TWI614210B - Method of manufacturing nanomaterial - Google Patents

Abstract

A method of manufacturing a nanomaterial, comprising the following steps. The dispersion is subjected to at least one of a homogenization treatment and an ultrasonic treatment, wherein the dispersion liquid comprises a substrate and a solvent. After the dispersion is subjected to at least one of homogenization treatment and ultrasonic treatment, the dispersion is subjected to a ball milling treatment.

Description

Method for manufacturing nano material

The present invention relates to a method of making a material, and more particularly to a method of making a nanomaterial.

At present, many nano materials having high mechanical strength, high light transmittance, good heat conduction or electrical conductivity have been proposed, such as graphene. Many of the possible applications can be derived from these material properties, such as photovoltaics, energy storage, green power generation, environmental biosensing or functional composites.

At present, the key to the research and application of nanomaterials is how to develop large-scale, low-cost and controllable nanomaterial manufacturing methods. Taking the production of graphene as an example, the liquid phase mechanical peeling method (ultrasonic oscillation) generally requires a long process time, cannot be mass-produced, and the quality of the produced graphene is not good. Although the graphite oxide reduction method can produce a large amount of graphene at a relatively low cost, the quality of the produced graphene is not good. The reason is that the electronic structure of the graphene produced by the graphite oxide reduction method and the crystal integrity are severely damaged by the strong oxidant, and the electronic properties thereof are affected, so that the application in the microelectronic device is limited. Although chemical vapor deposition can produce graphene with large area and excellent performance, the immaturity, high cost and low yield of the current stage limit its large-scale production application. In addition, the use of ball milling and homogenization to produce graphene also has a problem of low yield. Therefore, how to produce nanomaterials in high yield and high quality is the current research and development goal of the industry.

The present invention provides a method for producing a nano material which can obtain a high yield and high quality nano material.

The present invention provides a method of producing a nanomaterial comprising the following steps. The dispersion is subjected to at least one of a homogenization treatment and an ultrasonic treatment, wherein the dispersion liquid comprises a substrate and a solvent. After the dispersion is subjected to at least one of homogenization treatment and ultrasonic treatment, the dispersion is subjected to a ball milling treatment.

According to an embodiment of the present invention, in the method for producing a nanomaterial, the substrate is, for example, graphite, molybdenum disulfide or boron nitride.

According to an embodiment of the present invention, in the method for manufacturing a nano material, the nano material is, for example, graphene, graphene quantum dots (GQDs), molybdenum disulfide (MoS ₂ ) nanomaterials. Or boron nitride (BN) nanomaterials.

According to an embodiment of the present invention, in the method for producing a nano material, the solvent is, for example, N-Methyl-2-Pyrrolidone (NMP), dimethyl hydrazine (DMSO) or N,N-dimethylformamide (DMF).

According to an embodiment of the present invention, in the method for producing a nanomaterial, the concentration of the solvent is, for example, 70% to 100%.

According to an embodiment of the present invention, in the method for producing a nanomaterial, the time of the ball milling treatment is, for example, 0.5 hours to 4 hours, and the rotation speed of the ball milling treatment is, for example, 500 rpm to 1750 rpm.

According to an embodiment of the present invention, in the method for producing a nanomaterial, the dispersion may be subjected to homogenization treatment, ultrasonic treatment, and ball milling treatment in sequence.

According to an embodiment of the present invention, in the method for producing a nanomaterial, the dispersion may be subjected to ultrasonic treatment, homogenization treatment, and ball milling treatment in sequence.

According to an embodiment of the present invention, in the method for producing a nanomaterial, the dispersion may be subjected to a homogenization treatment and a ball milling treatment in sequence.

According to an embodiment of the present invention, in the method for producing a nanomaterial, the dispersion may be subjected to ultrasonic treatment and ball milling in sequence.

