石墨烯的分散液，用于后续电泳分离。
4、将石墨烯的分散液进行电泳，电泳的电压梯度为8V/cm，电泳的时间为4h，其中，每隔15min在电极侧取样，每次取样10mL，得到不同尺寸的石墨烯的分散液。
5、将不同尺寸的石墨烯的分散液加热至60℃，然后过滤，取固体，在氮气氛围中对该固体于200℃下干燥0.5h，得到不同尺寸的石墨烯粉体。
用原子力显微镜（AFM）对不同尺寸的石墨烯粉体进行表征，如图2（a）、图2（b）和图2（c）所示。其中，图2（a）所示的石墨烯粉体的尺寸为0.380μm，图2（b）所示的石墨烯粉体的尺寸为0.311μm，图2（c）所示的石墨烯粉体的尺寸为0.092μm，上述尺寸均指选区尺寸。由图2（a）~图2（c）可看出，采用上述石墨烯材料的分级分离方法，能够有效对石墨烯进行分级分离，得到不同尺寸的石墨烯。
实施例2
1、将四丁基碳酸氢铵加入去离子水中，搅拌均匀，配制成质量百分比浓度为10%的表面活性剂的水溶液。
2、将石墨烯加入上述表面活性剂的水溶液中，搅拌均匀得到混合液，其中，石墨烯的浓度为1mg/mL。
3、将上述混合液于180W的超声波下超声分散2h，然后于3000r/min下离心1min，取上清液，得到石墨烯的分散液；离心所得的沉淀重复上述步骤2和该步骤3，继续制备石墨烯的分散液，用于后续电泳分离。
4、将石墨烯的分散液进行电泳，电泳的电压梯度为30V/cm，电泳的时间为2h，其中，每隔15min在电极侧取样，每次取样10mL，得到不同尺寸的石墨烯的分散液。
5、将不同尺寸的石墨烯的分散液加热至80℃，然后过滤，取固体，在氮气氛围中对该固体于200℃下干燥1h，得到不同尺寸的石墨烯粉体。
实施例3
1、将十二烷基四甲基碳酸胍和十二烷基苯磺酸钠按质量比为1:1加入去离子水中，搅拌均匀，配制成总质量浓度为5%的表面活性剂的水溶液。
2、将石墨烯加入上述表面活性剂的水溶液中，搅拌均匀得到混合液，其中，石墨烯的浓度为0.5mg/mL。
3、将上述混合液于150W的超声波下超声分散4h，然后于2000r/min下离心2min，取上清液，得到石墨烯的分散液；离心所得的沉淀重复上述步骤2和该步骤3，继续制备石墨烯的分散液，用于后续电泳分离。
4、将石墨烯的分散液进行电泳，电泳的电压梯度为20V/cm，电泳的时间为3h，其中，每隔15min在电极侧取样，每次取10mL，得到不同尺寸的石墨烯的分散液。
5、将不同尺寸的石墨烯的分散液加热至70℃，然后过滤，取固体，在氮气氛围中对该固体于200℃下干燥0.8h，得到不同尺寸的石墨烯粉体。
实施例4
1、将氧化石墨烯分散于去离子水中，配制浓度为0.5mg/mL的氧化石墨烯的分散液，向氧化石墨烯的分散液中加入质量百分比浓度为5%的氨水，调节氧化石墨烯的分散液的pH值为10。其中，氧化石墨烯的分散液的体积与碱液的体积比为1:0.5。将pH值为10的氧化石墨烯的分散液放置于摇床上震荡3min。
2、将上述震荡后的pH值为10的氧化石墨烯的分散液进行电泳，电泳的电压梯度为15V/cm，电泳的时间为3.5h，其中，每隔15min在电极侧取样，每次取5ml，得到不同尺寸的氧化石墨烯的分散液。
3、分别向不同尺寸的氧化石墨烯的分散液加入浓度为5 mg/mL的碳酸氢铵的水溶液进行盐析，使氧化石墨烯被盐析析出，然后水洗至无碳酸氢根离子，再于60℃下烘干，得到不同尺寸的氧化石墨烯粉体。
实施例5
1、将氧化石墨烯分散于去离子水中，配制浓度为5mg/mL的氧化石墨烯的分散液，向氧化石墨烯的分散液中加入质量百分比浓度为10%的氨水，调节氧化石墨烯的分散液的pH值为11。其中，氧化石墨烯的分散液的体积与碱液的体积比为1:2。将pH值为11的氧化石墨烯的分散液放置于摇床上震荡5min。
2、将上述震荡后的pH值为11的氧化石墨烯的分散液进行电泳，电泳的电压梯度为25V/cm，电泳的时间为2.5h，其中，每隔15min在电极侧取样，每次取5mL，得到不同尺寸的氧化石墨烯的分散液。
3、分别向不同尺寸的氧化石墨烯的分散液加入浓度为2 mg/mL的碳酸氢铵的水溶液进行盐析，使氧化石墨烯被盐析析出，然后水洗至无碳酸氢根离子，再于80℃下烘干，得到不同尺寸的氧化石墨烯粉体。
实施例6
1、将氧化石墨烯分散于去离子水中，配制浓度为2mg/mL的氧化石墨烯的分散液，向氧化石墨烯的分散液中加入饱和碳酸氢铵的水溶液，调节氧化石墨烯的分散液的pH值为11。其中，氧化石墨烯的分散液的体积与碱液的体积比为1:1.5。将pH值为11的氧化石墨烯的分散液放置于摇床上震荡4min。
2、将上述震荡后的pH值为11的氧化石墨烯的分散液进行电泳，电泳的电压梯度为18V/cm，电泳的时间为3h，其中，每隔15min在电极侧取样，每次取10mL，得到不同尺寸的氧化石墨烯的分散液。
3、分别向不同尺寸的氧化石墨烯的分散液加入浓度为1mg/mL的碳酸氢铵的水溶液进行盐析，使氧化石墨烯被盐析析出，然后水洗至无碳酸氢根离子，再于70℃下烘干，得到不同尺寸的氧化石墨烯粉体。