Based on the above, in the method for producing a nanomaterial according to the present invention, since at least one of the homogenization treatment and the ultrasonic treatment is performed on the dispersion, the dispersion is subjected to ball milling treatment, thereby obtaining high yield and high quality. Nano material.

The above described features and advantages of the invention will be apparent from the following description.

1 is a flow chart showing the manufacture of a nanomaterial according to an embodiment of the present invention.

Referring to FIG. 1, step S100 is performed to perform at least one of a homogenization treatment and an ultrasonic treatment on the dispersion liquid, wherein the dispersion liquid comprises a substrate and a solvent. The substrate is, for example, graphite, molybdenum disulfide or boron nitride. For example, using graphite as a substrate, a nanomaterial of graphene or graphene quantum dots can be produced. Further, using molybdenum disulfide as a substrate, a molybdenum disulfide nanomaterial can be produced. A boron nitride nanomaterial can be produced by using boron nitride as a substrate. The solvent can be selected from chemical formulations with high dispersibility to increase the yield. The solvent is, for example, N-methylpyrrolidone, dimethyl hydrazine (DMSO) or N,N-dimethylformamide (DMF). The concentration of the solvent is, for example, 70% to 100%.

Homogenization allows the substrate to be uniformly dispersed in the solvent and provides shear to reduce the van der Waals between the layered structures of the substrate. The homogenization treatment is carried out, for example, by a homogenizer. The time of the homogenization treatment is, for example, 0.5 hours to 4 hours. The rotational speed of the homogenization treatment is, for example, 8,000 rpm to 30,000 rpm.

Ultrasonic treatment allows solvent molecules to be intercalated between the layered structures of the substrate and adsorbed on the surface of the substrate to achieve a reduced van der Waals effect. Ultrasonic processing is performed, for example, by an ultrasonic oscillator. The time of the ultrasonic processing is, for example, 2 hours to 6 hours. The frequency of ultrasonic processing is, for example, 37 kHz to 80 kHz.

In step S102, after at least one of the homogenization treatment and the ultrasonic treatment of the dispersion liquid, the dispersion liquid is subjected to a ball milling treatment. The ball milling process provides the energy of the delamination to obtain a nanomaterial. The time of the ball milling treatment is, for example, 0.5 hours to 4 hours, and the rotational speed of the ball milling treatment is, for example, 500 rpm to 1750 rpm.

In addition, the nano material which can be produced by the method for producing a nano material of the present embodiment is, for example, graphene, graphene quantum dots, molybdenum disulfide nano material or boron nitride nano material, but the present invention does not This is limited to this. In addition, the above nano materials can be applied to fields such as photovoltaic, energy storage, green power generation, environmental biomedical sensing or functional composite materials. Specifically, the above nano material can be applied to transparent conductive films, biochemical sensors, supercapacitors, lithium ion batteries, high frequency electronic components, photo sensors, water purification or high performance thermal conductive sheets.

According to the above embodiment, in the method for producing a nanomaterial according to the above embodiment, since at least one of the homogenization treatment and the ultrasonic treatment is performed on the dispersion, the dispersion is subjected to ball milling treatment, thereby obtaining high yield and High quality nano material. In detail, ball milling can be used to provide primary physical forces (eg, shear stress) to synthesize nanomaterials, and other physical forces (high-speed agitation and introduction) can be introduced by homogenization and/or ultrasonic treatment prior to ball milling. / or ultrasonic shock) to improve the yield of nanomaterials, and the quality of the nanomaterials produced is good.

Further, the method for producing a nanomaterial of the above embodiment has a simple and rapid synthesis procedure as compared with other liquid phase stripping systems, and a large number of industrialized manufacturing processes can be achieved as compared with the conventional ultrasonic oscillating mode.