实施例7
1、将石墨烯量子点分散于去离子水中，配制浓度为1mg/L的石墨烯量子点的分散液。
2、将上述石墨烯量子点的分散液进行电泳，电泳的电压梯度为18V/cm，电泳的时间为3h，其中，每隔15min在电极侧取样，每次取5mL，得到不同尺寸的石墨烯量子点的分散液。
3、分别将不同尺寸的石墨烯量子点的分散液蒸干，取固体，得到不同尺寸的石墨烯量子点粉体。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (11)

  1. 一种石墨烯材料的分级分离方法，其特征在于，包括如下步骤：
    制备石墨烯材料的分散液，所述石墨烯材料为石墨烯、氧化石墨烯或石墨烯量子点；及
    将所述石墨烯材料的分散液进行电泳，并每隔15min在电极侧取样，得到不同尺寸的石墨烯材料的分散液；其中，所述电泳的电压梯度为8V/cm~30V/cm，电泳的时间为2h~4h。
  2. 根据权利要求1所述的石墨烯材料的分级分离方法，其特征在于，所述石墨烯材料为石墨烯，所述石墨烯材料的分散液中还包含表面活性剂。
  3. 根据权利要求2所述的石墨烯材料的分级分离方法，其特征在于，所述表面活化剂选自四甲基碳酸氢铵、四乙基碳酸氢铵、四丁基碳酸氢铵、十二烷基四甲基碳酸胍、十六烷基四甲基碳酸胍、十六烷基三甲基溴化铵、十二烷基磺酸钠、十二烷基苯磺酸钠及十六烷基苯磺酸钠中的至少一种。
  4. 根据权利要求2所述的石墨烯材料的分级分离方法，其特征在于，所述石墨烯材料的分散液的制备方法包括如下步骤：
    配制表面活性剂的水溶液；
    将石墨烯加入所述表面活性剂的水溶液中，搅拌均匀得到混合液；及
    将所述混合液进行超声分散后再进行离心，取上清液，得到所述石墨烯材料的分散液。
  5. 根据权利要求4所述的石墨烯材料的分级分离方法，其特征在于，所述表面活性剂的水溶液中，所述表面活性剂的质量百分比浓度为1%~10%。
  6. 根据权利要求4所述的石墨烯材料的分级分离方法，其特征在于，所述混合液中，所述石墨烯的浓度为0.1mg/mL~1mg/mL。
  7. 根据权利要求2所述的石墨烯材料的分级分离方法，其特征在于，还包括对所述不同尺寸的石墨烯材料的分散液进行处理的步骤，所述对所述不同尺寸的石墨烯材料的分散液进行处理的步骤具体为：将所述不同尺寸的石墨烯材料的分散液加热至60℃~80℃，然后过滤，取固体，在保护气体氛围中对所述固体进行干燥，得到不同尺寸的石墨烯粉体。
  8. 根据权利要求1所述的石墨烯材料的分级分离方法，其特征在于，所述石墨烯材料为氧化石墨烯，所述石墨烯材料的分散液的pH值为10~11。
  9. 根据权利要求8所述的石墨烯材料的分级分离方法，其特征在于，通过向所述石墨烯材料的分散液加入碱液调节所述石墨烯材料的分散液的pH值为10~11，所述碱液为质量百分比浓度为5%的氨水、质量百分比浓度为10%的氨水、质量百分比浓度为10%的氢氧化钠的水溶液、质量百分比浓度为10%的氢氧化钾的水溶液、饱和碳酸钠的水溶液或饱和碳酸氢铵的水溶液。
  10. 根据权利要求8所述的石墨烯材料的分级分离方法，其特征在于，还包括对所述不同尺寸的石墨烯材料的分散液进行处理的步骤，所述对所述不同尺寸的石墨烯材料的分散液进行处理的步骤具体为：分别将所述不同尺寸的石墨烯材料的分散液进行盐析，水洗后干燥，得到不同尺寸的氧化石墨烯粉体。
  11. 根据权利要求10所述的石墨烯材料的分级分离方法，其特征在于，所述盐析的盐析剂为碳酸氢铵。
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CN108101039B (zh) * 2016-11-25 2019-08-16 中国科学院化学研究所 一种氧化石墨烯尺寸分离的方法
CN110194449A (zh) * 2019-05-13 2019-09-03 四川欧迅能源工程科技有限公司 一种利用石墨烯量子点机械剥离制备石墨烯的方法
CN111537597A (zh) * 2020-04-17 2020-08-14 上海超碳石墨烯产业技术有限公司 基于飞行时间质谱的石墨烯量子点横向尺寸表征方法
CN113617368A (zh) * 2020-04-22 2021-11-09 山东海科创新研究院有限公司 一种具有层状结构的二硫化钨/二硫化钼/石墨烯复合材料及其制备方法、应用
CN113617368B (zh) * 2020-04-22 2023-08-01 山东海科创新研究院有限公司 一种具有层状结构的二硫化钨/二硫化钼/石墨烯复合材料及其制备方法、应用
CN112758908A (zh) * 2020-12-31 2021-05-07 龙蟒大地农业有限公司 一种自组装磷酸铁锂及其制备方法、磷酸铁锂正极片、磷酸铁锂电池
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