2 to 5 are flow charts showing the manufacture of a nano material according to another embodiment of the present invention. The composition of the dispersion in FIGS. 2 to 5 and the parameter conditions of the homogenization treatment, the ultrasonic treatment, and the ball milling treatment can be referred to the description in the embodiment of FIG. 1, and details are not described herein again. Further, in the examples of FIGS. 2 to 5, for convenience of explanation, a nanomaterial in which graphene is produced using graphite as a substrate will be described as an example, but the invention is not limited thereto. That is, those skilled in the art can use the method of manufacturing the nanomaterial of FIGS. 2 to 5 to manufacture other nanomaterials.

Hereinafter, various aspects of the method for producing the nanomaterial of Fig. 1 will be described with reference to Figs. 2 to 5 . Referring to Fig. 2, the dispersion is subjected to homogenization treatment (step S200), ultrasonic treatment (step S202), and ball milling treatment (step S204). Referring to Fig. 3, the dispersion is subjected to ultrasonic processing (step S300), homogenization processing (step S302), and ball milling processing (step S304). Referring to Fig. 4, the dispersion is subjected to homogenization treatment (step S400) and ball milling treatment (step S402). Referring to Fig. 5, the dispersion is subjected to ultrasonic treatment (step S500) and ball milling (step S502).

In the embodiment of Figures 2 through 5, the homogenization treatment allows the graphite to be uniformly dispersed in the solvent and provides shear to reduce the van der Waals force between the graphite layers. Ultrasonic treatment allows solvent molecules to be intercalated between the graphite layers and adsorbed on the graphite surface to achieve a reduced van der Waals effect. The ball milling process provides the energy of the delamination to obtain graphene.

According to the above embodiment, in the above embodiment, at least one of the homogenization treatment and the ultrasonic treatment of the dispersion liquid is performed, and the dispersion liquid is subjected to ball milling treatment, whereby a nano material having high yield and high quality can be obtained.

Experimental Example 1: Production of graphene

In Experimental Example 1, the dispersion used contained graphite as a substrate and N-methylpyrrolidone (NMP, 70%, 80% or 100%) as a solvent. The homogenizer used for the homogenization treatment was T10 basic / S10N-10G (trade name, manufactured by IKA, Germany), and the rotation speed was set to 30,000 rpm. The ultrasonic oscillator used in the ultrasonic processing was an Elma sonic P60H (trade name, manufactured by Elma, Germany), and the frequency was set to 37 kHz. The ball mill used for the ball milling treatment was RETSCH High Energy Ball Milling E _max (trade name, manufactured by RETSCH, Germany), and the number of revolutions was set to 1,500 rpm.

The experimental design and experimental results of each example and comparative example are shown in Table 1 below.

Table 1         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> Instance</td><td> Manufacturing Method </td><td> Solvent</td ><td> I_D/I_G ratio</td><td> 2D band position (cm^-1) </td> <td> Resistance value of conductive paper (Ω/□) </td><td> Yield (%) </td></tr><tr><td> Step 1 (1 hour) </td>< Td> Step 2 (1 hour) </td><td> Step 3 (1 hour) </td></tr><tr><td> Instance 1 </td><td> Homogenization </td> <td> Ultrasonic processing</td><td> Ball milling treatment</td><td> 80% NMP/ 20% water</td><td> 0.343 </td><td> 2702.66 </td>< Td> 120.2±7.86 </td><td> 43.88 </td></tr><tr><td> Example 2 </td><td> Homogeneous Treatment</td><td> Ultrasonic Processing</ Td><td> Ball Milling</td><td> 100% NMP </td><td> 0.431 </td><td> 2702.50 </td><td> 179.2±14.90 </td><td> 19.60 </td></tr><tr><td> Example 3 </td><td> Homogeneous Treatment</td><td> Ultrasonic Processing</td><td> Ball Milling</td>< Td> 70% NMP/ 30% water</td><td> 0.373 </td><td> 2707.46 </td><td> 287.2±41.70 </td><td> 37.08 </td></tr ><tr><td> Instance 4 </td><td> Ultrasonic Processing</t d><td> homogenization treatment</td><td> ball milling treatment</td><td> 100% NMP </td><td> 0.461 </td><td> 2708.77 </td><td> 335.3 ±33.28 </td><td> 15.52 </td></tr><tr><td> Instance 5 </td><td> Homogenization </td><td> - </td><td> Ball Milling Treatment</td><td> 100% NMP </td><td> 0.527 </td><td> 2709.57 </td><td> 176.7±4.33 </td><td> 12.35 </td> </tr><tr><td> Instance 6 </td><td> - </td><td> Ultrasonic Processing</td><td> Ball Milling</td><td> 100% NMP < /td><td> 0.460 </td><td> 2709.48 </td><td> 805.4±38.88 </td><td> 10.85 </td></tr><tr><td> Comparative Example 1 </td><td> - </td><td> - </td><td> Ball Milling</td><td> 100% NMP </td><td> 0.418 </td><td> 2710.53 </td><td> 397.7±22.08 </td><td> 5.80 </td></tr><tr><td> Comparative Example 2 </td><td> Homogeneous Treatment</td>< Td> - </td><td> - </td><td> 100% NMP </td><td> 0.210 </td><td> 2710.22 </td><td> 14782.75± 5522.24 </td ><td> 0.68 </td></tr><tr><td> Comparative Example 3 </td><td> - </td><td> Ultrasonic Processing</td><td> - </ Td><td> 100% NMP </td><td> 0..329 </td><td> 2709.59 </td><td> 1185.98± 28 0.36 </td><td> 0.15 </td></tr><tr><td> Graphite</td><td> - </td><td> - </td><td> - </ Td><td> - </td><td> 0.0718 </td><td> 2716.14 </td><td> N/A </td><td> - </td></tr></ TBODY></TABLE>

1.1: Yield The yield was measured using a visible light ultraviolet spectrophotometer. As is apparent from Table 1, since Examples 1 to 6 are at least one of the homogenization treatment and the ultrasonic treatment of the dispersion, the dispersion is subjected to a ball milling treatment to produce graphene, and thus has a high yield. Among them, the yield of Example 1 was even higher as 43.88%. Further, Comparative Example 2 using the homogenization treatment and Comparative Example 3 using the ultrasonic treatment failed to provide more energy and shear stress to peel the graphite, and thus the yield was low. Comparative Example 1 using ball milling treatment resulted in a higher yield of graphene than Comparative Example 2 using homogenization treatment and Comparative Example 3 using ultrasonic treatment. However, since Comparative Example 1 to Comparative Example 3 were only subjected to a single treatment of the dispersion to produce graphene, the yield was much lower than that of Examples 1 to 6.

1.2: I _D /I _G is a graphene powder obtained by collecting the graphene dispersion, and the I _D /I _G ratio can be obtained by Raman spectroscopy (wherein I _D is a D band (D band) The intensity of I _G is the intensity of the G band, and the degree of defect of graphene is known by the ratio of I _D /I _G . When the I _D /I _G ratio is smaller, the degree of defects of graphene is low, that is, the quality is better. As is apparent from Table 1, the values of the I _D /I _G ratio of Examples 1 to 6 are low, and thus the degree of defects of graphene is low and the quality is good.

1.3: 2D band position The position of the 2D band in the Raman spectrum can be used to estimate the number of layers of graphene. When the 2D band is located at a position where the wave number is smaller, it means that the number of layers of graphene is smaller, that is, the quality is better. As can be seen from Table 1, the 2D band of the graphene after the reaction is located at a position where the wave number is small, that is, the number of layers is small and the quality is better than that of the unreacted graphite. Among them, the 2D bands of Examples 1 to 6 are located at positions where the wave number is small, and the number of layers of Examples 1 to 6 is small and the quality is good.

1.4: Resistance value

The graphene powder was made into a conductive paper, and its resistance value was measured. As can be seen from Table 1, the resistance values of Examples 1 and 2 were 120.2 Ω/□ and 179.2 Ω/□, respectively, and the resistance value of Comparative Example 1 was 397.7 Ω/□. It can be seen that the graphenes of Examples 1 and 2 have low electrical resistance and can be applied to the field of conductive materials.

Experimental Example 2: Application of Graphene to Surface Enhanced Raman Scattering (SERS)

Graphene can be applied to the field of surface enhanced Raman scattering. In detail, graphene can be used as a carrier for the growing metal nano-silver particles, and the metal nano-silver particles and the graphene are composited by an atmospheric atmospheric micro-plasma technology device. Next, the laser-enhanced Rhodamine 6G (R6G) was used as the standard analyte molecule to measure the surface-enhanced Raman scattering of R6G solution (concentration 10 ^-4 M) on silver-graphene composites. And further calculate the value of the enhancement factor (Enhance Factor), the results are shown in Table 2 below.

Table 2         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> Instance</td><td> Measurement Method</td><td> Wave Number< /td><td> Enhancement factor</td></tr><tr><td> 1647.2 cm^-1</td><td> 774.3 cm<sup>-1</sup ></td><td> 610.8 cm^-1</td></tr><tr><td> Comparative Example 4 </td><td> R6G Powder</td>< Td> 27.09 </td><td> 20.60 </td><td> 26.67 </td><td> 1 </td></tr><tr><td> Comparative Example 5 </td><td > R6G solution is coated on the composite of silver and traditional graphene oxide</td><td> 81.15 </td><td> 87.71 </td><td> 139.12 </td><td> 4.79×10 ⁴</td></tr><tr><td> Example 7 </td><td> The R6G solution was coated on the composite of silver and graphene of Example 1</td ><td> 874.99 </td><td> 581.70 </td><td> 1270.46 </td><td> 4.37×10⁵</td></tr></TBODY ></TABLE>

From the results of Table 2, the silver-graphene composite material produced using the graphene of Example 1 can greatly enhance the signal intensity of the Raman scattering effect as compared with Comparative Example 4 and Comparative Example 5.

As described above, in the method for producing a nanomaterial according to the above embodiment, since at least one of the homogenization treatment and the ultrasonic treatment is performed on the dispersion, the dispersion is subjected to ball milling treatment, thereby obtaining high yield and high. Quality nano material.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

S100, S102, S200, S202, S204, S300, S302, S304, S400, S402, S500, S502‧‧

1 is a flow chart showing the manufacture of a nanomaterial according to an embodiment of the present invention. 2 to 5 are flow charts showing the manufacture of a nano material according to another embodiment of the present invention.

S100, S102‧‧‧ steps

Claims (5)

A method for producing a nano material, comprising: sequentially performing a homogenization treatment, an ultrasonic treatment and a ball milling treatment on a dispersion, wherein the dispersion comprises a substrate and a solvent, the substrate is graphite, and the solvent is N- Methylpyrrolidone, and the concentration of the solvent is from 70% to 100%. The method of producing a nanomaterial according to claim 1, wherein the nanomaterial comprises graphene or graphene quantum dots. The method for producing a nanomaterial according to claim 1, wherein the ball milling treatment time is 0.5 hours to 4 hours, and the ball milling treatment rotation speed is 500 rpm to 1750 rpm. A method for producing a nano material, comprising: ultrasonically treating, dispersing, and ball-milling a dispersion, wherein the dispersion comprises a substrate and a solvent, the substrate is graphite, and the solvent is N- Methylpyrrolidone, and the concentration of the solvent is from 70% to 100%. A method for producing a nano material, comprising: ultrasonically treating and performing a ball milling treatment on a dispersion, wherein the dispersion comprises a substrate and a solvent, the substrate is graphite, and the solvent is N-methylpyrrolidone And the concentration of the solvent is from 70% to 100%.